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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 Jeffrey D. Winterton

Keywords: Copper, ion exchange, sulfonic acid, bis-picolylamine, ion exchange modeling, ion exchange kinetics As part of an investigation into the feasibility of using ion exchange resins to recover copper from aqueous waste streams generated during the manufacturing of semiconductor devices, the uptake of copper onto two ion exchange resins was investigated. The resins studied were DOWEX G-26, a standard gel type sulfonic acid resin, and DOWEX M4195, a macroporous chelating resin with a bis-picolylamine functional group. The equilibrium and kinetic behavior of the uptake of copper were investigated over a range of copper concentrations with constant sulfate concentration and different levels of acidity. The homogeneous structure of the G-26 resin yields equilibrium relationships that fit the Langmuir equation, and equilibration times of less than 30 minutes. The uptake behavior of M4195 is complicated by the need to absorb co-ions to maintain electroneutrality, resulting in uptake profiles that change character with increasing copper concentrations, and extended equilibration times.

Jan 1, 2005

By B. B. Agrawal

Iron ore fines is an area of concern in India. A possible avenue is to use these fines for sponge ironmaking. Work has been carried out to pelletize these fines with coal and a suitable binder, and cure them in ambient atmosphere to retain in-situ reductant. Pellets were characterized for physical strength and metallisation. Critical factors were granulometry was percentage of coal & binder. In laboratory tests, pellets got metallized faster compared to lump ore. Large-scale trials were conducted in a 12-meter long rotary kiln plant. For 90% metallization, required residence time was only 60 minutes against 240 minutes for lump ore. Coal requirement also decreased. Investigations established the fast reduction nature of pellets. This is due to reduction-reactions occurring simultaneously at many sited within the composite pellets, in addition to the diffusion of reducing gases from the surface of the pellets to its core. The developed process is a value addition in the conventional pelletmaking and is environment-friendly also.

Jan 1, 2006

By Elli Nurminen

In this work the thermodynamics of the metallic sulphate decomposition reactions were studied through thermodynamical calculations and thermogravimetric methods. The decomposition temperatures and mechanisms were determined for cupric sulphate, ferric sulphate and also for industrial flue dust from a copper flash smelting process. The aim was to determine the thermodynamic conditions for sulphate decomposition and to estimate whether the reactions are kinetically likely to take place in the flash smelting process heat recovery equipment. The information is essential in CFD-modelling of the reactions taking place in the boiler and for optimising the process.

Jan 1, 2006

By Murat Baydogan

Effect of retrogression and reaging treatment on hardness and stress corrosion cracking resistance of 7075 aluminum alloy was investigated. As received 7075 alloys in T6 temper condition were retrogressed at 170, 220, 240 and 380°C for different durations between 15 s and 60 min. Subsequent reaging was made at the T6 aging condition. Treated materials exhibited higher hardness and better stress corrosion cracking resistance than T6 temper in a wide range of retrogression temperature and time. The highest hardness was obtained after retrogression at 170°C for 210 s followed by reaging, corresponding to 20% hardness improvement. Improvement in stress corrosion cracking resistance of the alloy by as much as 85% was also observed. In this paper, improvements in hardness and stress corrosion cracking resistance are discussed on the basis of the microstructural changes during retrogression and reaging treatment.

Jan 1, 2006

By Emma Arakelova

An increase in concentration of a Zn-containing volatile complex for synthesis of ZnO films was investigated when processing their target by ultraviolet radiation emitted by mercury lamp. The experiments were carried out using a flow-type quartz reactor. ZnO tableted target was preliminarily irradiated during 2 to 7 hours. H2O2 (98%) vapor at 25Pa passed through the reactor with ZnO target at 373K. As substrate material, five subsequent quartz cylinders were used at 423K. The experiment lasts 4 hours. H2O2 decomposition on ZnO surface was accompanied by formation of a Zn-containing volatile complex which passed in gas phase and decomposed on the substrates with isolation of final ZnO. The concentration of the Zn-containing volatile complex (N) in gas phase increases with UV pre-irradiation time (t) (without irradiation N = 1.05 1011 particles/cm3; after t=2 hours, N = 5.19 1011 particles/cm3, after t=4 hours, N = 9.95 1011 particles/cm3; after t=7 hours, N = 1.86 1012 particles/cm3.

Jan 1, 2006

A novel, low-pressure adaptation of Praxair?s coherent jet technology utilizing CoJet lances was developed for application at Inco&apos;s Copper Cliff Smelter where oxygen is available in large tonnage quantities but only at relatively low supply pressures (< 193 kPa header pressure). The project objectives were to evaluate the effect of coherent jet technology on controlling oxygen lance accretion (?horn?) formation and to increase oxygen efficiency in the Inco Oxygen Top-Blowing Nitrogen Bottom Stirring (TBBS) MK Reactor used for converting nickel- contaminated chalcocite to semi-blister copper. This paper describes the development and subsequent implementation and testing of two CoJet lances in this application.

Jan 1, 2005

By Anja Pfennig, Axel Kranzmann, Phillip Zastrow

"Properties of pipe steels for CCS technology require resistance against the geothermal corrosive environment (heat, pressure, salinity of the aquifer, CO2-partial pressure). To predict the reliability of two different injection pipe steels with 13% chromium and 0.46% carbon (1.4034, X46Cr13) as well as 0.20% carbon (1.4021, X20Cr13) steel coupons were heat treated by comparable routines prior to long term corrosion experiment (60°C, 100 bar, artificial brine close to a CCS-site in the Northern German Basin, Germany). In general higher carbon content exhibits better corrosion resistance with respect to corrosion rate, amount of pits and maximum intrusion depth in the case of local corrosion. At 100 bar hardened steels with martensitic microstructure have the lowest corrosion rates with an average of 0.003 mm/a after 2000 h exposure time. At ambient pressure normalized steels show the lowest corrosion rates, indicating that the corrosion is driven by grain boundaries.IntroductionEngineering a geological on-shore saline aquifer CCS-site (CCS Carbon Capture and Storage [1-3]) corrosion of injection pipe steels may become an issue when emission gasses, e.g. from combustion processes of power plants, are compressed into deep geological layers [4-8]. Typically 42CrMo4 (1.7225, AISI 4140) is used for casing, and for injection pipe the steel X46Cr13 (1.4034, AISI 420 C) or X20Cr13 (1.4021, AISI 420 J) is used. Saline formations are the most favorable storage sites in Germany [9], because of their large potential storage volume and their common occurrence. Leakage of CO2 back into the atmosphere may be a problem in saline aquifer storage, especially around the water level within the borehole. Carbon dioxide corrosion may cause failure of pipelines and wells as known from the oil and gas industry [4,6,10,11, 12].From thermal energy production it is known, that the CO2-corrosion is sensitively dependent on alloy composition, contamination of alloy and media, environmental conditions like temperature, CO2 partial pressure, flow conditions and protective corrosion scales [6-8,13- 20]. Considering different environments, aquifer waters and pressures, the analyzed temperature regime between 40 °C to 60 °C is a critical temperature region well known for corrosion processes as shown by Pfennig et al. [21-23] and various other authors [10,24-28] (figure 1). Here a maximum around 4.7 mm/year was found for the pit intrusion depth of 13% Cr steel X46Cr13. Still this may be predicted by the rather conservative Norsok-Model used in the oil and gas industry to calculate surface corrosion rates of carbon steels [29]."

Jan 1, 2014

By A. J. Rigby

Refractory linings in converters or anode furnaces used to over-oxidize the blister copper will suffer rapid deterioration, due to prolonged contact with copper oxide-rich slag. Nitrogen stirring with COP KIN porous plugs and use of SEMTECH OPC in converters and anode refining vessels can considerably reduce both refractory wear and processing times. In addition, careful control of the vessel atmosphere and the use of real-time optical process control minimize both slag volume and contact time with the vessel refractory.

Jan 1, 2005

By Othon do Rêgo Monteiro Neto

[The present study has investigated the extraction of copper from a chalcopyrite flotation concentrate using an adapted strain of Thiobacillus ferrooxidans and shake flasks, tank leaching and Warburg respirometer techniques. From the shake flask experiments, the activation energy and the frequency factor have been determined to be ?ka = 59.4 kJ and A = 3.3 x 105 S-1, respectively. The temperature coefficient was found to be Q10 = 2.2 in the range of 20 to 35°C. It was suggested that the reaction mechanism of chalcopyrite leaching by T. ferrooxidans involves the formation of an activated complex. whose thermodynamic values have been calculated to be ?G? = 92.1 kJ, ?S? -148.8 J K-1 and ?H$ = 47.8 kJ. The maximum volumetric oxygen mass transfer coefficient for the reactor leaching was found to be achieved by using an optimum air flow rate of 1970 cm min l at a rotational frequency of 1000 min-1. The highest copper extraction in tank (reactor) leaching experiment was 86.8% after 17 days of leaching, while in the sterile runs the corresponding copper extraction was only 40.1%. The copper extraction was suggested to be diffusion controlled. The power requirement of the aerated reactor was calculated to be Pg = 2.02 watts. During leaching, the oxygen saturation concentration was found to be C* = 6.70 mg dm-3. Using the gassing out method the critical oxygen concentration was assessed to be CCrit 0.05 mg dm 3. From the Warburg experiments, the kinetic parameters of the Monad equation were derived with a new evaluation technique to be Vmsp = 9.0 µm3 02 min-1 mg protein-1 and K = 7.4% pulp density for the effect of substrate concentration. The order of reaction and the overall reaction rate constant were determined from the modified van&apos;t Hoff plot to be n = 0.0 and k = 1.49 p dm3 02 min-1 mg Protein -1 for the chalcopyrite concentrate oxidation by T. ferrooxidans. On the basis of this experimental work, a preliminary flow sheet has been proposed for the bioextraction of copper from flotation concentrates.]

Jan 1, 1985

By Nam-Il Um

Bottom ash contains several ferrous materials (ferrous metals, Fe3O4, Fe2O3, FeS, etc.). In particular, ferrous metals contain heavy metal because Ni and Cr are chemically attracted to iron. Likewise, Cu is used to coat Ni and Cr metals as polish or to prevent corrosion. In this study, an Fe3O4-Fe2O3 double layer (similar to pure Fe) was found to have been formed in ferrous metal during air-annealing in an incinerator (1000°C). A strong thermal shock such as one that occurs during the water-cooling of bottom ash results in the breakdown of this oxidation layer, facilitating the degradation of ferrous metals and formation of corrosion products. Therefore, Fe-ion (heavy metal) oxides may be formed on ferrous metals and may be separated from bottom ash via magnetic separation. This study sought to investigate the separation ratio of heavy metals as magnetic separation and mineralogical formation of Fe-ion (heavy metal).

Jan 1, 2006

By Hong Yong Sohn

Keywords: Barium sulfate, Barium sulfide, Environment, Kinetics, Pollutants, Sulfur dioxide conversion, Thermodynamics Nonferrous smelters and coal gasification processes generate sulfur dioxide streams, most of which are treated to produce sulfuric acid with the accompanying problems of market shortage and transportation difficulties. While the conversion of sulfur dioxide to elemental sulfur has many environmental advantages, no processes exist that are environmentally acceptable and economically viable. A method for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium or barium sulfide and calcium or barium sulfate without generating solid wastes has been developed. In this process, the sulfate, as the starting raw material, is reduced by a suitable reducing agent such as hydrogen to produce the sulfide, which is used to reduce sulfur dioxide producing elemental sulfur vapor and regenerating the sulfate. The latter is then reduced to reproduce the sulfide. This paper describes work on the BaS/BaSO4 system. Thermodynamic analysis and experimental results indicated that the BaS-SO2 reaction produces mainly sulfur vapor and solid barium sulfate and that the gaseous product from the BaSO4-H2 reaction is mainly water vapor. The rates of the two reactions are reasonably rapid in the temperature range 700-1050°C.

Jan 1, 2005

By Susan Jacob

The heat of fusion of silver was measured using high temperature differential scanning calorimetry (HTDSC). Heating rate, sample mass, calibration standard and cover gas flow rate were varied to determine their impact on instrument accuracy and reproducibility. Good reproducibility was achieved in most of the runs. Accuracy was not satisfactory in most of the runs, though three runs gave results within 1.7%, 3.3% and 3.5% of the literature value, within the acceptable limits. A larger mass and higher heating rate tend to generate more accurate results.

Jan 1, 2006

By F. Kavicka

An original application of ANSYS simulated the forming of the temperature field of a massive casting from ductile cast-iron during the application various methods of its cooling using chills. The numerical model managed to optimize more than one method of cooling but, in addition to that, provided serious results for the successive model of structural and chemical heterogeneity, and so it also contributes to influencing the pouring structure. The file containing the acquired results from both models brings new and, simultaneously, remarkable findings of causal relationships between the structural and chemical heterogeneity and the local solidification time in any point of the casting. The determined relations therefore enable the prediction of the face density of the spheroids of graphite in dependence on the local solidification time. The calculated temperature field of 500x500x1000 mm casting of ductile cast-iron with various methods of cooling has successfully been compared with temperatures obtained experimentally. Acknowledgments. This analysis was conducted using a program devised within the framework of the GA CR projects (No.106/04/1334, No. 106/04/1006 and No. 106/04/094), of the COSTAPOMAT-OC526.10, MPO/FI-IM/021, EUREKA No.2716 COOP and KONTAKT 14/ 2005/06.

Jan 1, 2006

By Slobodan Radosavljevic

The polymetallic W-Pb-Bi-Ag ore from the ?Nova jama? ore zone of the Rudnik ore field have been investigated. Contact-pneumatolytic (skarn), pneumatolytic-hydrothermal, and hydrothermal mineralization phases are defined in this ore zone. The most significant mineralization phase that gave compact ore bodies is pneumatolytic-hydrothermal phase. A relatively pure Mo-free scheelite is the only tungsten-bearing mineral. Lead minerals are mostly presented by Pb-Bi sulphosalts and much less with galena. The image analysis coupled with Energy Dispersive Spectrometry (EDS) analysis on a Scanning Electron Microscope (SEM) was applied to the characterization of a W-Pb-Bi-Ag ore as an efficient tool for mineral quantification. Results of EDS (Energy Dispersive Spectrometry) analyses gave the empirical formulae: Pb1.91Ag0.05Cu0.08Bi1.93S5 for cosalite, Pb0.98Ag0.03Cu0.05Bi1.99S4 for galenobismutite and galena Pb0.99Ag0.03S.

Jan 1, 2006

By Xiaowen Liu

The thermal decomposition of diaspore was investigated by thermogravimetry (TG),differential scanning calorimetry (DSC), X-ray power diffraction(XRD),infrared (IR)spectrain this paper. The thermal decomposition mechanism of diaspore was discussed according to Coat-Redfer equation. It was found that the decomposition of diaspore was carried out at 500?,and the peak temperature was 530?. The electrovalent balance of diaspore was destroyed. The previous crystal structure was changed. a- Al2O3 was obtained after thermal decomposition. The activation energy is 287KJ/mol.

Jan 1, 2006

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By Masaki Imamura

A novel hydrometallurgical process for copper concentrate treatment has been developed by Niihama Research Laboratories of Sumitomo Metal Mining Co., Ltd. The process has numerous advantages with respect to the operational and environmental aspects. For example, copper is leached effectively from chalcopyrite concentrates by chlorine gas under atmospheric pressure. The copper in the leach solution is then separated from iron and silver by solvent extraction and undergoes electrowinning for its recovery as a highly pure copper metal; this does not require any further purification. Moreover, iron metal can be produced from the purified raffinate by electrowinning without generating a large volume of goethite or hematite, which are solid wastes generated due to iron rejection in common hydrometallurgical processes. This process can also realize the efficient recovery of precious metals. The results of batch testing and continuous-operation testing are presented in this paper.

Jan 1, 2006

By Sergio Neves Monteiro

In the present work, a ceramic foam elaborated with illitic clays was characterized. Properties related to density and compression strength were determined in samples fired at 1300oC, a temperature that permits the clay structure to generate and retain gases that will produce the foamy structure. The microstructure of the ceramic foam was studied by X-ray diffraction, scanning electron microscopy and mercury porosimetry. The results showed that the ceramic foam presents a bulk density of 0.38 g/cm3. The microstructure is formed by large open pores, quartz particles and vitreous phase.

Jan 1, 2006

By Vincent Menard

The purpose of the present work is to demonstrate the removal of manganese from a neutral leach zinc-rich solution ([Zn] =150 g/L) at 80°C by oxidative precipitation using a gas mixture of sulphur dioxide (SO2) and oxygen (O2). In order to determine the optimum conditions for manganese removal, several bench-scale semi-batch experiments were performed, where the effects of ORP and gas mixing were investigated. These tests showed that SO2/O2 is a fast and effective oxidant for removing manganese down to ppm level as long as the appropriate ORP is attained/maintained and gas transfer kinetics are optimized.

Jan 1, 2006