Résumé : Le fluide chaud produit par les forages de la centrale géothermique de Bouillante (Guadeloupe) est enrichi en espèces dissoutes telles que la silice qui peuvent précipiter sous forme de dépôts solides lors de son refroidissement et gêner fortement la production électrique. L’un des principaux objectifs de ce travail de thèse a donc été d’améliorer l’état des connaissances sur les conditions physiques, chimiques et cinétiques de la précipitation de la silice amorphe à Bouillante. Après une étude des caractéristiques physico-chimiques des fluides et des dépôts associés au champ de Bouillante, des expériences sur la cinétique de précipitation de la silice, sur site, pour une large gamme de température (25 - 90°C) et de pH (4 - 12) ont été menées et analysées en détail.Pour l’ensemble de ces expériences, seule la polymérisation (réversible) de la silice dissoute, sous forme de suspensions colloïdales très stables en solution, a été observée. La modélisation des données expérimentales de cinétique montre que la vitesse de polymérisation de la silice suit une loi d’ordre 2 vis-à-vis de la silice dissoute jusqu’à l’équilibre en accord avec une dimérisation de la silice. Par contre, durant l’étape initiale de la réaction, une loi d’ordre 4 semble mieux adaptée, suggérant des réactions de polymérisation plus complexes avec formation de tétramères. La température a un effet limité sur la cinétique de polymérisation de la silice comparé à l’effet du pH qui est beaucoup plus important. L’énergie d’activation de la réaction globale est de 41 - 54 kJ pour des pH compris entre 5 et 8.La caractérisation de la silice précipitée a mis en évidence des différences notables entre la structure poreuse de la silice solide prélevée sur les installations de surface et celle de la silice colloïdale obtenue par polymérisation lors des expériences de cinétique, ce qui semble indiquer que des mécanismes différents interviennent dans ces deux contextes de précipitation de la silice dissoute.Le deuxième objectif de cette thèse était d’évaluer la possibilité de valoriser la silice extraite de l’eau géothermale de Bouillante dans un procédé de traitement des eaux naturelles par adsorption. Pour cela, les propriétés d’adsorption de la silice géothermale brute et fonctionnalisée par le poly(ethylèneimine) (ou PEI) ont été étudiées pour deux polluants : un colorant, le bleu de méthylène et un métal lourd, le plomb. Les résultats obtenus montrent que la silice brute possède une grande capacité d’adsorption vis-à-vis du bleu de méthylène. En outre, la fonctionnalisation de la silice par le PEI permet d’améliorer sa capacité d’adsorption vis-à-vis du plomb en solution, en accord avec un modèle cinétique du pseudo-second ordre suggérant une chimisorption. Le modèle d’isotherme de Redlich-Peterson est également en très bon accord avec les données expérimentales.
The hot geothermal fluid produced by the geothermal power plant of Bouillante (Guadeloupe) contains various dissolved components such as silica that can precipitate as solid deposits during their cooling and cause serious problems on the electricity generation. One of the aim of this study is to improve the understanding on the physical, chemical and kinetics conditions of the amorphous silica precipitation in the Bouillante geothermal field. After a study on the physical and chemical characteristics of the Bouillante fluids and deposits which can form during their exploitation, experiments on the kinetics of silica precipitation, on site, under a large range of temperature (25 – 90°C) and pH (4 – 12) have been carried out and analyzed in detail.During on site kinetics experimentations only dissolved silica polymerization (reversible) as colloidal gel, very stable in solution, was observed. Modeling of the experimental data showed that the kinetics polymerization is characterized by a 2-order kinetic law relative to dissolved silica until the equilibrium that is consistent with silica dimerization. On the other side, the initial stage of the reaction is better characterized by a 4-order kinetic law that suggested more complex polymerization reactions with tetramers formation.Temperature has a little effect on the polymerization kinetics compared with the pH which has an effect more important. The activation energy of silica precipitation calculated between 25 and 90°C, is about 41 - 54 kJ for pH ranging to 5 - 8.The characterization of the silica precipitate reveals significant differences in the porous structure of the silica collected on the surface installations and the one obtained from kinetic experiments that suggests different precipitation mechanisms. The second objective of this thesis was to evaluate the possibility to promote geothermal silica for the treatment of natural waters containing contaminants by adsorption. Adsorption properties of the untreated and functionalized by poly(ethylèneimine) (ou PEI) geothermal silica have been investigated for two pollutants: a colorant, the methylene blue and a heavy metal, the lead.Results showed that untreated silica has a great adsorption capacity concerning the methylene blue. Besides, silica functionalization by the PEI allows improving the adsorption capacity for lead in solution. The adsorption kinetics curves followed a pseudo-second order model consistent with a chimisorption. The isotherm model of Redlich-Peterson fitted well the experimental data.

http://www.theses.fr/2014AGUY0698/document

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Despite many studies, our understanding of silica precipitation from natural waters remains limited, in particular for geothermal waters. Here we present a detailed study on the kinetics of silica polymerization as a function of fluid temperature and pH using high-temperature (250-260 °C) seawater-derived geothermal fluids as those discharged from the Bouillante geothermal site.We monitored the on-site decrease in monomeric silica concentration(initial SiO2 concentration of about 600 mg/l)with time using the molybdenum blue spectrophotometric method on samples of separated water collected from the high-pressure separator at 167 °C and cooled to 25, 50, 75, and 90 °C and for pH values ranging from 5 to 8. During all these experiments, only silica polymerization was observed, with the formation of colloidal particles in suspension in the solutions. No scaling of amorphous silica was formed. The collected data were after modeled in order to determine the useful kinetic parameters for predicting and preventing amorphous silica precipitation in the production wells during fluid exploitation in the specific context of Bouillante. Results under the investigated experimental conditions show that the kinetics of silica precipitation is affected more strongly by pH than by temperature change. The reaction in the acidic Bouillante solution begins with a transition period that significantly decreases the kinetics of silica polymerization. Modeling the experimental data indicates that the silica polymerization up to the state of equilibrium is characterized by a 2nd-order kinetic law relative to dissolved silica; this could indicate that the polymerization is controlled mainly by the formation of dimers. However, the first hour of the experiments is better characterized by a 4th-order kinetic law, suggesting more complex polymerization reactions in the initial stage with the formation of nanocolloidal particles containing 3 to 4 monomers. In both cases, the corresponding kinetics rate constant k is linearly dependent on pH for pH between 5 and 7. The activation energy Ea for the overall reaction, calculated using the Arrhenius equation under the considered pH and temperature conditions, ranges between 41±9.8 and 54±9.6 kJ/mol. To complete this work, the colloid particles formed at the end of the kinetics experiments were extracted and analyzed by SEM and TEM microscopy, X-ray Diffraction and the BET method. Results show that the size of the colloids increase and their specific surface decrease with increasing pH and are thus dependent on pH. Globally, our work provides a reliable database for understanding silica polymerization kinetics in natural geothermal brines or geologic waters characterized by a near neutral pH and moderate dissolved silica concentrations.
ISSN: 0009-2541

hal-01403092
https://hal-brgm.archives-ouvertes.fr/hal-01403092
DOI : 10.1016/j.chemgeo.2016.08.031

Éditeur(s) : Elsevier Science Bv
Résumé : Mechanisms controlling the transfer and retention of silicon (Si) along continental margins are poorly understood, but play a major role in the functioning of coastal ecosystems and the oceanic biological pump of carbon. Deep-sea fans are well recognized as carbon sink spots, but we lack knowledge about the importance of the fans in the global Si cycle. Here, we provide a first estimate of the role played by the Congo deep-sea fan, one of the biggest in the world, in the Si cycle. Sediment cores sampled in the deep-sea fan were analyzed to build a Si mass balance. An exceptionally high accumulation rate of amorphous silica aSiO(2) (2.29 +/- 0.58 mol Si m(-2) y(-1)) was found, due to a high sedimentation rate and the presence of aluminum in the sediments. Although favored by bioirrigation, recycling fluxes remained low (0.3 mol Si m(-2) y(-1)) and reconstructed input fluxes could only be explained by lateral inputs coming from the canyon. Preliminary calculations show that the rapid transport of aSiO(2) through the canyon and the excellent preservation efficiency in the sediments imply that 50% of aSiO(2) river inputs from the Congo River accumulate annually in the deep-sea fan. Si:C ratios in deep-sea fan sediments were very low (0.2) and only three times as high as those measured in the river itself, which suggests that material from the river and the continental shelf was delivered directly through the canyon, with very little time for Si and C cycle decoupling to take place.
Journal Of Marine Systems (0924-7963) (Elsevier Science Bv), 2015-01 , Vol. 141 , P. 71-79

Droits : 2014 Elsevier B.V. All rights reserved.
http://archimer.ifremer.fr/doc/00251/36242/35797.pdf
DOI:10.1016/j.jmarsys.2014.07.010
http://archimer.ifremer.fr/doc/00251/36242/

Éditeur(s) : HAL CCSD
Résumé : EGU2012-6377- Geophysical Research Abstracts vol. 14
The hot geothermal fluid produced by the wells of the Bouillante power station, in Guadeloupe, contains various dissolved species such as silica or some metals (Zn, Pb, etc). During the exploitation, the geothermal fluid is flashing and cooling (from 260 to 160°C for the high-pressure steam-liquid separation and down to 110°C for the low-pressure phase separation of a part of the separated liquid at 160°C). Consequently, the dissolved species can form scale deposits such as amorphous silica or poly-metallic sulphides, according to the exploitation conditions, and cause serious scaling problems on the production and the surface installations. These minerals could also precipitate during the partial underground re-injection of the production fluids which is being set up in the Bouillante power station. In this study, in order to predict and prevent the possible silica precipitation at temperature lower than 160°C, during the partial underground reinjection of the production fluids of Bouillante or their thermal valorization down to 110°C temperatures, we propose to investigate on site the kinetics of silica precipitation as a function of temperature and pH. The experiments presented here were carried out on site on samples of separated waters collected after the steam-water separator at 160°C, containing about 600 ppm of SiO2, at four cooling temperatures: 22, 50, 75 and 90°C, and for pH ranging from 4 to 9. These experiments showed that the silica deposition was always initiated by a polymerization mechanism characterized by an order 2 kinetic law and the formation of a white colloidal gel, which slowed down the silica precipitation under solid form. This latter was observed much later, after the polymerization stage, and only in particular conditions (long time of atmospheric exposure, water stagnation,. . . ). The results also confirmed that the silica precipitation kinetics is strongly dependent on pH. In acidic solution, a transition period is observed before the beginning to the silica polymerization. At neutral-basic pH, there is no transition period and the rate of polymerization is maximal for pH close to 8. The undergoing modeling of these experimental data and specific surface area measurements on the colloidal gel will allow us to determinate the kinetics parameters useful for the prediction and prevention of silica precipitation under the specific exploitation conditions of Bouillante power station. This work is financially supported by ADEME (French Agency for Energy and Environment), BRGM and UAG.
EGU General Assembly 2012
Vienne, Austria

hal-00697627
https://hal-brgm.archives-ouvertes.fr/hal-00697627

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Abstract View references (38)Silicalite-1 (S-1) and ZSM-5 membranes prepared by secondary growth on tubular ceramic supports were tested using a pervaporation set up for the desalination of aqueous solutions containing NaCl in concentrations corresponding to brackish (0.3-1wt%), sea (3.5wt%) and brine (7.5-15wt%) water. ZSM-5 membranes delivered higher water fluxes when compared with S-1 membranes due to enhanced hydrophilicity of the Al-rich zeolite structure leading to fluxes as high as 11.5kgm -2h -1 for 0.3wt% NaCl feed solutions at 75°C. At higher salt concentration the water flux decreased alongside with the salt rejection rate, however the hydrophilic ZMS-5 membrane became more susceptible to performance loss, particularly at high temperatures. Detailed stability experiments carried out for up to 560h showed the dissolution of both S-1 and ZSM-5 top layers. This was attributed to the combined effects of ion exchange and water dissolution mechanisms. Interesting though, the MFI structure zeolite was still observed on the XRD patterns whilst EDX depth profile showed the presence of silica up to 30μm depth into the support. These results suggest the formation/infiltration of a compact amorphous phase in the substrate, derived from the aggregation of the dissolved silicate species and possibly together with the arrangement of MFI nano-slabs during the desalination tests. Despite generating lower water fluxes, the S-1 membrane exhibited relatively high robustness under the long term testing conditions which included temperature cycling, delivering salt rejections from initial >99% to <80% at the end of the testing period (560h). © 2012 Elsevier B.V.
ISSN: 0376-7388

hal-01683201
https://hal.univ-antilles.fr/hal-01683201
DOI : 10.1016/j.memsci.2012.05.074

Éditeur(s) : Academic Press Ltd- Elsevier Science Ltd
Résumé : The high heterogeneity of silica cycling in coastal margins and the lack of silica data (compared to nitrogen and phosphorus) prevent the estimation of global silica retention in estuaries. In this study, the spatial and temporal variability of porewater silicic acid (Si(OH)4) profiles e that integrate benthic transport and reaction processes e was investigated at different spatial (metre, longitudinal and crosssection, intra-estuary) and temporal (tidal, seasonal) scales in two macrotidal estuaries, very close geographically but essentially differing in their shape. Studying the spatial and temporal variability of Si(OH)4 concentrations in porewaters provided evidence for the importance of transport processes, e.g. bio-irrigation, tidal pumping, resuspension and any combination of these processes, in affecting Si(OH)4 concentrations and fluxes and therefore temporary or permanent retention along the landeocean continuum. We confirm that aSiO2 (amorphous silicate) transported by rivers and estuaries clearly needs to be better characterized as it provides an important source of reactive aSiO2 to sediments. This study allows us to: (1) interrogate spatial and temporal scales, although both are most often in complete interaction; (2) design the most appropriate sampling schemes to be representative of any given system and to extrapolate at the scale of the whole estuary; (3) quantify uncertainty associated to the estimations of Si(OH)4 stocks and fluxes in this type of ecosystem, essential for budget calculations. We showed that two adjacent small macrotidal estuaries, may exhibit different behaviours regarding Si retention. Temporary retention has been observed in the meanders of the Aulne Estuary and not along the more linear Elorn Estuary, demonstrating the importance of the morphology and hydrodynamic components of the estuarine filter. Research is needed in other systems and climatic zones, but our study suggests that the typology should not only account for the different types of landeocean continuum (fjord, delta, mangrove.), but also incorporate the physical or biological attributes of the estuarine filter.
Estuarine Coastal And Shelf Science (0272-7714) (Academic Press Ltd- Elsevier Science Ltd), 2013-03 , Vol. 119 , P. 31-43

Droits : 2013 Elsevier Ltd. All rights reserved.
http://archimer.ifremer.fr/doc/00124/23529/22370.pdf
DOI:10.1016/j.ecss.2012.12.008
http://archimer.ifremer.fr/doc/00124/23529/

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
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
Résumé : 1 page
The main aim of this study, co-funded by BRGM, Regional Council of Guadeloupe, European Union, ADEME and UAG, was to examine the silica deposition mechanisms and estimate their deposition kinetics at acidic and basic pH conditions, during the cooling from 260 to 25°C of separated waters, discharged from production wells, located in the Bouillante geothermal field. The acquisition of this type of information is very useful not only for the geothermal exploitation but especially, if production fluids are re-injected in the ground, as this is envisaged in the Bouillante geothermal field. The different on site experiments showed that, in these conditions, the silica deposition was always initiated by a silica polymerization mechanism and the formation of a white colloidal gel, which slowed down the silica precipitation. In agreement with the literature data, this polymerization mechanism is characterized by an order 2 kinetic law, strongly dependant on pH. The determination of the specific surface area by specific mercury porosimetry for this gel (250 m2/g) in the UAG laboratories, allowed estimating the corresponding kinetic constant at 25°C. Other experiments at different final temperatures (50, 75 and 100°C) are necessary in order to define this constant as a function of the temperature. The silica precipitation under amorphous silica form was observed much later, after the polymerization stage, and only in particular conditions (long time of atmospheric exposure, water stagnation...). The pH of the Bouillante geothermal fluid is estimated to be close to 5.3±0.3, at 260°C, in the reservoir conditions. If this parameter, very influent on the kinetics of silica deposition, can be preserved at values less than 7 during the re-injection of the production fluids in the ground at relatively high temperatures (150-160°C), it is strongly probable that no chemical treatment is necessary to avoid silica precipitation.
19ème Conférence Géologique de la Caraïbe - 2011
Gosier, Guadeloupe, France

hal-00575943
https://hal-brgm.archives-ouvertes.fr/hal-00575943