Kazuyo Matsubae

Thermodynamic Analysis of Contamination by Alloying Elements in Aluminum Recycling

In previous studies on the physical chemistry of pyrometallurgical processing of aluminum scrap, only a limited number of thermodynamic parameters, such as the Gibbs free energy change of impurity reactions and the variation of activity of an impurity in molten aluminum, were taken into account. In contrast, in this study we thermodynamically evaluated the quantitative removal limit of impurities during the remelting of aluminum scrap; all relevant parameters, such as the total pressure, the activity coefficient of the target impurity, the temperature, the oxygen partial pressure, and the activity coefficient of oxidation product, were considered. For 45 elements that usually occur in aluminum products, the distribution ratios among the metal, slag, and gas phases in the aluminum remelting process were obtained. Our results show that, except for elements such as Mg and Zn, most of the impurities occurred as troublesome tramp elements that are difficult to remove, and our results also indicate that the extent to which the process parameters such as oxygen partial pressure, temperature, and flux composition can be changed in aluminum production is quite limited compared to that for iron and copper production, owing to aluminums relatively low melting point and strong affinity for oxygen. Therefore, the control of impurities in the disassembly process and the quality of scrap play important roles in suppressing contamination in aluminum recycling.

Quality- and dilution losses in the recycling of ferrous materials from end-of-life passenger cars: input-output analysis under explicit consideration of scrap quality.

Metals can in theory be infinitely recycled in a closed-loop without any degradation in quality. In reality, however, open-loop recycling is more typical for metal scrap recovered from end-of-life (EoL) products because mixing of different metal species results in scrap quality that no longer matches the originals. Further losses occur when meeting the quality requirement of the target product requires dilution of the secondary material by adding high purity materials. Standard LCA usually does not address these losses. This paper presents a novel approach to quantifying quality- and dilution losses, by means of hybrid input-output analysis. We focus on the losses associated with the recycling of ferrous materials from end-of-life vehicle (ELV) due to the mixing of copper, a typical contaminant in steel recycling. Given the quality of scrap in terms of copper density, the model determines the ratio by which scrap needs to be diluted in an electric arc furnace (EAF), and the amount of demand for EAF steel including those quantities needed for dilution. Application to a high-resolution Japanese IO table supplemented with data on ferrous materials including different grades of scrap indicates that a nationwide avoidance of these losses could result in a significant reduction of CO(2) emissions.

MaTrace: Tracing the Fate of Materials over Time and Across Products in Open-Loop Recycling

Even for metals, open-loop recycling is more common than closed-loop recycling due, among other factors, to the degradation of quality in the end-of-life (EoL) phase. Open-loop recycling is subject to loss of functionality of original materials, dissipation in forms that are difficult to recover, and recovered metals might need dilution with primary metals to meet quality requirements. Sustainable management of metal resources calls for the minimization of these losses. Imperative to this is quantitative tracking of the fate of materials across different stages, products, and losses. A new input-output analysis (IO) based model of dynamic material flow analysis (MFA) is presented that can trace the fate of materials over time and across products in open-loop recycling taking explicit consideration of losses and the quality of scrap into account. Application to car steel recovered from EoL vehicles (ELV) showed that after 50 years around 80% of the steel is used in products, mostly buildings and civil engineering (infrastructure), with the rest mostly resided in unrecovered obsolete infrastructure and refinery losses. Sensitivity analysis was conducted to evaluate the effects of changes in product lifespan, and the quality of scrap.

Simultaneous Material Flow Analysis of Nickel, Chromium, and Molybdenum Used in Alloy Steel by Means of Input–Output Analysis

Steel is not elemental iron but rather a group of iron-based alloys containing many elements, especially chromium, nickel, and molybdenum. Steel recycling is expected to promote efficient resource use. However, open-loop recycling of steel could result in quality loss of nickel and molybdenum and/or material loss of chromium. Knowledge about alloying element substance flow is needed to avoid such losses. Material flow analyses (MFAs) indicate the importance of steel recycling to recovery of alloying elements. Flows of nickel, chromium, and molybdenum are interconnected, but MFAs have paid little attention to the interconnected flow of materials/substances in supply chains. This study combined a waste input-output material flow model and physical unit input-output analysis to perform a simultaneous MFA for nickel, chromium, and molybdenum in the Japanese economy in 2000. Results indicated the importance of recovery of these elements in recycling policies for end-of-life (EoL) vehicles and constructions. Improvement in EoL sorting technologies and implementation of designs for recycling/disassembly at the manufacturing phase are needed. Possible solutions include development of sorting processes for steel scrap and introduction of easier methods for identifying the composition of secondary resources. Recovery of steel scrap with a high alloy content will reduce primary inputs of alloying elements and contribute to more efficient resource use.

UPIOM: A New Tool of MFA and Its Application to the Flow of Iron and Steel Associated with Car Production

Identification of the flow of materials and substances associated with a product system provides useful information for Life Cycle Analysis (LCA), and contributes to extending the scope of complementarity between LCA and Materials Flow Analysis/Substances Flow Analysis (MFA/SFA), the two major tools of industrial ecology. This paper proposes a new methodology based on input-output analysis for identifying the physical input-output flow of individual materials that is associated with the production of a unit of given product, the unit physical input-output by materials (UPIOM). While the Sankey diagram has been a standard tool for the visualization of MFA/SFA, with an increase in the complexity of the flows under consideration, which will be the case when economy-wide intersectoral flows of materials are involved, the Sankey diagram may become too complex for effective visualization. An alternative way to visually represent material flows is proposed which makes use of triangulation of the flow matrix based on degrees of fabrication. The proposed methodology is applied to the flow of pig iron and iron and steel scrap that are associated with the production of a passenger car in Japan. Its usefulness to identify a specific MFA pattern from the original IO table is demonstrated.

Thermodynamic criteria for the removal of impurities from end-of-life magnesium alloys by evaporation and flux treatment

Abstract In this paper, the possibility of removing impurities during magnesium recycling with pyrometallurgical techniques has been evaluated by using a thermodynamic analysis. For 25 different elements that are likely to be contained in industrial magnesium alloys, the equilibrium distribution ratios between the metal, slag and gas phases in the magnesium remelting process were calculated assuming binary systems of magnesium and an impurity element. It was found that calcium, gadolinium, lithium, ytterbium and yttrium can be removed from the remelted end-of-life (EoL) magnesium products by oxidization. Calcium, cerium, gadolinium, lanthanum, lithium, plutonium, sodium, strontium and yttrium can be removed by chlorination with a salt flux. However, the other elements contained in magnesium alloy scrap are scarcely removed and this may contribute toward future contamination problems. The third technological option for the recycling of EoL magnesium products is magnesium recovery by a distillation process. Based on thermodynamic considerations, it is predicted that high-purity magnesium can be recovered through distillation because of its high vapor pressure, yet there is a limit on recoverability that depends on the equilibrium vapor pressure of the alloying elements and the large energy consumption. Therefore, the sustainable recycling of EoL magnesium products should be an important consideration in the design of advanced magnesium alloys or the development of new refining processes.

Forecasting Replacement Demand of Durable Goods and the Induced Secondary Material Flows: A Case Study of Automobiles

The aim of this article is to propose a method for forecasting future secondary material flows by combining a product lifetime distribution analysis with a waste input‐output analysis and present a simple case study of automobiles. The case study demonstrates that the proposed method enables us to estimate replacement demand of new vehicles, number of end‐of‐life (EOL) vehicles arising from the aging of vehicles, volume of shredder scraps recovered from EOL vehicles, and volume of shredder scraps required to meet final consumption in the future.

Dissolution behavior of selenium from coal fly ash particles for the development of an acid-washing process

Coal fly ash emitted from coal-fired electric power stations generally contains environmentally regulated trace elements. In particular, boron, arsenic, and selenium have been recognized as troublesome trace elements because elutions from the fly ash contain them. In order to design an effective removal process for these trace elements, we have developed and investigated an acid-washing process. The dissolution behavior of selenium from coal fly ash particles was focused on for the improvement of the process, and was found to greatly depend on the pH of the acid solutions. The species of selenium in solutions with a pH of around 0-1 was determined to be H2SeO3. The dissolved H2SeO3 transformed into HSeO3- and adsorbed onto the surface of the ash particles in solution upon elevation of the pH. The re-elution of the absorbed HSeO3- as SeO3(2-) at a pH of 10 was also confirmed, and will cause the elution of the excess selenium from the acid-washed ash.

Thermodynamic Analysis for the Refining Ability of Salt Flux for Aluminum Recycling

The removability of impurities during the aluminum remelting process by oxidation was previously investigated by our research group. In the present work, alternative impurity removal with chlorination has been evaluated by thermodynamic analysis. For 43 different elements, equilibrium distribution ratios among metal, chloride flux and oxide slag phases in the aluminum remelting process were calculated by assuming the binary systems of aluminum and an impurity element. It was found that the removability of impurities isn’t significantly affected by process parameters such as chloride partial pressure, temperature and flux composition. It was shown that Ho, Dy, Li, La, Mg, Gd, Ce, Yb, Ca and Sr can be potentially eliminated into flux by chlorination from the remelted aluminum. Chlorination and oxidation are not effective to remove other impurities from the melting aluminum, due to the limited parameters which can be controlled during the remelting process. It follows that a proper management of aluminum scrap such as sorting based on the composition of the products is important for sustainable aluminum recycling.

Thermodynamic estimation of minor element distribution between immiscible liquids in Fe-Cu-based metal phase generated in melting treatment of municipal solid wastes

Waste electrical and electronic equipment (WEEE) has become an important target in managing material cycles from the viewpoint of not only waste management and control of environmental pollution but also resource conservation. This study investigated the distribution tendency of trace elements in municipal solid waste (MSW) or incinerator ash, including valuable non-ferrous metals (Ni, Co, Cr, Mn, Mo, Ti, V, W, Zr), precious group metals (PGMs) originated from WEEE (Ag, Au, Pd, Pt), and others (Al, B, Pb, Si), between Fe-rich and Cu-rich metal phases by means of simple thermodynamic calculations. Most of the typical alloying elements for steel (Co, Cr, Mo, Nb, Ni, Si, Ti, V, and W) and Rh were preferentially distributed into the Fe-rich phase. PGMs, such as Au, Ag, and Pd, were enriched in the Cu-rich phase, whereas Pt was almost equally distributed into both phases. Since the primary metallurgical processing of Cu is followed by an electrolysis for refining, and since PGMs in crude copper have been industrially recovered from the resulting anode slime, our results indicated that Ag, Au, and Pd could be effectively recovered from MSW if the Cu-rich phase could be selectively collected.