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By Mary Cunningham

The EPA and DOE have collaborated on a series of studies to evaluate the effectiveness of treatment technologies at stabilizing bulk elemental mercury and wastes containing high concentrations (i.e., with greater than 260 mglkg total mercury) and multiple forms of mercury. The data from these treatment demonstrations are intended to help EPA to determine if regulatory revisions to allow a stabilization alternative for high-mercury subcategory wastes are warranted. In addition to mercury-contaminated wastes, the disposal of bulk elemental mercury is of concern because of the excess quantity of mercury in the Defense Logistics Agency (DLA) stockpile, as well as other potential sources of excess elemental mercury. The studies evaluated the effectiveness of several technologies at: I) stabilization of mercury in a "hard-to-treat" matrix; and 2) conversion of elemental mercury into a stable waste form for disposal. A surrogate waste was designed for the study on high-mercury wastes, which included an organic form of mercury, elemental mercury, and several mercury salts in an inorganic matrix. The surrogate waste and the bulk elemental mercury were treated by the vendors, and the treated waste forms evaluated for mercury Icachability, using both the TCLP and an automated, constant-pH leaching protocol. Constant pH leaching was conducted at pH 2,4,6,8 10 and 12 for 14 days at each pH. The leaching data demonstrate that the stability of the mercury in three treated waste forms varies widely across the pH range tested. Clearly, the stability of mercury in these treated waste forms will be highly dependant on the disposal conditions. The combination of site-specific disposal conditions and appropriate treatment technology must be considered as decisions are made about disposal of high-mercury wastes.

Jan 1, 2003

By Minji Jun

Leaching of the surface-coated metals from waste acrylonitrile butadiene styrene plastics (WABSP) has been investigated in the ammoniacal solution. The ammoniacal leaching of WABSP (typically containing 4.1 wt% Cu, 1.3 wt% Ni, 0.03 wt% Cr) efficiently dissolved copper and nickel, leaving unleached chromium as fine particles. The results indicate that the anions of different buffer media for metals leaching follow the order: CO3 2− > Cl− > SO4 2−. A declined leaching with high NH4OH–(NH4)2CO3 ratio (8:1) and a steep rise in extraction with high pulp in solution revealed the influence of anion (CO3 2−) and cation (Cu2+) present in the system. The leaching performed in carbonate solution by maintaining 5.0 M total NH3 concentration as NH4OH–(NH4)2CO3 ratio, 4:1; pulp density, 200 g/L; agitation speed, 400 rpm; temperature, 20 °C and time, 120 min yielded the maximum extraction (>99%) of copper and nickel. The study reveals a plausible recovery of the surface-coated metals from the WABSP without altering the properties of polymer material that can be recycled separatel

By In-Hyeok Choi

Currently, spent V2O5–WO3/TiO2 catalysts contribute significant amounts of solid waste following increasing levels of global demand. V2O5–WO3/ TiO2 catalysts usually consist of TiO2 anatase as a supporting oxide, vanadium as a catalytic agent, and other promoters such as tungsten, silicon, and calcium. Although vanadium is the main catalytic agent, a relatively high content of tungsten (WO3, 7–10 wt%) typically exists compared to vanadium (0.5–1.5 wt%). Considering the irreplaceable properties and industrial importance of tungsten, a feasible method for the recycling of spent V2O5–WO3/TiO2 catalyst should be established to utilize it as a secondary source. This paper presents a process to recover tungsten from spent V2O5–WO3/TiO2 catalyst. The processes proposed here involving roasting, decomposition using HCl, ammonia leaching, and crystallization. Within the process, ammonium paratungstate (71 wt% as WO3) is obtained as a final product. The total yield rate of tungsten from feedstock was found to be 96.3%.

By N. G. Azeredo

This work dealt with the evaluation of engineering structural clay brick samples that were sintered at estimated temperatures of 700 and 800°C. They were collected in a red-brick plant in Campos dos Goytacazes, RJ, Brazil. From a lot, a sample already sintered in its kiln at 700°C were collected and also a sample from the same lot only dried by the air, which were then sintered at 800°C controlled temperature. The samples were subjected to Brazilian Standard tests (ABNT NBR 15270:2005) to determine their geometric, physical and mechanical properties. In order to be classified as structural clay brick it is required minimum 3.0 MPa for the characteristic compressive strength (fbk) to be suitable for up to five floors structural building applications. We also used the Weibull Probability Plot and Weibull Maximum Likelihood Estimation to evaluate distribution parameters in order to compare the results of compressive strength obtained in the tests.

Jan 1, 2015

By J. Phillip Mackey

The Peter Hayes Symposium on Pyrometallurgy, held as part of Extraction 2018, is an acknowledgement of his contributions to the basic science and principles underpinning modern pyrometallurgical processing. After completing his PhD at Strathclyde University, Scotland, in 1974, Peter took up a teaching position at The University of Queensland, Brisbane, Queensland, Australia in 1976. Peter Hayes’ research at the University since then has been focussed on: • The mechanisms and kinetics of heterogeneous solid/solid, gas/solid and liquid/ solid reactions, and • Experimental measurement of phase equilibria in complex high temperature metallurgical systems. This paper provides a brief biography of Dr. Peter Hayes and gives a full listing of Peter Hayes’ publications.

By E. James Quinn

Solvent extraction technology using EHEHPA (2-ethylhexyl phosphonic acid, 2-ethyhexyl mono ester) is the norm for industrial separations of rare earth elements. This process has some shortcomings, including a large number of stages compared to most SX processes and high acid requirement for stripping of the heavy rare earths. In this work, we examine a number of alternative mixed solvent extraction systems: (i) Mixtures of organophosphonic and phosphinic acids such as EHEHPA/Cyanex 272 or Cyanex 572; (ii) Ionic liquid mixtures of EHEHPA with quaternary ammonium chloride (Aliquat 336); and (iii) Mixtures of carboxylic acids for yttrium/lanthanide separations. We discuss and compare the efficacy of these systems with reference to the Nd/Sm separation, which is of industrial significance. Based on the extraction chemistry and the use of modelling tools to define the counter-current solvent extraction circuit, we present a techno-economic analysis of a separation plant and discuss the impact of various solvent systems on the capital expenditure (CAPEX) and operating costs (OPEX).

By Xiang Ma, Halvor Dalaker, Kai Tang, Stefan Andersson

Silicon carbide (SiC) is one of the most important non-oxide ceramic materials for many industrial applications and is mainly synthesized by carbothermic reduction of silicon oxide by coke above 2200°C. Replacing natural gas (mostly methane, CH4) for coke in SiC synthesis could considerably reduce energy consumption and CO2-emissions owing to higher carbon activity of CH4 at lower temperature. The generally accepted reaction mechanism is that SiC is synthesized through gaseous intermediate silicon monoxide, SiO. In the present study, the reaction mechanism for the SiO and CH4 gaseous mixture has been examined using atomic scale modelling. Molecular dynamics (MD) using a reactive force field (ReaxFF) has been utilized to examine the initial stages of reactions involving a gas mixture of SiO and CH4 and surfaces of SiC. The MD results revealed some interesting SiC formation mechanisms. The reaction energies of the critical intermediate species were also estimated by density functional theory (DFT) calculations and the implications for the force field parameters used in ReaxFF was discussed.

Jan 1, 2015

By P. J. Mackey, J. B. See, D. G. C. Robertson

The production of iron and steel and non-ferrous metals by pyrometallurgical processes will remain a critical element in meeting the demand for materials in both developed and developing nations. Given the important need to reduce and minimise greenhouse gas emissions the technological focus of future pyrometallurgical R&D by universities and industry alike must concentrate on sustainability issues such as improved energy efficiency, recycling and waste minimization. Continued efforts are also needed on process optimization and new process development with a view to reducing capital and operating costs of the new large “mega” plants. Using the academic and industrial backgrounds of the authors, the present paper reviews the current status of R&D in pyrometallurgy in university departments with a particular emphasis on sustainability issues. The role of industry and government laboratories is also reviewed although primarily for developed countries. The paper also includes comments and suggestions on the future requirements for education and R&D in pyrometallurgy in developed countries to maximise sustainability. It is also suggested that future R&D in pyrometallurgy will be even more concentrated in developing countries – most notably China.

Jan 1, 2014

By Thomas P. Battle

Modern-day direct reduction of iron first developed as a small-scale, low capital and operating cost alternative to the blast furnace. Since commercialization of continuous DR technology in the late 1960s, the market for the products of direct reduction has grown to more than 74 million tonnes in 2012. The initial advantages of DR plants over BF facilities have grown over the years, for several reasons, including the increased size of DR modules, lower energy and emissions (particularly CO2), along with the flexibility to use a number of different reductants. The development of DR technology over the past forty years will be emphasized in this presentation, including recent developments that allow for even more direct sustainability comparisons with the iron blast furnace – and even combine the two technologies for improved synergies. Also briefly discussed will be the possibilities of using direct reduction for non-ferrous ores.

Jan 1, 2014

By Dirk Verhulst, V. I. Lakshmanan

Why Chloride Hydrometallurgy?The most available, cheapest and best known reagent for treating ores and other raw materials for the metallurgical industry is sulfuric acid. Hydrochloric acid is second in line. What often happens is that a process is developed on the basis of sulfuric acid, and that at some point the question arises: wouldn't hydrochloric acid do this better?Considering hydrochloric acid immediately opens a very interesting field of research. To summarize a few comments from another paper presented at this symposium [1]: chlorides are far more soluble than sulfates (with a few interesting exceptions); the hydrogen ion activity is greater in chloride than in comparable sulfate solutions; higher oxidative conditions are possible; regeneration is more straightforward; more diversity is possible and better conditions for the separation of species can be found for solvent extraction and ion exchange; sulfur in the ore can be separated as elemental S; higher metal concentrations in solution and more flexibility in the chosen oxidation state means significantly lower energy costs.Also, the volatility of many chlorides at higher temperature allows further separation without the need to go to a different system. Chlorides also form molten salts with a low melting point, providing another means of separation and purification in the same chloride medium.

Jan 1, 2011

By Stephen Northey, Nawshad Haque, Terry Norgate

"Life cycle assessment (LCA) is a recognized tool to evaluate various processing routes for metal production. Declining ore grades and higher specific energy requirements for primary metal production put greater emphasis on recycling. Greenhouse gas (GHG) emissions of steel and aluminium metal production were quantified with recycling scenarios using material recovery facility (MRF) data from the database of SimaPro LCA software. The GHG footprint of the MRF is relatively minor compared with that of associated transport during collection (i.e. 10 times more than MRF) of curbside recyclable material. Additionally, if the bulk recyclable material is sent overseas (i.e. Australia to China) from the MRF for further processing, the GHG footprint of shipping can significantly be larger compared with the sum of the collection and MRF (assuming electricity is from same source). Thus opportunities exist for reducing GHG emissions from secondary metal production if it is processed close to the MRF.IntroductionIt is a challenge to recycle metals significantly, although theoretically infinite recycling is possible due to their elemental nature. Leaks from the metal stocks in society occur through corrosion, wear and dispersive uses, or via land filling or similar activities that return metals to the earth. In order to provide a technically sound and transparent assessment of metal recycling, a methodology such as life cycle assessment (LCA) should be used. By taking a life cycle perspective, the beneficial recycling properties of metals can be evaluated in a manner that enables appropriate comparisons with other materials or product systems that do not have recycling loops. In practice, mixtures of primary and secondary metals are often used in new products, and also at the end-of-life various processing methods are used for recycling.The difficulty of introducing recycling into LCA is to set the right boundaries for the different flows ending in different product systems. It is a question of which observed material flow belongs to the first product system and which one to the second or subsequent systems. Recycling can be part of any product LCA. However, it is often a complex issue which requires specific considerations. As pointed out by Yellishetty et al. and Birat et al. [l, 2], LCA practitioners are left with much freedom in allocation of environmental burdens to account for recycling, thus making subjective judgments on recycling and allocation of credits to recycling. This often makes it difficult to compare the results of LCA studies conducted by two different practitioners even on the same processes. As LCA is often used to define policy in government, business and society circles, it should be based on a sound, objective and unbiased description of recycling."

Jan 1, 2014

By Brian G. Thomas

Quality problems in continuous casting of steel can be identified as they occur by monitoring mold signals (level sensor, thermocouples in the mold walls, friction etc.) and taking appropriate action (such as slowing casting speed, changing taper, changing a clogged nozzle, or later visual inspection of the surface for possible downgrading. Surface depressions and groups of deep oscillation marks form at meniscus and reduce local heat transfer as they move down the mold at the casting speed. This slows shell growth, increases shell surface temperature, and causes characteristic dips in mold thermocouple signals. More importantly, they are also associated with longitudinal cracks. Characteristic thermocouple signatures have been identified for many defects, including sticker breakouts, transverse depressions and deep oscillation marks, narrow-face bleeds, transverse comer cracks, longitudinal cracks, mold level fluctuation defects, and other problems. With the help of computational models, these mold signals should be used to troubleshoot defects, and to take appropriate corrective action. Keywords: Continuous casting, defect detection, thermocouple signals, on-line control

Jan 1, 2003

By Wenjie Zhu

Chromite ore processing residue (COPR) is a hazardous waste containing high concentration of chromium. We describe here a pioneer trial of detoxification of COPR in column reactor with an indigenous chromate reducing bacterium Leucobacter sp. Ch1, which showed high chromate reducing ability at high pH. Under the optimum conditions, at 30°C and pH 10.0, pH of leachate decreased from 10.3 to 8.3, and Cr(VI) concentration in solution decreased to zero mg L-1, and 76.4% of Cr(VI) was removed from COPR samples. The leaching toxicity of detoxified residue was 1.1 mg L-1 that was lower than national standard of China.

Jan 1, 2008

By G. Roderick Eggert

Material criticality reflects the degree to which a raw material is both necessary and subject to supply-chain risks. This study compares the criticality of selected raw materials from the differing perspectives of the manufacturing sectors of China, the European Union, Japan and the United States.

By E. Saez, M. Bellet, T. Coupez, O. Jaouen

"The paper presents a 3D finite element solver for non-steady state fluid flow. The thermomechanical simulation package REM3D® has been initially developed to model Stokes' flow for polymer injection. The mechanical module is based on a Eulerian velocitypressure formulation. The spatial discretization uses P 1+IP1 tetrahedral elements. The front tracking module consists of the resolution of a transport equation, thanks to a space-time discontinuous Galerkin formulation. It includes mesh adaptation, which permits a dynamic refinement at the front, thus controling the numerical diffusion. The same approach is used to solve heat transfer. In this paper, we focus on the specific adaptations done to treat Navier Stokes flow. The treatment of inertia is detailed, as well as the implementation of sliding conditions at mould surface, using conservative normals. Industrial applications are presented.IntroductionThe study of the mould filling stage in casting processes requires the ability to simulate complex non steady-state three-dimensional flows. Most commercial software use the volume of fluid (VOF) method, associated with a Eulerian formulation, see for instance the series of conferences ""Modelling of Casting, Welding and Advanced Solidification Processes"" [1-3]. The VOF method [4] consists in solving the conservation equation dF / dt = 0 for a variable F - the volumic fraction of fluid - whose value is 1 in filled regions and 0 elsewhere. Two fluids are actually considered: the molten alloy and a gas in the empty regions. This method suffers generally from numerical diffusion in the resolution of the free surface tracking equation, which is of pure advective type. The precision of the computation is then strongly dependent on the mesh density. Since the mesh is fixed (Eulerian formulation) this implies that in case of complex flow the user must have a priori a fairly good idea of the flow characteristics in order to capture properly the critical features of the flow. In addition, the method can hardly handle the discontinuity of the material viscosity at the interface. To prevent this difficulty, the viscosity value is smoothed around the interfuce, adding once again some inaccuracy. Since the value F = ½ is supposed to represent the free surface, it results in a smeared fluid surface. An alternative to the fixed mesh methods are the methods in which the mesh covers the fluid domain only, as proposed by Navti and Lewis [5-6], or Gaston and Bellet [7]. Based on updated Lagrangian schemes, they must be associated with an ALE formulation (arbitrary LagrangianEulerian) in order to reduce the number of full remeshing operations."

Jan 1, 2004

By P. Schloth, H. van Swygenhoven, N. Chobaut, J-M. Drezet

"In the current trend toward thicker aluminium plates, a major concern is the stress build-up during quenching which causes distortions during machining. Indeed, cooling rates are not high enough, especially at the core of such thick plates, to prevent any precipitation and quench induced precipitates lower the hardening potential. Multi-scale modelling is required when predicting macro-scale stresses after quenching for thick heat treatable aluminium components. The reason is the instantaneous strong coupling between phase precipitation at the nano-scale and material hardening due to precipitation or softening owing to solute depletion at the microscale. For thick parts, quenching intensities decrease when going from the skin to the core of the component, thus introducing a gradient of nanostructure and consequently a gradient of mechanical properties. In addition, large thermally induced deformations lead to high macroscale residual stresses although part of them is relaxed by plastic deformation. These stresses have been measured in water quenched thick plates of 7040 and 7449 aluminium alloys using neutron diffraction and layer removal techniques and the results when compared with a thermomechanical finite element model of quenching highlight the influence of precipitation.IntroductionIn the processing route of heat-treatable aluminium alloys (AA), a critical step is quenching from the solutionizing temperature. High cooling rates are desired, as they avoid formation of coarse precipitates, which reduce mechanical properties. Fast quenching, however, cannot be achieved in the centre of thick components, where the quenching rate can be more than one order of magnitude lower than at the surface. The existence of a thermal gradient between core and surface leads to a differential thermal deformation which is accommodated by elastic and plastic deformation to comply with the compatibility of deformation. Whenever the material yields, especially at high temperature when the yield strength is low, residual stress remains after quenching due to the irreversibility of plastic deformation. After quenching, the plates are in a state of residual stress that causes unacceptable distortions during machining and may reduce service life drastically. Since stress relaxation is negligible during ageing treatments [1 ], agehardened aluminium parts are usually stress relieved prior to ageing. This is typically achieved by applying plastic deformation: stretching from 1.5 to 3 % in the rolling direction (L) can reduce the internal stresses by a factor of approximately 10 [2, 3]. However, complex geometries or thicker components like thick sheets require other approaches. Reducing the quenching rate by using boiling water for instance leads to lower residual stresses [1, 4]."

Jan 1, 2013

By Naiyang Ma

Along with steel production, various steelmaking slags are constantly generated at considerably high rates. In general, steelmaking slags are not categorized into hazardous materials and do not cause any environmental issues. Therefore, recycling of steelmaking slags is often aimed at creating values by using the slags to replace high-cost raw materials. Chemical compositions and particle size distributions of slag products from steelmaking slags will determine what raw materials the slag products can replace. Consequently, maximizing the values of steelmaking slags will require to produce slag products with the highest values and to process the slags with the lowest costs. In this paper, several slag processing processes are assessed based on maximization of the values of the steelmaking slags.

Mar 1, 2017

By Dolf Gielen

This paper discusses the results of a Western European energy and materials systems engineering study that analyses the impact of greenhouse gas (GHG) emission reduction on the future of the steel and aluminum industry. he technology selection will be significantly affected by future CO2 policies. The avail- ability of C02 removal and storage technology and the social acceptance of this strategy for GHG emission reduction is of key importance for the strategy selection. The use of coal based smelting reduction technologies is optimal in case of weak C02 policies or in case of strong C02 policies and low CO2 removal and storage costs. The selection of CCF or Corex technology depends on the penalty regime. However, if C02 removal proves to be problematic, CCF development fails and strong C02 policies are introduced, the gas based DRI production processes will become more attractive. In both cases, the energy efficiency of the iron and steel industry will further increase in the next decades. The impact of GHG emission reduction on aluminum prices and aluminum use can be significant. However contrary to common notions the aluminum production will be positively affected by GHG emission reduction, notwithstanding the currently high emissions in aluminum production. A combination of emission mitigation in production and significant GHG emission reduction effects further down the product chain cause this effect. A significant potential exists for improved materials efficiency. This potential is generally neglected in energy efficiency and CO2 reduction studies. However improved steel qualities are of similar importance for C02 emission reduction as increased energy efficiency. It remains to see if this potential will be used to its full extent in the next decades. Model calculations indicate that the impact of C02 policies on the competition with other materials will be limited. Greenhouse gas emission mitigation will have much more impact on materials production and waste handling than on materials consumption.

Jan 1, 1999

By K. D. Peaslee, V. L. Richards, C. H. Rawlins, S. N. Lekakh

"Steel-making processes generate carbon dioxide air emissions and a slag co-product. The aim of this project was to develop a functional sequestration system using steelmaking slag to permanently capture carbon dioxide emitted in steelmaking offgas. A possible parallel benefit of this process would be rapid chemical stabilization of the slag minerals with reducing swelling or leaching.This paper summarizes the original results of the project, including mineralogical and structural features of carbon sequestration with steel making slag, mathematical modeling of reaction phenomena using a modified shrinking core model, METSIM modeling of several possible industrial applications, a thermo-gravimetrical study of the reaction between slags and different gases, and design and testing for a lab scale apparatus consisted of two reactors.1. IntroductionThe U.S. produces 9-14 Mt of steelmaking slag annually, which represents approximately 10-15 wt. % of crude steel output.1,2 Primary uses for steelmaking slag include high quality mineral aggregate, Portland cement, unconfined fill, soil conditioning, and pH neutralization of abandoned mine drainage.3,4 The key factor prescribing slag use is the alkaline-earth metal (e.g. Ca and Mg) oxides content, which contribute to overall basicity and cementitious strength. However, as-produced steelmaking slag is chemically unstable. Calcium and magnesium oxides readily form hydroxides and carbonates through reaction with atmospheric gases. Both hydroxide and carbonate formation produce substantial mechanical swelling leading to heave failure in confined construction applications, thus many states dictate stockpile aging for 3-6 months prior to commercial use.5,6 Sequestration of carbon dioxide is a natural corollary to forced carbonation. The conversion of CaO/MgO to carbonates serves both to stabilize the slag, and permanently capture and store the CO2."

Jan 1, 2008

Hazardous waste has often very complicated chemical compositions in a variety of physical forms and is normally processed in rotary kiln incinerators. Due to large variations in waste types and difficulties in feed characterization, the complex transport processes within the incinerator are not well understood, and the incineration process meets challenges in a smooth operation, and expects various uncertainties in the process chemistry and emission control. For better understanding of the incineration process, simulation was carried out by using Computational Fluid-dynamics (CFD) to characterize temperature and species distribution in the incinerator. In order to catch certain aspects of thermal and chemical behavior, a novel approach is proposed to represent approximately the waste streams and the subsequent combustion process. Hazardous waste in various forms from an industrial-rotary-kiln waste incinerator is firstly converted to a hydrocarbon-based virtual fuel mixture with approximately the same HIC molar ratio and calorific value. The simulation of the combustion process of the simplified hazardous waste was proceeded with a combustion model. The distribution of temperature and chemical species especially the remaining CO in the system is preliminarily investigated. Distribution of CO concentration, as a good indicator of emission level for the incineration process, could be used to evaluate the emission control. The predicted temperature distribution has been compared with available measurement data from an operating rotary kiln waste incinerator at A VR-Chieme, in the Netherlands. Reasonable agreement has been reached between the measured and predicted temperature data. [n the next step, measurement of species distribution in the system is planned to further validate the combustion model.

Jan 1, 2003