Hostname: page-component-848d4c4894-hfldf Total loading time: 0 Render date: 2024-06-12T01:46:09.839Z Has data issue: false hasContentIssue false

Rapid Dehydroxylation of Nickeliferous Goethite in Lateritic Nickel Ore: X-Ray Diffraction and TEM Investigation

Published online by Cambridge University Press:  01 January 2024

Matthew Landers*
Affiliation:
School of Earth and Environment (M087), University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia
Robert J. Gilkes
Affiliation:
School of Earth and Environment (M087), University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia
Martin A. Wells
Affiliation:
CSIRO, Exploration and Mining, Australian Resource Research Centre (ARRC), PO Box 1130, Bentley, WA 6102, Australia
*
* E-mail address of corresponding author: 10031821@student.uwa.edu.au

Abstract

A method for extracting Ni and other metals from lateritic ores by means of shock heating has been investigated. Shock heating releases some of the metal from its goethitic host. Even though the transformation of pure goethite to hematite is known to occur via intermediate hydroxylated phases, the effect of other metals such as Ni substituting for Fe in goethites on this thermal transformation to hematite is unknown. The purpose of this study was to fill this gap, with the hope that the results will lead to more energy-efficient extraction methods and/or a better understanding of Fe geochemistry in thermally activated soils. X-ray diffraction, transmission electron microscopy with EDS, and thermal analysis were used to investigate mineralogical changes in nickeliferous goethites from five oxide-type lateritic nickel ore deposits that had been subjected to shock heating at temperatures in the range 220–800°C. Acicular, nano-sized goethite was the main constituent of the samples with minor to trace amounts of quartz, talc, kaolinite, chromite, maghemite, and Mn oxides. Goethite was partially dehydroxylated to OH-hematite at 340–400°C and had completely altered to well ordered hematite at 800°C. The OH-hematite was characterized by broad XRD peaks for reflections associated with the Fe sublattice. The goethite unit-cell a and b lengths remained almost constant with increasing preheating temperature up to 300°C, while the size of the c axis dimension contracted. The neoformed hematite crystals were larger than the precursor goethite crystals due to development, by sintering and surface diffusion, of regularly ordered hematite domains. The increase (1.5–2.6 fold) in surface area with increasing heating temperature (up to 340–400°C) reflected the development of slit-shaped micropores (∼300°C), which further developed into elliptically shaped micropores (∼400°C) in OH-hematite. With increased heating temperature, well ordered hematite formed with only a few micropores remaining. Such results may contribute to the development of more efficient procedures for extracting Ni from lateritic nickel ores, as the rate of dissolution of goethite in acid in ‘heap and pressure’ leach facilities will be enhanced by the increases in surface area and microporosity. The results may also provide valuable information on the probable effects of natural heating on pedogenic Fe oxides.

Type
Research Article
Copyright
Copyright © The Clay Minerals Society 2009

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Anand, R.R. and Gilkes, R.J., 1987 The association of maghemite and corundum in Darling Range laterites, Western Australia Australian Journal of Soil Research 35 303311 10.1071/SR9870303.CrossRefGoogle Scholar
Alvarez, M. Rueda, E.H. and Sileo, E.E., 2007 Simultaneous incorporation of Mn and Al in the goethite structure Geochimica et Cosmochimica Acta 71 10091020 10.1016/j.gca.2006.11.012.CrossRefGoogle Scholar
Barrón, V. Gálvez, N. Hochella, M.F. and Torrent, J., 1997 Epitaxial overgrowth of goethite on hematite synthesized in phosphate media: A scanning force and transmission electron microscopy study American Mineralogist 82 10911100 10.2138/am-1997-11-1206.CrossRefGoogle Scholar
Bernstein, L.R. and Waychunas, G.A., 1987 Germanium crystal chemistry in hematite and goethite from Apex Mine, Utah, and some data on germanium in aqueous solution and in stottite Geochimica et Cosmochimica Acta 51 623630 10.1016/0016-7037(87)90074-3.CrossRefGoogle Scholar
Brown, G., Brindley, G.W. Brown, G., 1980 Associated minerals Crystal Structures of Clay Minerals and their X-ray Identification London Mineralogical Society 361410.CrossRefGoogle Scholar
Brunauer, S. Emmett, P.H. and Teller, E., 1938 Adsorption of gases in multimolecular layers Journal of the American Chemical Society 60 309319 10.1021/ja01269a023.CrossRefGoogle Scholar
Carvalho-e-Silva, M.L. Ramos, A.Y. Tolentino, H.C.N. Enweiler, J. Netto, S.M. and Alves, M.C.M., 2003 Incorporation of Ni into natural goethite: An investigation by X-ray absorption spectroscopy American Mineralogist 88 876882 10.2138/am-2003-5-617.CrossRefGoogle Scholar
Cornell, R.M. Mann, S. and Skarnoulis, A.J., 1983 A high resolution electron microscopy examination of domain boundaries in synthetic goethite Journal of the Chemical Society, Faraday Transactions 79 2672684.Google Scholar
Cornell, R.M. and Schwertmann, U., 2003 The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses Weinheim, Germany Wiley-VCH 10.1002/3527602097.CrossRefGoogle Scholar
de Faria, D.L.A. and Lopes, F.N., 2007 Heated goethite and natural hematite: Can Raman spectroscopy be used to differentiate them? Vibrational Spectroscopy 45 117121 10.1016/j.vibspec.2007.07.003.CrossRefGoogle Scholar
Francombe, M.H. and Rooksby, H.P., 1959 Structure transformations affected by the dehydration of diaspore, goethite and delta ferric oxide Clay Minerals Bulletin 4 114 10.1180/claymin.1959.004.21.01.CrossRefGoogle Scholar
Frost, R.L. Kloprogge, J.T. Russell, S.C. and Szetu, J., 1999 Dehydroxylation and the vibrational spectroscopy of aluminum (oxo)hydroxides using infrared emission spectroscopy. Part III: diaspore Applied Spectroscopy 53 829835 10.1366/0003702991947405.CrossRefGoogle Scholar
Frost, R.L. Ding, Z. and Ruan, H.D., 2003 Thermal analysis of goethite, relevance to Australian indigenous art Journal of Thermal Analysis and Calorimetry 71 783797 10.1023/A:1023365923961.CrossRefGoogle Scholar
Gerth, J., 1990 Unit-cell dimensions of pure and trace metal-associated goethites Geochimica et Cosmochimica Acta 54 363371 10.1016/0016-7037(90)90325-F.CrossRefGoogle Scholar
Golightly, J.P. (1981) Nickeliferous laterite deposits. Economic Geology, 75th Anniversary Volume, 710735.CrossRefGoogle Scholar
Gualtieri, A.F. and Venturelli, P., 1999 In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction American Mineralogist 84 895904 10.2138/am-1999-5-624.CrossRefGoogle Scholar
JCPDS, 1988 Mineral Powder Diffraction File, Data Book International 635 Center for Diffraction Data, Joint Committee on Powder Diffraction Standards, 636 Pennsylvania, USA JCPDS.Google Scholar
Klug, H.P. and Alexander, L.E., 1974 X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials New York John Wiley & Sons.Google Scholar
Landers, M. and Gilkes, R.J., 2007 Dehydroxylation and dissolution of nickeliferous goethite in New Caledonian lateritic Ni ore Applied Clay Science 35 162172 10.1016/j.clay.2006.08.012.CrossRefGoogle Scholar
Landers, M. Gilkes, R.J. and Wells, M., 2008 Dissolution kinetics of dehydroxylated nickeliferous goethite from limonitic lateritic nickel ore Applied Clay Science 42 615624 10.1016/j.clay.2008.05.002.CrossRefGoogle Scholar
Löffler, L. and Mader, W., 2006 Anisotropic X-ray peak broadening and twin formation in hematite derived from natural and synthetic goethite Journal of the European Ceramic Society 26 131139 10.1016/j.jeurceramsoc.2004.09.032.CrossRefGoogle Scholar
Lim-Nunez, R. (1985) Synthesis and acid dissolution of metal substituted goethites and hematites. MSc Thesis, Faculty of Natural and Agricultural Sciences, University of Western Australia.Google Scholar
Lima-de-Faria, J., 1963 Dehydration of goethite and diaspore Zeitschrift fur Kristallographie 119 176203 10.1524/zkri.1963.119.3-4.176.CrossRefGoogle Scholar
Mackenzie, R.C. Berggren, G. and Mackenzie, R.C., 1970 Oxides and oxyhydroxides of higher valency elements Differential Thermal Analysis London Academic Press 272302.Google Scholar
Manceau, A. Schlegel, M.L. Musso, M. Sole, V.A. Gauthier, C. Petit, P.E. and Trolard, F., 2000 Crystal chemistry of trace elements in natural and synthetic goethite Geochimica et Cosmochimica Acta 64 36433661 10.1016/S0016-7037(00)00427-0.CrossRefGoogle Scholar
Perrier, N. Gilkes, R.J. and Colin, F., 2006 Heating iron rich soils increases the dissolution rate of metals Clays and Clay Minerals 54 165175 10.1346/CCMN.2006.0540203.CrossRefGoogle Scholar
Pomiès, M.P. Menu, M. and Vignaud, C., 1999 TEM observations of goethite dehydration: Application to archaeological samples Journal of the European Ceramic Society 19 16051614 10.1016/S0955-2219(98)00254-4.CrossRefGoogle Scholar
Pozas, R. Rojas, C.T. Ocana, M. and Serna, C.J., 2004 The nature of Co in synthetic Co-substituted goethites Clays and Clay Minerals 52 760766 10.1346/CCMN.2004.0520611.CrossRefGoogle Scholar
Rooksby, H.P. and Brown, G., 1961 Oxides and hydroxides of aluminium and iron The X-ray Identification and Crystal Structures of Clay Minerals London Mineralogical Society 354392.Google Scholar
Ruan, H.D. and Gilkes, R.J., 1995 Dehydroxylation of aluminous goethite: Unit cell dimensions, crystal size and surface area Clays and Clay Minerals 43 196211 10.1346/CCMN.1995.0430207.CrossRefGoogle Scholar
Ruan, H.D. Frost, R.L. Kloprogge, J.T. and Duong, L., 2002 Infrared spectroscopy of goethite dehydroxylation. II. Effect of aluminium substitution on the behaviour of hydroxyl units Spectrochimica Acta Part A 58 479491 10.1016/S1386-1425(01)00556-X.CrossRefGoogle ScholarPubMed
Rupp, B., 1988 XLAT — a microcomputer program for the refinement of cell constants Scripta Metallurgica 22 6992.Google Scholar
Schulze, D.G. and Schwertmann, U., 1984 The influence of aluminium on iron oxides, X. Properties of Al-substituted goethites Clay Minerals 19 521539 10.1180/claymin.1984.019.4.02.CrossRefGoogle Scholar
Schwertmann, U. Gasser, U. and Sticher, H., 1989 Chromium-for-iron substitution in synthetic goethites Geochimica et Cosmochimica Acta 53 12931297 10.1016/0016-7037(89)90063-X.CrossRefGoogle Scholar
Schwertmann, U. and Latham, U., 1986 Properties of iron oxides in some New Caledonian Oxisols Geoderma 39 105123 10.1016/0016-7061(86)90070-4.CrossRefGoogle Scholar
Schwertmann, U. and Pfab, G., 1996 Structural vanadium and chromium in lateritic iron oxides: Genetic implications Geochimica et Cosmochimica Acta 60 42794283 10.1016/S0016-7037(96)00259-1.CrossRefGoogle Scholar
Stiers, W. and Schwertmann, U., 1985 Evidence for manganese substitution in synthetic goethite Geochimica et Cosmochimica Acta 49 19091911 10.1016/0016-7037(85)90085-7.CrossRefGoogle Scholar
Singh, B. and Gilkes, R.J., 1992 Properties and distribution of iron oxides and their association with minor elements in the soils of south-western Australia Journal of Soil Science 43 7798 10.1111/j.1365-2389.1992.tb00121.x.CrossRefGoogle Scholar
Singh, B. and Gilkes, R.J., 1992 XPAS: An interactive computer program for analysis of powder X-ray diffraction patterns Powder Diffraction 7 610 10.1017/S0885715600015992.CrossRefGoogle Scholar
Torrent, J. Schwertmann, U. and Barrón, V., 1992 Fast and slow phosphate sorption by goethite-rich natural materials Clays and Clay Minerals 40 1421 10.1346/CCMN.1992.0400103.CrossRefGoogle Scholar
Watari, F. Van Landuyt, J. Delavignette, P. and Amelinckx, S., 1979 Electron microscopic study of dehydration transformations: I. Twin formation and mosaic structure in hematite derived from goethite Journal of Solid State Chemistry 29 137150 10.1016/0022-4596(79)90218-4.CrossRefGoogle Scholar
Watari, F. Van Landuyt, J. Delavignette, P. Amelinekx, S. and Igata, N., 1982 X-ray peak broadening as a result of twin formation in some oxides derived by dehydration Physica Status Solidi 73 215244 10.1002/pssa.2210730128.CrossRefGoogle Scholar
Wells, M.A. Fitzpatrick, R.W. and Gilkes, R.J., 2006 Thermal and mineral properties of Al, Cr, Mn, Ni and Ti-substituted goethite Clays and Clay Minerals 54 176194 10.1346/CCMN.2006.0540204.CrossRefGoogle Scholar
Wolska, E., 1988 Relationship between the existence of hydroxyl ions in the anionic sublattice of hematite and its infrared and X-ray characteristics Solid State Ionics 28–30 13491351 10.1016/0167-2738(88)90385-2.CrossRefGoogle Scholar
Wolska, E. and Schwertmann, U., 1989 Nonstoichiometric structures during dehydroxylation of goethite Zeitschrift für Kristallographie 189 223237.CrossRefGoogle Scholar