Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study

The oxidative dissolution of chalcopyrite in ferric media often produces incomplete copper recoveries. The incomplete recoveries have been attributed to inhibition caused by the formation of a metal deficient sulphide and the deposition of elemental sulphur and jarosite. Although these phases have b...

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Main Author: Parker, Andrew Donald
Format: Thesis
Language:English
Published: Curtin University 2008
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/140
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author Parker, Andrew Donald
author_facet Parker, Andrew Donald
author_sort Parker, Andrew Donald
building Curtin Institutional Repository
collection Online Access
description The oxidative dissolution of chalcopyrite in ferric media often produces incomplete copper recoveries. The incomplete recoveries have been attributed to inhibition caused by the formation of a metal deficient sulphide and the deposition of elemental sulphur and jarosite. Although these phases have been qualitatively identified on the surface of chalcopyrite, none have been quantitatively identified. The aim of the project was to quantitatively analyse the surface before and after oxidative dissolution, with X-ray photoelectron spectroscopy (XPS), and to use the phases identified as the basis for mechanisms of dissolution and inhibition.XPS analysis was performed on chalcopyrite massive fractured under anaerobic atmosphere and chalcopyrite massive and concentrate oxidised in 0.1 M ferric sulphate (pH 1.9) and 0.2 M ferric chloride (pH 1.6) at 50, 65 and 80ºC. Quantitative XPS analysis of the chalcopyrite surfaces required the development of programs that accounted for the observed XPS spectra. The output of these programs was used to construct profiles of the chalcopyrite surfaces and the deposited phases. These surface profiles were correlated with copper recoveries determined for chalcopyrite concentrate dissolution under the same conditions.The surface of chalcopyrite before oxidative dissolution reconstructs to form a `pyritic' disulphide phase. This phase is oxidised in ferric media to form thiosulphate via the incorporation of oxygen atoms from the hydration sphere. The thiosulphate reacts in the oxidising conditions of low pH to form elemental sulphur, sulphite and sulphate. The sulphate complexes with ferric to produce hydronium jarosite. This reaction occurs at the surface during the initial stages of dissolution and in the bulk solution during the latter stages. This precipitation of hydronium jarosite during the latter stages of dissolution corresponds to inhibition of the dissolution reaction. It is therefore concluded hydronium jarosite is responsible for inhibiting the oxidative dissolution of chalcopyrite in ferric media.The identification of hydronium jarosite as the inhibiting phase is consistent with the industrial practice of removing `excess' iron from the ferric solution before oxidative dissolution. However, additional iron and sulphate are generated at the chalcopyrite surface during oxidative dissolution. These high iron and sulphate concentrations combine with the low pH and high temperatures favoured for the oxidative dissolution of chalcopyrite to produce ideal conditions for jarosite precipitation. Therefore, pH must be lowered further to prevent jarosite precipitation and enhance copper recoveries from chalcopyrite in ferric media.
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spelling curtin-20.500.11937-1402017-02-20T06:42:40Z Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study Parker, Andrew Donald jarosite x-ray photoelectron spectroscopy (XPS) metal deficient sulphide inhibition ferric media quantitative identification copper recoveries elemental sulphur chalcopyrite oxidative dissolution The oxidative dissolution of chalcopyrite in ferric media often produces incomplete copper recoveries. The incomplete recoveries have been attributed to inhibition caused by the formation of a metal deficient sulphide and the deposition of elemental sulphur and jarosite. Although these phases have been qualitatively identified on the surface of chalcopyrite, none have been quantitatively identified. The aim of the project was to quantitatively analyse the surface before and after oxidative dissolution, with X-ray photoelectron spectroscopy (XPS), and to use the phases identified as the basis for mechanisms of dissolution and inhibition.XPS analysis was performed on chalcopyrite massive fractured under anaerobic atmosphere and chalcopyrite massive and concentrate oxidised in 0.1 M ferric sulphate (pH 1.9) and 0.2 M ferric chloride (pH 1.6) at 50, 65 and 80ºC. Quantitative XPS analysis of the chalcopyrite surfaces required the development of programs that accounted for the observed XPS spectra. The output of these programs was used to construct profiles of the chalcopyrite surfaces and the deposited phases. These surface profiles were correlated with copper recoveries determined for chalcopyrite concentrate dissolution under the same conditions.The surface of chalcopyrite before oxidative dissolution reconstructs to form a `pyritic' disulphide phase. This phase is oxidised in ferric media to form thiosulphate via the incorporation of oxygen atoms from the hydration sphere. The thiosulphate reacts in the oxidising conditions of low pH to form elemental sulphur, sulphite and sulphate. The sulphate complexes with ferric to produce hydronium jarosite. This reaction occurs at the surface during the initial stages of dissolution and in the bulk solution during the latter stages. This precipitation of hydronium jarosite during the latter stages of dissolution corresponds to inhibition of the dissolution reaction. It is therefore concluded hydronium jarosite is responsible for inhibiting the oxidative dissolution of chalcopyrite in ferric media.The identification of hydronium jarosite as the inhibiting phase is consistent with the industrial practice of removing `excess' iron from the ferric solution before oxidative dissolution. However, additional iron and sulphate are generated at the chalcopyrite surface during oxidative dissolution. These high iron and sulphate concentrations combine with the low pH and high temperatures favoured for the oxidative dissolution of chalcopyrite to produce ideal conditions for jarosite precipitation. Therefore, pH must be lowered further to prevent jarosite precipitation and enhance copper recoveries from chalcopyrite in ferric media. 2008 Thesis http://hdl.handle.net/20.500.11937/140 en Curtin University fulltext
spellingShingle jarosite
x-ray photoelectron spectroscopy (XPS)
metal deficient sulphide
inhibition
ferric media
quantitative identification
copper recoveries
elemental sulphur
chalcopyrite
oxidative dissolution
Parker, Andrew Donald
Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
title Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
title_full Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
title_fullStr Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
title_full_unstemmed Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
title_short Oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
title_sort oxidative dissolution of chalcopyrite in ferric media: an x-ray photoelectron spectroscopy study
topic jarosite
x-ray photoelectron spectroscopy (XPS)
metal deficient sulphide
inhibition
ferric media
quantitative identification
copper recoveries
elemental sulphur
chalcopyrite
oxidative dissolution
url http://hdl.handle.net/20.500.11937/140