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
Résumé : Geological storage of CO2 is one of diverse technologies being explored to reduce atmospheric carbon fromindustrial processes (i.e. fossil fuel combustion). One of the specific features of CO2 injection is the possibility ofgeochemical reactions (dissolution – precipitation) between mobile reactive brine (e.g. formation water enrichedin CO2) and the host rock during the spatial and temporal evolution of CO2. That leads to modifications in thepore structure, which in turn change the flow dynamics of the reservoir (e.g. the permeability k). Then, thesesstructural modifications can largely control the injectivity, so that the pressure field in the reservoir and also theCO2 propagation. Accordingly, it is crucial to explore the changes in the reservoir properties (e.g. structural andhydrodynamic) induced during a CO2 injection and specially the relationships between them (e.g. k or reactivesurface-Sr versus porosity-φ , k versus rock heterogeneity), for developing predictive modelling tools of thetransport and reaction processes occurring during a CO2 injection and reliable risk assessment. In the case ofcarbonate rocks, the application of the predictive models of transport and reaction is still challenging, because oftheir high heterogeneity so that the incertitude in the reaction kinetics of carbonate minerals.From this perspective, we realized brine-enriched in CO2 percolation experiments through carbonate rocksamples in thermodynamic conditions expected during CO2 injection in deep reservoirs (T = 100°C et P =12MPa). The permeability changes k(t) is monitored during the experiments and the porosity variationφ (t) iscalculated from chemical analyses of the sampled outlet fluids, using ICP-EAS. The pore structure modificationsare investigated from high resolution X ray micro tomography images acquired from the synchrotron ofGrenoble (ESRF). Depending to the dissolution regime, controlled by the reservoir rock fabric and the chemicalcomposition of the brine (e.g. PCO2), we observed that a modification of pore structure can either improve(atypical result in dissolution context) or impair the value of the permeability k.
Le stockage géologique du CO2 est l’une des diverses technologies étant explorées afin deréduire les émissions de carbone atmosphérique des processus industriels (i.e. combustion del’énergie fossile). L’une des spécifiques caractéristiques de l’injection du CO2 en profondeurreste la possibilité de réactions géochimiques (dissolution-précipitation) entre la saumureréactive mobile (e.g. eau de formation enrichie en CO2) et la roche encaissante durantl’évolution spatiale et temporelle du CO2, conduisant à des modifications dans la structure despores et par conséquent dans les propriétés d’écoulement du réservoir (e.g. la perméabilité k).Donc, ces changements structuraux peuvent largement contrôler l’injectivité, ainsi que lechamp de pression dans le réservoir et aussi la propagation du CO2. Il demeure ainsi cruciald’explorer les changement dans les propriétés de réservoirs (e.g. structurales ethydrodynamiques) induits durant une injection de CO2 et explicitement les relations existantesentre eux (e.g. k ou surface réactive-Sr versus porosité-φ , k versus hétérogénéité de la roche),afin de développer des outils de modélisation prédictive des processus de transport etréactionnels se produisant durant une injection de CO2 et d’évaluer de façon fiable les risques.Dans le cas des réservoirs carbonatés, l’application des modèles prédictifs de transport réactifdemeure toujours un enjeu, car contrainte par la forte hétérogénéité en leur sein ainsi que parl’incertitude dans la cinétique de réactions des minéraux carbonatés dans ce contexte. Danscette optique, nous avons réalisé des expériences de percolation à travers des échantillons deroches carbonatées dans les conditions thermodynamiques de stockage en profondeur (T =100°C et P =12 MPa). L’évolution de la perméabilité k(t) est suivie au cours desexpériences ; et la variation de la porosité φ (t) est calculée à partir des résultats d’analyseschimiques au ICP-AES des fluides de sortie échantillonnés. L’investigation des modificationsapportées à la structure des pores est réalisée par le biais de la Micro-Tomographie hauterésolution à rayon X, acquise au synchrotron de Grenoble (e.g. ESRF).Dépendant du régime de dissolution, contrôlé par la fabrique de la roche réservoir et lacomposition chimique de la saumuré chargée en CO2 (e.g. PCO2 engagée), on a observéqu’une modification de la structure de la roche peut soit améliorer soit détériorer (résultatatypique en contexte de dissolution) la valeur de la perméabilité k.
https://hal.archives-ouvertes.fr/tel-01142136

tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136
https://hal.archives-ouvertes.fr/tel-01142136/document
https://hal.archives-ouvertes.fr/tel-01142136/file/thesemangane2013.pdf

Éditeur(s) : HAL CCSD
Résumé : In order to minimize CO2 atmospheric concentration, a solution consists in sequestrating CO2 in geological reservoirs. To estimate long term risks, it is necessary to quantify the couplings between reaction processes as well as structural and hydrodynamical modifications. We realised two experimental benches enabling injecting CO2-enriched-brine in conditions corresponding to in situ storage (T < 200 oC and P < 200 bar) and developed
an experimental protocol using X-Ray microtomography and fluid and rock analyses in order to measure the variations of physical and chemical parameters.
The study of carbonated reservoirs near the injection well, allows quantifying different k-phi relationships depending on the dissolution processes and triggered by the local fluid chemical composition and initials conditions. Away from the injection well, we observe carbonate precipitation decreasing the permeability. The study of fracturated caprock samples shows that alternative percolation of CO2-enriched-brine and CO2 gas increases the fracture permeability.
The study of silicated rocks indicates carbonate precipitation in zeolite sandstone and sintered dunite grains. Nevertheless, in zeolite sandstone we also observe the precipitation of clay particles located in the uid pathways which decrease strongly the permeability.
Afin de minimiser la concentration en CO2 dans l'atmosphère une solution consiste à le séquestrer dans les réservoirs géologiques. Pour évaluer les risques à long terme, il est nécessaire de quantifier les couplages entre les processus réactionnels et les modifications structurales et hydrodynamiques. Dans cette optique, nous avons construit deux dispositifs expérimentaux permettant d'injecter des saumures chargées en CO2 dans les conditions de stockage (T < 200 °C et P < 200 bar) et mis en oeuvre un protocole expérimental utilisant la microtomographie RX et l'analyse des roches et des fuides pour quantifier les variations des paramètres physiques et chimiques. Dans le cas des réservoirs carbonatés, on observe, près du puits d'injection, une forte variabilité des relations k-phi en fonction du régime de dissolution contrôlé par la chimie locale du fluide, ainsi que par les conditions initiales. A plus grande distance, on observe des processus de précipitation diminuant fortement la perméabilité. L'étude des roches de couverture fracturées (argilite) a montré qu'une percolation alternée d'une saumure chargée en CO2 et de CO2 gaz augmentait la perméabilité de fracture. Dans le cas des roches silicatées, la précipitation de carbonates est mise en évidence aussi bien dans les grès à zéolites que dans les frittés de dunite de San Carlos. Cependant, dans les grès à zéolites, la précipitation d'une phase argileuse est observée dans les chemins d'écoulement et engendre une forte diminution de la perméabilité.
https://tel.archives-ouvertes.fr/tel-00416408

tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408
https://tel.archives-ouvertes.fr/tel-00416408/document
https://tel.archives-ouvertes.fr/tel-00416408/file/These_Luquot.pdf

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 Oldendorf/Luhe
Résumé : International audience
Non-calcifying photosynthetic anthozoans have emerged as a group that may thrive under high carbon dioxide partial pressure (pCO(2)) conditions via increased productivity. However, the physiological mechanisms underlying this potential success are unclear. Here we investigated the impact of high pCO(2) on the dissolved inorganic carbon (DIC) use in the temperate sea anemone Anemonia viridis. We assessed the impacts of long-term exposure to high pCO(2), i.e. sampling in situ natural CO2 vents (Vulcano, Italy), and short-term exposure, i.e. during a 3 wk controlled laboratory experiment. We focused on photo-physiological parameters (net photosynthesis rates, chlorophyll a content and Symbiodinium density) and on carbonic anhydrase (CA) activity, an enzyme involved in the energy-demanding process of DIC absorption. Long-term exposure to high pCO(2) had no impact on Symbiodinium density and chlorophyll a content. In contrst, short-term exposure to high pCO(2) induced a significant reduction in Symbiodinium density, which together with unchanged net photosynthesis resulted in the increase of Symbiodinium productivity per cell. Finally, in both in situ long-term and laboratory short-term exposure to high pCO(2), we observed a significant decrease in the CA activity of sea anemones, suggesting a change in DIC use (i.e. from an HCO3- to a CO2 user). This change could enable a shift in the energy budget that may increase the ability of non-calcifying photosynthetic anthozoans to cope with ocean acidification.
ISSN: 0171-8630

hal-01546163
https://hal.archives-ouvertes.fr/hal-01546163
DOI : 10.3354/meps11916

Éditeur(s) : HAL CCSD Springer Verlag (Germany) Springer Verlag
Résumé : International audience
The dissolution of carbonate rocks usually leads to both porosity (ϕ) and permeability (k) increase. We present experimental evidences and physical-based models of positive and anti-correlated dynamics of k and ϕ observed during dissolution experiments of carbonate rocks. We study the way the rate of change of ϕ and k is controlled by the degree of undersaturation of the percolating solution for two different types of carbonate rocks. We document the occurrence of an anti-correlated k−ϕ trend when the flowing fluid (deionized water) has a weak capacity of dissolution. A positive correlation is found when CO2 is added to the deionized water to increase the potential dissolution rate. Detailed analyses of the microstructures of the rock performed by X-ray microtomography reveal that low dissolution rate favors detachment of solid particles and their subsequent accumulation at the pore-throat inlet. Particles are detached from the rock matrix due to the differential dissolution rate of the indurated grains and the microporous cement. We then propose a simple phenomenological model to interpret the effect of the pore-throat clogging by the accumulation of partially dissolved carbonate particles. We conjecture that permeability is controlled by the decrease of the effective hydraulic radius and the increase of the tortuosity due to partial and localized obstruction of the pore network. Conversely, increasing the level of undersaturation of the flowing solution leads to an augmented potential of dissolving most of the transported particles before they reach the throats. In this case, both k and ϕ increase and display power-law correlations.
ISSN: 0169-3913

hal-01174145
https://hal.archives-ouvertes.fr/hal-01174145
DOI : 10.1007/s11242-015-0456-2

Éditeur(s) : HAL CCSD Mineralogical Society of America
Résumé : International audience
In situ mineralization of CO2 in ultramafic rock-hosted aquifers is one of the promising solutions for decreasing CO2 concentrations in the atmosphere. Naturally altered ultramafic rocks suggest that carbonation processes are controlled by local heterogeneities in the structure of the rock and fluid transport at the water-rock interfaces. We studied the role of rock crystallographic anisotropy relative to the global fluid flow direction on the mineralization of CO2 by means of electron microscope analyses from the macro- to the micrometer scale (EBSD-FIB). The sample used for the measurements was a hot pressed olivine core percolated by water enriched in CO2 (pCO2 = 10 MPa) at 180 °C. During the percolation experiment, olivine was dissolved and two types of carbonates, dolomite, and magnesite, were precipitated on olivine surfaces. The results showed that the dissolution of olivine is controlled by its crystallographic properties as shown by the development of etch-pits only on the (010)ol planes and with elongated shapes parallel to the [010]ol axes. In contrast, the precipitation of carbonates is governed by hydrodynamic properties. Carbonates are heterogeneously distributed in the percolated rock. They are mainly located along the moderate (for dolomite) and the minor (for magnesite) flow paths, both oriented parallel to the principal fluid flow direction, which allow carbonates to be supplied with divalent cations (e.g., Ca2+, Mg2+, and Fe2+). In these flow paths, carbonate growth is systematically oriented normal to the flow that facilitates the development of chemical gradients with cationic supersaturation conditions for carbonate precipitation near the walls.In natural systems, the (010)ol planes are parallel to the Moho and the (100)ol planes are vertical; our study suggests that flow of CO2-rich fluids will induce precipitation of carbonates localized along, and preferentially clogging, vertical flow paths while favoring olivine dissolution along horizontal fluid pathways. This dual control of structure and fluid flow on carbonation mechanisms could be an important parameter allowing sustainable CO2 storage in peridotites, while limiting the risks of leakage toward the surface.
ISSN: 0003-004X

hal-01143393
https://hal.archives-ouvertes.fr/hal-01143393
DOI : 10.2138/am-2015-4913

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A shallow field experimental site for CO2 injection was established at Maguelone (Languedoc, France), in order to test in an integrated manner a suite of surface and downhole hydrogeophysical monitoring methods. The objective is to improve monitoring of gas transport in the shallow subsurface and to determine the sensitivity of CO2 monitoring systems for leakage detection. The site offers a natural laboratory to study the processes associated with CO2 injection in a clastic and clay-rich context saturated with saline fluids. Prior to CO2 injection, three nitrogen (N2) injections were undertaken in 2012 to measure the site response to neutral gas injection. In 2013, a volume of 111 m3 (mass of 220 kg) of CO2 was injected during 3.5 h at 15 m depth. During each experiment, the gas plumes were successfully detected from pressure monitoring, time-lapse induction logging and downhole resistivity monitoring with dipole–dipole array. Increases in resistivity are attributed to free gas propagation (either N2 or CO2) whereas decreases in resistivity correlate with CO2 dissolution in the pore fluid. Chemical analyses confirm this hypothesis with a decrease in pH and an increase in the concentration of dissolved species in the latter case.
ISSN: 1750-5836

hal-01355943
https://hal.archives-ouvertes.fr/hal-01355943
DOI : 10.1016/j.ijggc.2015.12.005

Éditeur(s) : HAL CCSD Wiley
Résumé : International audience
The paper is motivated by the long term safety analysis of the CO 2 geological storage. We present a methodology for the assessment of the ge-omechanical impact of progressive rock dissolution. The method is based on the use of X-ray tomography and the numerical dissolution technique. The influence of evolution of the microstructure on the macroscopic properties of the rock is analysed by using periodic homogenization method. The numerical computations show progressive degradation of all components of the stiffness (orthotropic) tensor. Moreover, the evolution of associated mass transfer properties (as tortuosity and conductivity tensors), by using the periodic homogenization method, is also calculated. The correlation between the mechanical parameters and the transfer properties during the dissolution pro-cess is presented. The results show that the highest increase of the hydraulic conductivity (in direction Y) is not associated with the highest decrease of Young modulus in this direction. Moreover, the highest decrease of Young modulus (in the direction X) is not associated with percolation in this direction. Finally, an incremental law to calculate settlement, in case of a rock with evolving microstructure, is proposed. The solution of the macroscopic settlement problem under constant stress and drained conditions showed that the geomechanical effects of the rock dissolution are rather limited.
ISSN: 0363-9061

hal-01104204
https://hal.archives-ouvertes.fr/hal-01104204
https://hal.archives-ouvertes.fr/hal-01104204/document
https://hal.archives-ouvertes.fr/hal-01104204/file/Numerical_computations_rock_dissolution_Wojtacki_al_2014.pdf
DOI : 10.1002/nag.2316

Éditeur(s) : HAL CCSD American Geophysical Union
Résumé : International audience
Claystone caprocks are often the ultimate seal for CO2 underground storage when residual CO2 gas reaches the reservoir top due to buoyancy. Permeability changes of a fractured claystone due to seepage of CO2-enriched brine and water vapor-saturated CO2 gas are investigated. Results show that brine flow induces a large porosity increase (up to 50%) in the vicinity of the fracture due to dissolution of calcite and quartz, while permeability remains unchanged. Conversely, cyclic flows of CO2-brine and CO2-gas increase the fracture aperture abruptly after each gas flow period, producing a progressive decrease of the caprock seal capacity. Aperture increase is controlled by decohesion of the clay framework within a micrometer-scale-thick layer induced by CO2-gas acidification. Results show that hydraulic aperture increases linearly with duration of the preceding CO2-brine flow period, emphasizing the kinetic control of the quartz grains dissolution during the brine flow periods.
ISSN: 0094-8276

hal-00412332
https://hal.archives-ouvertes.fr/hal-00412332
DOI : 10.1029/2008GL034467

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 Elsevier
Résumé : International audience
The main goal of the monitoring stage of Carbon Capture and Storage (CCS) is to obtain an accurate estimation of the subsurface CO2 accumulation and to detect any possible leakage. Laboratory experiments are necessary to investigate the small scale processes governing the CO2–brine–rock interaction. They also provide a means to calibrate the results coming from field scale geophysical methods. In this work we set up an experimental system which is able to perform Electrical Resistivity Tomography (ERT) measurements on centimeter-scale rock samples at various P–T conditions. We present the results of two new experiments related to CO2 monitoring, performed on a cylindrical (4 × 8 cm) Fontainebleau rock sample. In the first one, we have quantified the CO2 saturation at different volume fractions, representing zones from a deep saline aquifer with varying degrees of saturation. In the second one, we have monitored and quantified the effect of CO2 dissolution in the brine at a pressure of 40 bar during eight days, emulating the invasion of CO2 into a shallow aquifer. Results highlight the importance of accounting for the contribution of surface conductivity in highly CO2-saturated regions, even in clay-free rocks, and also for brine conductivity variation due to CO2 dissolution. Ignoring any of these effects will end up in a CO2 saturation underestimation. We present a modified CO2 saturation equation to account for these two influences.
ISSN: 0926-9851

hal-01356323
https://hal.archives-ouvertes.fr/hal-01356323
DOI : 10.1016/j.jappgeo.2016.03.039

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Carbonation of peridotite is a widespread process in nature, with emerging societal and environmental implications through geological storage of CO2. We studied the micro- and nano-scale structures associated with the carbonation of peridotite pervaded by a CO2-rich water and the induced changes of its hydrodynamic properties. Focused ion beam (FIB) nanotomography was coupled with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. An experimental sample of dunite core percolated by a CO2-rich fluid (pCO2 = 11 MPa) at 160 °C was compared with a naturally carbonated sample from the Atlantic Ridge (Exp. IODP 304). Results of the 8-days percolation experiment show continuous alteration of olivine into magnesite locally associated with a poorly crystalline serpentine-type mineral referred to as proto-serpentine. The experiment is also characterized by an overall decrease in rock porosity (from 7.7 to 6.4%) and permeability (from 8.5 × 10− 16 to 1.7 × 10− 16 m2). The primary inter-granular porosity (1 to 10 μm) is progressively filled with magnesite, leading to the overall decrease of permeability. At the same time, a secondary small-scale porosity (10 nm to 1 μm) is created at the tip of the dissolution features along the (010) cleavage planes of olivine grains. Carbonate crystals grow within these etch-pit structures behind the dissolution front. Dissolution and precipitation occur at a relative rate that maintains the secondary porosity over the timescale of the experiment (i.e. carbonate growth has to be the slowest one). This process is interpreted as an interface coupled dissolution-precipitation mechanism of olivine carbonation. Proto-serpentine is only formed in highly reduced flow areas, such as small olivine etch-pits (10 to 500 nm wide), which are more isolated from CO2 input. SEM-FIB analyses show the 3D preferential orientation of the dissolution-precipitation planes within a given olivine grain. It suggests the formation of lateral connections between the etch-pits (infra-micrometric “channels”) providing access to reactants and removing reaction products at the reaction sites. The experimental results show that olivine dissolution and magnesite precipitation converge to a quasi-steady state resulting in a constant carbonation rate controlled by reaction kinetics and not by mass transfer for this flow regime. The system self-regulates, independently of the porosity change at least during this incipient stage of olivine carbonation. Similar textures are observed in natural samples collected at 170 m-depth in the vicinity of veinlets driving late fluids down into the cooling oceanic lithosphere. This suggests that similar mechanisms are active in nature and can play an important role in the late, low temperature alteration stages of fractured peridotite. These results also highlight the critical role of nm-scale spatial arrangement of dissolution and precipitation features on mass transfers and on the sustainability of olivine carbonation through coupled dissolution-precipitation processes.
ISSN: 0009-2541

hal-01684733
https://hal.archives-ouvertes.fr/hal-01684733
DOI : 10.1016/j.chemgeo.2017.11.013

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
Carbonation of ultramafic rocks in geological reservoirs is, in theory, the most efficient way to trap CO2 irreversibly; however, possible feedback effects between carbonation reactions and changes in the reservoir permeability must be considered to realistically assess the efficiency and sustainability of this process. We investigated changes in the hydrodynamic properties of sintered dunite samples by means of percolation experiments, under conditions analogous to that of in situ carbonation. Our results show that carbonation efficiency is controlled by the local renewal of the reactants and the heterogeneity of the pore structure. Preferential flow zones are characterized by the formation of magnetite and of a silica-rich layer at the olivine surfaces, which eventually inhibits olivine dissolution. Conversely, sustainable olivine dissolution together with coprecipitation of magnesite, siderite, and minor Mg-TOT-phyllosilicates, occur in reduced-flow zones. Thus carbonate precipitation only decreases porosity in zones where diffusion-controlled transport is dominant. Consequently, while high flow rates will decrease the carbonation efficiency of the reservoir and low flow rates may reduce the permeability irreversibly close to the injection point, moderate injection rates will ensure a partial carbonation of the rock and maintain the reservoir permeability.
ISSN: 0013-936X

hal-00424540
https://hal.archives-ouvertes.fr/hal-00424540
DOI : 10.1021/es8018429

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
To test the impact of fluid flow on the reactivity of porous (ultra-)mafic rocks, reactive percolation experiments were realized during which CO2-enriched water was injected at two different injection rates (Q = 0.1 and 1 mL h−1) through sintered analogues of olivine-accumulation zones in basaltic flows at temperature and fluid composition conditions (T = 180 °C; NaHCO3 buffered solution) favorable for CO2-mineralization (carbonation).All experiments resulted in silicate dissolution, carbonate precipitation upstream and (proto-)serpentine formation downstream indicating a decrease in the fluid reactivity along flow paths. The measured bulk carbonation rates ranged from 4 to 7 × 10−8 s−1; these values were significantly lower than previously published values of olivine carbonation rate obtained on powders in closed batch and flow-through reactors. Our study show complex couplings, at pore scale, between fluid flow, localization of reaction zones, and chemical reaction kinetics which in turn control hydrodynamic properties, carbonation rate and efficiency and fluid reactivity. This results in carbonation rates being higher when injection rates are high and permeability ultimately controlling carbonation reactions by limiting fluid input. During experiments, notable changes in permeability occurred for only minor changes in porosity indicating a control by the geometry of the porous network: heterogeneities in the distribution of flow paths favored the localization of precipitated minerals which in turn resulted in the closure of flow paths. This mechanism was particularly efficient at low injection rates. These results imply that controlling the injection rate could allow enhancing/limiting the efficiency of in situ carbonation.
ISSN: 0883-2927

hal-01115284
https://hal.archives-ouvertes.fr/hal-01115284
DOI : 10.1016/j.apgeochem.2014.11.024

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 : International audience
This study explores the dynamics of porosity and reactive surface area changes during porous limestone dissolution by CO2-rich water. The Sr and Ca concentrations in both the rock and the outlet solution are used to evaluate the reactive surface area changes of the two rock-forming calcites, i.e. micrite grains and sparite crystals, which have different trace element signatures. The geometric surface area measured with X-ray microtomography decreases slightly whereas the reactive surface area increases continuously with increasing porosity from 20.3 to 30.2%. Surprisingly, changes in reactive surface areas are very different between the two calcites. The reactive surface area changes in the micrite are parabolic while the reactive surface area of sparite increases greatly. The numerical model HYTEC is used to model the change in reactive surface areas during the experiment. Different geometrical models are tested. The model based on spherical-grain dissolution and spherical-pore growth fails to reproduce the experimental results, while the sugar-lump model provides reasonable agreement with the experiment.
ISSN: 0009-2541

hal-00445274
https://hal.archives-ouvertes.fr/hal-00445274
DOI : 10.1016/j.chemgeo.2009.01.032

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
Résumé : The main purpose of this thesis was to characterize and to model the hydrodynamic and thermochemical processes leading to the alteration of the wellbore cement materials under borehole conditions. Percolation experiments were performed on fractured cement samples under CO2 storage conditions (60°C and 10MPa). Injection flow rate was dictated by the fracture aperture of each sample. CO2 enriched brine was flowed along the fracture aperture, and permeability changes as well as chemical evolution of major cations were continuously acquired during the experiment time. Reaction paths developed by the alteration of the cement were characterized using microtomography and ESEM images. The experiments conducted using samples presenting large fracture apertures during 5h showed that permeability was maintained constant during the experiment time. Three reacted layers were displaying by the alteration of portlandite and CSH. Long term experiment (26h) conducted with large initial fracture aperture showed a decrease of the permeability after 15hours of CO2 exposure. Otherwise, experiments performed on samples presenting narrow apertures indicated the conversion of portlandite and CSH to calcite leading to the permeability reduction and the fracture clogging. Assemblages of phases and chemical changes were modelled using GEMS-PSI speciation code. We studied also using a coupled transport-reactive model the conditions leading to the cement alteration and the formation of associated layers.
L'objectif de cette thèse était de modéliser à partir des expériences de percolation-réactive, les processus hydrodynamique et réactionnel qui gouvernent l'altération des ciments de puits. Différentes expériences ont été réalisées dans des conditions représentatives de celles du stockage du CO2. Des échantillons fracturés ont été utilisés pour injecter une saumure enrichie en CO2 à 60°C et 10MPa et à différentes pressions partielles de CO2. Le débitd'injection variait en fonction des propriétés hydrauliques de l'échantillon exposé. L'injection d'une saumure enrichie en CO2 à débit constant à travers une fracture supposée plane a permis d'étudier les modifications des propriétés hydrodynamiques et ces conséquences sur la géochimie et la microstructure du ciment altéré. L'impact dynamique de l'évolution microstructurale a été mis en évidence. Les expériences conduites sur des échantillons présentant de larges ouvertures, réalisées sur une durée de 5 h, ont montré que la perméabilité était maintenue constante le long de l'expérience. Trois couches d'altération se sont développées consécutivement à la dissolution de la portlandite et la décalcification des CSH. L'altération a entrainé la précipitation des carbonates et de la silice amorphe à proximité de la fracture. Dans le cas d'une expérience longue durée appliquant les mêmes conditions que précédemment on a observé que la croissance de la silice amorphe a entrainé la diminution de la perméabilité. Par ailleurs les expériences effectuées sur des échantillons présentant de faibles ouvertures, ont indiqué que la conversion de la portlandite en calcite conduit au colmatage de la fracture. L'évolution des assemblages de phases conduisant à la formation des carbonates et de la silice amorphe a été modélisée à partir du code géochimique GEMS. Les mécanismes de diffusion et les processus de mise en place des couches d'altération ont été étudiés à partir d'un modèle analytique et d'un modèle de transport réactif à partir du code géochimique PHREEQC.
https://tel.archives-ouvertes.fr/tel-01038034

tel-01038034
https://tel.archives-ouvertes.fr/tel-01038034
https://tel.archives-ouvertes.fr/tel-01038034/document
https://tel.archives-ouvertes.fr/tel-01038034/file/theseabdoulghafour.pdf

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study reports petrostructural observations in the pargasite and phlogopite-bearing Finero peridotite massif (Italian Western Alps), which suggest that the pervasive foliation in this massif was formed by deformation concomitant with percolation of hydrous Si-rich melts: (1) diffuse contacts, but systematic parallelism between the pyroxenitic layers and the foliation of the peridotite (2) strong shape and crystal preferred orientations (SPO and CPO), but subhedral or interstitial shapes and weak intracrystalline deformation of the hydrous phases, (3) CPO, but interstitial shapes of the pyroxenes, (4) very coarse olivine grain sizes, which are correlated to the olivine abundance, and (5) elongated shapes, but weak intracrystalline deformation, and extremely weak and highly variable CPO of olivine. The pervasive deformation of the Finero peridotite occurred therefore under conditions that allowed coexistence of H2O–CO2-bearing melts, pargasite, and spinel, that is, temperatures of 980–1080 °C and pressures <2 GPa. The petrostructural observations suggest that the presence of hydrous melts results in accommodation of large amounts of deformation by stress-controlled dissolution–precipitation and advective transport of matter by the melts and in fast grain boundary migration in olivine. By consequence, it produces significant rheological weakening. Water contents in olivine are <4 ppm wt., implying limited contribution of hydration of olivine to weakening. In addition, the analysis of protomylonites composing the external domains of the shear zones that overprint the pervasive foliation indicates that the transition to melt-free conditions results in enhanced contribution of dislocation creep to the deformation. The associated increase of the peridotites' strength leads to onset of strain localization. The latter is not correlated to the local abundance in pargasite or phlogopite, implying that crystallization of amphiboles or phlogopite, even at concentrations of 25 vol.%, does not produce rheological weakening in the upper mantle.
ISSN: 0012-821X

hal-01667879
https://hal.archives-ouvertes.fr/hal-01667879
DOI : 10.1016/j.epsl.2017.08.015