Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A set of four reactive flow-through experiments at temperature T = 100 degrees C and total pressure P=12 MPa was performed in limestone reservoir samples. By using various ranging from 0.7 to 10 MPa, these experiments mimic mass transfers occurring (1) near the injection well, where the brine is almost saturated with CO2 (i.e. P-CO2 approximate to P), and (2) at increasing distances from the injection well, where the fluid displays lower values and higher divalent cation concentrations due rock dissolution along the fluid pathway. Results for P-CO2 = 10 MPa show non-uniform dissolution features associated with transport-controlled mass transfer, while reaction-controlled uniform dissolution is observed for P-CO2 = 2.5 MPa. The experiment with P-CO2 = 6 MPa allows investigating in detail the transition from transport-to reaction-controlled dissolution. Conversely, the experiment reproducing conditions far from the injection well (P-CO2 = 0.7 MPa), shows a decrease of porosity triggered by the precipitation of Mg-rich calcite. For all the dissolution experiments, the time-resolved porosity phi(t) can be modeled by a simple non-linear equation including parameters that characterise the dissolution regime triggered by the reactivity of the inlet fluid (measured by the Damkohler number, Da). Furthermore, all dissolution experiments display power scaling between permeability (k) and porosity (phi) with distinctly different scaling exponents characterising the reactivity of the fluid percolating the sample, independently from the decrease with time of the reactive surface area. It is shown also that dissolution at moderate positive values of Da seems the most efficient to increase permeability and promote a rapid spreading of the reaction front, while inducing minimal modification of the porosity in the vicinity of the CO2 injection well. These results can be used to parameterize the k-phi function for modeling the earliest dissolution processes occurring in the vicinity of the reaction front.
ISSN: 0009-2541

hal-00445277
https://hal.archives-ouvertes.fr/hal-00445277
DOI : 10.1016/j.chemgeo.2009.03.028

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Underground CO2 sequestration is highly recommended as an effective means of significantly decreasing CO2 concentration in the atmosphere. Mineral storage is the more secure technology, but requires the presence of high concentration of divalent cations in the pore-fluid. Results from CO2 percolation experiments through chlorite/zeolite-rich sandstone samples from the Pretty Hill Formation (Otway Basin, Australia) are presented. The dissolution of the laumontite (7 wt.%) and chamosite (7 wt.%) are the potential sources of calcium, iron and magnesium required for carbonate precipitation. The percolation experiment was setup to reproduce, at laboratory scale, the in situ temperature and pressure conditions (T = 95 degrees C and P = 10 MPa). The fluid injected at constant flow rate is a rock-equilibrated brine subsequently enriched in CO2 up to partial pressure of 6 MPa. We observe feldspars, laumontite and chamosite dissolution, kaolinite and silica precipitation and a noticeable sink of CO2 in the sample which is attributed to the precipitation of both amorphous carbon due to the reduction of CO2 and Fe-rich carbonate. Permeability decreases of about one order of magnitude due to the localization of the kaolinite precipitation in the main flow paths, while porosity increases. The high reactivity of this sandstone makes this reservoir a valuable target for CO2 mineralization, but the associated permeability decrease may limit the injection rate and the spreading of the CO2 in the reservoir.
ISSN: 0009-2541

hal-00712829
https://hal.archives-ouvertes.fr/hal-00712829
DOI : 10.1016/j.chemgeo.2011.11.018

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Heletz sandstone (Israel) reactivity is studied by means of CO2-rich brine percolation experiments and modeling. Experiments are performed at in situ temperature and pressure conditions with two distinctly different injection flow rates and for two different brine compositions: the genuine Heletz brine and a similar brine but in equilibrium with gypsum. The Heletz sandstone is composed of quartz, dolomite, ankerite, K-feldspar, clay minerals and minor amounts of gypsum and pyrite. The main reaction is the dissolution of the carbonates which is fastest for the highest flow rate injection and for the genuine Heletz brine. Permeability increases during the five percolation experiments, regardless of flow rate and brine type. This increase in permeability is associated to a decrease in porosity during the gypsum-equilibrated brine experiments due to gypsum precipitation. The precipitation of secondary minerals (kaolinite, muscovite and smectite) is mainly controlled by the dissolution of K-feldspar and largest at low flow rate injection, indicating that these precipitation processes are diffusion-controlled and localized in immobile zones where favorable chemical micro-environments exist. These processes are quantified by means of a reactive transport model. These results indicated that the CO2 injection at the Heletz site should trigger both permeability increase in interface between brine and CO2, which may extend over a large extension and where mixing processes are very active, especially near the well under intermittent injection conditions.
ISSN: 1750-5836

hal-01356329
https://hal.archives-ouvertes.fr/hal-01356329
DOI : 10.1016/j.ijggc.2015.10.023

Éditeur(s) : HAL CCSD Elsevier
Résumé : Deficient sealing in the well cement plugs and annulus due to mechanical fracturing is an important risk of CO2 leakage from the reservoir to others permeable layers and the surface. Such situation was reproduced at laboratory scale in order to determine the hydro-chemical control on the fracture permeability. Specifically, we investigated the effect of CO2 rich-brine flowing through fractured Portland cements at T = 60 °C and P = 10 MPa and variable flow rates. We showed that carbonation process is dominant and induces permeability decrease and leakage mitigation for extremely low flow rate whereas for high flow rate injection the permeability remains constant due to the precipitation of a low density secondary Si-rich phase which maintains the initial fracture aperture. At intermediate flow rate the hydraulic aperture can increase due to the densification of the material triggered by the net precipitation of low porosity calcite. These results emphasize that more complex behaviors than those considered from batch experiments may take place in the vicinity of flowing fractures. Specifically, the redissolution of the neoformed calcite as well as the development of amorphous phases, both controlled by the CO2-rich brine renewing rate in the fracture may prevent the healing fracture.
ISSN: 1750-5836

hal-00857555
https://hal.archives-ouvertes.fr/hal-00857555
DOI : 10.1016/j.ijggc.2013.04.002

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
A CO2-rich brine core-flood experiment in calcite limestone for conditions representative of underground storage (P = 12 MPa and T = 100°C) was performed in order to explore the dissolution mechanisms arising at moderate CO2 partial pressure (0.3 MPa). An increase of the total porosity (φT) accompanied by a persistent permeability (k) decrease was measured. The mechanisms controlling this atypical anticorrelated k − φT relationship were investigated from the analysis of high-resolution X-ray microtomography images of the sample acquired before and after the experiment. All the evidences converge to the conclusion that the ubiquitous decrease of permeability measured during the 44 h of dissolution is due to the clogging of a fraction of the macroporosity by microporous material triggered by the rearrangement of the detached undissolved particles. This mechanism results in the development of low permeability zones bridging the macroporosity.
ISSN: 0094-8276

hal-00903585
https://hal.archives-ouvertes.fr/hal-00903585
DOI : 10.1002/grl.50595

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : Limestone dissolution by CO2 -rich brine induces critical changes of the pore network geometrical parameters such as the pore size distribution, the connectivity, and the tortuosity which govern the macroscopic transport properties (permeability and dispersivity) that are required to parameterize the models, simulating the injection and the fate of CO2 . A set of four reactive core-flood experiments reproducing underground conditions ( T=100∘C and P=12 MPa) has been conducted for different CO2 partial pressures (0.034
ISSN: 0169-3913

hal-00963597
https://hal.archives-ouvertes.fr/hal-00963597
DOI : 10.1007/s11242-013-0257-4

Éditeur(s) : HAL CCSD Elsevier
Résumé : We investigate experimentally the alteration of fractured class-G cement flowed by CO2-rich brine. The experiment mimics a mechanically damaged rough-walled fractured cement annulus at temperature 60 °C and pressure 10 MPa. The experiment consists of flowing a reservoir-equilibrated brine mixed with CO2 (partial pressure of 2.3 MPa) through the fracture of average aperture 14 μm at constant flow rate (100 μL min−1). This flow rate corresponds to pressure gradient representative of an average in situ hydrodynamic condition. Results indicate an intense alteration of the cement with a large removal of mass at the scale of the sample. However, the fracture alteration patterns are triggered by the initial heterogeneity of the fracture aperture; the aperture of the low aperture zones tends to decrease due to calcite precipitation whereas preferential paths develop in the zones of higher aperture associated. Nevertheless, the expected large permeability increase triggered by the mass removal is mitigated by the precipitation of a low density Si-rich amorphous material. The alteration rate will decrease with time because of the increasing distance of diffusion between the fracture where the reactants are actively renewed by advection and the portlandite and C-S-H dissolution fronts. The different zones of reaction can be adequately modeled by a simple 1D diffusion-reaction model using published kinetics coefficients and extrapolation to larger times than the experiment time can be drawn. Altogether, and in addition to the previous studies of the alteration of fractured well cement annulus, this study shows that the leakage potential is strongly controlled by the initial distribution of the aperture along the fracture: low aperture zones will tend to self-heal while localized flow in connected high aperture paths will be perennial.
ISSN: 1750-5836

hal-01346006
https://hal.archives-ouvertes.fr/hal-01346006
DOI : 10.1016/j.ijggc.2016.01.032

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : Experiments were conducted to assess the potential impact of fractured well-cement degradation on leakage rate. Permeability was monitored while CO2-enriched reservoir-equilibrated brine was flowed at constant rate through a single fracture in a class G cement core under conditions mimicking geologic sequestration environments (temperature 60 °C, pressure 10 MPa). The results demonstrate that, at least for the conditions used in the experiment, an initial leakage in a 42 μm aperture fracture (permeability = 1.5 × 10-10 m2) can be self-mitigated due to the decrease of the fracture hydraulic aperture after about 15 h. This decrease results from the development of continuous highly hydrated amorphous Si-rich alteration products at the edge of the fracture and the dense carbonation of the bulk cement that mitigate the penetration of the alteration front.
ISSN: 0013-936X

hal-00950088
https://hal.archives-ouvertes.fr/hal-00950088
DOI : 10.1021/es401317c