『Abstract
Sedimentary basins can contain close to 20% by volume of pore
fluids commonly classified as brines. These fluids can become
undersaturated with respect to calcite as a result of migration,
dispersive mixing, or anthropogenic injection of CO2.
This study measured calcite dissolution rates in geologically
relevant Na-Ca-Mg-Cl synthetic brines (50-200 g L-1
TDS). The dissolution rate dependency on brine composition, pCO2 (0.1-1 bar), and temperature (25.0-82.5℃) was
modeled using the empirical rate equation
R = k (1 - Ω)n
where R is the rate, k and n are empirical fitting terms and 1
- Ω the degree of disequilibrium with respect to calcite. when
Ω is defined relative to an apparent steady-state solubility,
n can be assumed first-order over the range of Ω investigated
(Ω = 0.2-1.0). Rates increased with increasing pCO2
as did its sensitivity to increased brine total dissolved salt
(TDS) concentration. At 0.1 bar, rates were nearly independent
of the TDS (k = 13.0±2.0×10-3 mol m-1 h-1).
However, at higher CO2 partial pressures,
rates became composition dependent and the rate constant, k, was
shown to be a function of temperature, pCO2,
ionic strength and calcium and magnesium activity. The rate constant
(k) can be estimated from a multiple regression (MR) model of
the form
k = β0 + β1(t) +
β2(pCO2) + β3(I)
+ β4(aCa2+)
+ β5(aMg2+).
A relatively high activation energy (Ea =
20 kJ mol-1) was measured, along with a stirring rate
independence suggesting that the dissolution is dominated by surface-controlled
processes at Ω>0.2 in these calcium-rich brines. The addition
of 1 g L-1 SO42- resulted
in a rate inhibition that was highly sensitive to increasing concentrations
of calcium and magnesium. Consequently, even though sulfate concentrations
in subsurface formation waters are generally less than that in
seawater, at TDS concentrations greater than 200 g L-1,
its effect on the rate may be of similar magnitude. These findings
provide an opportunity to improve reaction-transport models in
carbonate-bearing saline reservoirs, where pCO2
is >0.1 atm (pH<〜6.5), by adding considerably more realistic reaction
kinetics. This will be of considerable importance in modeling
of CO2 sequestration in carbonate-hosted
reservoirs.』
1. Introduction
2. Experimental
2.1. Materials
2.1.1. Aqueous solutions
2.1.2. Solution chemistry
2.2. Dissolution reactor
3. Results
4. Discussion
4.1. Calculation of dissolution rate
4.2. Apparent steady-state solubility
4.3. Calcite dissolution in ‘model’ brines
4.3.1. Effect of pCO2
4.3.2. Specific effects of Ca2+, Mg2+
and ionic strength
4.3.3. Temperature and stirring rate dependence
4.4. Multiple regression analysis of the dependence of k on Ca2+,
Mg2+, ionic strength, temperature and pCO2
4.5. The inhibitory effect of SO42-
in concentrated brines
5. Conclusion
Acknowledgments
References