Abstract
A large percentage of petroleum reserves are located in carbonate reservoirs, which can be divided into limestone, chalk and dolomite. Roughly the oil recovery from carbonates is below the 30% due to the strong oil wetness, low permeability, abundance of natural fractures, and inhomogeneous rock properties Austad (2013). Injection of adjusted brine chemistry into carbonate reservoirs has been reported to increase oil recovery by 5-30% of the original oil in place in field tests and core flooding experiments. Previous studies have shown that adjusted waterflooding recovery in carbonate reservoirs is dependent on the composition and ionic strength of the injection brine (Morrow et al. 1998; Zhang 2005). Many research works have focused on the role of the brine composition in altering the initial wettability state of carbonate rock, which is usually intermediate- to oil-wet.
Crude oils contain carboxyl group, -COOH, that can be found in the resin and asphaltenes fractions. The negatively charged carboxyl group, -COOH bond very strongly with the positively charged, sites on the carbonate surface. The carbonate surface, which is positively charged is believed to adsorb the SO42− that is negatively charged. On the other side cations Ca2+ and Mg2+ bind to the negatively charged carboxylic group and release it from the surface.
In this study we use a closed system geochemical model to study the effect of the surface-charge dominant species; Ca2+, Mg2+ and SO42− on the carbonate surfaces at 80 °C. The proposed geochemical interactions can possibly lead to a change in the surface charge, altering wettability of the rock by exchanging ions/cations. Brines with various concentrations of Mg2+ and SO42− were prepared in the lab and contact angle between carbonate substrate and crude oil was measured using a rising/captive bubble tensiometer at 80 °C. The composition of the carbonate system was collected from previous literature review and the composition of adjusted brines was used to build a surface sorption database to develop a geochemical model. This model is focused on identifying the reaction paths and the surface behavior that may represent the real system.
Changes in carbonate surface wettability were further evaluated using a series of contact angle experiments. Experimental observations and modeling results are concordant and imply that SO42− ions may alter the wettability of carbonate surface at high temperature.
Experimental and modeling study of wettability alteration through seawater injection in limestone: a case study