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By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By Pertti Koukkari, Nagendra Tripathi, Karri Penttilä, Justin Salmine

ChemSheet is a thermodynamic multi‐phase multi‐component simulation software, which is used as an Add‐in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off‐line modeling of Cu‐flash smelters and advanced thermochemical simulation coupled with on‐line process control of Cu‐Ni smelting. The presentation will describe an off‐line model of Cu‐smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si –system (slag, matte and liquid metal) by using the quasichemical model. A four‐stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on‐line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid‐bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Jan 1, 2014

By Meyer Steinberg

"Some early experiences of a Cooper Union Chemical Engineer on the Manhattan project and his latest studies on CO2 Greenhouse Gas Mitigation Technologies are presented. Mitigating Global Greenhouse effect while maintaining a fossil fuel economy, requires improving the efficiency of conversion and utilization of fossil fuels, use of high hydrogen content fossil fuels, decarbonization of fossil fuels and sequestration of carbon and CO2 applied to all energy consuming sectors of the economy including electric power generation, materials production, transportation and industrial domestic heating. Decarbonization means removal of carbon as C or CO2 either before or after fossil fuel utilization and sequestration means long term disposal of C or CO2. The review will cover the principles of removal and recovery from power plant, stacks, the oceanographic and geological disposal of CO2 and the conversion of CO2 to gaseous and liquid transportation fuels. The global economic aspects of CO2 mitigation technologies are touched upon.IntroductionThis is an odyssey of a chemical engineer. My career started with the production of U235 at the Gaseous Diffusion Plant in Oak Ridge, Tennessee and the production of PU-239 metal at Los Alamos on the Manhattan Project. After 40 years at Brookhaven National Laboratory, I wound up performing studies on CO2 mitigation technologies. The following is a power point presentation on the subject of global warmingThe DOE is proposing to increase its sequestration development program in order to maintain the utilization of our vast resources in coal both for power and for transportation fuel production. Congress is considering steps to promote energy efficiency in attempts to solve not only the CO2 problem, but also the prime problem of energy supply. We will be promoting increases in energy efficiency as time goes on."

Jan 1, 2008

By H. Y. Sohn, Joshua E. Ramos, Moo Eob Choi

"A new technology for ironmaking based on direct gaseous reduction of iron ore concentrate is under development. This technology would drastically lower CO2 emission and reduce energy consumption by nearly 38% of the blast furnace requirements. Experiments were performed using iron oxide concentrate at 1150oC in a bench-scale facility, which was the highest temperature that could be reached in the facility. The reduction extent was determined at residence times of 3.5 - 5.5 seconds in which the reduction extent approached 43% with 0% excess H2 and 95% with 860% excess H2. Separate kinetics measurements showed that the rate is much faster at 1200 - 1400 oC. Experiments were also carried out using syngas (mixtures of H2 + CO). About 90% reduction in 3.5 seconds with 860% excess hydrogen contained in the syngas demonstrated sufficiently fast reduction for a suspension process and the feasibility of usingsyngas instead of pure hydrogen.IntroductionDespite the improvements in the modern blast furnace (BF) process, it suffers from many drawbacks. The process requires the feed in the form of sinters or pellets and high-grade coking coal. Thus, BF iron production is projected to decrease gradually [1]. The main factors for this are the environmental regulations [2] and the high capital investment cost.A large number of new ironmaking technologies have been developed or are under development [3]. Most of these processes, however, are not sufficiently intensive to replace the blast furnace because they cannot be operated at high temperatures due to the sticking and fusion of particles. Therefore, a new technology is under development for producing iron directly from fine concentrates by a gas-solid suspension technology, which would reduce energy consumption by about 38% of the amount required by the blast furnace and drastically lower environmental pollution, especially CO2 emission, from the steel industry."

Jan 1, 2009

By Kazue Moriya

At the 1980 TMS-AIME world symposium, Dr. Davey mentioned that the traditional lead blast furnace is now being challenged by direct smelting processes. In the copper smelting field both the blast furnace and reverberatory furnace are also disappearing in favour of direct smelting processes such as Outokumpu flash smelting, Mitsubishi continuous smelting, Noranda furnace, Inco furnace and so on. Those new processes all have the following in common: (1) High degree of mechanization (2) Metallurgical reactions carried out in closed vessels (3) Application of oxygen and/or oxygen enriched air (4) Minimization of handling materials and gaseous volume (5) Minimum energy requirements (6) Removal of workers from near the furnace (7) Reduction of emissions of harmful gas to meet environmental regulations. (8) Improvement to the work place environment to avoid occupational hygiene hazards. Direct and continuous smelting of powdered concentrate in one vessel was a romance of the metallurgist since early times. However as mentioned above, in the copper field this objective is being achieved in practice. The industry however can't deny that the serious and severe regulation of environmental pollution in every country was the prime motive for the modernization of smelters. In early days, to meet regulations, it was anticipated that many economic difficulties such as higher capital and energy costs and extravagant use of resources and waste disposal would be the result. "Turn a misfortune into a blessing" is an old saying which reveals the current thinking and reacent developments in the nonferrous industries. In the last ten years in the lead smelting field, about two decades later than copper, commercial scale smelting using new furnance technology has started. The KIVCET process and QSL process, which is flash smelting and bath smelting respectively, are becoming major competitors. They will be sure to upgrade their processes to remain economically and environmentally viable in the comming decade.

Jan 1, 1990

By T. Plikas, L. H. Gunnewiek, L. Oshinowo

"Electric furnace smelting is one of the principal unit operations for ferroalloy production, and increased process intensity, improved availability, minimal maintenance and a longer campaign life are common objectives for electric furnace operation in order to obtain favourable economics of production. Furnace designers have continued to develop innovative solutions, e.g., furnace cooling systems, that have allowed these objectives to be realised and CFD modelling plays a key role in the design process. Enhanced understanding of the energy transfer process in the furnace and the ability to develop, evaluate and optimize components of the crucible design to match process requirements are the key motivators for modelling.This paper provides an overview of recent applications of CFD to the design of electric furnaces. The aim is to illustrate what can be done, and identify areas where further work is needed in this field. Examples include furnace bath simulation, crucible cooling system design, taphole design, baking of Soderberg electrodes, off-gas systems, and fume control and building ventilation. It is argued that the trend is for numerical models to become more encompassing while at the same time more accessible, and therefore further improvements in furnace design will be realised with continued and well validated modelling efforts.IntroductionOne of the main processing steps in ferroalloy production is the smelting of ore in electric furnaces. The three-electrode, AC submerged arc furnace is most prevalent method for smelting in the industry, with shielded-arc and DC plasma arc furnaces achieving limited application (1,2). Commercial furnaces range in size from a few megawatts to more than eighty megawatts of supplied power, and operate with the objective of maximising the return on capital invested. Maximising productivity and energy efficiency are two pathways to achieving this objective, through process intensification, increased availability, minimal maintenance, and increased campaign life for the furnace and associated equipment. Concurrently, the need to reduce the environmental impact of metal production by controlling the emission of particulate emissions, greenhouse gases, and other harmful by-products must also be met."

Jan 1, 2004

By J. K. Brimacombe

Since the Peirce-Smith converter was introduced to the non-ferrous industry in the early part of this century, there has been a paucity of research on process-engineering aspects of the reactor such as gas injection. This paper reviews studies conducted at UBC over the last decade on gas discharge dynamics, high-pressure injection, bath slopping, oxygen/bath reaction kinetics and out-of-stack heat transfer within the converter. The ultimate objectives of this work have been to extend refractory life and to increase converter productivity.

Jan 1, 1985

By Versiane Albis Leão

This work aims at the selection of an appropriate eluant for cyanide recycling using ion exchange resins. Based on a literature review as well as on experimental results, the elution of resins loaded with copper and minor amounts of iron and nickel is discussed. The resins Imac HP 555s, Amberlite IRA 900 (Rohm&Hass) and Purolite A860S (Purolite Co) were eluted using either NaCI, zinc and nickel cyanides, hydrochloric acid, sulfuric acid or acid thiourea solutions. The results indicate that saline solutions are effective only with polyacrylic resins (Purolite A860S), failing to desorb the metals, specially the nickel cyanocomplex, loaded on polystyrene-based resins. Cyanide solutions of both zinc and nickel are capable of eluting over 90% of the loaded metals. In contact with pure acid' solutions, iron precipitates onto the resin beads, as Cu(II) ferrous cyanideCu2Fe(CN)6.xH20. Thiourea is able to elute all the three metal cyanocomplexes owing to the increased solubility of copper cyanocomplexes in the presence of this complexing agent. The results demonstrate that a universal eluant is not available and the selection of the most appropriate resin-elution procedure should be based on the specific features of the system under consideration

Jan 1, 1998

By Salustio s. Guzman

The standard .free energies of formation of tin chlorides were estimated with reviewed and estimated basic thermodynamic data, and measured reversible potentials for the disproportionation of tin dichloride into metallic tin and tin tetrachloride. Values for cºp, Sº, Hº?-Hº 298, -(Gº - Hº298) /T,.Hºf, Gºf, and log Kp are given in tabular form, these estimations are compared with estimations reported in the literature.

Jan 1, 1985

By Alan M. Russell

In recent years, several rare earth intermetallic compounds with the B2-type structure have been reported to exhibit high tensile ductility and high KIC fracture toughness at room temperature. These materials retain considerable ductility even at 77K. These are noteworthy findings because most intermetallics possess poor room temperature ductility and low fracture toughness unless one or more special contrivances are applied (e.g., doping with small additions of interstitial elements, offstoichiometric compositions, testing in ultra-dry atmospheres, etc.). This paper summarizes recent findings on rare earth B2 intermetallics. These include the determination of the active slip systems; the strain rate sensitivities; yield strength maxima at elevated temperatures; the search for possible twinning and stress-induced phase transformations; ab initio calculations of their defect energies and the anisotropy of dislocation line tension. Potential applications of these materials and the possibilities that this study may suggest strategies for increasing ductility in other intermetallic compounds are discussed.

Jan 1, 2008

By M. Friák, L. G. Wang, M. Šob, V. Vitek

"The paper gives an account of applications of quantum-mechanical (first-principles) electronic structure calculations to the problem of theoretical tensile strength in metals and intermetallics. First, we briefly describe the way of simulating the tensile test and the electronic structure calculational method. Our approach is then illustrated on calculations of theoretical tensile strength in W, NiAl and transition metal disilicides MoSi2 and WSi2 with C11b structure. In Wand NiAl, we consider uniaxial tension along [001] and [111] directions. Although tungsten is elastically nearly isotropic (C44 = C”), theoretical tensile strength exhibits a marked anisotropy (oth/001 = 29 GPa, o'th/111 = 40 GPa). Calculated results compare favorably with experimental value of 24.7±3.6 GPa obtained for tungsten whiskers grown along the [110] direction. Similarly, in NiAl, the 'hard' orientation [001] differs very significantly from the [ill] orientation (oth/001 = 46 GPa, oth/111 = 25 GPa). This anisotropy is explained in terms of higher-symmetry structures present or absent on the calculated deformation paths. In disilicides, the theoretical strength is calculated for [001] loading (oth/001 = 37 GPa and 38 GPa for MoSi2 and WSi2 , respectively). The role of relaxation of internal structure parameter is discussed and changes in bonding conditions during the tensile test are analyzed.IntroductionIn most engineering applications, the strength of materials is limited by the presence of internal defects. If there were no defects, then, for example, the tensile strength could be several orders of magnitude higher and its value would be comparable with that of shear modulus. Therefore, the strength of ideal (defect-free) crystal represents an upper limit of attainable stresses, which is called the ideal strength. While it may not be possible to achieve the ideal strength in practice, it is not possible to exceed it. However, the ideal strength is already approached in situations which are technologically relevant. These include the low-temperature deformation of inherently strong materials, such as diamond, Si, Ge and some of the transition-metal carbonitrides, deformation of whiskers, nanoindentation of materials with low defect densities, hardened thin films and coatings etc. The ideal strength sets the limits of elastic stability of a solid. Its knowledge is useful for estimation of the ideal work of fracture stresses needed for homogeneous nucleation of dislocations and for modelling of crack propagation."

Jan 1, 2001

By Shawn A. Cefalu, Matthew J. M. Krane, Kent J. VanEvery

"Segregation during electroslag remelting (ESR) of a nickel-chromium-molybdenum alloy (Ni-8 wt% Cr-25 wt% Mo) has been modeled. Features of the model include species transport and AC electromagnetic effects coupled with fluid flow, heat transfer, and solidification. The effect of varying ingot diameter and melt rate, on macrosegregation patterns, local solidification time, and liquid pool profiles obtained from this model are demonstrated. The results show that the macrosegregation in the ingots correlates to the filling velocity.IntroductionElectroslag remelting (ESR) is a secondary melting process used to refine the chemical composition and the microstructure of metals. Macrosegregation of solute elements causes defects in ESR ingots, including freckles and the maldistribution of phases. These defects are not correctable through heat treatment due to the large length scales over which they occur. However, the frequency and distribution of these defects may be minimized, or even prevented, through process control based on an understanding of the conditions that lead to their formation.In the past, studies have been conducted on the effect of the process parameters on the shape of the melt pool and the thickness of the mushy zone [1-7]. In these studies, the shape of the liquid pool is determined by consideration of the heat and fluid flow induced by electromagnetic (Lorentz) force and thermal buoyancy. The transport of solute and the resultant solutal buoyancy effects were not considered in these macroscopic models. Defect formation is tied to formation of secondary phases (e.g., freckling and white spots in nickel superalloys) [5,8]. In cases where secondary phase formation is calculated (e.g., [6]), phase fractions are determined using a micro-scale model given the local solidification time (LST) and local thermal history from the macroscale model.Using the local thermal history from the macroscopic transport model to predict microstructure increases the importance of the accuracy of those results. This investigation models the macrosegregation of molybdenum during the ESR of a Ni-Cr-Mo alloy. The effect of macrosegregation on pool shape and depth is demonstrated, along with its effect on the local solidification time. By comparing the relative effects of the melt rate and ingot radius, a better understanding of the factors that affect macrosegregation, and ultimately secondary phase formation may be obtained."

Jan 1, 2004

By Messias dos Santos Machado, Renato B. Godoy, Roberta Lima, Andressa Silva, Francisco Valenzuela-Díaz, Rene R. Oliveira, Esperidiana Moura

This work aims to incorporate the Bof White Clay, from Boa Vista, Paraiba State, Brazil, as natural nanofiller in Ehylene vinyl alcohol copolymer (EVOH) and obtain flexible films. Nanocomposite was obtained using a twin-screw extruder, and film formed using a blow extruder machine. The flexible film nanocomposite was characterized, by tensile tests, XRD, DSC and their properties were evaluated. The results showed a good interaction between the clay and the EVOH resulting in an increase of properties of films nanocomposites as compared to films neat polymer.

Jan 1, 2015

By Phillip B. Messersmith, Emmanuel P. Giannelis

"A versatile in-situ polymerization approach is described for the synthesis of polymerceramic nanocomposites consisting of two-dimensional layers of mica-type silicate (MTS) within polymer matrices. Functionalized, organically modified mica-type silicates (OMTS) were used to promote delamination/dispersion of the host layers and initiate polymerization of organic rrionomer. Epoxy nanocomposites prepared in this manner exhibit substantial modulus reinforcement at low silicate loadings. The water vapor permeability of the poly(?-caprolactone) nanocomposite containing 4.8% silicate by volume was reduced by nearly an order of magnitude compared to pure poly (?-caprolactone).IntroductionPolymer matrix nanocomposites are a relatively new class of materials with dimensions typically in the range of 1-100 nm.1 In general, because of the ultrafine phase dimensions involved, nanocomposites exhibit new and improved properties when compared to their micro- or macrocomposite counterparts. We as well as others are currently investigating the design, synthesis and characterization of polymer-ceramic nanocomposites. Our effort, in particular, has focused on the use of mica-type silicates (MTS) with various thermoplastic and thermosetting matrices.2-5MTS's belong to the general family of 2: 1 layered silicates. Their crystal structure consists of layers of two silica tetrahedral sheets fused to an edge-shared octahedral sheet of either aluminum or magnesium hydroxide. Stacking of the layers leads to a regular van der Waals gap or interlayer.6 Isomorphic substitution within the layers generates negative charges that are counterbalanced by cations residing in the interlayers. Although the natural forms of MTS's usually contain hydrated Na+ or K+ ions, ion exchange reactions with organic cations (e.g. alkylammonium ions) can render the normally hydrophilic MTS's organophilic."

Jan 1, 1994

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By Francois Reizine

Infrared sensors will include scanning detectors and positioning sensors. The focus will be on 1, 2, and 4-color wavelength pyrometer systems which allow the accurate measurement of emissivity and, consequently, of the true temperature even in the presence of scale, slag, and fumes. Such sensors are being used in blast furnaces, BOF's, and galvanizing lines. Laser sensors will be presented using different principles of physics, mainly time-of-flight, pulsed infrared lasers for level measurement and dimensional measurement; triangulation lasers for width and thickness measurements; and laser Doppler velocimeters for velocity and length measurements, including mass flow, elongation, and tension control, cut-to-length applications. These sensors and systems are based on state-of-the-art technical developments to improve productivity and quality and reduce maintenance and downtime.

Jan 1, 2001

By Pingchao Ke

A crystalline polyferric sulfate (PFS) adsorbent was synthesized by oxidizing and precipitating ferrous ions under atmospheric conditions. The morphology, structure, composition and specific surface area (SSA) and adsorptive efficacy to As (III) of the adsorbent were characterized by SEM/EDS and TEM images, XRD patterns, FT-IR spectra, BET SSA analyses and adsorption experiments. The adsorbent presents as morphology of near-spherical aggregate and good crystallinity. A small amount of goethite co-precipitated with PFS in the case of the initial ferrous concentration of 1 mol/L and increased the SSA of the aggregates. The absorbent with co-precipitation of goethite showed good adsorption to As(III) and good filtering performance in the high As(III)-content solution of 10–100 mg/L under acidic, neutral and alkaline conditions (pH 2.09–9.01), and its maximal adsorption capacity and adsorption efficiency were 7911 μg/g and 96% separately. After Adsorption, the stability of the absorbents adsorbing As(III) were evaluated by TCLP tests, and the results indicated that the absorbents adsorbing As(III) were extremely stable, and the concentration of arsenic in all leaching solutions were less than 0.01 mg/L.

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 Donald R. Fosnacht

An investigation was initiated to obtain the scope of the problems associated with recycling various waste oxide materials generated at Inland Steel and to identify and? test techniques that could possibly aid in increasing the amount of waste oxide materials recycled to primary. operations. Based on the results of this work, several new techniques were developed ?and tested on ?a plant or laboratory scale. These include the use of cold-bond agglomeration methods for producing waste oxide agglomerates for use as a cooling agent or scrap substitute in steelmaking operations, and the use of various techniques for beneficiating blast furnace flue dust and soaking pit rubble so that the upgraded materials can be utilized in sinter plant or ironmaking operations. The physical and chemical characteristics of the waste oxide materials and the results of the laboratory and plant testing are discussed in this paper.

Jan 1, 1985