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By G Hope, C Young, R. N. Gow

"The presence of enargite (Cu3AsS4) is problematic in gold processing as it is refractory, increasing cyanide and oxygen consumption, and enviromnentally hazardous. Selective leaching and treatment of the arsenic would prove advantageous to conventional gold leaching methods. The reactivity of enargite samples from Montana, US and Quiruvilca, Peru were studied under alkaline conditions, pH range of 8-13, using a cyclic voltammetry corrosion cell setup. Raman spectra of the surface were taken during and after cycling to compare surface species against theoretical predominance diagrams. Under slightly oxidizing conditions, covellite (CuS) peaks were found on the surface in a short matter of time, above - 200m V vs SHE for pH 9-13, suggesting arsenic leaching, but for longer conditioning times, elemental sulfur peaks were also found, which created a passivating surface layer. By operating above pH 12, under reducing conditions, ~-500mV vs SHE, arsenic can be leached as a thioarsenate (AsS4-xOx3-), without sulfur formation.IntroductionEnviromnental limitations on pyrometallurgical processing of arsenic has pushed the desire to process enargite-, Cu3AsS4, bearing concentrates towards a hydrometallurgical solution. Attempts to process can be broken down into two categories - the co-dissolution of arsenic and copper under acidic conditions or the selective leaching of arsenic under basic conditions. The selective leaching of arsenic would preferably leave behind a chalcocite, Cu2S, or covellite, CuS, phase that would be more amenable to conventional processing methods of the copper and gold industries. These methods employ bi- or poly-sulfides to leach arsenic as Assl· [1-4], hypochlorite leaching [5-7], ammoniacal leaching [8] or fine grinding to mechanically activate the enargite surface and increase normally slow reaction kinetics[9]. This study looked into the surface formations of an enargite electrode under alkaline conditions, in a pH range from 8-13, as it cycled from -1000 mV to 1000 mV vs SHE. The understanding of the formations and under what conditions they form will be helpful in further development of any of the aforementioned processes."

Jan 1, 2012

By H. Kandemir

An experimental study of the bacterial oxidation of naturally occurring high-purity sulphide minerals (FeS2, Fe1-xS, Cu5FeS4, ZnS) is presented using a mesophilic strain of T. ferrooxidans. As well as metal analyses and solution pH, partitioning of sulphide sulphur into elemental sulphur and sulphate has been monitored as a function of leach time. Partially oxidized sulphide substrates have been characterized, at regular time intervals, by X-ray diffraction methods and extracellular organic compounds reporting into leach solution .have been identified by thin layer -chromatography.

Jan 1, 1985

By S. Peng, Vaughan R. Voller

"Free boundary problems are a common occurrence in materials processing operations. An important example is the filling of material into molds. This paper looks at filling problems associated with polymer processing, in particular Resin Transfer Molding (RTM) and Compression Molding. A general, single governing equation is developed which on numerical solution provides predictions for the position of the polymer front in the mold during filling. Both fixed and deforming finite element solutions are developed. Application to polymer filling test problems reveal that the fixed and deforming grid scheme are accurate and compare closely with each other.IntroductionProblems arising from the analysis of material processing operations often involve the tracking of a moving boundary, on which a balance conditions needs to be met, or the locating of a free surface that defines the solution domain. Material processing examples of so called ""free and moving boundary problems"" include; the tracking of solidification/melting fronts[l], the tracking of the metal/gas interface during the filling of a mold[2] and location and shape of a skull (freeze line) in a melting furnace[3].Computational solution of free and moving boundary problems usually fit into one of two classes, viz.1. Fixed grid scheme: In which the spatial domain is covered by a fixed grid (mesh) of node points and the solution uses an auxiliary variable (e.g. a local liquid fraction) to track the moving boundary or locate the free surface.2. Deforming grid scheme: In which the grid in the spatial domain is continuously deformed (or adapted in a steady state problem) such that a specified set of grid points lie on the moving boundary or the free surface.Details on the basic underlying features in these two classes of solution can be found in the excellent monograph by Crank [4]."

Jan 1, 1994

By J. D. McCain

Magma's San Manuel smelter has adopted new operating techniques resulting in 21% increased productivity and 87% reduction in lost time accidents. Reverberatory furnaces were converted to coal firing from expensive natural gas and fuel oil. Slag and matte flow problems and safety were improved by implementing hydraulic slag stopping and matte tapping machines. Coordination of furnaces, converters and acid plant was improved by using a computer-aided converter controller/scheduler function. Manual mudding of converter lips after each collar pull was replaced with a gunning system for coating the mouth castings. One converter punch car was automated using robotic technology. An automatic anode take-off was installed with fewer moving parts and a mechanism for ear twisting one cell contact. Anode copper refining was improved by replacing propane/hydrogen mixtures with high pressure/velocity natural gas tuyeres. Improved converter scheduling increased acid plant production 43% with more autothermal operation time. Six dedicated computers/microprocessors are utilized for automation, data acquisition, process monitoring and on-line air quality information for the Supplementary Control System.

Jan 1, 1983

By Yun Soon Han, Joo Hyun Park

Indium (In) solubility in the FeO-SiO2-Al2O3-5%CaO slag was measured under p(O2)=10¯¹¹ atm at 1573 K to clarify the dissolution mechanism of In in FeO-bearing metallurgical slag. The In solubility increased with increasing oxygen partial pressure, whereas it decreased by increasing the activity of basic oxide, viz. FeO. Thus, a dissolution mechanism of In in the FeO-SiO2- Al2O3-5%CaO slag was described by the following equation. In(s)+1/4O2(g)=(In+)+1/2(o2-) The enthalpy change of the In dissolution reaction was negative, indicating that the dissolution reaction was an exothermic reaction. This is consistent with the above reaction mechanism.

Jan 1, 2014

By Takahiro Furuzono

Saganoseki Smelter and Refinery of Pan Pacific Copper Co., Ltd. started treating copper anode slimes using a unique hydrometallurgical process in chloride media in 1997. The process comprises the following stages, decopperizing, wet chlorination, solvent extraction for gold, silver chloride reduction, and separate reduction stages that treat the gold extraction raffinate with sulfur dioxide gas. Precious metals and rare metals in the copper anode slimes are dissolved in an aqueous solution of hydrochloric acid by oxidative leaching, which is termed wet chlorination. Gold is efficiently extracted from the chlorination liquor by dibutyl carbitol in the solvent extraction stage. Gold is reduced by oxalic acid from goldloaded dibutyl carbitol and recovered as gold powder. The gold powder is cast directly into granules or ingots of more than 99.99% purity without electrorefining. Selenium is recovered as a selenium residue by reduction with sulfur dioxide gas and refined through vacuum distillation. The plant was designed to process 132 tonnes of copper anode slimes per month and has a current capacity of 206 tonnes per month due to several enhancements. Compared with the conventional process, the hydrometallurgical process described here provides some advantages, in particular, a higher product quality, shorter gold-retention time, and reduction in environmental load.

By H. Deveci

Bioleaching/biooxidation is essentially a dissolution process with the involvement of acidophilic bacteria acting as the "catalyst" to accelerate the dissolution of metals from sulfide minerals. The contribution of bacteria to the metal dissolution is closely controlled by the growth of bacteria, which is itself affected by the physico-chemical conditions within the bioleaching environment. There are a number of operating parameters controlling bioleaching processes, which are required to be maintained within a certain range in the leaching environment whereby the activity of bacteria with the resultant oxidation of sulfide minerals can be optimized. In this regard temperature, acidity, oxidizing conditions, availability of nutrients, oxygen and carbon dioxide, surface area and presence of toxic ions are of prime importance for control and optimization of bioleaching of sulfide ores/concentrates. Bioleaching processes are temperature and pH dependent with optimum metal dissolution occurring in a particular range where the bacterial strain is most active e.g. mesophiles at 35-40°C and pH 1.6-2.0. Provision of nutrient salts is required to maintain the optimnm growth and hence metal dissolution with the quantity of nutrients apparently being dependent on the availability of substrate i.e. head grade/pulp density of an ore/concentrate. Oxygen transfer is one of the most critical factors since the oxygen levels below 1-2 mgll may adversely affect the oxidizing activity of bacteria. Bioleaching rate tends to improve with increasing the surface area at low pulp densities but, in practice. the pulp density is limited to -20010 w/v. Increasing concentrations of ions such as cr may also adversely affect the oxidative activity of bacteria. Keywords: Bioleaching, Biooxidation, Acidophilic bacteria

Jan 1, 2003

By Xue Wang, Callie Babbitt, Chelsea Bailey, Matt Ganter, Gabrielle Gaustad, Brian Landi

"Current trends, motivated by fossil fuel dependence and unprecedented greenhouse gas (GHG) emissions, show lithium-ion batteries (LIBs) emerging as a competitive energy storage technology due to higher power and energy densities compared to Pb-acid and Ni-metal hydride chemistries. These trends may be of concern, however, as environmental impacts are not well understood for either the LIB itself, or for the nanoparticles consumed or released during the battery's production, use, or end-of-life. This study combines economic modeling, dynamic material flow analysis, and fundamental material characterization methods in order to quantify some of the economic and environmental trade-offs for LIBs at their end-of-life. As expected, results show that as chemistries transition from Li-Co based cathodes to Li based Fe, Mn, and S cathodes, LIB recovery value correlates to the value of the raw materials used. These initial results aim to inform collection policies being proposed currently as well as enable future deployment of novel recycling techniques.IntroductionGlobal fossil fuel dependence and unprecedented GHG emissions have led to increasing attention on energy alternatives, for both electricity production and personal transportation. However, development of renewable energy systems is contingent on concurrent technological development of energy storage systems, primarily batteries used for power grid load-leveling, renewable energy storage, and hybrid and battery electric vehicles. In this sector, lithium-ion batteries (LIBs) are emerging as a competitive technology due to higher power and energy densities compared to lead-acid and nickelmetal hydride chemistries[!]. LIBs represent close to 20% of the total rechargeable battery market and 75% of the portable rechargeable battery market, which is the fastest growing segment of the rechargeable battery market, with a 20% global growth in 2008 [2].This surge in production ofLIBs indicates a looming waste problem; total waste from Li-ion batteries has likely grown substantially from the 500 metric tons estimated in 2003 [3]. Figure IA shows the substantial increase in world-wide lithium production that has occurred in the last several decades with batteries making up the largest share of applications (Figure lB). California and New York state legislators have attempted to proactively address this looming waste by issuing diposal bans on rechargeable batteries in their states[4, 5]. However, quantification of the costs involved in collection, transportation, and processing of these materials has not been examined in depth."

Jan 1, 2012

By J. Borlée, J. P. Birat

"ULCOS is a large European program launched by a consortium of 48 partners led by arcelor and a core group of steel producers, which was started in 2004 with the support of the European Commission (RFCS and 6FP programs) to search for breakthrough process routes that could, in the future, when fully developed, demonstrate the potential of large cuts in CO2 emissions for the production of steel from iron ore.The timescale for commercial implementation is the post-Kyoto period, i.e. 15 to 20 years from today.The present paper presents the progress made in the first 2 years of this 5 year program.Several concepts are being investigated in parallel: re-engineering of the blast furnace to incorporate CCS in the core of the process, smelting reduction with CCS capabilities, massive use of natural with more CO2-lean technologies than today, hydrogen steelmaking and electrolysis of iron ore. Biomass also offers very attractive perspectives, while raising major challenges.None of these new steelmaking routes are ""no regret"", which means that the European Steel Industry has already incorporated extensive energy saving steps in its present process technology and is working as close to thermodynamics limits as is cinematically and economically feasible, and that decreasing GHG emissions further means introducing breakthrough technologies that add significant costs to the operation of the Steel Mills.They will also require much research and development before they can be proven and implemented commercially.IntroductionThe ULCOS program (Ultra Low CO2 Steelmaking) is a large research program of the European Steel Industry and its industrial and research partners launched in September 2004 to investigate steelmaking technologies that have the potential of reducing the CO2 emission of the Industry by a large amount, typically in the order of 50%. It is supported in the European Community by the 6th Framework and the RFCS programs through 3 complementary European projects [1,2].The present paper summarizes the work carried out in the phase 1 of ULCOS and in framing the program of phase 2."

Jan 1, 2008

By Sung-Mo Jung

Experiments were carried out on a system with artificially prepared slags in a graphite crucible, in order to examine the possibility of recycling BOF slags produced in the steelmaking process. More than 80% of FeO and P2O5 was reduced within 20 minutes and the FeO reduction rate was greater than that of P2O5. P2O5 reduction began after more than 60% of FeO was reduced. Increasing slag basicity enhanced the reduction of FeO and P2O5. Temperature also improved slag reduction. The overall reduction rate was controlled by the chemical reaction at the slag/carbon interface. The reduction rates of FeO and P2O5 were second and first order with respect to their respective contents. Most of the reduced phosphorous is believed to vaporize in the form of P2 gas.

Jan 1, 2006

By D. Gregurek

In non-ferrous metal furnaces the installed magnesia-chromite refractory lining is exposed to several stresses, rather complex in their interaction. Therefore, a detailed investigation and understanding of wear mechanisms through “post mortem studies” is an important prerequisite for refractory producer. Additionally, in order to determine the most suitable refractory products and to improve the lining life of refractories, practical corrosion testing with processing slags is performed. For this purpose the test-facilities, such as induction furnace, rotary kiln but also cup test and drip slag test, allow the best possible understanding of chemothermal brick wear on pilot scale. Prior to testing a complete mineralogical investigation, thermo-chemical calculation via FactSageTM of the slag was carried out. Based on such research results, combined with specific process knowledge RHI Magnesita can recommend appropriate brick lining solutions for non-ferrous metal furnaces.

By N. B. Gray, I. F. Taylor

"Gas injection to promote chemical reactions or mixing is a feature of many metallurgical processes. Often the aim of gas injection is to bring about a chemical reaction between the gas and liquid but most of the past physical and mathematical modelling work has ignored the influence of such reactions. In the work reported here, cold model studies have been conducted in which gas reacts with the liquid into which it was injected. The rate of liquid mixing has been measured as an indication of the mechanical energy transfer. It has been found that gas generated chemically within the liquid is significantly less effective at promoting mixing than the equivalent volume of inert gas. The relative ineffectiveness of chemically produced gas is thought to be due to smaller bubble sizes in comparison to the inert gas case. Small bubbles characteristic of chemically generated gas move with low slip velocities relative to the liquid and lead to different turbulence generation mechanisms.IntroductionIn processes such as steelmaking, copper conversion, bath smelting and ladle steel finishing gas is injected into liquid metal where it reacts chemically or simply serves as a source of agitation. An understanding of fluid flow phenomena in such situations is an essential pre-requisite to the calculation of process intensity and the optimisation of vessel productivity. Traditional physical cold modelling approaches to prediction of liquid flow in such situations are now often augmented by the techniques of computational fluid dynamics. Even with the availability of numerical modelling techniques cold physical models continue to have an important role for validation because it is generally difficult to obtain quantitative data from high temperature processes.Almost all previous cold modelling work has been based on the injection of an inert gas into water or some other non-reactive liquid. Such models do not include the significant increase in gas volume inherent in some processes. For example the oxidation of carbon in steelmaking leads to a twofold increase in molar gas flux through the reaction:"

Jan 1, 1996

By W. -S. Hwang, R. A. Stoehr, P. Ingerslev

"The flow of molten metal entering complex two-dimensional foundry molds has been modeled using the Simplified Marker and Cell (SMAC) and Solution Algorithm (SOLA) techniques. The molds were for a series of four and three-spoke wheel designs. The computer calculations were compared to physical experiments in which molten cast iron was poured into C02-bonded sand molds. The metal was photographed with a high speed motion picture camera focused through a Pyrex glass window on one face of the mold. To get good agreement between the calculations and the experiments, it was necessary to accurately represent the velocity through the ingate. This was calculated by application of the Bernoulli equation to flow through the feed system. Some difficulties were experienced with mathematical instability, expecially in the three-spoke design with a narrow ingate. This was overcome by using 100% upwind differencing, and over relaxation parameter near 1.0 (i.e. no over relaxation), and variable mesh spacing.IntroductionModeling the flow of molten metal entering molds has the potential for making significant contributions to the design of feed systems. It will supply information to the computer-aided-design systems of the future that will enable the designer to optimize the placement of gates, dimensioning of passages, and designation of casting speeds. Such design criteria have generally been based on application of energy balance (Bernoulli equation) principles to flow in the sprues, runners, and gates. Indeed, this is the easiest way to determine the proper dimensions to give a suitable filling time for a casting of a given size. A number of computer programs, including one by some of the present authors, have integrated such calculations into CAD systems. l Modeling the flow of metal inside the mold cavity requires other techniques that will handle free-surface transient flow. Stoehr and Hwang reported on the application of the Marker-and-Cell (MAC) technique to mold filling problems at the previous conference in this series at Hennicker, N.H. in 1983. 2 Although considerable progress has been made since that time in improving the accuracy, stability, and convenience of these techniques, the shapes to which they were applied remained limited. Also, physical verification of the results of the calculations was limited to water models.The work to be reported in this paper was undertaken with two objectives: (1) to apply these techniques to more complex and realistic shapes, and (2) to verify the results by comparison with flow patterns observed in molten metal poured into actual sand molds."

Jan 1, 1986

By C. H. Bucknam

A review of phase analysis methods used to characterize refractory gold ores is presented. Updating of assay methods using database technology, on-line instrument interfacing and response surface modeling is highlighted. The use of assay results to classify ores for metallurgical purposes is demonstrated.

Jan 1, 1987

By Dave Tahija

"Many investigations are being performed with the goal of removing carbon dioxide from the atmosphere and permanently storing it in geologically stable settings. At the same time, carbon dioxide in the form of dissolved carbonate is steadily accumulating in the world's oceans. Both carbon dioxide sequestration and oceanic accumulation are constrained by the aqueous thermodynamics of the carbonate system. These constraints are illustrated using the STABCAL computer model to generate potential-pH and aqueous distribution diagrams of seawater in contact with various pressures of carbon dioxide gas. STABCAL diagrams and titration simulations are also used to model some potentially useful cation-carbonate sequestrationsystems.IntroductionAtmospheric carbon dioxide concentrations have risen dramatically in the past couple of centuries and are rising still, primarily as a result of human activities, especially the burning of fossil fuels. Increased atmospheric carbon dioxide concentrations have been implicated as a main cause of global warming but have other effects as well.Rising levels of atmospheric carbon dioxide result in increased concentrations of dissolved carbonate complexes in water, including the oceans. These dissolved carbonates interact with other dissolved substances, altering overall seawater chemistry, most noticeably causing lowered pH levels.Some of these chemical changes are observed directly, for instance the general drop in oceanic pH, [1], while others can be inferred and predicted using thermodynamic modeling. The chemistry of dissolved carbonate in seawater is not especially intricate, as such chemical systems go, but neither is it simple enough to be worked out on the back of an envelope. Interactions between the several simple carbonate species and all the major dissolved cations in seawater should be considered, as well as the effects of competing anions, especially chloride and sulphate, since they are much more abundant than carbonate in seawater."

Jan 1, 2011

By Saskia Duyvesteyn

Ion flotation is a technique applicable to the removal of metal ions from dilute solutions, using ionic surfactants.- While there are a number of physical and chemical parameters that influence the ion flotation process, this paper focuses on two of the important chemical ones, namely frother concentration and ionic strength. The effect of several frothers, including ethanol, iso-propanol and MIBC at concentrations ranging from 0% to 0.4%, was studied for the model Cd-dodecylsulfate and Cu-dodecylsulfate systems. The ionic strength, as well as the effect of monovalent and multivalent counter ions, was also studied in the range of 1@3 - 1 M, at constant pH. The results are discussed in terms of applicability to a range of effluents from minerals and materials processing operations.

Jan 1, 1994

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By Jiakai Zhang

Many postconsumer electrical and electronic equipment wastes contain a considerable amount of rare earth elements (REEs); however, the current level of REE recycling from them is limited (<1%). Neodymium–iron–boron (NdFeB) magnets, used at both small- and large-scale, from computer hard disk drives and small tools to wind turbines and cars, are a good example of such waste materials that contain high content of neodymium (Nd) and dysprosium (Dy). These elements are considered critical metals because they are the main building block of emerging green technologies that will allow for GHG emission reductions. Because demand for these green products is increasing around the world, the demand for REEs is increasing quickly, putting their supply at risk in the near future. Thus, it is critical to develop efficient, robust, and cost-effective processes to recycle these elements from this class of electronic waste materials. Here, we performed a thorough characterization of a N52–NdFeB magnet to identify its composition, crystal structure, and morphology. Furthermore, we developed an efficient hydrometallurgical process to extract Nd and Dy with high efficiency (more than 95%).

By Shaohua Ju, Jin-hui Peng, Ya-jian Wang, Shuai-dan Lu, Li-bo Zhang, Lei Guo

"The granulation of a red mud is of great importance for recycling this material as an adsorbent for waste water or gas. A new granulating process was developed and its effect was evaluated. To reduce the cost of the granulation process, the wet filter cake (containing 25% water) was directly mixed with different cement contents (4%, 6%, 8% and 10% based on wet material). The mixtures were placed in a moist environment for 4 days, and then were washed with deionized water until the pH values of leachants were lower than 9.0. The efflorescence ratio, surface area and particle size of the aged mixture were determined, respectively, by bottle shaking experiments, N2 adsorption and screening. The results showed that the best addition of cement is 2%, and this yielded granulated material with a particle size of less than 2 mm, an efflorescence ratio of 4.83% and a specific surface area of 17.42 m2/g.IntroductionRed mud is a residue of the aluminium industry that is produced during the alkaline extraction of alumina from bauxite by the Bayer process. For every ton of alumina that is produced, the amount of red mud generated can vary from 0.3 to 2.5 tons, depending on the characteristics of the bauxite. In its typical form, red mud is brick red in colour, caustic, about three times as dense as water and, when un-neutralised, has a high pH, typically around pH 13 [1]. It is primarily composed of iron oxide, silica and alumina, along with traces of heavy metals. Red mud particles are quite small; typically 99% will pass through a 0.6 mm sieve and 87% through a 0.038 mm sieve [2],"

Jan 1, 2012

By In-Hyeok Choi

Currently, spent V2O5–WO3/TiO2 catalysts contribute significant amounts of solid waste following increasing levels of global demand. V2O5–WO3/ TiO2 catalysts usually consist of TiO2 anatase as a supporting oxide, vanadium as a catalytic agent, and other promoters such as tungsten, silicon, and calcium. Although vanadium is the main catalytic agent, a relatively high content of tungsten (WO3, 7–10 wt%) typically exists compared to vanadium (0.5–1.5 wt%). Considering the irreplaceable properties and industrial importance of tungsten, a feasible method for the recycling of spent V2O5–WO3/TiO2 catalyst should be established to utilize it as a secondary source. This paper presents a process to recover tungsten from spent V2O5–WO3/TiO2 catalyst. The processes proposed here involving roasting, decomposition using HCl, ammonia leaching, and crystallization. Within the process, ammonium paratungstate (71 wt% as WO3) is obtained as a final product. The total yield rate of tungsten from feedstock was found to be 96.3%.