Search Documents

By K. C. Li

ARSENIC and antimony are always grouped together by chemists, since they are both members of group V of the periodic table of elements and exhibit a general similarity in the formation of compounds. Metallurgists generally think of them as less closely related because they do not have similar uses. In metallurgical operations, especially lead and copper smelting, arsenic tends to go off as a vapor phase and collect as fume in the flues, while antimony tends to remain with the bullion. Broadly speaking, the frequency of occurrence, practical utility and the effects on associated metals of arsenic and antimony are such that the metallurgist is inclined to think of arsenic as a troublesome impurity in ores, but of antimony as a valuable constituent that is recovered either as a byproduct or through the metallurgical treatment of antimony ores. Estimating the world production of arsenic as about 40,000 tons annually, probably not more than about 200 tons yearly is produced and used in metallic form, whereas one half of the approximately 40,000 tons of antimony produced annually is metallic. ARSENIC The modern uses of arsenic differ little from ancient ones. Though it has been known from early times, its poisonous quality is almost the only one that yet finds extensive use. The shift in the past century from its utilization in poisoning people to the poisoning of insects, beginning in 1860, has not only led to a considerable increase in

Jan 1, 1953

By Jonkion M. Font, Ramana G. Reddy

A thermodynamic model for a priori predictions of arsenic and antimony impurity capacity in Ni-Cu mattes and slags was developed based on the Reddy-Blander (RB) capacity model. The As and Sb capacities were calculated a-priori considering the RB capacity model in Ni-Cu mattes and FeO-FeO1.5-MgO-CuO0.5-NiO-SiO2 slag at 1573 K and 0.1 to 1 atm partial pressure of SO2. The results showed an excellent agreement between the model calculated and experimental data of arsenic and antimony capacities between the mattes and slag. The impurity capacity model developed here, can be extended for prediction of impurity capacities in multi-component base metal slags and base metal mattes. Such a priori predictions of impurity capacities can lead to develop or improve the efficiency of impurity removal from the base metal smelting, converting and refining processes.

Jan 1, 2014

By S. Strömberg, A. Jokilaakso

Two complex copper concentrates and one arsenical nickel concentrate were oxidized in simulated flash smelting conditions using a laminar-flow furnace. The concentrates contained tetrahedrite as Sb-bearing mineral and arsenopyrite and gersdorfite as As-bearing minerals. At high temperatures and low oxygen potentials, Sb tended to vaporize, but with high oxygen potentials it was captured in mixed oxide phases with copper and iron. Arsenic was found to follow antimony in copper concentrates, although with less sharp contrast between low and high oxygen potentials. In the nickel concentrate studied, arsenic was found to vaporize from the gersdorffite particles and, subsequently, condense on the other particles.

Jan 1, 1998

By Alex Moyano

The Codelco-Chile is considering different processing options for the projected concentrate from the Alejandro Hales mine (former Mansa Mina mine with high arsenic and antimony content of 6% and 0.6%, respectively), that will produce complex blister copper with high impurities contents, higher than the present values produced at the converting process of the Codelco Norte smelter processing only Chuquicamata concentrates. In order to know both the anodic copper quality and the metallurgical implications when a complex blister copper is processed in the refining process of the CN smelter, the Codelco and IM2 ?task force? evaluated positively the refining process for the complex blister copper by addition of alkaline fluxes at laboratory and industrial scale tests. The promising results of the tests done at laboratory scale at the Tohoku University facilities, allowed a large scale test planning to validate the lab-scale results in 3 refining furnaces of 250 t capacity at the CN smelter. The obtained results demonstrate the industrial technical feasibility to process a complex blister copper in the refining furnaces producing an anodic copper quality suitable for the electrolytic process.

Jan 1, 2006

By Felipe Daroch, Maria C. Ruiz, Rafael Padilla

Copper concentrates with high arsenic contents must be pretreated before conventional smelting to prevent environmental pollution with arsenic compounds. In this work, experimental results concerning the selective removal of arsenic and antimony from copper concentrates are presented. The process consists of an alkaline digestion using concentrated NaHS-NaOH solutions to transform the arsenic and antimony sulfides into soluble compounds. A water leaching follows the digestion to dissolve the arsenic and antimony, leaving clean copper sulfide solid residues. The laboratory scale tests were carried out using a copper–arsenic concentrate with 15.05% As and 1.42% Sb. The results showed that the most important digestion variables were temperature and concentrations of NaHS and NaOH. Over 97% of arsenic and 92% of antimony could be removed in 10 min of digestion using 8.9 M NaOH and 100% excess of NaHS at 80 °C. The subsequent water leaching was performed at 80°C for 20 min.

Jan 1, 2015

By D Craw

A glasshouse experiment was set up to investigate arsenic uptake in rye corn grown in different arsenic rich substrates. Sods of material were taken from various locations and planted with rye corn seeds. The plants grew for 13 weeks after which time the above ground biomass was harvested. Analysis of the rye corn plants showed a narrow range of arsenic concentrations, which did not reflect the arsenic contents of the soil. Comparison of the results from this study with previous work showed the glasshouse rye corn to have lower arsenic concentrations in above ground biomass than rye corn grown in field conditions. The environmental conditions present on the tailings and water-rock interactions were considered the main factors involved with the difference in arsenic uptake between field studies and the glasshouse study. This suggests that bioavailability processes are influenced by a variety of factors and cannot necessarily be predicted by the use of soil factors or glasshouse trials alone as is often done when planning phytoremediation work and mine shut down.

Jan 1, 2007

By X. J. Guo, Q. K. Wang, S. P. Zhong

With depletion of traditional clean copper reserves and fast expansion of the global copper demand and smelting capacity in the past decade, more and more copper smelters have to treat copper concentrate with increasing content of complex arsenic-bearing minerals. Developing economically viable and environmentally reliable methods and approaches for arsenic control in copper smelting has become more critical for sustainable growth of the copper industry. This paper will report the recent effort of Zijin Mining Group Ltd. in developing processes for improving arsenic control and management in the Zijin Copper Smelter. The arsenic distribution and balance data for matte smelting, converting and refining operations in Zijin Copper Smelter is reviewed for understanding of the current challenges in arsenic control. The processes developed for treating the arsenic bearing waste acid bleed stream from the smelting-converting off-gases wet cleaning circuit and the arsenic sludge produced in the refining electrolyte purification circuit for arsenic disposal are discussed. INTRODUCTION With fast expansion of the global copper smelting capacity to meet the world copper demand and depletion of traditional clean copper reserves, more and more copper smelters have to treat copper concentrate with an increasing content of complex arsenic-bearing minerals. China is the world largest copper consumer and also has the largest copper smelting and refining capacity, but majority of its smelting capacity relies on supply of imported copper concentrate. In order to meet the increasing copper demand and ease the tight supply of clean copper concentrate, the Chinese copper industry has to look at the domestic opportunity of developing non-traditional copper resources, specifically those of lower grades, more complex mineralogy, and increasing level of deleterious elements especially arsenic and also process imported copper concentrate with increased arsenic content. Due to a significant and growing environmental issue associated with arsenic contamination, developing economically viable and environmentally reliable methods and approaches for arsenic management and control in unlocking the maximum value of such arsenic bearing copper resources has become more critical for sustainable growth of the industry.

Jan 1, 2019

By E. Fiset, T. Hennebel, F. Verbruggen, A. Prévoteau, K. Rabaey

Arsenic (As), bismuth (Bi) and antimony (Sb) are known to affect the quality of copper deposits in copper electrowinning operations. The codeposition of As was previously believed to occur only at current densities far exceeding the range of typical current densities for copper electrowinning. In this study, we investigate the copper electrodeposition on different pretreated stainless steel (SS) substrates from bleed electrolyte in galvanostatic mode at –45 mA/cm². Scanning electron microscopy (SEM) micrographs illustrate that during the initial phases of copper nucleation and growth, the current density was locally increased due to the pretreatments. It was reasoned that the codepostion of As could possibly occur in normal electrowinning conditions, but the risk can be substantially reduced by good SS substrate handling and maintenance practices. INTRODUCTION The presence of As, Bi and Sb is known to have a deleterious effect on the copper cathode quality in copper electrowinnings (Hiskey & Maeda, 2003; Hoffmann, 2004; Xiao, Cao, Shen, & Volinsky, 2012; Xiao, Cao, Mao, Shen, & Ren, 2014; Jafari et al., 2017). They are known to influence both the chemical and physical quality of the copper as they can contaminate the copper (Jafari et al., 2017) and affect the copper deposit structure (Hiskey & Maeda, 2003; Kim, Kim, & Chung, 2009), which contributes to a degraded market value of the copper (Tuddenham, 1984). The incorporation mechanisms of these impurities are believed to occur mainly through slime inclusion (F. Xiao et al, 2012) and electrolyte inclusion (Hiskey & Maeda, 2003). Other studies suggested that codeposition of these impurities is possible by their standard reduction potential being close to the one of copper (Xiao et al, 2014). Hiskey and Maeda (2003) investigated the copper electrodeposition on a copper electrode substrate in Cu electrolytes with a Cu, H2SO4, As, Bi, Sb composition representative for commercial copper tankhouses. The combination of voltammographic techniques and Auger electron spectroscopy showed that As was the first impurity to be electrodeposited from this electrolyte, yet at potentials where the limiting current density of the copper electrodeposition reaction is exceeded. The copper tankhouses usually operate at a current density ratio of 0.3 to the limiting current density in order to achieve tolerable copper quality deposits. The codeposition of As could be considered impossible in this current density condition. However, it is known that during the initial phases of electrodeposition on foreign substrates, a substantial part of the reaction proceeds by growth of individual nuclei where the current density is locally high and diffusion limited (Radisic, Ross, & Searson, 2006). Furthermore, it was observed that copper nucleation on TiO substrates occurred preferentially in the scratched oxide free areas which could serve as parts with high localized current densities (Chang, Choe, & Lee, 2005).

Jan 1, 2019

By M. A. Cocquerel

The future economic necessity of mining copper ores with a high impurity content and increased environmental awareness will require closer examination of the distribution of arsenic within copper smelting processes. A generalized approach is developed which can be adapted to specific projects for the determination of an overall process configuration to satisfy all requirements in a cost effective manner.

Jan 1, 1983

By Esther Carrera Martinez

Caraiba Metals is the sole brazilian copper custom smelter. The sulfur present in the various concentrates processed is recovered as sulfuric acid and oleum ,which are sold in the local market For quality assurance purposes, a study was carried out in order to determine how to control the arsenic content in the acid, allowing the continuous processing of concentrates with high levels impurity, The study was based on the process parameters of the washing towers and mist precipitators, Others process variables were investigated and their effects were used in support to confirm the results, After many analyses performed some interventions to improve the quality of the acid were implemented in the plant, which proved to be successful even by using a conventional purification system,

Jan 1, 1996

By Quast K

A series of laboratory flotation tests were conducted to evaluate the effectiveness of various depressants as arsenic (and zinc) depressants in the lead cleaner stage of the NBHC mill at Broken Hill. The depressants used included potassium cyanide, ferrous sulphate, sodium hypochlorite, potassium ferricyanide and two Cyanamid commerical depressants, Aerodepressants 610 and 633. A standard roughing stage was completed before the addition of the reagents in the cleaning stage. All reagents tested produced significant arsenic depression, with the best results being obtained with the addition of potassium cyanide and sodium hypochlorite. Some of the depressants activated the zinc in the process of arsenic depression. The best result was obtained with the addition of 90 g/t potassium cyanide at a pH of 10 when arsenic recovery was only 1/4 that of the value obtained for the standard test.

Jan 1, 1991

By P. A. Riveros

The literature on the arsenic disposal practices of the metallurgical industry and the long term stability of the disposed arsenic compounds were reviewed from a Canadian perspective. The review was complemented with visits to selected operating metallurgical sites to obtain information on their specific arsenic disposal practices and the behaviour of their impounded residues. The arsenic disposal procedure currently favoured by the industry involves the formation of an insoluble ferric arsenate compound which is allowed to sediment at the bottom of tailings or residue ponds. It has been shown recently that this poorly formed crystalline compound is similar to ?arsenical ferrihydrite? which is ferrihydrite containing strongly adsorbed arsenate anions. Despite concerns about its long term stability on thermodynamic grounds, arsenical ferrihydrite appears to be stable for many years in the proper environment which includes a slightly acidic pH and oxidizing conditions. A high Fe/As ratio and the presence of heavy metals appear to increase the stability of arsenical ferrihydrite. High temperature operations, such as those encountered in the autoclave treatment of refractory gold ores, are conducive to the formation of scorodite, FeAsO42H2O, and/or a series of ferric arseno-hydroxy-sulphate compounds depending on the solution composition. Scorodite has several advantages over arsenical ferrihydrite as a disposal compound including a lower iron demand, a higher density and a greater thermodynamic stability. New procedures have been developed to generate scorodite at ambient pressure. These procedures would offer significant reductions in capital cost because of the elimination of the need for autoclaves. Lime precipitation which was widely used in the past is being abandoned as a result of strong evidence showing that calcium arsenate compounds decompose slowly in contact with atmospheric CO2 to form calcium carbonate and soluble arsenic acid. In all cases, the long term stability of the disposed arsenic compounds depends on a number of factors including disposal site characteristics, particle crystallinity and size distribution, the presence of complexing agents and the effect of bacterial activity.

May 1, 2002

By C. M. Acuna, M. Sherrington

In high temperature processes thermodynamic equilibrium is assumed and therefore chemical potential of elements, among the condensed phases, have to be the same. In such situation impurities distribute accordingly and their fractional distributions are affected by the masses of the coexisting phases. It has been claimed Teniente Converters perform quite well for smelting high impurity concentrates, especially in respect to volatilization and/or slagging. Production of high matte grade near white metal composition, requiring moderate oxygen enrichment in the process air, results in a huge mass of gas and therefore a high fraction of impurities report to it. Similarly, by recycling different sources of slag, flue dust or other materials, the mass of the final slag is increased and so do the masses of impurities reporting to the slag. Nevertheless, above a certain level the recycling of smelter byproducts is no longer feasible and the cycle has to be halted, unless higher impurity mattes are accepted. Although the process might be continued during converting and refining, lengthy and expensive measures have to be taken if suitable anode copper for electrolytic refining is to be achieved. In the present study samples of high arsenic matte grade and slag were obtained on a pilot scale. The matte samples, on the order 75%Cu, were equilibrated with slag at varying ratios in magnesia crucibles under CO/C02 atmospheres at 1523 K. After 24 hours equilibrium matte and slag were rapidly solidified and analyzed by copper, sulfur, iron and arsenic. Furthermore, industrial samples of matte and slag, in the order 75%Cu at 1523 K, were obtained via a special quenching sampling device to determine the association of copper and suspension of matte and copper in slag. Based on the results, the distribution coefficient of arsenic between slag and matte was evaluated along with copper species in slag and the fractional distribution of arsenic, in the coexisting phases, was determined as a function of the ratio mass of slag to mass of matte.

Jan 1, 2007

By S. Y. Tan

The thermal stability of fully silicided NiSi with arsenic doping on silicon was investigated. The aims of the work were to investigate the Ni silicide phase-related issues associated with arsenic dopant and thermal annealing on Ni-FUSI/HfO2/Si and Ni-FUSI/HfSiO/Si gate stacks. It was found that arsenic-incorporation demonstrated some improvement in both morphology and phase stability of nickel silicided films at high processing temperatures regardless underlying gate dielectrics. The correlations of Ni-Si phase transformation and arsenic doapnt with their electrical and physical changes were established by sheet resistance measurements, X-ray diffraction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) analysis. Furthermore, the modulation of the work function (WF) of Ni fully silicided gates by arsenic impurity is presented, comparing the effects of dopant (As) on the WF and silicide phases (NiSi and NiSi2). It confirmed that the work function of NiSi can be tuned by implanting arsenic dopant, but it ineffective for NiSi2 phase.

Jan 1, 2010

By Gerardo Fuentes

Arsenic extraction from Chilean copper concentrates up to nearly 99% was achieved, using hydrothermal reactions. Arsenic appears in nature in more than 200 mineral species, being arsenopyrite (FeAsS), enargite (Cu3AsS4), and tennantite (Cu12As4S13) the most common species. In addition, arsenic is present in a large amount of copper concentrates, produced in northern Chile. Medical statistics show that in northern Chile, the amount of cancer to the lung, skin and bladder are the highest in the country. The latter situation, demonstrates the importance of studying metallurgical processes that do not generate atmospheric pollution. The hydrometallurgical processes such as hydrothermal treatment in autoclave reactors, do not produce gaseous emissions. On the other hand, the arsenic remains in solution from where it can be transformed in scorodite by widely known methods. Previous works about hydrothermal treatment of enargite have shown the feasibility of transforming the enargite of the copper concentrates into chalcocite or mineral species of the chalcocite family such as djurleite, digenite and for this reason enrich the concentrate in copper and pass the arsenic to solution. For this research, two Chilean copper concentrates were used, concentrate 1 with 5.5% arsenic and concentrate 3 with 1.8% arsenic. These concentrates were subjected to a complete chemical and mineralogical characterization. Later these concentrates were carry out to batch tests of hydrothermal treatment. Also, these concentrates were subjected to grinding to have different particle sizes. For the hydrothermal tests, a liter capacity Autoclave Engineer reactor was used. Characteristic of this reactor was the maximum temperature 350°C, 5000 PSI pressure, and 900 rpm agitation speed. Kinetic tests were carried out with the two concentrates maintaining the same solid: liquid relationship, the same agitation velocity and the variables studied were treatment temperature, time of reaction, concentration of copper in the solution and grain size of the concentrates. The conclusions of the study indicated arsenic extraction of the order of 93.98% from the concentrate 1 and arsenic extraction of the order of 98.74% from concentrate 3. After the hydrothermal treatment, the solids and solutions were characterized chemically, by electron microscopy and X ray diffraction. Also the solids were characterized by grainsize through a particle size analyzer (MICROTRAC). Results of batch treatment shows that arsenic can be release almost completely from real copper concentrates using this hydrothermal process and the next stage will be a scale up process in order obtain results for pilot plant design. INTRODUCTION Arsenic is an impurity that appears associated with copper minerals forming enargite, tennantite, tetrahedrite, and that due to the pyrometallurgical treatment either in conversion or roasting furnaces, it goes into the atmosphere together with the sulfur dioxide. A great quantity of literature can be found to eliminate arsenic or try to separate arsenic from copper. The methods used are mainly leaching processes with or without pressure (Padilla, Jerez & Ruiz, 2015) with different reagents like chloride media (Herreros, Fuentes, Quiroz & Viñals, 2003) or chloride media with sulphuric acid (Riveros & Dutrizac, 2008) or sodium hypochlorite (Mihajlovic, Strbac, Zivkovic, Kovacevic & Stehernik, 2007). It is known too that Chile is the first copper producer in the world and a great quantity of its minerals are in the north of the country, in Antofagasta.

Jan 1, 2019

By F. Parada Luna, F. Parada Torres, J. Salvo, A. Reghezza

In the pyrometallurgical processes of copper concentrates, arsenic is preferentially concentrated in the dusts carried by the gases as a result of their volatility and subsequent condensation in the gas cleaning train. In this work results obtained by alkaline leaching of the dusts from Ministro Hales roasting plant, belonging to Codelco, are presented. For the Ministro Hales plant the alkaline leaching would be an alternative to the recirculation of dusts to the roasting furnace. The experimental study considered NaOH and NaOH plus NaHS leaching of two samples of dusts, with 4.24 and 2.55% arsenic respectively. The results show that it is feasible to extract 90% of the arsenic and 50% of the antimony at room temperature using only NaOH, and when the temperature increases to 95ºC, the extractions of As and Sb increase. Copper remains in the solid residue with less than 1% dissolution, and the NaOH net consumption was approximately 140 kg/t of dust. In leaching tests with NaOH + NaHS, two types of methods were tested, baking plus leaching with water and direct leaching with a NaOH+NaHS solution. With the second method arsenic extraction increased to 95% and copper dissolution was less than 0.01% at 85ºC, NaOH 100 g/L, NaHS 90 g/L, 1.5 h and L/S ratio of 5/1 (L/kg). The bismuth remains stable in the solid in all cases. INTRODUCTION The presence of arsenic in copper concentrates has increased with time and the environmental regulations are becoming increasingly more stringent. In concentrate treatment pyrometallurgical plants, most of the arsenic is volatilized condensing in the gas train and is collected along with the entrained solids to form the flue dusts. Under these conditions, in smelters of copper concentrates with high arsenic content, the dusts are being treated in hydrometallurgical plants to extract and stabilize the arsenic, which also means that most of the copper contained in the dust is co-extracted with the arsenic. This affects the recovery of copper in the smelter and an alternative such as the selective alkaline leaching of arsenic, would allow the copper from flue dust to be recovered.

Jan 1, 2019

By K. D. Mills, R. G. Robins, C. G. Anderson, L. G. Twidwell

Arsenic is a metalloid which has attracted great environmental scrutiny in recent decades. Moreover, its control and deportment is becoming increasingly important in the metallurgical processing of modern complex ores and concentrates. As such the authors of this publication have a combined professional experience of well over 100 years in the study and hydrometallurgical treatment of arsenic. Hence, this paper will cover arsenic fundamentals along with a review of technology for removal, fixation and stabilization. Finally, an application of industrial Alkaline Sulfide Leaching (ASL) of a copper enargite concentrate will be elucidated.

Jan 1, 2014

By lchimura. R. .

Japan Oil, Gas and Metals National Corporation (JOGMEC) and Centro de Investigation Minera y Metalurgica (CIMM) commenced a five year project from 2001 to modify the treatment of the furnace dust from Teniente converter containing harmful elements like arsenic and lead. The project was supported by Japanese and Chilean governments, and a demonstration plant was installed and operated at Las Ventanas Smelter and Refinery (Division Ventanas CODELCO). The basic and detailed engineering was made by Mitsui Mining and Smelting Co., Ltd (MMS) based on the joint study among JOGMEC, CIMM and Division Ventanas CODELCO. Arsenic in flue dust is lixiviated by sulfuric acid and fixed as crystalline ferric arsenate, where leachability of arsenic will be lower enough than the regulation, 5mg/I by TCLP (Toxicity Charactaristic Leaching Procedure) of USEPA. On the other hand, the recovered copper from the dust will be fed to the copper production process at Las Ventanas Smelter and Refinery, while zinc will be recovered as the exportable product. As introducing the crystallization and growing stage, the stable crystalline ferric arsenate formation can be achieved under the normal pressure.

Jan 1, 2007

By George P. Demopoulos

In this paper the author will provide an overview of over 20 years of research & developments in the area of hydrometallurgical arsenic immobilization that culminated recently in the industrial implementation of the atmospheric scorodite process. The paper will consider various aspects of arsenic fixation in the non-ferrous metal industry from the iron-arsenic co-precipitation process employed to arsenic-bearing effluent solutions; to autoclave processing of arsenical copper and gold feedstocks and the fate of the in-situ formed iron sulphato-arsenate precipitate phases; the precipitation and stability of scorodite; the possible stabilizing role of mineral phases like yukonite, and the development of "scoroditeplus" processes employing novel encapsulation strategies. Emphasis is placed on the characterization and long-term stability of the various forms of arsenic-immobilized phases under either oxic or anoxic conditions over a wide pH range and the establishment of critical links between process parameters and hazardous material stability, contributing thus to advancement of new generation safe and sustainable waste management technologies.

Jan 1, 2014

By M Tayebi-Khorami

There is an increasing trend in the extraction and development of copper resources from complex deposits. The complex deposits pose mineral processing challenges, as they often contain low grade copper ore, relatively large quantity of clay minerals, complex texture, very fine disseminated ore, high amount of pyrite, and high level of impurity elements such as arsenic. With the amount of arsenic in concentrates increasing and with environment, occupational health and safety regulations becoming more restrict, there is a need for a processing method that results in no arsenic emissions and captures all arsenic while immobilizing it in a compound that is stable under a wide range of conditions, so it is suitable for long-term disposal. Some development work has been undertaken to examine the most effective arsenic treatment option for complex orebodies that contain arsenic, but a technically robust and economically viable option has not yet been developed. Previous research has demonstrated the possibility of separating arsenic-copper sulphides from other copper minerals by controlling the potential of the flotation pulp in the single mineral systems. The selective flotation of enargite from copper sulphides in a real complex ore system was studied by Tayebi-Khorami (2016), which is summarised in this paper. CITATION: Tayebi-Khorami, M, 2018. Arsenic in complex orebodies, in Proceedings Complex Orebodies Conference 2018, pp 132–134 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Nov 21, 2018