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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 Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By Motoyasu Sato

Highly pure pig irons were produced in a multimode microwave reactor from powdered iron ores with carbon as a reducing agent in the nitrogen atmosphere. The grains in compacted powder absorb microwave energy selectively. Microwave-matter interaction creates thermal non-equilibrium state microscopically and enhances chemical reactions and the phase mixing at the grain boundaries very rapidly. The visible light spectroscopic techniques was used to monitor the progress of the reactions. Up to 650°C, the heated powders radiate the continuous spectrum of blackbody emission. The small non-equilibrium hot spots rise, move and finally burst in to brighter light emitting from all over the surface at 650°C. CN molecules and Fe (I) atoms were identified in the recorded spectrum. These bursts are similar to the ?ignition propagation? normally observed in chemical reactions. The line spectra originated from CO molecules have not been detected yet. The solid-solid reaction could be expected between the iron oxides and carbon to produce CO2 directly. A loss in the sample weight was accelerated during the excess-emission. These are the clear evidence that microwaves cause thermally non-equilibrium state and accelerate reduction process. The reduction of iron ore is completed at 1380°C and relatively very pure pig iron was produced. It should be noted that the impurity level of Mg, S, Si, P and Ti is only 5-10% of what is found in the pig irons produced by modern conventional blast furnaces in the steel industries. The necessary amount of carbon needed was 1/2 compared to conventional blast furnace to produce the unit weight of steel, if we applied renewable energy or nuclear power for the microwave excitations.

Jan 1, 2006

By Debbie Marshall

Process water is an important consideration in the development of a nickel laterite project. Depending on the location of the ore body, sufficient fresh water may not be available and it may be necessary to use seawater (or saline groundwater) for ore preparation. This introduces various species, which have major effects on materials of construction and leaching chemistry. This paper summarizes batch testwork completed at the Falconbridge Technology Center. The leaching behaviour of eleven different laterite ore samples were compared using seawater and fresh water. For brevity, six of the eleven samples are reported here-the other five samples showed similar results. Each ore type was leached under identical conditions in both freshwater and seawater and the leaching chemistry compared. The batch test results were confirmed in a continuous pilot plant, and leach kinetics for the two systems were compared. Keywords: high pressure acid leaching, laterites

Jan 1, 2004

By Suzzann Nordwick

Over the past decade, significant advances have been made in the development of sulfate-reducing bacteria (SRB) technology to treat acid mine drainage (AMD). Bench-scale testing, field demonstrations, and engineered applications of SRBs for the treatment of AMD will be presented. Designs include an in situ bioreactor installed in the subsurface workings of the Lilly Orphan Boy Mine in 1994, the SRB bioreactors installed at the Calliope Mine from 1998 to 2001, the integrated biological reactors built at the Surething Mine in 2001, and the ongoing development of a replaceable cartridge system. SRB technology benefits include the reduction of dissolved metal ions to insoluble metal sulfides and the neutralization of the AMD resulting from the production of bicarbonate from the oxidation of organic nutrients. This paper will address engineering design criteria including the selection of organic media and system permeability and complete mitigation of AMD. Research was funded under Interagency Agreement No. DW899388-70-01-1 between the US EPA and the US DOE and was conducted by MSE Technology Applications, Inc., through the National Environmental Technology Laboratory (DOE Contract No. DE-AC22-96EW96405) at the Western Environmental Technology Office located in Butte, Montana.

Jan 1, 2003

By Zhigang Zak Fang, Michael L. Free, Jaehun Cho, Syamantak Roy, Amarchand Sathyapalan

Leaching characteristics of impurity removal from the Upgraded Titania Slag (UGS) using hydrochloric and boric acids has been investigated. Specifically, this study has focused on removal of iron oxides from the UGS that has been reduced by hydrogen gas and magnesium at 750oC for 5 hours. Reduced UGS is mainly composed of titanium hydride and impurities like iron oxides, silicon oxide, aluminum oxide, and magnesium oxide. The concentration of hydrochloric and boric acids and the leaching temperature have been chosen as the prime variables to identify the optimum conditions and leaching characteristics for removal of iron oxides. It was observed that under the constraint that 1 wt % of titanium hydride loss is the maximum amount tolerable, 0.1M HCl with 1M boric acid and 90oC are the most effective parameters for iron removal from the reduced UGS. Also, the overall rate of reaction seems to follow interfacial reaction controlled kinetics. The calculated activation energy of the reaction is 73.90kJ/mol.

Jan 1, 2016

By R. C. Hubli

Copper (II) chloride has proven to be an efficient lixiviant for copper sulphide ores and secondary sources of copper such as scrap. Nickel sulphides are generally associated with copper ores and copper-nickel matte is an intermediate product of processing mixed sulphides. While the copper species in aqueous chloride media are present as chlorocomplexes, the presence of nickel as Ni++ offers effective separation between the two by solvent extraction techniques. Oxidation of millerite by cupric chloride in sodium chloride solutions has been studied as a function of rate of agitation, leaching time, temperature, acid concentration and total initial cupric concentration. The reaction has a 1/2 order of dependence on initial cupric concentration in the range of 0.0 to 0.5M. The activation energy for the temperature range 333 -363 K has been found to be 59.2 kJ/mol with chemical reaction at the unreacted mineral surface as the rate controlling step. The rate expression, according to the shrinking-core model, for initial cupric concentrations between 0.0 to O.5M, is evaluated as

Jan 1, 1996

By K. A. Dudley

Basic solvent extraction theory indicates that pH initiates the basis of an oxime's metal complex formation and therefore its selectivity toward certain metal species. The recommended optimum pH for some of the commercial copper reagents is in a range that should maximise copper loading of the oxime. However, this pH range also tends to maximise iron(III) loading under certain operational conditions resulting in low selectivity values. Recent operational parameters at Girilambone Copper Company have highlighted some of these conditions that have a major influence on the oxime's selectivity for copper over iron(III) in the leach solutions. The result is that the pH for maximum copper extraction is no longer within the optimum range to maximise oxime selectivity. Therefore, specific copper and iron(III) pH isotherms have been determined on-site for the changing leach solutions that are fed to the solvent extraction plant in order to optimise oxime selectivity. The influences of solvent extraction plant configurations are also discussed as a controlling parameter.

Jan 1, 1999

By V. Vergara

Four copper composites were obtained by mechanical alloying, using as dispersed phases of four carbide powders; they were: boron carbide, chromium carbide, silicon carbide and zirconium carbide. The purpose of this work was to study some characteristics of these compounds and their feasibility for use as materials for electrical equipment. Raw materials used were copper powder finer than 150 mesh, and 2-4 vol % of powder carbides finer than 325 mesh. The alloying process was carried out using both a Spex 800-D mill with tungsten jars and balls and a hardened stainless steel jar and balls, the purpose of which was to measure the degree of contamination induced by the milling media. The changes in particle size, morphology and microstructure of copper alloys were studied with SEM and TEM for each alloyed powder. The degree of saturation of copper by the carbides was measured by X-ray diffraction. Sound samples were obtained by hot isostatic pressing at 1073°K. The best characteristics were obtained for the compound copper-chromium carbide, based on their hardness, tensile strength and electrical conductivity values. The other alloys failed due to their excessive brittleness after hot pressing.

Jan 1, 1999

By Jiang Fan, Wang Haigang

"The three-dimensional complex multiphase turbulent flow in U-beam separators was simulated using the Reynolds stress equation models (RSM). To account for the effect of the stochastic characteristic of the instantaneous gas velocity on the particles, the improved Lagrangian stochastic model based on the Reynolds stress model for gas phase was adopted, which attributed to the successful prediction of the turbulence anisotropy and particle crossing trajectories effects. The interaction between the particles was also considered using the HardSphere model. To treat the particle-wall collision, the influence of the roughness of the wall on the motion of the solid particles was taken into consideration by imposing random collision angles. The result from this study not only shows the dynamic characteristics of the multiphase flow- in the separators, but also gives the relationship among the efficiency, structure and pressure losses of the separator.IntroductionCirculating fluidized bed (CFB) combustion is one of the most promising clean coal techniques. A main feature of CFB boilers is the un-delayed recycle of solid, coal and sorbant particulate, in an external loop. Separator, which is required to separate the solid particle from the flue-gas leaving the reactor of CFB, plays an importance role in the external solids recycle loop. It affects the combustion of CFB system greatly. Presently cyclone is the most commonly used as separators for CFB system and other chemical industrial processes. It provides high level of separation for CFB system for fine particles. However it suffers from some inherent disadvantages. It's volume and size is huge. Moreover, it is difficult to design and install when the CFB workload rises. The application of U-beam separators instead of hot cyclone separators in CFB boilers has many advantages. Publications indicate proposals or successful use of Ubeam separators in Swedenr11, USA 21, Russia r3land China [4]• But it is not possible to find results in the literature of detailed investigations of this new. type of separators or recommendations on the choice and calculation of an optimal design. For this reason, numerical simulation for the three-dimensional gas-particle two-phase flows with several rows of vertical U-beam elements, local in the chess order and blocking a way of outgoing from a CFB boilers dusted gases was carried out in this study."

Jan 1, 2004

By G. A. Brooks

The problem of treating concentrates with increasingly higher levels of arsenic and antimony is compounded by the trend to stricter environmental guidelines regarding the disposal of smelter wastes. Much of the arsenic and antimony from non-ferrous processes is recovered as oxide fume. The options for handling these fumes include recycling them to the smelter, stabilising and disposing of them, and recovering values from them. Whilst arsenic oxide has little value, there is a market for antimony oxide and this provides an incentive for devising techniques for separating antimony oxide from arsenic oxide before disposal of the arsenic oxide. Arsenic can be separated from antimony oxide by selectively volatilising the more volatile arsenic trioxide from a mixed oxide sample or by selectively condensing the less volatile antimony tetroxide at high temperatures, leaving arsenic trioxide to condense out at lower temperatures. The results of selective volatilisation experiments at 379 to 587 °C indicate that it is difficult to achieve an arsenic content below 5.0 wt.% using air or nitrogen as carrier gas due to the formation of solid solutions between the two oxides. Injection of oxygen into a mixed vapor stream improved separation by selective condensation and antimony tetroxide containing as low as 0.23 wt.% was obtained in laboratory experiments.

Jan 1, 1994

By Nelson Collao I.

Loss of the organic phase from solvent extraction circuits is a major cost factor for SXEW operations. Recognized sources of loss include evaporation, entrainment, and biological degradation. The mechanisms for both entrainment and evaporative losses are well recognized. Biological degradation of the organic has not been as extensively evaluated as the other mechanisms but is a major source of loss. This paper discusses the impact of biological degradation on an operating plant, potential mechanisms for degradation, conditions under which biodegradation of plant organic can occur and plant conditions that may assist in promoting biodegradation.

Jan 1, 2003

By S. G. Galbraith

We have used the principles of supramolecular chemistry to develop reagents to transport metal salts. These reagents have separated charged "compartments" which recognize a metal cation and its attendant anion(s). They are easy to manufacture as they are structurally related to the commercial hydroxy-oxime extractants for copper. Efficient protocols for loading and stripping of these extractants depend on the novel feature that they bind the metal salt in a zwitterionic form of the ligand. Transfer of the phenolic protons to the pendant amines generates the charged "compartments" to accommodate the metal cation and its attendant anion(s). This paper focuses on how these types of reagent can be used to recover base metals from sulfate and chloride media in flowsheets in which solvent extraction effects separation and concentration operations, interfacing between conventional leach and electrowin/reduction processes. Work on the development of reagents that have high selectivity for metal chloride/sulfate transport, convenient stripping protocols and appropriate hydrolytic stability will be described.

Jan 1, 2003

By K. Krishnapisharody

A mathematical model has been developed to predict the interface dynamics and droplet generation of the buoyant phase in a two-fluid system. The model employs the well-known SIMPLE algorithm for obtaining flow fields and the Volume of Fluid (VOF) method, for interface tracking. The implementation of the model in water-oil systems, where the oil layer is placed above a recirculating water bath, is discussed. The evolution of the water-oil interface leading to the formation of oil droplets is computed realistically.

Jan 1, 2008

By Heng Yi

The salt lake brines that lithium is extracted from have high chloride levels making the brine very corrosive to stainless steel extraction column internals. This is a significant problem in column scale-up to industrial production. Two types of corrosion-resistant ceramic internals, the hybrid ceramic internal and ceramic plate, were designed and tested under pilot conditions for future industrial application in this field. The hydrodynamic results (Yi et al. Ind Eng Chem Res 56 (4):999–1007 (2016), [1]) show that holdup of hybrid ceramic internal is higher than that of ceramic plate by around 50%, while Sauter mean diameter when using the hybrid ceramic internal is smaller than when using the ceramic plate by around 30%. This results in a larger mass transfer area, hence better mass transfer efficiency for the hybrid ceramic internal. Axial dispersion and mass transfer parameters are also examined (Yi et al. Ind Eng Chem Res 56(11):2049–3058 (2017), [2]). The results show that the column with hybrid ceramic internals has 50% lower axial dispersion coefficient and 50% higher mass transfer coefficient, leading to higher mass transfer efficiency. The transfer unit height of the column using hybrid ceramic internals can be as low as 0.2 m, showing very good efficiency. This is promising for near-future applications. Two-phase computational fluid dynamics (CFD) models have been developed for the two columns with ANSYS FLUENT commercial software. CFD successfully predicts the higher holdup and lower axial dispersion coefficients for the hybrid sieve plate pulsed column as measured in the experiments, and the cause for the difference in performance has been explained with information from CFD.

By Batric Pesic

Silver dissolution with thiourea was studied by using the rotating disk technique. The major parameters studied were: thiourea concentration (0-0.5M), ferric sulfate concentration (0-0.5M), sulfuric acid concentration (0-0.5M), and the effect of many foreign ions (Mn, o.i, Co, Ca, Na, etc.). Temperature effect was studied in the range 5-35 .C. The activation energy was 5.4 Kcal/mole. The dissolution of silver was first order with respect to ferric sulfate, and the secord order with respect to thiourea. Among the additives, copper had a dramatically negative effect. The strong oxidants such as hydrogen peroxide and manganese dioxide were also detrimental for silver dissolution. Silver does not dissolve with thiourea in the absence of ferric ions. Sulfuric acid does not participate in the dissolution reaction either. Chemically, the most important parameter for silver dissolution is the ferric sulfate/thiourea ratio. Thus, in the solutions with excess of ferric sulfate, a solid silver-thiourea complex is formed, which precludes transfer of silver into solution. In the solutions with the excess of thiourea, the free thiourea reacts with formed solid silver-thiourea complex and silver goes into the solution. The solid silver-thiourea complex was characterized according to its chemical composition. The complex contains 6.54%C, 2.49\H, 14.77%N, 16.09%0, 21.62%8, and 37.13% Ag. This composition corresponds to a Ag2so4.3'1U.2ff:i0 compound The soluble silver species are present in the solution as the dimers of AgTU+3 complexes.

Jan 1, 1989

By E. Kozeschnik

A new model is presented for the simulation of the evolution of precipitates in a multi-component multi-particle multi-phase environment The mathematical formulation as well as the physical background of the model are briefly introduced and its capabilities are discussed on the example of a precipitation sequence in a complex steel. Keywords: Modeling, precipitation kinetics, nucleation, growth, coarsening

Jan 1, 2003

By Isabel Lázaro

A detailed study has been undertaken into the electrochemistry of the leaching of chalcopyrite in acidic solutions containing ferric ions. Mixed potential measurements have shown that the maximum potential achievable on a chalcopyrite disk in a ferric sulfate medium lies within the so-called passive or prewave region in the anodic behavior of chalcopyrite. The very low current densities due to the anodic oxidation of chalcopyrite at potentials in the region of the mixed potential has made studies of the initial stages of dissolution difficult. However a careful rotating ring-disk electrode (RRDE) study has enabled data to be obtained for the stoichiometry of the initial dissolution reaction to be obtained. Thus, in addition to the detection of soluble iron and copper as products in this potential region, a soluble sulfur species has also been detected. A comparison of the experimental with the expected collection efficiencies of the products on the ring has revealed that this soluble sulfur species is likely to be thiosulfate. The characteristic transient anodic behaviour of chalcopyrite in this potential region has been interpreted in terms of a rate limiting solid-state diffusion process. Thus, extrapolated rates based on reported measured solid-state diffusion coefficients for the mineral at elevated temperatures have been shown to be consistent with the potentiostatic current-time transients. Furthermore, comparative studies of the anodic characteristics of the copper sulfide minerals covellite and bornite has confirmed their greater reactivity in this potential region. The results of this investigation have been combined with a parallel study of the non-oxidative behaviour of chalcopyrite in order to derive a model for the dissolution process which is consistent with other published studies of the electrochemistry and dissolution of the mineral.

Jan 1, 2003

By Noriaki Kurita, Norihiko Fulcatsu, Teruo Ohashi

"An electrochemical sensing device for hydrogen in molten metal has now been available owing to the development of the proton conducting solid electrolyte made of ceramics of metal oxide. The structure of the sensor and the theoretical limitations of its applications are discussed based on the electrochemical properties of the electrolyte used. The practical performance of the sensor is reviewed from the results of test measurements at the plants of aluminum and copper melting industries. The effectiveness of the sensor to the process control of continuous casting of copper is also discussed.IntroductionSince the in-line monitoring of the amount of oxygen dissolved in molten metal was realized by using the oxygen concentration cell based on zirconia solid electrolyte a similar method has been expected to be developed for sensing of hydrogen, which is a very important element of gas species in liquid metals, especially, in aluminum and copper. In 1981; Iwahara and coworkers found the dominant proton conduction at a high temperature in some perovskite-type oxide (1). Since then, the effort has been made to apply this proton conducting material as the electrolyte of the hydrogen concentration cell for high temperature use. The hydrogen sensor for liquid aluminum of this kind was first produced in 1991 (2) and released commercially from TYK Co., Ltd. Recently, we have developed the mother one usable at higher temperature such as copper and silver melting processes (3). In this note we discuss their structure, design and applicable limitations based on the electrochemical properties of this new type electrolyte. The performance of the sensor and benefit to use it to control the melting process is also discussed"

Jan 1, 2000

By Gordon A. Irons, Diancai Guo

"Uneven movement of scrap during melting in an Electric Arc Furnace causes operation problems: cave-ins interrupt electric power input. The movement also influences the radiation heat loss to water-cooled side panels and roof. An apparatus has been built to simulate the flow of scrap that may be interlocked. It has been observed that flow starts at the point where the suspended length of the pile bottom reaches the average scrap size, and proceeds in the form of cave-ins, but scrap pieces slide with each other as ordinary granules. After a cave-in, the pile angle usually remains much larger than the normally observed angle of repose. The force balance of a partially suspended scrap pile has been analyzed, and the equivalent cohesion due to interlocking estimated. A numerical model has been developed to simulate the scrap flow. Simulated results agree reasonably with observed phenomena.IntroductionWhen one considers the melting of steel scrap in an electric arc furnace (EAF), it is helpful to understand the movement of the material during meltdown. As industrial experience demonstrates, scrap movement greatly affects EAF operation. In a typical operation, scrap is dropped into the furnace from scrap buckets. The roof and electrodes are swung into position, and power is applied to the electrodes situated over the scrap. The electrodes ""bore"" into the scrap by melting into the steel in the immediate vicinity of the electrodes as they are lowered. If solid scrap pieces gradually slide towards the arc area, the electric power supply can be maintained at a high level, with few interruptions or drastic electrode adjustments. This results in a high production rate and low power consumption per tonne of steel produced. On the other hand, if the charge moves down unevenly, i.e. in large surges, usually called cave-ins, the electrodes must be drastically raised, and power supply frequently interrupted. This is also accompanied by a high level of harmonics induced in the power network, deteriorating the quality of electricity supplied to other users.In addition, the movement of scrap in an EAF also influences the furnace heat efficiency, as the scrap pile is much closer to the electric arcs compared to the furnace wall and roof, and absorbs more radiated heat. Early exposure of the wall and roof to the arcs will increase the heat loss due to radiation, and reduce the service life of the furnace."

Jan 1, 2004