Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study
Abstract
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 (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$$\overline{3}$$) 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. Finally, 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.
- Authors:
-
[1];
[1];
[1];
[1];
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE). Solar Energy Technologies Office (EE-4S); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1544698
- Report Number(s):
- LA-UR-19-22797
Journal ID: ISSN 0884-2914
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Research
- Additional Journal Information:
- Journal Volume: 34; Journal Issue: 19; Journal ID: ISSN 0884-2914
- Publisher:
- Materials Research Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES; 36 MATERIALS SCIENCE; pyrite; pyrrhotite; troilite; neutron diffraction; deferential thermal analysis; thermogravimetric analysis; desulfurization; thermal expansion; crystal structure; phase transformation; kinetics
Citation Formats
Xu, Hongwu, Guo, Xiaofeng, Seaman, Lani Anne, Harrison, Aaron J., Obrey, Stephen J., and Page, Katharine. Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study. United States: N. p., 2019.
Web. doi:10.1557/jmr.2019.185.
Xu, Hongwu, Guo, Xiaofeng, Seaman, Lani Anne, Harrison, Aaron J., Obrey, Stephen J., & Page, Katharine. Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study. United States. https://doi.org/10.1557/jmr.2019.185
Xu, Hongwu, Guo, Xiaofeng, Seaman, Lani Anne, Harrison, Aaron J., Obrey, Stephen J., and Page, Katharine. Tue .
"Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study". United States. https://doi.org/10.1557/jmr.2019.185. https://www.osti.gov/servlets/purl/1544698.
@article{osti_1544698,
title = {Thermal desulfurization of pyrite: An in situ high-T neutron diffraction and DTA–TGA study},
author = {Xu, Hongwu and Guo, Xiaofeng and Seaman, Lani Anne and Harrison, Aaron J. and Obrey, Stephen J. and Page, Katharine},
abstractNote = {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 (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$\overline{3}$) 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. Finally, 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.},
doi = {10.1557/jmr.2019.185},
journal = {Journal of Materials Research},
number = 19,
volume = 34,
place = {United States},
year = {2019},
month = {6}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
A new polymorph of eucryptite (LiAlSiO 4 ), ε-eucryptite, and thermal expansion of α- and ε-eucryptite at high pressure
journal, April 2002
- Zhang, Jianzhong; Celestian, Aaron; Parise, John B.
- American Mineralogist, Vol. 87, Issue 4
High-pressure and high-temperature polymorphism of iron sulfide (FeS)
journal, July 1982
- King, H. E.; Prewitt, C. T.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 7
Sulfide Mineralogy and Geochemistry: Introduction and Overview
journal, January 2006
- Vaughan, D. J.
- Reviews in Mineralogy and Geochemistry, Vol. 61, Issue 1
A review on the mineral chemistry of the non-stoichiometric iron sulphide, Fe 1− x S (0 ≤ x ≤ 0.125): polymorphs, phase relations and transitions, electronic and magnetic structures
journal, September 2005
- Wang, Haipeng; Salveson, Ian
- Phase Transitions, Vol. 78, Issue 7-8
Dynamic Simulation of the Thermal Decomposition of Pyrite Under Vacuum
journal, February 2014
- Deng, Jiushuai; Wen, Shuming; Chen, Xiumin
- Metallurgical and Materials Transactions A, Vol. 45, Issue 5
Structural Behavior of Ba 1.24 Al 2.48 Ti 5.52 O 16 Hollandite at High Temperature: An In Situ Neutron Diffraction Study
journal, September 2014
- Xu, Hongwu; Costa, Gustavo C. C.; Stanek, Christopher R.
- Journal of the American Ceramic Society, Vol. 98, Issue 1
Decomposition and oxidation of pyrite
journal, January 2006
- Hu, Guilin; Dam-Johansen, Kim; Wedel, Stig
- Progress in Energy and Combustion Science, Vol. 32, Issue 3
Magnetic Phase Transitions in Stoichiometric FeS Studied by Means of Neutron Diffraction.
journal, January 1960
- Andresen, Arne F.; Hofman-Bang, Niels; Bak, Thor A.
- Acta Chemica Scandinavica, Vol. 14
The application of variable atmosphere thermomagnetometry to the thermal decomposition of pyrite
journal, June 1990
- Hurst, H. J.; Levy, J. H.; Warne, S. St. J.
- Reactivity of Solids, Vol. 8, Issue 1-2
High-pressure neutron-diffraction study of FeS
journal, May 2000
- Marshall, W. G.; Nelmes, R. J.; Loveday, J. S.
- Physical Review B, Vol. 61, Issue 17
Anisotropic thermal expansion and hydrogen bonding behavior of portlandite: A high-temperature neutron diffraction study
journal, April 2007
- Xu, H.; Zhao, Y.; Vogel, S. C.
- Journal of Solid State Chemistry, Vol. 180, Issue 4
Rietveld refinement with spallation neutron powder diffraction data
journal, December 1982
- Von Dreele, R. B.; Jorgensen, J. D.; Windsor, C. G.
- Journal of Applied Crystallography, Vol. 15, Issue 6
High-temperature neutron diffraction study of deuterated brucite
journal, July 2013
- Xu, Hongwu; Zhao, Yusheng; Hickmott, Donald D.
- Physics and Chemistry of Minerals, Vol. 40, Issue 10
Crystal structure, phase transitions and magnetic properties of pyrrhotite-type compounds Fe7−xTixS8
journal, September 2014
- Baranov, N. V.; Ibrahim, P. N. G.; Selezneva, N. V.
- Physica B: Condensed Matter, Vol. 449
The kinetics and mechanism of pyrite thermal decomposition
journal, December 1997
- Hong, Y.; Fegley, B.
- Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 101, Issue 12
Röntgenographische Untersuchung der Kristallstrukturen von Magnetkies, Breithauptit, Pentlandit, Millerit und verwandten Verbindungen
journal, January 1925
- Alsén, Nils
- Geologiska Föreningen i Stockholm Förhandlingar, Vol. 47, Issue 1
Structure and magnetism in synthetic pyrrhotite : A powder neutron-diffraction study
journal, July 2004
- Powell, Anthony V.; Vaqueiro, Paz; Knight, Kevin S.
- Physical Review B, Vol. 70, Issue 1
Reaction kinetics by differential thermal analysis: A physical chemistry experiment
journal, November 1961
- Wendlandt, Wesley W.
- Journal of Chemical Education, Vol. 38, Issue 11
Thermal expansion of iron pyrites
journal, January 1965
- Chrystall, R. S. B.
- Transactions of the Faraday Society, Vol. 61
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS
journal, September 2012
- Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John
- Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287
Shape and Thermodynamic Stability of Pyrite FeS 2 Nanocrystals and Nanorods
journal, August 2007
- Barnard, A. S.; Russo, S. P.
- The Journal of Physical Chemistry C, Vol. 111, Issue 31
Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study
journal, May 2009
- Xu, Hongwu; Zhao, Yusheng; Vogel, Sven C.
- Physics and Chemistry of Minerals, Vol. 37, Issue 2
Thermochemistry of microporous silicotitanate phases in the Na 2 O–Cs 2 O–SiO 2 –TiO 2 –H 2 O system
journal, March 2000
- Xu, Hongwu; Navrotsky, Alexandra; Nyman, May D.
- Journal of Materials Research, Vol. 15, Issue 3
Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4
journal, September 2016
- Guo, Xiaofeng; Wu, Di; Xu, Hongwu
- Journal of Nuclear Materials, Vol. 478
In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature
journal, February 2007
- Xu, Hongwu; Zhao, Yusheng; Zhang, Jianzhong
- Physics and Chemistry of Minerals, Vol. 34, Issue 4
In situ high-temperature phase transformation studies on pyrite
journal, June 2009
- Bhargava, S. K.; Garg, A.; Subasinghe, N. D.
- Fuel, Vol. 88, Issue 6
Predicting the mobility of Zn, Fe, Cu, Pb, Cd from roasted sulfide (pyrite) residues—A case study of wastes from the sulfuric acid industry in Sweden
journal, January 1996
- Lin, Zhixun; Quvarfort, Ulf
- Waste Management, Vol. 16, Issue 8
Phase Transitions in Fe(x)S(x = 0.90--1.00) Studied by Neutron Diffraction.
journal, January 1967
- Andresen, Arne F.; Torbo, Per; Östlund, Eric
- Acta Chemica Scandinavica, Vol. 21
The crystal-structure and vacancy distribution in 6C pyrrhotite
journal, December 2009
- de Villiers, J. P. R.; Liles, D. C.
- American Mineralogist, Vol. 95, Issue 1
Reaction Kinetics in Differential Thermal Analysis
journal, November 1957
- Kissinger, H. E.
- Analytical Chemistry, Vol. 29, Issue 11
29 Si and 27 Al MAS-NMR spectroscopy of β-eucryptite (LiAlSiO 4 ): The enthalpy of Si,Al ordering
journal, January 2000
- Phillips, Brian L.; Xu, Hongwu; Heaney, Peter J.
- American Mineralogist, Vol. 85, Issue 1
A profile refinement method for nuclear and magnetic structures
journal, June 1969
- Rietveld, H. M.
- Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71
Competing Interactions between Various Entropic Forces toward Assembly of Pt 3 Ni Octahedra into a Body-Centered Cubic Superlattice
journal, March 2016
- Li, Ruipeng; Zhang, Jun; Tan, Rui
- Nano Letters, Vol. 16, Issue 4
Encapsulation kinetics and dynamics of carbon monoxide in clathrate hydrate
journal, June 2014
- Zhu, Jinlong; Du, Shiyu; Yu, Xiaohui
- Nature Communications, Vol. 5, Issue 1
Thermal Decomposition of Pyrite FeS<sub>2</sub> under Reducing Conditions
journal, June 2010
- Charpentier, Ludovic; Masset, Patrick J.
- Materials Science Forum, Vol. 654-656
From pyrrhotite to troilite: an application of the Landau theory of phase transitions
journal, November 1994
- Li, Fan; Franzen, Hugo F.
- Journal of Alloys and Compounds, Vol. 215, Issue 1-2
The kinetics and mechanism of the pyrite-to-pyrrhotite transformation
journal, April 1998
- Lambert, J. M.; Simkovich, G.; Walker, P. L.
- Metallurgical and Materials Transactions B, Vol. 29, Issue 2
Energetics of metastudtite and implications for nuclear waste alteration
journal, November 2014
- Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
Electrochemical behavior of pyrite in sulfuric acid solutions containing silver ions
journal, May 1988
- Hiskey, J. B.; Pritzker, M. D.
- Journal of Applied Electrochemistry, Vol. 18, Issue 3
Thermal expansion of troilite and pyrrhotite determined by in situ cooling (873 to 373 K) neutron powder diffraction measurements
journal, April 2005
- Tenailleau, C.; Etschmann, B.; Wang, H.
- Mineralogical Magazine, Vol. 69, Issue 2
Enthalpies of formation of polyhalite: A mineral relevant to salt repository
journal, November 2017
- Guo, Xiaofeng; Xu, Hongwu
- The Journal of Chemical Thermodynamics, Vol. 114
The Kinetics of the Thermal Decomposition of Pyrite
journal, May 1966
- Coats, A. W.; Bright, Norman F. H.
- Canadian Journal of Chemistry, Vol. 44, Issue 10