Kinetics of Calcite Dissolution and Ca–Mg Ion Exchange on the Surfaces of North Sea Chalk Powders

Abstract

Calcite dissolution and Ca–Mg ion exchange on carbonate rock surfaces have been proposed as potential mechanisms occurring during smart waterflooding in carbonate reservoirs. However, there is still a lack of fundamental understanding of these reactions to quantitatively evaluate their effects in the reservoir flooding process. Especially, the data on precipitation and dissolution kinetics are insufficient. In this work, the equilibration kinetics of calcite dissolution and Ca–Mg exchange was experimentally studied. The behavior of three powders was compared: pure calcium carbonate, Stevns Klint outcrop chalk, and North Sea reservoir chalk. It was found that the equilibration time for calcite dissolution was of the order of seconds for a given surface-area-to-liquid-volume ratio. The existing theory of calcite dissolution could well reproduce our observations. The Ca–Mg exchange showed two-step kinetics: the first step was fast, and it dominated the process within the first hour of reaction; the second step was slow, and it continued longer than the time of observation (2 weeks). Characteristic times for the two steps were extracted by fitting the experimental curves. A two-layer adsorption model was proposed to characterize the kinetic process and successfully matched with experimental data. The findings were further extended to flow-through scenarios. By comparing with literature data and surface complexation models, it was concluded that calcite dissolution alone was unlikely to be able to explain the additional recovery reported in the literature. The Ca–Mg exchange process could dominate the fluid–rock interactions at a high temperature in pure calcium carbonate rocks, while competitive adsorption of cations appeared to control the process at a lower temperature. Different carbonate rocks possess different properties with regard to the ion-exchange process.

Sorption of Arsenate, Selenate, and Molybdate on the Barite (001) Surface

“…In contrast, this topographic difference may not affect the incorporation, which results from atomic exchange processes that are inherent to the dynamic exchange seen at ionically bonded minerals. 98,99 In addition, our previous study shows that the hydration of surface Ba 2+ sites is stronger than that of surface SO 4 2− sites by both X-ray reflectivity measurements and molecular dynamics simulations. 66 Therefore, anion adsorption to surface Ba 2+ can be energetically less favored because it requires disruption of the strong hydration layer compared to cation adsorption to less strongly hydrated sulfate groups.…”

Crude Oil–Brine–Rock Interactions in Tight Chalk Reservoirs: An Experimental Study

“…The specific surface area of Danish North chalk is well studied and modelled. The specific surface area of pure calcite powder, Stevns Klint chalk and Dan reservoir chalk has previously been measured by the BET method by Hao et al ( 2020) to be 0.34, 2.21, and 2.70 m 2 /g, respectively [48]. Although the Danish North Sea chalk is a mono-mineralic carbonate rock that consists 80-90% calcite (CaCO 3 ) with less amounts of clay minerals, the amount of clay varies slightly between the Tor and Ekofisk formations.…”

“…The specific surface area of Danish North chalk is well studied and modelled. The specific surface area of pure calcite powder, Stevns Klint chalk and Dan reservoir chalk has previously been measured by the BET method by Hao et al ( 2020) to be 0.34, 2.21, and 2.70 m 2 /g, respectively [48].…”