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By R. Rajiv Srivastava

Brine leaching of a TSL processed zinc-plant residue (ZPR), containing 83.3% anglesite, has been investigated for lead recovery. A prior treatment of ZPR in acid solution did not show any significant effect of acid concentration in zinc dissolution. The study reveals that the solubility limits of PbCl2 is as an important factor with respect to the brine concentration and pulp density in lixiviant. The dissociated sulfate ions hinder the formation of PbCl2 on prolong leaching (above 60 min), while exhibiting the reverse solubility of lead as PbSO4. A 3-step leaching process could yield >92% leaching efficiency when the parameters were maintained as: 10% pulp density in a 250 g/L NaCl solution, 80 °C temperature, and 60 min time. This leaves the insoluble ferrite, sulfides and oxy-sulfates of zinc and lead in the final residue as revealed by the XRD characterization.

By John A. Mavrogenes

The Texaco gasification system developed at the Monte Bello pilot plant efficiently bums petroleum-coke thereby producing syn-gas and electricity. This system produces more electricity than conventional burners, yet the only by-products are pharmaceutical grade sulfur and V -rich slag. Vanadium is known to exist in multiple valence states in compounds which possess a wide range of melting points and physical properties. Consequently, it becomes important to carefully regulate oxygen fugacity throughout the system in order to control vanadium valence state. Vanadium phase equilibria is presently poorly understood, in large part because of the multiple oxidation states of vanadium (-I, 0, +2, +3, +4, and +5) and the difficulty of unequivocally identifying the valence state(s) in many compounds. The operation of these gasifiers at approximately 1400°C is well above the melting point of V20S but considerably below the melting temperature of V02 and V 203. If J02 can be regulated to keep the burner within the V 205 field, slag material would more likely remain molten and more easily flow out of the bottom of the burner. In pure V oxides. the oxidation state is readily determined by microprobe analysis. where V20S (V+5) is 56% V, V02 (V+4) is 61.4% V, and V203 (V+3) is 68% V. However, V valence in multi-element phases (especially phases containing other elements of variable valence) cannot be resolved by microprobe analysis alone. Petroleum-coke gasification slags collected from within the gasifier under different oxidation conditions were studied by electron microprobe analysis (EMPA). X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectrometry in conjunction with microprobe analysis was found to resolve the valence of vanadium in the phases of these slags. Raman spectra collected from homogeneous single phase V-oxide standards in vacuum at low temperatures (-150°C) yielded peaks characteristic to each valence state. Gasifier slag samples are, however, much more complicated. Oxidized samples contain: fine grained (Ca. Mg, Fe. V) oxide matrix of variable composition, (Fe. V, Ni) spinel. (Fe, AI, V, Ni, Mg) spinel, V205laths, AI-Si glass blebs and Ni sulfides. Reduced samples contain: crystalline Ca-siIicate matrix, subhedral to euhedral (V, Fe, Mg, AI) spinel, subhedral V02, Fe and Fe-Ni sulfides, Fe-Ni alloys, and complex Ca-oxide matrix. The different spinel assemblages, the characteristic V-oxides and the distinctly different character of the matrices makes the oxidized and reduced slags readily discernible.

Jan 1, 1995

By Mark Khinkis, Huajun Yuan, Mark Zak, Yaroslav Chudnovsky, Aleksandr Kozlov

"An afterburner for green petroleum coke calcination in electrothermal fluidized bed was designed, fabricated, installed, and tested on a pilot fluidized bed calcination furnace. The experimental set-up comprised a combustion chamber, in which fine particles and volatiles of the furnace off-gas were fully combusted, and a cooler equipped to calculate the related heat recovery and losses. Off-gas composition was analyzed to evaluate the combustion process. The energy balance confirmed the potential to recover a large part of the heat value of volatiles and fme particles from the GPC. Potential future applications of the results are discussed.IntroductionGreen petroleum coke (GPC) is an oil refining byproduct that can be used directly as solid fuel or as feedstock for the production of calcined petroleum coke [1-2]. GPC contains a high amount of volatiles and sulfur. With coke calcination, the GPC is heated to remove the volatiles and sulfur in the calciner off-gas to produce purified calcined coke, which is used in the production of graphite, electrodes, metal carburizers, and other carbon products. Currently, more than 80% of calcined coke is produced in rotary kilns or rotary hearth furnaces. These technologies provide partial heat utilization of the calcined coke to increase efficiency of the calcination process, but they also share some operating disadvantages [3]. On the other hand, coke calcination in an electrothermal fluidized bed opens up a number of potential benefits for the production enhancement while reducing the capital and operating costs.The increased usage of heavy crude oil in recent years has resulted higher sulfur content in green coke produced from oil refinery process, which requires a significant increase in the calcinations temperature and residence time [ 4]. The calorific value of the process off-gas is quite substantial and can be effectively utilized for combined heat and power (CHP) production to complement the energy demand. Waste heat recovered from the product cooling could also contribute to the overall economics of the calcination process. Preliminary estimates indicated the decrease in energy consumption by 35-50% as well as a proportional decrease in greenhouse gas emissions. So, efficiency improvement of the coke calcinations systems is attracting close attention of the researchers and engineers throughout the world."

Jan 1, 2014

By T. Manlyama

The Tamano Smelter of Hibi Kyodo Smelting CO., Ltd. went into operation in 1972. The Flash Smelting Furnace that was originally adapted was equipped with electrodes that were attached to the settler substitute of the slag cleaning furnace. Later the development of our own original coke combustion technology was promoted and a new Tamano Type Flash Smelting Furnace (T-FSF), without electrodes, was put into operation in 1988, T he technology of coke combustion and combustion the burner have continued to improve. As a result the copper losses in the Wag have been reduced as well as a stable operation has been achieved, Furthermore; this has been accomplished while increasing the concentration feed and the matte grade. The current objective is to continue to strive for high matte grade operation and to raise production efficiency while paying attention to the important subject of copper losses in the slag. In this report, the data related to the copper loss in the slag reduction are presented along with the influence of the thickness, settling time and coke. The recent operation conditions of the T-FSF are also presented.

Jan 1, 2003

By S. Ferlay

"The main purpose of the ZIMA VAL project (Label EUREKA EU1367 and LIFE ENV/F/000278) is to demonstrate industrial scale recovery and recycling of the main components of used dry batteries (zinc, manganese dioxide, mercury, and stainless steel) into high added value products. The originality of the ZIMA VAL process resides in:1- the use of hydrometallurgy2- alkaline treatment implementation (highly selective) for zinc and mercury3- electrochemical recovery of high quality products.4- the recycling of all the battery components (zinc, mercury, manganese dioxide, stainless steel) ·5- low operating and investment costs.The process consists of physical classification, mechanical dismantling, hydrometallurgy and electrochemistry. The purpose of the demonstration plant in FALAISE (Calvados - France) is to define the technical and technological parameters of an industrial unit for the treatment of 2400 tonnes per year of used batteries."

Jan 1, 2000

The generation of acid mine water is? due to the oxidation and weathering of sulfide bearing tailings and overburdens. Ferrite precipitation prooess has been applied to treat acid mine water. The conventional ferrite preC1pitatlon requires air oxidation at high temperature, or long aging time or addition of magnetite powder ,as promoter. In this investigation, a modified ferrite, precipitation process is developed by which magnetic ferrite can be produced at an ambient temperature. Acid mine waters from Berkeley Pit (Montana, U. S. A.) and from Noranda Tailings (Quebec, Canada) were used. The co precipitation of heavy metals from these two acid mine waters is studied as a function of FeIM molar ratio, oxidation time and settling rate under applied magnetic field. The investigation indicates that the modified ferrite co precipitation can remove substantially all of the, dissolved metal ions from acid mine water. The ferrite product obtained after precipitation' is characterized by XRD, SEM, BET and saturation magnetization. The results show that spinel ferrite, precipitation can be achieved at room temperature and the saturation magnetization of ferrite product from,acid mine water is comparable to that of pure ferrites.

Jan 1, 1995

By W. G. Davenport

This chapter shows how flash furnace industrial oxygen and oil requirements are affected by different: (a) product temperatures (b) conductive, convective and radiative heat losses (c) electrical energy inputs (d) hydrocarbon fuels. The calculations of the chapter are all for production of 65% Cu matte from pure CuFeS2 concentrate. Blast temperature is? 298 K throughout.

Jan 1, 2001

By Shabnam Sabah, Geoffrey Brooks

In oxygen steelmaking, splashing and droplet formation play a key role in the kinetics of the process. Though splashing has been studied by previous investigators, there is only limited understanding of how different cavity modes affect splashing. Therefore, a cold model study (at various lance heights and gas flow rates) has been carried out focusing on the issue of cavity modes and how it affects splashing phenomenon. Analysis using Fast Fourier Transform (FFT) was carried out on cavity oscillation that showed that frequency and amplitude of oscillation was highest in penetrating mode. Measurements of splashing over a range of conditions showed splashing greatly reduced when cavities went from splashing to penetrating mode. The results were validated and compared with plant data and previous model investigations.

Jan 1, 2014

By Jörn E. Fischer

Cracks were observed at the top of spray formed billets for some alloys. In this paper the effect of process parameters on crack probability is discussed. After the spray run the thermal conditions at the top of the billet change rapidly. A hot spot with melt residue] can occur inside the billet and shrinkage will be suppressed due to the solidified surface of the billet. In this situation hot cracks can be initialized. The temperature history of the billet during and after the spray run is calculated. The temperature difference between core and outside diameter of the billet is taken as indicator for hot crack probability. The effect of different process parameters on the hot crack probability is discussed. The results lead to a better understanding of the process. The calculations are taken as a tool to find process parameters in order to reduce or avoid hot cracks in spray formed billets.

Jan 1, 1999

By C. J. Beyke

Slags and/or mattes from three secondary lead producers were studied as part of an effort to develop treatment methods for these lead-bearing residues. Each company used a somewhat different production process. Company A used a reverberatory furnace followed by a blast furnace. Company B used only a blast furnace. Company C used both a reverberatory and a blast furnace, and the scrap material was desulfurized with sodium carbonate prior to smelting. The slag matrix produced from sulfur-bearing scrap consisted mainly of iron-calcium silicates; the slag from desulfurized material was similar, but also contained sodium. In all the slags most lead was present in metallic form, often alloyed with tin, antimony, arsenic, and/or iron. Slag from Company B contained the most alloying elements, often as discrete subparticles within the lead droplets. Mattes were produced at Companies A and B; predominant phases were pyrrhotite and magnetite, while lead was present in metallic form and as galena.

Jan 1, 1995

By Zuoren Huang

The flowsheet of the hyd.rametallurgical zinc plant which is in use at Zhuzhou Smelters is described. The principal features of the process are fluid bed roasting, continuous calcine leaching, solution purification, zinc electrolysis, electrolyte cooling, and finally, the melting and casting of zinc forms. The Zhuzhou process for the flotation of silver from the leach residue collected on the Moor filters is described. The technical details of the process are outlined and the operating data are analyzed. The flotation facilities are described in detail and concentrate grades and recoveries are presented. The waelz process is used to concentrate In, Ge and Ga remaining in the leach residue after silver flotation. These elements subsequently are recovered by selective leaching in sulphuric acid, and details of this operation also are presented.

Jan 1, 1990

By Soumendra Basu, Uday Pal, Yang Yu, Srikanth Gopalan, Karl Ludwig, Deniz Cetin, Jacob Davis

"A limiting factor for Solid Oxide Fuel Cell (SOFC) performance is the oxygen reduction reaction (ORR) at the cathode surface. Changes in the surface composition and structure on annealing at 800°C has been studied, since these can influence the ORR. Idealized single crystals of cathode materials La0.8Sr0.2MnO3 (LSM) and La1-xSrxCoyFe1-yO3 (LSCF) were grown as heteroepitaxial thin films on lattice matched single crystal substrates. Changes upon heating the films to operating temperature and pressures were characterized using various synchrotron x-ray techniques. Total Reflection X-ray Fluorescence (TXRF) measurements, which probe compositional changes, were made at high temperature in real time. The LSM surfaces were found to develop manganese enrichment when heated. Highly strontium doped LSCF were found to develop strontium-rich surfaces. HArd X-ray PhotoElectron Spectroscopy (HAXPES) was used to investigate the electronic structure of the materials. Highly strontium doped LSCF precipitates a surface strontium phase that contains both oxide and carbonate contributions.IntroductionSolid oxide fuel cells (SOFCs) are chemical to electrical energy conversion devices that could potentially reshape how energy demands are fulfilled. SOFCs have a potential efficiency over 70%, fuel flexibility, low emissions, and low degradation over long time scales. Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating stack as well as coatings to contain the oxidation of the metallic interconnects. Lowering the temperature of an operating device would allow for more conventional materials to be used, thus lowering overall cost. Understanding the reaction kinetics of the oxygen reduction reaction at the surface of the cathode is vital to designing a system that will perform well at lower temperatures. A commercialization goal is to reduce operating temperatures without sacrificing performance.In order to exploit the advantages of SOFCs, an understanding is needed of the surface chemical states of cations on the surface of the cathode and how this relates to the oxygen reduction reaction (ORR):"

Jan 1, 2014

By Qingbo Yu, Qin Qin, Junxiang Liu

"Dry-granulation is a new process of molten blast furnace slag treatment and air is used as heat exchange medium. There are some shortages: poor effectiveness of granulation, high air-slag ratio and high energy consumption, which are the obstacles to popularize dry-granulation. Based on rotary cup atomization, the technique of recovering waste heat of molten blast furnace slag through waste heat boiler producing high pressure steam is exploited. The molten blast furnace slag is granulated to uniform small slag granules with high temperature, and slag granules pour into the waste heat boiler. It could produce steam, obtained in first row and second row tubes, when descending velocity of slag granules equaled 1.1mm/s and the Reynolds number equaled 7100. The application of the system for recovering waste heat from high temperature molten blast furnace slag has a significant meaning.IntroductionBlast furnace slag is one kind of solid waste in iron making process, which is discharged at the temperature range from 1723 to 1923K. In China, there was 0.162 billion tons of slag discharged in 2009, and the energy contained in the slag is equivalent to the energy in 9.4 million tons of coal equivalent. The sensible heat of molten slag is a very valuable waste heat source, so it is worthwhile to recover the sensible heat. At present, the molten slag is treated by a water quenching method. But in this process, the sensible heat is not recovered, moreover, an amount of water is consumed and harmful waste gas is discharged into the environment. Due to the considerations of energy conversation and environmental protection, the iron making industry pays close attention to dry-granulation, which is useful to obtain more benefits [1-4]. The sensible heat is recovered and an amount of water is saved by the method of dry-granulation. The amorphous content of slag granules obtained from dry-granulation is over 95% [5, 6], so the slag granules can be used as a perfect raw material for cement [7, 8].In the late 1970s, the Sumitomo Metal Industries, Ltd. and the Ishikawajima-Harima Heavy Industries, Ltd. jointly undertook the research of rotary drum granulation. This method has several disadvantages: the processing capacity and efficiency are low, and it is not adoptive to operate continuously in production [9]. From 1980, Nippon Steel, NKK, Kawasaki Steel, Kobe Steel, Sumitomo Metal Industries and Nisshin Steel were engaged on air granulation, and the experiments were operated for 6 years on the blast furnace in Nippon Steel. In the process of air granulation, there was great power consumption. The complexity of structure and the great floor space of the air granulation device caused high cost of investment. In 1986, Ukraine exploited a new method of heat recovery referring to the technology of Continuous Casting and Rolling [10]."

Jan 1, 2011

By Petre Stelian Nita

In small steelmaking shops, in foundries and forging plants, there are not too many option to recycle the basic slags, which are not suitable for many purposes of recycling, because of their low chemical and structural stability. A solution of an adequate recycling is a direct recycling in EAF. Several quality requirements, physico-chemical properties and proportions of slags must be analysed. The progress in this fields permites to establish an adequate proportion of recycled slag, based on enough exact computation of the related property. For oxydizing slag, obtained during melting and in the first part of decarburization operation, the problem of phosphoms contents can be analysed using the phosphate capacity (C PO34-). For reducing periods, during deoxidization operation, desulphurization also occurs and the problem of the sulphur contents can be analysed using the sulphur and sulphide capacities ( Cs / Cs) Between this two complex thermodynamic indicators of the slags. a direct relation is established, using thermodynamic aspects, resulting from the equilibrium constants for dephosphorization and desulphurization process and also, using the optical basicity of slags, computable from the chemical analysis of the slags. On this basis starting from the steel quality requirements. adequate strategies can be established in order to obtain high rates of recycling (between 50-80%) of steelmaking slags. Important cost savings are obtained through this procedure, based on the correct amounts of the fresh lime, iron ore and fluidizers. Keywords: Slag, Properties, Recycling

Jan 1, 2003

By J. M. Demarthe

The recovery of minor metals from zinc concentrates is dependent on the process used for their treatment. The behaviour of gennanium and indium in pyrometallurgical processes such as the Imperial Smelting furnace or the cupola furnace is of practical importance. The .Anaconda process for the treatment of zinc leach residues is not well suited to the recovery of valuable minor metals, and new technologies must be studied. In this regard, a solvent extraction process, using Kelex 100, developed by Minenet Recherche for the recovery of gennanium from dilute sulphate leach solutions is described. Also, new hydranetallurgical techniques in chloride media can be applied to the purification and concentration of minor metals depending on the stability of their chloro-complexes and the valency of associated inpurities. A synthesis of methods is proposed to address the problems related to the recovery of valuable minor metals in the zinc industry.

Jan 1, 1990

By Feng Liu, Bingji Yan, Zhiwen Shi, Hongwei Guo, Jianliang Zhang

During production of a large quantity of steel, slag is produced at the same time. This paper chooses blast furnace slag (BFS) as the main material for the research. The purpose of the research is to explore its optimal physicochemical properties and the use of BFS in building stone field. The paper elaborates the experimentation process of producing glass-ceramics and presents the results. The results show that SiO2 content in BFS and amount of Cr2O3 and Fe2O3 added as nucleating agents have certain effect on the properties of glass-ceramics. The results also show that the exothermic peak temperature of base glass is the lowest when adding 20% SiO2 to the BFS, and 2% Cr2O3 and 3% Fe2O3 as nucleating agents, which makes easy crystallization and optimal properties of the glass-ceramics.

Jan 1, 2015

By R. N. O'Brien, E. Peters

"It has been discovered that copper concentrates can be leached in strong (40-60%) sulfuric acid with nitric acid, or with oxygen if nitric acid is present as a catalyst. Chalcopyrite is rapidly decomposed at temperatures well below the boiling temperature of the lixiviant (-150 C.) and the resulting copper and ferric salts are precipitated as CuS04.H20 and FeH(S04)z.4H20. Other metal sulfides such as zinc, lead, nickel, etc. are also converted to sulfates that are nearly insoluble. Sulfur is partially converted to elemental and partially to sulfuric acid. Reduction products of nitric acid can be recovered from the distillate with good recovery. Conversion of as-received copper concentrates is largely complete in about 1 hour. Introduction9 molar sulfuric acid is an unusual hydrometallurgical lixiviant: it has a boiling point of about 150 C. and a low solubility for base metal sulfates. Below about 6 molar acid, the boiling point falls below 120 C. and yields much higher sulfate salt solubility, while above 12 or 13 molar acid and at higher temperature sulfuric acid becomes an oxidizing agent, yielding gaseous S02' Thus, sulfuric acid within this range of concentration is capable of acting well above the temperature of boiling water without requiring autoclave conditions, and if typical oxidative leaching conditions are applied to suspended mineral sulfide concentrates, it is possible to obtain a conversion of these sulfides into 'crystalline sulfates. Thereafter, the sulfates can be separated by filtration or by solid - bowl centrifuge and the solution can be recirculated to the reactor vessel. Meanwhile, the solid sulfates can be treated in a typical hydrometallurgical circuit, i.e., dissolved in a return stream that is essentially water, separated from each other by, for example, solvent extraction, and recovered as metals by electrowinning."

Jan 1, 1997

By Martín Reyes

Iron concentration by ion flotation techniques, from sulfate solutions in presence of zinc was studied in a laboratory flotation column by continuous mode using a synthesized sand shell plate sparger, an anionic collector, promoters, and surfactant propylenglicol 400. Effects of experimental parameters, such as the concentration of reagent: potassium amyl xanthate and dithiophosphate, superficial gas velocity, and superficial liquid velocity were studied in terms of the recovery and enrichment of Fe (III). The results show that the iron elimination from the solution in the presence and absence of zinc (II) are of 59 % and 72 % respectively. The flotation efficiencies decrease with an increase of the concentration of xanthate and air flow rate. The best recovery was achieved, at Jg 0.1 cm/s, Jl 0.72 cm/s and a mixture of xanthate and dithiophosphate as promoter. It was also demonstrated that it is possible to selectively separate and concentrate iron (III) from solutions containing zinc. The behavior of iron ion flotation in a flotation column is reported in this research as a gas hold up, superficial gas velocity, bubble size and superficial bubbles area flux function. The results show that the extraction of aqueous ions of metal iron by ion flotation is strongly affected by: [C], Jg (cm/s), eg (%), Db (mm), Jl (cm/s), y Sb (s-1).

Jan 1, 2009

By H. Kamarudin

The behaviour of cassiterite-sulphosuccinamate flotation system was examined in the light of zeta potentials measured by micro-electrophoresis method. It was observed that sulphosuccinamate substantially affects the zeta potentials of cassiterite, lowering its i.e.p. to pH 2.5 and indicating a specific adsorption and/or chemical interaction. The optimum concentration for flotation, as seen in micro-flotation tests, was found to be associated with the most effective lowering of the zeta potentials, the optimum pH being 3.0. The effect of cations in the pulp was examined for the presence of ferrous, ferric, aluminium and lead ions. The ions ferric and aluminium were observed to create an intense effect of increasing the potentials to positive side, possibly due to adsorption of cation hydroxy complexes, as indicated by their respective species distribution diagrams.

Jan 1, 1994

By Klaus-Markus Peters, James G. Hemrick, John Damiano

"Work was performed by Oak Ridge National Laboratory (ORNL), in collaboration with industrial refractory manufacturers, refractory users, and academic institutions, to employ novel refractory systems and techniques to reduce energy consumption of molten material processing vessels found in industries such as aluminum, glass and pulp and paper. The energy savings strategies discussed are achieved through reduction of chemical reactions, elimination of mechanical degradation caused by the service environment, reduction of temperature limitations of materials, and elimination of costly installation and repair needs. Key results of several case studies resulting from US Department of Energy (DOE) funded research programs are discussed with emphasis on applicability of these results to high temperature processing industries.IntroductionRefractory materials are limited in their application by many factors including chemical reactions between the service environment and the refractory material, mechanical degradation of the refractory material by the service environment, temperature limitations on the use of a particular refractory material, and the inability to install or repair the refractory material in a cost effective manner or while the vessel is in service. All of these limitations reduce the energy efficiency of the process as degraded refractory materials lead to loss of process heat (reduced insulation by refractories) and the need for maintenance through repair or replacement of refractory linings.This situation is conceptualized in Figure 1 which shows that when the thickness of the refractory wall is reduced by chemical or mechanical degradation, the heat losses through the wall increase exponentially. The subsequent maintenance to repair such conditions often requires cooling of the furnace or refractory lined vessel which entails loss of energy due to cooling and consumption of energy due to reheating. Additionally, production time and capability are sacrificed.Additionally, in most applications where refractories are used (metal melting furnaces, glass furnaces, steel making furnaces, gasifiers, etc.) wear of the refractory lining is not uniform. Very often, specific areas will wear (become thinner) more rapidly due to exposure to more corrosive or erosive conditions. This concept is illustrated in Figure 2, through the example of excessive metal line corrosion."

Jan 1, 2009