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Ayirala, Subhash

Publications and source records attributed to Ayirala, Subhash.

Systematic observations of enhanced oil recovery and associated changes at carbonate-brine and carbonate-petroleum interfaces

Enhanced oil recovery (EOR) from carbonates is obtained by injection of controlled ionic strength brines containing “active ions” (e.g., SO 4 2- , Mg 2+ , Ca 2+ ). It is generally believed that this occurs through the interaction of the active ions at the carbonate-brine interface (e.g., within a thin brine layer separating the petroleum and the carbonate phases). Here, in-situ observations show how one active ion, SO 4 2- , alters behavior at the carbonate-petroleum interface. Displacement of petroleum from initially oil-wet carbonate rocks using brines with variable SO 4 concentrations systematically changes oil recovery, in situ contact angles, and connectivity of the oil phase, confirming that the active ion alters interactions at the oil/brine/carbonate interface, as expected. Measurements of model calcite-fluid interfaces show that there is no measurable sorption of SO 4 to carbonate-brine interfaces but reveals that the carbonate-petroleum interface is altered by previous exposure to SO 4 -containing brines. These results suggest that EOR in carbonates is controlled indirectly by active ions. We propose that this may be due to a reduced oleophilicity of the carbonate caused by chemical complexation between the active ion and petroleum’s acidic and basic functional groups. This mechanism explains how both anions and cations act as active ions for EOR in carbonates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pore-Scale Oil Connectivity and Displacement by Controlled-Ionic-Composition Waterflooding Using Synchrotron X-Ray Microtomography

Controlled-ionic-composition waterflooding is an economic and effective method to improve oil recovery in carbonate oil reservoirs. Recent studies show controlling the salinity and ionic composition of injection water can alter the wettability of carbonate mineral surfaces. The pore-scale oil connectivity and displacement by controlled-ionic-composition waterflooding in heterogeneous carbonate reservoirs, especially at the early stage, is still unclear. The goal of this study is to examine the role of ion concentrations and types in the oil displacement efficiency and investigate the impact of the waterflooding on the pore-scale oil displacement using the national synchrotron facility. A carbonate rock sample was flooded with synthetic high-salinity water and other water solutions with different sulfate concentrations. The waterflooding processes were visualized with synchrotron X-ray microtomography to follow the evolution of pore-scale oil/brine interactions at typical field flow rates. Experimental results show that the water with lower sulfate concentration and higher salinity did not change the wettability of the pore surfaces. Higher sulfate ion concentrations in the water, in contrast, altered the wettability of carbonate pore surfaces from oil-wet to neutral-wet within the first few minutes of waterflooding. Finally, novel insight was gained on the ability of water with high-sulfate concentration to displace oil in the small pores and through abundant oil channels, which could consequently lead to higher oil recovery from the carbonate rock.

04 OIL SHALES AND TAR SANDS↗

Molecular-scale origins of wettability at petroleum–brine–carbonate interfaces

Wettability control of carbonates is a central concept for enhanced petroleum recovery, but a mechanistic understanding of the associated molecular-scale chemical processes remains unclear. We directly probe the interface of calcium carbonate (calcite) with natural petroleum oil, synthetic petroleum analogues, and aqueous brines to understand the molecular scale behavior at this interface. The calcite–petroleum interface structure is similar whether or not calcite was previously exposed to an aqueous brine, and is characterized by an adsorbed interfacial layer, significant structural changes within the calcite surface, and increased surface roughness. No evidence for an often-assumed thin-brine wetting layer at the calcite–petroleum interface is observed. These features differ from those observed at the calcite–brine interface, and for parallel measurements using model synthetic petroleum mixtures (consisting of representative components, including dodecane, toluene, and asphaltene). Changes to the interface after petroleum displacement by aqueous brines are also discussed.

02 PETROLEUM↗