Search Documents

By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

By N. Voennann

Stillwater Mining Company operates an electric furnace at its smelter in Columbus, Montana to treat a Ni-Cu-platinum group metal concentrate along with secondary PGM bearing materials. Hatch Associates has designed several improvements to this furnace, which was originally built by others. Implementation of these relatively low cost improvements has resulted in substantial increases in furnace availability and capacity, along with reduced unit costs. ? The improvements included: ? Installation of water-cooled copper cooling elements to stabilize refractory wear and increase furnace life.- ? Improved furnace 'bindings, to enhance the furnace's structural integrity by improving the contact between the refractory and cooling elements, and by promoting tight brick joints resistant to matte or slag leaks. ? Adjustment of the electrode regulator to allow higher furnace power levels. ? Installation of an automated air-slide (aeration conveyor) feed system to evenly distribute the furnace feed in an insulating layer on the bath surface. This "black-top" practice reduces unit energy costs and makes available additional smelting capacity.- ? Electrode seals to reduce ingress of air that absorbs heat before exiting the furnace in the off-gas stream. The saved energy can be used to smelt additional concentrate. This paper describes the above furnace modifications, and the benefits derived from their implementation.

Jan 1, 1998

By W. R. McDonald

The U.S. Bureau of Mines investigated treatment of gold and silver refractory ores and concentrates that respond poorly to conventional cyanidation techniques due to the complex mineralogy of the ore. Three types of ores were investigated: gold locked placer sands, gold locked in sulfides, and gold that is robbed from the pregnant cyanide solutions by minerals in the ore. Ore treatment included grinding, flotation, cyanidation, air oxidation, pressure oxidation, hypochlorite oxidation, roasting, and carbon in leach.

Jan 1, 1991

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as Sulphuric acid or liquid S02. On the other hand, natural gas may contain over 20% of hydrogen sulphide (H2S) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert S02 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By lchiro Aoi, Hideo Nakae, Makoto Yoshida, Makoto Ishino

"The influence 6f gravity on the microstructure of unidirectionally solidified Cu-Pb monotectic, Ag-Si and Fe-C eutectic alloys is studied. In order to examine the influence of gravity in a lg environment, both the upward (opposite to direction of gravity) and downward (direction of gravity) unidirectional solidifications are carried out. The results are as follows: (1) For the upward solidified Ag-Si eutectic alloy, the eutectic Si continuously grows. On the other hand, in the downward solidified Ag-Si alloy, the Si grows discontinuously and disperses into the ex-Ag matrix. (2) No morphological difference in the eutectic growth is observed between the upward and downward solidified Fe-C eutectic alloys. (3) In the case of the upward solidified Cu-Pb monotectic alloy, a banded structure, which consists of Pb-rich layers and Cu-rich layers, is observed. However, such a banded structure -is not observed in the downward specimen. (4) The banded structure is not found in the upward solidified Cu-Pb-0.05 mass % Al and Cu-Pb-0.1 mass % Al alloys. In the Cu-Pb-0.05 mass% Al alloy, a fibrous -L 2 phase grows continuously parallel to the growth direction at low growth rate. Only 500 mass ppm addition of aluminum induces the morphological change of the monotectic L2 phase.IntroductionThe influence of gravity on the solidification of eutectic and monotectic alloys has been investigated in microgravity environments [l-9]. The purpose of these studies was to obtain a homogeneous microstructure of eutectic or monotectic alloys, most of which alloys tend to solidify with macro-segregation under gravity. However, in most of the previous experiments, e.g., in free fall systems, in aircraft or in space laboratories, the growth rate was too high to realize a planar solid/liquid interface. This would be due to the limited time for solidification. Thus, it was difficult to examine the influence of gravity on the planar coupled growth of the eutectic or monotectic alloy. In this study, both the downward U.D.S. (unidirectional solidification by gravity) and upward U.D.S. (opposite direction to gravity) are carried out in order to examine the influence of gravity on the coupled growth in a lg environment [l0, 11]. In the case of the downward U.D.S. using the current Bridgman method, the molten alloy must be confined between the crucible and the solid."

Jan 1, 2000

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. Nona C. Liddell

There is a significant amount of early work that has been largely forgotten that deals with the validity of the pseudo-steady approximation for liquid-solid reactions. Much of this was originally published in the chemical engineering literature but is highly relevant to hydrometallurgical processes. The purpose of this paper is to summarize some criteria that were been developed by various authors for determining the error associated with use of shrinking core models for liquid-solid systems.

Jan 1, 2002

By D. M. Dabbs

A static dew point technique has been used to evaluate the solubility of arsenic in ?slag and its dependency on P02 at temperatures of 1458 and 1523K. The ferrous-ferric ion ratio of the slags ranged from 3.9 to 23.8. These values correspond to partial pressures of 02 ranging from 10-8 to 10-12 atm. The solubility of arsenic in slag was found to be independent of? P02? The data indicate that elemental arsenic exists in silicate ?slags. This result was further substantiated by mass .spectrometric analysis of doped slag specimens.

Jan 1, 1983

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By John B. Cocanour

The U.S. Bureau of Mines (USBM) has developed a laboratory-scale on-line analysis and process control system for a decopperization electrolytic circuit. This system is software driven, running on a 486DX-33 personal computer (PC) utilizing a portable energy- dispersive x-ray fluorescence (XRF) spectrometer as the sample analyzer. The XRF copper reading obtained was used as the control variable through an RS-232 serial interface to the PC for software-based control of feed flowrates. When the copper concentration in the electrolytic cell (as measured by the XRF) deviated from the set point, the feed flowrate to the cell was automatically altered using software-based proportional-integral-differential (PID) computer control to yield the desired copper concentration at the electrolytic cell outlet.

Jan 1, 1994

By F. Ajersch, P: Tsantrizos, K: Shanker

"TiN films have been deposited on various substrates by a novel reactive plasma technology. In this process, a nitrogen source (NH3 or N2) and TiCl4 are reacted in the jet of a plasma torch, and are deposited onto a substrate forming TiN films at a high growth rate ( > 2µm/min). It was found that the process parameters strongly affect the microstructure, thickness, density, and growth rate of the TiN films. These parameters include source of nitrogen (NH3 or N2, N/Ti ratio, temperature of substrate, and spray distance. In general, it was found that thick and dense coatings were deposited when the N:Ti ratio was kept low, and the substrate temperature was high. Also, for the series of conditions investigated, NH3 was found to give much better results than N2•. The limitations and advantages of this technique are also discussed in this paper.IntroductionTiN is an extremely hard material and is used in many wear applications, particularly as a protective coating on cutting tools to extend their Iife(1.2). Owing to its excellent chemical stability, TiN is also frequently used as a diffusion barrier in the electronics industry for sub-micron Al/TiN/Si ohmic contact systems (3) or as a coating on high-temperature resistant alloys in gas turbine applications (4), based on its good resistance to oxidation. Other applications include decorative coatings in the jewelry industry, and specialized applications such as solar energy absorbers and transparent heat mirrors(5).TiN films can be deposited/formed using various techniques. The main techniques of deposition are CVD (Chemical Vapour Deposition) and PVD (Physical Vapour Deposition). Each of these techniques can have many variations in equipment characteristics, reactants as well as a range of process parameters (pressure and temperature). In the CVD process, TiN is generally deposited onto a heated substrate where a chemical reaction takes place. The reaction can be one of reduction(6) (e.g.: TiCI4 + 0.5N2 + 2H2 --> TiN + 4HCI), of thermal decomposition(7) (e.g. decomposition of titanium dialkylamide), or of displacement (e.g. TiCI4 + NH3 --> TiN + 3HCI + 0.5CI2)' The displacement and reduction reactions are the most common."

Jan 1, 1994

By C. Burton Clark

The important role of the petrographic microscope in the petrology of refractories is discussed, based on 45 years of industrial experience by the author. Highlights of his career are used to illustrate improvements in equipment and techniques during the period. Two specific investigations are described which emphasize the interrelated use of the petrographic microscope with other instruments such as the x-ray diffractometer and scanning electron microscope. Emphasis is placed on the use of phase equilibrium diagrams for guidance in predicting and interpreting reactions that occur under non-equilibrium conditions in the manufacture and use of refractories.

Jan 1, 1982

By S. K. Wu, Ray Y. Lin, Sunil Annaji

Infrared joining of TiAI using aluminum foils as the filler material was investigated at temperatures between 1050 °C and 1350 °C in a flowing argon environment for times varying between 15 and 60 seconds. Using aluminum foils, the attempt was to form the Al3Ti phase in the joint as a result of reaction between Al and TiAI at temperatures above the melting point of Al. It has been found based on X-ray diffraction and TEM analysis that, Al3Ti, indeed is the product of infrared joining of TiAI using Al as the joining alloy. Al3 Ti was detected even in the joint processed at 1050 °C for only 15 seconds. Since the aluminum foil used in this study contains 27 at% Si, the t 2 phase in the Ti-Al-Si ternary system is believed to have also formed at the joint/base TiAI interface. Cross sectional studies on the joined specimens have shown different degrees of reaction depending on the temperature and time of joining. Micro hardness evaluations across the joint show that the hardness near the center of the joint is typically smaller than that near the joint edge next to the base material. However, as the joining temperature and time increase, the increment of the hardness at the center of the joint is faster than that around the periphery of the joint.

Jan 1, 1996

By V. I. Lakshmanan

The demand for elements such as nickel, cobalt, titanium and gold in various applications has increased significantly. Innovation to recover these elements now plays a major role in metallurgical processes as established technologies have challenges in treating the types of ores that are available while meeting the increasingly stricter environmental regulations. Alternative chloride based processes have been developed that can be used to recover the value elements from the available feed stocks with potentially lower environmental impact. Chloride-based hydrometallurgical processes have several advantages, including higher leachability of complex ores/tailings and relative stability of chloro-complexes of the metals. Process Research ORTECH Inc. (PRO) has developed mixed-chloride process flowsheets, where innovative solvent extraction process steps are used for the separation of nickel, cobalt, titanium and gold from their respective chloride solutions. This paper will discuss the potential aqueous chloro-chemistry of these metals and separation reaction mechanisms involved in the solvent extraction process.

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 D. L. Jones

The leaching of natural chalcopyrite was studied in both ferric sulfate and ferric chloride solutions. The chemistry of the two reactions is quite different, with substantial sulfur oxidation occurring only in sulfate solutions. Ferric chloride is a more effective reagent, for the leaching rate is greatly increased with finer particles and higher (Fe+++), and unaffected by high (Fe++); none of these advantages are found with ferric sulfate. In addition, the morphology of leaching appears to be different, with ferric sulfate leaching preferentially along fissures or grain boundaries. The kinetics were found to be linear over an extended period, rather than parabolic as reported elsewhere. An explanation of the observed phenanena is proposed using the electrochemical theory of leaching, and experimental measurement of the mixed potential of the mineral during leaching.

Jan 1, 1976

By Derek J. Fray

Electric arc furnace dusts, especially those containing zinc ferrite, are notoriously difficult to process to give valuable products and non-toxic residues. The ideal process would remove and recover the toxic non-ferrous metals as pure metals, of commercial value, and non-toxic residue which can be used as a raw material in the steel industry. From an examination of the thermodynamics of the oxides and chlorides of the various elements in the dust, it is apparent that the chlorides of the toxic non-ferrous elements are more stable than the oxides while the reverse applies to the ferrous elements. This offers the opportunity for a complete separation of the zinc, lead and cadmium from the iron oxide. Results are presented for the chlorination of electric arc furnace dusts under oxidising conditions and the subsequent treatment of the chlorides to recover the pure metals and chlorine which can be recycled back to the reactor.

Jan 1, 1994

By Anne Kvithydl

Printed circuited boards contain considerable quantities of valuable metal, while also containing many environmental pollutants making them unsuitable for landfill. In this study the decomposition of common plastics used in printed circuit boards were studied. Polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC) and polyethylene (PE) were heated in both CO, and argon atmospheres using a thermo-gravimetric furnace (TG) coupled to a mass spectrometer (MS). Soda ash Na,C03 and baking soda NaHC03 were used as reactants. The degradation temperatures and evolved gases are presented for single plastics and mixtures. Mixed plastics are shown to behave as a sum of the individual plastics. The mass loss temperature is the same in CO, and argon. However, less residue is formed when heated in CO,.

Jan 1, 2008