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By Emil B. Milosavljevic

Problems associated with distillation and other classical methods for analyzing operationally defined cyanide (CATC, WAD, Total and Free Cyanide) will be discussed. These methods often achieve incomplete, species dependent cyanide recoveries and suffer from serious interferences. Depending on the relative concentrations of interferents and other matrix constituents, underestimation (ultimately Type II errors probability of not detecting a constituent when it is actually present) or overestimation (ultimately Type I errors -probability of deciding a constituent is present when it is actually absent) of the cyanide levels present in a ,given sample may occur, causing in the first case false security and in the second case, excessive cyanide treatment costs. Mahy, if not all, enumerated problems can be solved by using novel flow injection (FI) gas-diffusion amperometric methods. A modification of the recently approved FI ligand exchange (FIILE) method for determination of available cyanide (USEPA Method OIA-'l677) that obviates sulfide interference will be discussed. Eight laboratory round-robin data obtained for the FI UV -digestion (FIIUV) method that determines total cyanide (Proposed Method OIA-1678) will also be presented. In addition, some methods for cyanide speciation will be presented. Finally, research needed for developing reliable methods for determination of operationally defined cyanide in solid samples will be summarized.

Jan 1, 1998

By Lloyd R. Nelson

Selective carbothermic reduction is the preferred method of treatment of electric arc furnace (EAF) dust (listed hazardous waste, K061). The process maximizes the recovery of recyclable constituents by concurrent production of saleable zinc metal (directly condensed from the furnace off-gases), an innocuous, disposable iron oxide-rich slag, and some metallic iron. Results of a mineralogical investigation of a foaming slag produced during selective carbothermic reduction treatment of EAF dusts are presented. Wiistite and tricalcium silicate were identified by reflected light microscopy as the primary crystalline phases contained in a glassy matrix, but this technique failed to reveal any solid phases that could have significantly contributed to foam stability. It was concluded therefore, that the foam had been unstable, and had been primarily generated by copious gas evolution associated with the sudden reduction of the slag by an inadvertent addition of carbonaceous reductant. This is consistent with the susceptibility to foaming, when subjected to sudden excesses of carbon, of the slags produced by selective carbothermic reduction, because they still contain unreduced components such as iron oxide.

Jan 1, 1994

By Ji-He Wei

The ESR of Cu-Cr-Zr alloy has been experimentally investigated. The remelting experiments have been carried out with different slag fluxes in the Cal, + Nal, CaF2 + ZrO2 and CaF2 + NaF + ZrO2 systems on an ESR furnace of 25kg capacity; using a water-cooled copper mould of 96.5 mm diameter, with the forged square bar electrodes of 50x50 mm2. The slag amount was taken to be 1.5 kg. The remelting current and voltage used were 1600-1800A and !5-25K, respectively. The influence of the slag composition on the stability of the remelting process and the losses of alloying elements (2r and Cr) has been considered and examined. The technologies of hot working and heat treatment of the ES ingot have been described and discussed. Some physical properties of the slag in a CuF2 + NaF + ZrO2 system and the remelted Cu-Cr-Zr alloy have been determined. The results indicated that with the slag flux of CaF2 + NaF + l0 mass % ZrO2 and the other operation parameters employed, a high quality ingot of Cu-Cr-Zr alloy may be obtained at the considerably high yields of Zr and Cr by means of ESR. For the remelted Cu-Cr-Zr alloy with a specified composition of 0.5 mass % Cr and 0.1 mass % Zr, the appropriate electrical conductivity, hardness and softening temperature are as high as 45-46S/m, HRB 82-84 and 550°C. respectively. The properties of the Cu-Cr-Zr alloy products are in accordance with and superior to the requirements and specifications of ISO5l82-l99l(E).

Jan 1, 2000

By R. A. Roberti

Most copper refineries use conventional wheel systems to cast anodes. over a period of time the copper moulds that are used become warped and cracks develop. To control mould warpage, the mould's are either rejected after a certain warpage is reached, or the shape is restored by mechanical means. The cracks, unless they are very severe, are repaired by a peening process. Even with regular maintenance to control warpage and cracks, the moulds have a limited useful life. If warpage and cracks are not controlled, anode quality deteriorates and tankhouse operations are seriously affected. -An intensive study was initiated to develop means of controlling mould warpage which culminated in the d?evelopment of technology to control mould warpage to within ±1. 5 mm, and at the same time effectively contr0l: cracking and significantly increase the mould life-. The warpage control has been achieved by using a unique mould design. Mould cavities are present on both sides of the mould and periodic inverting controls the wa-rpage in the cavities. The mould casting procedure has been developed and all production wheels have been converted to the new mould design. The performance characteristics of these moulds will be detailed. 21

Jan 1, 1987

By Zhao-feng Xie

A new process of recycling valuable metals containing in the slag of jamesonite smelting in the blast furnace was studied. In this process, the valuable metals such as Pb, Sb, Zn and In etc. were fumed and volatilized and enriched in the dust firstly and then the dust was leached by sulfuric acid. In the leaching procedure, Zn and In in the dust entered into the leaching solution and were separated from Pb and Sb which remained in the residue.The optimal operation conditions of the fuming procedure are as follows: the mass ratio of the blast furnace slag, coal powder and lime are 100:22:10 respectively and the fuming time are 1.5~2.5 h, the fuming temperature is not below 1200C and the volatilization rates of Pb, Sb, Zn and In are 95%, 92%, 86% and 75% respectively. The optimal conditions for the leaching procedure are also presented: the consumption of sulfuric acid is 1.15 times of the theoretical consumption, the ratio of liquid to solid is 4:1 and the leaching temperature, leaching -1time and stirring speed are 90, 1.5h and 300 r?min separately. The leaching rates of Zn and In are 98.5% and 95.2% respectively. The experimental results shows that the valuable metals in the dust can be recovered and separated effectively by this process and the?ir recovery efficiencies are as follows: Pb94%,Sb91%, Zn84% and In69%.

Jan 1, 2009

By Yan Yuan

Stable Nitroxyl polymers, such as poly (2,2,6,6-tetramenthyl-1-piperidinyloxy-4-yl methacrylate) (PTMA), are known to be effective as cathode active materials for lithium rechargeable betteries.The nitroxide radicals displayed a reversible and very rapid redox performances.We present a new synthesized method to get PTMA powder, then a doctor-blading method was used to prepare the PTMA composite electrodes, enabling successful production of homogeneous electrodes. It was characterized through FT-IR and SEM methods.The organic radical battery consists of lithium metal anode and PTMA cathode with an active material content of 65wt%.The best performance is achieved with a thin cathode that shows nearly 100% utilization of the active material (111mAh/g) at 0.1C.Through the electrochemical tests, it was found that there was a stable plateau at 3.5V while discharging. Besides, the cycling stability and rate capability were measured in detail. Although they showed a certain quantity of irreversible capacity on the first cycle, the capacity stabilized after the second cycle.

Jan 1, 2009

By Paul L. Wichlacz

A mathematical model of growth and ferrous iron oxidation for attached bacteria was applied to rotating biological contactor (RBC) units treating acidic mine drainage. The model describes attached bacterial growth as a saturation function, where the rate of substrate utilization is determined by a maximum substrate oxidation rate constant, a half saturation constant, and the concentration of substrate within the RBC. The maximum oxidation rate constant was proportional to flow rate and the substrate concentration in the reactor varied with influent substrate concentration. The model was tested at three separate sites and with three different size RBC units. The ability of the model to predict the rate of iron oxidation under all test conditions was significant. The accuracy of the model was found to be affected by unit size and vary with specific test site.

Jan 1, 1985

By André L. B. Bittencourt

The copper content in the waste slag represents the greatest loss in the process of Caraíba Metais' Smelter. By identifying the variables responsible for copper stabilization in the slag, a minimization on these losses is expected, producing a granulated waste slag with a copper content lower than 0.7%. Statistics resourses such as control charts, Pareto's diagram and correlations curves were applied for the data obtained in the first semester of 1992. The magnetite and the calcium oxide contents in the slag of the Flash Smelter Furnace were most prominent variables. Some operational changes introduced during and after this investigation have shown good results.

Jan 1, 1994

By Michael A. Lllga

Electrically Switched Ion Exchange (ESIX) is an approach for ion separation that combines Ion exchange (IX) and electrochemistry by utilizing electro active IX films to provide a selective, reversible, and economical separation method that greatly reduces secondary waste generation compared with conventional ion exchange. Studies on the development of films with improved stability and capacity and their use in continuous flow systems for ion separations will be. reported. Both technical and economic evaluations demonstrate ,the viability of once-through or batch recycle waste processing with ESIX.

Jan 1, 1999

By E. J. Peterson

Oil shale retorting induces mineral and chemical reactions to occur on the macroscopic and microscopic levels in the kerogen-bearing marlstone. The nature and extent of the reactions is dependent upon process variables such as maximum temperature, time at temperature, atmosphere, and raw shale composition. This report describes the investigation of the mineral, chemical, and trace element release properties of spent shales retrieved from an experimental in situ retort at Occidental Oil Shale, Inc. 's Logan Wash site in Garfield County, Colorado. Correlation between mineralogy of the spent materials and the mobility of major, minor, and trace elements are indicated, and relationships with important process parameters are discussed. The progress .of carbonate decomposition reactions and silicat ion reactions is indicative of the processing conditions experienced by the shale materials and influences the mobility of major, minor, and trace elements when the solids are contacted by water. Shale minerals that are exposed to the extreme conditions reached in underground retorting form high temperature product phases including akermanite-gehlenite and diopside-augite solid solutions, kalsilite, monticellite, and forsterite. The persistence of relatively thermally stable phases, such as quartz, orthoclase, and albite provide insight into the extremes of processing conditions experienced by the spent shales. Leachate compositions suggest that several trace elements, including vanadium, boron, fluoride, and arsenic are not rendered immobile by the formation of the high-temperature silicate produce phase akermanite-gehlenite.

Jan 1, 1981

By Asmo Vartiainen

Background of Direct-to-Blister Flash Smelting is discussed; especially slag chemistry relating to copper solubility, slag fluidity and impurity behavior. In December, 2000, Mini-pilot Flash Smelting test runs were carried out at Outokumpu Research Oy to produce blister copper from Chilean concentrate and white metal and from a mixture of them. Tested slag types were iron silicate slag, ferrous calcium silicate slag and calcium ferrite slag with different slag compositions and different concentrate/white metal ratios. The test runs were successful. The fluxing effect of copper oxide was clearly demonstrated and ferrous calcium silicate slags remained fluid on a very wide liquidus range. The distribution of arsenic between ferrous calcium silicate slag and blister copper is much higher than between iron silicate slag and blister copper. This successful test run with the new slag type offer new possibilities in Direct- to-Blister process design.

Jan 1, 2003

By H. Cui

Rapid technological development has caused an increase in the demand for rare earths. Ancylite, a strontium rare earth carbonate, is a potentially significant source of rare earths. In this research paper, essential aspects of the magnetic separation and flotation processes for Bear Lodge ore are presented. A flowsheet is proposed based on an optimization of the variables and flotation simulation. The economic feasibility of the proposed processing operation is analyzed.

By William Petruk

"Heap leaching is a developing technology for recovering native gold and electrum from low grade deposits and from tailings. Recovery depends on permeability of the rock and ore minerals, size of particles in the heap, and ore textures that influence exposure of gold grains to cyanide solutions. These ore textures include gold-bearing veinlets and microveinlets along fractures and microfractures, gold grains in porous minerals and rocks, and gold graim. occurring along grain boundaries of other minerals. On the other hand, small encapsulated gold grains arc not likely tote exposed even with fine grinding. Most gold grains that occtir along grain boundaries of other minerals can be exposed with a moderate to fine grind, but the. resulting material will be too fine-grained to be permeable in a heap. Such finely ground ore, as well as tailings from flotation operations, can however be prepared for heap leaching by agglomerating the material into porous briquettes. Oxidized and weathered zones above. orebodies are frequently amenable to heap leaching because the gold-bearing pyrite and arsenopyrite have become permeable by conversion to porous iron oxides and ferric oxyhydroxides. A review of ore textures in several types of gold deposits suggests that:(1) the gold in vein deposits would gtmerally be amenable to heap leaching of both oxidized ores and fresh non-refractory ores,(2) the gold in Carlin-type deposits and in volcanogenic massive sulfide deposits is not likely to be amenable to heap leaching fresh ore, but oxidized zones above the orebodies are generally amenable to cyanidation, and(3) the gold in porphyry copper-gold deposits and in Witwatersrand-type deposits would likely be amenable to heap leaching of both fresh and oxidized ores but with high cyanide consumption."

Jan 1, 1997

By William C. Spindler

Five industrial installations of large lead-acid battery energy storage systems in operation in the United States, West Germany and the 'Republic of South Africa will be described. One example is for a deep mine shaft in which air ventilation and personnel evacuation require the highest reliability for emergency power. The battery system is designed for additional cost-effective benefits of peak load lopping and reactive power control. Commercially available lead-acid batteries of the following types are in use1 traction, truck, submarine, high power, and gel. Electrode grids of both the calcium and antimony alloy types are used. Applications include deep and shallow cycling as well as float and intermittent use. The advantages of sealed lead-acid batteries in UPS (uninterruptible power source) systems are well established throughout the world, and such system suppliers could readily develop markets for industrial emergency and peak power lead-acid storage battery installations.

Jan 1, 1990

By Hylton McWhinney, Doanh Tran, Jewel Andrew Gomes, George Irwin, Sameer Pallavkar, Md Islam, David Cocke, Mohammad Rafiqul Islam

"High-performance nickel-based nanocrystalline zinc oxide adsorbents have been prepared adjusting Ni/Zn mol ratio of 1 :5 by thermal decomposition, coprecipitation and sol-gel method for selective adsorption of thiophene in liquid hydrocarbon fuels at ambient temperature and pressure. To understand the nature of reactive adsorption of thiophene (C4H4S) on Ni/ZnO, the effect of preparation techniques, morphological and textural structure on the desulfurization activity was investigated. A model fuel (20 mL) consisting of pentane (C5H12) and thiophene was prepared and adsorption experiments were performed by a batch method under ambient conditions. The physicochemical behaviors of the fresh adsorbents were obtained using X-ray diffraction (XRD) with EDAX, scanning electron microscopy (SEM). The sulfur concentration in the mixture was monitored by UV-vis spectrophotometry. The adsorption reaction confirmed that ZnO played a crucial role in taking up S element to convert it into ZnS. The deposition of nickel on ZnO is an innovative approach which takes advantage of the selectivity of Ni towards S-species and the high adsorptive capacity of ZnO support.IntroductionLow temperature deep desulfurization of fuels via selective adsorption of sulfur compounds keeping coexisting aromatic hydrocarbons and olefins intact is receiving increasing attention in the research community worldwide in order to satisfy the upcoming environmental regulations and fuel specifications. The sulfur compounds in the transportation fuels is a matter of concern when global crude oil slate is becoming heavier and sourer and environmental restrictions on both the refining process and the refined products are becoming more stringent. According to the current refinery technologies, the sulfur content in refinery fuel is typically around 300-500 ppm by weight (ppmw) [1-3]. Starting in 2006, sulfur limits in highway diesel and gasoline were set to 15 ppm and 30 ppm, respectively. During combustion sulfur in the fuel are converted to toxic sulfur oxide (SOx) and contributes to air pollution and acid rains [ 4]."

Jan 1, 2011

By B. Mishra

The application of various bydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, eg. metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been 'investigated and suggested for dealing with some of these wastes' and scrap material. The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained? from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EMI' and decontamination and decommissioning [D&D].

Jan 1, 1996

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By G. C. Gullo, H. Wabusseg, P. J. Uggowitzer, H. Kaufmann

"The basic concept of New Rheocasting (NRC) is described and the application of wrought alloys with this process is discussed. Practical experiments with the aluminium alloy AIMgSi I are explained. For this alloy the proper NRC - casting temperature was determined by using Thermo Cale - computer software and DT A and the essential processing conditions are shown. In the experiments the melt was taken from an aluminium holding furnace and cast into NRC steel cups. After controlled cooling the resulting slurries were cast into a 4-step die on an UBE HVSC 350 Squeeze Casting machine. The characteristic microstructural values such as grain size and shape factor were measured and compared with classical casting alloys. The influence of the wall thickness of the step part (6 mm, 10 mm and 14 mm) on the microstructure is described. Tensile properties in different heat treatment states are compared with characteristic prope1ties of the same alloys in forged condition. The ew Rheocasting - process CNRC)The NRC process is a recently developed new semi-solid processing method which allows the production of pore-free, pressure tight components.In the NRC process a fu lly liquid, but only slightly superheated melt is taken from a holding furnace and poured into specially designed steel crucibles, which are placed on a carousel next to the Vertical Squeeze Casting machine. In this ,NULL,slurry maker'· globul ar a-Al grains grow, following forced homogeneous nucleation at the cup wall [ 1, 2]. In the few minutes during which the melt is cooled to sem i-so lid processing temperature, a stable ske leton of a-Al phase forms. The resulting slug keeps a cylindrical shape during its slide into the sleeve of the Vertical Squeeze Casting machine, where it is cast into shape."

Jan 1, 2000

By H. Matsuda, T. Iwashita, H. Awata, H. Liwei, D. Hirabayashi, Y. Saito, S. Ozawa, Y. Goto

"The present study is concerned with investigating the effect of chemical treatment on enhancing the HCl absorption capacities of coal burnt ash and slag. It was found that the HCl absorption capacity of coal burnt ash discharged from fluidized bed combustor was improved by hydration with water and 5% polyethylene glycol solution. This phenomenon was based on an increase of the specific surface area of treated coal burnt ash. The HCl absorption capacity of hydrated ash with polyethylene glycol solution was almost equivalent to that of standard CaO and Ca(OH)2. In particular, the specific surface area of hydrated ash with polyethylene glycol solution was found to be 19 m2/g, which was more than over eight times larger than that of raw sample. Hydrated slag treated with lON sodium hydroxide solution also showed high HCl absorption capacity, with highly improved surface area. It was found that the absorption capacity of slag for HCl depended on the treatment time, showing the maximum absorption capacity for 12 hours of hydration treatment.IntroductionA large amount of coal burnt ash, slag and dust are discharged from such industrial processes as coal combustion and metal refinery etc., and it becomes an serious problem to recover and diminish these solid wastes because of the shortage of dump sites and subsequent metal elution to the environment. Figure 1 shows the present situation of reutilization of coal burnt ash and slag in Japan [1,2]. It is shown in this figure that these solid wastes are recycled as materials in the fields of earthwork, agriculture and forestry etc. A part of these solid wastes, however, is still dumped to landfill. To decrease this dumped amount, the development of environmentally friendly reutilization technique for these solid wastes is of great importance."

Jan 1, 2000

By John J. J. Chen, Barry J. Welch

"As in many industrial processes, the detailed mechanisms involved must first be understood before being able to redesign, or to carry out improvements or optimisation of the process and equipment performance. In a great majority of metallurgical processes, visual observation and actual measurement of process variables are either very difficult or near impossible. Often, the cost and effort involved are prohibitive. Consequently, physical modelling is often used to provide some understanding of the process and for the validation of computer numerical models. In this paper, we summarise some of the work carried out at The University of Auckland on the modelling of the Hall-Héroult electrolytic cell, the in-line melt treatment process, and the steel casting tundish. IntroductionIn any industrial process, it is essential to understand the underlying mechanisms before any optimization or process improvement can be carried out. In many metallurgical operations, the processes are conducted at elevated temperature and under rather hostile environments. Consequently, it is often difficult, and sometimes impossible, to observe the actual processes occurring, or conduct measurements which are pertinent. In some situations, it is possible to formulate mathematical equations purported to describe the process, and obtain the solutions numerically. However, in this latter case, the validity of the simplifying assumptions made are often uncertain. Physical modelling may provide the necessary information for the validation of such numerical models. Furthermore, through an application of the principle of similitude, it is possible to apply data obtained from physical modelling to actual metallurgical processes. This paper will summarise some the work carried out at The University of Auckland on the physical modelling of gas-induced flow in the Hall-Héroult electrolytic cell, an in-line melt treatment unit, and the flow in a steel casting tundish.Gas-Induced Flows in a Hall-Héroult CellIn an aluminium cell, the effects due to electro-magnetic forces have been addressed and various design modifications such as magnetic shielding and the positioning of risers have been carried out to control or lninimise the effects of magnetic fields'. Consequently, the effects of gas-induced flows are now becoming significant providing the impetus for the study of the gas behaviour in the bath. Furthermore, the shape and size, and the rate of evacuation of the anodically generated gases affect the cell voltage affecting the energy efficiency; at the same time, the back-reaction between the anode gas and the metal produced is the predominant cause of the loss of current efficiency. Figure 1 shows a cross-section of a conventional cell in which the gas evolution occurs directly under the anodes, and the gas induced flow is confined mainly to the region occupied by the bath"

Jan 1, 1994