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By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By Neil E. Izatt

The use of Molecular Recognition Technology (MRT), a selective separations technology using specifically designed ligands, has been established as an effective process for removal of metal ions found in many hydrometallurgical, chemical, and wastewater streams. The MRT process has been proven to be highly efficient and effective for indium extraction and recovery from zinc acid leach, electrolyte, chemical process and waste streams. A high percentage of the indium is recovered in a solid product format. MRT has also proven effective for germanium extraction and recovery from similar feed streams. This paper provides the indium and germanium metal recovery flow sheets and analytical results of the metal load and recovery steps.

Jan 1, 2006

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By Nan Wang

Based on the commercial computational fluid dynamics software, Fluent, a three dimensional finite-volume model has been established, and the fluid flow and heat transfer in the super-wide slab mold (cross section 3250mm×150mm) of Nanjing Iron and Steel Company has been simulated. The basic feature of flow and temperature field in a super-wide mold has been analyzed, and the effects of mold width, the submergence depth of SEN, outlet angle of SEN, casting speed, superheat and cooling rate on the flow and temperature field have been investigated. The results by comparing several simulated calculations for 3250mm×150mm slab show that a more proper fluid flow and temperature field in the super-wide mold can be obtained with 15°outlet angle, 120~150mm submergence depth of SEN and 1.2~1.4m/min casting speed. The results through numerical simulation provide a theoretical basis for optimizing the configuration design of SEN and choosing reasonable processing parameters for the continuous casting mold of super-wide slab.

Jan 1, 2009

By J. E. Murphy

Neodymium was electrowon into a Mg-Cd molten cathode at 650 °C from NdC1,-KC1 electrolyte. With the chloride system, neodymium was deposited into the molten alloy cathode until the neodymium concentration reached 20 wt pct. The alloy was then vacuum melted to remove the Mg and Cd. The current efficiency exceeded 80 pct under optimum conditions and the purity of the metal was 99.9 pct after vacuum melting. As an alternative approach, neodymium was electrowon at 1,030 °C from Nd,O, dissolved in a molten fluoride eleotrolyte. With the oxide-fluoride electrolyte, the metal was electrowon in a molten state with current efficiencies up to 60 pct. The purity of the metal was 99.8 pct with oxygen and carbon as major impurities. A number of problems were encountered including anode effect, low oxide solubility in the electrolyte, high neodymium metal solubility in the electrolyte, and reactivity of the metal with the cell materials. Approaches to improved cell, operation and prospects for commercial adoption of the electrolytic production of neodymium metal are discussed.

Jan 1, 1995

By N. S. Narayanan

Monazite, one of the major sources of rare earths, is normally opened by digestion with hot concentrated caustic soda solution. Caustic digestion dissolves phosphate and leaves a hydrated mixed metal oxides cake containing thorium, uranium and rare earths. By leaching this cake with hydrochloric acid at pH 3.0 to 3.2 bulk of the rare earths are preferentially removed and separated. The slurry left after removal of major portion of rare earths contains all the thorium and uranium present In the feed monazite. In addition this slurry also contains substantial quantities of rare earths. Solvent extraction tests were carried out to develop a process to separate rare earths, thorium and uranium present in the mixed chloride solution obtained by dissolving the above slurry in hydrochloric acid. Based on these tests a solvent extraction flow sheet was developed with di-2-ethyl hexyl phosphonic acid mono 2-ethyl hexyl ester as the extractant. The details of experimental work and results obtained are discussed and a flow sheet for processing monazite Incorporating the new process is suggested.

Jan 1, 1997

By Graeme Miller

The geotechnical characteristics of the ore are important in understanding the kinetics of a copper heap leach. These characteristics can indicate potential problems and can be used to determine the semi-quantitative changes in field kinetics as compared with column kinetics. The application of this approach allows a more rigorously based determination of ?scale up factors? than has been the case the date. The shrinking core model has been shown to be a poor predictor of leach kinetics based on the crushed ore size distribution. However the model itself is a very useful tool to analyse commercial heap data. Significant geotechnical parameters such as: bulk density / stress characteristic, limit moisture capacity and particle density are used to determine the effect of changes on the diffusion controlled leach rate. By consideration of the geotechnical reaction of the ore mass the leach rate changes are related to changes in these variables. Analysis of commercial heap data has indicated effective diffusion lengths of up to ten times the largest particle size.

Jan 1, 2003

By Y. W. Miao

Along the south-west coast of Taiwan is about 550,000 metric tons of heavy sand deposit containing about 10 % black monazite. The Institute has developed a separation process to recover the individual rare earths and the developed process has been commercialized by a local private company. The decomposition of the local black monazite by sodium hydroxide through hydrothermal and fusion methods has been investigated. In the hydrothermal process 4.5 wt. % of aqueous alkali solution was used in an autoclave. In the fusion process, caustic soda (9.8% NaOH) was employed in am open cylindrical reactor. The same product of hydrous rare earth oxides were obtained and then dissolved by hydrochloric acid and the p-H adjusted in order to separate the thorium from the rare earths. After filtration, the filtrate contained rare earth chloride and the cake contained mainly the silica and thorium hydroxide. Both methods give a yield of 90 % with respect to the rare earths recovery. A detailed description of operation and comparison of the two methods are given.

Jan 1, 1989

By Th. Probst, M. Reuter, H. Orbon, U. Boin, J. Vonken, P. Vonk

Although secondary aluminum industry is well established in the world, the recycling process still requires further development to adequately control the process for a higher aluminum yield and a better product quality. In the present paper, recyclabilities of different aluminum scraps have been experimentally studied. Four types of commercial scraps were characterized and melted at 800 - 900 °C to recover 'aluminum metal with the protection salt flux of NaCl-KCl-Na3AlF6 under nitrogen atmosphere. According to the results, the difficulty of recycling aluminum scrap depends on the cleanness and the ratio of surface area to body volume. More non-metallic contaminates and higher ratio of surface area to body volume usually led to a lower metal yield. Usually cast ingots gave better results than rolling mill cuttings under similar conditions. Bottle caps can be recycled more easily than the margarine foil. The effect of temperature was not as significant as the composition of salt flux. The addition of cryolite was essential for a better metal recovery, especially for the scraps with higher surface area. Recycling

Jan 1, 2000

By Scott Shuey

The processing of post-consumer materials is an area being addressed by many industries and multiple engineering disciplines. While metal scrap and high-value uniform waste streams tend to find their way back to their respective parent processes, the more complex and low-cost ubiquitous materials, such as Polyvinalchloride (PVC) and Polytetrafluorethane (PTFE), tend to show up in many processing streams. From a metallurgical perspective, pyrometallurgical processing of a mixed metal/organic/oxide waste material allows for the recovery of thermal energy in conjunction with the recovery of metal values. The evolution of halogenic acids during elevated temperature processing can create complications with both the materials of construction of the processing equipment as well as gas stream processing. The need for dust collection coupled with a high acid content, necessitation high-volume scrubbing, increases the costs associated with gas handling. Control of the halides through entrapment as a solid in-situ during processing would simplify downstream processing. Alkali-halide complexes are being evaluated by researchers at CSM for mixed metal/polymer waste material treatment, recovering halogens as salt complexes.

Jan 1, 2006

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 K. Santowski, S. B. Breyner, T. Prietl

"The material properties of alumina products can be significantly improved by adding Cr203 containing raw materials. Cr203 and Alz03 form an alumina-chromia solid solution during firing, reducing the solution potential when in contact with acidic slags. During service, both a high chemical and high thermomechanical load are present for example in the tuyere zones and taphole areas of metallurgical vessels. For such applications conventional alumina-chromia products suffer from discontinuous spalling as a result of high and frequent thermal shock. Therefore, alumina-chromia materials were developed that exhibit improved thermal shock resistance, compared to the standard products, combined with sufficient corrosion resistance. Laboratory tests evaluated the physical properties of the newly developed alumina-chromia grades and a field test in a Peirce-Smith copper converter demonstrated that the material properties meet the corrosion and thermal shock resistance required for this application. IntroductionTo develop refractory products tailored to specific service conditions it is important to have a profound knowledge of the metallurgical processes and furnace conditions [l]. This enables the specific refractory consumption to be minimized and increases the overall operational efficiency. Economic considerations such as steadily increasing energy and resource costs have resulted in companies investing in recycling processes. In the base metal industry for example, recycling operations involve modifications to the smelter feed, process conditions and chemical composition of the process slags. This adversely affects the performance of standard linings and drives refractory producers to search for material innovations."

Jan 1, 2013

By S. H. Amini

The effects of CaF2 and ilmenite on dissolution rate and diffusivity of CaO in calcium alumino-silicate based slag in a temperature range of 1500 ? 1600 ºC were studied by using the rotating disk/cylinder technique. The effect of rotation speed on the rate of dissolution in the base slag indicated that mass transfer in liquid slag played a significant role in controlling the dissolution. At a constant rotation speed, the effect of 5 wt% addition of fluxes tothe slag on the dissolution rate was investigated at various temperatures. While CaF2 had the highest effect, addition of ilmenite increased the rate of dissolution significantly. The diffusivity of lime in these slags was quantified using the dimensionless mass transfer correlations for rotating disk/cylinder in the melt. The diffusivity values were deduced using the data on dissolution rate and solubility of lime in the slags. The measured diffusivity in base slag at 1500 C was found to be about 1.32 10-5 cm2/s and increased to 3.07 10-5 cm2/s at 1600 °C. Addition of 5wt% CaF2 increased the diffusivity by a factor of 3 to 5, while 5wt% ilmenite increased the diffusivity by a factor of 2 to 3 in the temperature range of 1500 to 1600 ºC. The two examined fluxes reduced the activation energy of diffusion.

Jan 1, 2006

By Mike Santaluce

Smelting furnace rebuild projects often require a significant capital expenditure and an extended smelter outage. Smelter operators are increasingly searching for methods and initiatives to shorten furnace rebuild schedules, maintain manageable cost levels, enhance furnace performance and achieve excellent safety results. This paper describes the ?MEPC? Model for furnace rebuilds; a project driven approach which Auburn has developed in response to the need for improving furnace rebuild project outcomes. The ?MEPC? (Management, Engineering, Procurement and Construction) approach better addresses the unique challenges presented by furnace rebuild projects when compared to the traditional EPCM (Engineering, Procurement, Construction Management) model widely in use for these projects today. One key feature of the MEPC model is that a dedicated project management team with representation from all of the major project stakeholder groups is put in place at the onset of the project. The project management team has ownership and accountability for meeting overall project goals over the entire lifecycle of the furnace rebuild project. A second key aspect of the model is emphasis on project management as a completely separate project function with its own specific skill sets, techniques, tools and best practices. These features of the MEPC model offer several advantages in terms of improved planning, coordination, communication and alignment with project goals which contribute to the overall success of furnace rebuild projects. Similar MEPC concepts have been used to deliver excellent project results in other industries and the MEPC approach has been successfully utilized on furnace rebuild projects.

Jan 1, 2006

By I. C. Knight

The current levels of copper smelter by-product acid production are reviewed on a regional basis, together with the possible changes in the future. There will be increasing pressure for all smelters to achieve a sulphur capture level of at least 95% by the end of the decade.

Jan 1, 1996

By Qian Fu

Although chlorine fluxing to remove magnesium has been widely practiced in the aluminum industry for many years, there appear to have been few fundamental studies of the kinetics and transport phenomena involved. The paper describes such a study in which the rates of reaction of individual argon/chlorine bubbles with aluminum/magnesium melts were measured. The detachment of bubbles from a submerged nozzle, at variable depth in the melt, was detected by a microphone and the arrival of the bubble at the top surface by conductivity probes. Analysis of exit gases and mass balances yielded the overall progress of reaction. Experimental results are interpreted in terms of heterogeneous reaction kinetics and mass transport to the bubble-melt interface,

Jan 1, 1996

By Robert F. Jenkins

This document addresses the use of practical and basic engineering principles to develop a computer model for the analysis of the various issues which affect heat transfer in aluminum sidewell furnaces. These issues include furnace charge conditions, furnace operating conditions, furnace general arrangement, furnace combustion conditions, and furnace ambient heat loss. The engineering principles applied to this model were first put to test over 20 years ago. A prototype computer model developed 12 years ago has been in continuous use by Thorpe Technologies to determine the performance of sidewell furnaces for the aluminum industry. A new computer model has enhanced capabilities for more detailed performance analysis including regenerative and oxygen enriched combustion.

Jan 1, 2000

By Z. R. Llanos, W. G. Deering

Gulf Chemical and Metallurgical Corporation (GCMC) has been operating facility for treatment of spent catalysts in Freeport, Texas since 1974. Recently, GCMC expanded its operations with the addition of an electric furnace for the production of fused alumina and mixed alloys. GCMC and its affiliate Sadaci, started up a new pre-treatment facility in Ghent, Belgium in 1998. GCMC is also part owner of Bear Metallurgical Corporation, a major producer of ferroalloys in the United States. This paper reviews the processes at these facilities. Changes in the management of hydrotreating and hydrorefining spent catalysts are discussed in light of recently issued federal regulations that made the majority of spent catalysts a listed hazardous waste.

Jan 1, 2000

By Junji Shibata

The waste acid mixture whose main component is phosphoric acid, is discharged from the etching process in the liquid crystal production industry. In order to separate impurity acids from the phosphoric acid, trioctyl phosphate (TOP) is used as an extractant. TOP can extract acetic and nitric acids selectivity. The extraction and stripping operations are carried out for the acid mixture by beaker-scale experiments and countercurrent multistage operations with mixer-settler equipment. TOP selectively extracts the acetic and nitric acids in the acid mixture. From the results of the McCabe-Thiele analysis obtained by beaker-scale tests, the extraction for acetic and nitric acids are approximately 100%, respectively, by 6-stage extraction with a phase ratio (A/O) of 0.4. On the other hand, almost all of acetic and nitric acids are stripped with water from the organic phase by 4-stage stripping with a phase ratio (A/O) of 1.0. About 95% of acetic and 98% of nitric acids can be removed from the acid mixture without extracting phosphoric acid in case of the mixer-settler equipment operation. There are several steps such as slicing, lapping, chemical etching and mechanical polishing in the silicon wafer production process. The chemical etching step is necessary to remove any damaged layer caused in the slicing and lapping steps. The typical etching liquor is the acid mixture comprising nitric acid, acetic acid and hydrofluoric acid. The waste acid is treated by a neutralization method with a high alkali cost and balky solid residue. A solvent extraction method is applicable to separate and recover each acid. Acetic acid is first separated from the waste liquor using 2-ethlyhexyl alcohols as an extractant. Then, nitric acid is recovered using TBP (Tri-butyl phosphate). Finally hydrofluoric acid is separated with TBP solvent extraction. The expected recovered acids in this process are 2mol/L acetic acid, 6mol/L nitric acid and 6mol/L hydrofluoric acid. The yields of this process are almost 100% for acetic acid and nitric acid. On the other hand, it is important to recover and reuse the metal values contained in various industrial wastes from a viewpoint of environmental preservation. Most industrial products are made through processes to separate impurities in raw materials, solid and liquid wastes being necessarily discharged as industrial wastes. Chemical methods such as solvent extraction, ion exchange and membrane separation, and physical methods such as heavy media separation, magnetic separation and electrostatic separation are considered as the methods for separation and recovery of the metal values from the wastes. Some examples of the application of solvent extraction to the treatment of wastes such as Ni-Co alloy scrap, Sm-Co alloy scrap, fly ash and flue dust, and liquid wastes such as plating solution, the rinse solution, etching solution and pickling solution are introduced.

Jan 1, 2003

By Philip L. Sibrell

A new process utilizing pulsed fluidized limestone beds was tested for the remediation of acid mine drainage at the Friendship Hill National Historic Site, in southwestern Pennsylvania. A 230 liter-per-minute treatment system was constructed and operated over a fourteen-month period from June 2000 through September 2001. Over this period of time, 50,000 metric tons of limestone were used to treat 50 million liters of water. The influent water pH was 2.5 and acidity was 1000 mg/L as CaCO3. Despite the high potential for armoring at the site, effluent pH during normal plant operation ranged from 5.7 to 7.8 and averaged 6.8. As a result of the high influent acidity, sufficient CO2 was generated and recycled to provide a net alkaline discharge with about 50 mg/L as CaCO3 alkalinity. Additions of commercial CO2 increased effluent alkalinity to as high as 300 mg/L, and could be a useful process management tool for transient high flows or acidities. Metal removal rates were 95% for aluminum (60 mg/L in influent), 50 to 90% for iron (Fe), depending on the ratio of ferrous to ferric iron, which varied seasonally (200 mg/L in influent), and <10% of manganese (Mn) (10 mg/L in influent). Ferrous iron and Mn removal was incomplete because of the high pH required for precipitation of these species. Iron removal could be improved by increased aeration following neutralization, and Mn removal could be effected by a post treatment passive settling/oxidation pond. Metal hydroxide sludges were settled in settling tanks, and then hauled from the site for aesthetic purposes. Over 450 metric tons of sludge were removed from the water over the life of the project. The dried sludge was tested by the Toxicity Characteristics Leaching Protocol (TCLP) and was found to be non-hazardous. Treatment costs were $43,000 per year and $1.08 per m3, but could be decreased to $22,000 and $0.51 per m3 by decreasing labor use and by on-site sludge handling. These results confirm the utility of the new process in treatment of acid impaired waters that were previously not amenable to low cost limestone treatment.

Jan 1, 2003