CO2 production in tar sand reservoirs under in situ steam temperatures: Reactive calcite dissolution

Recovery of highly viscous oil from some of the deeper oil sand deposits of northern Alberta, Canada, is made possible through injection of heat by steam or hot water flooding of the reservoirs. The rise in temperature lowers the viscosity of the bitumen allowing it to be produced. The increase in temperature accelerates the reactions between the matrix and pore minerals of the formation and can produce reaction products which can significantly alter the permeability of the reservoir. If carbonate minerals are present in the reservoir, inorganic CO₂ may also be a reaction product.

The Grand Rapids reservoir consists of relatively clean quartz sand containing 7 wt.% kaolinite, 1 wt.% calcite and a trace of smectite. Core floods of this sand by a neutral NaCl brine at 265°C, 8.2-MPa overburden pressure, 6.0-MPa fluid pressure and a flow velocity of 0.4 pore volumes per hour were used to determine the potential for hydrothermal reactions between clays and carbonate minerals in a natural reservoir sand. Reaction progress was followed by continuous sampling of the production fluids. The produced water was analyzed and the phase chemistry was calculated back to the run conditions using the computer code SOLMNEQF.

Mass-balance considerations on produced total inorganic carbon (TIC) show that calcite broke down very quickly, the maximum in CO₂ production occurring after only one pore volume of fluid had passed through the core. The Ca released from the breakdown of calcite was incorporated in the formation of smectite as was shown by post-run clay mineral analysis by the following unbalanced chemical reaction:

calcite+kaolinite+H₄Si04Ca-smectite+H₂0+CO₂

Silica was supplied by the dissolution of quartz. Silica concentrations analyzed in the production fluid were depressed from those predicted by previously published quartz rate equations because of the rapid rate of smectite synthesis.

These observations were used to formulate the following model for the passage of the first pore volume of NaCl brine through the core. Initially calcite is present throughout the core. As the brine enters the inlet of the core, it equilibrates with calcite. The brine remains in equilibrium with calcite throughout the core as quartz and kaolinite react to form smectite. This model was tested with the computer code PATH.UBC using CO₂ production as a measure of the progress variable ξ. A best fit was achieved to the produced fluid chemistry by varying relative dissolution rates of kaolinite and quatz and varying the suppression of precipitation of certain minerals.