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By Tianzu Yang, Weifeng Liu, Lin Chen, Wei Chen, DUCHAO ZHANG, HUI XIAO

Carbonaceous refractory materials are widely accepted in many reducing smelting processes such as iron and ferroalloys. Oxidizing processes such as copper concentrate smelting traditionally use magnesia and/or alumina/silica refractory materials. The main objection to the use of carbon-based refractories as the exposed working lining in oxidizing applications is the potential for free oxygen to react with the carbon at high temperature, which could rapidly degrade the refractory lining. In 2013, Outotec and GrafTech conducted joint trials of a thermally conductive, carbonaceous lining for smelting copper concentrates in the Outotec® pilot-scale top-submerged-lance (TSL) furnace in Dandenong, Australia. This testwork had two equally important goals; to demonstrate the ability of carbon refractories to withstand oxidizing process conditions, while ensuring that neither furnace operating conditions nor process stability were negatively affected by the refractory material. The paper discusses the input parameters of the trials, key observations during the testwork program, and the results and conclusions from both process and refractory design standpoints.

Jan 1, 2016

By Hector M. Henao

To provide thermodynamic data for converting nickel matte to liquid nickel at high temperature, an experimental study was conducted on the phase equilibrium between the Ni-S alloy and the FeOX-SiO2, FeOx-CaO, and CaO-A12O3 base slag in a magnesia crucible and the CaO-Al2O3-MgO slag in an alumina crucible. All experiments were carried out at 1773 K under controlled pso2 of 0.1 atm and po2 in a range between 5x10- and 10-5 atm by using CO-CO2-SO2 gas mixtures. The dissolution of nickel in the slag was found to be minimum for the CaO-Al203¬-MgO slag with a molar ratio of NCaO/NA1203=1.7. The solubility of nickel in this slag at p02 of 6x10 atm (just before the precipitation of solid NiO) was 4 mass%. This result suggests that a CaO-A12O3 base slag could be used in converting Ni-S melt to nickel while minimizing nickel losses to the slag.

Jan 1, 2002

By B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By K. S. Raja, M. Misra, S. K. Mohapatra

"Ordered arrays of TiO2 nanotubular photocatalysts were prepared by a simple anodization process. Band gap states of the TiO2 were altered by controlling the anodization electrolyte composition and thermal annealing conditions that resulted in enhanced photo activity. These nanotubes were used for reducing CO2 to methanol either by photochemical or photo electrochemical routes. Pd nano-particle loaded TiO2 nanotubes were employed for photochemical reduction of CO2 to methanol that showed a conversion rate of 12 x 10-3 mol m- 2h-1. Carbon modified TiO2-xCx type nanotubes were used as photo anode and Ti as cathode for photo electrochemical reduction of CO2. The potential of Ti cathode was maintained at -0.5 V SCE. The formation rate of methanol was determined as 13 x 10-3 mol.m-2h-1.1. IntroductionGlobal warming due to emission of carbon dioxide is a serious environmental concern. The atmospheric concentration of CO2 is about 384 ppm by volume and about 3 x 1012 tonnes by weight. Burning of fossil fuels and deforestation are the leading causes for increase in the anthropogenic CO2. More than 32 x 109 tonnes of CO2 are released per year (based on 2006 data) worldwide from the fossil fuel. Pumping CO2 from the fossil fuel power plants into deep ocean basin is one of the most discussed disposal options. The other potential option is converting this green house gas into valuable fuels.Carbon dioxide feed stock can be converted into fuels of solid, liquid or gas phase by chemical, electrolytic, photocatalytic and photo-electrocatalytic methods. Reduction of CO2 to fuel form of any phase requires energy. The reduction process should be energy efficient so that we do not spend more energy and emit more (indirect) CO2 in the process of converting CO2. From this point of view, conversion processes occurring at room temperature look attractive.Electrolytic conversion of CO2 into various forms such as methane1, ethane2, ethylene3, methanol4,5, ethanol6, n-propanol, formic acid7, and formaldehyde has been widely reported. The standard equilibrium potential (at pH: 0) for reduction of CO2 to methanol is 0.14 VSHE and to methane is 0.2 VSHE which is thermodynamically more favorable than hydrogen reduction. However, the gas phase reduction is kinetically complex requiring effective electrocatalyst. The major issues with electrolytic conversion of CO2 to useful products are:"

Jan 1, 2010

By K. J. Richards

The converting of copper mattes to blister copper has seen few technical advances since the introduction of batch furnaces using submerged tuyeres over a hundred years ago. The first side-blown converting vessel, operated by P. Manhes in 1882, was an offshoot of the 'Bessemer steelmaking process, and subsequent improvements in the conversion of molten mattes resulted In the Peirce-Smith converter, still the Industry standard today. While Peirce-Smith' converting has served the industry well since the early 1900!s, increasingly stringent environmental regulations, burgeoning energy costs, and a trend toward continuous processing have set the stage for a major improvement in this area of copper production. In contrast to a growing number of approaches for continuous converting using molten copper mattes, Kennecott is developing a process for treatment of solidified matte which allows improved' control, higher oxygen enrichment and a separation or decoupling of smelting and converting operations not possible with the other converting technologies. The new process known as Solid Matte Oxygen Converting, or SMOC, eliminates the need for molten matte transfers, minimizes fugitive emissions, and produces high strength SO2 off gases which substantially reduce offgas handling requirements. The SMOC process, despite additional matte solidification and size reduction steps, offers both capital and operating cost advantages for new smelters and the upgrading of existing plants, when compared with conventional converting technologies. Capital cost reductions of up to 35% in converting, gas handling, and sulfur fixation are indicated. Kennecott has successfully tested the new process concept and continued' development work is now under way to commercialize the technology. This paper reviews the limitations of batch copper converting with emphasis on the need for a continuous process, previous industry approaches to continuous converting of molten mattes, and the new Kennecott development.

Jan 1, 1983

By W. J. Guay

Scrubbing of simulated copper reverberatory furnace gases containing 1.0 percent sulfur dioxide with the minus 74 ~m fraction of the San Manuel tailings has shown sulfur dioxide removals of almost 100 percent over an effluent pH range of 3.1 to 4.6 and a wide range of liquid to gas ratios with absorptions of 11 to 17 Kg of sulfur dioxide per tonne of minus 74 um slimes. The high reactivity of the tailings slimes with S02 indicates that the reaction rate is not controlled by the slow dissolution of calcium carbonate in sulfurous acid which characterizes scrubbers using ground limestone. The interpretation of these results has been considerably enhanced by wet chemical analysis and emission spectrographic analysis which show that calcium and iron account for about 90 percent of the SO2 absorption with the rest being accounted for by aluminum, magnesium, potassium, and sodium. Mineralogic examination confirms the, chemical and spectrographic analyses showing that the major constituent removed from the slimes is calcium carbonate, with lesser amounts of chlorite and montmorillonite (silicates containing iron, magnesium, aluminum, and calcium) being removed.

Jan 1, 1981

By William R. Opie

Considerable effort by extractive metallurgical research organizations has been devoted recently to developing pollution-free processes for treating copper sulfide concentrates. A number of hydrometallurgical processes are in various stages of development and have been subjected to economic evaluation. Although the hydrometallurgical approaches eliminate SO2 emission problems, they create objectionable effluents and residues, make precious metals recovery complex, and are not very efficient for treating chalcopyrite. Furthermore, they are consumers of considerably more energy than pyrometallurgical processes which produce blister copper that can be electrorefined to commercial grade cathodes. This paper discusses a pyrometallurgical process under development by AMAX Base Metals Research & Development, Inc. (1) The original objectives set for the process development were: 1. Sulfur control of at least 95% with elimination of fugitive emissions. 2. Copper and precious metal recoveries as good as or better than conventional processes. 3. Low capital cost. 4. Competitive operating costs 5. Use of known proven technology where applicable.

Jan 1, 1976

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

By Ann M. Hagni

The mineralogical, chemical, microtextural, and particle size character of electric arc furnace (EAF) dusts are being studied by reflected light microscopy, scanning electron microscope-energy dispersive spectroscopic analysis (SEM-EDS) and electron probe microanalysis (EPMA). The dusts consist predominantly of metallic iron, iron oxide, and calcium-iron-manganese silicate phases, together with smaller amounts of iron-manganese-zinc-calcium, iron-calcium-zinc-manganese, and calcium-iron-manganese silicates. The samples vary in their zinc contents. Chlorine occurs in phases containing iron, lead, zinc, manganese, and calcium. The dust particles range greatly in size from 1 to more than 300 ~m, but most particles are about 1 to 6 ~m. Larger particles. about 20-50 um across. also are present. They are predominantly spherical in shape, but some are cenospheres, and others are more angular particles, some of which are broken spheres and cenospheres. Their internal microtextures exhibit evidence of liquid immiscibility, exsolution, skeletal crystal growth, and oxidation react i on rims. Because EAF dusts have been classified by EPA as hazardous wastes, there is heightened interest in the treatment of these dusts to render them non-hazardous. The mineralogy of products of pyrometallurgical treatment of EAF dusts by flash furnace and pyrohydrolysis are currently under study.

Jan 1, 1991

By I. Perus, M. Fazarinc, G. Kugler, M. Tercelj

"Ledeburitic tool steels are highly alloyed steels used for specific highly loaded applications but are characterized by low and variable hot workability. In this contribution the importance of selecting the right choice of some essential process parameters, i.e. casting temperature, solidification rate and soaking temperature, needed for improving the intrinsic hot deformability of ledeburitic tool steels, is studied. An inappropriate selection of casting temperature and cooling rate results in precipitation of unusual eutectic carbides that decreases the hot workability, whereas with the selection of appropriate soaking temperature the temperature range of safe hot working can be broadened. For each initial as-cast microstructure individually determined soaking temperature should be selected.IntroductionThe surface cracking during hot deformation of ledeburitic tool steels reduces mechanical properties and their industrial yield. These tool steels have high hardness, wear resistance and high tempering resistance on one hand, and high flow stresses and low hot deformability on the other. Decreased hot deformability of the tool steels is attributed to the type, size, shape, distribution, fraction of eutectic carbides and/or other phases, grain growth, etc. at upper limit while precipitation of secondary carbides and decreased recrystallization rate at lower limit of the safe hot deformation temperature range, [1-6].The occurrence of cracks on most exposed areas of workpiece are related to the areas where similar conditions related to upper and/or lower limit of temperature working range prevail, i.e. areas with accelerated cooling, areas with higher value of accumulated strains where also decreased recrystallization rate with simultaneously presence of higher tensile stresses takes place, furthermore areas of workpiece which are due to combustion conditions in furnace heated to higher temperatures, etc. Thus the areas, where combination of previously mentioned conditions prevails, are more exposed to cracking. This additionally requires that hot deformability of ledeburitic tool steel should be considered as a complex problem. Publications in the literature with regards to hot deformability of tool steels are predominately of a partial nature thus all reasons for unexpected occurrence of cracks are not sufficiently explained in available literature so far. Furthermore modern practice proves that previous processing parameters significantly influence the hot deformability and thus this cannot be considered as a constant value. During heating, soaking and hot deformation various processes take place: decay (decomposition) of carbides, formation of new carbides, dissolution of carbides and of alloying elements, etc. Thus depending on variation of process parameters and chemical composition, that consequently influences the processes related to carbides, shifting of decreased deformability at both limits of temperature working range to higher and/or to lower temperatures can occur, [1-14]."

Jan 1, 2012

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a 'reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991

By S. Seetharaman

A mathematical model has been developed to evaluate the viscosities of melts at high temperatures. The viscous flow in liquid is described by the equation, {n = Aexp(AG*/RT)} based on the absolute reaction rate theory. The Gibbs energy of activation,{ AG* } is considered to be a function of the temperature as well as the composition of the melt. The model has been applied successfully to various metallic and slag systems from unary to quaternary. On the basis of this model, a relationship has been suggested to relate the Gibbs activation energy of viscosity to the Gibbs energy of mixing in binary metallic melts. The viscosities predicted from available thermodynamic data in the case of a number of binary metallic systems using this correlation show satisfactory agreement with the reported experimental values.

Jan 1, 1994

By Yuanbo Zhang, Zhaokun Tang, Mingjun Rao, Guanghui Li

The ballability of hematite ore with addition of a certain amount of pulverized anthracite and the induration features of anthracite–containing hematite pellets were studied. The results indicate that adding a certain proportion of anthracite can improve the quality of green pellets as well as the roasting performance of roasted pellets. The suitable mass dosage of anthracite is 1.0%–1.5%. Under the conditions of roasting temperature 1280 oC–1350 oC and roasting time 15 min–20 min, the compressive strength of roasted pellets is found to be more than 2500 N/P. Compared with hematite pellets in the absence of anthracite, the proper induration temperature is diminished by 20 oC, whereas optimal induration temperature range expands by 50 oC, and induration time is shortened by 5 min–10 min. Adding anthracite is an effective measure to improve the pelletization of hematite.

Jan 1, 2015

By Goran Vukovic

The use of gas purging plugs in the copper industry is a widely used practice. They provide substantial improvements especially in anode refining furnaces, where savings in process time and energy are obtained as well as refractory wear and buildups inside the furnace are minimized. The newly developed system, enables purging plugs to be implemented in both stationary and tilting furnaces, is in operation in vessels on three continents. An additional advantage in these furnaces above all other benefits is the significantly improved melting rate. This innovative and patented gas purging system consists of a purging plug cooling device and a slidable, cooled piping system. It provides compensation for any thermal expansion in the furnace lining and minimizes the risk of undesirable copper infiltration. User experiences and results of this widely used system are reported in this paper.

Jan 1, 2014

By Nobuo Kikumoto

Recently, the treatment of industrial waste materials has been a serious social problem here in Japan. Filling them in ponds is now strictly prohibited due to a limited land area and incineration method is also regulated as not to generate DXN. In these conditions, Onahama Smelter has begun to treat shredder dusts (SD) of car at reverberatory furnaces to recover various metals such as copper, gold, silver and palladium without generation of DXN. The total volume of these dusts is expected more than 1 million metric tonnes a year in Japan. Onahama Smelter is now planning to treat about 20% of them in the near future by using tonnage oxygen. In this paper, the heat balance, control method of DXN and treatment of these dusts in reverberatory furnaces are described. DXN : Dioxin (The generic term of PCDD and PCDF)

Jan 1, 2000

By K. L. Money, R. R. Bleakney, R. H. Hanewald

The processing of EAF baghouse dusts, rolling mill scales, and belt grinding swarfs from the specialty steel industry will be reviewed. In addition, the INMETCO process has been modified so as to recover nickel, chromium and iron from many other waste materials such as pickling solutions, filter cakes, spent nickel and chromium plating baths, super alloy wastes, and nickel-cadmium batteries. INMETCO is the only North American company presently capable of recycling nickel-cadmium batteries by high temperature metals recovery.

Jan 1, 2000

By M. I. Kalashnikova

Results of investigations concerning precipitation of heavy non-ferrous metals from solutions using precipitators based on elemental sulphur and lime with gypsum transfer to a separate product are given.

Jan 1, 2003

By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By R. E. Sundell, S. M. Correa

"A mathematical model is developed for the fluid flow in tungsten-inert gas weld pools. The fluid is taken to be incompressible, viscous, electrically conducting, and confined within a pool of specified shape. The flow is driven by surface-tension gradient (thermocapillary), electromagnetic, and buoyancy forces generally in this order of importance. Analysis indicates that the electromagnetic field may be calculated a priori and so decoupled from the nonlinear fluid mechanics and heat-transfer problem. The resulting set of equations is solved numerically by a line relaxation process. Computational errors caused by truncation in finite-difference schemes and by inadequate grid distributions are considered. The model is used to study several cases of differing heat and current input to the pool with and without surfactant-induced thermocapillary forces. The principal conclusions are that the thermocapillary flow, when present, is dominant with surface velocities on the order of 1 m/s. The heat transfer, as deduced from isotherms within the pool, is crucially dependent on the flow. Also, flow velocities and weld-pool surface temperatures were measuredand agree well with the model.2. IntroductionThe requirements of improved control and of automation in the TIG (tungsten-inert gas) welding process have led to the development of mathematical models for the heat transfer to the workpiece. It is now widely recognized that the fluid flow in weld pools sufficiently distorts the conduction heat transfer pattern to warrant inclusion in a process model. The experiments of Woods and Milner (1), among others, demonstrated that TIG weld pools could be driven by the electromagnetic J x B body forces present, J being the current distribution and B the induced magnetic field. Atthey (2) calculated that in typical pools the buoyancy force was about an order of magnitude less important - despite the large temperature gradients present - and neglected it in a computational study of the magnetohydrodynamic (MHD) flow. This work also reviewed many earlier studies of MHD flow caused by a source of current at a fluid surface, including analytical studies by Shercliffe (3), Sozou (4), and Sozou and Pickering (5), and a numerical study by Andrews and Craine (6). These works establish the importance of the electromagnetic force in the weld-pool flow."

Jan 1, 1986