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

Xu, Hongwu; Guo, Xiaofeng; Seaman, Lani Anne; Harrison, Aaron J.; Obrey, Stephen J.; Page, Katharine

doi:10.1557/jmr.2019.185

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

Journal Article · Tue Jun 04 00:00:00 EDT 2019 · Journal of Materials Research

DOI:https://doi.org/10.1557/jmr.2019.185· OSTI ID:1544698

^[1];

^[1]; Harrison, Aaron J. ^[1];

^[1]; Page, Katharine ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

To study thermal desulfurization of pyrite (FeS₂), we conducted in situ neutron diffraction experiments in the temperature range 298–1073 K. Additionally, on heating, pyrite remained stable up to 773 K, at which it started to decompose into pyrrhotite (Fe_1-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$$\overline{3}$$) to be α_V = 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 (Fe_1-xS) at 873 K. Unit-cell parameters of Fe_1-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 Fe_1-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. Finally, detailed peak profile and Arrhenius (k = A exp(-E_a/RT)) analyses yielded an activation energy E_a 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.

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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE). Solar Energy Technologies Office (EE-4S); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1544698

Report Number(s):: LA-UR-19-22797

Journal Information:: Journal of Materials Research, Vol. 34, Issue 19; ISSN 0884-2914

Publisher:: Materials Research SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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Related Subjects

58 GEOSCIENCES
36 MATERIALS SCIENCE
pyrite
pyrrhotite
troilite
neutron diffraction
deferential thermal analysis
thermogravimetric analysis
desulfurization
thermal expansion
crystal structure
phase transformation
kinetics

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

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