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By N. Verbaan, Ph. Henry, S. Lamotte

Hydrometal(lurgy) provides an adequate technology to reintroduce otherwise lost metal units into the industrial cycle, thereby saving resources and energy, while keeping the environment cleaner. Three case studies at an integrated hydrometallurgical recycling facility (Hydrométal) in Belgium are discussed. (1) Non-ferrous leach residues are treated by a leach-SX process to recover their minor metals (Ge) contents. The remaining acid waste solution is used by the fertilizer industry nearby. (2) Residual low quality acid and caustic are used in the processing of zinc industry cements to produce copper, nickel, cobalt and zinc concentrates by several consecutive selective leach - precipitation processes. (3) Copper anode slimes are treated and their precious metal contents are recovered. Depending on the composition of the slimes, separate or combined concentrates of copper, bismuth, tellurium/selenium and silver/precious metals can be produced.

Jan 1, 2004

By H. Arima, Y. Kudo

In general, the iron content of zinc leach residue produced by sulphuric acid leaching from calcine is disposed as jarosite or goethite into a tailing dam. More recently, these iron residues have been treated pyrometallurgically to avoid waste disposal. The Iijima refinery selected a different zinc leach residue treatment process for iron control when it was established in 1971. The Iijima refinery is the only plant in the world that has processed a zinc leach residue by the combination of SO2 pressure leaching and O2 pressure hematite precipitation. The process enhances zinc recovery and recovers gold, silver, copper, lead and rare metals in saleable by-products. This paper focuses on the two stages of autoclave application in the zinc leach residue treatment process. The detailed flowsheet and recent advancements to improve the quality of by-products are discussed.

Jan 1, 2004

By A. Siegmund, F. Mucciardi, Z. Yuan, B. Bulnes

With conventional heat pipe science as the starting point, a new heat transfer technology --- termed Thermopump technology, has been developed at McGill University and is now being tested at a number of industrial operations. This technology is of particular importance for transferring energy in high temperature / high heat flux environments where solutions based on current techniques are not available. One important application for this technology is in the metals recycling area wherein this technology has been used to make a waterless, non-consumable, high efficiency Thermopump oxygen lance. The viability and efficiency of this oxygen lance have been demonstrated by preliminary plant trials in a reverb furnace for the recycling of lead-acid batteries at the RSR Corporation. Full-scale commercial trials of the Thermopump (TP) oxygen lance have been carried out at the RSR Corporation. The results from these tests will be presented. In addition, some applications of the Thermopump technology for other metal recycling processes will also be discussed in this paper.

Jan 1, 2004

By Ozdemir. O.

Magnesium additions to aluminum enhance strength and hardness, lowering density, and improving corrosion resistance. However, during melting and casting processes, significant amounts of magnesium are lost due to selective oxidation. Preventing these losses would reduce the production cost and improve the quality of the final product. The effects of strontium addition on the oxidation behaviour of aluminum-0.5% and 1% magnesium alloys were investigated by monitoring sample weight gains with time with a thermogravimetric balance at 750°C. Sample cross sections have been examined using Field Emission Gun Scanning Electron Microscope.

Jan 1, 2004

By Z. F. Zhou, X. Y. Zhou, V. G. Papangelakis, Z. D. Jankovic, S. M. Ulyanov, S. N. Lvov

Recently developed flow-through electrochemical techniques (1,2) were employed for measuring pH in high concentration aqueous solutions and geothermal brines. The pH values of (1) 5.0 mol kg-1 NaCl + x mol kg-1 HCl, (2) 3.0 mol kg-1 of NaCl + 0.5 mol kg -1 of KCl + 1.0 mol kg-1 of CaCl2 + x mol kg-1 HCl (x < 0.1 mol kg-1), and (3) mixtures of Al2(SO4)3-H2SO4-H2O, MgSO4-H2SO4-H2O, and NiSO4-H2SO4-H2O solutions have been measured at temperatures from 100 to 280°C. The obtained experimental data and their thermodynamic analysis demonstrated that the electrochemical system can be used for on-line pH monitoring of high concentration aqueous solutions with an accuracy of ±0.1-0.3 pH units over a wide range of temperatures. Greater deviation exists in real laterite leach solution measurements due to in situ precipitation of Na-alunite. The system is excellent for research and process development work. Further work is needed to ensure robust operation under pressure leach conditions of laterites.

Jan 1, 2004

By J. Robison, H. Pieterse, C. C. Smith, M. Luque, S. Chipman

Phase change during pressure let down releases significant amounts of energy that must be controlled to avoid undo wear and tear on equipment. Hydrometallurgical slurries require flow control equipment (valves and tanks) made of expensive materials to withstand the abrasive, and often corrosive nature of the slurry. Presented is a model of the nozzle of a let-down choke which is designed to control the flow pattern that exits the choke (valve) as it enters the receiving tank. This model can be used to design chokes which allow for the dissipation of the energy released during pressure let down by spreading the stream over a significant portion of the slurry pool in the receiving tank to minimize wear on equipment near the nozzle exit and the bottom of the slurry tank. An example uses the model to choose the nozzle expansion (area) ratio to select the outlet slurry velocity and slurry expansion angle.

Jan 1, 2004

By Masafumi Maeda

Metal recycling and waste treatment have become common issues in various metal industries, notably, the iron and steelmaking industry and the nonferrous industry. The former tends to treat mass wastes such as municipal wastes or plastics. However, volatile compounds are condensed in dusts of their incineration processes and they should also be treated, likely by the nonferrous industry. Those "end-of-life" products contain heavy metals that might be harmful to mankind and should be handled by the non-ferrous industry. Not only revenue derived from regeneration of metals from the secondary materials but also the revenue generated from the treatment charges is a strong attraction for nonferrous industry to process secondary materials. The present study presents some statistical data of the Japanese corporations in the iron and steelmaking industry as well as the nonferrous industry on their revenues generated from processing of secondary materials. Some of the companies are now concentrating their business resources on new areas of the market. Although the quantity of waste or recyclable material is still small at present, the quantity will increase in the near future, and it is anticipated that international collaboration is required to handle the greater variety and the larger quantity of secondary materials.

Jan 1, 2004

By Hämäläinen M., O. Hyvärinen, E. Jääskeläinen

HydroCopperTM is a new hydrometallurgical process for the treatment of copper sulphide concentrates, which has been developed by Outokumpu. The process includes chloride leaching of copper concentrate, solution purification and precipitation of copper(I) oxide, an intermediate product, which is reduced and cast into copper products. The reduction can be carried out by pyrometallurgical methods or hydrometallurgically in an autoclave. This paper discusses the thermodynamic and kinetic aspects of the hydrogen reduction of copper(I) oxide in an autoclave. The results of the laboratory tests are presented and discussed. Finally, the autoclave method is compared with other options.

Jan 1, 2004

By Y. Mitsuda, Y. Kayanuma, T. H. Okabe, M. Miyake

A new process to recover platinum group metals (PGMs) from automotive catalyst scrap using metal vapor was developed. To improve the efficiency of the acid dissolution process of PGMs, metal vapor of reactive elements such as magnesium or calcium were contacted with spent automotive catalyst. It was expected that metal vapor would react with metal selectively and form intermetallic compounds. The specimen of the spent catalyst was treated at 1173 K for 3 h, and it was then dissolved in aqua regia for 1 h to recover PGMs. After the reactive metal treatment, 88% of Pt, 81% of Pd, and 72% of Rh in the catalyst scrap was dissolved, while only 77% of Pt, 69% of Pd, and 38% of Rh was dissolved from untreated scraps.

Jan 1, 2004

This paper describes results of an investigation of fracture during tube expansion of 5052 and 5754 aluminum seam-welded tubes to optimize the forming of aluminum tubes during hydroforming. The tubes were produced in laboratory by press forming of tubular blanks and pilot-scale high frequency induction welding. The effect of property mismatch between the weld and base metal has been investigated. The material work-hardening was obtained by roll forming of sheet blanks in the 0-temper and H32 temper condition. The results showed that a significant work-hardening can be present in aluminum tube without causing weld fracture during tube expansion. The work-hardening increases the yield-strength mismatch between base metal and weld. Annealing reduces the hardness of base metal leading to more uniform deformation during tube expansion. As a result the occurrence of weld fracture is reduced. The study showed significant deformation of the welds during tube expansion. Weld thinning can be as large as parent-material thinning before fracture. To avoid fracture at the weld joint, good formability and high yield strength of the weld is needed. FEM simulation showed that minimizing the width of the weld joint can reduce thinning of the weld.

Jan 1, 2004

By F. Czerwinski

Mechanically fragmented chips of an AZ91D magnesium alloy were transformed into a semisolid slurry within the Thixomolding® system. Microstructural analysis of a material at various processing stages revealed that the cold deformation of the alloy, experienced during chipping, led to the recrystallization and growth of equiaxed grains which were subsequently converted to the globular structures by melting the grain-boundary network.

Jan 1, 2004

By B. T. Lu, J. L. Luo, H. X. Guo

This paper investigated the synergistic effect in the slurry-erosion process of carbon steel. In line with the mechanisms of material loss, the synergism due to interaction of erosion and corrosion was divided into the corrosion enhanced by erosion and erosion enhanced by corrosion. The erosion-corrosion tests were conducted with A1045 steel in slurries containing silica sand. Experimental results showed that the rotating of the sample in corrosive media raised both OCP and corrosion rate, but the impingement of solid particles did not affect the corrosion current significantly. In the quiescent solutions, the Faraday&apos;s law gave a good prediction for the weight loss caused by corrosion but for rotating samples, the weight loss experimentally measured was virtually greater than that predicted by the Faraday&apos;s law, indicating that the corrosion-enhanced erosion could occur in corrosive fluids in absence of solid particles. A half-logarithm relationship was observed between the weight loss due to corrosion-enhanced erosion and the anodic current density.

Jan 1, 2004

By E. Paransky, M. Rigaud, G. Paschek, S. Palco

Some of the negative impacts of carbon addition on the strength of castables are yet to be overcome in order to fulfill its potential benefits for oxidation resistance. This paper reports the results of recent studies conducted at CIREP on the effects of different types of carbon additives on the thermo-mechanical properties of magnesia-based castables. Experimental techniques included measurements of the hot modulus of rupture (HMOR), hot modulus of elasticity (HMOE), as well as the wedge-splitting test (WST). The comparison of evolving microstructures was carried out employing scanning electron microscopy with microanalysis attachment (SEM/EDS) and X-ray diffraction (XRD). HMOR values of 12 MPa at 1300°C have been reached in MgO-Si02-C castables containing up to 7% carbon.

Jan 1, 2004

By Jean-Pierre Birat, François Hanrot, Gérard Danloy

Global warming presents an enormous challenge to the steel industry, which is both carbon-intensive and energy efficient. Lean production can provide some short-term emission mitigation, at the level of the Kyoto requirements. In the middle term, more use of scrap will also help alleviate emissions. But to reach much larger reductions in GHG emissions, on a par with the likely targets that will be set after the Kyoto period, the steel industry will have to imagine new production paradigms, which constitutes its most formidable challenge for the years to come. Carbon capture and sequestration, processes leaner in carbon use, electricity and hydrogen from green sources will have to be added together in a patchwork of process routes, which will have to be developed at great risk in the next decade, hopefully through broad international cooperation.

Jan 1, 2004

By M. S. Millman

Close monitoring of performance at each process stage, from raw material through to finished product, is vital for operational consistency and the production of high quality steel. However, many of the integrated iron and steelmaking process route stages operate under such severe conditions of temperature, dust, water, thermal radiation, vibration, pressure, vacuum, extreme dynamic events, high material flows, corrosion, erosion, electrical-noise, electromagnetic-noise, or audio-noise that, in general, it is a very difficult challenge to obtain useful information for control. Thus, state-of-the-art non-contact and remote sensors are applied to help monitor and control specific process operations. Often, these sensor systems have been developed especially for the steel industry and they are based on four principal technologies: Laser, Microwave, Electro-Magnetics and Thermal Imaging with supporting technologies such as: X-ray Fluorescence, Audiometry, Digital Image Processing, Radio Telemetry, GPS and many others. These advanced sensor technologies are reviewed with respect to their application at various stages along the integrated process route.

Jan 1, 2004

By P. Toscano

The objective of this investigation was to determine how the losses of nickel, copper and cobalt in fayalite slags could be controlled for nickel mattes with iron contents below 5 wt%. Laboratory-converting and slag-cleaning experiments were carried out at 1250°C. Several variables were investigated during and after converting to help minimize the amount of nickel and cobalt that reports to the slag. The variables used were oxygen concentration in the blast, coke breeze addition and nitrogen injection stirring. In all the experiments, slag and matte co-existed. Coke additions during converting have little effect on the losses of nickel, copper and cobalt. In fact, coke additions retard the converting process by consuming some of the oxygen injected. On the other hand, coke additions and nitrogen injection applied after converting was completed resulted in decreased slag losses.

Jan 1, 2004

By P. Au, R. Kearsey, D. Y. Seo, Patnaik. P. C.

Three nickel based superalloys (7.5%Cr+5%Co+2%Mo+1%Ti+5%Al and Ni balance (wt%)) containing different amounts of W and Re were produced in the single crystal (SX) condition utilizing the Bridgman casting process. First, the effect of different levels of Re, and W on chemical microsegregation were investigated by EPMA quantitative analysis, and eutectic phase fraction analysis. Second, in order to investigate the effect of these refractory elements addition on oxidation behaviour, isothermal oxidation testing of the SX nickel based superalloys was conducted at 1000°C for 277 hours under 3 ppm moisture content of air in a thermogravimetric analyzer (TGA). All three SX nickel based superalloys revealed an excellent SX solidification structure with a common primary dendrite arm spacing of -250 µm and a large fraction of ?/?&apos; eutectic located between the secondary dendrite arms. From the average EPMA compositional results, with the exception of Ni, elements such as Cr, Co, Re, Mo, and W all tended to segregate towards the dendrite core during solidification, while Al, Ti, and Ta were present in greater quantity in the last liquid phase to solidify, which resulted in large eutectic ?/? &apos; phases to form within the interdendritic regions. As the nominal level of Re increased, microsegreagation of Re, W, Cr and Mo increased, indicating that Re had a much greater influence on partitioning behavior compared to W. Figure la shows the specific mass gain as a function of exposure time for each alloy. An alloy with 2wt% of W and Re (Alloy B) exhibited less weight gain compared to two other alloys with either higher content of W or Re (Alloy A and C). Microstructural and compositional analyses of oxidized samples were conducted using SEM and EDS. Figure lb shows the typical surface morphologies of the oxidized Alloys A and B. It is evident that more oxide nodules (indicated by arrows in the figure) were presented in Alloy A. It is speculated that the amount of these nodules was responsible for more mass gain in Alloy A compared to the two other alloys. From the examination of the longitudinal section of the oxidized samples as shown in Figure 2, for Alloy A, nodules actually penetrated deep into the material. For Alloy B, however, a relatively uniform and continuous oxide layer was developed and deeply attacked areas were not observed. It was also found that preferential oxidized regions were located at the area between the ?/?&apos; eutectic phase and the dendrite arms where the concentration of refractory elements was relatively high. Therefore, it is plausible that the oxidation kinetics of these alloys is related to the extent of microsegregation.

Jan 1, 2004

To produce high quality castings, one must monitor the melt quality by evaluating such parameters as the grain refinement and silicon inoculation and modification during the production of the commercial casting. Thermal analysis is a tool one can use for both monitoring and providing input to the process control of the operation. The current technique of performing thermal analysis in commercial foundries is to pour a relatively small quantity of the molten aluminum alloy into a sampling cup and to then acquire the cooling curve. This approach is somewhat simplistic in that one has limited control of the cooling rate and hence the solidification rate of the sample. Moreover, this process requires a fair amount of user intervention and effort. In the past, studies have been conducted in an attempt to develop a system for conducting thermal analysis in-situ. In a study at McGill University, an alkali based heat pipe system was developed for conducting thermal analysis in-situ. While the concept was deemed as very desirable, the complexity of the equipment and procedure was a substantial negative component. In order to improve the technique of accomplishing real-time thermal analysis with an in-situ probe, a new method that is based on McGill heat pipe technology was developed. In the new system, a controllable and flexible water based heat pipe probe is used to solidify a small quantity of metal while residing in the melt. The solidified aluminum is remelted after completing the thermal analysis. This is a key feature of the probe. It resides permanently in the melt yet it is able to both solidify a sample of the melt and then to subsequently remelt it. Various solidification rates encountered in commercial castings are attainable by adjusting the heat extraction rate of the unit.

Jan 1, 2004

By J. Aguilar-Santillan, H. Balmori-Ramirez, R. C. Bradt, I. Vernet-Patiño, F. Cunha

Kyanite is an alumino-silicate mineral that has been widely used for the production of refractory products for industrial applications. Kyanite provides a high alumina content, it readily produces mullite during firing, good hot strength of products and can be adapted to produce dimensional stability of products during firing. This research addresses the application of kyanite in mixes to produce (0 dense mullite aggregates with the addition of alumina, (ii) dense composite refractory aggregates of forsterite / spinel with additions of magnesia, and (iii) dense cordierite aggregates with the addition of talc. Effects of attrition milling and conventional ceramic processing are addressed as they affect the properties of these unique aggregates.

Jan 1, 2004

By P. R. G. Brandão, E. E. Ferreira

The presence of metallic cations in solution will affect the aggregation or dispersion of the fine hematite particles, depending on the type of cation adsorption: either specific or non specific adsorption. In this work, the zeta potential measurements were carried out on a sample of pure hematite as a function of pH and metallic cations concentration (Ca2, Mg2+, Mn2+, K+, Na+ and Al3+). The objective of these studies was to clarify the effect of these metallic cations on the surface chemical properties of pure hematite. The cations K+ and Na+ adsorbed as non-specific species and caused only the reduction on the values of zeta potential (in terms of absolute value) over the entire range of pH values tested. For the Al3+ cation, in the acidic pH range it adsorbed as a specific species and increased the zeta potential values. The cations Ca2+, Mg2+ and Mn2+, adsorbed as a non specific species at pH levels less than 6.0 and caused the reduction of zeta potential due to the compression of the electrical double layer. However, for pH values greater than 6.0, these cations adsorbed as a specific species causing the zeta potential to increase and became more positive as the pH value increased (alkaline). This effect could be due to the adsorption of some hidroxy complex species of these cations, which contributed to the positive charge. The effect of metallic cations (Ca2+, Mg2+ and Al3+ concentration, at pH 4.0, 7.0 and 10, showed the following results: a) at pH 4.0, increasing the concentrations of Ca2+ and Mg2+ resulted in on a small reduction in the value of the zeta potential. At this pH, increasing the concentration of A131 cations caused the zeta potential to increase due to specific adsorption of a negatively charged Al3+ hydroxy complex b) at pH 7 and 10, increasing the concentrations of Ca2+ and Mg2+ caused the zeta potential to change its charge from negative to positive.

Jan 1, 2004