Surfactant inhibition mechanisms of carbonate mineral dissolution in shale

Kim, Kyung Tae; Jagannath, Mantha Pavan; Su, Gregory M.; Freychet, Guillaume; Zeng, Tongzhou; Mohanty, Kishore K.; Henkelman, Graeme; Katz, Lynn E.; Werth, Charles J.

doi:10.1016/j.colsurfa.2021.126857

Title: Surfactant inhibition mechanisms of carbonate mineral dissolution in shale

Journal Article · Wed May 19 00:00:00 EDT 2021 · Colloids and Surfaces. A, Physicochemical and Engineering Aspects

DOI:https://doi.org/10.1016/j.colsurfa.2021.126857· OSTI ID:1813335

Kim, Kyung Tae ^[1]; Jagannath, Mantha Pavan ^[1]; Su, Gregory M. ^[2];

^[3]; Zeng, Tongzhou ^[1]; Mohanty, Kishore K. ^[1];

^[1]; Katz, Lynn E. ^[1]; Werth, Charles J. ^[1]

Univ. of Texas, Austin, TX (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

Surfactants are common additives to hydraulic fracturing and enhanced oil recovery (EOR) fluids, and are under consideration for amendment to supercritical carbon dioxide for geological carbon sequestration (GCS). The effect of a common anionic surfactant, internal olefin sulfonate (IOS), on mineral dissolution from shale into brine was evaluated. When added to brine at concentrations exceeding the critical micelle concentration (94 mg/L), IOS inhibited carbonate mineral dissolution in an Eagle Ford shale, as well as dissolution of optical quality calcite (the dominant carbonate in the shale). Laser profilometry images provide spatial resolution across > 3 orders of magnitude, and indicate that IOS addition to brine both enhances the formation of new etch pits in calcite, and impedes their further growth. Time-of-flight secondary ion mass spectrometry surface profiles show for the first time that IOS preferentially adsorbs at calcite pit edges versus flat calcite surfaces (i.e., terraces). Surface pressure calculations, sulfur K-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy results, and density functional theory (DFT) calculations support this observation; the DFT results indicate that the sulfonate head group of the IOS molecule binds strongly to the calcite step site as compared to the terrace site. The S K-edge NEXAFS results indicate that IOS adsorbed more to etched calcite surfaces compared to smooth calcite surfaces. Overall, the results indicate that weak adsorption on flat calcite surfaces (i.e., terraces) disrupts water structure and enhances mass transfer of dissolution, while strong adsorption on calcite pit edges displaces adsorbed water and inhibits further etch pit growth. This work provides the first direct evidence of preferential adsorption of IOS to etched calcite surfaces and links it to macroscopic dissolution kinetics. Finally, this work has implications for surfactant-containing fluids used in hydraulic fracturing, EOR and potentially GCS for subsurface injection into carbonate rich reservoirs.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; SC0017328; SC0019272; AC02-05CH11231

OSTI ID:: 1813335

Alternate ID(s):: OSTI ID: 1815249; OSTI ID: 1828003

Report Number(s):: BNL-221955-2021-JAAM

Journal Information:: Colloids and Surfaces. A, Physicochemical and Engineering Aspects, Vol. 625; ISSN 0927-7757

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
Eagle Ford shale
calcite
anionic surfactant
density functional theory
time of flight secondary ion mass spectrometry
near edge X-ray absorption fine structure spectroscopy

Title: Surfactant inhibition mechanisms of carbonate mineral dissolution in shale

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