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By Frustino L. Prado

For more than a century, the AAC (ammonia I ammonium carbonate) process has been applied to the recovery of various metals. A variation of it, the Caron Process was first used in the early 1940's in Cuba for the extraction and recovery of nickel from laterites. The original Nicaro plant has been in continuous operation since then. Years later the Caron process was used again in Australia at the Greenvale (Yabulu) NickelICobalt plant, commissioned in 1974. Other projects (Sered, Niquelandia, Nonoc, Punta Gorda, Albania) as well as several studies have been carried out. The Caron Process is alive and still promising. Members of our organization have been working with AAC and the Caron Process since 1952. This paper will review current approaches and potential improvements (enhancement of recoveries of Ni and Co, reduced energy consumption and maintenance simplification). Keywords: Caron Process, Ammonia, Ammonium Carbonate, Laterites, Nickel, Cobalt

Jan 1, 2004

By James E. McNulty

Today's energy era is the beginning of a transition from the Petroleum Age to a future age of renewable fuel resources. Fuels for the transition era will come from unconventional sources and conversion technology. Affecting the practicability of transition technologies are attitudes of the public, capital requirements and availability, patterns of fuels utilization, producibility of fuels and the actions of governments. Primary energy sources to replace deficiencies of oil and gas and provide growth in the period of transition will be coal, oil shale, nuclear energy and peat.

Jan 1, 1981

By Henk Dijkman

Existing metallurgical operations can be optimized by implementing engineered bioreactor systems in the process configuration. For instance, metals can be recovered safely and economically from process and waste streams using biogenic sulfide. This paper focuses upon possible applications of high rate biotechnology in metallurgy and mining. Metal recovery from liquid streams (process bleed streams, leach water, waste streams), integrated removal of (fugitive) SO2, treatment of acid blowdown and other options will be described. Practical examples are given. A large-scale application of biotechnology at Pasminco's Budel Zink refinery is described. Here, acid plant blowdown is treated together with electrolyte magnesium bleed. Concentrated zinc sulfide (10 tpd) is produced biologically, eliminating the production of gypsum and closing the refinery sulfur cycle. Recovery of metals from solution at Kovehute Pribram in the Czech Republic is the second practical example. In this case, H2S is produced on-site for metal removal from an alkaline slag dump leachate. At the Caribou mine in New Brunswick, Canada, acid mine drainage is treated with biogenic sulfide. This plant is situated upstream of a lime neutralization plant. As a result, reusable ZnS is produced, the volume of the sludge (gypsum and hydroxides) from the lime plant is reduced by 50%, the sludge is free of heavy metals and the final effluent concentration of heavy metals is in the ppb range. In the second phase of this project, metals will be recovered from stored tailings, resulting in significant revenues.

Jan 1, 2002

By H. Sieber

Multilayer samples of tantalum and aluminum with the composition of Al-25Ta were prepared by cold rolling of elemental foils. The microstructure and phases were characterized by XRD, SEM and TEMISAED and the reactive phase formation was examined by DSC and DTA measurements in multilayer foils rolled for different deformation levels. The rolling procedure yields a decrease of the Ta particle size in the Al matrix and also results in the formation of a multilayer structure with a thickness of the elemental foils down to 200 nm in average. No phase formation is observed during the cold rolling procedure. While XRD and DSC measurements show no phase formation up to the melting of aluminum for samples rolled up to 40 F&R (fold and rolling) passes, in samples rolled for 50 or more F&R passes a first phase formation reaction yield an interfacial layer of TaAl3. Contrary to former studies in the investigated cold rolled Al- 25Ta multilayers the reaction starts at temperatures as low as about 340°C. The first stages of the reaction are associated with two exothermic maxima, that increase in amplitude and shift to lower temperatures with increasing number of F&R passes. At higher temperature the TaA13 reaction layer thickens very sluggishly and yields a third exothermic maxima at about 600°C. Isothermal DSC scans show the reaction is not finished for samples containing elemental particles larger than 1 pm after annealing at 550°C for 5h. In all the investigated samples no Al- Ta phase other than Tad3 was observed to grow for heat treatments up to 800°C. Multilayer samples heated up to 1400°C show a morphology consisting of small AITa2 particles embedded in a single phase TaA13 matrix. The multilayer microstructure and reaction product morphology are characterized by SEM and TEM investigations in cross-section and plan view geometry.

Jan 1, 1998

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By Yang Cui

The partition ratios of lead and antimony between liquid copper and MgO saturated Cu2O-CaO-SiO2 flux and their removal rate by using CuCl-based flux were measured between 1423 K and 1573 K. For Cu2O-CaO-MgOsatd. system, the partition ratio of Pb was not affected by the CaO content at 1573 K, while that of Sb increased with increasing CaO content. The maximum value was 160 at the CaO content of 15.4 mass%. For Cu2O-CaO-SiO2-MgOsatd. system, two liquid phases of calcium silicate rich phase and Cu2O rich phase were observed at 1573 K. The partition ratios of Pb and Sb between calcium silicate phase and liquid copper depended on the (mass%CaO)/(mass%SiO2) ratio. When the (mass%CaO)/(mass%SiO2) ratio increased, the partition ratio of Pb decreased and that of Sb increased. For CuCl flux, the removal of Pb from liquid copper at 1473 K was possible, and a relatively low concentration could be reached. Moreover, most of lead as metal chloride vaporized from flux. For the removal of antimony from liquid copper at 1423 K, it was difficult by CuCl flux, and the removal ratio was approximately 20% for 75 minutes. However, the addition of CaO or Na2CO3 to CuCl flux was relatively effective to remove antimony, and the concentration of antimony reached a relatively low value after 15 minutes by using CuCl-CaO or CuCl-Na2CO3fluxes. Moreover, a small part of antimony as chloride vaporized from flux.

Jan 1, 2006

By John J. J. Chen, Barry J. Welch

"The production of primary aluminium can potentially lead to metal that, with minimum treatment, meets a high purity standard. Smelters that can achieve a significant proportion of their production in this manner have a competitive edge which is of growing importance as the use grows for such items as compact discs and the like. Superimposed on the desire to produce high quality metal are stringent environmental requirements that the industry must adhere to. The environmental legislation focuses on fluoride emissions and the approach adopted is towards a zero waste management philosophy. The fluoride recycling process does, however, result in volatile impurities being captured and recycled to the cell. Aluminium has an extremely high reduction potential and this results in a significant proportion of the recycled impurities being reduced at the electrolyte metal interface and thus contaminating the metal. This paper reviews sources of impurities and the impact of the operating procedures adopted on metal treatment.IntroductionSeveral factors have contributed to the immense growth in the aluminium smelting industry. Initially the ready availability of hydro electricity provided a primary reduction energy source for the production of the light-weight metal. Because of its unique properties and innovation in the industry there has been a continued exploitation of its unique properties, especially at the high purity end of the metal. The industry has shown considerably versatility and innovation in adapting to the ever increasing demands of quality and purity. It is however a competitive industry and the ability to produce high purity grade metal (>99.9% pure) gives a competitive edge. Emerging markets such as for CD ROM disc production etc, will keep the quality demand stringent.While the industry has met the continuing demands for metal quality, it has also had to respond to stringent environmental requirements for emissions from the production plant. Like all extractive metallurgical processes carbon dioxide is an inevitable reaction byproduct. However, the volatilization and hydrolysis of the solvent electrolyte leads to fluoride emissions that are potentially harmful. Accordingly, the industry has adopted essentially a zero non-process waste management approach. All cell emissions, including reducible impurities, are recycled back to the cell. This has had a significant influence on the metal treatment processes."

Jan 1, 1996

By Bob Drew, Alfred Spanring, Kirschen. Marcus

"Increasing material conversion and energy efficiency, and decreasing carbon dioxide emission levels are crucial for sustainable production processes in the aluminum, cooper, and steel industries. RHI supports these targets by providing a diverse range of solutions including high quality refractory linings, optimum lining maintenance, and process improvements. In this paper examples are provided of process improvements and increased energy efficiency in copper refining, potential energy savings during electric arc furnace and ladle operations in the steel industry, and increased energy efficiency by improved heat transfer in anode baking furnaces in the aluminum industry. In all cases, RHI’s expertise in close collaboration with the customer resulted in an improved performance of the reactor lining and the actual high temperature process with a positive impact on the material conversion and energy efficiency and as a result a decrease in specific carbon dioxide emission levels.IntroductionRefractory linings play an important role in heat transfer during high temperature processes in for example the aluminum, copper, and steel production industries. Due to constantly increasing energy prices worldwide and the increasing demands for environmental and climate protection, improving the energy efficiency and decreasing emission levels of these energy intensive production processes is of significant importance. In this paper, the contribution of modern RHI lining technologies to energy saving measures and the corresponding reduction of specific carbon dioxide emission are described. The type of current refractory solutions for energy intense processes are illustrated with four examples: Optimization and increase of material conversion and energy efficiency in copper refining, energy saving potentials in both electric arc furnace and transport ladle operations in the steel industry, and heat transfer improvements during the carbon anode annealing process in the aluminum industry. These examples focus on particular production processes operating with a high proportion of recycled copper, steel, and carbon anodes. Increased energy efficiency directly decreases the specific energy related carbon emission levels whereas improvements to the metallurgical processes aim to increase material conversion efficiency and, therefore, decrease specific process related carbon emission levels. Significant energy savings can be achieved by maximizing the refractory campaign length through a combination of appropriate refractory material selection, grade zoning, correct installation, careful preheating, and effective maintenance strategies. Besides the efforts to improve the performance and energy efficiency of customer high temperature processes, RHI continuously promotes the development of new low emission carbon-containing refractory bricks and unshaped products."

Jan 1, 2008

By Robert E. Brown

Magnesium recycling has been used to recover both new scrap and old scrap. It was used extensively in Germany during WWII to expand the magnesium supply. There were a large number of magnesium recyclers in the US who got their start smelting old scrap, old airplanes and old waste dumps from the WWII build up. As the world magnesium industry dwindled, only a few companies were left that did magnesium recycling as a primary business. The sand foundries tended to recycle of their production scrap in their melting furnaces. Even the original die casters tended to put scrap directly back into melting furnaces at the die casting machines. As high purity alloys were developed and the use of die castings in automotive work increased, the tendency was to let the magnesium recyclers convert the scrap back to high quality ingot. Automotive use has grown because of the low density of magnesium. This property is the one of the biggest problems to overcome in shipping scrap. Gates and runners from die casting are very irregular shapes and it is very hard to load a truck with enough material to get a low shipping cost per pound. Recent new equipment companies have developed magnesium equipment that is specifically designed to recycle, refine and cast secondary magnesium metal. These melt cells are supplied as integrated units to magnesium casting sites. The cost and effectiveness of this approach will be discussed.

Jan 1, 2000

By Nobuhiro Ishikawa

The in-situ observation of the effect of impurities on the reduction process of iron oxides by C in TEM was carried out. A few wt% of CaO or AbO, was used as impurities in FeO was prepared. Some precipitates grew into the C layer expect for using 3.0wtCa. The reaction between FeO and carbon was much different from using pure FeO at about 800-1 lOOK. The rate of reaction became much slower including Ca and almost no reaction was happened with the concentration of CaO up to 3.0wt%. On the contrary, AbO, had ahuost no effect on the reaction. The results indicated that Ca suppressed the reaction and the effect of Al was much less. The precipitates which grew into C layer accompanied almost no Ca and AI. Only Fe was detected in the precipitates.

Jan 1, 2008

By O. Nakai

In the copper electrorefining process, the quality of the starting sheet is one of the basic factors for producing high quality copper cathodes. A highly automated and advanced facility for the production of copper starting sheets was constructed at the Toyo Copper Refinery in 1992, bringing various improvements into an automatic stripping system using stainless steel mother blanks. In 1998, the refinery expanded the tankhouse by another 128 commercial cells, and introduced 64 polymer concrete cells in a first stage conversion. As a result, the Toyo Copper Refinery now has the capacity to produce 103,200 t/y of cathode copper. Construction has led to great improvements in the materials handling facilities and computer associated short-circuit detection technology. This report summarizes the improvements made in the quality of the cathodes and in plant productivity.

Jan 1, 1999

By Batric Pesic

The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were examined during the entire growth stage of bacteria (fermentation), The pyrite ?surface invariably drastically changed ' its. properties at the second day of fermentation. Beyond two .. days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The product layer was examined by SEM,. X-ray diffraction and chemical analysis. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became .insensitive to convective diffusion in solution (stirring). The x-r:ay diffraction study confirmed jarosite as a product layer. A mechanism of T. ferrooxidans cells serving as nucleation sites for jiarosite formation is proposed.

Jan 1, 1991

By Daniel Gauthier, Patrick Sharrock, Cedric Verwilghen, Gilles Flamant, Ange Nzihou, Jocelyn Ramaroson

Clean processes are needed to dispose of many wastes. The incineration of 1 ton of municipal solid waste generates 6000 Nm3 of combustion gases contaminated with heavy metals and other pollutants. Gas scrubbing processes are required to clean incineration fumes in order not to transfer pollution to the atmosphere. We are investigating the use of Hydroxylapatite (Ca-HA) particles for use as sorbent for the removal of volatile heavy metals. We have carried out the synthesis of Ca-HA by two precipitation methods from solution and obtained solids with specific surface areas reaching more than 100 m2/g. Preliminary adsorption experiments were conducted in a horizontal furnace by mixing Ca-HA with 5% by weight of cadmium chloride in solid state. The mixture was heated to 600°C under air atmosphere during 6 hours. Chemical analysis of the solids confirmed that 85 % of the cadmium was retained in the solid phase. Such laboratory results showed that Ca-HA is capable of adsorbing cadmium chloride vapors, and pilot scale studies confirmed cadmium abatement in an industrial context.

Jan 1, 2008

By L. Petitnicolas

The experimental study of nitrogen absorption and its removal from a liquid Ni-20%Cr alloy at 1873 K has been undertaken, using an experimental, apparatus based on the Sieverts technique in order to determine the solubility of nitrogen in the alloy. as well as the kinetics of nitrogen transfer across the gas/melt interface. Experiments show that nitrogen solute equilibrium content can be calculated using the Sievens law. Measurements point out the nitrogen absorption reaction rate to be well described by first order kinetics, whereas experiments on nitrogen removal reveal that the rate is better expressed using a second order equation.

Jan 1, 1996

By J. Alexandre

The use of bricks of soil-cement is proving to be an important constructive methodology due to low environmental impact in the production process of these blocks comparing with conventional bricks are burnt, besides being easy to produce. However during the process of production of bricks, which are compressed, knowledge of the properties of the soil used is critical to the quality and durability of the blocks. The objective of this work is to evaluate the feasibility of using soil from the municipality of Goytacazes for the production of soil-cement bricks. Assays were performed the compaction, liquid limit, plastic limit, particle size analysis, EDX and X-Ray diffraction for later pressed blocks and analyze their compressive strength and water absorption.

Jan 1, 2015

By Florian Kongoli

While calcium ferrite slags have been successfully used in continuous copper converting for the last 30 years, ferrous calcium silicate slag was proposed about 8 years ago as an additional alternative for copper smelting. Although both slags are normal extensions of each other their phase relations have not been completely clarified. In this paper the liquidus relations of both slags have been quantified at various areas that cover both of them. The existing experimental data have been first reviewed and discussed in relation to the solidification procedure. An original physical model is then used to predict various diagrams of the liquidus surface of both slags. It is shown that the ternary liquidus diagrams normally used for FeOx-SiO2-CaO system are not suitable for industrial slags. The new model diagrams of Fe/CaO versus SiO2 and Fe/SiO2 versus CaO as well as Fe/CaO versus Temperature and Fe/SiO2 versus temperature are proven to be much more convenient for ferrite and ferrous calcium silicate slags. Based on these diagrams the effect of SiO2 and CaO on the melting temperature is quantified. The effect of Cu2O is also quantified through the model. Some Fe/CaO versus Cu2O and Fe/SiO2versus CaO at various copper contents are predicted and the results show good agreement with the experimental data. It is also shown that in the presence of liquid copper, Cu2O is dissolved in the slag depending on the oxidation degree of the system and might lower the liquidus temperature. Some discussions are also presented taking into account plant observations and important conclusions are drawn for copper smelting and converting

Jan 1, 2006

By Ashish Kumar

Comminution is an essential mineral processing operation to liberate the minerals from the ore. This however, is an energy intensive step in mineral processing industries. This work highlights the possibility of saving in grinding energy for ore comminution reducing work index of the ore by effective utilization of microwave energy. This reduced work index results in increased throughput of the grinding circuit in mineral beneficiation plant in order not to shift the product size. The fundamental principle behind this application remains the ability of microwave to heat individual phases within the ore matrix. The constituents of the ore typically having different thermal and mechanical properties develop stress of sufficient magnitude to create intergranular and transgranular fractures during heating and subsequent quenching of the ore. The experiments conducted with the ore samples of Zawar Mines and Rampura Agucha Mine of Hindustan Zinc Limited, India (A member of Vedanta Resources Plc) reflect a substantial up-shift in cumulative weight percentage passing in finer sieve fractions under quenched conditions. Further, the experiments carried out on Rampura Agucha ore reveal 20-30% reduction in work index, which result in decreased milling time or saving in grinding energy. The simulation studies estimates a 2-4% increase in plant throughput. Moreover, preliminary flotation studies indicated a significant increment in total metal recovery and concentrate grade for the desired grade and recovery values respectively. This paper is a technical note on the laboratory investigations carried out at Central Research & Development Laboratory of Hindustan Zinc Limited. Results have been encouraging to progress the work further. It is also proposed to carry out modeling work for simulation so as to predict the changes in minerals.

Jan 1, 2006

By M. Patel, A. W. Piper, R. A. Forsdick

"Lead bullion is refined in kettles to remove the contained impurities such as copper, antimony, silver and bismuth. These impurities are removed sequentially by the addition of one, or more, reagents to the bath. Impurity elements react selectively with the reagents to form a dross layer on the surface that is subsequently removed for further processing. Mixing the lead bath using specific impeller designs, which form a vortex to ensure that good contact takes place, carries out the reactions. It is important that the mixing is controlled to achieve the optimum bath conditions and hence good dross grades.This paper presents initial modelling work on the kettle refining process using both physical modelling (Water Models) and mathematical modelling (Computational Fluid Dynamics - CFD). Comparisons between measured plant data and simulation results are given.IntroductionThe refining of lead bullion takes place in hemispherical kettles of varying sizes. It is normal practice to remove the impurity elements sequentially, by the addition of reagents, which selectively react with the impurity element. The impurity element forms a dross layer on the surface, which can be removed for subsequent processing at the end of the reaction period.All the refining stages in the production of lead and lead alloys involve mixing the lead bath, although different conditions are required for each stage. At Britannia Refined Metals mixing is achieved using either 3 or 4 angled or flat blade impellers, which generate a vortex in the central region of the kettle. However, throughout the industry a wide range of mixer types are used which are all trying to achieve the same result."

Jan 1, 1999

By Guojun Ma

The entrainment of charge materials, evaporation or volatilization of elements and ejection of slag and metal by spitting or the bursting of gas bubbles are mechanisms whereby stainless steel plant dust are generated from the electric arc furnace and refining converter. TCLP and ASTM D 3987-85 tests on dust that was collected from the baghouse filter system of a South African Stainless Steel plant showed that this dust can be considered hazardous according to South African legislation, due to the high degree of Cr (VI) leachability (~13mg/l for TCLP and ~8mg/l for ASTM vs. regulation threshold of 0.05mg/l in drinking water). The dust is therefore considered to be harmful to both the environment and human health, due to its high solubility in water and carcinogenic properties. It should therefore be treated before being stockpiled or land filled. This paper consequently describes an investigation into the formation of Cr(VI)-containing stainless steel plant dust and the stabilisation thereof in a sintering process, whereby the dust was mixed with a silica-rich clay. It is postulated that Cr(VI) form when the (Mg,Fe,Mn,Cr)3O4spinel phase, CaO, Ca(OH)2 and CaF2 (all of which are present in the dust) react. This reaction was found to take place both at ambient and at high temperatures (1100°C). Stabilization of Cr(VI) in the dust could be achieved at an optimum sintering temperature of 1100°C for a 50mass% dust : 50mass% clay mixture. Chromium emission during the sintering process was found to be low, and within environmental limits.

Jan 1, 2006

By Dexter G. Mendoza

To analyze the behavior of minor elements in the copper smelting process, the phase relations and the activities of arsenic and antimony in the miscibility gap of Cu-Fe-S-X (X = As or Sb) system have been determined at 1473K by the quenching method and the double Knudsen cell- mass spectrometric method, respectively. The experiments have been conducted for the charges in the miscibility gap with different mass%Fe/mass%Cu ratios with varying arsenic or antimony content. The activity measurements indicate that the arsenic activities in both the metal and matte phases show extremely negative deviation from the ideal behavior. The Raoultian activity coefficients at infinite dilution in the metal and matte phases are found to be almost constant against the charges in the miscibility gap, and they are 4.3 x 10-3 and 5.5 x 10-2 for the metal and matte phases, respectively. Moreover, the activity measurements of antimony show an activity value larger than that of arsenic but it still deviates negatively from Raoult's law. The activity coefficients of antimony at infinite dilution are found to be 1.2 x and 2.2 x 10-1 for the metal and matte phases, respectively. The vapor pressures of the predominant As, AS2, AsS, Sb, Sb2, and SbS species in the gas phases of arsenic and antimony, respectively, equilibrated with the immiscible solutions have been calculated on the basis of the determined activity coefficients and they are very small at less than 1 Pa, even when their contents in the metal phase are increased up to 10 mass%.

Jan 1, 2002