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By D. M. Muir

Thiosulfate offers a non-toxic alternative to cyanide for processing gold ores. The mechanism of leaching gold using ammoniacal thiosulfate solution is driven by the Cu(II)-Cu(I) redox couple and is complicated by competing ligands such as NH3 and S2O32-. It is shown that an understanding of the copper speciation and sulfur speciation is required to optimise this system. This paper presents Eh-pH and speciation diagrams for varying concentrations of Cu(II), S2O32- and NH3 and discusses the conditions under which various copper and sulfur species are stable.

Jan 1, 2001

By O. Alonso-Gonzalez, F. Nava-Alonso, A. Uribe-Salas, C. Jimenez-Velasco

"Most of the gold produced worldwide is still obtained by cyanidation, in spite of the difficulties encountered in the processing of some gold ores such as the dissolution of copper-bearing minerals in cyanide solutions. The leached copper forms complexes with cyanide and causes several operating problems, which have led to the development of copper removal/recovery processes, among them the industrially accepted SART process (sulfidization, acidification, recycling and thickening). Although the SART process is in use in gold production plants around the world, new challenges are appearing with the continuous varying of the mineralogy of ores (such as higher copper grades, changing the solution composition and complexity). The optimal SART operating conditions for a specific solution are not the same when the composition of the solution changes; consequently, the efficiency of this process can decrease.The present study is a thermodynamic approach, corroborated by laboratory experiments, to explain how the main variables of the process affect the efficiency of copper precipitation as cuprous sulfide (Cu2S). The variables considered were pH value, copper concentration, cyanide/copper molar ratio and sulfur/copper molar ratio, all of which werevaried within the limits encountered in typical cyanidation solutions presenting the problem of copper.It was found that the variable that most affects the efficiency of the process was the pH value, since poor or no control of it can cause cuprous sulfide redissolution. The S/Cu molar ratio is also important: raising this ratio increases copper removal, but high ratios will also cause sulfide and cyanide losses. The effect of changing the CN/Cu molar ratio was negligible between 4 and 8. For a solution containing 300 mg/L copper and 490 mg/L cyanide, copper removal as high as 98.8% can be obtained with the addition of 0.6 moles of sulfide per mole of copper at pH = 6.IntroductionThe main process for gold production is cyanidation, because it is the most economical and efficient process so far. Precious-metal leaching occurs when the ore is placed in contact with a dilute alkaline cyanide solution. The dissociation of cyanide salts provides free cyanide ions, which allow the formation of the aurocyanide complex Au(CN)2 -. This complex can be retrieved from the solution by adsorption on activated carbon or by zinc precipitation. Although the use of cyanide represents an issue to health and the environment, there are technologies for its management and treatment that can be easily applied. Furthermore, it is a low-cost process compared with other methods that are available or under development."

Jan 1, 2015

By RIINA SALMIMIES, Paula Vehmaanperä, Antti Häkkinen

The dissolution of iron oxides in mixtures of acids is fairly uncommon but can result in a more efficient dissolution process. The objective in this work was to investigate the dissolution of synthetic hematite powder in mixtures of oxalic and sulfuric acid. Experiments were done at different acid ratios and temperatures. An increase in temperature from 15 to 35 °C increased solubility, whereas an increase from 35 to 50 °C did not change the solubility but had a profound effect on the kinetics. An important finding was that oxalic acid advanced the dissolution process since increasing the amount of oxalic acid in the system resulted in faster kinetics and higher solubilities. The dissolution kinetics were well described with the Kabai model, which was the only studied model able to describe the whole reaction time. However, the solid specific constant a varied for the different acid ratios and this is argued to be a result of changes in the solid phase. The changes in the constant a were not in line with the original study of Kabai, which indicates that a cannot be the solid specific constant but it can be the constant connected to dissolving media describing the changes in the dissolution mechanism.

Sep 23, 2020

By RIINA SALMIMIES, ANTTI HAKKINEN, PAULA VEHMAANPERA

Better understanding of the mechanisms and kinetics of dissolution can benefit several industrial processes. For example, iron can be leached from clays, which can be further used as a raw material in the ceramic industry. Another important application is the regeneration of ceramic filter media, which are used in the dewatering of iron ores. Dissolution of iron oxides in mixtures of acids is fairly uncommon and a less well-understood phenomenon, but it can result in a more efficient process. This work also shows that the determination of dissolution mechanisms and kinetics is not straightforward in different acid systems.

By Víctor Vázquez, Guillermo Tiburcio, Martin Encinas, Jesús L. Valenzuela, Erick Montaño, Alejandro Valenzuela, José Parga

Merrill-Crowe is the primary process used for the concentration and purification of silver in a cyanide solution. The Langmuir Adsorption model for silver recovery in a cyanide solution was used for the study. The maximum adsorption capacity was 6.19 mmol/g for silver. This model properly adjusts the experimental results of the adsorption equilibrium with high correlation coefficients, which also favors the formation of a single layer of molecules adsorbed for the silver in the electrocoagulation- generated species. The thermodynamic parameters ΔG, ΔH, and ΔS were estimated, and it was found that the adsorption process is exothermic and spontaneous. For the kinetic study, the Lagergren second-order equation was used to study the adsorption speed. To characterize the solids coming from the electrocoagulation, X-ray diffraction (XRD), and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX) were used; the results of this study suggest that silver is present in aluminite, hydroniumjarosite, and alunogen.

Oct 30, 2021

The present study refers to passive systems for the treatment of acidic liquid effluents emanating from mixed-sulphide mines by means of an-aerobic compost wetlands. An effort was made for the thermodynamic study of the chemical systems that are involved in the reactions during the simulation of this specific system using laboratory columns and a pilot scale application. The substrate used was a mixture of cow manure, a high alkalinity organic substrate and chestnut woodchips, while the synthetic solutions prepared for the laboratory experiments contained the three basic metal contaminants i.e. Fe, Zn and Mn. The precipitation mechanism of the contained metals and the form in which these are precipitated was therefore investigated by constructing the equilibrium phase diagrams (Eh-pH diagrams) of the Me-S-C-H2O systems. Based on the experimental results from laboratory and pilot scale tests the stability conditions of the chemical species taking part in the aqueous solutions were also determined and verified with the thermodynamic data available. The thermodynamic analysis of the system was performed for ambient temperature, which is the prevailing temperature on field constructed compost wetlands. Results were further validated with the results obtained by the application of a five step sequential extraction procedure in the remaining substrate in order to determine the form in which the metals were precipitated.

Jan 1, 2006

By P. Piga, O. Sammarco

There is a markedly increasing tendency to design deeper and deeper mines, to use larger amounts of explosive per round, to increase the advance rate of the excavations and so the natural ventilation tends to be more intense in the new mines. For this reason, the mines that make use of powerful mechanical ventilation should also take into account such factors as natural ventilation pressures, especially in the case of mines excavated in high-temperature rocks for which natural ventilation is particularly intense. The results of the studies reported here refer to a very hot mine excavated in an area with a high geothermal flow (the Boccheggiano - Campiano mine, southern Tuscany). At various external temperatures, experimental measurements and analyses have been made of the trend of the thermodynamic characteristics of the ventilation air and of the trends of the air/rock heat exchange along the downcast shaft and along the upcast shaft. These data were then used to work out approximate values of the corresponding natural ventilation pressures. After having identified the most conspicuous variations of the thermodynamic parameters of the ventilation air and the factors causing them, an assessment was made of the repercussions they have on the air flow rates and, above all, on the climatic conditions of the underground excavation sites. The natural ventilation pressures were found not to be constant in time; indeed they change continously and it is difficult to predict the changes. Moreover, it was found that their influence on the ventilation of a section of the mine network is greater if the effect of mechanical ventilation on that section is weaker. In the mine section where the measurements were carried out, some portions were found where the ventilation could become insufficient as a result of the effects of natural ventilation pressures. Finally, some guidelines to be followed in designing hot mines have been put forward which ensure efficient ventilation throughout the network at times with the aid of the natural ventilation pressures, which in certain circumstances may reach very high values in mines of this type.

Jan 1, 1987

By A. D. Davis

Limestone-based material is effective for reducing arsenic concentrations below the current limit of 10 parts per billion for drinking water, typically resulting in final concentrations of about 4 to 6 ppb. However, in laboratory and field testing, further reductions to the 1 ppb range are difficult to achieve with limestone unless other material such as iron is added. The removal mechanism with untreated limestone appears to be the formation of a low-solubility precipitate of hydrated calcium arsenate, in the form of arsenate-apatite. Likely reactions and thermodynamic data indicate a theoretical removal limit of about 2 to 4 ppb for arsenic using raw limestone. Limestone also can reduce concentrations of cadmium and lead below 1 ppb in water, resulting in >99% removal efficiency. Thermodynamic constraints appear to be favorable for reactions involving the formation of otavite during cadmium removal and the formation of hydrocerussite during lead removal.

Feb 27, 2013

By P. C. O. Chukabarah

Atkinson's resistance square law is the cornerstone equation for traditional expression of energy losses in mine ventilation engineering. But the nomenclature for the various forms of energy losses are often confused for one another, misapplied or misinterpreted. These forms of energy were re-examined from thermodynamic and fluid-dynamic perspectives. Resultant expressions showed that both incompressible and compressible flow regimes in underground mines can easily be accommodated. Given the well-known three major energy forms, which are equivalent to one another but numerically unequal, corresponding equations to Atkinson's (pressure loss) for headloss and workloss were derived. The thermodynamic weight relational resistance ([w] s2/m5) associated with energy per unit weight (headloss) was dimensionalized for the first time. Also, normalized Atkinson-like equations for headlosses and worklosses were derived to ease direct computations in mine ventilation practice.

Jan 1, 1995

By C. A. Young, J. D. Miller

Thermodynamic data has been obtained for oleate chemisorption at fluorite (CaF2) and calcite (CaCO3) surfaces using adsorption isotherms determined previously at room and elevated temperatures by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS). Linear regression analysis was used to statistically derive free energy data as a function of temperature assuming oleate chemisorption followed Langmuir-type adsorption. Enthalpy and entropy changes were subsequently ascertained from the Clausius-Clapeyron equation and fundamental thermodynamic relationships. Essentially, no difference in the free energy of chemisorption at the two mineral surfaces was found; however, the differences in enthalpy and entropy values were significant. By comparison, the results showed that oleate chemisorption at fluorite surfaces was more extensive and more entropically driven due to more water being displaced. Results correlate well with values determined in the literature for other mineral collector systems. These findings help explain the greater hydrophobic character of fluorite than calcite in both the absence and presence of oleate.

Jan 1, 2002

By H. Arima, T. Fujita, W. Yen

The copper catalyzed gold oxidation and reduction mechanisms in ammonium thiosulfate solution were investigated by Eh-pH diagram based on the optimum reagent combination for 60 mass% -75 µm silicate ore at 16g/t Au with the maximum gold extraction of 92% and the minimum ammonium thiosulfate consumption of 23 kg/t-ore for 24 hour’s leaching at ambient temperature. The gold recovery by cementation was nearly 100% by Zn and Al powders at Metal/Au mass ratio of 30, and around 95% by Cu powder at Cu/Au+ mass ratio of 50. In order to oxidize the gold efficiently with the less thiosulfate consumption, the stable region of [Cu(NH3)4]2+ should be as wide as possible in the region, where [Cu(S2O3)2]3- was more stable than [Cu(NH3)2]+. In order to reduce gold from the pregnant solution with the less metal powder’s (Zn, Cu, Al) consumption, the stable region of [Cu(S2O3)2]3- should be wider than [Cu(NH3)2]+ on copper precipitation. Zinc powder may recover gold more efficiently than copper powder with the similar trend on the effect of ammonia, copper and thiosulfate. However, the large amount of copper will be co-precipitated along with gold since the stability of zinc ammine and thiosulfate complexes are higher than that of copper’s. Aluminium may reduce gold efficiently at higher thiosulfate concentration and pH. These results were confirmed and compared with the optimum reagent combination for finer grind sample at 100 mass% -75 µm, which is the optimum ore size for the standard cyanidation at 1.0 g/ l NaCN to obtain about 95% gold extraction. The optimum reagent combination was concluded as 0.5 mol/l NH4OH, 0.0001 mol/l CuSO4*5H2O and 0.05 mol/l (NH4)2S2O3 with the result of 94% gold extraction and 3kg/t-ore of ammonium thiosulfate consumption. Gold and copper stabilities were well agreed with the result of coarser grind ore thermodynamically. The lower reagent combination will reduce gold oxidation power, but significantly minimize the reagent consumption. From this pregnant solution, nearly 100% of gold was successfully recovered by zinc precipitation at Zn/Au+ mass ratio of 30. Aluminium and copper precipitations resulted in less than 40% of gold recovery at Metal/Gold mass ratio of 30. The reagent consumption cost on this lower reagent combination followed by zinc precipitation was $1.6/t-ore, while the cyanidation was $3.1/t-ore. Thiosulfate oxidation mechanism indicated the similarity to Belousov-Zhabotinsky reaction.

Jan 1, 2002

By Tuncel M. Yegulalp, Anuta Belova

This paper expands on the ZECA (Zero Emission Coal Alliance) technology, which is aimed at making coal a sustainable source of clean energy in the near future. The technology proposed immediate capture of carbon dioxide and other pollutants upon generation, thus alleviating their negative effects in the Earth’s atmosphere. ZECA proposes using chemical energy of coal to produce hydrogen; the latter is then used to produce electricity via fuel cells or Hyrogen-Oxygen turbines. In this study, a chemical engineering package, AspenPlus 12.1, is used to simulate the reactor (reformer) in which hydrogen is produced from methane water and lime as part of the zero emission power plant. Thermodynamic conditions, pressure and temperature, are optimized with respect to molar hydrogen production. Under the proposed conditions, molar conversion efficiency, carbon to hydrogen, of 95% is achieved. Further studies are required to model the complete power plant and to optimize it for efficiency.

Jan 1, 2005

By A. J. Monhemius, R. G. Reddy, G. W. Warren, E. Peters

Thermodynamic solubility of chromium in pickling solutions (i.e., HF- HN03-H2O solutions) was determined as a function of HF and HNO3 acid concentrations at 298K. Pure Cr, AISI type 316 and 416 stainless steel were used in this study. The results showed that the solubility of Cr increased with increase in the concentrations of HF and HNO3 acids in solutions. The solubility of Cr increased in the order of pure Cr > 416 SS > 316 SS. The theoretically calculated Cr solubility data were in reasonable agreement with the experimental data.

Jan 1, 1993

By P. M. May, J. S. Solis, G. T. Hefter

Chemical speciation plays a critical role in many areas of gold processing. These include the formation of HCN in plant liquors, interference by copper in the extraction efficiency of gold, the recovery of adsorbed gold, and the behaviour of plant effluents in the environment. Thermodynamic modelling provides a cost-efficient method of rationalizing and even predicting of chemical behaviour. Unfortunately, because thermodynamic data for cyanide complexes are of poor quality and few are known under hydrometallurgical conditions. Such models are currently of limited use. This paper describes recent work on the thermodynamics of cyanide complexes of a range of metal ions. Data will be presented on the stabilities and enthal­pies (heats) and entropies of formation of a variety of metal ion species determined by potentiometry and calorimetry. Particular emphasis will be placed on the Cu(I)/CN- system.

Jan 1, 1995

By Shahab Alizadeh, Ahmad Khodadadi Darban, Mehdi Mohseni, Mahmoud Abdollahy

This study probed the selective separation of lanthanum and yttrium in a nitrate medium in the presence of aluminum and calcium impurities using di-(2-ethylhexyl) phosphoric acid (D2EHPA). The factors studied in a central composite design (CCD) included extractant concentration, pH, concentration ratio of total impurities to rare earth elements, and interaction of these three factors. The extraction mechanism and types of extracted metal-containing species were delineated by the slope analysis method. The obtained thermodynamic data showed that lanthanum and yttrium extraction by the D2EHPA extractant was exothermic. The extraction of both rare earth elements was accompanied by an entropy reduction. The negative magnitude of ΔS in yttrium extraction reaction suggests stronger D2EHPA-Y(III) complexation relative to La(III). As entropy decreased and enthalpy increased, the extraction process became unspontaneous. Using the proposed flowsheet, lanthanum and yttrium products with > 90% purity were obtained.

Aug 10, 2021

By C. Basilio

Thermodynamic calculations based on a rigorous mass balance technique have been carried out for the chalcocite-potassium ethyl xanthate (KEX) system. The results of the calculations are used to: i) construct Eh-pH diagrams for KEX additions ranging from 0 to 10-4 M, ii) determine the amounts of cupric ions and copper xanthate formed at different Eh and pH values to make three-dimensional diagrams, and iii) determine the minimum KEX addition required to form CuX and CuX2.. This allows prediction of the optimum conditions for flotation and comparison of this with microflotation test data. In addition, voltammetry experiments have been conducted on chalcocite electrodes at pH 9.2 and pH 6.8 in order to gain information on the role of metastable species in flotation. On the basis of these experiments, possible reaction mechanisms are discussed and comparisons are made with what is expected on the basis of thermodynamics.

Jan 1, 1985

By T. Yegulalp, R. Farrauto, A. Belova, M. Castaldi

Calcium oxide, with its ability to capture and store carbon dioxide, is emerging to become an important tool in carbon management. Calcium oxide can be used reversibly to capture carbon dioxide in situ and then be regenerated to produce a pure stream of carbon dioxide ready for sequestration; the Zero Emission Coal Alliance technology utilizes this property of calcium oxide to generate emissions-free electric power from coal. The reaction of calcium oxide with carbon dioxide resulting in thermodynamically stable carbonate is well understood; however, the efficiency of this reaction is limited by the diffusion of gases through bulk calcium oxide and through a layer of carbonate formed on the surface. In addition, the regeneration of calcium oxide is an endothermic reaction and is favored at high temperatures. The purpose of this paper is twofold: first, to address the diffusion limitation, a thin layer of calcium oxide, supported on a high surface area material, is studied thermogravimetrically to demonstrate the physical adsorption of carbon dioxide on calcium oxide. The adsorption is to take place at temperatures lower than required to form calcium carbonate.

Jan 1, 2007

By Paul F. Gnirk, Ralph A. Wagner, Joe L. Ratigan

This thermomechanical analysis used the finite element method to investigate the behavior of crushed salt backfill in a waste disposal room situated in a salt dome repository. The first of two objectives was to determine the transient temperature rise and degree of thermomechanical consolidation that occur in the backfill as a function of drillhole depths. The second objective involved the evaluation of closure due to salt creep of unlined emplacement drillholes and the determination of pressure on steel sleeve liners in the drillholes should liners become necessary for canister retrieval. The retrievability period was considered to extend for 25 years after waste emplacement. The canisters were assumed to contain ten-year old high level waste with a thermal output of 4.3 kW at the time of emplacement.

Jan 1, 1981

By W. C. Patrick

The Spent Fuel Test-Climax (SFT-C) was con- ducted to evaluate the feasibility of retrievable deep geologic storage of commercially generated spent nuclear-reactor fuel assemblies. One of the primary aspects of the test was to measure the thermomechanical response of the rock mass to the extensive heating of a large volume of rock. Instrumentation was emplaced to measure stress changes, relative motion of the rock mass, and tunnel closures during three year of heating from thermally decaying heat sources, followed by a six month cooldown period. The calculations reported here were performed using the best available input parameters, thermal and mechanical properties, and power levels which were directly measured or inferred from measurements made during the test. This report documents the results of these calculations and compares the results with selected measurements made during heating and cooling of the SFT-C.

Jan 1, 1986

A thermomechanistic model was developed for the thermal decomposition of the enargite contained in a copper concentrate at 650° to 750°C in a fluidized bed with an inert atmosphere. At the particle level, the model permits one to predict the thermal profile inside the reacting enargite particles, as well as their thermal cycle. At the macroscopic level, a population-based model coupled to the bubbling-bed fluidized bed model allows one to predict the fractional conversion (dearsenification) of an enargite-bearing copper concentrate.

Jan 1, 2002