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

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]; ^[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.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (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, Journal Name: Journal of Materials Research Journal Issue: 19 Vol. 34; ISSN 0884-2914

Publisher:: Materials Research SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (42)

The kinetics and mechanism of pyrite thermal decomposition Hong, Y.; Fegley, B. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 101, Issue 12 https://doi.org/10.1002/bbpc.19971011212	journal	December 1997
Electrochemical behavior of pyrite in sulfuric acid solutions containing silver ions Hiskey, J. B.; Pritzker, M. D. Journal of Applied Electrochemistry, Vol. 18, Issue 3 https://doi.org/10.1007/BF01093767	journal	May 1988
In situ neutron diffraction study of deuterated portlandite Ca(OD)2 at high pressure and temperature Xu, Hongwu; Zhao, Yusheng; Zhang, Jianzhong Physics and Chemistry of Minerals, Vol. 34, Issue 4 https://doi.org/10.1007/s00269-007-0141-2	journal	February 2007
Thermal expansion and decomposition of jarosite: a high-temperature neutron diffraction study Xu, Hongwu; Zhao, Yusheng; Vogel, Sven C. Physics and Chemistry of Minerals, Vol. 37, Issue 2 https://doi.org/10.1007/s00269-009-0311-5	journal	May 2009
High-temperature neutron diffraction study of deuterated brucite Xu, Hongwu; Zhao, Yusheng; Hickmott, Donald D. Physics and Chemistry of Minerals, Vol. 40, Issue 10 https://doi.org/10.1007/s00269-013-0614-4	journal	July 2013
Dynamic Simulation of the Thermal Decomposition of Pyrite Under Vacuum Deng, Jiushuai; Wen, Shuming; Chen, Xiumin Metallurgical and Materials Transactions A, Vol. 45, Issue 5 https://doi.org/10.1007/s11661-014-2206-4	journal	February 2014
The kinetics and mechanism of the pyrite-to-pyrrhotite transformation Lambert, J. M.; Simkovich, G.; Walker, P. L. Metallurgical and Materials Transactions B, Vol. 29, Issue 2 https://doi.org/10.1007/s11663-998-0115-x	journal	April 1998
The application of variable atmosphere thermomagnetometry to the thermal decomposition of pyrite Hurst, H. J.; Levy, J. H.; Warne, S. St. J. Reactivity of Solids, Vol. 8, Issue 1-2 https://doi.org/10.1016/0168-7336(90)80016-D	journal	June 1990
From pyrrhotite to troilite: an application of the Landau theory of phase transitions Li, Fan; Franzen, Hugo F. Journal of Alloys and Compounds, Vol. 215, Issue 1-2 https://doi.org/10.1016/0925-8388(94)90812-5	journal	November 1994
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 Lin, Zhixun; Quvarfort, Ulf Waste Management, Vol. 16, Issue 8 https://doi.org/10.1016/S0956-053X(97)00009-3	journal	January 1996
In situ high-temperature phase transformation studies on pyrite Bhargava, S. K.; Garg, A.; Subasinghe, N. D. Fuel, Vol. 88, Issue 6 https://doi.org/10.1016/j.fuel.2008.12.005	journal	June 2009
Enthalpies of formation of polyhalite: A mineral relevant to salt repository Guo, Xiaofeng; Xu, Hongwu The Journal of Chemical Thermodynamics, Vol. 114 https://doi.org/10.1016/j.jct.2017.05.031	journal	November 2017
Thermodynamic studies of studtite thermal decomposition pathways via amorphous intermediates UO3, U2O7, and UO4 Guo, Xiaofeng; Wu, Di; Xu, Hongwu Journal of Nuclear Materials, Vol. 478 https://doi.org/10.1016/j.jnucmat.2016.06.014	journal	September 2016
Anisotropic thermal expansion and hydrogen bonding behavior of portlandite: A high-temperature neutron diffraction study Xu, H.; Zhao, Y.; Vogel, S. C. Journal of Solid State Chemistry, Vol. 180, Issue 4 https://doi.org/10.1016/j.jssc.2007.03.004	journal	April 2007
The Nanoscale Ordered MAterials Diffractometer NOMAD at the Spallation Neutron Source SNS Neuefeind, Jörg; Feygenson, Mikhail; Carruth, John Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 287 https://doi.org/10.1016/j.nimb.2012.05.037	journal	September 2012
Decomposition and oxidation of pyrite Hu, Guilin; Dam-Johansen, Kim; Wedel, Stig Progress in Energy and Combustion Science, Vol. 32, Issue 3 https://doi.org/10.1016/j.pecs.2005.11.004	journal	January 2006
Crystal structure, phase transitions and magnetic properties of pyrrhotite-type compounds Fe7−xTixS8 Baranov, N. V.; Ibrahim, P. N. G.; Selezneva, N. V. Physica B: Condensed Matter, Vol. 449 https://doi.org/10.1016/j.physb.2014.05.040	journal	September 2014
Reaction Kinetics in Differential Thermal Analysis Kissinger, H. E. Analytical Chemistry, Vol. 29, Issue 11 https://doi.org/10.1021/ac60131a045	journal	November 1957
Competing Interactions between Various Entropic Forces toward Assembly of Pt ₃ Ni Octahedra into a Body-Centered Cubic Superlattice Li, Ruipeng; Zhang, Jun; Tan, Rui Nano Letters, Vol. 16, Issue 4 https://doi.org/10.1021/acs.nanolett.6b00564	journal	March 2016
Reaction kinetics by differential thermal analysis: A physical chemistry experiment Wendlandt, Wesley W. Journal of Chemical Education, Vol. 38, Issue 11 https://doi.org/10.1021/ed038p571	journal	November 1961
Shape and Thermodynamic Stability of Pyrite FeS ₂ Nanocrystals and Nanorods Barnard, A. S.; Russo, S. P. The Journal of Physical Chemistry C, Vol. 111, Issue 31 https://doi.org/10.1021/jp0738199	journal	August 2007
Encapsulation kinetics and dynamics of carbon monoxide in clathrate hydrate Zhu, Jinlong; Du, Shiyu; Yu, Xiaohui Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5128	journal	June 2014
Thermal expansion of iron pyrites Chrystall, R. S. B. Transactions of the Faraday Society, Vol. 61 https://doi.org/10.1039/tf9656101811	journal	January 1965
Energetics of metastudtite and implications for nuclear waste alteration Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina Proceedings of the National Academy of Sciences, Vol. 111, Issue 50 https://doi.org/10.1073/pnas.1421144111	journal	November 2014
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 Wang, Haipeng; Salveson, Ian Phase Transitions, Vol. 78, Issue 7-8 https://doi.org/10.1080/01411590500185542	journal	September 2005
Röntgenographische Untersuchung der Kristallstrukturen von Magnetkies, Breithauptit, Pentlandit, Millerit und verwandten Verbindungen Alsén, Nils Geologiska Föreningen i Stockholm Förhandlingar, Vol. 47, Issue 1 https://doi.org/10.1080/11035892509443177	journal	January 1925
High-pressure neutron-diffraction study of FeS Marshall, W. G.; Nelmes, R. J.; Loveday, J. S. Physical Review B, Vol. 61, Issue 17 https://doi.org/10.1103/PhysRevB.61.11201	journal	May 2000
Structure and magnetism in synthetic pyrrhotite Fe 7 S 8 : A powder neutron-diffraction study Powell, Anthony V.; Vaqueiro, Paz; Knight, Kevin S. Physical Review B, Vol. 70, Issue 1 https://doi.org/10.1103/PhysRevB.70.014415	journal	July 2004
A profile refinement method for nuclear and magnetic structures Rietveld, H. M. Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71 https://doi.org/10.1107/S0021889869006558	journal	June 1969
Rietveld refinement with spallation neutron powder diffraction data Von Dreele, R. B.; Jorgensen, J. D.; Windsor, C. G. Journal of Applied Crystallography, Vol. 15, Issue 6 https://doi.org/10.1107/S0021889882012722	journal	December 1982
High-pressure and high-temperature polymorphism of iron sulfide (FeS) King, H. E.; Prewitt, C. T. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 7 https://doi.org/10.1107/S0567740882007523	journal	July 1982
Structural Behavior of Ba _1.24 Al _2.48 Ti _5.52 O ₁₆ Hollandite at High Temperature: An In Situ Neutron Diffraction Study Xu, Hongwu; Costa, Gustavo C. C.; Stanek, Christopher R. Journal of the American Ceramic Society, Vol. 98, Issue 1 https://doi.org/10.1111/jace.13245	journal	September 2014
The Kinetics of the Thermal Decomposition of Pyrite Coats, A. W.; Bright, Norman F. H. Canadian Journal of Chemistry, Vol. 44, Issue 10 https://doi.org/10.1139/v66-176	journal	May 1966
Thermal expansion of troilite and pyrrhotite determined by in situ cooling (873 to 373 K) neutron powder diffraction measurements Tenailleau, C.; Etschmann, B.; Wang, H. Mineralogical Magazine, Vol. 69, Issue 2 https://doi.org/10.1180/0026461056920247	journal	April 2005
Thermochemistry of microporous silicotitanate phases in the Na ₂ O–Cs ₂ O–SiO ₂ –TiO ₂ –H ₂ O system Xu, Hongwu; Navrotsky, Alexandra; Nyman, May D. Journal of Materials Research, Vol. 15, Issue 3 https://doi.org/10.1557/JMR.2000.0116	journal	March 2000
²⁹ Si and ²⁷ Al MAS-NMR spectroscopy of β-eucryptite (LiAlSiO ₄ ): The enthalpy of Si,Al ordering Phillips, Brian L.; Xu, Hongwu; Heaney, Peter J. American Mineralogist, Vol. 85, Issue 1 https://doi.org/10.2138/am-2000-0117	journal	January 2000
A new polymorph of eucryptite (LiAlSiO ₄ ), ε-eucryptite, and thermal expansion of α- and ε-eucryptite at high pressure Zhang, Jianzhong; Celestian, Aaron; Parise, John B. American Mineralogist, Vol. 87, Issue 4 https://doi.org/10.2138/am-2002-0421	journal	April 2002
The crystal-structure and vacancy distribution in 6C pyrrhotite de Villiers, J. P. R.; Liles, D. C. American Mineralogist, Vol. 95, Issue 1 https://doi.org/10.2138/am.2010.3266	journal	December 2009
Sulfide Mineralogy and Geochemistry: Introduction and Overview Vaughan, D. J. Reviews in Mineralogy and Geochemistry, Vol. 61, Issue 1 https://doi.org/10.2138/rmg.2006.61.1	journal	January 2006
Magnetic Phase Transitions in Stoichiometric FeS Studied by Means of Neutron Diffraction. Andresen, Arne F.; Hofman-Bang, Niels; Bak, Thor A. Acta Chemica Scandinavica, Vol. 14 https://doi.org/10.3891/acta.chem.scand.14-0919	journal	January 1960
Phase Transitions in Fe(x)S(x = 0.90--1.00) Studied by Neutron Diffraction. Andresen, Arne F.; Torbo, Per; Östlund, Eric Acta Chemica Scandinavica, Vol. 21 https://doi.org/10.3891/acta.chem.scand.21-2841	journal	January 1967
Thermal Decomposition of Pyrite FeS₂ under Reducing Conditions Charpentier, Ludovic; Masset, Patrick J. Materials Science Forum, Vol. 654-656 https://doi.org/10.4028/www.scientific.net/MSF.654-656.2398	journal	June 2010

Similar Records

Reversible reactions between pyrite and pyrrhotite in SO sub 2

Journal Article · Sun Mar 31 23:00:00 EST 1991 · JOM (Journal of the Minerals, Metals and Materials Society); (United States) · OSTI ID:5467712

Method for desulfurization of coal

Patent · Tue Jul 07 00:00:00 EDT 1987 · OSTI ID:7260559

CORRELATION OF TGA AND DTA TEMPERATURES IN DECOMPOSITION REACTIONS

Journal Article · Thu Dec 31 23:00:00 EST 1959 · Journal of the American Ceramic Society (U.S.) · OSTI ID:4217053

Related Subjects

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

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

Citation Formats

References (42)

Similar Records

Related Subjects