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Formation of hard hematite-cemented solids in steam generators: An analog of lithification of Fe-containing sedimentary rocks

Published online by Cambridge University Press:  01 January 2024

Ewa Labuda ,
Galina Cherepakhov  and
Aaron Barkatt
Ewa Labuda
Affiliation:
Sheppard T. Powell Associates, LLC, 1915 Aliceanna Street, Baltimore, Maryland 21231, USA
Galina Cherepakhov
Affiliation:
Consolidated Edison Co. of New York, Inc.
Aaron Barkatt*
Affiliation:
The Catholic University of America, 620 Michigan Avenue, N.E. Washington, DC 20064, USA
*
*E-mail address of corresponding author: barkatt@cua.edu
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Abstract

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The formation of hard hematite in steam generators with relatively high levels (5–10 µg/L) of dissolved oxygen at temperatures around 280–290°C and pressures around 6–8 MPa can serve as an analog for the formation of hard hematite in sedimentary processes. Furthermore, in steam generators, as well as in nature, hematite is an effective cementing agent, capable of incorporating as much as twice its own weight of other solids to form a hard composite material. Laboratory simulations showed ferrihydrite to be the likely starting material for the formation of hard, dense hematite at temperatures much lower than those required for sintering of anhydrous hematite. These laboratory simulations, performed at temperatures around 260°C and pressures of ∼500 MPa, resulted in the formation of hard hematite or hematite-based composite solids over periods of 3–5 h, compared with several months in steam generators and many years in nature. The amount of water present during the synthesis (10–15% of the weight of dry ferrihydrite) and the gradual removal of water proved to be key parameters in the formation of hard, dense hematite. The mechanism, studied by means of X-ray diffractometry, Mössbauer spectroscopy and infrared spectroscopy, appeared to involve build-up, then gradual condensation of OH bridges, leading to the conversion of ferrihydrite to hydrohematite with approximately 4–5% of residual water. The presence of other solids, such as copper and its oxides, alumina and silica, in large quantities, resulted in smaller grain size of the hydrohematite product but did not affect its mechanical properties. On the other hand, the use of hydrazine to provide a reducing environment produced goethite during the precursor synthesis stage and soft magnetite during the pressing stage. However, whenever hematite was produced, it could not be subsequently reduced to magnetite by hydrazine under the reaction conditions specified above. The mechanical properties as well as the spectroscopic characteristics of the product of pressing agreed with observations on sedimentary hematite-cemented rocks.

Keywords

CementationDehydrationFerrihydriteHardeningHematiteHydrohematiteFe OxidesLithificationOxyhydroxideSedimentary Rock
Type
Research Article
Information
Clays and Clay Minerals , Volume 55 , Issue 1 , February 2007 , pp. 59 - 70
Copyright
Copyright © 2007, The Clay Minerals Society

References

Bagchi, T.P. and Sen, P.K., (1982) Kinetics of densification of powder compacts during the initial stage of sintering with constant rates of heating. A thermal analysis approach Thermochimica Acta 56 269–283 10.1016/0040-6031(82)87035-4.CrossRefGoogle Scholar
Barron, V. Rendon, J.L. Torrent, J. and Serna, C.J., (1984) Relation of infrared, crystallochemical, and morphological properties of Al-substituted hematites Clays and Clay Minerals 32 475–479 10.1346/CCMN.1984.0320605.CrossRefGoogle Scholar
Burns, R. Cherepakhov, G. Mark, J.T. Skulte, P., McIlree, A. Millett, P. and Wood, C.J., (1996) Indian Point 2 Station PWR Secondary Water Chemistry Guidelines — Revision 4, EPRI TR-102134-R4 Palo Alto, California, USA Electric Power Research Institute A-43–A-47.Google Scholar
Campbell, A.S. Schwertmann, U. and Campbell, P.A., (1997) Formation of cubic phases on heating ferrihydrite Clay Minerals 32 615–622 10.1180/claymin.1997.032.4.11.CrossRefGoogle Scholar
Carlson, L. and Schwertman, U., (1981) Natural ferrihydrites in surface deposits from Finland and their association with silica Geochimica et Cosmochimica Acta 45 421–429 10.1016/0016-7037(81)90250-7.CrossRefGoogle Scholar
Childs, C.W., (1992) Ferrihydrite: A review of structure, properties and occurrence in relation to soils Zeitschrift fuer Pflanzenernaehrung und Bodenkunde 155 441–448 10.1002/jpln.19921550515.CrossRefGoogle Scholar
Cornejo, J., (1986) The effect of heat treatment on textural evolution of ferrihydrite Materials Chemistry and Physics 15 369–377 10.1016/0254-0584(86)90022-2.CrossRefGoogle Scholar
Cornell, R.M. and Giovanoli, R., (1988) The influence of copper on the transformation of ferrihydrite (5Fe2O3·9H2O) into crystalline products in alkaline media Polyhedron 7 385–391 10.1016/S0277-5387(00)80487-8.CrossRefGoogle Scholar
Cornell, R.M. and Schwertmann, U., (2003) The Iron Oxides 2 Weinheim, Germany Wiley-VCH 10.1002/3527602097.CrossRefGoogle Scholar
Cornell, R.M. Giovanoli, R. and Schindler, P.W., (1987) Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkaline media Clays and Clay Minerals 35 21–28 10.1346/CCMN.1987.0350103.CrossRefGoogle Scholar
Cornell, R.M. Giovanoli, R. and Schneider, W., (1989) Review of the hydrolysis of iron(III) and the crystallization of amorphous iron(III) hydroxide hydrate Journal of Chemical Technology and Biotechnology 46 115–134 10.1002/jctb.280460204.CrossRefGoogle Scholar
Crosby, W.O., (1891) On the contrast in color of the soils of high and low latitudes American Geologist 8 77.Google Scholar
Dang, M.-Z., Rancourt, D.G., Dutrizac, J.E., Lamarche, G. and Provencher, R. (1997) Protohematite-hydrohematite-hematite: structuro-chemical phase relationships in hematite-like materials. Clays Our Future, Proceedings of the 11th International Clay Conference, 265–270.Google Scholar
Drits, V.A. Sakharov, B.A. Salyn, A.L. and Manceau, A., (1993) Structural model for ferrihydrite Clay Minerals 28 185–207 10.1180/claymin.1993.028.2.02.CrossRefGoogle Scholar
Drits, V.A. Gorshkov, A.I. Sakharov, B.A. Salyn, A.L. Manceau, A. and Sivtsov, A.B., (1995) Ferrihydrite and its phase transformations during heating in the oxidizing and reducing environments Lithology and Mineral Resources 1 76–84.Google Scholar
Eggleton, R.A. and Fitzpatrick, R.W., (1988) New data and a revised structural model for ferrihydrite Clays and Clay Minerals 36 111–124 10.1346/CCMN.1988.0360203.CrossRefGoogle Scholar
Fischer, W.R., Stucki, J.W. Goodman, B.A. and Schwertmann, U., (1988) Microbiological reactions of iron in soils Iron in Soils and Clay Minerals Dordrecht, The Netherlands D. Reidel Publishing Company 715–748 10.1007/978-94-009-4007-9_20.CrossRefGoogle Scholar
Friedman, G.M. and Sanders, J.E., (1978) Principles of Sedimentology New York, NY Wiley 235.Google Scholar
Glasauer, S.M. Hug, P. Weidler, P.G. and Gehring, A.U., (2000) Inhibition of sintering by Si during the conversion of Si-rich ferrihydrite to hematite Clays and Clay Minerals 48 51–56 10.1346/CCMN.2000.0480106.CrossRefGoogle Scholar
Inouye, K. Ishii, S. Kaneko, K. and Ishikawa, T., (1972) Effect of copper(II) on the crystallization of α-iron oxide hydrate [α-FeOOH] Zeitschrift für Anorgische und Allgemeine Chemie 391 86–96 10.1002/zaac.19723910111.CrossRefGoogle Scholar
Jambor, J.L. and Dutrizac, J.E., (1998) Occurrence and constitution of natural and synthetic ferrihydrite, a widespread iron oxyhydroxide Chemical Reviews 98 2549–2585 10.1021/cr970105t.CrossRefGoogle ScholarPubMed
Kündig, W. and Bömmel, H., (1966) Some properties of supported small a-Fe2O3 particles determined with the Mössbauer effect Physical Review 142 327–333 10.1103/PhysRev.142.327.CrossRefGoogle Scholar
Labuda, E., (1996) Reactions of iron oxides at elevated pressures and temperatures Washington, D.C. The Catholic University of America 262 pp.Google Scholar
Lewis, D.G. and Schwertmann, U., (1979) The influence of aluminum on the formation of iron oxides. IV. The influence of aluminum concentration, hydroxide concentration, and temperature Clays and Clay Minerals 27 195–200 10.1346/CCMN.1979.0270304.CrossRefGoogle Scholar
Lunden, D.G. Dean, W., Trudinger, P.A. and Swaine, D.J., (1979) Biochemistry of iron Biogeochemical Cycling of Mineral-forming Elements Amsterdam Elsevier 211–251 10.1016/S0166-1116(08)71060-4.CrossRefGoogle Scholar
Pfaff, G. and Feltz, A., (1990) Solid-state reactivity and mechanisms in oxide systems. VI. Sintering behaviour of hematite prepared by the hydrothermal method Solid State Ionics 38 25–29 10.1016/0167-2738(90)90441-S.CrossRefGoogle Scholar
Ruan, H.D. Frost, R.L. Kloprogge, J.T. and Duong, L., (2002) Infrared spectroscopy of goethite dehydroxylation: III. FT-IR microscopy of in situ study of the thermal transformation of goethite to hematite Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 58A 967–981 10.1016/S1386-1425(01)00574-1.CrossRefGoogle Scholar
Russell, J.D., (1979) Infrared spectroscopy of ferrihydrite: Evidence for the presence of structural hydroxyl groups Clay Minerals 14 109–114 10.1180/claymin.1979.014.2.03.CrossRefGoogle Scholar
Schultz, M.F. Benjamin, M.M. and Ferguson, J.F., (1987) Adsorption and desorption of metals on ferrihydrite: Reversibility of the reaction and sorption properties of the regenerated solid Environmental Science and Technology 21 863–869 10.1021/es00163a003.CrossRefGoogle Scholar
Schwertmann, U. and Cornell, R.M., (2000) Iron Oxides in the Laboratory 2 Weinheim, Germany Wiley-VCH 10.1002/9783527613229.CrossRefGoogle Scholar
Schwertmann, U. and Murad, E., (1990) The influence of aluminum on iron oxides: XIV. Aluminum-substituted magnetite synthesized at ambient temperatures Clays and Clay Minerals 38 196–202 10.1346/CCMN.1990.0380211.CrossRefGoogle Scholar
Schwertmann, U. Fitzpatrick, W.R. Taylor, R.M. and Lewis, D.G., (1979) The influence of aluminum on iron oxides. Part II. Preparation and properties of aluminum-substituted hematites Clays and Clay Minerals 27 105–112 10.1346/CCMN.1979.0270205.CrossRefGoogle Scholar
Schwertmann, U. Friedl, J. and Stanjek, H., (1999) From Fe(III) ions to ferrihydrite and then to hematite Journal of Colloid and Interface Science 209 215–223 10.1006/jcis.1998.5899.CrossRefGoogle ScholarPubMed
Stanjek, H. and Weidler, P.G., (1992) The effect of dry heating on the chemistry, surface area, and oxalate solubility of synthetic 2-line and 6-line ferrihydrites Clay Minerals 27 397–412 10.1180/claymin.1992.027.4.01.CrossRefGoogle Scholar
Torrent, J. Guzman, R. and Parra, M.A., (1982) Influence of relative humidity on the crystallization of Fe(III) oxides from ferrihydrite Clays and Clay Minerals 30 337–340 10.1346/CCMN.1982.0300503.CrossRefGoogle Scholar
Turner, P., (1980) Continental Red Beds Amsterdam Elsevier.Google Scholar
Towe, K.M. and Bradley, W.F., (1967) Mineralogical constitution of colloidal hydrous ferric oxides Journal of Colloid and Interface Science 24 384–392 10.1016/0021-9797(67)90266-4.CrossRefGoogle Scholar
Van Houten, F.B., (1972) Iron and clay in tropical savanna alluvium, Northern Colombia. Contribution to the Origin of Red Beds Geological Society of America Bulletin 83 2761–2772 10.1130/0016-7606(1972)83[2761:IACITS]2.0.CO;2.CrossRefGoogle Scholar
Van Houten, F.B., (1973) Origin of Red Beds. A review. 1961–1972 Annual Review of Earth and Planetary Science 1 39–61 10.1146/annurev.ea.01.050173.000351.CrossRefGoogle Scholar
Varrin, R.D. Jr., (1996) Characterization of PWR Steam Generator Deposits, EPRI TR-106048 Palo Alto, California, USA Electric Power Research Institute.Google Scholar
Vempati, R.K. and Loeppert, R.H., (1989) Influence of structural and absorbed Si on the transformation of synthetic ferrihydrite Clays and Clay Minerals 37 273–279 10.1346/CCMN.1989.0370312.CrossRefGoogle Scholar
Walker, T.R., (1967) Formation of Red Beds in modern and ancient deserts Ganz-mavag Bulletin 78 353–368.Google Scholar
Walker, T.R., (1974) Formation of Red Beds in moist tropical climates. Hypothesis Geological Society of America Bulletin 85 633–638 10.1130/0016-7606(1974)85<633:FORBIM>2.0.CO;2.2.0.CO;2>CrossRefGoogle Scholar
Weidler, P.G., (1995) Surfaces of iron oxides Germany Technical University of Munich 108 pp.Google Scholar
Wightman, P.G., (2002) New insights into bacteria-related geochemical processes: co-adsorption, temperature dependence of protonation, and effects on iron-hydroxide precipitation Indiana, USA University of Notre Dame 104 pp.Google Scholar
Wolska, E., (1977) The significance of aluminum traces in the elimination of the goethite phase during the ageing of amorphous iron(III) hydroxide Monatshefte für Chemie 108 819–828 10.1007/BF00898046.CrossRefGoogle Scholar
Wolska, E., (1981) The structure of hydrohematite Zeitschrift für Kristallographie 154 69–75.CrossRefGoogle Scholar
Wolska, E. and Schwertmann, U., (1989) Nonstoichiometric structures during dehydroxylation of goethite Zeitschrift für Kristallographie 189 223–237.CrossRefGoogle Scholar
Zhao, J. Huggins, F.E. Feng, Z. and Huffman, G.P., (1994) Ferrihydrite: surface structure and its effect on phase transformation Clays and Clay Minerals 42 737–746 10.1346/CCMN.1994.0420610.Google Scholar