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
We describe an experimental system including monitoring of temperature, pressure, pH, oxidation reduction potential and optical density at 600 nm, designed for studying the role of microorganisms on the geological sequestration Of CO2 and its transformation into solid carbonate phases. Measurements were performed in an artificial ground water (AGW) supplemented with urea (2 g.l(-1)) and equilibrated at controlled temperatures with a gaseous phase before bacterial inoculation. We used the ureolytic strain Bacillus pasteurii as a model carbonate precipitating bacteria and showed that it can successfully promote strong pH increases by ureolysis in the AGW equilibrated with CO2 pressures of up to I bar. Increasing salinities (5.8,13.5 and 35.0 g.l(-1)) have a positive effect on the rate of pH increase, whereas the effect of increasing temperatures (30,35 and 38 degrees C) is less important. Calcium is also shown to have a specific positive influence on the rate of ureolysis. The number of viable cells present in solution decreases greatly during the carbonate precipitation event but the population partially recovers once precipitation is over.
ISSN: 0009-2541

hal-00445282
https://hal.archives-ouvertes.fr/hal-00445282
DOI : 10.1016/j.chemgeo.2008.12.012

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Saline aquifers in deep sedimentary formations are considered the primary candidates for geological storage of CO2, due to their large volumetric capacity that would be sufficient to meet the needs for CCS storage space in a global scale. In comparison to depleted oil and gas reservoirs the deep saline aquifers are, however, less investigated as there has previously been little economic interest in them. Effective methods for characterizing the storage aquifers are crucial for a successful implementation of any CCS project and therefore being developed and transferred from other applications in a various CCS projects.The objective of EU FP7 funded project MUSTANG project (A multiple space and time scale approach for the quantification of deep saline formations for CO2 storage, www.co2mustang.eu) has been to develop methods for characterizing saline aquifers and for understanding their properties. An essential part of this was establishment of a CO2 injection site at Heletz, Israel, where small-scale scientifically motivated injection experiments are planned to be carried out in presently ongoing continuation projects TRUST (http://trust-co2.org/) and CO2QUEST (www.co2quest.eu).While a large number of publications has been already produced based on the work in the MUSTANG project and its successors, and published in different journals, including this one, the objective of this Special Edition has been to gather some of the concluding work in the same journal issue. The focus has in particular been in summarizing the site characterization work carried out at the Heletz site, thereby providing readers an easy overview of the findings and characteristics of the site. In addition, some related work from some of the other sites investigated in MUSTANG project is also included, namely work from the sites Hontomin, Maguelone and a natural analog site in the North Sea. The results are intended to add to our understanding on relevant properties of geological formations as candidates for CO2 geological storage.
ISSN: 1750-5836

hal-01356326
https://hal.archives-ouvertes.fr/hal-01356326
DOI : 10.1016/j.ijggc.2016.02.007

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 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 : Adequate hydrogeophysical monitoring of CO2 geological storage remains a challenge as different parameters might be modified during storage. That implies to compare real-time measurements to an adequate baseline. At the Maguelone shallow experimental site a representative baseline for electrical resistivity was built from a large number of downhole geophysical measurements. At this coastal site this issue is particularly important due to the production of biogenic gas from the subsurface sediments. For this, a modified petrophysical model based on the Waxman-Smits model is proposed to estimate gas saturation found to vary from 2 to 7% within shallow sand layers.
ISSN: 1876-6102

hal-01412685
https://hal.archives-ouvertes.fr/hal-01412685
https://hal.archives-ouvertes.fr/hal-01412685/document
https://hal.archives-ouvertes.fr/hal-01412685/file/pezard2015.pdf
DOI : 10.1016/j.egypro.2015.07.910

Éditeur(s) : HAL CCSD
Résumé : International audience
The injection of reactive mineral suspensions is a possible process to either reinforce or seal wells in geologic carbon sequestration sites. Among others, olivine slurries could be used as CO2-triggered cements, as they carbonate under the thermodynamic conditions of deep storage. However, injection of such slurries requires to control their initial fluidity and its evolution during the displacement. For this purpose, we have characterized the rheological evolution of olivine suspensions, of particle sizes 1−10 μm, sheared at 100 s−1, in the ranges of 10−40% for the volume fractions, 20−50 bars for the CO2 pressure, and 60-110°C for the temperature. The apparent viscosity, measured at 100 s−1, increases exponentially, with a characteristic time ranging from less than 1 h to more than 10 h, and decreasing with olivine concentration, CO2 pressure, and temperature. Moreover, a careful characterization of the slurry rheology carried out in the initial stages of slow evolution, shows that the slurry obeys a Bingham plastic law, with a yield stress ΣB, and a Bingham viscosity µB increasing from 1 to 20 Pa and from 4 to 110 mPa s, respectively, when the olivine volume fraction φ is increased from 10 to 30%. Such variations can be accounted by classical models (Wildemuth and Williams [1984]: Rheologica Acta, 23,627-635, Krieger [1972]: Advances in Colloid and Interface Science, 3, 111-136).
Environmental Progress & Sustainable Energy

hal-01054131
https://hal.archives-ouvertes.fr/hal-01054131
DOI : 10.1002/ep.11826

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