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Validation and Recalibration of the Solubility Models in Support of the Heater Test in Salt Formations

Published online by Cambridge University Press:  24 January 2020

Yongliang Xiong ,
Kris Kuhlman ,
Melissa Mills  and
Yifeng Wang
Yongliang Xiong*
Affiliation:
Department of Nuclear Waste Disposal Research & Analysis, Sandia National Laboratories (SNL), 1515 Eubank Boulevard SE, Albuquerque, NM 87123, USA
Kris Kuhlman
Affiliation:
Department of Applied Systems Analysis & Research, Sandia National Laboratories (SNL), 1515 Eubank Boulevard SE, Albuquerque, NM 87123, USA
Melissa Mills
Affiliation:
Department of Applied Systems Analysis & Research, Sandia National Laboratories (SNL), 1515 Eubank Boulevard SE, Albuquerque, NM 87123, USA
Yifeng Wang
Affiliation:
Department of Nuclear Waste Disposal Research & Analysis, Sandia National Laboratories (SNL), 1515 Eubank Boulevard SE, Albuquerque, NM 87123, USA
*
*Corresponding author email: yxiong@sandia.gov
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Abstract

The US Department of Energy Office of Nuclear Energy is conducting a brine availability heater test to characterize the thermal, mechanical, hydrological and chemical response of salt at elevated temperatures. In the heater test, brines will be collected and analyzed for chemical compositions. In order to support the geochemical modeling of chemical evolutions of the brines during the heater test, we are recalibrating and validating the solubility models for the mineral constituents in salt formations up to 100°C, based on the solubility data in multiple component systems as well as simple systems from literature.

In this work, we systematically compare the model-predicted values based on the various solubility models related to the constituents of salt formations, with the experimental data. As halite is the dominant constituent in salt formations, we first test the halite solubility model in the Na-Mg-Cl dominated brines. We find the existing halite solubility model systematically over-predict the solubility of halite. We recalibrate the halite model, which can reproduce halite solubilities in Na-Mg-Cl dominated brines well.

As gypsum/anhydrite in salt formations controls the sulfate concentrations in associated brines, we test the gypsum solubility model in NaCl solutions up to 5.87 mol•kg–1 from 25°C to 50°C. The testing shows that the current gypsum solubility model reproduces the experimental data well when NaCl concentrations are less than 1 mol•kg–1. However, at NaCl concentrations higher than 1, the model systematically overpredicts the solubility of gypsum.

In the Na+—Cl–—SO42–—CO32– system, the validation tests up to 100°C demonstrate that the model excellently reproduces the experimental data for the solution compositions equilibrated with one single phase such as halite (NaCl) or thenardite (Na2SO4), with deviations equal to, or less than, 1.5 %. The model is much less ideal in reproducing the compositions in equilibrium with the assemblages of halite + thenardite, and of halite + thermonatrite (Na2CO3•H2O), with deviations up to 31 %. The high deviations from the experimental data for the multiple assemblages in this system at elevated temperatures may be attributed to the facts that the database has the Pitzer interaction parameters for Cl–—CO32– and SO42–—CO32– only at 25°C.

In the Na+—Ca2+—SO42–—HCO3– system, the validation tests also demonstrate that the model reproduces the equilibrium compositions for one single phase such as gypsum better than the assemblages of more than one phase.

Keywords

thermodynamicswaste managementenvironment
Type
Articles
Information
MRS Advances , Volume 5 , Issue 5-6: Scientific Basis for Nuclear Waste Management XLIII , 2020 , pp. 233 - 243
Copyright
Copyright © Materials Research Society 2020

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References

Mills, M., Kuhlman, K., Matteo, E., Herrick, C., Nemer, M., Heath, J., Xiong, Y.-L., Lopez, C., Stauffer, P., Boukhalfa, H., Guiltinan, E., Rahn, T., Weaver, D., Dozier, B., Otto, S., Rutqvist, J., Wu, Y., Hu, M., Crandall, D., Salt Heater Test (FY19). Sandia National Laboratories, Albuquerque, NM, SAND2019-10240 R (2019).CrossRefGoogle Scholar
White, M., Wilmot, R., Crawford, M., Smith, J., Gilbert, A., Evans, D., Hough, E., Field, L., Reay, D., Milodowski, A., McHenry, J. and Wolf, J., Contractor Report to RWM UK Halite Deposits Structure, Stratigraphy, Properties and Post-closure Performance, Radioactive Waste Management, UK, Contractor Report no.1735-1(2018).Google Scholar
Teeple, J.E., The industrial development of Searles Lake brines with equilibrium data. The Chemical Catalog Company, Inc.; New York (1929).Google Scholar
Dai, Z., Kan, A.T., Shi, W., Yan, F., Zhang, F., Bhandari, N., Ruan, G., Zhang, Z., Liu, Y., Alsaiari, H.A., and Lu, Y.T., Industrial & Engineering Chemistry Research 56, 6548 (2017).CrossRefGoogle Scholar
Soliev, L., Jumaev, M.T., and Makhmadov, K.R., Russian Journal of Inorganic Chemistry, 64, 270 (2019).CrossRefGoogle Scholar
Wolery, T.J., Xiong, Y.-L, and Long, J.J., Verification and Validation Plan/Validation Document for EQ3/6 Version 8.0a for Actinide Chemistry, Document Version 8.10. Carlsbad, NM: Sandia National laboratories. ERMS 550239 (2010).Google Scholar
Xiong, Y.-L., WIPP Verification and Validation Plan/Validation Document for EQ3/6 Version 8.0a for Actinide Chemistry, Revision 1, Document Version 8.20. Supersedes ERMS 550239. Carlsbad, NM. Sandia National Laboratories. ERMS 555358 (2011).Google Scholar
Chou, I.M., Buizinga, B., Clynne, M.A., and Potter, R.W., “The Densities of Halite-Saturated WIPP-A and NBT-6 Brines and Their NaCl Contents in Weight Percent, Molal, and Molar Units from 20 to 100°C”, US Geological Survey Open-File Report, pp.82-899 (1982).Google Scholar
Xiong, Y.-L., and Lord, A.S., Applied Geochemistry 23, 1634 (2008).CrossRefGoogle Scholar
Greenberg, J.P., and Moller, N., Geochimica et Cosmochimica Acta 53, 2503 (1989).CrossRefGoogle Scholar
Pabalan, R.T., and Pitzer, K.S., “Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO4-OH-H2O,” In Molecular Structure and Statistical Thermodynamics: Selected Papers of Kenneth S Pitzer (pp. 461-474) (1993).CrossRefGoogle Scholar
Raju, K. U., Atkinson, G., Journal of Chemical and Engineering Data 35, 361 (1990).CrossRefGoogle Scholar
Bock, E., Canadian Journal of Chemistry 39, 1746 (1961).CrossRefGoogle Scholar
Robie, R.A. and Hemingway, B.S., Thermodynamic Properties of Minerals and Related Substances at 298.15K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures, Bulletin 2131, Reston, Virginia, U.S. Geological Survey (1995).Google Scholar
He, S. and Morse, J.W., 1993, The carbonic acid system and calcite solubility in aqueous Na-K-Ca-Mg-Cl-SO4 solutions from 0 to 90 deg.C. Geochimica Cosmochimica Acta, Vol. 57, p. 3533-3554.CrossRefGoogle Scholar
Pitzer, K.S., “Ion interaction approach: theory and data correlation”, Activity Coefficients in Electrolyte Solutions, 2nd Edition, Chapter 3, p. 75-153, CRC Press, Boca Raton, Florida, ed. Pitzer, K.S. (1991).Google Scholar
Potter, R.W II and Clynne, M.A., Solubility of highly soluble salts in aqueous media-part 1, NaCl, KCl, CaCl2, Na2SO4, and K2SO4 solubilities to 100°C. Journal of US Geological Survey Research, US DEPARTMENT OF THE INTERIOR, 6(6), pp.701-705 (1978).Google Scholar
Soliev, L., Dzhumaev, M.T. and Usmonov, M.B., Russian Journal of Inorganic Chemistry 61, 1041 (2016).CrossRefGoogle Scholar