Search Documents

By Donald O. Voit

A BASIC language program has been written that simulates the performance of an integrated solvent extraction circuit consisting of an extractor, a reflux fed scrubber, and a stripper. The program is designed to simulate the performance of a circuit having an aqueous feed containing each of the lanthanides as well as yttrium. The Kremser equation is used to determine the separation occuring in each section of the circuit. The required input variables are the feed composition, the separation factors, the light key extraction factors and extractor feed zone distribution coefficient, the number of stages, and the reflux ratios. The program calculates the composition of the streams at each node in the circuit, the total loading, and the remaining distribution coefficients. User interaction with the program is essential. The program has no capability to determine if the calculated values are consistent with various real restraints. Knowledge of the physical, chemical, and equilibrium behavior is essential to successfully utilize the program. The number of iterations required to achieve steady-state provides insight to the circuit response times. With suitable supervision the program can be used as a simulator for operator training.

Jan 1, 1989

Iron, chloride and manganese are the three major impurities transferred to copper electrowinning tankhouses via chemical and/or physical entrainment. The control of these impurities via bleeding of tankhouse electrolyte is costly. Recently, Eichrom Industries have developed an improved iron control process and tested this process in a pilot study at the Girilambone Copper Company (GCC). The patented process utilizes a fixed bed ion exchange reactor filled with Eichrom's Diphonix® resin. Iron is loaded on the resin and subsequently eluted by a cuprous sulfate eluant. The control of chloride and manganese has been studied using different chemical techniques. The removal of chloride from electrowinning electrolytes was tested using precipitation of chloride as cuprous chloride. Copper wire cuttings are used to produce cuprous ions. Chloride levels are reduced to around 30 ppm in electrolyte at 40°C. The removal of manganese using a precipitation process practiced in zinc electrowinning purification has been tested for implementation. The process involves reacting manganous ions in solution with permanganate ions. The reaction produces an insoluble manganese dioxide reaction product. The bench scale and pilot plant results from testing of these purification processes are reported.

Jan 1, 1999

By Christopher Solnordal

A mathematical model was developed to simulate the performance of the reaction shaft at BHP-Billiton?s Olympic Dam copper flash smelter. In order to have confidence in the predictions of the mathematical model, validation was performed by comparing and reconciling the predictions from the model with the results from a campaign of sampling and plant measurements. The model was based on the computational code CFX4.4 utilizing a combustion sub-model purpose-built by CSIRO. The combustion sub-model employed the concept of a composite particle which contained the three components of the solid charge: concentrate, flux and returned dust. Plant measurements were made and samples taken immediately below the burner and through a port halfway down the reaction shaft. Parameters measured included temperature, solid loading and SO2 concentration in the gas. Comparison of the measured and predicted values then showed that: predicted far field gas temperatures were within ±50C of measured values; predicted temperatures in the central plume were lower than measured, and, the predicted plume width was slightly smaller than measured. An optimum composite particle size of 19 m was identified for use in future modeling work at Olympic Dam.

Jan 1, 2006

By Ron H. Schonewille

Experiments were conducted by injecting air-oxygen gas mixtures through a ceramic lance into molten copper matte and measuring the sulphur dioxide content of the offgas. The injection conditions were characterized by measuring pressure fluctuations immediately upstream of the lance and capturing the information on an oscilloscope screen. The parameters investigated were gas flowrate, lance geometry, lance immersion, orifice diameter and melt composition. An overhead nitrogen lance was used in specific tests to create an inert gas blanket directly above the bath surface to inhibit reaction in this region. The extent of oxidation was modeled by separating the gas-liquid contact into three stages; bubble growth, bubble rise and bubble rupture. The contribution of each stage to oxygen utilization was determined by varying the lance immersion and by performing tests both with and without an inert gas blanket. Bubble rise was found to be relatively unimportant, accounting for less than 5% of the total oxygen utilization. Bubble rupture and bubble growth were found to contribute approximately equally, with bubble rupture becoming more important with increasing gas flow rate. This study highlights the importance of reactions taking place above the bath surface in a copper converter.

Jan 1, 1999

By Leonard J. Friedman

The contact process for the production of sulfuric acid has been used commercially since before the turn of the century (1880?s), and rapidly replaced the chamber process after the development of vanadium catalysts in the early 1900's (1910's - 1920's). Plant size has increased from a few tons per week to single train units in excess of 4,000 tons per day. Much of the history of the contact process is in the minds of the few remaining early process pioneers that started in the industry in the 1920's and 1930?s, and in sulfuric acid industry books published in 1921, 1925, 1936, and the last Deucker and West in 1959. Since those not familiar with history are doomed to repeat the failures and mistakes of the past, this paper includes a brief history of the contact process along with the history and development of equipment and materials in each equipment area of the process. The main focus of the paper is to present the development and analysis of equipment and materials in the contact section of the sulfuric acid plant - from the dry tower to stack.

Jan 1, 1999

By Hidekazu Nakagawa

We investigated the anodic dissolution behavior of titanium in TMHA-Tf2N molten salt, which has a wide electrochemical window of about 5 V, in order to develop an electrodeposition method for titanium. By etching a titanium electrode in HF?HNO3?H3PO4 solution, the titanium electrode became electrochemically active, and a redox reaction was observed at around -0.15 V vs. I-/I3- in (TMHA-Tf2N)?HTf2N solution. We identified the redox reaction consists of the reduction of the proton and the oxidation of hydrogen. The diffusion coefficient of the proton in TMHA-Tf2N was calculated to be 6.9 10-8 cm2 s-1 at 50 °C from the cathodic peak current in the cyclic voltammogram. Anodic decomposition of the molten salt was not observed up to 6.0 V vs. I-/I3- on titanium electrode, while it was observed at around 2.0 V vs. I-/I3- on platinum and glassy carbon electrodes. Cathodic decomposition of the molten salt was observed at around -3.0 V on the titanium electrode, as well as on the platinum and glassy carbon electrode.

Jan 1, 2006

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By L. L. Sutter

Fly ash is a by-product produced from the combustion of most hels including municipal solid waste. Currently, most combustion residuals are disposed of in landfills at a continually increasing cost and with questionable impact on the environment. Due to the presence of heavy metal compounds, municipal waste combustor (MWC) fly ash has the potential to leach these metals (e.g., lead and cadmium) above regulatory limits. The heterogeneous nature of MWC fly ash makes detailed characterization difficult. This research focuses on the identification of lead compounds in MWC fly ash. Samples obtained from the Olmsted Waste-to-Energy Facility in Rochester, Minnesota were examined in this study. The fly ash was fractionated into six size ranges and prepared as geological thin sections for analysis. The worked discussed in this paper involves using an electron microprobe analyzer to determine phase composition in MWC fly ash. In addition, backscattered electron imaging, digital image processing, and mineral liberation analysis software were used to determine phase distributions and phase associations as a function of particle size. Several lead containing compounds in several forms are identified. The results of this study show that lead can be identified in small sectioned particles which would not be apparent using normal backscattered electron imaging.

Jan 1, 1994

By Cody Burcher-Jones

The recovery of rare earth elements (REEs) through heap leach/in situ techniques from so-called ion adsorption clays (IACs) is attractive due to their inherent simplicity. However, the underlying mechanisms of these processes are poorly understood. In this study, the deportment of REEs in a typical IAC material has been investigated and was found to concentrate in the phyllo-layers of the clays, especially hallyosite, and was readily desorbed by various ion-exchange reagents indicating various potential routes to liberate them. Here we are reporting the use of seawater (0.5 M NaCl), spiked with various amounts of (NH4)2SO4, and found better extraction using a reagent mixture than NaCl on its own. Further, the leaching of REEs from a bed of clay material was investigated over time to understand the rate of transport through the stagnant material. Results indicate that REE release is likely to be controlled by diffusion through the clay material, while desorption in agitated systems is rapid. A degree of fractionation between different REEs can be observed during diffusion. Nonetheless, the successful operation of in situ leach operations for this type of material would depend primarily on how easily solution cocktails can be made to flow through the bed material.

By M. C. Ruiz

The conventional pyrometallurgical methods to treat copper sulfide concentrates include generally, one or more oxidizing steps where the formation of SO2 gas can not be prevented. From the economical point of view and the nature of some of the processes in which SO2 is produced, its complete capture is not feasible; therefore an important fraction is released to the atmosphere as fugitive emissions. In this research, the reduction of chalcocite was studied in the presence of lime as an alternative method, which overcomes the pollution problems related to SO2 emissions. The effect of temperature, time, concentration of carbon and CaO on the reduction rate were studied. Among these variables, temperature affects most the reduction rate. Conversions over 95 % can be obtained in less that 20 minutes at temperatures over 1000 ° C. The measured partial pressures of the gaseous components indicated that the chalcocite reduction proceeded through the gaseous intermediate species CO, C02, and the overall kinetics was controlled by the Boudouard reaction. The kinetic model In(1-X)= kt fits well the experimental data. Apparent activation energy of 3 14 kJ/mol was calculated for the temperature range of 900 0C-1050 °C.

Jan 1, 1999

By R. Padilla, M. C. Ruiz, L. Salinas

Chloridizing roasting of bismuthinite (Bi2S3) with NaCl–O2 has been studied to remove the impurity Bi by volatilization from copper concentrates that contain bismuthinite. The study was conducted using mixtures of Bi2S3 and NaCl in a horizontal furnace and TGA apparatus. The variables were temperature, oxygen partial pressure, and NaCl concentration. The chlorination was analyzed by weight loss measurement method. XRD results of calcines reacted for short times in 21% O2, and 850–1000 °C showed the presence of Bi, BiOCl, and Na2SO4, while at longer times in the same conditions, Bi2O3 was identified as a stable phase. Thus, the chloridizing-volatilization of Bi2S3 proceeds through the formation of Bi and BiOCl. Temperature affected significantly the fraction of weight loss of samples. At 600 and 900 °C in 10.3% oxygen, the maximum weight loss was 4 and 20%, respectively. An increment in the partial pressure of oxygen in the range 1–21% affected negatively the Bi2S3 conversion. At normal roasting temperatures (550–700 °C), bismuth volatilization by NaCl roasting was found to be marginal.

Mar 1, 2017

By Kosei Morita, Osamu Nakano, Katsuhiko Nagai, Kazuhiro Mori

"The Sumitomo Toyo Smelter and Refinery commenced its operation in 1971 with three Peirce- Smith (PS) converters. “2 hot – 1 blowing” operation was practiced, that is one of two available converters was blowing and the other was standby in a hot state while the third converter was under repair. After several improvements, the stack time ratio reached around 90%; and processing 5 batches a day became possible.As a result of the expansion program of the Toyo smelter and refinery that started in 2001, the converter operation pattern was shifted from “2 hot – 1 blowing” to “2 hot – 2 blowing” with the installation of second converter blowers and an additional ladle crane.In 2005 a, the fourth converter was installed and “3 hot – 2 blowing” operation began. Also, with improvements experienced in the anode furnaces and the anode-casting wheel operation, today, the number of cycles has been increased up to more than 8.5 a day.The treatment techniques of fugitive gas containing sulfur dioxide from converter furnaces have been gradually reinforced, and the fixation rate of treated sulfur is currently being maintained at more than 99.9%. This paper introduces the operations described above, and the improvements in environmental management techniques for the Toyo PS converter operation."

Jan 1, 2009

By Jorge Alberto Soares Tenório, Amilton Barbosa Botelho Jr, Denise Crocce Romano Espinosa, Mónica M. Jiménez Correa

Wastewater from nickel lateritic process still has valuable metals that could be recovered. Using an ion exchange to recovery these metals, the iron becomes a problem due to the fact that it precipitate at pH 2. The aim of this research was to make iron soluble by reducing Fe+3 to Fe+2. A synthetic solution was prepared with sulfate ferric. The reducing agent sodium dithionite was used and the potential was varied (initial potential: 700, 600, 500, 450 e 400 mV) using as a reference the Pourbaix diagram for iron created by HydroMedusa software. The pH was ranged between 0.5 and 2.5, the reducing agent’s concentration was 0.5 M and the reaction time ranged between 30 and 120 min at room temperature. The ferric iron and total iron concentration were verified using a spectrophotometer with 5-sulfosalicylic acid (SSA) to determine Fe(III) and ammonia to determine Fe(II) and Fe(III) in 500 and 425 nm, respectively. The results indicated that total reduction was at 400 mV in any pH between 0.5 and 2, but less than 40% in pH 2.5 at this potential value.

Mar 1, 2017

By Jeaneth S. Benedetto

The physical and chemical processes developed for recovery of uranium and phosphor from phosphoro-uraniferous ore bodies consists of three basic steps: concentration of the phosphate bearing uranium by flotation, chemical dissolution of the concentrate by wet phosphoric acid and extraction of uranium by solvent. In this process two products are obtained: 1) uranium and 2) phosphoric acid. The purpose of this work was to develop technological know-how of phosphoric acid purification though an extraction of P2O5 by solvents. It was investigated by two lines of research. In the first one the uranium was extracted before the phosphoric acid purification. In the second, the phosphoric acid was extracted before uranium recovery. The comparison of the two processes is shown in this paper. Experimental work was developed on a laboratory scale to select and optimize the process variables. After the laboratory study, the research of extraction and stripping was continued on a pilot scale in pulsed perforated-plate columns in order to investigate the main operational and process conditions. The first phosphoric acid extraction experiments showed good results using a raffinate sample obtained from the uranium extraction process. It was possible to obtain a high purity phosphoric acid.

Jan 1, 2003

By C. A. Morais

The present work describes the development of an efficient and relatively simple process to obtain high grade CeO2 from a mixed rare earth chloride solution. The process involves cerium oxidation and precipitation by addition of a KMnO4-NaCO3 solution. The experiments were carried out at room temperature (25 1° C). The results indicated that the major parameters affecting cerium recovery are the molar ratio of KMnO4/Ce, the initial acidity of the chloride feed solution and final pH of Ce(OH)4 precipitation. In strong acid solutions (pH < 1), the oxidation of Cl to Clo took place in addition to the oxidation of Ce(III) to Ce(IV), so increasing the permanganate consumption. Conversely, low acidity (pH >3) led to coprecipitation of the other rare earth elements. Under the selected conditions, cerium was selectively precipitated as ceric hydroxide, together with some manganese dioxide. Further purification was carried out by the dissolution of Ce(OH)4 in HCl, followed by precipitation as cerium carbonate. The filtrate was neutralised with a Na2CO3 solution in order to recover the associated rare earth elements for further separation. The final product, assaying 99.7 % CeO2, was obtained with a recovery of nearly 100%.

Jan 1, 2003

By Maria Cristina Ruiz

The removal of iron from the leaching circuits is a common problem in the hydrometallurgical processing of non ferrous metals. Among the currently available processes, hematite precipitation is the most recommendable from an environmental point of view. This paper is concerned with the batch precipitation of hematite from ferrous sulfate solutions. One of the main objectives of the study was to determine the effect of the experimental conditions on the extent of iron precipitation as well as the purity and the particle size distribution of the precipitates. The main variables studied were temperature (180 to 220 ºC), concentration of sulfuric acid (1 to 10 gpl), initial iron concentration (1 to 15 gpl) and partial pressure of oxygen (3 to 7 atm). The results showed that increasing the oxygen partial pressure from 3 to 7 atm produced a very small increase on the rate of hematite precipitation indicating that a large partial pressure of oxygen is not needed for an effective ferrous to ferric oxidation. An increase in the temperature produced finer precipitates with lower sulfur contents. On the other hand, an increase in sulfuric acid concentration and initial iron concentration produced precipitates with larger particle sizes and higher sulfur contents.

Jan 1, 2006

By Yoshio Waseda

A laser flash method has been applied to obtain the thermal diffusivity values of Zr55Al10Ni5Cu30 alloy in the liquid, glassy, crystallized and supercooled liquid states. The electrical resistivity of this particular alloy was measured in the glassy, and crystallized states by a direct current four probe technique. A specific heat of Zr55Al10Ni5Cu30 alloy was also determined by a differential scanning calorimeter in the glassy state. On the other hand, thermal diffusivity values for two alloys of Zr60Al15Ni25 and Zr65Al7.5Cu27.5 were measured in the crystallized and liquid states. The thermal diffusivity values of three Zr-based alloys in the liquid state are summarized in the linear equations with positive temperature dependency and it is noted that the lower the thermal diffusivity values of Zr-based alloys at liquidus temperature, the lower the critical cooling rate to obtain metallic glass phase becomes. The thermal diffusivity values of Zr-based alloys were compared with those of Pd-based alloy case. These results suggest that thermal diffusivity of alloy liquids might be an indicator of the glass-forming ability of Zr-based and Pd-based alloys.

Jan 1, 2006

By M. I. Zinigrad

A model of an ideal associated solution is presented. This model takes into account the existence of complexes of various compositions, sizes and geometries and allows calculating thermodynamic properties and phase diagrams of binary alloys. The model has been used formerly to calculate thermodynamic parameters and the position of the liquidus line for binary eutectic systems and also those having a stable compound in the solid phase. In all the cases the model parameters were not adjusted rather estimated from melting temperatures of the components. The recent studies dealt with the influence of arbitrary-stoichiometry associates on the equilibrium thermodynamic properties of liquid alloys. The application of the model to eutectic systems and systems having an unlimited solubility in solid and liquid states close to liquidus has been considered. It was shown that if the difference in melting temperatures of the components was small, different types of fusibility diagrams were possible: eutectic diagrams, cigar-shaped diagrams or diagrams with upper or lower azeotropic points. Peritectic transformations could take place when the difference in melting temperatures of the components was large. The present work is devoted to calculation of phase diagrams and thermodynamic properties of binary systems on the basis of chrome.

Jan 1, 2006

By E. J. Peuraniemi

Recently commissioned Kennecott-Outokumpu flash converting was developed to replace the approved but environmentally outdated Peirce-Smith -converting to satisfy the globally tightening emission regulations. In the present study, dust formation and reaction mechanisms of two copper mattes with different experimental parameters were studied in lean suspension conditions. Both mattes had very high copper content of approximately 75 wt% and low iron content of 4.5 wt% and 1.2 wt% Fe. A laboratory scale, vertical laminar-flow furnace with a low feeding rate was used to simulate the phenomena taking place in the reaction shaft of a flash converter. Experimental conditions included temperature of 1300 °C with reaction gas oxygen contents of 20 vol%, 50 vol%, and 75 vol%. In the experiments, sieved particle fractions were fed to the furnace and sampled after short reaction time intervals by quenching them into a water film. Collected particles were analysed chemically for their main elements to define their removal rates. Also, optical and scanning electron microscopy with EDS-analyser were applied to determine phenomena occurring during reactions. Kinetics of oxidation as well as ignition of particles are discussed. Changes in particle morphology, size, and composition are reviewed to describe dust formation and reaction mechanisms.

Jan 1, 1999

By T. Takasu

Overall productivity in copper refining is currently determined by the electrorefining process. Previous research showed that forced convection of the electrolyte improves the morphology of the copper deposit on the cathode and suppresses passivation of the anode. In this paper, electrorefining experiments under forced convection were carried out in the presence of As, Sb and Bi impurities, both in electrolyte and in the anode, to determine the effect of the impurities on the electrorefining process. The concentrations of the impurities in the deposit increased with increasing current density without forced convection. An increase in the fluid velocity suppressed the increase in impurity concentration. These concentrations were high, especially in the initial stage of deposition without forced convection, corresponding to a decrease in the cathode potential measured during that period. This indicates that the enrichment of impurities was induced electrochemically. The reason for the decrease in cathode potential was the low concentration of copper ions on the electrode surface because of ion consumption by the electrolysis. The forced convection of the electrolyte enhanced the ionic mass transfer and thus suppressed the polarization and deposition of the impurities. The fluid motion was shown to be effective in achieving electrolysis under high current density conditions.

Jan 1, 1999