Measurement & Prediction of Phase Behaviour of Carbon Dioxide Mixtures

Acquiring a comprehensive understanding of the behaviour of carbon dioxide under reservoir conditions is essential for optimizing its usage in enhanced oil recovery (EOR) and for developing sequestration schemes. In order to obtain this understanding, it is necessary to study the physical properties and phase behaviour of mixtures of carbon dioxide with hydrocarbons and brines under conditions of high pressure. In this work we are addressing both the experimental and the theoretical aspects of this problem. A new apparatus, based on the static-analytical method, has been developed to measure phase equilibrium. The equipment comprises a high-pressure cell with sapphire windows for visual observation and phase sampling, with on-line gas chromatography analysis, for measuring the phase compositions. The experimental work is complemented with a theoretical modelling for these mixtures, using the statistical association fluid theory for potentials of variable range (SAFT-VR). As an example of the predictive capabilities of the equation, the fluid phase behaviour of the mixture (carbon dioxide + n-decane) is presented

Shallow Gas Hydrate Accumulations at a Nigerian Deepwater Pockmark—Quantities and Dynamics

The evolution of submarine pockmarks is often related to the ascent of fluid from the subsurface. For pockmarks located within the gas hydrate stability zone, methane oversaturation can result in the formation of gas hydrates in the sediment. An ~600 m‐wide sea floor depression in deep waters offshore Nigeria, Pockmark A, was investigated for distributions and quantities of shallow gas hydrates, origins of hydrocarbons, and time elapsed since the last major fluid ascent event. For the first time, pressure coring of shallow sediments and drilling of more than 50 m‐long cores with the sea floor drill rig MARUM‐MeBo70 were conducted in this pockmark. Unusually, high hydrate saturations of up to 51% of pore volume in the uppermost 2.5 m of sediment in the pockmark center substantiate that deepwater pockmarks are a relevant methane reservoir. Molecular and stable C and H isotopic compositions suggest that thermogenic hydrocarbons and secondary microbial methane resulting from petroleum biodegradation are injected into shallower sediments and mixed with primary microbial hydrocarbons. Two independent pore water chloride and sulfate modeling approaches suggest that a major methane migration event occurred during the past one to three centuries. A rough sea floor topography within the pockmark most likely results from combined sediment removal through ascending gas bubbles, hydrate clogging and deflection of migration pathways, gas pressure build‐up, and hydrate sea floor detachment. This study shows for the first time the chronological interrelationship between gas migration events, hydrate formation, and sea floor shaping in a deep sea pockmark

Inter-Comparison of the Spatial Distribution of Methane in the Water Column From Seafloor Emissions at Two Sites in the Western Black Sea Using a Multi-Technique Approach

Understanding the dynamics and fate of methane (CH 4 ) release from oceanic seepages on margins and shelves into the water column, and quantifying the budget of its total discharge at different spatial and temporal scales, currently represents a major scientific undertaking. Previous works on the fate of methane escaping from the seafloor underlined the challenge in both, estimating its concentration distribution and identifying gradients. In April 2019, the Envri Methane Cruise has been conducted onboard the R/V Mare Nigrum in the Western Black Sea to investigate two shallow methane seep sites at ∼120 m and ∼55 m water depth. Dissolved CH 4 measurements were conducted with two continuous in-situ sensors: a membrane inlet laser spectrometer (MILS) and a commercial methane sensor (METS) from Franatech GmbH. Additionally, discrete water samples were collected from CTD-Rosette deployment and standard laboratory methane analysis was performed by gas chromatography coupled with either purge-and-trap or headspace techniques. The resulting vertical profiles (from both in situ and discrete water sample measurements) of dissolved methane concentration follow an expected exponential dissolution function at both sites. At the deeper site, high dissolved methane concentrations are detected up to ∼45 m from the seabed, while at the sea surface dissolved methane was in equilibrium with the atmospheric concentration. At the shallower site, sea surface CH 4 concentrations were four times higher than the expected equilibrium value. Our results seem to support that methane may be transferred from the sea to the atmosphere, depending on local water depths. In accordance with previous studies, the shallower the water, the more likely is a sea-to-atmosphere transport of methane. High spatial resolution surface data also support this hypothesis. Well localized methane enriched waters were found near the surface at both sites, but their locations appear to be decoupled with the ones of the seafloor seepages. This highlights the need of better understanding the processes responsible for the transport and transformation of the dissolved methane in the water column, especially in stratified water masses like in the Black Sea

Multidisciplinary investigation on cold seeps with vigorous gas emissions in the Sea of Marmara (MarsiteCruise): Strategy for site detection and sampling and first scientific outcome

MarsiteCruise was undertaken in October/November 2014 in the Sea of Marmara to gain detailed insight into the fate of fluids migrating within the sedimentary column and partially released into the water column. The overall objective of the project was to achieve a more global understanding of cold-seep dynamics in the context of a major active strike-slip fault. Five remotely operated vehicle (ROV) dives were performed at selected areas along the North Anatolian Fault and inherited faults. To efficiently detect, select and sample the gas seeps, we applied an original procedure. It combines sequentially (1) the acquisition of ship-borne multibeam acoustic data from the water column prior to each dive to detect gas emission sites and to design the tracks of the ROV dives, (2) in situ and real-time Raman spectroscopy analysis of the gas stream, and (3) onboard determination of molecular and isotopic compositions of the collected gas bubbles. The in situ Raman spectroscopy was used as a decision-making tool to evaluate the need for continuing with the sampling of gases from the discovered seep, or to move to another one. Push cores were gathered to study buried carbonates and pore waters at the surficial sediment, while CTD-Rosette allowed collecting samples to measure dissolved-methane concentration within the water column followed by a comparison with measurements from samples collected with the submersible Nautile during the Marnaut cruise in 2007. Overall, the visited sites were characterized by a wide diversity of seeps. CO2- and oil-rich seeps were found at the westernmost part of the sea in the Tekirdag Basin, while amphipods, anemones and coral populated the sites visited at the easternmost part in the Cinarcik Basin. Methane-derived authigenic carbonates and bacterial mats were widespread on the seafloor at all sites with variable size and distributions. The measured methane concentrations in the water column were up to 377 μmol, and the dissolved pore-water profiles indicated the occurrence of sulfate depleting processes accompanied with carbonate precipitation. The pore-water profiles display evidence of biogeochemical transformations leading to the fast depletion of seawater sulfate within the first 25-cm depth of the sediment. These results show that the North Anatolian Fault and inherited faults are important migration paths for fluids for which a significant part is discharged into the water column, contributing to the increase of methane concentration at the bottom seawater and favoring the development of specific ecosystems

Exploring methane-hydrate formation and dissociation in geologic materials through laboratory experiments: Kinetic behavior and morphology

To gain in-depth understanding of natural gas hydrate behavior it is necessary to identify key parameters that affect their formation, distribution and destabilization within sediments. Hydrate formation kinetics in porous media is amongst the aspects which deserve important considerations as it may provide useful information on the formation history and the formation mechanisms of natural gas hydrate accumulations. Yet, it is at its early stage. In this paper, experiments on methane hydrate formation and dissociation in porous media are reported and discussed. The first part of this work is devoted to the investigation of the kinetics of methane hydrate formation within silica sand using a custom-design apparatus. The latter is suitable for investigating small hydrate-bearing cores. The influence of the methane injection flow-rate is examined, and then a straightforward method is proposed to quantify the amount of hydrate-bound gas. In the second part, three mixtures of clays and sand are used as geologic matrix to study the influence of clay content on the hydrate morphology for a predetermined amount of injected water. Visual observations showed that the morphology shifts from disseminated through massive to moussy hydrates with increasing proportion of clays

Équilibres de phases à basse température de systèmes complexes CO2 - hydrocarbures légers - méthanol - eau (mesures et modélisation)

Le besoin de développer et d'améliorer les procédés de traitement de gaz est réel. Or la complexité des équilibres mis en jeu a pour conséquence une rareté des données dans la littérature qui limite le développement des modèles thermodynamiques. La première partie de ce travail est consacrée à l'étude expérimentale de systèmes constitués d'hydrocarbures légers, de méthanol, d'eau et de gaz acides. Nous présentons un nouvel appareillage de mesure d'équilibres liquide-vapeur et liquide-liquide-vapeur. Il nous a permis d'une part d'acquérir de nouvelles données compositionnelles du binaire éthane-méthanol et de différents mélanges, et d'autre part de déterminer une partie de l'enveloppe d'équilibre triphasique de ces mêmes systèmes. Dans la deuxième partie de ce travail, nous développons un modèle thermodynamique basé sur l'équation d'état CPA. Grâce à son terme associatif, il prend en compte les associations moléculaires dues à la présence d'eau, du méthanol et du sulfure d'hydrogène. Un tel modèle est nécessaire pour dimensionner correctement les unités de traitement de gaz et pour déterminer les conditions opératoires optimales. Il permet de prédire les équilibres multiphasiques de nombreux systèmes binaires et restitue de façon satisfaisante les équilibres de phase de systèmes complexesLYON1-BU.Sciences (692662101) / SudocSudocFranceF