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By Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By S. Seetharaman

In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements, In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid, as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences oldie electronic contribution to the conduction of the electrolyte. The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper, The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments' in the field of sensor technology, as applied to metals processing are highlighted.

Jan 1, 1996

By Jerome P. Downey

In the thermal treatment of electric arc furnace (EAF) dusts, zinc is reduced, volatilized, and ultimately recovered either as liquid metal in a splash condenser or as solid zinc oxide in bag filters. During the process, the duet's chlorine and fluorine content also enters the gas phase and condenses as dross in the splash condenser or as salts which contaminate the zinc oxide product. Pretreatment of EAF dust by pyrohydrolysis appeared to offer a means of minimizing the duet's halogen content. The primary research objectives were to experimentally verify the technical viability of pyrohydrolysis and delineate the process parameters requisite for efficient halogen removal. To this end, representative EAF duet samples were secured and characterized by x-ray diffraction, scanning electron microscopy, and Mössbauer analyses. Specific- experimentation focused on the response of halogen extraction to variations in temperature, retention time, water vapor partial pressure, and various additives. The experimental results proved that 97 to 99 percent chlorine extraction and 80 to 85 percent fluorine extraction are consistently achieved when EAF dusts are blended with silica and roasted at temperatures of 850°C or greater in a furnace atmosphere of 75% steam (diluted by air). A statistical analysis further established that more than- a single optimal point exists, thus affording flexibility in parameter selection (e.g., by increasing temperature, the necessary retention time and additive concentrations are decreased). The findings substantiate the feasibility of pyrohydrolysis roasting in reducing the chlorine and fluorine in the EAF dust to a level that will obviate industrial concerns about halogen contamination. The end-product of the pyrohydrolysis procedure is a de-halogenated, self-fluxing calcine which can be directly charged to a plasma or flame reactor. The paper includes design parameters and flow diagrams illustrating the pyrohydrolysis process integrated with the plasma and flame reactor technologies.

Jan 1, 1992

By Sasa Djokic

In developed countries, the difference between demanded and produced quantities of non-ferrous and rare metals are compensated by secondary raw materials recycling and reprocessing of by-products from both ferrous and non-ferrous extractive metallurgy. Utilization of non-ferrous and rare metals from the metallic secondary raw materials is very significant, both for recovery of the metal value and contribution to the environment protection. Similar to all non-developed countries, the extractive metallurgy in Serbia was based on available natural resources and not so strict environment protection regulations, which was either insufficient or completely absent. Today, Serbia is at the beginning of development of efficient and economical technical and technological solutions in order to ?ecologize? technogenic systems by waste materials, secondary raw materials and degraded soils regeneration (by recycling and revitalization). Several metallurgical technogenic systems in Serbia, together with secondary raw materials classification according to their potentiality for metal extraction by using the existing technologies and expected economical and ecological effects of recycling, are discussed in this paper.

Jan 1, 2005

By Tengfei Qi, Liqiang Fan, Huiqing Tang

A new method to process the oolitic high phosphorus iron ore for phosphorus removal has been proposed in this research. It is an integration of direct reduction and melting separation with carbon-containing pellets prepared using biomass char. Experiments of direct reduction were preceded using a tubular furnace and three parameters were investigated and they were reduction temperature, biomass char adding ratio(molar ratio of carbon to oxygen） and atmosphere. Results show that the optimum condition is of reduction temperature is 1373 K, biomass adding ratio 0.9, PCO2/PCO 1.0 and reduction time 15~25 min. Under this condition, the reduced briquettes with a metallization of 75.0~80.0 % and a residual carbon content of 0.69~0.11 wt% could be obtained. Subsequent melting separation experiments were conducted using a Si-Mo high temperature furnace. Results show metal with phosphorus content of about 0.4 mass% could be obtained from the reduced sample.

Jan 1, 2015

By S. N. Sinha

The distribution coefficients of lead and silver between copper and matte phases have been measured at two different temperatures. Experiments covered the ranges of 0.009-1.8, 0.07-0.13, and 0-11 wt pct lead, silver, and iron in matte, respectively. The distribution coefficients of lead have been measured at 1405 and 1505 K and correlated with lead and iron concentrations in metallic copper and matte. The values of the distribution coef¬ficient of lead between copper and iron-free matte, at infinite dilution of lead, have been determined to be 3.60 and 4,06 at 1505 and 1405 K, respectively. The distribution coefficient of silver between copper and iron-free matte is independent of silver concentrations and has been measured to be 2.13 and 2.21 at 1400 and 1500 K, respectively. For an iron-bearing matte, the distribution coefficient of silver has been correlated with iron concentration in the matte at both 1400 and 1500 K. From the measured values of distribution coefficients, the Raoultian activity coefficients of PbS and AgS0.5 in copper-saturated matte have been calculated. At infinite dilution, the following equations correlating the Raoultian activity coeffici¬ents of PbS and AgS0.5 with matte- composition and temperature have been obtained: log Y° PbS =1.515 + 1080/T 0.14 NFes lbS Fog YAgS = -0.074 - 425/T + 0.09 NFes. - 0.5

Jan 1, 1983

By Gabriella Tranell

In the manganese ferroalloys industry, there is increasing focus on the performance of different carbonaceous materials within the smelting processes. With a developing scarcity of traditional raw materials, new carbon sources are being identified for potential use in the processes. For this purpose, it is important to be able to predict the suitability of different materials in the process. Hence, the effects of both the physical and chemical properties of the carbon material on the reduction kinetics of manganese and silicon from slag to metal, have been investigated using an advanced sessile drop technique. Using this technique, the reaction patterns of SiO2-MnO containing slag droplets in contact with various solid carbon materials (graphites with different properties as well as cokes and charcoals) at 1400 to 1600\\176;C were studied in-situ. In addition, slag and metal reaction products from kinetic experimental series were analysed. From these results, differences in reactivity between various carbon materials and slags were demonstrated and explained. Mechanisms for both manganese and silicon reduction were proposed.

Jan 1, 2006

By Larry M. Southwick

Considerable process and equipment development and analysis were conducted during design of Freeport Sulfur's laterite nickel facilities in the late 1950's. These covered ore concentration at Moa Bay, Cuba, and concentrate refining at Port Nickel, Louisiana. Both facilities utilized acid pressure leaching and product refining steps that were similar to those later used elsewhere in the laterite processing industry. Unfortunately, developments in Cuba removed the Moa Bay facilities from Freeport control. This deprived the project of a start-up that would have allowed thorough resolution of difficulties and a quicker attainment of production capacity. This meant lost opportunity to positively prove and complete the technology when optimum resources and staff were available. This paper reviews the original rationale of how design was developed via laboratory, bench scale and pilot studies by Freeport Sulfur. Some later operating problems will also be discussed. This case is unusual, but the lessons learned may be instructive in the application of difficult and complicated technologies, as well as the need to understand and retain access to the original development and design activities Keywords: Moa Bay, Freeport Sulfur, Port Nickel, acid pressure leaching, pilot plant, pachuca, Chemical Construction, pressure letdown, cobalt, titanium

Jan 1, 2004

By Edgar Peek

"The two dominant metallurgical problems in treating most base metal sulphide concentrates in both the chloride and sulphate system are iron removal and sulphur elimination, respectively [1-3]. In this paper the opportunities, limitations and fundamentals of the chloride metallurgy system are described against this background. Only the treatment of oxide and sulphide ores is considered. Both hydrometallurgical and pyrometallurgical unit process operations are highlighted, since most successful base metal processes are based on a combination of the two. Hence, an overview of the technical and also some economical aspects of chloride metallurgy are presented.This overview summarizes the successful applications of chloride metallurgy, but it will not give exhaustive process and plant descriptions. It predominantly focuses on the essential technical features of the metallurgical unit process operations, while providing numerous references separately."

Jan 1, 2011

By F. T. Principe

In order for solvent extraction technology to be acceptable as an alternative to existing jarosite precipitation circuits, iron must be cleanly separated and concentrated into a feed stream suitable for downstream iron by-product recovery which meets market specifications and economics. Ten years ago, significant progress was made in a joint McCill University/CANMET project that involved iron extraction with mono(2-ethylhexyl) phosphoric acid and stripping with HCI. Our iron solvent extraction research was reactivated recently by looking into this and other members of the organophosphorus extractant family. Our research focuses on the mechanisms and control of anion (SO42/CI) transport across the various phases (Rafinate/Organic/Strip), iron build-up in the strip liquor, and extractant stability/selectivity. In this paper, these issues along with some other performance parameters are discussed using data derived from an extensive search of the two commercially available and best known members of the organophosphorus family, di-2-ethylhexyl (D2EHPA) and mono-2-ethylhexyl (M2EHPA) phosphoric acid. Further in this discussion, the challenges lying ahead in the development of sx systems that overcome the deficiencies of D2EHPA and M2EHPA are outlined. In particular, the necessity of considering secondary separation technologies that can further concentrate iron values in the chloride strip liquor to levels economically attractive for the production of saleable iron oxide by pyrohydrolysis is addressed.

Jan 1, 1998

By Derek J. Fray

"In order to extend the application of fused salts in\the electrowinning and electrorefining of metals, it is necessary to maximise the current density, minimise the voltage drop and greatly increase the area of electrode surface so as to compete with the space-time yield of pyrometallurgical reactions. The various designs of electrowinning cell are reviewed and it is shown that by the application of a modest centrifugal field it is possible to reduce the anode to cathode interelectrode spacing to 4 mm whilst still maintaining a current efficiency of 85-90%.The thermodynamic potential for electrorefining is far less than for electrowinning yet fused salt electrorefining is only applied in limited cases. The reasons for this are discussed and the important design parameters evaluated. It is concluded that by using packed bed electrodes, separated by a diaphragm, the possibility of electrorefining with very low energy consumption can be achieved. Carbothermically-produced metals are always cheaper than those produced by electrolysis but suffer from the disadvantage of low purity. It is proposed that fused salt electrorefining may offer an energy efficient way of upgrading the metal. IntroductionThe majority of metals can be deposited from fused salts (1,2) but as commercial production is restricted to the more reactive elements, it is worthwhile considering the advantages and disadvantages of fused salt electrolysis as' compared to smelting and aqueous electrolysis. The advantages over aqueous extraction are as follows:1) the much higher conductivities and diffusivities result in much lower IR losses and higher current densities can be achieved at modest voltages;2) the elevated temperatures of operation result in larger exchange currents which give rapid kinetics and lower activation polarisation for the electrode reactions;3) the absence of water as a solvent means that it is not necessary to consider the evolution of hydrogen as a competing cathodic reaction. Furthermore, alkali halide salts, often used as solvents in fused salt electrolytes, have high deposition potentials;4) molten salts generally are mutually soluble and, therefore, concentration polarisation effects are minimised."

Jan 1, 1988

By D. D. Rodier

Most zinc concentrates contain some silver and varying amounts of such valuable trace elements as gold, indium, germanium and gallium. With increasing similarities in plant installations, the predominance of electrolyte process and the increasing environmental constraints on iron disposal, it is essential that zinc smelters optimize the recovery of any valuable elements in their feed stocks. The process options, to date, of smelting, flotation or leaching of silver-rich leach residues cannot be applied economically to all installations. It is therefore necessary that new innovative processes, to recover silver and other valuable metals from relatively low grade feeds, be developed. This paper attempts to place this strategy in the context of today's constraints and will also provide a simple evaluation tool for any process alternatives.

Jan 1, 1990

By Run Huang, Xuewei Lv, Songli Liu, Chenguang Bai

"Titanium alloy was prepared from titania-bearing blast furnace slag (Ti-BF slag) by aluminothermic process in an induction furnace. The effects of aluminum amount on the titanium silicon yield and titanium recovery ratio were studied. The phase transformation and chemical composition of the prepared alloy were investigated by X-ray diffractometry (XRD) and X-ray fluorescence (XRF) respectively. It was found that the mass fraction of silicon and aluminum increased with increasing the aluminum amount, however, the mass fraction of titanium increased first and then decreased with increasing the aluminum amount. Furthermore, both the titanium alloy yield and titanium recovery ratio increased with the increase of aluminum amount. The main phases of the alloy were TixSiy and AlTi3. The titanium alloy samples prepared in various conditions had a composition (wt.%): 38–50% Ti, 29-34% Si, 4-11 Al%, 1.6-2.2 Mn%.IntroductionPanzhihua and Xichang regions in the southwest of China are rich in vanadium-titanium magnetite containing iron, vanadium, titanium and gangue. According to the characteristics of the resource, iron and vanadium are successfully recovered with a blast furnace process and a converter process. However, most content of titanium are entered in the blast furnace slag with TiO2 22% -26% and metallic Fe 2%–6% called Ti-BF slag. Due to the dispersed distribution of Ti in various fine grained mineral phases with a complex combination between Ca, Al and Si, it is difficult to recover the Ti components[1]. This slag is generated at a current rate of 3.6 million tons per year, which adds to the existing 70 million tons of slag produced so far[2]. The slag has had to be piled as large as the mountains, which not only waste of resources but also cause a pollution of the environment. Therefore, the study of integrated utilizing Ti-BF slag has become very significant."

Jan 1, 2012

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

Equilibrium calculational software programs can be effectively utilized to illustrate the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation to students studying hydrometallurgy. The calculational program STABCAL will be demonstrated. illustrative examples for the creation of diagrams such as EH-pH, activity or concentration-pH and activity or concentration-EH will be presented to demonstrate the fundamentals of real hydrometallurgical systems. Speciation, titration and mixing will be used to simulate or predict operational processes. Applications will include treatment of Acid Mine Drainage (Berkeley Pitlake water and sediments), mass balance potential/pH diagrams, leaching and selective separation of metals from electroplating sludge, metal adsorption at femhydrite surfaces, and flowsheet development for treating mercury sulfide K106 sludge.

Jan 1, 2002

By Joerg Hammerschmidt, Marcus Runkel, Andreas Wirtz, Kent Pope

"Fluidized bed reactor systems in the minerals industry have been progressively developed and widely implemented over a period of more than sixty years for a multitude of process applications. Their versatility is manifested in calcining, roasting and combustion treatment of minerals including solid fuels. Experiences from metallurgical processes have expanded to new applications in the oil shale processing, biomass combustion and renewable energy sector. This paper focuses on the most important aspects of fluidized bed technology for a variety of Outotec processes. Energy recovery is a major topic for all applications and will be addressed, as well as environmental aspects, particularly regarding the off-gas treatment. Outotec is one of the pioneers of roasting and the fluidized bed process including gas cleaning and sulphuric acid production where applicable. Process development is strongly supported by significant investment in R&D, thus enabling process adaptation and scale-up to meet specific customer/market requirements.Introduction to Fluidized Bed TechnologyThe early days of fluidized bed technology were characterized by the use of bubbling fluidized bed reactors (BFB). This technology was popular for roasting zinc and copper ores. The introduction of circulating fluidized bed technology led to increased plant capacities and improved process control for the traditional processes. Furthermore, the technology has been applied in many other industries, including the renewable energy industry, which will be part of this design and process comparison. The paper starts out with the fundamentals on particle fluidization as the main common design parameter, leading to the importance of heat recovery and offgas treatment.In fluidized reactor systems, the particle concentrations can reach several hundred kilograms per cubic meter of fluidization gas. This high solid concentration leads to large surface areas and enables direct contact of gas molecules with particle surface molecules. Excellent conditions for enhanced heat and mass transfer thus provide nearly ""ideal"" heat exchange conditions and better reaction kinetics. The bubbling bed exhibits a better heat transfer coefficient within the bed in comparison to the circulating fluidized bed (CFB). The different conditions of gas velocities and solid concentrations allowing the classification of fluidization reaction regimes are shown in the Reh diagram in Figure 1."

Jan 1, 2014

By Akira Yazawa

In the field of pyrometallurgy, the equilibrium evaluation has recently become easy by use of thermodynamic software, but it is strongly desired to estimate the amounts of non-equilibrium minor components to simulate practical processes. However, simple physico-chemical technique can not be applied to evaluate practical non-equilibrium components for many reasons. As an engineering solution for postulated equilibrium system, the activity coefficient is modified and introduced as the simulation parameter referred to as the "adjustment coefficient." This modified thermodynamic calculations were adopted to various sulfide roasting processes where many solid phases are participating and the system is not necessarily in equilibrium. Successful simulation was realized by assigning suitable adjustment coefficients for minor components which form a pseudo solid solution in the calcine. Some examples from sulfation roasting and dearsenizing roasting were discussed. In the smelting system, the loss of copper in slag is caused by equilibrium and non- equilibrium reasons, that is, chemical dissolution and entrainment of copper in slag. The total copper content of slag was simulated by use of the adjustment coefficient for entrained copper.

Jan 1, 1998

By D. J. Murdock

Cominco Ltd. has developed a number of innovative technologies for electrowinning. The paper discusses the application of these technologies to the copper industry. Tankhouse and cell design will be discussed in addition to anode cleaning and cathode handling. Specific examples of the application of this technology to the copper industry are cited.

Jan 1, 1987

By Run-sheng xu, Hai-yang WANG, Di ZHAO, Teng-fei SONG, Jian-Liang Zhang

This paper was mainly focused on the different semi-cokes and charcoal which could be new fuels for blast furnace injection. Through the comparative study with bituminous coal and anthracite coal, the properties of semi-cokes and charcoal were presented in this research. 10 indexes of different fuels were obtained by different standard experiment, including proximate analysis, ultimate analysis, igniting point, explosivity, transportation characteristic, ash properties, grindability, calorific value, combustibility and reactivity with CO2. According to the data analysis, it provided a theoretical basis for rational utilization of various blast furnace fuels, and helped to broaden the scope of the blast furnace injection fuels. This research could contribute to energy conservation, emissions reduction, and sustainable development of iron and steel enterprises.

Jan 1, 2015

By Zhihong Liu

Monodisperse micron size nickel oxalate particles with rhombohedron morphology were prepared from condensed Ni(OH)2 suspension by a novel gel-sol process proposed by one of the authors. Firstly, condensed nickel hydroxide gel was formed by fast adding 1 mol dm-3 NaOH solution into 0.2 mol dm-3 nickel chloride solution, and then oxalic acid solution with a concentration of 0.25 mol dm-3 was dropped into the gel drop wise through a pump equiped with a pH controller under preset pH value, and in this process, Ni(OH)2 gel was converted gradually into monodisperse nickel oxalate sol. The formation of the nickel oxalate particles was found to proceed through a dissolution-recrystallization mechanism from the nickel hydroxide gel. The product particles exhibited rhombohedron like shape with micron size long axis and sub-micron size short axis. The effects of such factors, as temperature, surfactants, et al, were evaluated experimentally on the particles sizes and morphologies.

Jan 1, 2006