Influence of Sodium Chloride on the Formation and Dissociation Behavior of CO2 Gas Hydrates

We present an experimental study on the formation and dissociation characteristics of carbon dioxide (CO2) gas hydrates using Raman spectroscopy. The CO2 hydrates were formed from sodium chloride/water solutions with salinities of 0–10 wt %, which were pressurized with liquid CO2 in a stirred vessel at 6 MPa and a subcooling of 9.5 K. The formation of the CO2 hydrate resulted in a hydrate gel where the solid hydrate can be considered as the continuous phase that includes small amounts of a dispersed liquid water-rich phase that has not been converted to hydrate. During the hydrate formation process we quantified the fraction of solid hydrate, xH, and the fraction of the dispersed liquid water-rich phase, xL, from the signature of the hydroxyl (OH)-stretching vibration of the hydrate gel. We found that the fraction of hydrate xH contained in the hydrate gel linearly depends on the salinity of the initial liquid water-rich phase. In addition, the ratio of CO2 and water was analyzed in the liquid water-rich phase before hydrate formation, in the hydrate gel during growth and dissociation, and after its complete dissociation again in the liquid water-rich phase. We observed a supersaturation of CO2 in the water-rich phase after complete dissociation of the hydrate gel and were able to show that the excess CO2 exists as dispersed micro- or nanoscale liquid droplets in the liquid water-rich phase. These residual nano- and microdroplets could be a possible explanation for the so-called memory effect

Geologic controls on the genesis of the Arctic permafrost and sub-permafrost methane hydrate-bearing system in the Beaufort–Mackenzie Delta

The Canadian Mackenzie Delta exhibits a high volume of proven sub-permafrost gas hydrates that naturally trap a significant amount of deep-sourced thermogenic methane (CH4) at the Mallik site. The present study aims to validate the proposed Arctic sub-permafrost gas hydrate formation mechanism, implying that CH4-rich fluids were vertically transported from deep overpressurized zones via geologic fault systems and formed the present-day observed GH deposit since the Late Pleistocene. Given this hypothesis, the coastal permafrost began to form since the early Pleistocene sea-level retreat, steadily increasing in thickness until 1 Million years (Ma) ago. Data from well logs and 2D seismic profiles were digitized to establish the first field-scale static geologic 3D model of the Mallik site, and to comprehensively study the genesis of the permafrost and its associated GH system. The implemented 3D model considers the spatially heterogeneously distributed hydraulic properties of the individual lithologies at the Mallik site. Simulations using a proven thermo-hydro-chemical numerical framework were employed to gain insights into the hydrogeologic role of the regional fault systems in view of the CH4-rich fluid migration and the geologic controls on the spatial extent of the sub-permafrost GH accumulations during the past 1 Ma. For >87% of the Mallik well sections, the predicted permafrost thickness deviates from the observations by less than 0.8%, which validates the general model implementation. The simulated ice-bearing permafrost and GH interval thicknesses as well as sub-permafrost temperature profiles are consistent with the respective field observations, confirming our introduced hypothesis. The spatial distribution of GHs is a result of the comprehensive interaction between various processes, including the source-gas generation rate, subsurface temperature, and the hydraulic properties of the structural geologic features. Overall, the good agreement between simulations and observations demonstrates that the present study provides a valid representation of the geologic controls driving the complex permafrost-GH system. The model’s applicability for the prediction of GH deposits in permafrost settings in terms of their thicknesses and saturations can provide relevant contributions to future GH exploration and exploitation

Gas hydrates in sustainable chemistry

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Hassanpouryouzband, A., Joonaki, E., Farahani, M. V., Takeya, S., Ruppel, C., Yang, J., English, N. J., Schicks, J. M., Edlmann, K., Mehrabian, H., Aman, Z. M., & Tohidi, B. Gas hydrates in sustainable chemistry. Chemical Society Reviews, 49(15), (2020): 5225-5309, doi:10.1039/c8cs00989a.Gas hydrates have received considerable attention due to their important role in flow assurance for the oil and gas industry, their extensive natural occurrence on Earth and extraterrestrial planets, and their significant applications in sustainable technologies including but not limited to gas and energy storage, gas separation, and water desalination. Given not only their inherent structural flexibility depending on the type of guest gas molecules and formation conditions, but also the synthetic effects of a wide range of chemical additives on their properties, these variabilities could be exploited to optimise the role of gas hydrates. This includes increasing their industrial applications, understanding and utilising their role in Nature, identifying potential methods for safely extracting natural gases stored in naturally occurring hydrates within the Earth, and for developing green technologies. This review summarizes the different properties of gas hydrates as well as their formation and dissociation kinetics and then reviews the fast-growing literature reporting their role and applications in the aforementioned fields, mainly concentrating on advances during the last decade. Challenges, limitations, and future perspectives of each field are briefly discussed. The overall objective of this review is to provide readers with an extensive overview of gas hydrates that we hope will stimulate further work on this riveting field.A. H. and K. E. were partially supported by funding from UKRI-EPSRC (grant number EP/S027815/1). C. R. was partially supported by DOE-USGS Interagency agreement DE-FE0023495. C. R. thanks L. Stern and W. Waite for insights that improved her contributions. E. J. is partially supported by Flow Programme project sponsored by Department for Business, Energy and Industrial Strategy (BEIS), UK. Any use of trade, firm or product name is for descriptive purposes only and does not imply endorsement by the U.S. Government

Gas hydrate technology: state of the art and future possibilities for Europe

Interest in natural gas hydrates has been steadily increasing over the last few decades, with the understanding that exploitation of this abundant unconventional source may help meet the ever-increasing energy demand and assist in reduction of CO2 emission (by replacing coal). Unfortunately, conventional technologies for oil and gas exploitation are not fully appropriate for the specific exploitation of gas hydrate. Consequently, the technology chain, from exploration through production to monitoring, needs to be further developed and adapted to the specific properties and conditions associated with gas hydrates, in order to allow for a commercially and environmentally sound extraction of gas from gas hydrate deposits. Various academic groups and companies within the European region have been heavily involved in theoretical and applied research of gas hydrate for more than a decade. To demonstrate this, Fig. 1.1 shows a selection of leading European institutes that are actively involved in gas hydrate research. A significant number of these institutes have been strongly involved in recent worldwide exploitation of gas hydrate, which are shown in Fig. 1.2 and summarized in Table 1.1. Despite the state of knowledge, no field trials have been carried out so far in European waters. MIGRATE (COST action ES1405) aims to pool together expertise of a large number of European research groups and industrial players to advance gas-hydrate related activity with the ultimate goal of preparing the setting for a field production test in European waters. This MIGRATE report presents an overview of current technologies related to gas hydrate exploration (Chapter 2), production (Chapter 3) and monitoring (Chapter 4), with an emphasis on European activity. This requires covering various activities within different disciplines, all of which contribute to the technology development needed for future cost-effective gas production. The report points out future research and work areas (Chapter 5) that would bridge existing knowledge gaps, through multinational collaboration and interdisciplinary approaches

A Counter-Current Heat-Exchange Reactor for the Thermal Stimulation of Hydrate-Bearing Sediments

Since huge amounts of CH4 are bound in natural gas hydrates occurring at active and passive continental margins and in permafrost regions, the production of natural gas from hydrate-bearing sediments has become of more and more interest. Three different methods to destabilize hydrates and release the CH4 gas are discussed in principle: thermal stimulation, depressurization and chemical stimulation. This study focusses on the thermal stimulation using a counter-current heat-exchange reactor for the in situ combustion of CH4. The principle of in situ combustion as a method for thermal stimulation of hydrate bearing sediments has been introduced and discussed earlier [1,2]. In this study we present the first results of several tests performed in a pilot plant scale using a counter-current heat-exchange reactor. The heat of the flameless, catalytic oxidation of CH4 was used for the decomposition of hydrates in sand within a LArge Reservoir Simulator (LARS). Different catalysts were tested, varying from diverse elements of the platinum group to a universal metal catalyst. The results show differences regarding the conversion rate of CH4 to CO2. The promising results of the latest reactor test, for which LARS was filled with sand and ca. 80% of the pore space was saturated with CH4 hydrate, are also presented in this study. The data analysis showed that about 15% of the CH4 gas released from hydrates would have to be used for the successful dissociation of all hydrates in the sediment using thermal stimulation via in situ combustion

Lightscattering experiments under high pressure at polyethylene/n-alcanesystems

In the theoretical part of this dissertation theintroduction of the thermodynamics of mixtures is followed by the basicknowledge of lightscattering. The correlation between thermodynamics atthe one hand and lightscattering at the other is demonstrated. In the apparativeand practicel part the development, build and handeling of the high pressurecell and the carrying out of the light scattering experiments are shown.In the part "results and discussion" the interesting and partly surprisingresults are presentet and discussed

Influence of Gas Supply Changes on the Formation Process of Complex Mixed Gas Hydrates

Natural gas hydrate occurrences contain predominantly methane; however, there are increasing reports of complex mixed gas hydrates and coexisting hydrate phases. Changes in the feed gas composition due to the preferred incorporation of certain components into the hydrate phase and an inadequate gas supply is often assumed to be the cause of coexisting hydrate phases. This could also be the case for the gas hydrate system in Qilian Mountain permafrost (QMP), which is mainly controlled by pores and fractures with complex gas compositions. This study is dedicated to the experimental investigations on the formation process of mixed gas hydrates based on the reservoir conditions in QMP. Hydrates were synthesized from water and a gas mixture under different gas supply conditions to study the effects on the hydrate formation process. In situ Raman spectroscopic measurements and microscopic observations were applied to record changes in both gas and hydrate phase over the whole formation process. The results demonstrated the effects of gas flow on the composition of the resulting hydrate phase, indicating a competitive enclathration of guest molecules into the hydrate lattice depending on their properties. Another observation was that despite significant changes in the gas composition, no coexisting hydrate phases were formed

The Coexistence of Two Different Methane Hydrate Phases under Moderate Pressure and Temperature Conditions: Kinetic versus Thermodynamic Products13

NRC publication: Ye

The Driving Forces of Guest Substitution in Gas Hydrates—A Laser Raman Study on CH4-CO2 Exchange in the Presence of Impurities

The recovery of CH4 gas from natural hydrate formations by injection of industrially emitted CO2 is considered to be a promising solution to simultaneously access an unconventional fossil fuel reserve and counteract atmospheric CO2 increase. CO2 obtained from industrial processes may contain traces of impurities such as SO2 or NOx and natural gas hydrates may contain higher hydrocarbons such as C2H6 and C3H8. These additions have an influence on the properties of the resulting hydrate phase and the conversion process of CH4-rich hydrates to CO2-rich hydrates. Here we show results of a microscopic and laser Raman in situ study investigating the effects of SO2-polluted CO2 and mixed CH4-C2H6 hydrate on the exchange process. Our study shows that the key driving force of the exchange processes is the establishment of the chemical equilibrium between hydrate phase and the surrounding phases. The exchange rate is also influenced by the guest-to-cavity ratio as well as the thermodynamic stability in terms of p-T conditions of the original and resulting hydrate phase. The most effective molecule exchange is related to structural changes (sI-sII) which indicates that hydrate decomposition and reformation processes are the occurring processes