Flow assurance is crucial in the oil industry since it guarantees the success and economic production of hydrocarbon fluid, especially in offshore and deep water oil fields. In fact, the ultimate goal of flow assurance is to maintain flow in the wellbore and pipelines as long as possible. One of the most common challenges in flow assurance is the buildup of solids, such as asphaltene and scale particles. These Solid particles can deposit in the wellbore, flowline, and riser and affect the wellbore performance by reducing the cross section of the pipeline, which eventually results in pipeline blockage. Hence, neglecting the importance of flow assurance problems and failure in thorough understanding of the fluid behavior in the production systems may result in plugged pipeline, production loss, flowline replacement, and early abandonments of the well. As a result, continuous evaluations are needed at the development stage and during the life of reservoirs to predict the potential, the extent, and the severity of the problem to plan for inhibition and remediation jobs. In fact, it is more preferable to prevent flow assurance problems through the designing and operating procedures rather than remediating the problems, which has higher risks of success and higher loss of revenue due to frequent well shut down. As a part of this research, we enhanced the capabilities of our in-house compositional wellbore simulator (UTWELL) to model various production and flow assurance scenarios. Initially, we developed and implemented a robust gas lift model into UTWELL to model artificial lift technique for reservoirs with low pressure. The developed model is able to model both steady state and transient flow along with blackoil and Equation-of-State compositional models. The improved version was successfully validated against a commercial simulator. Then, we applied our dynamic model to track the behavior of asphaltene during gas lift processes and evaluated the risk of asphaltene deposition. Several deposition mechanisms were incorporated to study the transportation, entrainment, and deposition of solid particles in the wellbore. The simulation results illustrated the effect of light gas injection on asphaltene deposition and well performance. Finally, a step by step algorithm is presented for coupling a geochemical package, IPhreeqc, with UTWELL. The developed model is able to model homogenous and heterogeneous, non-isothermal, non-isobaric aqueous phase reactions assuming local equilibrium or kinetic conditions. This tool was then utilized to model scale deposition in the wellbore for various scenarios. In addition, the results showed that integrating IPhreeqc has promise in terms of CPU time compared to the traditional approach of reading and writing the input and output files. / text

Les asphaltènes et autres constituants lourds du pétrole, comme les résines et les alcanes de haut poids moléculaire, posent des défis importants dans tous les segments de la chaîne de production pétrolière. Parmi les nombreux problèmes, la déstabilisation et le dépôt des asphaltènes dans les opérations en amont ont fait perdre beaucoup de temps à la recherche et ne sont pas encore complètement compris. Une partie de la difficulté à saisir la véritable physique derrière de tels phénomènes est l'utilisation répandue des systèmes modèles et des molécules extraites, modifiant considérablement l'organisation fluide complexe des pétroles bruts, et donc en contournant les processus réels. À ce jour, deux extrêmes de la structure organisationnelle asphaltenes peuvent être dessinés, en tant que partie d'un agrégat, avec des attractions pi-pi simples et des chaînes d'alcane répulsion, contrôlant l'agrégation; et dans le cadre d'une structure macromoléculaire, avec une participation significative d'autres composants bruts. La dernière structure étant beaucoup plus difficile à modéliser, elle capture sa physique et est difficilement reproductible à l'aide de systèmes modèles. Un autre aspect important de la recherche des dépôts d'asphaltènes est la manière dont se produit la déstabilisation des asphaltènes. Lorsque l'on utilise des asphaltènes extraits dans des systèmes modèles, l'affirmation précédente n'a pratiquement aucune moyenne, car les nombreuses fractions d'asphaltènes ont été préalablement mélangées. Cependant, lorsqu'il s'agit de tout le pétrole brut, la voie de la déstabilisation est importante et est encore largement dépassée au sein de la communauté scientifique. Pour résumer les sujets exposés, il y a plutôt la non-spécificité de la majorité des techniques expérimentales utilisées sur la recherche de la déstabilisation et du dépôt des asphaltènes en relation avec les dépôts d'échelle des particules.Les techniques de spectroscopie, capables de balayer les paramètres physiques interfaciaux, sont de bons candidats pour améliorer les points exposés délétères. Dans la présente thèse, le résonateur à quartz connecté à un analyseur de réseau vectoriel présente le potentiel de révéler de nombreux aspects sur la déstabilisation et le dépôt des asphaltènes directement à partir de pétrole brut (huiles vivantes, recombinées ou mortes) et de systèmes modèles. L'équilibre du pétrole brut est perturbé par les changements de solubilité dans un processus continu ou en gradin imitant les processus de production. L'interprétation des paramètres de résonance des cristaux de quartz, de la fréquence et de la dissipation d'énergie, est effectuée de manière qualitative et, dans une certaine mesure, quantitative. L'étude innove dans le sens d'étendre l'utilisation du cristal de quartz pour interpréter le processus, non seulement en détectant les changements de phase, comme c'est le cas de la majorité des études précédentes. L'évaluation des produits chimiques de production est effectuée une fois que la méthodologie a fait l'objet d'une discussion approfondie. Le potentiel de l'analyse proposée est crédité par la microscopie à force atomique qui ouvre l'horizon pour plus de recherche et d'applications potentielles de la méthodologie. Parmi les applications possibles figure le développement de capteurs d'assurance de débit capables de détecter les changements de phase et d'évaluer les dépôts in situ. / Asphaltenes and other heavy petroleum constituents, like resins and high molecular weight alkanes, pose significant challenges in all segments from the petroleum production chain. Among the many problems, asphaltenes destabilization and deposition within upstream operations has rendered tons of research time and is still not completely understood. Part of the difficulty in capturing the real physics behind such phenomena is the widespread use of model systems and extracted molecules, greatly altering the complex fluid organization of crude oils, and thus bypassing real processes. To date two extremes of asphaltenes organizational structure can be drawn, as a part of an aggregate, with simple pi-pi attractions and alkane chains repulsion, controlling aggregation; and as a part of a macromolecular structure, with significant participation of other crude components. The last structure being way more difficult to model, and captures its physics and being poorly reproducible with the use of model systems. Another important aspect when researching asphaltene deposition is the way asphaltenes destabilization occurs. When using extracted asphaltenes in model systems, the former affirmation has virtually no mean, as the many asphaltenes fractions were beforehand mixed. However, when dealing with the whole crude oil, the path of destabilization matters and is still greatly bypassed within the scientific community. Summing up to the exposed topics, there is the rather non-specificity from the majority of experimental techniques used on the research of asphaltenes destabilization and deposition in relation to the depositing particles size scales.Spectroscopy techniques, capable of sweeping interfacial physical parameters are good candidates for improving the deleterious exposed points. In the present thesis quartz crystal resonator, connected to a vector network analyzer is used is shown to present the potential of revealing many aspects on asphaltene destabilization and deposition directly from crude oils (live, recombined or dead oils) as well as model systems. Crude oil equilibrium is disturbed by solubility changes in a continuous or step gradient mimicking production processes. The interpretation of the quartz crystal resonance parameters, frequency and energy dissipation, is performed in a qualitative and to some extend quantitative way. The study innovates in the sense of extending the use of the quartz crystal to interpret process, not only detecting phase changes, as it is the case of the majority of the former studies. The evaluation of production chemicals is undergone once the methodology is thoroughly discussed. The potential of the proposed analysis is credited by atomic force microscopy which opens the horizon for more research and potential applications of the methodology. Among the possible application is the development of flow assurance sensors capable of detecting phase changes and evaluate deposition in situ.

Understanding when hydrates will nucleate has notable importance in the area of flow assurance. Attempts to model hydrate formation in subsea pipelines currently requires an arbitrary assignment of a nucleation subcooling. Previous studies showed that sII hydrate containing a model water-soluble former, tetrahydrofuran, would nucleate over a narrow temperature range of a few degrees with constant cooling. It is desirable to know if gas phase hydrate formers, which are typically more hydrophobic and hence have a very low solubility in water, also exhibit this nucleation behavior. In this study, differential scanning calorimetry has been applied to determine the hydrate nucleation point for gas phase hydrate formers. Constant cooling ramps and isothermal approaches were combined to explore the probability of hydrate nucleation. In the temperature ramping experiments, methane and xenon were used at various pressures and cooling rates. In both systems, hydrate nucleation occurred over a narrow temperature range (2-3°C). Using methane at lower pressures, ice nucleated before hydrate; whereas at higher pressures, hydrate formed first. A subcooling driving force of around 30°C was necessary for hydrate nucleation from both guest molecules. The cooling rates (0.5-3°C/min) did not show any statistically significant effect on the nucleation temperature for a given pressure. The isothermal method was used for a methane system with pure water and a water-in-West African crude emulsion. Two isotherms (-5 and -10°C) were used to determine nucleation time. In both systems, the time required for nucleation decreased with increased subcooling.

Hydrate plugging of hydrocarbon production conduits can cause large operational problems resulting in considerable economical losses. Modeling capabilities to predict hydrate plugging occurrences would help to improve facility design and operation in order to reduce the extent of such events. It would also contribute to a more effective and safer remediation process. This paper systematically describes different operational scenarios where hydrate plugging might occur and how a hydrate plug formation prediction tool would be beneficial. The current understanding of the mechanisms for hydrate formation, agglomeration and plugging of a pipeline are also presented. The results from this survey combined with the identified industrial needs are then used as a basis for the assessment of the capabilities of an existing hydrate plug formation model, called CSMHyK (The Colorado School of Mines Hydrate Kinetic Model). This has recently been implemented in the transient multiphase flow simulator OLGA as a separate module. Finally, examples using the current model in several operational scenarios are shown to illustrate some of its important capabilities. The results from these examples and the operational scenarios analysis are then used to discuss the future development needs of the CSMHyK model.

L’activité scientifique du sujet porte sur l’acquisition de données expérimentales et la modélisation de la composition des clathrates hydrates de gaz. Les domaines d’application concernent la séparation et le stockage de gaz, la purification de l’eau, et le stockage d’énergie par matériaux à changement de phase.L’équipe a mis en évidence il y a quelques années que la composition des hydrates de gaz était sensible aux conditions de cristallisation, et que le phénomène de formation se produisait en dehors de l’équilibre thermodynamique.Le travail de thèse a permis d’explorer plusieurs modes de cristallisation à partir de solutions de même composition initiale pour observer les différences concernant l’état final, compositions notamment, et les relier à la vitesse de cristallisation. Suivant le mode de cristallisation, lent ou rapide, l’acquisition des données expérimentales peut prendre de quelques jours à plusieurs semaines. Les expériences sont réalisées en réacteur pressurisé dans lequel nous mesurons en ligne la composition de la phase gaz et de la phase liquide, pour calculer par bilan de matière la composition de la phase hydrate.Nous avons bien mis en évidence des variations dans la composition de la phase hydrate suivant le mode de cristallisation. Nous avons dû établir un modèle thermodynamique donnant la composition de la phase hydrate à l’équilibre pour des mélanges de gaz qui n’avaient jamais été traité par la littérature, et qui ont donc nécessité des campagnes de mesure extrêmement lentes et donc longues pour être sûr de l’état thermodynamique à l’équilibre.Nous sommes en cours d’établir un modèle cinétique pour modéliser les écarts à cet état d’équilibre de référence pour nos expériences réalisées à vitesse de cristallisation rapide. / The scientific goal of this thesis is based on the acquisition of experimental data and the modeling of the composition of clathrates gas hydrate. The domains of application concern the gas separation and storage, water purification, and energy storage using change phase materials (PCMs).Our research team has recently demonstrated that the composition of gas hydrates was sensitive to the crystallization conditions, and that the phenomenon of formation was out of thermodynamic equilibrium. During this thesis, we have investigated several types of crystallization, which are based on the same initial states. The goal is to point out the differences between the initial solution composition and the final solution composition, and to establish a link between the final state and the crystallization rate.Depending on the rate of crystallization (slow or fast), the acquisition time of experimental data lasted from a few days to several weeks. The experimental tests were performed inside a stirred batch reactor (autoclave, 2.44 or 2.36 L) cooled with a double jacket. Real-time measurements of the composition of the gas and the liquid phases have been performed, in order to calculate the composition of the hydrate phase using mass balance calculations. Depending on the crystallization mode, we have identified several variations of the composition of the hydrate phase and final hydrate volume.We have established a successful thermodynamic model, which indicates the composition of the hydrate phase and hydrate volume in thermodynamic equilibrium state using a gas mixture which had never been used before in the literature. So this thermodynamic model has required an extremely slow experimental test. These tests were also long in order to be sure of the thermodynamic equilibrium state.We are currently establishing a kinetics model in order to model the deviations from the reference point of equilibrium of our experimental tests which were carried out at a high crystallization rate.

The use of Kinetic Hydrate Inhibitors (KHI) is one of the optimum methods employed to control gas hydrate formation issues and provide flow assurance in oil and gas production systems. The application of this technology has several advantages to operators, including significant cost savings and extended life of oil and gas systems. This paper will highlight a specific case where a Major operator in the North Sea (UK sector) significantly reduced the cost of well intervention operations by applying a KHI in a subsea gas lift line. Considerable cost savings were realized by reducing volume of chemical required and this enabled the application to be performed from the FPSO eliminating the need for a dedicated Diving Support Vessel (DSV). Furthermore, the application of KHI also reduced manual handling and chemical logistics usually associated with this particular treatment. In order to prevent mineral scale deposition occurring in downhole tubing and near well bore and in the formation; scale inhibitor squeeze applications are standard practice. For subsea wells the fluids can be pumped down in to the well via gas lift lines. However, upon completion of previous scale squeeze operations at this particular location, hydrate formation was observed when a mixture of MEG and water was used following interventions via the gas lift line. By applying 1% KHI with a mixture of MEG and Water, the well was brought back into production following scale squeeze operations without hydrate formation occurring.

A hydrate plugging and formation model for oil and gas pipelines is becoming increasingly important as producers continue to push flow assurance boundaries. A key input for any hydrate plugging model is the rate of hydrate growth and the volume fraction of hydrate at a given time. This work investigates a fundamental approach toward predicting hydrate growth and volume fraction in a water saturated gas pipeline. This works suggests that, in the absence of free water, hydrate volume fraction can be predicted using a wall growth and sloughing model. Wall growth can be predicted using a one-dimensional, moving boundary, heat and mass transfer model. It is hypothesized that hydrate sloughing can be predicted when a coincident frequency exists between hydrate natural frequency and flow induced vibrations over the hydrate surface.

Using a combination of micromechanical force and flowloop measurements, hydrate deposition on a pipe wall surface was investigated for ‘dry’ hydrates formed in the bulk phase and for hydrates growing on the pipe surface. Cyclopentane ‘dry’ hydrates (without a free water phase) were used to predict whether hydrates, formed in a bulk condensate phase, would adhere to a pipe wall. Adhesion forces between cyclopentane hydrates and steel were measured using a micro-mechanical force apparatus. The average force of adhesion was measured to be very small, less than 0.01 N/m. This force was used in a particle force balance, predicting that hydrates formed in the bulk phase would not deposit on the pipe wall. It was hypothesized than in the presence of a water saturated hydrocarbon, hydrates would grow on the pipe wall as the fluid cooled below its equilibrium temperature. This hypothesis was confirmed using a single pass condensate flowloop. Water was continuously dissolved into the flowloop inlet stream as water deposited in the flowloop test section, resulting in both a pressure drop and fluid temperature increase. This work illustrates the need for a hydrate wall growth model.

An understanding of the blockage potential for an oil dominated system is an important step in moving from hydrate prevention to hydrate management. To better understand this problem a series of experiments were performed by varying the water cut, fluid velocity, and gas-liquid volume fraction using the ExxonMobil (XoM) flow loop in Houston, Texas, USA. The XoM large loop is a three pass, four inch internal diameter flow loop with a sliding vane pump capable of generating liquid velocities of up to 4 m/s. The systems that were studied include a range of water cuts from 5%-50% in a light crude oil (Conroe crude) and a gas phase of either pure methane for sI or 75% methane and 25% ethane which has sII as the thermodynamically stable phase. The results are compared with the hydrate plug prediction tool, CSMHyK, integrated into the multiphase flow simulator OLGA5®. The comparison between the model and the flow loop results serve as a basis for improving hydrate formation and plug prediction. In addition, the experimental variables that promote plug formation in the flow loop and how these may translate into the field are discussed.

The use of Kinetic Hydrate Inhibitors (KHI) is one of the optimum methods employed to control gas hydrate formation issues and provide flow assurance in oil and gas production systems. The application of this technology has several advantages to operators, including significant cost savings and extended life of oil and gas systems. This paper will highlight a specific case where a Major operator in the North Sea (UK sector) significantly reduced the cost of well intervention operations by applying a KHI in a subsea gas lift line. Considerable cost savings were realized by reducing volume of chemical required and this enabled the application to be performed from the FPSO eliminating the need for a dedicated Diving Support Vessel (DSV). Furthermore, the application of KHI also reduced manual handling and chemical logistics usually associated with this particular treatment. In order to prevent mineral scale deposition occurring in downhole tubing and near well bore and in the formation; scale inhibitor squeeze applications are standard practice. For subsea wells the fluids can be pumped down in to the well via gas lift lines. However, upon completion of previous scale squeeze operations at this particular location, hydrate formation was observed when a mixture of MEG and water was used following interventions via the gas lift line. By applying 1% KHI with a mixture of MEG and Water, the well was brought back into production following scale squeeze operations without hydrate formation occurring.