Miroslaw {Mirek} S Gruszkiewicz

Direct measurements of pore fluid density by vibrating tube densimetry.

The densities of pore-confined fluids were measured for the first time by means of vibrating tube densimetry (VTD). A custom-built high-pressure, high-temperature vibrating tube densimeter was used to measure the densities of propane at subcritical and supercritical temperatures (between 35 and 97 °C) and carbon dioxide at supercritical temperatures (between 32 and 50 °C) saturating hydrophobic silica aerogel (0.2 g/cm(3), 90% porosity) synthesized inside Hastelloy U-tubes. Additionally, supercritical isotherms of excess adsorption for CO(2) and the same porous solid were measured gravimetrically using a precise magnetically coupled microbalance. Pore fluid densities and total adsorption isotherms increased monotonically with increasing density of the bulk fluid, in contrast to excess adsorption isotherms, which reached a maximum and then decreased toward zero or negative values above the critical density of the bulk fluid. The isotherms of confined fluid density and excess adsorption obtained by VTD contain additional information. For instance, the maxima of excess adsorption occur below the critical density of the bulk fluid at the beginning of the plateau region in the total adsorption, marking the end of the transition of pore fluid to a denser, liquidlike pore phase. Compression of the confined fluid significantly beyond the density of the bulk fluid at the same temperature was observed even at subcritical temperatures. The effect of pore confinement on the liquid-vapor critical temperature of propane was less than ~1.7 K. The results for propane and carbon dioxide showed similarity in the sense of the principle of corresponding states. Good quantitative agreement was obtained between excess adsorption isotherms determined from VTD total adsorption results and those measured gravimetrically at the same temperature, confirming the validity of the vibrating tube measurements. Thus, it is demonstrated that vibrating tube densimetry is a novel experimental approach capable of providing directly the average density of pore-confined fluids, and hence complementary to the conventional gravimetric or volumetric/piezometric adsorption techniques, which yield the excess adsorption (the Gibbsian surface excess).

EXPERiMENTAL STUDIES IN HIGH TEMPERATURE AQUEOUS CHEMISTRY AT OAK RIDGE NATIONAL LABORATORY

Experimental research is conducted and models developed in a long- standing program at Oak Ridge on aqueous chemistry at high temperatures of broad classes of electrolytes emphasizing thermodynamics of reaction equilibria and excess thermodynamic properties of electrolytes. Experimental methods, their capabilities, data analysis, and results are summarized. Relevance of the work to problems in power plants, natural and industrial processes as well as basic solution chemistry and geochemistry are given. Progress in potentiometry, electrical conductivity, flow calorimetry, and isopiestic research is described. Future in this field demands greater precision in measurements and significant gains in our understanding of the solvation phenomena especially in the vicinity and beyond the critical point for water. The communities who do research on scattering, spectroscopy, and computer simulations can help guide these efforts through studies at extreme conditions.

Water adsorption at high temperature on core samples from The Geysers geothermal field, California, USA

Abstract For the first time, water sorption on representative geothermal reservoir rocks from The Geysers steam field has been determined in the laboratory at actual reservoir temperature. The Oak Ridge National Laboratory (ORNL) isopiestic apparatus has been used to measure quantities of water retained at various temperatures and relative pressures by plug samples of three representative reservoir metagraywacke cores. The measurements were made at 150, 200 and 250°C as a function of relative pressure in the range 0.00 ⩽ p / p 0 ⩽ 0.98, where p 0 is the saturated water vapor pressure. Both adsorption (increasing pressure) and desorption (decreasing pressure) runs were made in order to investigate the phenomenon of hysteresis. Low-temperature gas adsorption analyses were completed on the same rock samples. Nitrogen or krypton adsorption and desorption isotherms at 77 K were used to obtain BET (Brunauer, Emmet, Teller) specific surface areas and pore volumes and their distributions with respect to pore sizes. Mercury-intrusion porosimetry was also used to obtain similar information extending to very large pores (macropores). A qualitative correlation was found between the surface properties obtained from nitrogen adsorption and the mineralogical and petrological characteristics of the solids. In general, however, there is no direct proportionality between BET specific surface areas obtained from nitrogen adsorption and the capacity of the rocks for water adsorption at high temperatures. An analysis of the temperature dependence of adsorption/desorption indicates that multilayer adsorption rather than capillary condensation is the dominant water storage mechanism in The Geysers reservoir rocks at high temperatures.

MIXTURES OF CO2-SF6 AS WORKING FLUIDS FOR GEOTHERMAL PLANTS

In this paper, mixtures of CO2 and SF6 were evaluated as working fluids for geothermal plants based on property measurements, molecular dynamics modeling, thermodynamic cycle analysis, and materials compatibility assessment. The CO2 - SF6 was evaluated for a reservoir temperature of 160°C. Increasing the efficiency for these low reservoir sources will increase the options available for geothermal energy utilization in more sites across the country. The properties for the mixtures were obtained either from thermodynamic property measurements and molecular dynamics simulations. Optimum compositions of the CO2 - SF6 were identified for a well reservoir temperature and a given water-cooling condition. Concerning the global warming potential, it was estimated that the equivalent CO2 emissions per 1kWh for a Rankine cycle operating with 100% SF6 would be approximately of 7.6% than those for a coal-fired power plant.Copyright

In Situ 27Al NMR Spectroscopy of Aluminate in Sodium Hydroxide Solutions above and below Saturation with Respect to Gibbsite

Aluminum hydroxide (Al(OH)3, gibbsite) dissolution and precipitation processes in alkaline environments play a commanding role in aluminum refining and nuclear waste processing, yet mechanistic aspects underlying sluggish kinetics during crystallization have remained obscured due to a lack of in situ probes capable of isolating incipient ion pairs. At a molecular level Al is cycling between tetrahedral ( T d) coordination in solution to octahedral ( O h) in the solid. We explored dissolution of Al(OH)3 that was used to produce variably saturated aluminate (Al(OH)4-)-containing solutions under alkaline conditions (pH >13) with in situ 27Al magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy, and interrogated the results with ab initio molecular dynamics (AIMD) simulations complemented with chemical shift calculations. The collective results highlight the overall stability of the solvation structure for T d Al in the Al(OH)4- oxyanion as a function of both temperature and Al concentration. The observed chemical shift did not change significantly even when the Al concentration in solution became supersaturated upon cooling and limited precipitation of the octahedral Al(OH)3 phase occurred. However, subtle changes in Al(OH)4- speciation correlated with the dissolution/precipitation reaction were found. AIMD-informed chemical shift calculations indicate that measurable perturbations should begin when the Al(OH)4-···Na+ distance is less than 6 Å, increasing dramatically at shorter distances, coinciding with appreciable changes to the electrostatic interaction and reorganization of the Al(OH)4- solvation shell. The integrated findings thus suggest that, under conditions incipient to and concurrent with gibbsite crystallization, nominally expected contact ion pairs are insignificant and instead medium-range (4-6 Å) solvent-separated Al(OH)4-···Na+ pairs predominate. Moreover, the fact that these medium-range interactions bear directly on resulting gibbsite characteristics was demonstrated by detailed microscopic and X-ray diffraction analysis and by progressive changes in the fwhm of the O h resonance, as measured by in situ NMR. Sluggish gibbsite crystallization may arise from the activation energy associated with disrupting this robust medium-range ion pair interaction.

Partitioning of HCl Between Concentrated Brines and Supercritical CO2 Under Geologic Reservoir Conditions

HCl is generated in subsurface brines exposed to high CO2 pressures via reactions such as CO2 + NaCl + H2O ↔ NaHCO3 + HCl. The extent of partitioning of HCl between a concentrated chloride brine and supercritical CO2 (scCO2) has not been measured before and it cannot be estimated with the accuracy sufficient for predictive modeling of subsurface processes. The partitioning of HCl between 4.92 mol/kg aqueous solutions of NaCl and scCO2 was measured at 100 and 150 °C and at pressures between 9 and 16.2 MPa. At P = 15 MPa, the concentrations of HCl in the scCO2 phase were 7 × 10–4 and 4 × 10–3 mol/L at 100 and 150 °C, an increase by more than 5 and 3 orders of magnitude, respectively, relative to the concentrations in water vapor in the absence of CO2. These levels of HCl may accelerate reactions with reservoir rocks, natural seals (shale caprocks) and downhole materials, potentially enhancing or impairing operation and long-term performance of subsurface technologies such as geologic carbon sequestration/st...