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By Marc Verhaege

The effluent under investigation results from a catalic oxidation unit in which paraxylene is oxydised to terephtalic acid. The solution contains cobalt and manganese as their acetates in a concentration range of 0,4 - 1,2 g/I of cobalt and 0,8 - 2,4 g/l of manganese. Before being fed into the main waste stream treatment unit of the plant it is advisable to apply a petreatment step in which both metals are eliminated to a great extent from this effluent. Conventional treatment is done by precipitation of both metals either through pH increment with a base or by adding a suitable reagent producing insoluble species. The aim of this study was to look for a treatment (elimination of both metal species) in which no sludge or precipitate is formed.

Jan 1, 1995

By Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By Dan Wang, Yuanbo Zhang, Guihong Han, Guanghui Li, Tao Jiang, Yanfang Huang

"Hematite concentrates are characterized by bad high-temperature reactivity and poor balling index, which restrict their large-scale application in the production of oxidized pellets. An organic additive, namely MHA, was authorized and used as binder recently in China. Compared with bentonite, the effects of MHA on compressive strength of hematite pellets at various firing conditions were investigated in this study. Experimental results showed the compressive strengths of preheated pellets with different binders were increased with increasing the preheating temperature and time. The compressive strength of preheated pellets with MHA binder was lower than that of pellets with bentonite, which can be ascribed to the high porosity of pellets with MHA binder. However, the compressive strength of roasted pellets with MHA binder was higher than that of pellets with bentonite. The compressive strength of finished pellets balled with MHA binder 1.0 wt% could meet the operation requirements of grate-kiln process.IntroductionHematite concentrates are characterized by bad high-temperature reactivity and poor balling index, which can lead to the appearance of those problems with increasing the energy consumption, shortening the useful life of equipment, and finally increasing the operation cost of oxidized pellets plants [1-2]. Some investigations have been conducted based on improving the pelletizing technique of hematite concentrates, such as pretreatment of raw materials [3-7], optimization of ore proportioning [8], addition of solid fuels [9-16], and so on. Employing high pressure grinding roller for the treatment of hematite concentrates revealed that the mechanical strength of wet green pellets could be improved. However, the mechanical strength of fired pellets was not improved obviously [7]. Huang, et al., pointed out that the preheating and roasting temperature may be decreased and the compressive strength of fired pellets could be increased by blending a certain proportion of magnetite concentrates with hematite [8]. Nevertheless, there are a variety of magnetite ores different in physical and chemical properties in China, resulting in the instability operation [17]."

Jan 1, 2012

By Adam J. Gesing

Eddy current separators are increasingly used by the auto shredder operators to produce higher grade of nonferrous metal concentrate for recycling. While this increases the unit price of the concentrate, metal losses through inefficient metal recovery quickly offset the price differential. We show how to optimize the eddy current separation system at the shredder to maximize mate- rial throughput, nonferrous metal recovery and grade of the nonferrous metal concentrate.

Jan 1, 1998

By J. Brent Hiskey

The global copper industry faces a technological challenge to develop processing schemes for more complex and impure ores and concentrates. Group 15 elements (As, Sb, and Bi) represent impurities that are troublesome both in terms of environmental impact and metallurgical processing. The so-call "dirty" copper concentrates are either unacceptable for smelting and refining or incur high penalties. The behavior of the Group 15 elements is of critical importance in maintaining product quality and process performance. During copper electrorefining, these impurities are released to the electrolyte by electrochemical dissolution of the anode. Depending mainly on temperature, concentration, and oxidation state these elements can spontaneously coprecipitate from the electrolyte. Some of these precipitates are referred to as floating slimes and their formation can have extremely detrimental effects on cathode purity. In this paper, the mechanism of floating slimes formation will be discussed and the fundamental thermochemistry will be reviewed and analyzed in relation to solubility properties.

Jan 1, 2012

By Kenneth N. Han

Ammonia has been found to be an effective leaching reagent for gold, silver and platinum group metals in the presence of appropriate oxidants. Electrochemical and kinetic aspects of the dissolution of elemental gold in ammoniacal solutions have been investigated. The cathodic reaction of aurous di-ammine on the gold cathode has been investigated first. From this investigation, the standard electro-potential of the cathodic reaction .and hence. the Gibbs free energy of formation of the aurous di-ammine were established. The solubility of gold in ammoniacal solutions was also examined in relation to ammonia concentration, temperature and concentration of various oxidants. The anodic reaction of the gold disk in ammonia? in the presence? of various oxidants including oxygen, ozon, hypochlorite, hydrogen peroxide, cupric and cobaltic ammine, and iodine was also examined and the results have been discussed. Excellent dissolution yielding of gold and many other metals, typically better than 95% recovery in 1'-2 'hours of leaching at a temperature ranging 80°C to 190°C has been observed. Test results of the dissolution of gold from elemental state as well as other sources including sulfidic ores and scrap are presented.

Jan 1, 1998

By Hiroyuki Matsuura, Fumitaka Tsukihashi

"Emission of CO2 gas from steelmaking industry covers more than 12 % of total CO2 emission in Japan. Though many efforts have been made to curtail energy consumption and high energy efficiency of Japanese steel production process has been achieved so far, further reduction of CO2 emission is strongly requested to develop sustainable steel production process and produce “green material”. Recently, authors have proposed the innovative hydrogen production process, in which water vapor is reacted with discharged steelmaking slag to produce hydrogen gas. This reaction can be achieved without any external energy source and operated by huge thermal energy associated with steelmaking slag and FeO or unrecovered Fe droplets that are relatively rich in the slag. In this paper, thermodynamic calculation results with various initial conditions in terms of hydrogen productivity were presented. Laboratory-scale experiments were also conducted to clarify the validity of thermodynamic calculation and the reaction rate in realistic conditions.IntroductionIronmaking and steelmaking process from iron ore through blast furnace and BOF is an essential steel production route for Japanese steel industries to supply high quality steel products in large quantity to society stably. Blast furnace – BOF process requires huge amount of fossil fuels such as mainly coal, resulting the emission of considerable amount of CO2 gas. Since the emission of CO2 gas from steel industries, about 147 Mt (FY2011), accounts for approximately 12 % of domestic CO2 gas emission in Japan (FY2011),[1] it is an urgent issue for steel industries to develop environmental-friendly ironmaking and steelmaking process and reduce CO2 emission. Various kinds of gases and by-products generated from ironmaking and steelmaking processes have been recycled as much as possible at present. Enormous thermal energy is also generated from processes and released to surrounding atmosphere as various forms such as sensible heats of gases, molten steels or by-products, and as heat losses. However, these energies are not utilized before final dissipation to atmosphere. Although various technologies to utilize thermal energy from ironmaking and steelmaking processes have been attempted to develop, practical application of these technologies has not been achieved because the thermal energy is not always useful as an energy source. In steelmaking process by BOF, fluxing agent such as CaO is added during reefing and thus about 100 kg/t-steel of steelmaking slag are generated. Since the steelmaking slag is discharged at temperature range between 1873 and 1923 K after discharge of refined molten steel, it also has large thermal energy. Amount of generated BOF slag is 11.0 Mt/y (FY2012) in Japan.[2] Assuming the amount of steelmaking slag is 10 Mt/y and its average heat capacity from room temperature to 1923 K is 1 kJ/kg·K,[3] unutilized heat is estimated to be 16 PJ/y, which is equal to annual energy consumption of 420 thousand families in Japan.[4]"

Jan 1, 2014

By Raymond F. Dalton

Despite the ready availability of numerous zinc sources, the process of solvent extraction- electrowinning (SX-EW) has as yet found little favour in the zinc industry. It is suggested that this is largely due to the previous lack of availability of suitable selective reagents having the particular features required to enable them to fit in to a solvent extraction-electrowinning based process for zinc, particularly with regard to strength and selectivity for zinc over iron. This paper describes work on the development of new selective extractants for the recovery of zinc from both sulfate and chloride aqueous solutions and suggests how they might be integrated into new zinc processes.

Jan 1, 1994

By W. G. Davenport

The offgas from flash furnaces inadvertently contains dust. The dust contains 25 to 30% Cu so it must be treated for Cu recovery. This is almost always done by recycling it back through the flash furnace*. This chapter shows how dust production/recycle is included in our matrix calculations. It then discusses the effects of dust production/recycle on flash furnace industrial oxygen and oil requirements. It concludes that re-smelting of dust requires considerable industrial oxygen and fuel, so that dust production should be minimized. Recycled dust also takes the place of new concentrate in the flash furnace feed system, decreasing Smelter productivity -another reason to minimize dust production. Compositions of industrial dusts are given in Appendix VII and Table 18.3. Industrial quantities are given in Tables 2.1, 3.1, 19.1,20.1' and Appendix VI.

Jan 1, 2001

By C. Hennesmann, D. Maijer, S. L. Cockcroft, P. Yo

"Die cast aluminum wheels are one of the most difficult automotive castings to produce because of stringent cast surface and internal quality requirements. As part of a collaborative research agreement between researchers at the University of British Columbia and Canadian Auto Parts Toyota Incorporated, work has been underway to predict heat transport and porosity formation in die cast A356 wheels. The basic heat transfer equations have been solved using the commercial finite element package ABAQUS to which specialized routines have been added to predict porosity. Preliminary work on predicting porosity formation focused on using the Niyama parameter as a measure of the probability of porosity. The latest version of the model incorporates a new fundamentally based porosity criterion, which takes into account the effect of hydrogen concentration. The development of this model together with its application to a series of cylindrical test castings as well as a production cast wheel are presented.I. IntroductionDie cast aluminum wheels are one of the most difficult automotive castings to produce because of stringent cast surface and internal quality requirements. Microporosity, in particular, is a common defect that can adversely affect wheel quality. The mechanism of microporosity formation in aluminum alloys is complex owing to its dependence on the interaction of a number of phenomena occurring during solidification including the decrease in hydrogen solubility, the decrease in volume, the development of the solidification structure, and the increase in difficulty in interdendritic feeding [1]. As a result, the amount, size, and distribution of microporosity is affected by a large number of casting parameters including thermal variables, melt composition, grain structure, modification, and inclusion content, making optimization by trial-and-error methodologies difficult.The use of criteria functions, based on thermal conditions during casting, offers a relatively simple approach to predicting microporosity. In practical terms, they are useful because they provide a straightforward method of assessing the impact of varying casting parameters on porosity through various thermal parametersl21 such as thermal gradient, cooling rate, solidification time, and solidus velocity. Drawbacks of criteria functions include insensitivity to varying hydrogen concentration and the limitation to qualitative predictions. Consequently, in aluminum alloys, attempts have been made to develop models incorporating the effects of hydrogen gas and microstructure evolution. However, these types of models represent a significant increase in complexity and sacrifice the simplicity and ease of application of the thermally based criteria functions."

Jan 1, 2001

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By C. E. Abbey

Cobalt, iron and manganese play various roles in copper electrowinning using lead–calcium–tin alloyed anodes. Cobalt catalyzes electrochemical water decomposition resulting in lower anode potential and reduced corrosion rates. Iron reduces cathodic current efficiency, but is used to reduce higher oxidation states of manganese that oxidize organics in solvent extraction. Manganese also produces anode scale and is generally considered a problematic impurity. The effect of the combined interaction of these three metal ions on the anode potential has not been quantified yet. The current work used a three factor, two level, three replicate central composite design of experiments to analyze the effects and potential interactions among cobalt, iron and manganese. The experiments consisted of chronopotentiometric analysis to assess anode potential after 24 h of operation. Higher [Co], lower [Mn] and either high or low [Fe] yielded lower anode potentials. Two regression models were developed to predict anode potential as a function of [Co], [Fe] and [Mn]. A method to estimate electrical energy consumption for copper electrowinning is also presented.

By Kelly J. Driscoll

Impure zinc (98.5%) was electrorefined to high purity zinc (99.995%) using a fused salt electrolyte of molar composition 1: 1 : 1 :2 ZnCI2:KCl:NaCl:LiCl with a current efficiency of about 90% at 723 K. A recessed channel electrorefining cell was developed which achieved excellent mixing of both the metal and the electrolyte and by ensuring a very small anode to cathode spacing the voltage drop across the cell was 0.16 V and at a current density of 7kA m-2. The physical characteristics of the cell were observed using a low temperature model which showed the formation of droplets and rivulets which provided mixing. The application of this approach to the refining of other non-ferrous metals is discussed.

Jan 1, 1992

By V. Yahorava

Mintek has developed a non-destructive Resin-in-Leach method for the recovery of Rare Earth Elements (REE) from phosphogypsum (PG) waste dumps. However, PG from different sources was found to be highly variable in terms of REE recovery and physical properties. Development of a pre-treatment process was initiated to improve the robustness of the current REE recovery process in order to render it effective for any type of PG. Extensive research into the mineralogy of REE associations with PG revealed that the majority of REE are trapped inside phosphogypsum clusters which inhibits their recovery. Hydrothermal treatment of PG-containing slurry was found to result in re-crystallisation of gypsum with the release of REE phases encapsulated in it. This process was tested on various PG samples and subsequent REE recoveries improved from 5 to 80%. This approach carries a large potential for unlocking value associated with gypsum dumps worldwide.

By B. Manana

In heap leaching, the oxidative dissolution of value minerals encapsulated deep within large particles cannot be fully understood on the basis of the bulk solution conditions relative to variable solution conditions near the mineral surface. In the present study, the diffusion of the oxidising species through inner particle pores is simulated in a model apparatus that separates an inert platinum electrode under controlled reduction potential from the bulk solution through narrow pores of varying length. The Cu-NH3 system was selected as a model system and Cu(II)/Cu (I) as the redox couple of interest. Platinum probes inserted in the pores allowed the measurement of varying redox potentials along the pore length. Results showed that in a 10 mm pore, there exists a narrow (0.5 mm) zone near the reduction surface that is depleted of the oxidant and in which its supply is strongly diffusion limited, even if it is in abundance in the bulk solution. The consistent presence of this narrow diffusion region across all experimental results indicated that the transportation of the reduced species away from the reaction surface had the most significant influence on the potential variations within the pore. This was further supported by the minimal effect of varying concentrations of both Cu(II) and dissolved oxygen on the solution potential within this region.

By T. Feldmann

Despite the ubiquity of applications for germanium, there is a lack of practically useful solubility data in acidic solutions. Previous studies were done at ambient temperature and only for commonly used acids (H2SO4, HCl). Hence, an investigation of the solubility of GeO2 in different acids was undertaken. Several inorganic and organic acids were studied in the concentration range of 1–11 mol/L and at 23, 40, and 60 °C. In the case of H2SO4 and HCl previous data was confirmed. Lower acidity resulted in a higher solubility for Ge at all tested temperatures. Tests done at 40 and 60 °C and low to moderate acidity levels, gave slightly increased solubility values at higher temperatures compared to 23 °C. This wasn’t the case at higher acidity levels, i.e., the solubility curves at different temperatures converge at high acidity. Lastly, a relationship of water activity and GeO2 solubility in different acid media was established.

By Heikki K. Jalkanen

Thermodynamic properties of copper-iron mattes and slag-matte distribution of copper and some minor matte constituents (Ni, Co, Mo, As, Sb and Bi) are discussed on? the basis of equilibrium measurements: a change from. oxidic to sulfidic solubility as the predominant form of dissolution of copper takes place as matte grade decreases. Distribution coefficients of minor matte constituents are complex functions of sulfur and/or oxygen potentials?. The distribution behaviour of different? metals can be qualitatively derived from their affinities to copper and stabilities. of their sulfides and oxides. The equilibrium results are compared with commercially observed values. from Outokumpu.Oy flash smelting furnace.

Jan 1, 1983

By John A. Clark, Danylo Oryshchyn, Casey Carney, Stephen Gerdemann, Cathy Summers, Thomas Ochs

"Limited analysis of combustion gas streams where carbon capture is not of interest is done mainly to ascertain operation parameters. Stringent regulations on acid gases and particulates promote careful flue gas analysis. Unregulated components are typically not analyzed. Typically not more than four points (two in the boiler, and one each in the flue and the stack) are sampled. A successful oxy-fuel process with carbon capture and compression is anticipated to require as many as 12 sample points with analysis for water, nitrogen, oxygen, argon, NOx, SOx, and carbon monoxide. Carbon dioxide captured for beverages produces a high value product and the cost associated with analysis is warranted. However, carbon capture for disposal must keep all costs to a minimum. This paper will compare alternative approaches for cost-effective sampling and analysis of the carbon dioxide product streams from oxy-fuel combustion, through all stages of production through compression and pipeline/vessel delivery.IntroductionAnalysis of gases in an oxy-combustion process with carbon capture is essential to the operations of the oxy-fired boiler and the subsequent collection, compression, and purification of carbon dioxide. The process is charged with pure oxygen and not-so-pure carbon in the form of coal at the front end, generating a product of mainly carbon dioxide with traces of argon, nitrogen, sulfur compounds, nitrogen compounds, oxygen, hydrogen, and mercury. It is possible that hydrogen chloride and hydrogen sulfide may also be present in trace amounts [1]. The trace components primarily come from impurities contained in coal such as water, sulfur, nitrogen, and volatile organic compounds. Coal also contains a good deal of mineral matter that is transformed into ash during combustion, becoming particulates that can complicate the analysis regimes utilizing standard analytical equipment."

Jan 1, 2010

By Jan Smit

Sulphidic copper concentrates are generally processed by pyrometallurgical means; while oxidative pressure leach processing of such materials has been shown to be technically feasible, there has traditionally been little incentive to choose this route in favour of a smelting option. However, for concentrates with elevated arsenic levels, oxidative pressure leaching offers distinct advantages, as smelter air emission standards and restrictions on concentrate importation have tightened. The current state of pressure leach technology allows for high copper extractions from arsenical copper concentrates, while producing an environmentally stable process residue, without atmospheric emissions of sulphur dioxide or arsenic. In its studies on pressure leaching of copper concentrates, Sherritt has shown that arsenical feed materials can be converted into environmentally stable residues, with excellent copper extractions. The results of recent batch and pilot plant test work are discussed, including the deportments of copper, arsenic and precious metals.