Hostname: page-component-586b7cd67f-tf8b9 Total loading time: 0 Render date: 2024-11-29T22:09:06.626Z Has data issue: false hasContentIssue false
  • English
  • Français

The experimental replacement of ilmenite by rutile in HCl solutions

Published online by Cambridge University Press:  05 July 2018

A. Janssen ,
A. Putnis ,
T. Geisler  and
C. V. Putnis
A. Janssen*
Affiliation:
Institut für Mineralogie, University of Münster, Corrensstrasse 24, 48149 Münster, Germany
A. Putnis
Affiliation:
Institut für Mineralogie, University of Münster, Corrensstrasse 24, 48149 Münster, Germany
T. Geisler
Affiliation:
Institut für Mineralogie, University of Münster, Corrensstrasse 24, 48149 Münster, Germany Mineralogie, Department Geowissenschaften, University of Hamburg, Grindelallee 48, 20146 Hamburg, Germany
C. V. Putnis
Affiliation:
Institut für Mineralogie, University of Münster, Corrensstrasse 24, 48149 Münster, Germany
*
*E-mail: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

To determine the mechanism of acid-leaching of ilmenite to ultimately forming rutile, we have carried out an experimental study of ilmenite alteration in autoclaves at 150ºC in HCl solutions. The resulting products were studied by X-ray diffraction, scanning electron microscopy, electron microprobe and Raman spectroscopy. In some experiments the solution was initially enriched in 18O and the distribution of the isotope in the alteration products mapped from the frequency shift of cation oxygen stretching bands in the Raman spectra. The alteration begins at the original ilmenite crystal surface and has also taken place along an intricate branching network of fractures in the ilmenite, generated by the reaction. Element-distribution maps and chemical analyses of the reaction product within the fractures show marked depletion in Fe and Mn and a relative enrichment of Ti. Chemical analyses however, do not correspond to any stoichiometric composition, and may represent mixtures of TiO2 and Fe2O3. The fracturing is possibly driven by volume changes associated with dissolution of ilmenite and simultaneous reprecipitation of the product phases (including rutile) from an interfacial solution along an inward moving dissolution-reprecipitation front. Raman spectroscopy shows that the 18O is incorporated in the rutile structure during the recrystallization. Throughout the alteration process, the original morphology of the ilmenite is preserved although the product is highly porous. The rutile inherits crystallographic information from the parent ilmenite, resulting in a triply-twinned rutile microstructure. The results indicate that the ilmenite is replaced directly by rutile without the formation of any intermediate reaction products. The reaction is described in terms of an interface-coupled dissolution-precipitation mechanism.

Keywords

ilmenitepseudorutilerutilehydrothermal alterationinterface-coupled dissolution-reprecipitation
Type
Research Article
Information
Mineralogical Magazine , Volume 74 , Issue 4 , August 2010 , pp. 633 - 644
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2010

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

Armbruster, T. (1981) On the origin of sagenites — structural coherency of rutile with hematite and spinel structure types. Neues Jahrbuch fur Mineralogie, 7, 328–334.Google Scholar
Daneu, N., Schmid, H., Recnik, A. and Mader, W. (2007) Atomic structure and formation mechanism of (301) rutile twins from Diamantina (Brazil). Amercian Mineralogist, 92, 1789–1799.CrossRefGoogle Scholar
El-Hazek, N., Lasheen, T.A., El-Sheikh, R. and Zaki, S.A. (2007) Hydrometallurgical criteria for TiO2 leaching from Rosetta ilmenite by hydrochloric acid. Hydrometallurgy, 87, 45–50.CrossRefGoogle Scholar
Force, E.R., Richards, R.P., Scott, K.M., Valentine, P.C. and Fishman, N.S. (1996) Mineral intergrowths replaced by elbow-twinned rutile in altered rocks. The Canadian Mineralogist, 34, 605–614.Google Scholar
Frost, M.T., Grey, I.E., Harrowfield, I.R. and Mason, K. (1983) The dependence of alumina and silica contents on the extent of alteration of weathered ilmenites from Western Australia. Mineralogical Magazine, 47, 201–208.CrossRefGoogle Scholar
Geisler, T., Pöml, P., Stephan, T., Janssen, A. and Putnis, A. (2005a) Experimental observation of an interface-controlled pseudomorphic replacement reaction in a natural crystalline pyrochlore. American Mineralogist, 90, 1683–1687.CrossRefGoogle Scholar
Geisler, T., Seydoux-Guillaume, A.-M., Pöml, P., Golla-Schindler, U., Berndt, I., Wirth, R., Pollok, K., Janssen, A. and Putnis, A. (2005a) Experimental hydrothermal alteration of crystalline and radiation-damaged pyrochlore. Journal of Nuclear Materials, 344, 17–23.CrossRefGoogle Scholar
Grey, I.E. and Li, C. (2003) Hydroxylian pseudorutile derived from picroilmenite in the Murray Basin, southeastern Australia. Mineralogical Magazine, 67, 733–747.CrossRefGoogle Scholar
Grey, I.E. and Reid, A.F. (1975) Structure of pseudo-rutile and its role in natural alteration of ilmenite. American Mineralogist, 60, 898–906.Google Scholar
Grey, I.E., Watts, J. and Bayliss, P. (1994) Mineralogical nomenclature: pseudorutile revalidated and neotype given. Mineralogical Magazine, 58, 597–600.CrossRefGoogle Scholar
Grey, I.E., MacRae, C., Silvester, E. and Susini, J. (2005) Behaviour of impurity elements during the weathering of ilmenite. Mineralogical Magazine, 69, 437–446.CrossRefGoogle Scholar
Grey, I.E., Bordet, P., Wilson, N.C., Townend, R., Bastow, T.J. and Brunelli, M. (2010) A new Al-rich hydroxylian pseudorutile from Kalimantan, Indonesia. American Mineralogist, 95, 161–170.CrossRefGoogle Scholar
Hovelmann, J., Putnis, A., Geisler, T., Schmidt, B.C. and Golla-Schindler, U. (2010) The replacement of plagioclase feldspars by albite: Observations from hydrothermal experiments. Contributions to Mineralogy and Petrology, 159, 43–59.CrossRefGoogle Scholar
Ignatiev, V.D. (1999) Solid phase mechanism of the ilmenite leucoxenisation. Lithology Mineral Resources, 34, 184–189.Google Scholar
Jamtveit, B., Putnis, C.V. and Malthe-Sorenssen, A. (2009) Reaction induced fracturing during replacement processes. Contributions to Mineralogy and Petrology, 157, 127–133.CrossRefGoogle Scholar
Kieffer, S.W. (1982) Thermodynamics and lattice-vibrations of minerals. 5. Applications to phase-equilibria, isotopic fractionation and high pressure thermodynamic properties. Reviews in Geophysics, 20, 827–849.CrossRefGoogle Scholar
Knauss, K.G., Dibley, M.J., Bourcier, W.L. and Shaw, H.F. (2001) Ti(IV) hydrolysis constants derived from rutile solubility measurements from 100 to 300°C. Applied Geochemistry, 16, 1115–1128.CrossRefGoogle Scholar
Malthe-Sorenssen, A., Jamtveit, B. and Meakin, P. (2006) Fracture patterns generated by diffusion controlled volume changing reactions. Physical Review Letters, 96, 245501.CrossRefGoogle ScholarPubMed
Miicke, A. and Bhadra Chaudhuri, J.N. (1991) The continuous alteration of ilmenite through pseudorutile to leucoxene. Ore Geology Reviews, 6, 25–44.CrossRefGoogle Scholar
Niedermeier, D.R.D., Putnis, A., Geisler, T., Golla-Schindler, U. and Putnis, C.V. (2009) The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions. Contributions to Mineralogy and Petrology, 157, 65–76.CrossRefGoogle Scholar
Olanipekun, E. (1999) A kinetic study of the leaching of a Nigerian ilmenite ore by hydrochloric acid. Hydrometallurgy, 53, 1–10.CrossRefGoogle Scholar
Pöml, P., Menneken, M., Stephan, T., Niedermeyer, D.R.D., Geisler, T. and Putnis, A. (2007) Mechanism of hydrothermal alteration of natural self-irradiated and synthetic crystalline titanate-based pyrochlore. Geochimica et Cosmochimica Ada, 71, 3311–3322.CrossRefGoogle Scholar
Pownceby, M.I. (2010) Alteration and associated impurity element enrichment in detrital ilmenites from the Murray Basin, southeast Australia: a product of multistage alteration. Australian Journal of Earth Sciences, 57, 243–258.CrossRefGoogle Scholar
Putnis, A. (2002) Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Mineralogical Magazine, 66, 689–708.CrossRefGoogle Scholar
Putnis, A. (2009) Mineral replacement reactions. Pp 87–124 in: Thermodynamics and Kinetics of Water-Rock Interaction (Oelkers, E.H. and Schott, J., editors). Reviews in Mineralogy and Geochemistry, 70. Mineralogical Society of America, Chantilly, Virginia, USA.CrossRefGoogle Scholar
Putnis, C.V. and Mezger, K. (2004) A mechanism of mineral replacement: isotope tracing in the model system KCl-KBr-H2O. Geochimica et Cosmochimica Ada, 68, 2839–2848.CrossRefGoogle Scholar
Putnis, A. and Putnis, C.V. (2007) The mechanism of reequilibration of solids in the presence of a fluid phase. Journal of Solid State Chemistry, 180, 1783–1786.CrossRefGoogle Scholar
Schroeder, P., Le Golvan, J. and Roden, M. (2002) Weathering of ilmenite from granite and chlorite schist in the Georgia Piedmont. American Mineralogist, 87, 1616–1625.CrossRefGoogle Scholar
Sinha, H.N. (1984) Hydrochloric acid leaching of ilmenite. Proceedings of the Symposium on Extractive Metallurgy AusIMM Melbourne (Australia), The Australasian Institute of Mining and Metallurgy, Level 3, 15—31 Pelham street, Carlton Victoria, 3053, Australia, pp. 163–168.Google Scholar
van Dyk, J., Vegter, N. and Pistorius, P. (2002) Kinetics of ilmenite dissolution in hydrochloric acid. Hydrometallurgy, 65, 31–36.CrossRefGoogle Scholar
Xia, F., Brugger, J., Chen, G., Ngothai, Y., O'Neil, B., Putnis, A. and Pring, A. (2009) Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite. Geochimica et Cosmochimica Ada, 73, 1945–1969.CrossRefGoogle Scholar
Zhao, J., Brugger, J., Grundler, P.V., Xia, F., Chen, G. and Pring, A. (2009) Mechanism and kinetics of a mineral transformation under hydrothermal conditions: Calaverite to metallic gold. American Mineralogist, 94, 1541–1555.CrossRefGoogle Scholar