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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 Sergei A. Degterov

A thermodynamic database for the slag, matte and liquid copper phases in the Cu-Ca-Fe-Pb-Zn-Si-O-S system has been developed for the ranges of compositions of importance to the production of copper. When used with the Gibbs energy minimization software and other databases of the F*A*C*T thermodynamic computing system, this database will permit the calculation of matte-slag-copper-gas phase equilibria that take place during copper smelting and converting. The calculations reproduce within experimental error limits all available experimental data on phase diagrams, activities of components, enthalpies of mixing, matte - alloy miscibility gap and tie-lines. The calculated solubilities of Cu in both S-free slag and slag equilibrated with matte are also in good agreement with experiment under all studied conditions, such as at SiO2 saturation, in equilibrium with Fe, Cu or Cu-Au alloys, at fixed oxygen or SO2 partial pressures and at different contents of Pb, Zn and CaO in the slag. Sulfide contents (sulfide capacities) of the slags are predicted within experimental error limits. The distribution of Pb and Zn among matte, slag, copper and gas has been calculated. The calculations are in good agreement with experimental data and predict the distributions under conditions which are difficult to study experimentally, such as at magnetite saturation or under various oxygen partial pressures and iron to silica ratios in the slag.

Jan 1, 1999

By Florian Kongoli

The liquidus surface of multicomponent slags is an important parameter in various smelting and converting processes. It helps not only to optimize the slag, chemistry of current processes and their fluxing strategies, but also to determine the availability of new slags for more advanced technologies. In a series of our previous publications, the liquidus surface of some multicomponent iron oxide slags has been quantified at several constant oxygen potentials and the effect of the latter, ignored until that moment, was quantified along with the effect of some minor components. In this work, the liquidus surface of some iron oxide slags is quantified at constant CO2/CO ratios. This is a new convenient way for the quantitative description of the slag liquidus surface and the effect of several fluxes, especially in those processes such as slag solidification, where oxygen potential changes continuously. This type of diagram also describes more dynamically the effect of oxygen potential, clarifies the relation between CO2/CO ratio and oxygen potential in terms of the liquidus surface, which is not widely understood by metallurgist today, and reduces the gap between laboratory work and industrial experience.

Jan 1, 2002

By I. S. Escobar

Copper, particularly the oxygen-free grade Cu-OFP, is a candidate material for containers for the long-term isolation and disposal of high-level radioactive waste (HLW) in underground repositories. After having been buried for a few hundred years, all oxygen will have been consumed in the repository, and corrosion of the copper will be caused entirely by contact with dissolved sulfides. Chloride is another potential corrodant, but in deep repositories where groundwater is neutral or slightly alkaline, the effect of chlorides can be ignored on thermodynamic grounds. Thus, the corrosion of copper in the presence of sulfide ion and under reducing conditions has been studied using cyclic voltammetry and Tafel slope measurements. It is possible to determine the effect of sulphide ion on copper corrosion resistance which is minimized at low temperature and also at low sulphide concentration. The presence of anions such as HCO3 under environmental conditions produces a beneficial effect because these ions are inhibitors.

Jan 1, 1999

By Manolete Mena

WC-Co nanocomposite powder is among the first group of materials with a promising potential for nanocrystalline-materials application. A chemical vapor synthesis (CVS) process that has previously been used for preparing the aluminides of titanium and nickel, and other metallic and intermetallic powders has been applied to the preparation of WC-Co nanocomposite powder. This CVS system was designed so that a tungsten precursor (WCl6 powder) and a cobalt precursor (CoCl2 powder) were separately fed into each evaporator in a reactor by means of specially designed powder feeders. The reduction and carburization of the vaporized chlorides by methane-hydrogen mixtures produced nanosized WC and Co composite powder. The product is a very uniform mixture of the constituent powders, which is important to ensure a high quality of the bulk cemented tungsten carbide product after consolidation. In the present work, the effects of reaction temperature, CH4 to WCl6 ratio, CH4 to H2 ratio, residence time, and Co content on the powder composition and particle size were determined. The products were characterized using XRD, carbon analyzer, and TEM.

Jan 1, 2006

By Michael S. Moats, Daniel Kim, Shijie Wang

"The behavior and deportment of lead, arsenic, antimony and bismuth are critical in producing high quality cathode by copper electrorefining. A critical review of research related to these elements is presented along with a comparison to industrial data, where appropriate. These elements exist predominantly in the anode as complex oxides along die grain boundaries. Upon dissolution, Group 15 elements report both to the electrolyte and slimes while lead essentially enters the slimes. The deportment of the Group 15 elements appears to be influenced by several chemical interactions which are discussed. The effect of these elements on floating slimes and anode passivation is reviewed. Under normal electrorefining conditions, lead, antimony and bismuth are thought to enter the cathode through the encapsulation of slime particles. The literature indicates that arsenic enters the cathode predominately by electrolyte entrainment. Finally, areas for future research regarding these elements are presented.IntroductionControlling lead, arsenic, antimony and bismuth is critically important for the production of high quality cathode in copper electrorefining. The reasons for this are twofold. First, ASTM Grade 1 Cathode specifications [1] for these elements are low, as listed in Table 1. Second, they can affect the efficiency of the electrorefining process (e.g., through passivation, current efficiency, slime processing)."

Jan 1, 2012

By V. Bojarevics, K. Pericleous

"A number of different methods have been developed for noncontact electromagnetic treatment of liquid metal and to investigate the melting/solidification processes. Applying AC magnetic field in terrestrial conditions, along with the buoyancy and thermo-capillary forces, results in turbulent flow. The use of a homogenous DC magnetic field allows damping both of the turbulence and the large scale flow at different rates leading to surprising results at some stages. The dynamic interaction of the turbulent flow with the oscillating interface needs to be accounted if it is required to levitate liquid metal of up to few kilograms without the contact to container walls. At the high values of magnetic field some oscillation modes are damped quickly, while others are modified with a considerable shift of the oscillating droplet frequencies and the damping constants from the non-magnetic case. Numerical models are used to investigate behavior of liquid metal suspended in high DC magnetic fields providing microgravity-like conditions with laminar viscosity and heat transfer to the surroundings.IntroductionSince the early Electro Magnetic (EM) levitation experiments [1] in AC magnetic field it became apparent that the levitated liquid metal is prone to oscillation and instability. The EM and electrostatic levitation experiments with liquid metal droplets show difficulties related to confinement stability and a need for complex correction functions to establish a correlation between the measurements and the droplet material properties [2,3]. Intense internal fluid flow is visually observed, apparently being in the turbulent regime for earthbound conditions."

Jan 1, 2012

By Marko Suput

Titanium is a high-strength, low-density metal nearly immune to corrosion, but limited in use by its high price. The high price is due to the cost of smelting and processing the ore. The research on titanium production using the Solid Oxide Membrane (SOM) process aims to consolidate most of the processing steps required for conventional titanium production into a single step making it an energy-efficient and cost-effective method for producing CP billet and ingot and possibly also powders used to make titanium alloys. In the SOM process experiment, a steel crucible contains MgF2-CaF2-TiO2 flux; an inert metal/carbon rod serves as the cathode; an oxygen-ion-conducting yttrium-stabilized-zirconia (YSZ) membrane in the form of a one-end-closed tube contains either a liquid metal that acts as the anode or liquid MgF2-CaF2 ionic flux that connects the YSZ membrane to an anode. During electrolysis, when the voltage between anode and cathode is higher than the reduction potential of titanium oxide, titanium ions are reduced at the cathode and the oxygen ions pass through the YSZ membrane and are oxidized at the anode. The oxygen ions are oxidized at the anode by a reducing agent, hydrogen gas or carbon, forming steam or CO(g), respectively. To date, a suitable MgF2-CaF2-TiO2 flux has been selected and the operating temperature for the SOM process has been determined. Several electrolysis experiments have been performed. As expected, lower valence deposits of titanium oxides have been witnessed at the cathode prior to depositing pure titanium. Continuing work will aim to extend the electrolysis time in order to pass enough charge to produce a significant amount (100 g) of titanium at the cathode.

Jan 1, 2006

By Lanre Oshinowo

The trend in process engineering is to design compact, more efficient processes, there is the paramount requirement to get the job done right the first time going from the drawing board to full-scale commercial operation. To accomplish this goal, there is also the need for tools beyond the traditional engineering toolkit to evaluate designs through virtual prototyping, thereby reducing the risks associated with making design decisions. One of the most important tools that has recently come to the forefront of process design and development is Computational Fluid Dynamics (CFD). CFD has been used at HATCH to address the key process parameters that drive the design of hydrometallurgical unit operations. This paper will detail the role of CFD at HATCH in achieving a superior level of confidence in the process design of autoclave circuits. Specifically, the optimum application of multiphase modeling including hydrodynamic, heat and mass transfer to hydrometallurgy operations, the impact of non-Newtonian slurry rheology on autoclave performance, and the challenges of optimizing the mixing of key reactants into slurries in autoclave reactors, is discussed.

Jan 1, 2003

By Anestis Vlyssides, Elli Maria Barampouti, Sofia Mai, ?postolos Vlyssides

"A new anaerobic reactor variation, the UASB/CO2-stripper reactor was conceived. It consisted of a conventional UASB reactor that recirculated the biogas produced. The sludge characteristics of this system were examined when treating high strength wastewater. From the data collected, it was obvious that the UASB/CO2-stripper system can satisfactorily operate at higher loading rates (25 g COD·L-1·d-1). A pronounced effect on the quality of the granular sludge was observed. The VSS/TSS ratio decreased sharply. A considerable decrease in the mean granule diameter was observed, while the specific gravity of the granules increased. The sludge bed porosity increased significantly leading to a considerable expansion of the sludge bed. These changes in the sludge properties led to a gradual shift of the system towards a fluidized bed process as far as its hydraulic characteristics were concerned.IntroductionIn recent years energy considerations and environmental concerns have increased the interest in direct anaerobic treatment of industrial wastes. The anaerobic method of waste treatment offers, under the present circumstances, a number of significant advantages with trivial or more serious drawbacks over other treatment methods. The major obstacle to the application of the process for this specific purpose is perhaps the difficulty of extending it to a stable and simple operational form. A number of reactor configurations has been developed leading to high biomass concentrations, e.g. the contact process, the filter reactor, the UASB reactor, and the fluidized bed systems, but the process stability problem still remains [1].A prime objective in the operation of anaerobic waste treatment process is the maintenance of a proper pH range. Thus, a possible solution to the process stability problem could be obtained by increasing alkalinity in the anaerobic systems. Therefore, the main objective of this paper is to present and evaluate the results of a system (UASB/ CO2-stripper) with increased alkalinity concentrations."

Jan 1, 2008

By V. A. Luganov

During the treatment of raw materials containing arsenic and antimony, problems in the distribution of these elements in the process products occur. In a number of cases in processing of copper-bearing materials, it is possible (or necessary) to obtain speiss. The purpose of the present research is to study the theoretical aspects and analyze the technological possibilities of producing copper-bearing speiss and the subsequent electrometallurgical processing with copper extraction as well as arsenic and antimony utilization. Copper arsenide (Cu3As) and copper antimonide (Cu3Sb) are the main components of the speiss. A thermodynamic analysis of the electrochemical oxidation of Cu3As and Cu3Sb, carried out using Pourbaix diagrams, showed that in a pH range from 0 to 2, oxidation potential 0.45-0.55V, ions of copper and arsenic and antimony trioxide are in the equilibrium. The kinetic study has shown, that with an increase in the polarization potential, the dissolution process changes from chemical to diffbsion control. An increase in temperature stabilizes the electrolysis process due to dissolution of arsenic trioxide forming on the anode. Electrolysis of speiss using a cathode diaphragm with the solution pH = 1-2, current density 150-200 A/m2 and temperature 60-70°C makes it possible to obtain cathode copper with a current efficiency of 95-96% and to remove the arsenic from the process during the electrolyte cleaning process. The arsenic content in the cathode copper did not surpass 0.002%. As the result of the research, a technological flowsheet for copper-lead speiss processing was developed. At the present time this technology is undergoing pilot testing.

Jan 1, 1999

By N. Solak

CrN, TiN and Ti-B-N coatings were deposited onto H13 hot-working tool steel and alumina substrates by arc-PVD. The coatings were characterized with respect to their mechanical and structural properties. Oxidation behavior of the coatings on alumina substrates was investigated by TG/DTA. Samples coated on H13 substrates were oxidized in a tube furnace under atmospheric conditions at specific temperatures determined from TG/DTA tests of the same coatings deposited on alumina substrates. The oxide scale morphology was characterized by scanning electron microscopy and X-ray diffraction. Oxide scale thickness change and TG data were used to calculate oxidation reaction activation energies. It was determined that boron addition into TiN coating improves not only mechanical properties but also oxidation resistance. Depending on the substrate material different oxidation activation energy values for the TiN and Ti-B-N coatings were determined revealing the importance of film morphology on oxidation resistance.

Jan 1, 2006

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 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 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 M. Urda-Kiel

Stainless steel is increasingly used as a cathode starting sheet. It was shown earlier that even when depositing copper on copper, a substrate-influenced zone appears in the deposit structure, followed by a transition zone and finally by the electrolysis-influenced structure. On copper, the substrate-influenced zone has a thickness of twenty micrometers and on titanium, eventually more than fifty micrometers. Initial nucleation and growth have a considerable influence. In this paper, copper was deposited in a channel cell on four different 304 stainless steel substrates: mechanically polished and anodized, respectively, at 0, +400 and +800 mV/SHE in 1M H2SO4 at 20°C. Copper was deposited under electrowinning conditions after solvent extraction (SX) (40 g/l Cu++, 180 gh/l, H2SO4, 20 or 60°C). The results showed that, although Auger surface analyses of the substrates were only slightly different one from another including the oxide thickness, nucleation and initial stages of growth were very sensitive to the surface treatment of the substrate. Potential step and current step methods gave similar results : progressive nucleation followed by 3D diffusion controlled growth. The highest nucleation frequency was observed on stainless steel anodized at 0 mV/SHE, under various electrolysis conditions. The potential influence of these findings on industrial practice is discussed.

Jan 1, 1999

By P. C. Guillaume

Global plant modernizations or expansions cannot be considered in the same light as any other industrial investment project. Relationships between the partners, relationships and communications with the client, structure and organisation of the teamwork, schedule of the work, and a lot of other tasks and missions devoted to external contractors have to be defined considering one fundamental input: an operating plant. For an engineering company expert in processing, like UM Engineering, such a context requires a specific approach as well as specific procedures able to efficiently challenge the generated constraints. First of all, even if a detailed audit had been conducted at the beginning of the conceptual engineering phase, new elements will be discovered during the preparation and realization of the project, and must be continuously integrated. Consequently, a close proximity to the site is necessary. This is one reason why UM Engineering, most often, works in partnership with a local engineering company. The second important point for the client is that the operation must not be interrupted during the realization. In order to make that possible, UM Engineering has defined a specific project structure and organisation, integrating on a permanent basis the operators (the "users") in the project teams. This paper presents the way UM Engineering copes with this type of "multi-constraints" context with reference to the recent copper cellhouse modernization under realization for the CCR Refinery of Noranda Inc. in Canada.

Jan 1, 1999

By C. T. Yavuz

Higher environmental standards have made the removal of arsenic from water an important problem for environmental engineering. Iron oxide is a particularly interesting sorbent to consider for this application. Its magnetic properties allow relatively routine dispersal and recovery of the adsorbent into and from groundwater or industrial processing facilities; in addition, iron oxide has strong and specific interactions with both As(III) and As(V). Finally, this material can be produced with nanoscale dimensions which enhance both its capacity and removal. The objective of this study was to evaluate the potential arsenic adsorption by nanoscale iron oxides, specifically magnetite (Fe3O4) nanoparticles. We focused on the effect of magnetite particle size on the adsorption and desorption behavior of As(III) and As(V). The results show that the nanoparticle size has a dramatic effect on the adsorption and desorption of arsenic. As particle size is decreased from 300 nm to 12 nm the adsorption capacities for both As(III) and As(V) increase nearly 1000 times. Interestingly, this increase is more than expected from simple considerations of surface area and suggest that nanoscale iron oxide materials sorb arsenic through different means than bulk systems. The desorption process however, exhibits some hysteresis with the effect becoming more pronounced with small nanoparticles. This hysteresis most likely results from a higher arsenic affinity for magnetite nanoparticles. This work suggests that magnetite nanocrystals and magnetic separations offer a promising method for arsenic removal.

Jan 1, 2006

By A. A. Bustos

Four Air Liquide Shrouded Injectors (ALSI ) were installed and operated for over one year in a Peirce-Smith converter at the Falconbridge nickel smelter in Falconbridge, Ontario, Canada. A shrouded injector consists of an inner pipe and an annulus, through which high oxygen enriched air and nitrogen flow, respectively The nitrogen cools the injector and protects the refractory in the vicinity of the injector tip, allowing for substantial increases in oxygen flow rates to the converting reactions. Several injector designs were tested to study the effect of changes in the cross-sectional area and changes in the entrance geometry of the annulus. An optimum design would minimize the injection pressure required for a given flow rate to achieve choked flow conditions at the tip of the injector. The operation of the ALSI was simple and did not require any special care or maintenance, either between blows or between converter cycles. In particular, the shrouded injectors did not require punching, as is the case with conventional tuyeres. In terms of refractory performance, the ALSI, operating at 30-40 % oxygen enrichment, were superior or equal to the conventional tuyeres, which operated at 21-23% oxygen. The results of the demonstration program led Falconbridge Limited to implement the ALSI technology on a commercial scale The paper presents the demonstration program results in terms of gas flow rates, accretion formation, punchless operation and refractory wear.

Jan 1, 1999

By M. E. Ramos Rada

Mexicana de Cobre, which is part of Grupo Mexico, carried out studies for the construction of a copper refinery in the La Caridad Metallurgical Complex located in Nacozari, in the state of Sonora, Mexico. After the studies were concluded, the decision was made to construct a 180,000 t/y refinery using the state of the art permanent cathode Kidd Process. The basic engineering was developed by Fluor Daniel and the detail engineering and the construction were carried out in record time by the Mexican company Bufete Industrial. During the construction phase, Grupo Mexico decided to expand the refinery, and actions were taken to increase its capacity by an additional 120,000 t/y; the final result was a refinery capable of producing 300,000 tonnes of grade A cathode per year. Construction began in January 1996, and the operation of the first stage began on July 1, 1997. The operation of the second stage commenced on January 7, 1998. The capacity of the first stage was reached in November, 1997 and the total capacity of the refinery was achieved in May, 1998. This presentation describes the process and equipment installed in the refinery, the steps leading to the start-up, the operation and the results obtained during the first two years, the handling of anodes with high impurity contents, and the problems confronted and the way they have been solved. It also includes personnel productivity, the control parameters and the most relevant data on the operation of the process.

Jan 1, 1999