skip to main content


Title: Site‐Selective In Situ Grown Calcium Carbonate Micromodels with Tunable Geometry, Porosity, and Wettability

Micromodels with simplified porous microfluidic systems are widely used to mimic the underground oil‐reservoir environment for multiphase flow studies, enhanced oil recovery, and reservoir network mapping. However, previous micromodels cannot replicate the length scales and geochemistry of carbonate because of their material limitations. Here a simple method is introduced to create calcium carbonate (CaCO3) micromodels composed of in situ grown CaCO3. CaCO3nanoparticles/polymer composite microstructures are built in microfluidic channels by photopatterning, and CaCO3nanoparticles are selectively grown in situ from these microstructures by supplying Ca2+, CO32−ions rich, supersaturated solutions. This approach enables us to fabricate synthetic CaCO3reservoir micromodels having dynamically tunable geometries with submicrometer pore‐length scales and controlled wettability. Using this new method, acid fracturing and an immiscible fluid displacement process are demonstrated used in real oil field applications to visualize pore‐scale fluid–carbonate interactions in real time.

 
more » « less
NSF-PAR ID:
10234287
Author(s) / Creator(s):
 ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Functional Materials
Volume:
26
Issue:
27
ISSN:
1616-301X
Page Range / eLocation ID:
p. 4896-4905
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    This study investigates the pore-scale displacement mechanisms of crude oil in aged carbonate rocks using novel engineered carbon nanosheets (E-CNS) derived from sub-bituminous coal. The nanosheets, synthesized by a simple top-down technique, were stable in brine without any additional chemicals. Owing to their amphiphilic nature and nano-size, they exhibited dual properties of surfactants and nanoparticles and reduced the oil/brine interfacial tension (IFT) from 14.6 to 5.5 mN/m. X-ray micro-computed tomography coupled with miniature core-flooding was used to evaluate their ability to enhance oil recovery. Pore-scale displacement mechanisms were investigated using in-situ contact angle measurements, oil ganglia distribution analysis, and three-dimensional visualization of fluid occupancy maps in pores of different sizes. Analysis of these maps at the end of various flooding stages revealed that the nanofluid invaded into medium and small pores that were inaccessible to base brine. IFT reduction was identified as the main displacement mechanism responsible for oil recovery during 1 to 8 pore volumes (PVs) of nanofluid injection. Subsequently, wettability alteration was the dominant mechanism during the injection of 8 and 32 PVs, decreasing the average contact angle from 134° (oil wet) to 85° (neutral wet). In-situ saturation data reveals that flooding with only 0.1 wt% of E-CNS in brine resulted in incremental oil production of 20%, highlighting the significant potential of this nanofluid as a recovery agent.

     
    more » « less
  2. Abstract

    Planktonic calcifying organisms play a key role in regulating ocean carbonate chemistry and atmospheric CO2. Surprisingly, references to the absolute and relative contribution of these organisms to calcium carbonate production are lacking. Here we report quantification of pelagic calcium carbonate production in the North Pacific, providing new insights on the contribution of the three main planktonic calcifying groups. Our results show that coccolithophores dominate the living calcium carbonate (CaCO3) standing stock, with coccolithophore calcite comprising ~90% of total CaCO3production, and pteropods and foraminifera playing a secondary role. We show that pelagic CaCO3production is higher than the sinking flux of CaCO3at 150 and 200 m at ocean stations ALOHA and PAPA, implying that a large portion of pelagic calcium carbonate is remineralised within the photic zone; this extensive shallow dissolution explains the apparent discrepancy between previous estimates of CaCO3production derived from satellite observations/biogeochemical modeling versus estimates from shallow sediment traps. We suggest future changes in the CaCO3cycle and its impact on atmospheric CO2will largely depend on how the poorly-understood processes that determine whether CaCO3is remineralised in the photic zone or exported to depth respond to anthropogenic warming and acidification.

     
    more » « less
  3. Abstract

    The cycling of biologically produced calcium carbonate (CaCO3) in the ocean is a fundamental component of the global carbon cycle. Here, we present experimental determinations of in situ coccolith and foraminiferal calcite dissolution rates. We combine these rates with solid phase fluxes, dissolved tracers, and historical data to constrain the alkalinity cycle in the shallow North Pacific Ocean. The in situ dissolution rates of coccolithophores demonstrate a nonlinear dependence on saturation state. Dissolution rates of all three major calcifying groups (coccoliths, foraminifera, and aragonitic pteropods) are too slow to explain the patterns of both CaCO3sinking flux and alkalinity regeneration in the North Pacific. Using a combination of dissolved and solid‐phase tracers, we document a significant dissolution signal in seawater supersaturated for calcite. Driving CaCO3dissolution with a combination of ambient saturation state and oxygen consumption simultaneously explains solid‐phase CaCO3flux profiles and patterns of alkalinity regeneration across the entire N. Pacific basin. We do not need to invoke the presence of carbonate phases with higher solubilities. Instead, biomineralization and metabolic processes intimately associate the acid (CO2) and the base (CaCO3) in the same particles, driving the coupled shallow remineralization of organic carbon and CaCO3. The linkage of these processes likely occurs through a combination of dissolution due to zooplankton grazing and microbial aerobic respiration within degrading particle aggregates. The coupling of these cycles acts as a major filter on the export of both organic and inorganic carbon to the deep ocean.

     
    more » « less
  4. Abstract

    Micro‐gel particle suspensions (MGPS) have been proposed for enhanced oil recovery (EOR) in reservoirs with harsh conditions in recent years, yet the mechanisms are still not clear because of the complex property of MGPS and the complex geometry of rocks. In this paper, the micro‐gel particle‐based flooding has been studied by our microfluidic experiments on both bi‐permeability micromodels and reservoir‐on‐a‐chip. A method for reservoir‐on‐a‐chip design has been proposed based on QSGS (quartet structure generation set) to ensure that the flow geometry on chip owns the most important statistical features of real rock microstructures. In the micromodel experiments with heterogeneous microstructures, even if the MGPS has the same macroscopic rheology as the hydrolyzed polyacrylamides (HPAM) solution for flooding, MGPS may lead to significant fluctuations of pressure field caused by the nonuniform concentration distribution of particles. In the reservoir‐on‐a‐chip experiments, clustered oil trapped in the swept pores can be recovered by MGPS because of pressure fluctuation, which hardly happens in the HPAM flooding. Compared with the water flooding, the HPAM solution flooding leads to approximately 17% incremental oil recovery, while the MGPS results in approximately 49.8% incremental oil recovery in the laboratory.

     
    more » « less
  5. Abstract

    Calcium carbonate (CaCO3) is abundant on Earth, is a major component of marine biominerals and thus of sedimentary and metamorphic rocks and it plays a major role in the global carbon cycle by storing atmospheric CO2into solid biominerals. Six crystalline polymorphs of CaCO3are known—3 anhydrous: calcite, aragonite, vaterite, and 3 hydrated: ikaite (CaCO3·6H2O), monohydrocalcite (CaCO3·1H2O, MHC), and calcium carbonate hemihydrate (CaCO3·½H2O, CCHH). CCHH was recently discovered and characterized, but exclusively as a synthetic material, not as a naturally occurring mineral. Here, analyzing 200 million spectra with Myriad Mapping (MM) of nanoscale mineral phases, we find CCHH and MHC, along with amorphous precursors, on freshly deposited coral skeleton and nacre surfaces, but not on sea urchin spines. Thus, biomineralization pathways are more complex and diverse than previously understood, opening new questions on isotopes and climate. Crystalline precursors are more accessible than amorphous ones to other spectroscopies and diffraction, in natural and bio-inspired materials.

     
    more » « less