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By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By Guohua Bai, Lin Zhang, Shan He, Xuling Chen, Min Gan, Xiaohui Fan, Yanbin Tang

"For reducing the dust content in flue gas during copper smelting in the Ausmelt, technologies and mechanism of strengthening the pelletizing of copper concentrate were studied. The results show that adding bentonite, organic binder or composite binder can effectively enhance the strength of green pellet and reduce the rate of shedding powder in drying process, and composite binder works best. When adding 1 % of composite binder, the drop strength of green pellet increased from 1.9 times/P to 4.5 times/P, the rate of damage dropping from 2 m reduced from 50.12% to 13.08% and the rate of shedding powder reduced from 60.28% to 25.13% at drying temperature of 400111. In addition, the mechanism of binder absorbed in the surface of mineral was investigated by infrared spectroscopy. The results showed that composite binder absorbed in the surface of copper concentrate was in the form of chemisorptions, which made hydrophilic enhanced, while bentonite absorbed in the surface of copper concentrate was physisorption.IntroductionWith the technologies of copper smelting developing, the equipment of copper smelting steps into a large-scale and efficient level in recent years. As Ausmelt smelting is characterized by being efficient, environmentally-friendly and energy-saving, it is generally recognized by the enterprises of copper smelting [l]. The process of Ausmelt smelting starts with materials mixing, and then pelletizing. From this point onwards, pelletized balls are charged to the top of the furnace, undergoing drying and smelting reaction[2]. Since copper concentrate is fine-grained, directly adding into smelting furnace can make it blown out of the furnace together with the airflow upwards, rendering flue gas high in flue dust, which can cause the loss of concentrate greatly, and make smelting environment poor as well. The concentrate transported into the furnace and smelted after disc balling is conducive to improve the capacity of melting furnace during copper concentrate smelting, reduce the powder shedding rate and improve enterprise benefits."

Jan 1, 2013

By G. B. Harris

Jaguar Nickel Inc. is developing the Sechol Nickel-Cobalt Laterite Project in Guatemala, Central America. Recognizing the potential advantages offered by chloride brine chemistry, Jaguar, at the facilities of Process Research ORTECH Inc, Mississauga, has developed an Atmospheric Chloride Leaching Process using a mixed chloride lixiviant to recover the nickel and cobalt, whilst leaving the majority of the iron and magnesium in the leach residue. Subsequent solution purification and mixed nickel/cobalt hydroxide product recovery is by standard precipitation methods, using recycled caustic magnesia, with a final stage of pyrohydrolysis of a portion of the concentrated magnesium chloride brine for recycling both the caustic magnesia and chloride lixiviant. The flowsheet that has been developed also offers opportunities for by-product recovery and efficient, environmentally clean process effluent management. The paper discusses some of the early leaching results in the context of strong chloride brine chemistry, with emphasis on how the controlling of water activity, hydrogen ion activity and chloride concentration permits the selective leaching of nickel and cobalt from an iron-magnesium matrix. Keywords: nickel, cobalt, iron, magnesium, Sechol, Guatemala, chloride, pyrohydrolysis

Jan 1, 2004

By W. G. Davenport

This chapter demonstrates how our matrices can be used for controlling a flash furnace. Specifically, it shows how we can determine the adjustments in industrial oxygen, air, oil and flux input rates that will; (a) correctly alter product temperatures and compositions to newly targeted values (b), maintain set-point product temperatures and compositions with varying feed compositions and feed rates. It also discusses corrective actions that might be taken when furnace temperature and matte grade unexpectedly change.

Jan 1, 2001

By Juan Hernández Ávila

This work studies the Molybdenum effect on the microestructure, mechanical properties of an as-cast ductile iron. For this study five ductile irons with different amounts of Molybdenum each were made in an induction furnace. In this material nodule count and nodularity is affected by the Molybdenum additions; The iron´s matrix, nodules and the phase were analyzed using scanning electron microscopy detecting Molybdenum only in the matrix. Mechanical properties such as hardness, microhardness, tensile strength and yield strength show increments as the Molybdenum amount is increased. In the same way, ferrite and pearlite phases display a variation in their percentage as the contents of the alloy element increase. This element has a marked influence on the pearlite interlaminar spacing. From the obtained results we conclude that Molybdenum in these quantities dissolves in solid ferrite solution during the solidification process, improving the material´s mechanical properties.

Jan 1, 2009

By Fuxing Yin, Akira Sato, Yoshiaki Ohsawa, Kohji Kawaharai

"INCRAMUTE alloy (nominally 45Mn-53Cu-2Al wt. %) has a specific damping capacity as high as 0.4, through a solid-solution and aging treatment. The damping behavior of the alloy is highly temperature-dependent and shows a peak near room temperature. The inadequate strength in the high damping condition restrains the practical application of the alloy, as structural components. Ferromagnetic MnB particles are dispersed in the alloy during induction remelting the matrix alloy in an argon atmosphere. Surface modification of the MnB particles by mechanical alloying (MA) and suitable control of the addition process cause a homogeneous distribution of MnB particles in the alloy. In the composite containing 2 wt. % MnB particles, temperature dependence of damping capacity is improved, and higher damping capacity is still retained in the temperatures over 60 °C. Meanwhile, the Young's modulus and tensile strength were also increased by about 20%. The roles of the MnB particles in improving both damping behavior and mechanical properties were also discussed.IntroductionMany viscoelastic materials, such as rubbers, polymers and plastics, have the superior ability to damp vibration and noise. However, in the applications as structural materials the high damping capacities of materials are pursued upon the satisfactory mechanical properties, especially those at elevated temperatures. Damping alloys are finding more and more applications in structures where noise and vibration ·should be ·eliminated. Specific damping capacity (SDC), defined as the ratio of the energy dissipated to the maximum vibration energy stored per cycle, is usually used to evaluate the damping capacity of alloys. INCRAMUTE damping alloy, developed by the International Copper Research Association, Inc., has a nominal composition of 45Mn-53Cu-2Al in weight percent. The high damping· microstructure of this alloy is obtained through the solution treatment at 820 °C followed by a water quench and aging at 400°C for 10 hours followed by cooling to room temperature [1]. With the heat treatment, a SDC peak ·vs. temperature of as high as 0.4 was observed in the alloy at the strain amplitude of about 10-3 while a tensile strength of about 500MPa was sustained."

Jan 1, 2000

By Ling-yun Yi, Yuan-bo Zhang, Bing Hu, Zhu-Cheng Huang, Zhen-yuan Liao

"Nucleation and growth mechanism of iron crystal grain in coal-based shaft furnace direct reduction process by microwave heating were investigated by optical microscope, scanning electron microscope and EDX. The results indicate that microwave has selectivity on various minerals which absorb microwaves. The high temperature in certain area of pellets and thermal stress on the interface of minerals are formed, results in the wustite grain smashed along the joints, and iron crystal grains turned out a spherical shape obviously. The iron crystal nucleus is formed firstly at the edge of wustite, on the interface between grains and in the holes in pellets, and grows gradually while reduction carries on from surface layer to inner core. Microwave heating promotes the rate of transportation and accumulation of the iron crystal grain, increases growth rate of iron crystal grain and contributes to formation of dense iron-jointed crystal texture eventually.IntroductionMicrowave energy as a new energy, which selectively heating materials through internal energy dissipation, has the advantages of heating uniformity, high thermal efficiency, fast heating, clean and pollution-free compared to conventional heating motheds. Microwave energy also has obvious superiority in increasing productivity. Thus, it has been widely used in many areas, including electronics, food processing, chemical, medicine, environmental protection, and family life etc [1]. As a rapidly developed green metallurgical method, microwave heating also has been widely recognized by areas of grinding, pretreatment, pre-reduction, drying, furnacing, metal extraction, and waste materials processing and utilization. Some research achievements are gradually putting into practice, showing great potential in chemical and metallurgical industry [2-3]."

Jan 1, 2011

By S. A. Shuey

The present industrial practice used to separate aqueous cobalt from nickel is multistage solvent extraction processing. This paper describes a different but simpler treatment technology. The proposed technology has been applied to cobalt/nickel hydroxide intermediate solids produced from the treatment of Electrochemical Machining (ECM) waste sludge, The process consists of dissolving the cobalt/nickel hydroxides in basic cyanide solutions. Cobalt and nickel form aqueous .solution metal cyanide complexes. Nickel can be selectively precipitated from the solution as a nickellic hydroxide solid. Cobalt can be recovered from the leach solution by precipitation of a cobaltous/cobaltic cyanide double salt. The double salt product can then be subsequently treated to produce an appropriate cobalt product. The process chemistry, proposed fiowsheet and preliminary reagent costs are presented and discussed.

Jan 1, 1998

By Tadashi Aiura, Yasuhiro Miura

"A small amount(0.2mass%) of Scandium(Sc) was added to the 7.NOl and 5083 Al alloys as a refiner and stabilizer of microstructure, and the resulting microstructures were discussed in comparison with the effects of the conventional additives. The followings are summarized: 1) in the as-solidified structure, a ·decreased tendency of constitutional supercooling and increased solubility of Mg were recognized for the Sc-added 5083 alloy. Sc is a -better microstructure refiner for the 7N01 alloy than Zr, in a sense that it does not suppress the favorable effect of· coexisting Ti. 2) Sc effectively suppresses recrystallization both in the 5083 and 7N01 alloys. 3) The rod like primary Al3Sc crystals formed during solidification, as well as the fine dispersion of Al3Sc precipitates formed by subsequent heat treatment, can act as a strong recrystallization suppresser. IntroductionThe 7N01 and 5083 alloys are the most popular industrial Al alloys and they are widely' used for various structures because of their superior properties. Fine macro and micro structures of the materials are required for obtaining acceptable sec resistance,consistent appearance of anodized surface and good weldability, as well as good mechanical properties. In order to produce fine grain structures, transition metals, such as Cr, Zr, and Mn, have been conventionally added.It has been reported that Sc is an efficient refiner [l, 2] and can be an alternative for the conventional and also suppresses recrystallization in Al alloys [3,4]. Scandium is the lightest transition element and forms an equilibrium intermetallic phase. The equilibrium phase, Ll2-Al3Sc, is coherent with the matrix, and of _spherical shape. A fine dispersion of the spherical precipitates is obtained by quenching and aging after solutionizing annealing. The authors have already reported a part of the experimental results on the effect of Sc on the as homogenized microstructure of the 5083 alloy [5]. In the present study, the effects of Sc on the macro and micro structures of the industrial high strength Al alloys(7N01 and 5083) for extrusion are investigated, and the superior role of Sc as a grain refiner is shown"

Jan 1, 2000

By Singareddy R. Reddy, Ramana G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. An expression for the activity coefficient of a dilute solute, 2(oxygen), in a binary solvent 1-3 is derived. It is used to calculate the logarithmic activity coefficient of oxygen in Pb-O-Gu, Pb-O-Bi, AgO- Sn, Pb-O-Sn and Ag-O-Pb metallic systems. Self interaction parameter of the solute is derived from the partial Gibbs energy of solute using constant compositional path. The derived equation is used successfully to deduce the self interaction parameter of oxygen in Pb-O-Gu and Pb-O-Bi metallic systems. The predicted thermodynamic parameter data i.e activity coefficient and self-interaction parameters are in an excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionThe nature of solute interactions such as oxygen, nitrogen and sulfur with the metallic solutions are important for a number of chemical and metallurgical processes. Several theories [1-23] have been developed to evaluate fundamental thermodynamic properties of solutes constituting two elements. The activity of solutes has been calculated using statisticalor quasi- chemical approach.Wagner's [4] Ideal Solvent Model is based on one energy parameter to describe the compositional dependencies of the activity coefficient of nonmetallic solutes such as oxygen in binary metallic solutions. This model depends on a constant energy of interaction for the exchange of atoms from the coordination shell of an oxygen atom to the shell of an interstitial site and cannot account for properties of strongly interacting systems [4]. Therefore, several attempts have been made to improve the Wagner's model for the strongly interacting systems. [10-16]."

Jan 1, 1996

By Phillip A. Armstrong, Charles A. Lewinsohn, John H. Gordon

"This paper describes the opportunity offered by employing systems based on mixed conductive ceramics, in particular, ceramics conductive to oxygen ions and electrons, in reducing CO2 emissions from metallurgical production. Membranes based on these mixed conducting properties enable commercial viability of several attractive metallurgical processes. One of these processes utilizes modular, ceramic-membrane structures for the generation of pure oxygen, in tonnage quantity. The membrane-based systems offer significant capital savings and operating efficiencies in various metallurgical processes. The current status of this technology is summarized below.IntroductionCryogenic oxygen supply technology is currently the state-of-the-art for applications that require large quantities of oxygen (hundreds to thousands of tons per day). Cryogenic technology, however, requires substantial energy inputs and, hence, adds significant costs and emissions to processes. Furthermore, cryogenic oxygen supply technology is mature and there is relatively little potential for substantial capital cost reduction or efficiency improvement in coming decades. Non-cryogenic technologies offer a means to reduce the environmental footprint and cost of the oxygen supply facility in various applications.Ion Transport membranesCommercially available non-cryogenic air separation technologies, such as adsorption-based and polymeric membrane-based methods, do not afford the economies of scale that the cryogenic distillation enjoys. Therefore, industrial gas industry researchers began searching for alternatives to the relatively inactive and unselective polymeric membrane materials available. In the late 1980’s, Air Products began developing a new class of highly selective membrane materials with exceptionally high activity for oxygen transport. The materials constitute a class of oxide ceramics, and conduct both oxygen (as oxygen ions) and electrons in the same membrane, separating oxygen from air electrochemically. Numerous detailed process economics studies have shown that, based on these ion-transport membranes (ITM’s), the cost of oxygen can be reduced by approximately one-third relative to that obtained from state-of-the-art cryogenic oxygen supply technology, through a combination of capital cost savings and efficiency improvements. [1,2,3]"

Jan 1, 2008

By P. J. Mackey

Over the course of Dr. Robertson’s career, the ferrous and non-ferrous plants have seen enormous changes in technology and increases in plant capacity, essentially amounting to a “technological revolution”. In iron and steel, the “mega” blast furnace of some 6,000 m3 working volume is now standard (~10,000 tonnes (mt) of pig iron/day). Similar huge changes in process technology and plant size have occurred in the non-ferrous industry. As an example, the fuelfired reverberatory furnace, once the mainstay of the copper industry, has disappeared - replaced by large capacity flash and bath smelting technologies. The energy consumption per unit mass of metal produced has also been reduced considerably. Our understanding of the thermodynamics and mechanisms of metallurgical reactions, a field to which Dr. Robertson has significantly contributed, has made great strides. This paper reviews these changes with particular reference to the copper smelting industry, providing also comments on expected future trends.

Jan 1, 2014

By A. D. Damodaran

Batch scale and continuous rotary kiln carbothermic metallisation of ilmenite followed by different down-stream treatments such as catalytic rusting, acidic chloride leaching, oxidation-leaching etc. has given rise to a high grade synthetic rutile (98% TiO2). Rotary reactor metallisation experiments had concurrently given important information with respect to mean residence time, dispersion number, hold-up and axial velocity profiles of the solids bed. A mathematical model based on law of additive reaction times has indicated that Boudouard reaction becomes faster than reduction reaction at higher conversions. A possible use of high grade synthetic rutile in paint industry and metallised ilmenite as welding electrode flux material are discussed.

Jan 1, 1992

By Dong Liang, Honggang Zhong, Zhenxing Yin, Qijie Zhai

"2507 super duplex stainless steel (SDSS) has been widely applied in a marine environment, attributing to its excellent pitting corrosion resistance and mechanical properties which are particularly determined by the nitrogen precipitation behaviors and volume fraction of ferrite. In this paper, various cooling rates were obtained by applying four different moulds with the common gating system. By which the influence of cooling rates on nitrogen precipitation behaviors and the ferrite fraction in cast 2507 SDSS was comparatively investigated. The results showed that nitrogen porosity could easily precipitate in cast 2507 SDSS under standard atmospheric pressure. The number of nitrogen holes increased with decreasing the cooling rates, and the holes mainly distributed in three zones, i.e. the interface between the horizontal and vertical columnar grains, top vertical columnar grains and the final solidification region. Additionally, higher ferrite fraction was obtained with lower cooling rates.IntroductionDuplex stainless steels (DSS) have a dual-phase microstructure consisting of ferrite (d) and aus-tenite (?). Due to the combined advantageous properties of d and ? phase, their application rapid-ly increased in industry [1, 2]. Super duplex Stainless Steel (SDSS) is the third generation of du-plex stainless steels, of which the alloy elements Cr, Ni and N content are higher than the stand-ard 2205 DSS. Because it has high contents of alloy elements, the SDSS has better mechanical properties, and its pitting resistance equivalent number (PREN) reached a point 43. Hence SDSS has been used in petroleum chemical industry, the marine equipment and harsh corrosion environments [3]. SDSS contains ferrite stabilizing elements, such as Cr, Mo and Si, and austenite stabilizing elements like Ni, Mn and N [4]. Many researchers have studied the effects of these elements on the stabilization of d and ? phase and the ratio of the two phases. High nitrogen con-tent is another prominent feature of SDSS. Nitrogen addition to SDSS is very effective for improving its mechanical properties [5] and corrosion resistance [6], such as pitting resistance in NOx environment. To increase the nitrogen content in steels, a lot of work had been done. N. Nakamura and S. Takaki [7] examined the behavior of nitrogen absorption in Fe-23Cr alloy powder by sintering in nitrogen gas atmosphere, they found nitrogen content easily up to 1.0 wt. %. Using devised NH3 gas injection system, W. Park et al. [8] successfully produced austenitic Fe–23.5Cr alloys containing over 3 wt. % of nitrogen. Further-more, W.P. Tong et al. [9] stated that nitrogen percent was extraordinary high (about 10 wt. %) in pure iron plate. However, the above methods are difficult to be applied to large-scale industrial production."

Jan 1, 2012

By Y. Y. Sheng

Plume flows created by gas injection into liquid metals have been studied extensively, however the dynamics of bubbles within the plume have not received adequate attention, particularly for large, irregular bubbles, characteristic of the processing of liquid metals. The present model uses a combined Eulerian-Lagrangian approach in which an estimated void fraction distribution is used to calculate the liquid flow field with a conventional Eulerian scheme. The trajectories of bubbles are then computed in a Lagrangian manner using the estimated flow field, and experimentally measured information on bubble drag coefficients', lateral migration due to lateral lift forces and interaction with turbulent eddies, and variation in bubble size due to break-up. Turbulence in the two-phase zone is modeled with a modified k-e model with extra source terms to account for the second phase which have been recently determined by the present authors. The computed void fraction and turbulent liquid flow field distributions are in good agreement with experimental measurements.

Jan 1, 1993

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By Heikki Tuovinen

The total utilization of raw materials and energy is the most important criterion when planning. industrial processes. The main goal is clearly to use the raw materials and energy as effectively as possible in order to make the desired products directly in the primary process itself', or to recycle unused materials and energy either as such, or after cleaning back into the process. However, few industrial processes are so straightforward. Most processes generate by-streams of materials and energy, which cannot be recycled directly and it is namely these by-streams which tend to remain as wastes. These by-streams are slags, dusts, vaporized metals, liquids, slurries, sludges, gases etc. Most base metal processes produce all these by-products. Waste water and gas emission controls and regulations are tightening all the time, so new processes must be developed to keep pace with these requirements. These processes generate more solid wastes, which must be utilized or at least processed into a harmless form landfilling. Municipal and hazardous wastes also contain valuable materials and energy, which must be used to minimize landfilling. The development of processes for these purposes places even greater demands on research and development. The same principles and methods developed for mining, ore dressing and metal refining processes can also be adapted for research and development work on processes for waste minimization. However, the problems encountered are much more complicated and less familiar, demanding more versatile and accurate tools and equipment. This paper presents principles, examples and some references of R & D work on processes for waste minimization.

Jan 1, 1992

By Masaru Imaizumi, Hiroyuki Nomura, Mitsuharu Takita

"Cast iron possesses many superior characteristics caused from precipitated graphite structure, for example, castability, wear resistance, solid lubrication, damping capacity. But the more graphite hyper-eutectic cast iron contains, the lower its mechanical strength becomes, because graphite gives a negative effect to strength of cast iron. In addition, primary graphite tends to segregate during solidification, so uniform materials are difficult to be produced.In this study, authors introduced semi-solid processing in developing new and high quality cast iron. A series of semi-solid processing experiments were carried out to clarify the effect of stirring condition; solidification temperature and etc. on microstructures and characteristics of cast iron. In particular much attention is paid to the appearance of ternary eutectic zone at the final stage of solidification. As the results advanced hyper-eutectic cast iron was obtained with high quality of both the mechanical strength and wear resistance. As for the mechanical strength, 300MPa and 0.60% are obtained as the tensile strength and the elongation values, respectively, under the controlled stirring condition. This indicates that semi-solid processed hyper-eutectic cast iron is used prospectively without spheroidization.IntroductionCast iron has various good properties such as wear resistance, solid lubrication, damping capacity and machinability. The characteristics of cast iron are mainly decided by graphite structure, namely graphite shape and its distribution in the matrix. Mechanical strength of cast iron is large in the case of small quantity of graphite particles which are precipitated uniformly, however, it becomes small in the case of large quantity of graphite precipitated flakily."

Jan 1, 2000

By Hidefusa Takahara, Koichi Miyake, Dierk Raabe

"Mechanical properties of copper wires were examined. The copper wires containing 5-10 mass % chromium and 1-3 mass % silver were produced through heavily cold deformation. It was expected that the copper wire was easily fractured during cold deformation because of the existence of brittle chromium phase in the alloy. In fact, the copper wire was fractured due to large work hardening, when the true strain [n] exceeded 5. However, the copper wire annealed at 1273K for 6 ks ·in the middle of deformation process could be smoothly drawn to 11=8. After precipitation treatment for silver phase at 473k for 1.8 ks, the wire was able to further drawn to n=8.4. The final deformed wire showed tensile strength higher than 1200MPa.IntroductionDownsizing of electronic devices has led to the demand of finer and higher strength materials for cables. Conventional copper alloys have about 800MPa in ultimate tensile strength. These strength are mainly obtained by precipitation hardening. Nowadays, a process for higher strength wire has been developed, where dual phase copper alloy is used. When it is drawn heavily, the' second phase is elongated along drawing direction and the wire gets high strength due to fiber reinforcement (1). That alloy is so called in-situ formed fiber reinforced ·alloy. Cu-Ag(2), Cu-Nb(3) and Cu-Cr(4) systems are well known as such alloys. It is also well known that chromium is brittle material except single crystal and high purity of chromium. However, Mihara et al. C5l have achieved 1 GPa in ultimate tensile strength in the Cu-Cr-Zr and Cu-Cr-Ti alloys by appropriate thermo-mechanical processing.In this study, the Cu-Cr-Ag systems were investigated: The alloys contained 10 or 5% chromium and 3 or 1 % silver. It was demonstrated that silver precipitated in copper matrix contributed on further hardening."

Jan 1, 2000

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997