Anomalous Acid Reaction Rates in Carbonate Reservoir Rocks

Summary It is generally assumed that the reaction of acid with limestone reservoir rock is much more rapid than acid reaction with dolomite reservoir rock. This work is the first to show this assumption to be false in some cases, because of mineral impurities commonly found in these rocks. Trace amounts of clay impurities in limestone reservoir rocks were found to reduce the acid dissolution rate by up to a factor of 25, to make the acid reactivity of these rocks similar to that of fully dolomitized rock. A rotating disk instrument was used to measure dissolution rates of reservoir rock from a deep, dolomitic gas reservoir in Saudi Arabia (275°F, 7,500 psi). More than 60 experiments were made at temperatures of 23 and 85°C and HCl concentration of 1.0 M (3.6 wt%). Eight distinctly different rock types that varied in composition from 0 to 100% dolomite were used in this study. In addition, the mineralogy of each rock disk was examined before and after each rotating disk experiment with an environmental scanning electron microscope (ESEM) using secondary and backscattered electron imaging and energy dispersive X-ray (EDS) spectroscopy. Acid reactivity was correlated with the detailed mineralogy of the reservoir rock. It was also shown that bulk anhydrite in the rock samples was converted to anhydrite fines by the acid at 85°C, a potential source of formation damage. Introduction A study of acid reaction rates and reaction coefficients of a dolomitic reservoir rock was recently reported by Taylor et al. (2004a). In that work, it was found that reaction rates depended on mineralogy and the presence of trace components such as clays. This paper examines in detail the relationship between acid reactivity and mineralogy of a deep, dolomitic gas reservoir rock. An accurate knowledge of acid reaction rates of deep gas reservoirs can contribute to the success of matrix and acid fracture treatments. Many studies of acid stimulation treatments of Formation K, a deep, dolomitic gas reservoir in Saudi Arabia, have been published (Nasr-El-Din et al. 2001, 2002a, 2002b; Bartko et al. 2003). It is generally assumed that the reaction of acid with limestone reservoir rock is much more rapid than acid reaction with dolomite reservoir rock during acidizing treatments. However, much of the reported data were obtained with pure limestones, dolomites, and marbles. These include calcite marble (CaCO3) (Lund et al. 1975; de Rozieres 1994; Frenier and Hill 2002), dolomite marble [CaMg(CO3)2] (Lund et al. 1973; Herman and White 1985), Indiana limestone (Mumallah 1991), St. Maximin and Lavoux limestones (Alkattan et al. 1998), Haute Vallée de l'Aude dolomite (Gautelier et al. 1999), Bellefonte dolomite (Herman and White 1985), San Andres dolomite (Anderson 1991), Kasota dolomite (Anderson 1991), and Khuff dolomite reservoir cores (Nasr-El-Din et al. 2002b). The effects of common acid additives on calcite and dolomite dissolution rates were reported in detail (Frenier and Hill 2002; Taylor et al. (2004b; Al-Mohammed et al. 2006). The effects of impurities such as clays on rock dissolution have not been reported.