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

  • Yongliang Xiong (a1), Kris Kuhlman (a2), Melissa Mills (a2) and Yifeng Wang (a1)

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.

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Corresponding author

*Corresponding author email: yxiong@sandia.gov

References

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1.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).
2.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).
3.Teeple, J.E., The industrial development of Searles Lake brines with equilibrium data. The Chemical Catalog Company, Inc.; New York (1929).
4.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).
5.Soliev, L., Jumaev, M.T., and Makhmadov, K.R., Russian Journal of Inorganic Chemistry, 64, 270 (2019).
6.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).
7.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).
8.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).
9.Xiong, Y.-L., and Lord, A.S., Applied Geochemistry 23, 1634 (2008).
10.Greenberg, J.P., and Moller, N., Geochimica et Cosmochimica Acta 53, 2503 (1989).
11.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).
12.Raju, K. U., Atkinson, G., Journal of Chemical and Engineering Data 35, 361 (1990).
13.Bock, E., Canadian Journal of Chemistry 39, 1746 (1961).
14.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).
15.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.
16.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).
17.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).
18.Soliev, L., Dzhumaev, M.T. and Usmonov, M.B., Russian Journal of Inorganic Chemistry 61, 1041 (2016).

Keywords

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

  • Yongliang Xiong (a1), Kris Kuhlman (a2), Melissa Mills (a2) and Yifeng Wang (a1)

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