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

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

Sensitivity Analysis of Parameters Governing the Recovery of Methane from Natural Gas Hydrate Reservoirs

Naturally occurring gas hydrates are regarded as an important future source of energy and considerable efforts are currently being invested to develop methods for an economically viable recovery of this resource. The recovery of natural gas from gas hydrate deposits has been studied by a number of researchers. Depressurization of the reservoir is seen as a favorable method because of its relatively low energy requirements. While lowering the pressure in the production well seems to be a straight forward approach to destabilize methane hydrates, the intrinsic kinetics of CH4-hydrate decomposition and fluid flow lead to complex processes of mass and heat transfer within the deposit. In order to develop a better understanding of the processes and conditions governing the production of methane from methane hydrates it is necessary to study the sensitivity of gas production to the effects of factors such as pressure, temperature, thermal conductivity, permeability, porosity on methane recovery from naturally occurring gas hydrates. A simplified model is the base for an ensemble of reservoir simulations to study which parameters govern productivity and how these factors might interact

Numerical Simulation of Hydrate Formation in the LArge-Scale Reservoir Simulator (LARS)

The LArge-scale Reservoir Simulator (LARS) has been previously developed to study hydrate dissociation in hydrate-bearing systems under in-situ conditions. In the present study, a numerical framework of equations of state describing hydrate formation at equilibrium conditions has been elaborated and integrated with a numerical flow and transport simulator to investigate a multi-stage hydrate formation experiment undertaken in LARS. A verification of the implemented modeling framework has been carried out by benchmarking it against another established numerical code. Three-dimensional (3D) model calibration has been performed based on laboratory data available from temperature sensors, fluid sampling, and electrical resistivity tomography. The simulation results demonstrate that temperature profiles, spatial hydrate distribution, and bulk hydrate saturation are consistent with the observations. Furthermore, our numerical framework can be applied to calibrate geophysical measurements, optimize post-processing workflows for monitoring data, improve the design of hydrate formation experiments, and investigate the temporal evolution of sub-permafrost methane hydrate reservoirs

Numerical Simulation of Coastal Sub-Permafrost Gas Hydrate Formation in the Mackenzie Delta, Canadian Arctic

The Mackenzie Delta (MD) is a permafrost-bearing region along the coasts of the Canadian Arctic which exhibits high sub-permafrost gas hydrate (GH) reserves. The GH occurring at the Mallik site in the MD is dominated by thermogenic methane (CH4), which migrated from deep conventional hydrocarbon reservoirs, very likely through the present fault systems. Therefore, it is assumed that fluid flow transports dissolved CH4 upward and out of the deeper overpressurized reservoirs via the existing polygonal fault system and then forms the GH accumulations in the Kugmallit–Mackenzie Bay Sequences. We investigate the feasibility of this mechanism with a thermo–hydraulic–chemical numerical model, representing a cross section of the Mallik site. We present the first simulations that consider permafrost formation and thawing, as well as the formation of GH accumulations sourced from the upward migrating CH4-rich formation fluid. The simulation results show that temperature distribution, as well as the thickness and base of the ice-bearing permafrost are consistent with corresponding field observations. The primary driver for the spatial GH distribution is the permeability of the host sediments. Thus, the hypothesis on GH formation by dissolved CH4 originating from deeper geological reservoirs is successfully validated. Furthermore, our results demonstrate that the permafrost has been substantially heated to 0.8–1.3 °C, triggered by the global temperature increase of about 0.44 °C and further enhanced by the Arctic Amplification effect at the Mallik site from the early 1970s to the mid-2000s

A Review of Reactor Designs for Hydrogen Storage in Clathrate Hydrates

Clathrate hydrates are ice-like, crystalline solids, composed of a three-dimensional network of hydrogen bonded water molecules that confines gas molecules in well-defined cavities that can store gases as a solid solution. Ideally, hydrogen hydrates can store hydrogen with a maximum theoretical capacity of about 5.4 wt%. However, the pressures necessary for the formation of such a hydrogen hydrate are 180–220 MPa and therefore too high for large-scale plants and industrial use. Thus, since the early 1990s, there have been numerous studies to optimize pressure and temperature conditions for hydrogen formation and storage and to develop a proper reactor type via optimisation of the heat and mass transfer to maximise hydrate storage capacity in the resulting hydrate phase. So far, the construction of the reactor has been developed for small, sub-litre scale; and indeed, many attempts were reported for pilot-scale reactor design, on the multiple-litre scale and larger. The purpose of this review article is to compile and summarise this knowledge in a single article and to highlight hydrogen-storage prospects and future challenges

THE CHARACTERISTICS OF GAS HYDRATES FORMED FROM H2S AND CH4 UNDER VARIOUS CONDITIONS

Shallow marine gas hydrates occurring above the Sulfate-Methane-Interface (SMI) often contain small amounts of H2S beside methane and other hydrocarbons, but the distribution of H2S in these natural samples is not always homogeneous. To learn more about the formation of H2Scontaining hydrates, gas hydrates with different ratios of H2S/CH4 were synthesized under various conditions. The samples were synthesized from ice and water phases, with constant feed gas compositions or controlled changes in feed gas compositions. It turns out that the detailed nature of the synthetic hydrate samples depends on the method of sample preparation. The sample prepared with gas containing small amounts of H2S (1% H2S and 99% CH4) appeared homogeneous in composition, while that prepared in a water-H2S-CH4 system with higher H2S contents was heterogeneous. The samples were analysed with Raman spectroscopy, and differential scanning calorimetry (DSC).Non UBCUnreviewe

Reservoir formation damage during hydrate dissociation in sand-clay sediment from Qilian Mountain permafrost, China

Permeability is known as a key factor affecting the gas production effectiveness from the natural gas hydrate-bearing reservoir. We studied the permeability behavior of natural clayey sand core samples from a natural hydrate-bearing reservoir in the Qilian Mountain permafrost before and after hydrate formation, as well as after hydrate decomposition. We found a substantially lower permeability after hydrate decomposition and assumed a formation damage process involving fines mobilization, migration and deposition at pore throats. The assumption was proved by SEM analysis of the filter paper separating the sample and the end caps containing the fluid ports. The analysis showed fines trapped in the paper from the outlet side. Fines migration and resulting formation damage is known from enhanced oil recovery by low salinity water flooding, but was unexpected for hydrate decomposition. The underlying mechanism was identified by a series of different permeability tests. The results indicate that fresh water released from the hydrate dissociation causes the fines mobilization, migration and redeposition at pore throats leading to the observed permeability decrease. Obviously the large volume of released methane gas displaces the remaining saline water and separates it from the fresh water released from the hydrate. The fresh water in contact with parts of the grain framework causes the detachment of clay particles by increased electrostatic forces and clay swelling, if swellable clays are present. This is an important mechanism that has to be taken into account in the planning of gas production from low-permeability clayey hydrate-bearing formations