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Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study

Published online by Cambridge University Press:  04 June 2019

Hongwu Xu ,
Xiaofeng Guo Open the ORCID record for Xiaofeng Guo [Opens in a new window] ,
Lani A. Seaman ,
Aaron J. Harrison ,
Stephen J. Obrey  and
Katharine Page
Hongwu Xu*
Affiliation:
Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
Xiaofeng Guo
Affiliation:
Earth and Environmental Sciences Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
Lani A. Seaman
Affiliation:
Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
Aaron J. Harrison
Affiliation:
Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
Stephen J. Obrey
Affiliation:
Chemistry Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
Katharine Page
Affiliation:
Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

To study thermal desulfurization of pyrite (FeS2), we conducted in situ neutron diffraction experiments in the temperature range 298–1073 K. On heating, pyrite remained stable up to 773 K, at which it started to decompose into pyrrhotite (Fe1−xS) and S2 gas. Rietveld analysis of the neutron data from 298 to 773 K allowed determination of the thermal expansion coefficient of pyrite (space group Pa$\bar 3$) to be αV = 3.7456 × 10−5 K−1, which largely results from the expansion of the Fe–S bond. With further increase in temperature to 1073 K, all the pyrite transformed to pyrrhotite (Fe1−xS) at 873 K. Unit-cell parameters of Fe1−xS (space group P63/mmc) increase on heating and decrease on cooling. However, the rates in cell expansion are larger than those in contraction. This hysteresis behavior can be attributed to continuous desulfurization of pyrrhotite (i.e., x in Fe1−xS decreases) with increasing temperature until the stoichiometric troilite (FeS) was formed at 1073 K. On cooling, troilite underwent a magnetic transition to an orthorhombic structure (space group Pnma) between 473 and 573 K. In addition, using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) implemented with a differential scanning calorimeter, we performed kinetic measurements of pyrite decomposition. Detailed peak profile and Arrhenius (k = A exp(−Ea/RT)) analyses yielded an activation energy Ea of 302.3 ± 28.6 kJ/mol (based on DTA data) or 302.5 ± 26.4 kJ/mol (based on TGA data) and a ln(A) of 35.3 ± 0.1.

Keywords

pyritepyrrhotitetroiliteneutron diffractiondeferential thermal analysisthermogravimetric analysisdesulfurizationthermal expansioncrystal structurephase transformationkinetics
Type
Invited Paper
Information
Journal of Materials Research , Volume 34 , Issue 19: Focus Issue: Thermodynamics of Complex Solids , 14 October 2019 , pp. 3243 - 3253
Copyright
Copyright © Materials Research Society 2019 

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Footnotes

b)

Present address: Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.

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