Effect of individual ions on rock-brine-oil interactions: A microcalorimetric approach

Cobos, Jacquelin E.; Søgaard, Erik Gydesen

doi:10.1016/j.fuel.2020.119955

Cited by 7 publications

(11 citation statements)

References 41 publications

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“…Comparison of measured and predicted enthalpy changes arising from the calcite interaction with different aqueous fluids at 75 °C. Experimental data from Cobos et al …”

Section: Resultsmentioning

confidence: 99%

“…This enthalpy was inferred indirectly from isothermal titration calorimetry experiments of chalk with crude oil and brine, crude oil with brine, and chalk with crude oil. Data from ref . Reproduced with permission from ref .…”

Section: Methodsmentioning

confidence: 99%

“…Microcalorimetry. Last, we assessed the compatibility of the model with the enthalpy measurements from the microcalorimetry studies carried out by Cobos et al 36 These experiments consisted of recording enthalpy changes upon injecting 10 μL of several electrolyte solutions (e.g., NaCl, CaCl 2 , MgCl 2 , Na 2 SO 4 , and NaHCO 3 ) in a vial containing 100 mg of chalk. However, for the rock−brine system, the enthalpy change could not be measured directly as the heat of evaporation of the aqueous solutions masked the effect of any enthalpic effects stemming from the rock−brine interactions.…”

Section: ■ Methodologymentioning

confidence: 99%

“…The equilibrium constants at different temperatures can then be derived from the equilibrium constants at standard conditions and the enthalpy of the reactions according to eq . Several publications have reported microcalorimetry measurements on chalk–brine–oil systems at 75 °C. , These measurements, however, captured the overall enthalpy change occurring in the system, and the enthalpy change associated with each interaction at the chalk surface, e.g. (de)protonation, and adsorption of Mg 2+ and Ca 2+ , was not individually assessed.…”

Section: Introductionmentioning

confidence: 99%

“…Several publications have reported microcalorimetry measurements on chalk−brine−oil systems at 75 °C. 35,36 These measurements, however, captured the overall enthalpy change occurring in the system, and the enthalpy change associated with each interaction at the chalk surface, e.g. (de)protonation, and adsorption of Mg 2+ and Ca 2+ , was not individually assessed.…”

Section: ■ Introductionmentioning

confidence: 99%

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Thermodynamic Analysis of the Temperature Effect on Calcite Surface Reactions in Aqueous Environments

2021

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Reactive transport models for subsurface applications, particularly those for modified salinity waterflooding (MSW) in carbonates, have to be equipped with thermodynamic models that can reliably predict/describe adsorption phenomena at variable temperature conditions. To advance the understanding of the calcite reactivity at high temperatures, combining experimental and modeling studies is required. Therefore, we used a surface complexation model (SCM) to describe the reactivity at the calcite−water interface and obtained the enthalpies of the surface reactions by fitting the SCM either to hightemperature electrokinetic data obtained through streaming potential measurements on limestone samples or to the effluent concentration from single-phase flooding experiments. We assumed that the equilibrium constants of the surface reactions follow a temperature dependence according to van't Hoff equation. Our calculations suggest that calcite protonation is more exothermic compared to other minerals (e.g., silica, hematite) and that the adsorption of Ca 2+ , Mg 2+ , and SO 4 2− are all endothermic, with SO 4 2− having the highest reaction enthalpy. We further show that the inferred enthalpies were in agreement with enthalpy changes from published microcalorimetry experiments. Despite the consistency with microcalorimetry data, the obtained enthalpies are not undisputable, and additional data are necessary to unequivocally constrain the temperature effect on the calcite surface reactivity.

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“…Comparison of measured and predicted enthalpy changes arising from the calcite interaction with different aqueous fluids at 75 °C. Experimental data from Cobos et al …”

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Methodologymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Thermodynamic Analysis of the Temperature Effect on Calcite Surface Reactions in Aqueous Environments

2021

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Microscopic and macroscopic assessment of carbonate dissolution for geologic $${{\hbox {CO}}_{2}}$$ storage

Cobos,

Folkvord,

Søgaard

et al. 2023

Discov Energy

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Carbon capture and storage in underground formations might be considered as a relevant technology to curb anthropogenic climate gas emissions. However, carbon dioxide ($${{\hbox {CO}}_{2}}$$ CO 2 ) injection can lead to severe rock-fluid interactions depending on the thermodynamic conditions, rock and fluids composition. The progressive dissolution of $${{\hbox {CO}}_{2}}$$ CO 2 in the formation brine results in mineral dissolution/precipitation processes that may drastically change the properties of the reservoir. This study is an attempt to get a deeper understanding of the dissolution/precipitation processes in a heterogeneous limestone at microscopic and macroscopic levels by a synergy between Isothermal Titration Calorimetry (ITC) and core flooding experiments with in-situ imaging to quantify uneven displacement fronts and understand the influence of reactions on a larger scale. Rock-fluid and fluid-fluid interactions, evaluated by ITC experiments, indicate that the carbonate dissolution is unfavorable with respect to enthalpy change but thermodynamically favorable with respect to entropy change (cations and hydrogen carbonate increase in the brine). Core flooding experiments with in-situ imaging by PET/CT show that complex pore structures cause a variation in the availability and ratio of the reactive fluid throughout the porous medium, hence, non-uniform dissolution was confirmed at core scale. The synergy between microcalorimetry and core flooding provides relevant insights into the dissolution of heterogeneous carbonate rocks at both microscopic and macroscopic scales.

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Modified salinity waterflooding in chalk reservoirs: A journey from rock and fluid interfaces to field scale applications

Hosseinzadehsadati,

Bonto,

Mokhtari

et al. 2024

Fuel

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Effect of individual ions on rock-brine-oil interactions: A microcalorimetric approach

Cited by 7 publications

References 41 publications

Thermodynamic Analysis of the Temperature Effect on Calcite Surface Reactions in Aqueous Environments

Thermodynamic Analysis of the Temperature Effect on Calcite Surface Reactions in Aqueous Environments

Microscopic and macroscopic assessment of carbonate dissolution for geologic $${{\hbox {CO}}_{2}}$$ storage

Modified salinity waterflooding in chalk reservoirs: A journey from rock and fluid interfaces to field scale applications

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