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By T. C. -M. Cheng

Iron removal and disposal in zinc plants has imposed a major environmental challenge to the industry. Among the existing options of precipitating iron as jarosite, goethite, and hematite, the Hematite Process seems to be the best candidate for the future development of a waste-free technology, because of its potential of producing saleable iron oxide residues for feed in iron-steel making industry. Unfortunately, under the current practice of the Hematite Process, it is not possible to produce iron residues clean enough to meet the specifications of the said industry. In this paper, the practice of industrial hematite precipitation and the relevant technical literature are reviewed with the objective to identify the critical processing parameters which are responsible for the contamination of hematite, particularly with sulfur and zinc. The analysis is conducted from a crystallization theory standpoint with emphasis given to the role of supersaturation with respect to the cleanliness of hematite precipitates.

Jan 1, 1997

By Ilija Ilic

Recovery of tin from tinplate and production of good-quality detinned-plate for further processing in ironworks has been the subject of interest for many years. Tinplates are mostly used for production of tin containers for food industry and consumer goods. The research carried out so far included determination of the parameters of dissolution of tin from tinplates by alkaline solution of NaOH and electrochemical recovery of tin from the alkaline solutions. During leaching, NaNO3 and methanitrobenzoic acid (MNBA) as oxidants were studied. By leaching the waste tinplate which contains 0.31 % of tin with a solution of 1.12 mol/dm3 NaOH, 0.26 mol/dm3 Na2CO3 and 0.09 mol/dm3 MNBA at temperature of 70°C for 60 mm, a degree of tin leaching of 97 % was attained. MNBA facilitates oxidation of Sn2+ into Sn4+ suitable for obtaining compact, and not spongy, Sn cathode deposit, as it was the ease earlier. Recovery of tin by electrolysis from solutions obtained by leaching was studied to determine the effect of electrolyte composition on the quality of cathode deposit and the degree of electric current efficiency. Experimental results obtained at a laboratory level were checked on an enlarged laboratory set up where continuos leaching of tin from waste tinplate and its electrolytic recovery from the solution obtained were carried out. The experimental set-up -operated under semi-industrial conditions, and about 500 kg of waste tinplate was processed yielding about 1.160 kg of tin (99 % Sn).

Jan 1, 2000

By G. B. Harris

Much has been written over the past decade concerning the disposal of arsenic from metallurgical processes. In Canada, there are proposed regulations which would classify arsenic in the Primary Group of twenty one persistent, toxic pollutants to be banned or phased out. Since many nickel and cobalt ores, not to mention those of copper, gold and uranium, contain significant amounts of arsenic, it is pertinent to assess the current state-of-the-art of its disposal. The literature is reviewed, and it is demonstrated that from a purely chemical point of view, the family of ferric arsenates largely immobilize arsenic. There is clear evidence from laboratory studies that both crystalline ferric arsenate (scorodite) and amorphous ferric arsenates in which the molar Fe/As ratio is at least three (Fe/As = 3) have very low arsenic solubility; plant data are given to support this. The debate over the long term stability of these compounds continues however; the evidence presented for long term stability and for compound breakdown is critically reviewed in the light? of the recent structural studies, and the role of base metals in these compounds evaluated. Finally, conclusions are drawn as to the viability of a purely chemical process for the long term disposal of arsenic from metallurgical processes.

Jan 1, 1993

By E. O. Ávila-Davila, F. R. Barrientos-Hernández, I. A. Lira -Hernández, Miguel Pérez-Labra, M. Reyes-Pérez, J. Antonio Romero-Serrano

Slag from smelting reduction processes were characterized by chemical analysis, XRD, SEM-EDS and XRF. The results revealed Ag concentrations of 362 g/t of slag, the slag mineralogical characterization by XRD and SEM-EDS showed mineralogical species oxidized complex containing Pb, Zn, Ca, Si, Fe, As, S in its structure, silver was found in globules associated lead in the slag and the furutobeite specie. The leaching study was conducted to evaluate process variables such as NaCN concentration: from 7.8x10-3M - 1.26x10-1M, temperature: 25-50°C, particle size: +140 mesh to -400 mesh, stirring speed of 750 rpm - 900 rpm. All studies were performed with a NaOH concentration of 0.2 M. The optimal values of silver recovery encountered in conditions of 7.8x10-3M NaCN, agitation rate of 750 rpm, temperature of 35°C and with a treatment time of 240 min. We also observed that a particle size -400 mesh will have optimum recoveries compared to +140 mesh, +200, +270 and +325.

Jan 1, 2015

By Dong Joon Min, Joo Hyun Park, Mi Sun Choi, Jae Hong Shin

Sublimation of ZrCl4 is important for the production of nuclear grade metallic Zr in Kroll’s process. The sublimation kinetics of ZrCl4 was investigated by TGA under both isothermal and non-isothermal conditions. The sublimation rate of ZrCl4 increased with increasing temperature under isothermal conditions. ZrCl4 sublimation was confirmed to be a zero-order process under isothermal conditions, whereas it was first-order kinetics under non-isothermal conditions. The activation energy of ZrCl4 sublimation under isothermal conditions was 21.7 kJ/mol. The activation energy for non-isothermal sublimation was 101.4 kJ/mol and 108.1 kJ/mol with the Kissinger method and Flynn- Wall-Ozawa method, respectively. These non-isothermal activation energies were very close to the heat of sublimation (103.3 kJ/mol). Sublimation occurs by two elementary steps: surface reaction and desorption. Therefore, the overall activation energy of ZrCl4 sublimation is 104.8(±3.4) kJ/mol. The activation energy of the surface reaction and desorption steps are proposed to be 83.1 kJ/mol and 21.7 kJ/mol, respectively.

Jan 1, 2014

By Emil H. Geus

A process has been developed to recover aluminum from dross which does not require the use of salt flux as commonly employed, This results in a salt-free residue which has potential industrial uses or alternatively can be safely land-filled. The dross is first heated by an air-fuel or oxy-fuel burner in a sealable rotary furnace. At a suitable temperature the burner is turned off and the temperature of the dross thereafter controlled by means of an atmosphere of oxidative and inert gases. When the free metal has agglomerated it is first discharged from the furnace, followed by the residues.

Jan 1, 1995

By Barry Welch, Kai Grjotheim

"The capital intensive nature of the present process for aluminium smelting, the low productivity per unit reactor, and pressure to reduce the electdcal energy demand have motivated the search for an alternative process. Optional routes include carbo-thennal reduction of alumina (using an alloy phase immediate), chlorination followed by electrolysis of aluminium chloride, and electrolytic decomposition of alumina using inert electrodes. Materials performance and reactor design constraints have been a major limitation for alternatives. However parallel research has led to considerable advances in the process efficiencies and scale of both the Bayer process and the Hall-Heroult cells.Future development of alternatives is dependent on breakthroughs in Materials Science such as the development of stable conducting anodes and stable wettable cathode materials. However if successful it is probable that some spin-offs will be retrofitted to existing cells. Therefore the basic Hall-Heroult technology will continue as the dominant process for at least the next half century.IntroductionThe present Bayer/Hall-Heroult process for production of aluminium is just over 100 years old. Frequently, during the century of its technological development questions have been raised as to whether it is the ideal route for metal production. The questioning was particularly intense in the period between the mid-1950s and the mid-1060s when the limitations of the Hall-Heroult electrolytic stage were evident. Then the cells were only 30 to 35 % efficient with respect to the utilisation of the hydro-electricity (requiring 16 18 kWh/kg, thus making it strongly dependent on cheap electrical energy), while the size of cells being installed were 80 to 130 kA. Hence the process was capital intensive, the productivity per reactor volume low, and the process was labour intensive (requiring about 15 man hours per tonne of aluminium). In addition, the use of pitches for Soderberg anodes and the fluoride electrolyte were creating problems through emission. At that time material science had paid little attention to the manufacture and use of carbonaceous materials or the development of alternatives that were corrosion resistant to cryolite or liquid aluminium. Hence cell lives were short - typically 600 to 1000 days - thus adding to operating costs. Thus the grass over the fence, as foreseen in 1960s vintage crystal balls appeared much greener for alternative processes."

Jan 1, 1988

By E. Krystad, G. Tranell

"The kinetics of boron removal from liquid silicon during slag refining, as a process step in the production of solar grade silicon, has been investigated by means of small scale mass transfer experimental series at 1600°C, using a graphite crucible. The slags were SiO2-CaO based, with or without addition of approx. 19 wt% MgO. Experiments were carried out at slag-metal ratios of 1 or 2, where the silicon initially contained approx. 250 ppm boron. The metal-slag mass transfer coefficients for boron were found to be in the order of 1-3 · 10-6 m/s and were largely influenced by slag composition. The mass transfer rate was higher for the MgO-containing slag than the slags without MgO. The final equilibrium distribution of boron between metal and slag, LB, was determined to be in the order of 2.3-3.3.I. INTRODUCTIONRecent years have seen a race in industry and research aimed at obtaining a reliable metallurgical route for production of silicon for solar cells (SoG-Si) from metallurgical grade (MG) silicon. Metallurgical routes can successfully challenge the traditional chemical routes for production of SoG-Si if they generate metal of sufficient purity while being less expensive in terms of production cost and energy consumption. Efficient removal of boron is one of the greatest obstacles in the refining of silicon by a metallurgical route, because the segregation coefficient of boron in silicon makes directional solidification unfeasible; in addition, the vapour pressure of boron is not high enough for removal by vacuum refining. However, the thermodynamic properties of boron makes removal from silicon by oxidation possible, and thus the process of slag refining of silicon has been receiving increasing attention as a method for boron removal."

Jan 1, 2012

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By Cang Daqiang, Li Yu, Liu Xiaoming, Zong Yanbin

"Utilization of high-quality heat in melting slag is a great challenge for iron and steel industry. In the paper, a new method is put forward to concurrently utilize heat and slag by converting the melting slag directly into high valued materials, slag glass-ceramic. A glassceramic with a higher basicity of 0.7 than traditional basicity of 0.45 was prepared from steelmaking slag in order to utilize more hot melting slag. Effects of Alz03 on its crystallization processes were researched by XRF, DTA, XRD and SEM. Results show that Alz03 in glassceramic would have great effected on its property. When the Alz03 content ranges within 12%-15%, glass-ceramics with basicity of0.7 could reach the best performances. The change of dominant phase in glass ceramics from akermanite and wollastonite to akermanite and gehlenite would significantly degrade its mechanical property. An increase of Al2O3 content leads to a rise of the viscosity and crystallization activation energy of the glass, while results in increasing sintering temperature and crystallization temperature of glass, which contributed to its fully crystallization and densification process.IntroductionSteel slag is a by-product under a process of converting iron to steel at above 1600°C, and 0.1-0.15 ton molten steel slag would be discharged for producing per ton of steel in the process. The discharged steel slag at 1600°C has heat of 68 kgce/t. In 2012, China's steel output reached 716 million tons, and produces about 100 million tons of steel slag and 68,000 tee of heat in it [1,2]. But at present, utilization of both slag and its heat at 1600°C is a great challenge for iron and steel industry.Dry granulation of melting steel slag by air and then recovering the heat of the hot air are a traditional technology which have not yet been put into practice for very low heat conductivity of the slag and low efficient of heat exchange among the different processes [3,4]. Therefore, a new method for high efficient utilization of both steel slag and its high temperature sensible heat is put forward [5,6], which is on-line reducing and extracting iron from molten steel slag and then directly preparing glass-ceramic by use of the residual molten slag."

Jan 1, 2014

By Gordon A. Irons

"Powder injection for melt refining is widely practiced in the steel industry, and is gaining acceptance in the non-ferrous industries. In these commercially-important systems, the thermodynamics and kinetics may be very complicated. More than one element may be removed by refining, and often the refining agents are not just one compound. In this paper, the thermodynamic and kinetic aspects of these processes are reviewed. A number of examples are given, such as the desulphurization of iron with a variety of reagent mixtures, and selenium removal from copper with several different reagent combinations.IntroductionI am very pleased and honored to present a paper at this Symposium recognizing the many contributions of Professor Howard Womer. Even at the time I was an undergraduate student, the WORCRA process was part of the curriculum. I remember at the time that I was fascinated by the concept, and due to it and the many other rapid developments in Process Metallurgy, I chose it as my field of study. I think the Symposium is testimony that Professor Womer has touched the lives of many others as well.My original assignment was an overview of the basic aspects of gas and solids injection. However, I reviewed most of this material at the Savard/Lee Symposium [1]. In the present paper, I will present some of the basic issues related to refining with powder injection, using work that we have recently completed in both ferrous and non-ferrous systems."

Jan 1, 1996

By Richard B. Diver, Mark D. Allendorf, Daniel E. Dedrick, James E. Miller, Roy E. Hogan, Andrea Ambrosini, Eric N. Coker, Anthony H. McDaniel, Nathan P. Siegel, Gary L. Kellogg

"Converting carbon dioxide and water to hydrocarbons is an attractive option for storing solar energy and, coupled with appropriate CO2 capture technology, for recycling carbon and impacting atmospheric CO2 concentrations. For any process, high solar-to-fuel efficiency is necessary for large scale viability and favorable economics. Thermochemical approaches for solar-to-fuel conversion are potentially highly efficient as they avoid the inherent limitations of photosynthesis and also sidestep the solar-to-electric conversion necessary to drive electrolytic reactions. Solar-driven two-step metal-oxide-based thermochemical cycles for producing the components of syngas, CO and H2, from CO2 and H2O are the basis of the “Sunshine to Petrol” project. Multi-cycle production of both H2 and CO has been demonstrated over several iron- and cerium-based compositions fabricated into monolithic pieces both in the laboratory and at the National Solar Thermal Test Facility. These compositions are being developed for deployment in a unique and continuous solar-driven reactor prototype, the counter-rotating-ring receiver reactor recuperator or CR5.IntroductionThe interconnected challenges posed by increasing global competition for petroleum and the increasing concentration of atmospheric carbon dioxide are now widely recognized. Meeting these challenges requires recognition that although hydrocarbon fuels are ideal energy carriers, they can no longer be thought of as primary energy sources. It is necessary to take the realistic view that our conventional fossil fuels are in fact “stored sunlight” in the form of “sequestered carbon.” This view leads to a search for options to use and store sunlight more directly.Sunshine to PetrolIn combusting hydrocarbons we unlock the energy for utilization, but we also release the carbon to the atmosphere. However, nature teaches us that with an appropriate persistent energy source, e.g. solar irradiation, it is possible to effectively reverse the combustion process and “reenergize” CO2 and H2O back into hydrocarbon form."

Jan 1, 2010

By Eoghan T. M Doyle

Oxide mixtures of nickel (NiO), cobalt (COO) and chromium (Cr203) were prepared with graphite in stoichiometric amounts and the powder mixtures were compacted to produce cylindrical pellets. The composition of chromium oxide in these mixtures were varied. Pressed pellets were reduced in a flowing stream of argon-4% hydrogen gas (500 ml/min). Both slow and rapid heating methods were adopted to raise the temperature of a pellet during reduction of oxides to form superalloy powder. The reduction temperature was varied between. 1523 and 1623K. The effect of heating rate and niobium oxide addition on the microstructure of the superalloy produced was studied by using ordinary light and scanning electron microscopes. New phases formed as a result of reduction were identified by X-ray powder diffraction technique. The mechanism of reduction of oxides together with the microstructure of NiCrCo alloy are discussed. The thermodynamics of formation of ternary alloy phase is elucidated on the basis of binary phase equilibria and Gibbs free energy of mixing data for the constituent alloy compositions.

Jan 1, 1992

By Zhucheng Huang, Ronghai ZHONG, Tao Jiang, Jun ZOU

The method of reduction roasting and magnetic separation of low-grade, micro- fine disseminated refractory iron ore following granulation with coal produced unexpected success. Pellets of iron ore with diameter between 3 and 8mm were granulated with coal, bentonite and water. The raw pellets and reduction products were analyzed by scanning electron microscopy and x-ray diffraction. Results show uniformly distributed coal powders inside the pellets improved the kinetics of the reduction process and accelerated the reduction rate. Reduction time was higher at temperatures below 890℃, which resulted in the formation of substantial amounts of fayalite. When temperature was increased, micro- fine hematite was then quickly reduced to iron metal and the amount of fayalite decreased sharply. When pellets were reduced at 950℃ for 25min, reduction products with 56.73% metallization rate were obtained. After grinding and magnetic separation, a concentrate with 72.18% Fetot was obtained.

Jan 1, 2015

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By Batric Pesic

Solvent extraction of nickel and cobalt from the real leach solutions was studied by using a novel extraction system. The extraction system was a mixture of 2,6-bis-[5-n-nonylpyrazol-3¬y]] pyridine (BNPP) and dinonylnaphthalene sulfonic acid (DNSSA). The BNPP represents a novel molecule, which was designed and synthesized in our laboratory. Real solutions for the study were prepared by leaching of two different cobalt-nickel bearing concentrates, cobaltite [CoAsS] concentrate from Blackbird Mine, Idaho, and siegenite [(Ni,Co)3S4] concentrate from Missouri Lead-Belt. The major strength of the system was the selectivity of extraction toward nickel and cobalt from iron containing solutions. Other metals such as Mn, Mg, Ca, Al and As were not extracted. Due to the irreversibility of copper extraction, its removal from solution was required prior to the extraction of nickel and cobalt. Zinc was not as strongly extracted (i.e. its stripping was readily achieved) as was copper . Flowsheets for the recovery of nickel and cobalt were also developed.

Jan 1, 1997

By Amy Anderson

The Silica (SME) Technology has been utilized on three separate projects focusing upon the stabilization of mercury-contaminated materials: at the Mother Lode Mine in Oregon, the Sulfur Bank Mercury Mine in California and at a former chloralkali plant in British Columbia. Each of the projects relied primarily on the results collected via EPA Method 1311 TCLP, with additional tests such as SPLP, humidity cell tests and other supporting tests employed as well. Both technical and economic performance of the silica-based technology was evaluated as well as that of competing technologies in some cases. Results established that in each of the three projects an SME chemical dosage rate of 3% chemical by weight of soil/sludge was the optimal ratio required to achieve project treatment objectives, TCLP test results exhibited a reduction in the leachable mercury from the treated materials ranging between 75% and 99% as compared to untreated material, satisfying the technical objectives for each project, Project costs ranged from $l5.00 - $18.26 per metric ton.

Jan 1, 2003

By Gregory A. Knapp

Treatment of industrial wastewaters generally advances with specific chemical concentration and mass-flow targets, established by National Pollutant Discharge Elimination System (NPDES) permits. Treated discharges must also address toxicity to test and receiving water organisms. Various parameters might need consideration during treatment design and planning, such as the known toxicants, hardness, alkalinity, solids, nutrients, metals in both the dissolved and particulate state, and even flow. Since toxicity is used as a "catch all" regulatory monitoring tool, design of treatment systems should focus on the various factors contributing to toxicity.

Jan 1, 1996

By A. F. Kaczmarek

Cerro Negro is an undeveloped ore body located at the Cerro Verde mine near Arequipa, Peru. The mineable reserve contains 70 Mt of oxide ore grading 0.532% copper. Mineralization is hosted in three distinct rock types: tourmaline breccia, crackle breccia and granodiorite. Rock type effects copper recovery and acid consumption. The paper describes Cyprus' testwork philosophy and the resulting four-phase metallurgical program used to define the commercial leaching parameters. Copper recovery and acid consumption were monitored as functions of crush size, heap height, irrigation rate and acidulation conditions. Single lift, on-off and permanent multi-lift heaps were considered. Leach cycle times were based on incremental copper extraction and acid consumption rates, with added constraints imposed by operational requirements. The optimum leach system involves an on-off pad using tertiary crushed ore acidulated with 20 kg/t acid and stacked to a height of 6.5 m. The active leach cycle is 82 days at an irrigation rate of 0.26 l/min/m2. Under these conditions copper recovery is expected to average 81% over the life of the mine.

Jan 1, 1999