THERMODYNAMIC MODELS OF ALUMINUM SILICATE MINERAL SOLUBILITY FOR APPLICATION TO ENHANCED GEOTHERMAL SYSTEMS

In this paper we report progress on the development of a thermodynamic model that correctly predicts solvent/solute activities and monomeric aluminum hydrolysis speciation as well as solid-liquid equilibria in the H, Na, Al, Cl, Si(OH)4, SiO(OH)3 , OH, Al(OH), Al(OH)2 , Al(OH)3 , Al(OH)4 − system as a function of pH to high salt concentrations (I ≤ 5 m NaCl), for temperatures up to 300C and for saturation pressures. This model, which incorporates the Pitzer specific interaction equations (Pitzer, 1987, 1991), accurately predicts the fluid compositions for the low Al (≤ 10 m) and Si(OH)4 (≤ 10 m) concentrations commonly encountered in the intermediate pH ranges typical of most natural fluids. For high and low pH regions where the formation of polymeric Al hydrolysis species is low, the model will apply to higher total aluminum concentrations. The successful prediction of the solubility of aluminiosilicate solid phases falling within this system is described.

[1]  D. A. Palmer,et al.  Aluminum speciation and equilibria in aqueous solution: III. Potentiometric determination of the first hydrolysis constant of aluminum(III) in sodium chloride solutions to 125°C , 1993 .

[2]  Kenneth S. Pitzer,et al.  A thermodynamic model for aqueous solutions of liquid-like density , 1987 .

[3]  A. Navrotsky,et al.  New thermochemical evidence on the stability of dickite vs. kaolinite , 2003 .

[4]  David J. Wesolowski,et al.  Aqueous high-temperature solubility studies. I. The solubility of boehmite as functions of ionic strength (to 5 molal, NaCl), temperature (100–290°C), and pH as determined by in situ measurements , 2001 .

[5]  J. Dandurand,et al.  Gibbs free energy of formation of kaolinite from solubility measurement in basic solution between 60 and 170 °C , 1996 .

[6]  K. Knauss,et al.  Aluminum hydrolysis constants to 250°C from boehmite solubility measurements , 1993 .

[7]  J. Schott,et al.  An experimental study of kaolinite and dickite relative stability at 150–300 °C and the thermodynamic properties of dickite , 1998 .

[8]  G. Furrer,et al.  The formation of polynuclear Al13 under simulated natural conditions , 1992 .

[9]  David J. Wesolowski,et al.  Aluminum speciation and equilibria in aqueous solution: I. The solubility of gibbsite in the system Na-K-Cl-OH-Al(OH)4 from 0 to 100°C , 1992 .

[10]  R. Henley,et al.  Geothermal systems ancient and modern: a geochemical review , 1983 .

[11]  R. Howie,et al.  An Introduction to the Rock-Forming Minerals , 1966 .

[12]  Wuu-Liang Huang Stability and kinetics of kaolinite to boehmite conversion under hydrothermal conditions , 1993 .

[13]  J. Schott,et al.  An experimental study of kaolinite and dickite relative stability at 150-300 degrees C and the thermodynamic properties of dickite , 1998 .

[14]  D. A. Palmer,et al.  Aluminum speciation and equilibria in aqueous solution: V. Gibbsite solubility at 50°C and pH 3–9 in 0.1 molal NaCl solutions (a general model for aluminum speciation; analytical methods) , 1994 .

[15]  John H. Weare,et al.  The prediction of borate mineral equilibria in natural waters: Application to Searles Lake, California , 1986 .

[16]  J. W. Akitt Multinuclear Studies of Aluminum Compounds , 1989 .

[17]  D. Nordstrom The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K , 1982 .

[18]  John H. Weare,et al.  Computer Modeling for Geothermal Systems: Predicting Carbonate and Silica Scale Formation, CO2 Breakout and H2S Exchange , 1998 .

[19]  D. White,et al.  Chemical composition of subsurface waters , 1963 .

[20]  J. Dandurand,et al.  Boehmite solubility and aqueous aluminum speciation in hydrothermal solutions (90–350°C): Experimental study and modeling , 1993 .

[21]  John H. Weare,et al.  Models of mineral solubility in concentrated brines with application to field observations , 1987 .

[22]  Nancy Moller,et al.  A chemical equilibrium model of solution behavior and solubility in the H-Na-K-Ca-OH-Cl-HSO , 2004 .

[23]  D. A. Palmer,et al.  Aluminum speciation and equilibria in aqueous solution: II. The solubility of gibbsite in acidic sodium chloride solutions from 30 to 70°C , 1992 .

[24]  C. Baes,et al.  The hydrolysis of cations , 1986 .

[25]  M. Jackson,et al.  Gibbsite solubility and thermodynamic properties of hydroxy-aluminum ions in aqueous solution at 25°C , 1979 .

[26]  C. Christov,et al.  MODELS OF SUBSURFACE ROCK-WATER PROCESSES AFFECTING FLUID FLOW , 2005 .

[27]  Jerry P. Greenberg,et al.  The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-K-Ca-Cl-SO4-H2O system to high concentration from 0 to 250°C , 1989 .

[28]  J. Hemley,et al.  Equilibria in the system Al 2 O 3 -SiO 2 -H 2 O and some general implications for alteration/mineralization processes , 1980 .