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By James R. Craig

The slags generated during gasification of petroleum coke are heterogeneous and con-sist of many different phases. These phases are important because their physical properties affect the operability of gasifiers and because they concentrate many elements that are present in the petroleum coke feed in only minor to trace quantities. An understanding of the chemistry and physical nature of these slag phases is necessary to predict behavior in the gasifier and in considering the ultimate use or disposal of the materials. Slags typically consist of silicate glasses, calcium-silicates, free iron-nickel metallic phases, iron sulfides, and aluminum oxide spinels enriched in iron, chromium, and vanadium. The partitioning of elements among these phases has been analyzed and will be discussed.

Jan 1, 1989

By Batric Pesic

A hydrometallurgical process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge was developed. The process is unique because it treats an unusual combination of metals, Zn and Mn. Another non-standard feature of the process is that leaching takes place with ~S04 in the presence of a reductant (SO2). Zn and Mn are recovered simultaneously by electrowinning, Zn on a cathode and Mn on an anode, as MnO2 The major purpose of the process is to detoxify the sludge by removing toxic heavy metals. The recovered metal values could be marketed to offset the overall costs of water and sludge processing. This work is presented in two separate parts, 1. Leaching and Solution Purification, and II. Electrowinning. This paper covers only the first part of the hydrometallurgical process: Leaching and Solution Purification. Initially, the paper briefly discusses the history of the pollution problem at the Bunker Hill Superfund Site, the origin of heavy metals in the mine waters, and the development and use of the water treatment plant. The leaching of sludge was examined as a function of the following parameters: constant vs. initial pH, initial vs. delayed addition of SO2, temperature, and pulp density. It was found that leaching with H2SO4 at pH 2.0 for 15 minutes (at 60°C), followed by S02 addition for another 15 minutes, could completely dissolve Zn and Mn. Solution purifIcation was done in three stages. In the first stage iron was removed by adjustment of pH (to pH 5.0) and oxidation offerrous to ferric iron (with H2O2). In the second stage, Cu and Cd were removed by Zn dust cementation. Finally, Co and Ni were precipitated with the organic reagents 1-2 nitroso-naphthol and nitroso, respectively. Electrowinning of Zn and Mn is discussed separately in Part II of this paper.

Jan 1, 1996

By A. P. Paiva

With the aim of establishing a valuable alternative to the conventional methods, studies regarding the recovery of precious metals by solvent extraction have been increasing over the past few years. In this work, the selectivity of extraction presented by Cyanex 471X toward silver is investigated. Simulated chloride solutions considering contents of iron and copper usually present in actual leaching practice were used. The characterization of the aqueous solutions - in terms of the multiple equilibria established by the chlorocomplexes of the different metals and their relation to the total chloride concentration of the base-electrolyte - was successfully carried out by cyclic voltammetry. The results obtained support the important contribution of the electrochemical techniques for the understanding of the overall extraction phenomena.

Jan 1, 1994

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

The carbon composite brick is a new refractory used in blast furnace hearth and bottom. It caused wide attention due to its high thermal conductivity and low erosion by molten iron. In this paper, chemical constituents, SEM-EDS and X-ray diffraction were carried out in order to understand reaction mechanisms. A series of experiments of oxidation resistance characteristics were made. The oxidation mechanisms of carbon composite bricks in the presence of air were analyzed. According to the analysis on many experimental results, the oxidation process of carbon composite bricks under different temperatures were controlled by different mechanisms. In the condition of high temperature, SiO2 as oxidation product hindered the diffusion of O2, and reduced the oxidation loss of graphite in the internal.

Jan 1, 2015

By Asmo Vartiainen

The viscosity of liquid Fe-O-SiO2 -slag at copper smelting conditions was investigated using a rotational viscometer. The studied parameters were oxygen partial pressure (10" °-10"6 bar ); composition of slag (Fe/SiO2 ratio), and temperature (1250-1400°C). The viscosity values are presented as a function of Fe/SiO2 ratio and as isoviscosity curves in ternary FeO-Fe2O3-SiO2 diagrams. The increase in viscosity at high silica contents can be accounted for the polymerisation effect of SiO4/4- -anions. At high ferric iron contents, higher oxygen partial pressure, the viscosity values increase especially near the magnetite saturation. The viscosity values are highest at the double saturation of silica and magnetite. At lower silica and ferric iron contents the viscosity values are more uniform in the homogenous liquid slag area. The viscosity values were lowest at high temperatures and highest at low temperatures.

Jan 1, 1998

By K. Pagalthivarthi, P. V. Desai

"During solidification of alloys, many inter-related physical processes, such as melt convection, mass diffusion, heat transport, macrosegregation and melt-undercooling occur. Several research workers have studied one or more of these effects separately. To answer important questions on solidification behavior, an overall approach interrelating the processes is necessaryAs a first step toward accomplishing the overall modeling, the freezing of a binary liquid metal is examined. The various stages during freezing of the alloy are critically described to build a continuum model for the entire process. Diffusive mixture theory is used to write the conservation equations for the liquid and the mushy zones. The concept of local thermodynamic equilibrium in the presence of curvature effects is used to restrict the number of degrees of freedom within the mushy zone. Constitutive equations relating flux quantities and affinities, the governing differential equations and boundary conditions are discussed briefly for the freezing process.IntroductionA solidification study encompasses such facets as solifidication time, microstructure, macrosegregation of the solute, shrinkage effects and soundness of the casting. Influence of one or more of the coupled heat and mass transfer phenomena such as local solute redistribution, thermosolutal convection, melt undercooling at dendrite tips and heat dissipation to the ambient have all been previously examined [1-3J. Several studies have examined the individual facets of alloy solidification as isolated processses. In fact, the transport processes occur simultaneously and a comprehensive model should include their inter-relationships. In particular, some of the existing studies of the mushy zone [4-6J do not emphasize thermodynamic completeness. This work represents an attempt to develop a thermodynamically consistent model of the entire solidification process on physical grounds."

Jan 1, 1986

By A. Pagliero

The coulombimetric reduction method has been used as an evaluation technique for Pb-Ca-Sn anode corrosion in the LIX-SX-EW process. The proposed methodology involves three consecutive steps, i.e., cleaning, oxidation and reduction. They are carried out in the same experimental unit, in solutions containing 180 g/L H2S04 with and without the addition of cobalt. The authors have worked in a wide range of oxidation current densities, from 150 to 500 A/m2 for in a period from 0.5 to 120 hours. It can be concluded from the results that there would be a linear relationship between the applied electrical charge I*T (Coulomb) and the anode corrosion expressed as transformed Pb mass (mg), for solutions with or without the addition of cobalt. The exception is that for the last one the corrosion rate is 5 times faster, which was observed for every layer. From the evaluation of different corrosion layers, one can point out that its composition is mainly in the form of sulphate. In the presence of cobalt, about 67% of Pb would be as sulphate (PbSO4), about 27% as a basic oxide (PbO) and only 6% as oxide PbO2 on the surface. From this result, it appears that great transformations occurred in the metal/sulphate interface. Without the addition of cobalt, the proportion of oxide Pb02 on the surface increased up to 11.5%. According to the previous statement and considering that Pb was found mainly as sulphate, the authors recommend its determination be used as quality selection criterion. Its evaluation should be performed in the acid solutions with 200 ppm cobalt addition at an oxidation current density of 300 A/m2 for a period of 24 hours.

Jan 1, 1999

By John A. Clark, Danylo Oryshchyn, Casey Carney, Stephen Gerdemann, Cathy Summers, Thomas Ochs

"Limited analysis of combustion gas streams where carbon capture is not of interest is done mainly to ascertain operation parameters. Stringent regulations on acid gases and particulates promote careful flue gas analysis. Unregulated components are typically not analyzed. Typically not more than four points (two in the boiler, and one each in the flue and the stack) are sampled. A successful oxy-fuel process with carbon capture and compression is anticipated to require as many as 12 sample points with analysis for water, nitrogen, oxygen, argon, NOx, SOx, and carbon monoxide. Carbon dioxide captured for beverages produces a high value product and the cost associated with analysis is warranted. However, carbon capture for disposal must keep all costs to a minimum. This paper will compare alternative approaches for cost-effective sampling and analysis of the carbon dioxide product streams from oxy-fuel combustion, through all stages of production through compression and pipeline/vessel delivery.IntroductionAnalysis of gases in an oxy-combustion process with carbon capture is essential to the operations of the oxy-fired boiler and the subsequent collection, compression, and purification of carbon dioxide. The process is charged with pure oxygen and not-so-pure carbon in the form of coal at the front end, generating a product of mainly carbon dioxide with traces of argon, nitrogen, sulfur compounds, nitrogen compounds, oxygen, hydrogen, and mercury. It is possible that hydrogen chloride and hydrogen sulfide may also be present in trace amounts [1]. The trace components primarily come from impurities contained in coal such as water, sulfur, nitrogen, and volatile organic compounds. Coal also contains a good deal of mineral matter that is transformed into ash during combustion, becoming particulates that can complicate the analysis regimes utilizing standard analytical equipment."

Jan 1, 2010

By Xiang Sun, Zheng Zhang, Jiann-Yang Hwang, Zhiwei Peng

"Nickel oxide nanoparticles were synthesized using sodium dodecyl sulfate as the surfactant and urea as the hydrolyzing agent and different calcination temperatures and time were selected for preparation. Nitrogen adsorption (BET), X-ray diffraction (XRD) and scanning electron microscope (SEM) were subsequently used to characterize the prepared samples. The effect of an external electric field on hydrogen adsorption over a prepared nickel oxide was carried out. The electric filed was introduced by a piezoelectric element, which is capable of autogenously generating charges under hydrogen pressure. Increased hydrogen adsorption was obtained from this study, which indicated a stronger interaction between the adsorbent surface and hydrogen.IntroductionMetal oxide has attracted great attention for adsorption because of their wide application in catalysis [1-7], gas storage [8,9] and sensors [10,11]. However, with respect to the usage in hydrogen adsorption, few research outcomes have been reported [12,13], since there remains the difficult task of synthesizing highly porous metal oxides with unsaturated metal centers, which account for the strong interaction with hydrogen [14,15]. Nickel oxides are polar materials with an intrinsic dipole moment. The external applied electric field could further enhance the dipole moment so that the hydrogen could be more strongly adsorbed."

Jan 1, 2012

By Mao Chen, Baojun Zhao, Zhixiang Cui, Leonel Contreras

Viscosity is one of the important physiochemical properties of metallurgical slags which is important for slag tapping, metal loss in slag, freeze lining and fluid dynamics. High temperature viscosity measurements are time- and cost-consuming and the number of experiments is limited. Viscosity model is an effective way to predict the viscosities of the complex slags at high temperature. However, a reliable viscosity model can only be developed on the base of accurate experimental data. A unique high-temperature viscosity measurement apparatus developed at The University of Queensland enabled accurate viscosity data to be measured for the “FeO”-SiO2-CaO-MgO-Al2O3 system in equilibrium with Fe. An accurate viscosity model has been developed based on Eyring’s theory and extensive viscosity measurements. The viscosities of copper smelting, converting and cleaning slags over a wide range of compositions and temperatures can be predicted and applied in the process control.

Jan 1, 2016

By William Brinkman, Mark Jolly, Nasim Soleimanian, Karl Dearn, Oliver Brinkman

"Glass manufacturing is a heat intensive process. There is a direct correlation between the batch distribution techniques and the furnace energy consumption, productivity, and quality of the glass manufactured. All four major segments (float, container, fibre, and specialty glasses) would benefit from using an optimised batch distribution technique where possible. Oscillating batch chargers (OBC) have been in use since the early 70s, despite their superior batch shape, coverage, and in turn positive effects on the energy consumption and productivity of the furnace they are almost exclusively used in container glass manufacturing. The OBC’s main difference compared with other charging methods is its ability to directly influence the batch initial velocity. This paper reports on results achieved in CFD models (GFM) used to study effect of the machine on the overall energy consumption in the doghouse and the melt space.IntroductionGlass manufacturing can be divided to four major segments float glass, container glass, fiberglass, and specialty glasses. The financial cost of manufacture, its impact on the environment, lack of standardisation and mounting pressure imposed by the authorities for reduction in emissions means that the industry and its suppliers are utilising CFD modelling in order to tackle these challenges. The need for high temperature to create and maintain the viscous flow, homogenisation of the glass melt, and maintenance of the process to allow continuous output of glass of the right quality are the contributors to the energy intensive activities that are involved in continuous glass manufacturing. This in turn has resulted in design of large container glass furnaces which have high energy consumption, low specific performance, and high CO2 emissions where the most efficient furnaces in the container glass sector have a specific primary energy consumption of 3.8 GJ /tonne of glass at a level of 50% cullet in the batch making even very small improvements in efficiency by operation optimisation a value adding activity [1-14].The theoretical calculated energy required to melt glass is 2 to 3 times less than the energy actually used to melt glass as a result of glass melt passing a zone 5 to 8 times before leaving the tank.[8]. This causes contamination as the result of mixing between the completely molten glass free from bubbles returning to the batch area where there is freshly molten non-homogeneous glass, still containing very large numbers of bubbles and un-molten batch. At high temperature some components are dissolved rather than melted. Given that an un-molten batch is a good thermal insulator, it can be transported a long way into the furnace, increasing the need for homogenization which also increases the glass residence time of glass melt. This is why large unbroken strings of batch should be avoided, as should an overall blanket without gaps."

Jan 1, 2014

By V. Ramachandran

In view of the increasing environmental regulations that have been promulgated in the last 30 years, non-ferrous smelters and refineries have learnt to handle effectively the process waste streams that need to be bled from the system for impurities' control The cations of concern are copper, lead, zinc, cadmium, mercury, thallium, nickel, silver, sodium and potassium. Anionic species of arsenic and selenium also need to be addressed, Sulfates and chlorides-not a major concern at present-have come under scrutiny in the recent past. The current paper reviews several treatment options with reference to a) types of waste streams processed b )process chemistry c)discharge options and recovery of treated water and d) sludge disposal The long term goal of any smelter and/lor refinery should be to achieve zero liquid discharge from the plant. Methods to obtain zero discharge are discussed.

Jan 1, 2003

By Tatsuzo Kitamura

The tank house of Tamano refinery, that started its operation in January, 1972, was constructed incorporating the application of Periodic Reverse Current (P.R.C.) from the outset of design works. In 1973, the production of electrolytic copper came up to 8,000 mtpm, a sharp increase ds compared with the designed capacity of 7,000 mtpm, and successful operation has been achieved up to the present. P.R.C. has been employed for the purpose of raising productivity level and reducing copper inventories. Since there were various problems in P.R.C. application to such a large sized cathode as 1 m x 1 m, special attentions were paid to the following items: -Development of a unique bus bar to make an electrolytic current to each electrode as uniform as possible. -Improvement of circulating method of electrolyte. -Application of high-performance equipment to realize a uniform spacing between anode and cathode. Owing to these creative technical developments mentioned above, technical level for operation up to 350 amp per sq m of cathode current density has been established. The quality of electrolytic copper, which was a matter of interest, has been proved to be as excellent as those of conventional electrolysis products through a long term supply to the field of SCR and Dip forming where high levels in quality are required.

Jan 1, 1976

By David B. George

In spite of the many well-known problems inherent in Pierce-Smith converting, it remains the dominant copper converting process. Continuous copper converting and direct concentrate to blister smelting have been commercially available for over 25 years and now produce approximately 15% of copper smelter production. The two fully commercialized continuous converting processes, Mitsubishi MI Process and Kennecott-Outokumpu Flash Converting, and several emerging converting processes are reviewed with view of their potential, limitations, and environmental performance. Some myths regarding these technologies and Peirce-Smith converting are also challenged.

Jan 1, 2002

By J. P. Constantinea

The use of fluidized beds for the roasting of zinc sulphide concentrates marked a milestone in the electrolytic production of zinc. Stable operation of a fluidized bed for zinc roasting requires a particle size distribution that minimizes the risk of defluidization and helps control carryover to manageable levels. However, the understanding of the roasting process is limited, and changes in operating conditions mainly rely on intuition, experience, and trial and error. A research program has been initiated at UBC to study the phenomena that influence the particle size distribution of fluidized bed zinc roasters. In preparation for the experimental phase, this paper reviews the current literature on the phenomena that affect the particle size distribution during fluidized bed roasting and other fluidized bed processes.

Jan 1, 2002

By K. Verbeken, E. Wettinck, M. Verhaege

Iron (III) can easily and selectively be removed from acidic sulphate solutions with organo-phosphoric acids like Di-2-Ethyl-Hexyl-Phosphoric Acid [D2EHPA]. Stripping of the iron (III) loaded organic, however, is difficult unless highly concentrated inorganic acid solutions are used. In this paper results are shown for the enhanced stripping of iron from loaded D2EHPA by electro-reduction. The loaded solvent is contacted with a 2 M H2SO4 solution, which is continuously recycled in an electrochemical reactor where iron (III) is reduced to iron(II). As iron (II) is not extracted by D2EHPA, the equilibrium for iron (III)- D2EHPA is shifted towards the aqueous iron (Il)-sulphuric acid solution. The electro-reduction unit is a vessel with separated catholyte and anolyte chambers. The catholyte is the actual stripping solution where iron (III) is reduced to iron (II) on a stainless steel electrode. The anolyte is a 2 M H2SO4 solution where oxygen is evolved on a lead alloy electrode. A sintered glass plug separates the compartments. With this unit, enhanced stripping of iron from the solvent is possible under mild acid conditions [2 M H2SO4], and a concentrated ferrous sulphate solution can be obtained. The results shown have mainly been obtained by studying the parameters affecting the electro-reductive stripping of a D2EHPA loaded organic phase in a batch reactor. From an iron (IH)-saturated 20 vol. % D2EHPA solvent containing ~ 12.5 g/1 Fe (III) over 90% of the iron can be stripped in one stage with a 2 M H2SO4 solution at 50°C. It is shown that in this way it should be possible to obtain a concentrated ferrous sulphate solution which can be processed downstream to recover a pure iron product.

Jan 1, 2000

By H. K. Lin

Pyrite oxidation in chloride solutions was investigated with cyclic voltammetry, ac impedance and potential step techniques. The pyrite oxidation in quiescent electrolytes is irreversible and controlled by diffusion. Depression of the semi-circle in the complex plane plot has been explained mathematically based on the concept of the equivalent circuit. When the semi-circle is depressed, the mathematical formula indicates that the reaction resistance should be obtained from the intersection of the semi-circle with Z-axis instead of the semi- circle diameter. The peak charging current densities at 1.10 and 0.90 V vs. SHE obtained from the equivalent circuit coupled with the ac impedance measurements match the peak current densities obtained with the potential step measurements.

Jan 1, 1997

By Yoshihiko Maeda

It is said that the 21 st century will be an era of the remedy of the global environment. In order to reserve natural resources for the future and to avoid the dispersion of heavy metals after usage and to avoid pollution problems, it is extremely important to recycle heavy metals as much as possible by reasonable recovery procedures. The nonferrous metal industry is expected to play a important role in the recycling of heavy metals that are originally their products. From the depressed metal price experienced in Japan in 1980th due to the sudden change in current exchange rate between US dollar and Japanese yen, one of major nonferrous metal company, Dowa Mining, has diversified its business area not only to the so-called down stream, but also to the environmental business including metal recycling, industrial waste treatment and soil remediation by utilizing technologies and facilities once used or still used for mining and smelting of copper, zinc, lead and precious metals. In this paper some of these applications will be presented.

Jan 1, 2003

By A. Rosenfeld

The feasibility of applying laser induced optical emission spectroscopy to the high speed sorting of mixed alloy aluminum scrap is investigated. The basic spectroscopy for analysing aluminum alloys for the major alloying elements over their full concentration ranges is established. Materials handling issues are also described and the components of an overall sorting system are presented.

Jan 1, 1995

By Mao Chen, Baojun Zhao, Zhixiang Cui

Bottom blown oxygen copper smelting process, operated at high grade matte (up to 75 wt% Cu) with relatively low (2-3 wt%) Cu in slag, has been commercialized for more than five years at Dongying Fangyuan Nonferrous Metals CO., Ltd. Quenched slag and matte samples have been collected at different operating conditions while the slag temperature was measured by thermocouple. The samples were analysed by X-ray Fluorescence and Electron Probe X-ray Microanalysis. FactSage computational software was used to explain the observations of the industrial samples. The analyses show that the copper loss was closely related to the operation parameters. The Fe/SiO2 in slag and temperature determine the solid proportion, which significantly affects the physical entrained and also chemically dissolved copper in the slag. The present study will be useful in understanding the slag chemistry of bottom blown copper smelting furnace and in optimization of the operating conditions to lower Cu loss in the slag.

Jan 1, 2015