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By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

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 Burkhard Seeger et al.

The oxidation of copper sulfides can be highly accelerated in the presence of nitrous gases (NOx) as reaction catalysts. Sulfur and sulfate are simultaneously produced in this highly exothermic reaction. This process, carried out in sulfuric acid medium, is performed at an approximately normal pressure and at a temperature of around 110 °C, in a closed container, adding either oxygen or air. The oxidation is automatically controlled through a computer. The process covers the following steps: Catalytic oxidation, filtration and crystallisation of the hot concentrated liquid, electrowinning, mother liquor treatment through jarosite formation, recovery of dissolved copper and zinc and regeneration of industrial water, and non-soluble residue treatment with extraction of sulfur and recovery of silver and gold. No combustibles are needed. No air is contaminated, and no waste water is produced. Solid residues are in a stable, non-toxic and non-corrosive state of equilibrium. Risk of accident is low. Investment costs are small compared to those of the comparable pyrometallurgical process, and production costs are competitive.

Jan 1, 1999

By Roberto Parra

The wear and corrosion phenomena in the furnace lining of the ferrous and non ferrous pyrometallurgical processes are complex problems where chemical, interfacial and mechanical phenomena are presents. The characteristics of the processes determine the conditions to which these materials are submitted, where the thermal conditions reached during the operation is one of the most important parameter. Assuming that all the degradation phenomena are thermal activated, the rate of the different steps of the wear mechanism will depend on the thermal field in the lining. In view to apply the independent physicochemical knowledge of degradation mechanisms to the analysis and design of furnace lining the methodology of the Nodal Wear Model (NWM) was done. It combines the mathematical modelling of the heat transfer in the lining with the physicochemical control equation for the wear-corrosion phenomena. The NWM has been applied to different examples: theoretical analysis, laboratory scale test and industrial applications. We present in this paper the theoretical background of the model and two examples of applications: the sole of an electric furnace and the earth of a blast furnace.

Jan 1, 2006

By David G. Dixon

From its first implementation for the recovery of gold from low-grade ores by cyanidation in the early 1970s, heap leaching has developed into a key hydrometallurgical technology, in conjunction with solvent extraction and electrowinning, for the recovery of base metals, including most notably copper from both oxides and secondary sulphides, and more recently, nickel and zinc. And, given recent advances in bioleaching with thermophilic microbes, the successful application of heap leaching technology to low-grade primary copper ores seems only a matter of time. However, with each new development, it becomes increasingly apparent that the successful application of heap leaching technology will ultimately depend on our having an ever more complete understanding of the fundamental processes underlying it. Much work has been done toward the development of this understanding, on many different fronts. In this paper, a critical overview of heap leach modeling work to date is presented in terms of the most important phenomena which occur during heap leaching, and potential directions for future work are discussed.

Jan 1, 2003

By Hong Yong Sohn

A thermodynamic and experimental investigation has been performed to develop a new process for converting sulfur dioxide to elemental sulfur by a cyclic process. The most promising new process is a cyclic reaction scheme involving calcium sulfide and calcium sulfate. In this process, the reaction between sulfur dioxide and calcium sulfide produces elemental sulfur vapor and solid calcium sulfate. The latter is reduced by a suitable reductant such as hydrogen to regenerate calcium sulfide. 'Experimental results showed that up to 60 % of calcium sulfide powder was converted to calcium sulfate in 10 min at 1153 K under a sulfur dioxide partial pressure of 25.8 kPa. More than 95 % of nickel-catalyzed calcium sulfate powder was converted to calcium sulfide in 20 min at 1123 K under a hydrogen partial pressure of 86.1 kPa, water vapor being the only gaseous product. Sulfur dioxide-containing streams from certain new sulfide smelting plants contain much higher partial pressures of SO2. The rate of the first reaction is expected to be accordingly higher than in the test conditions reported in this paper.

Jan 1, 2002

By V. L. Stolyarova

As part of an effort to develop the fluoride electrolysis route for the production of rare earth metals and alloys, a study of the thermodynamic properties of DyF3 has been carried out by Knudsen cell mass spectrometry. A quadrupole mass spectrometer QMS 420 was used in conjunction with the Knudsen cell arrangement. The experiments were carried out in the temperature range 1280-1440 K. Vaporization was carried out from platinum, molybdenum and tantalum cells. The Dy*, DyF+, DyF2+ fragment ions and the DyF3 parent ion were identified in the mass spectrum of the DyF3 vapour. The DyF, vapour pressure was obtained by the complete isothermal vaporizadon method as well as the ion current comparison method, and the enthalpy of sublimation of DyF3 was evaluated. From the DyF3 vapour pressure data obtained at different temperatures, the enthalpies of formation of DyF3 in the gaseous as well as condensed phases have been evaluated. The experimental data are compared with the thermodynamic information available in literature.

Jan 1, 1995

By V. Jiricny

The novel spouted-bed electrode (SBE) is a cathode system where copper is deposited at a high current density in a moving bed of copper particles. Preliminary results on the deposition of copper from acidic sulfate electrolytes using this novel cathode system were described during Copper '95 conference. Despite a high current density, the electrical energy consumption was equal to or lower than that in the conventional electrowinning. The present paper describes more investigations on SBE. The SBE consists of copper particles with approximately 1 mm diameter onto which copper is deposited from acidic sulfate electrolyte whose composition is similar to conventional electrowinning. Three types of anodes were used in conjunction with the spouted-bed cathode, namely, DSA anode for oxygen evolution, and two novel anodes. One anode is less expensive than DSA; however it showed much promise in energy consumption. At a superficial current density of 2200 A/m2, the energy consumption was around 1.0 kWh/kg copper. The research activities described in this paper were supported by BHP Copper.

Jan 1, 1999

By Dhanesh Chandra

Long term stability studies were conducted on four variants of LaNi5; 10,000 hydriding/dehydriding cycles were used to evaluate their suitability for a metal hydride cooling system. Thermodynamic and structural studies were conducted to determine changes in these materials during cycling test period. The hydrogen sorption properties of LaNi5.2, and Lao 9Gd0.1Ni5 and LaNi4.75In0.27 were seriously degraded during the tests but the LaNi4.8Sn0.22 hydride was virtually unaffected. Hydride isotherms were measured at the beginning and at intervals through out the test period to observe the nature and extent of damage degradation in the sorption properties. X-ray diffraction studies of the alloys (LaNi5.2, LaO.9Gd0.1Ni5 LaNi4 8Sn0.22) and their respective hydride, before and after test, provided insight with regards to the observed changes in the hydride properties. Electron microscopic studies were also conducted to evaluate the changes in particle sizes.

Jan 1, 1989

By D. Quattrini

The aim of the present work is to present the gas chromatography (GC) as an alternative method of analysis in the thermal decomposition of calcium carbonate. Therefore, a furnace/GC on-line system was employed to study the kinetics of the reaction, measuring the CO2 produced in the decomposition. One of the advantages of the GC method is the possibility to perform an in-situ characterization and quantification of the gaseous products to obtain kinetic parameters, besides the method is simple and shows a good reproducibility. The decomposition of calcium carbonate was carried out in isothermal conditions at temperatures from 655 to 715°C with nitrogen as purge gas. Several gas velocities were used to determine the adequate flow that minimizes the effect of external mass diffusion as rate controlling step. It was made a preliminary analysis of the sample size influence on the reaction rate. The activation energy of the reaction was determined by Flynn method. The value obtained was in a good agreement with other authors. On the other hand, gravimetric measurements were employed for compare GC results.

Jan 1, 2006

By Khosrow Nikkhah

Increasingly ion exchange systems are being included in design of hydrometallurgical plants for metal extraction or impurity removal. Because such systems operate sequentially and are based on resins that exchange one ion for another, store it temporarily and release it to a regenerating solution, the usual steady state heat and mass balancing tools and spreadsheets cannot be used to design them successfully. This paper outlines the role of dynamic simulation in design of ion exchange systems. Examples are given for use of dynamic simulation in design and investigation of equipment based on consideration of the effect of input criteria such as expected ion loading and elution profiles. The methodology for dynamic modeling using IDEAS in design of multi column ion exchange trains operating in parallel is presented. Results shown include the non-steady state distribution of extracted metal and limitations imposed on operating conditions. These conditions include proposed sequencing of columns for loading and elution cycles, loading, elution and recycle flow rates as well as size and choice of related ion exchange plant equipment.

Jan 1, 2003

By Antrekowitsch Jürgen

The recycling of residues from metal producing by-products has become a main field of interest in metallurgical investigations. Forced by a stricter environmental legislation and the resulting increase of landfilling costs, combined with the aim to recover as many valuable metals as possible, a lot of different processes have been developed in the last two decades. Because of the high yearly tonnage residues from the iron and steel industry like slags, dusts and sludges have moved in the center of interest. Dusts from the steel mill, containing heavy metal oxides and halides did not play a considerable role as secondary raw materials for a long time. They even contain a huge amount of leachable elements and compounds which cause noticeable problems in case of a dumping. Nevertheless, the implementation of a new landfilling regulation, including a prohibition of aboveground dumping without inertisation, caused a rising interest concerning recycling technologies for such residues. In addition, the zinc content of these dusts became higher and higher and began to play the most important role for the economy of dust recycling.

Jan 1, 2006

By B. C. Blakey

Unlike most hydrometallurgical slurries, those containing significant concentrations of goethite are typically highly viscous and shear-thinning, even at solid volume fractions below 5%. The viscosity may also depend upon time. These characteristics must be taken into consideration in slurry transport and heating. The technical literature is replete with apparent contradictions regarding the viscous behavior of these slurries, which may be due, in part, to variations in viscosity-measuring techniques. We present techniques that yield consistent results suitable for use in process design. A striking degree of time-dependent behavior is demonstrated for a laterite slurry. Reliable methods to design and analyze tubular transport and heating systems for time-independent slurries are summarized. Rules of thumb are then offered to account for the effects of time-dependency.

Jan 1, 2000

By Reed M. Izatt

SuperLig® materials are capable of individually separating Rh, Pd, and/or Pt in highly purified form (99.95 to 99.99%) from a variety of chloride-based feed streams in a single stage operation. The hydrophillicity and associated kinetics of the supported materials allow for operation at relatively high flow rates of both loading and elution in a packed bed format. Pilot and commercial systems have been operated with Rh, Pd, and/or Pt present in the feed from single digit ppm (mg/l) to tens of g/l. A dual SuperLig® system for one pass Au(CN)2- separation followed by Cu and CN- recovery for CN- recycle has also been tested up to a pilot level,

Jan 1, 1999

By C. Pereira

Spent nuclear fuel (SNF) can be treated in a molten salt electro refiner for conversion into metal and mineral waste fonns for geologic disposal. The fuel is dissolved in molten chloride salt. Non-transuranic fission products in the molten salt are ion-exchanged into zeolite A, which is subsequently mixed with glass and consolidated. Zeolite was found to be effective in removing fission product cations from the molten salt. Breakthrough of cesium and the alkaline earths occurred more rapidly than was observed for the rare earths. The effluent composition as a function of time is presented, as well as results for the distribution of fission products along the length of the column. Effects of temperature and salt flow rate are also discussed.

Jan 1, 1996

By E. Oshilna

The Mitsubishi process has many advantages pertaining to economical and environmental matters. These advantages have led to the installations of the Mitsubishi process in constructing new smelters: The Mitsubishi process utilizes highly oxygen enriched blast air and uses a special lime slag in the C?furnace. These characteristics change the . distribution of Impurities from other processes which use P.S. converters, Recently an Increased amount of secondary materials which contain impurities Is being treated at Naoshima Smelter. In order to cope with an Increment of the Impurities load and maintain the cathode quality, many Improvements have been Implemented. This paper discusses the impurities behavior In the Mitsubishi process and describes the measures taken to treat an Increased ?amount of secondary materials:

Jan 1, 1998

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

By A. Erçin Ersundu

In the present work, three different domestic iron ores; Sivas Divrigi B Head high grade hematite lump ore, Malatya-Hekimhan-Hasançelebi medium and low grade magnetite lump ores reduced with Soma-Kisrakdere lignite coal to investigate their suitability for sponge iron production. A laboratory scale box furnace was used to carry out the reduction experiments. In the experimental studies different operation parameters were selected being Cfix/Fetot. ratio, temperature in the range of 1100 - 1250 oC and time, to determine their effects on metallization. Metallization degree up to 90 % was found in the reduction experiments realized by using Sivas Divrigi B Head high grade hematite lump ore, whereas for Malatya-Hekimhan-Hasançelebi medium and low grade magnetite lump ores 60 - 65 % metallization degrees were obtained.

Jan 1, 2008