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The formation of natural gas hydrates presents significant economic and safety challenges to the petroleum and gas industry, necessitating the development of effective prevention strategies. This study investigates an environmentally sustainable Tenebrio molitor antifreeze protein (TmAFP) modified to be a potential kinetic hydrate inhibitor. The aim of this study was to enhance the inhibitory activity of TmAFP by systematically substituting threonine (Thr) residues with glycine (Gly), alanine (Ala), or serine (Ser) at positions 29, 39, and 53. The Ala mutant demonstrated superior inhibition of hydrate formation, attributed to its optimized spatial conformation and enhanced hydrophobic interactions, followed by the Gly and Ser mutants. The wild-type TmAFP showed limited efficacy. The radial distribution function (RDF) analysis indicated that the mutations facilitated a better accommodation of adjacent residues within the hydrate crystal structure by adjusting the distance between Thri and Thri+2 to closely match the second peak in the RDF of methane molecules at 6.4 Å. The potential of mean force (PMF) calculations revealed that the Ala and Ser mutants exhibited enhanced interactions with hydrate cages, with PMF values of −0.73 and −0.71 kJ/mol, respectively, compared to the Gly mutant, which had a PMF value of 1.46 kJ/mol. By identifying the optimal mutation combination (T29 39 53A) to significantly increase the potency of TmAFP, this study provides a fundamental basis for the further development of hydrate inhibition strategies. [ABSTRACT FROM AUTHOR]

Complex organic molecules are widespread in different areas of the interstellar medium, including cold areas, such as molecular clouds, where chemical reactions occur in ice. Among the observed molecules are oxygen-bearing organic molecules, which are of high interest given their significant role in astrobiology. Despite the observed rich chemistry, the underlying molecular mechanisms responsible for molecular formation in such cold dilute areas are still not fully understood. In this paper, we study the unique chemistry taking place in astronomically relevant ices, where UV radiation is a central driving force for chemical reactions. Photofragmentation of ice components gives rise to highly reactive species, such as the O(1D) atom. These species provide a pathway for chemical complexity even in cold areas. Using quantum chemistry calculations, we demonstrate that O(1D) reacts barrierlessly with hydrocarbons. Moreover, photoprocessing of the reaction products (and other components of the ice), followed by radical recombination, is found to be an essential part of the overall mechanism. In ice containing O(1D) and hydrocarbons, the formation of formaldehyde in methane ice, acetaldehyde in ethane ice, and carbon monoxide in acetylene ice, and the consumption of alcohol in all systems, was predicted in agreement with experimental results. [ABSTRACT FROM AUTHOR]

We explore the solubilities of guest CH4 and/or CO2 in the aqueous state coexisting with the corresponding hydrate. The equilibrium conditions are estimated by calculating the chemical potentials of water and guest species in the hydrate on the basis of a statistical mechanical theory using pairwise intermolecular potentials. This requires the least computational cost while covering a wide range of temperature, pressure, and composition of guest species, even for the binary hydrate. The nonstoichiometric nature, one of the most important characters of hydrates, is invariably taken into account when evaluating its phase behaviors and the driving force for nucleation of hydrates. The two-phase equilibrium concerning CO2 hydrate is evaluated considering a low but finite value of CO2 solubility in water. It is found that the finite solubility gives rise to a small systematic deviation of the dissociation temperature of CO2 hydrate. The solubility of CO2 coexisting with fluid CO2 decreases with temperature but the opposite temperature dependence is obtained in the presence of hydrate, as in the case of CH4. This method is applied to CH4–CO2 binary hydrates of various guest compositions. We also find a significant difference in composition of guests among the phases involved in the equilibria. [ABSTRACT FROM AUTHOR]

Molecular simulations are a powerful tool to understand phenomena and obtain properties of gas hydrate systems. The direct coexistence method (DCM) in the NVT or NPT ensembles, the most commonly used method to determine hydrate dissociation temperatures, can be computationally expensive due to the need for several long simulations. Through an extensive set of simulations, we report here the details of the DCM within the NPH (isobaric–isenthalpic) ensemble, which require fewer and shorter trajectories. The dissociation pressure of methane hydrates is obtained for pressures of 4, 8, 15, 30, and 50 MPa. The values are in agreement with other literature simulations and experimental data. The results are further validated with the calculation of the enthalpy of dissociation, with a value of 50 kJ/mol of methane, also in agreement with the literature. The complexity of a multiphase and multicomponent system presents challenges lacking in simpler water/ice systems. These are found to be dependent on energy conservation. The optimal set of parameters to achieve it is also reported, including a smaller time step and the use of double precision, along with an analysis of some factors that could affect the convergence of the method. Although these parameters require more computational cost, the NPH ensemble is successful in providing the dissociation temperature of gas hydrates in fewer simulations than other ensembles and with productions lasting only 500 ns. [ABSTRACT FROM AUTHOR]

Due to their high computational efficiency, the coarse-grained water models are of particular importance for practical molecular simulations of gas hydrates. In these models, the mW model is successfully used to study many thermodynamics and dynamics of methane hydrate. Yet, despite several decades of intense research, the mW model is still found to overestimate the melting temperature of methane hydrate. We here employ the minimum mean squared error estimation to revisit the key parameter of the mW model, which determines the strength of the tetrahedral angle of the water system. Relying on the free energy calculations, we first estimate the chemical potentials of water in the liquid phase for temperatures at which methane hydrate forms. We then turn to the mean squared error to describe the chemical potential deviation between the mW model and the TIP4P/ice model (the latter could reproduce the experimental phase diagram of methane hydrate). By minimizing the mean squared error, we finally have an optimized parameter for the mW model. In this part, we also discuss the pressure effect on such reparameterization procedure. Moreover, relying on the direct coexistence method, the melting temperature determined using the reparameterized mW model is found to be consistent with the experimental data. This strategy provides a means to improve the coarse-grained model to match the experimental observations for temperatures in the range of interest. [ABSTRACT FROM AUTHOR]

Understanding the underlying physics of natural gas hydrate dissociation is necessary for efficient CH4 extraction and in the exploration of potential additives in the chemical injection method. Silica being "sand" is already present inside the reservoir, making the silica nanoparticle a potential green additive. Here, molecular dynamics (MD) simulations have been performed to investigate the dissociation of the CH4 hydrate in the presence and absence of ∼1, ∼2, and ∼3 nm diameter hydrophilic silica nanoparticles at 100 bar and 310 K. We find that the formation of a CH4 nanobubble has a strong influence on the dissociation rate. After the initial hydrate dissociation, the rate of dissociation slows down till the formation of a CH4 nanobubble. We find the critical concentration and size limit to form the CH4 nanobubble to be ∼0.04 mole fraction of CH4 and ∼40 to 50 CH4 molecules, respectively. The solubility of CH4 and the chemical potential of H2O and CH4 are determined via Gibbs ensemble Monte Carlo simulations. The liquid phase chemical potential of both H2O and CH4 in the presence and absence of the nanoparticle is nearly the same, indicating that the effect of this additive will not be significant. While the formation of the hydration shell around the nanoparticle via hydrogen bonding confirms the strength of interactions between the water molecules and the nanoparticle in our MD simulations, the contact of the nanoparticle with the interface is infrequent, leading to no explicit effect of the nanoparticle on the dynamics of methane hydrate dissociation. [ABSTRACT FROM AUTHOR]

In this study, peptides designed using fragments of an antifreeze protein (AFP) from the freeze-tolerant insect Tenebrio molitor, TmAFP, were evaluated as inhibitors of clathrate hydrate formation. It was found that these peptides exhibit inhibitory effects by both direct and indirect mechanisms. The direct mechanism involves the displacement of methane molecules by hydrophobic methyl groups from threonine residues, preventing their diffusion to the hydrate surface. The indirect mechanism is characterized by the formation of cylindrical gas bubbles, the morphology of which reduces the pressure difference at the bubble interface, thereby slowing methane transport. The transfer of methane to the hydrate interface is primarily dominated by gas bubbles in the presence of antifreeze peptides. Spherical bubbles facilitate methane migration and potentially accelerate hydrate formation; conversely, the promotion of a cylindrical bubble morphology by two of the designed systems was found to mitigate this effect, leading to slower methane transport and reduced hydrate growth. These findings provide valuable guidance for the design of effective peptide-based inhibitors of natural-gas hydrate formation with potential applications in the energy and environmental sectors. [ABSTRACT FROM AUTHOR]

Methane is considered to be a cubic structure I (CS-I) clathrate hydrate former, although in a number of instances, small amounts of structure II (CS-II) clathrate hydrate have been transiently observed as well. In this work, solid-state magic angle spinning 13C NMR spectra of methane hydrate formed at low temperatures inside silica-based nanoporous materials with pores in the range of 3.8–20.0 nm (CPG-20, Vycor, and MCM-41) show methane in several different environments. In addition to methane encapsulated in the dodecahedral 512 (D) and tetrakaidecahedral 51262 (T) cages typical of the CS-I clathrate hydrate phase, methane guests in pentakaidecahedral 51263 (P) and hexakaidecahedral 51264 (H) cages are also identified, and these appear to be stabilized for extended periods of time. The ratio of methane guests among the D and T cages determined from the line intensities is significantly different from that of bulk CS-I samples and indicates that both CS-I and CS-II are present as the dominant species. This is the first observation of methane in P cages, and the possible structures in which they could be present are discussed. Broad and relatively strong methane peaks, which are also observed in the spectra, can be related to methane dissolved in an amorphous component of water adjacent to the pore walls. Nanoconfinement and interaction with the pore walls clearly have a strong influence on the hydrate formed and may reflect species present in the early stages of hydrate growth. [ABSTRACT FROM AUTHOR]

Clathrate hydrates are vital in energy research and environmental applications. Understanding their stability is crucial for harnessing their potential. In this work, we employ direct coexistence simulations to study finite-size effects in the determination of the three-phase equilibrium temperature (T3) for methane hydrates. Two popular water models, TIP4P/Ice and TIP4P/2005, are employed, exploring various system sizes by varying the number of molecules in the hydrate, liquid, and gas phases. The results reveal that finite-size effects play a crucial role in determining T3. The study includes nine configurations with varying system sizes, demonstrating that smaller systems, particularly those leading to stoichiometric conditions and bubble formation, may yield inaccurate T3 values. The emergence of methane bubbles within the liquid phase, observed in smaller configurations, significantly influences the behavior of the system and can lead to erroneous temperature estimations. Our findings reveal finite-size effects on the calculation of T3 by direct coexistence simulations and clarify the system size convergence for both models, shedding light on discrepancies found in the literature. The results contribute to a deeper understanding of the phase equilibrium of gas hydrates and offer valuable information for future research in this field. [ABSTRACT FROM AUTHOR]

Developing highly efficient methane (CH4) hydrate storage methods and understanding the hydrate dissociation kinetics can contribute to advancing CH4 gas storage and transport. The effects of tetrabutylammonium bromide (TBAB) (a thermodynamic promoter) addition on the kinetics of CH4 hydrate were evaluated on the microscopic scale using synchrotron x-ray computed tomography (CT) and powder x-ray diffraction. Microscopic observations showed that a 5 wt. % TBAB solution facilitated the nucleation of CH4 hydrate owing to the initial growth of TBAB semi-clathrate hydrate particles. The CH4 hydrate crystals in the CH4 + TBAB hydrate sample were sponge-like with many internal pores and exhibited slightly enhanced self-preservation compared to the pure CH4 hydrate, both in the bulk and after pulverization to a fine powder. This study demonstrates the feasibility of controlling the rate of CH4 hydrate formation and preservation by using aqueous TBAB solutions in CH4 hydrate formation. [ABSTRACT FROM AUTHOR]

The crystallization process of methane hydrates in a confined geometry resembling seabed porous silica sedimentary conditions has been studied using molecular dynamics simulations. With this objective in mind, a fully atomistic quartz silica slit pore has been designed, and the temperature stability of a methane hydrate crystalline seed in the presence of water and guest molecule methane has been analyzed. NaCl ion pairs have been added in different concentrations, simulating salinity conditions up to values higher than average oceanic conditions. The structure obtained when the hydrate crystallizes inside the pore is discussed, paying special attention to the presence of ionic doping inside the hydrate and the subsequent induced structural distortion. The shift in the hydrate stability conditions due to the increasing water salinity is discussed and compared with the case of unconfined hydrate, concluding that the influence of the confinement geometry and pore hydrophilicity produces a larger deviation in the confined hydrate phase equilibria. [ABSTRACT FROM AUTHOR]

Understanding the ignition and dynamic processes for the combustion of hydrate is crucial for efficient energy utilization. Through reactive force field molecular dynamics simulations, we studied the high-temperature decomposition and combustion processes of methane hydrates in a pure oxygen environment. We found that at an ignition temperature of 2800 K, hydrates decomposed from the interface to the interior, but the layer-by-layer manner was no longer strictly satisfied. At the beginning of combustion, water molecules reacted first to generate OH•, followed by methane oxidation. The combustion pathway of methane is C H 4 → CH 3 • → C H 3 O • → C H 2 O → H C • O → HCO O • → CO (C O 2 ). During the combustion process, a liquid water layer was formed between melted methane and oxygen, which hindered the reaction's progress. When there is no heat resistance, oxygen will transform into radicals such as OH• and O•, which have faster diffusion rates, allowing oxygen to conveniently cross the mass transfer barrier of the liquid water layer and participate in the combustion process. Increasing the amount of OH• may cause a surge in the reaction. On the other hand, when significant heat resistance exists, OH• is difficult to react with low-temperature hydrate components, but it can transform into O• to trigger the oxidation of methane. The H• generated has a sufficient lifetime to contact high-temperature oxygen molecules, converting oxygen into radicals that easily cross the water layer to achieve mass transfer. Therefore, finding ways to convert oxygen into various radicals is the key to solving the incomplete combustion of hydrates. Finally, the reaction pathways and microscopic reaction mechanisms of each species are proposed. [ABSTRACT FROM AUTHOR]

Before hydrates can be widely used in industry, we should better understand the problematic issues of hydrate nucleation, particularly its stochastic nature. Here, we report on measurements of the nucleation probability of mixed-gas hydrates in which the guest molecules are a mixture of methane and propane. For the pure cases, at a supersaturation near 1.0, we had previously measured an induction time for the methane hydrate of about 1 h, whereas for the propane hydrate, it was over one day. Using the same experimental setup, we examine here the nucleation probability for a mixture of 90% methane and 10% propane as the guest gas for a range of supersaturations. For the experiments, the temperature was 274 ± 0.5 K and the stirring rate was about 300 rpm. The experiments were repeated at least ten times under the same condition, exchanging the sample water every time. We define the nucleation probability at a given time as the fraction of trials that nucleated by that time and then determine the nucleation probability distribution. The resulting nucleation frequency is found to have a power-law relation to supersaturation. Then, we examine how the nucleation frequency is affected by the existence of ultrafine bubbles in the initial water. We find that the ultrafine bubbles increase the nucleation frequency but much less than that of typical changes in supersaturation. [ABSTRACT FROM AUTHOR]

In this study, we observed natural methane (CH4) hydrate sediments, which are a type of unconventional natural gas resources, using x-ray computed tomography (CT). Because CH4 hydrates are formed by hydrogen bonding of water molecules with CH4, material decomposition becomes challenging when CH4 hydrates coexist with liquid or solid water in natural sediments. Tri-contrast (absorption, refraction, and scattering) imaging was performed via diffraction enhanced x-ray CT optics using monochromatic synchrotron x rays. The quantitative characterization of the contrast changes successfully enabled the decomposition of CH4 hydrates coexisting with frozen seawater (ice) in natural sediments obtained from the Okhotsk Sea. This study reveals complementary structural information about the microtexture and spatial relation among CH4 hydrates, ice, and pores by utilizing the distinct physical properties of x rays when passing through the materials. These results highlight the exceptional capabilities of high-resolution multicontrast x-ray tomography in materials science and geoscience applications. [ABSTRACT FROM AUTHOR]

Natural gas hydrates, mainly existing in permafrost and on the seabed, are expected to be a new energy source with great potential. The exploitation technology of natural gas hydrates is one of the main focuses of hydrate-related studies. In this study, a large-size liquid aqueous solution wrapping a methane hydrate system was established and molecular dynamics simulations were used to investigate the phase equilibrium conditions of methane hydrate at different methane concentrations and interfacial geometries. It is found that the methane concentration of a solution significantly affects the phase equilibrium of methane hydrates. Different methane concentrations at the same temperature and pressure can lead to hydrate formation or decomposition. At the same temperature and pressure, in a system reaching equilibrium, the size of spherical hydrate clusters is coupled to the solution concentration, which is proportional to the Laplace pressure at the solid–liquid interface. Lower solution concentrations reduce the phase equilibrium temperature of methane hydrates at the same pressure; as the concentration increases, the phase equilibrium temperature gradually approaches the actual phase equilibrium temperature. In addition, the interfacial geometry of hydrates affects the thermodynamic stability of hydrates. The spherical hydrate particles have the highest stability for the same volume. Through this study, we provide a stronger foundation to understand the principles driving hydrate formation/dissociation relevant to the exploitation of methane hydrates. [ABSTRACT FROM AUTHOR]

In this work, we determine the dissociation line of the nitrogen (N2) hydrate by computer simulation using the TIP4P/Ice model for water and the TraPPE force field for N2. We use the solubility method proposed recently by some of us to evaluate the dissociation temperature of the hydrate at different pressures, from 500 to 1500 bar. Particularly, we calculate the solubility of N2 in the aqueous solution when it is in contact with a N2-rich liquid phase and when in contact with the hydrate phase via planar interfaces as functions of temperature. Since the solubility of N2 decreases with temperature in the first case and increases with temperature in the second case, both curves intersect at a certain temperature that determines the dissociation temperature at a given pressure. We find a good agreement between the predictions obtained in this work and the experimental data taken from the literature in the range of pressures considered in this work. From our knowledge of the solubility curves of N2 in the aqueous solution, we also determine the driving force for nucleation of the hydrate, as a function of temperature, at different pressures. In particular, we use two different thermodynamic routes to evaluate the change in chemical potential for hydrate formation. Although the driving force for nucleation slightly decreases (in absolute value) when the pressure is increased, our results indicate that the effect of pressure can be considered negligible in the range of pressures studied in this work. To the best of our knowledge, this is the first time the driving force for nucleation of a hydrate that exhibits crystallographic structure sII, along its dissociation line, is studied from computer simulation. [ABSTRACT FROM AUTHOR]

This study investigates the transport of methane released from gas hydrate decomposition through sedimentary layers to quantify its flux into the atmosphere, a critical process given methane's role as a major greenhouse gas. A novel methodology was developed to model two-phase, unsteady gas flow in regions of hydrate decomposition, incorporating key factors such as relative permeability curves, capillary pressure, hydrostatics, and gas diffusion. Numerical simulations revealed that to achieve a gas front rise rate of 7 m/year, the gas accumulation rate must not exceed 10−8 kg/m3·s. At higher accumulation rates (10−6 kg/m3·s), gas diffusion has minimal impact on the saturation front movement, whereas at lower rates (10−8 kg/m3·s), diffusion significantly affects the front's behavior. The study also established that the critical gas accumulation rate required to trigger sediment blowout in the hydrate decomposition zone is approximately 10−6 kg/m3·s, several orders of magnitude greater than typical bubble gas fluxes observed at the ocean surface. The proposed model improves the ability to predict the contribution of Arctic shelf methane hydrate decomposition to atmospheric methane concentrations. [ABSTRACT FROM AUTHOR]

To safely and effectively explore the natural methane hydrate, it is crucial to examine the mechanical behavior of methane hydrate‐bearing sediments (MHBSs). Natural methane hydrate unevenly distributes in pores or bonds with soil particles in MHBS, changing the mechanical behavior of MHBS including stiffness, shear strength, and dilatancy. This paper presents an anisotropic critical state model for MHBS considering hydrate pore‐filling and cementing effects. Based on the unified critical state model for both clay and sand, an equivalent hydrate ratio is defined to address pore‐filling effect. Cohesive strength and its hardening law are introduced to characterize hydrate cementation. To describe the anisotropic behavior, the inherent anisotropy of soil particles and hydrates are modeled separately, and rotation hardening is introduced to describe the stress‐induced anisotropy. Comparisons with existing triaxial tests of both synthetic and natural MHBS demonstrate that the proposed model comprehensively describes the mechanical behavior of MHBS. Detailed predictions indicate that hydrate pore‐filling affects the hydrate‐dependent stiffness and dilatancy of MHBS, which become more pronounced with increasing hydrate saturation. Cementing effect increases the initial stiffness and peak strength of MHBS. The pronounced influence of inherent anisotropic parameters on pre‐peak stress–strain relation of MHBS is noted, and increasing hydrate saturation enhances the effect of hydrate anisotropy. These predictions contribute to a better understanding of the relation between hydrate morphologies and MHBS mechanical properties. [ABSTRACT FROM AUTHOR]

Developing an exceptional reaction medium with high promotion efficiency, desirable biodegradability and good recyclability is necessary for hydrate-based methane storage. In this work, a kind of eco-friendly hydrogel, polyvinyl alcohol-co-acrylic acid (PVA-co-PAA), was utilized to absorb dilute sodium p-styrenesulfonate (SS) solution, for constructing a hybrid reaction medium for methane hydrate formation. Hydrogels or dilute SS solutions (1–4 mmol L−1) had weak or even no promoting effects on hydrate formation kinetics, while the combination of them could synergistically promote methane hydrate formation. In hydrogel-SS hybrid media containing 1, 2, 3 and 4 mmol L−1 of SS solutions, the storage capacity reached 121.2 ± 1.6, 121.5 ± 3.1, 122.6 ± 1.9 and 120.6 ± 1.6 v/v, respectively. In this binary reaction system, the large surface area of hydrogels provided hydrate formation with sufficient nucleation sites and an enlarged gas–liquid interface, and in the meantime, the dilute SS solution produced an adequate capillary effect, which together enhanced mass transfer and accelerated hydrate formation kinetics. Additionally, the hybrid medium could relieve wall-climbing hydrate growth and improve poor hydrate compactness resulting from the bulk SS promoter. Moreover, the hybrid medium exhibited a preferable recyclability and could be reused at least 10 times. Therefore, the hydrogel-SS hybrid medium can serve as an effective and eco-friendly packing medium for methane hydrate storage tanks, which holds great application potential in hydrate-based methane storage technology. [ABSTRACT FROM AUTHOR]

This investigation reports the first study to predict natural gas hydrate formation using both Aspen HYSYS® and HydraFlash software for various gas compositions and thermodynamic inhibitors (monoethylene glycol [MEG] concentrations at 10, 20, 30, and 40 wt.% and methanol concentrations at 10 and 20 wt.%). The simulated predictions are compared with the results of the experimental data in the literature. It has been shown that HydraFlash software can accurately predict hydrate formation conditions for a given industrial case, without having to carry out costly experimental work. This work also evaluated the effect of inhibitors and it appears that inhibitor type and concentration are determined according to condition of gas composition. MEG is consequently selected as the most ideal hydrate inhibitor for the industrial case. This also was confirmed through COSMO‐RS studies in which the sigma profile and sigma potential of the considered inhibitors were obtained and presented using density functional (DFT) calculations to verify the hydrogen bonding affinities of the inhibitors to water molecules. HydraFlash was utilized to predict the dissociation conditions of hydrates under the influence of a high concentration of MEG inhibition, reaching up to 40 wt.% at 313 K and a pressure of 311.1 bar. Finally, it is shown that both software packages are quite accurate and useful tools for the prediction of hydrate for simple systems. However, HydraFlash can simulate more complex systems, including different types of salts at higher pressures. Investigation results indicate insightful guidance for accurately predicting hydrate dissociation under simulated conditions. [ABSTRACT FROM AUTHOR]

The overburden of marine hydrate sediment is usually a permeable cover, and the presence of permeable overburden directly affects the depressurization effect. However, previous studies have mainly focused on the effect of the permeable overburden without considering seawater infiltration, and the influence of seawater infiltration on the production of hydrate cannot be ignored. In this article, a new numerical model considering seawater infiltration is developed and this study is completed by numerical simulation. The results show that seawater infiltration significantly reduces hydrate dissociation, and the presence of seawater substantially reduces cumulative gas production and increases water production compared to non-permeable overburden, with higher permeability resulting in lower gas production and higher water production. It is an effective means to extract hydrates through lower bottom-hole pressure by increasing the gas–water ratio. It is of great significance to further understand the production characteristics of hydrate reservoirs. [ABSTRACT FROM AUTHOR]

The concept of photovoltaic thermal (PVT) systems holds the potential to reduce global energy consumption by simultaneously generating electricity and heat. However, the widespread adoption of these systems is impeded by technical challenges, particularly the rise in panel temperature and constraints on operation during night hours. The present research aims to explore the effect of coolant flow rate and solar radiation on the electrical output and thermal output of PV, PVT, salt hydrate integrated PVT system (PVT-SH), and modified multi-walled carbon nanotubes infused salt hydrate integrated PVT (PVT-SHMM) systems. Additionally, the study examines the heat transfer analysis of a fabricated PVT system incorporated serpentine flow thermal absorber and modified multi-walled carbon nanotubes infused salt hydrate phase change materials (PCMs). In this experiment, water was used as a cooling fluid, with a flow rate of 0.008 to 0.023 kg s−1 and irradiation of 400 to 800 W m−2. The findings show that the thermophysical properties of formulated nanocomposite have significantly improved, and the thermal conductivity of nanocomposites improved up to 97.2% compared to pure salt hydrate. The pressure drops enhancement increases become more pronounced at the higher mass flow rate, primarily because of the outlet's elevated viscosity of the cooling fluid. As the water flow rate increases, the heat removal factor exhibited 1.06 times rise, with relatively lower values in turbulent flow regions than in laminar flow conditions. Furthermore, the investigation notes a substantial decrease in panel temperature, an increase in electrical power with higher flow rates, and a higher heat gain at lower flow rates. Thus, the experimental findings confirm that integrating SH and SHMM into the PVT system significantly enhances its performance, allowing stored heat energy to be utilized during periods of unavailable solar energy. [ABSTRACT FROM AUTHOR]

AbstractNatural gas hydrate is one of the main clean energy sources. It has abundant reserves and high exploitation value in the world. At present, the injection inhibitor decomposition method is the most effective extraction method. In order to further clarify the mechanism of thermodynamic inhibitors for methanol, this paper combines experimental and molecular simulation methods to study the dynamic influence mechanism of methanol on hydrate formation and decomposition in simulated seawater. The specific mechanism of how salt ions and alcohol molecules affect hydrate growth is analyzed, and an explanation is given accordingly. The results show that: ① Methanol at a concentration of 1 wt% has a promoting effect of 9.91% on the formation of methane hydrates. At lower concentrations of 3 wt% and 5 wt%, methanol shows a weak inhibitory effect on hydrates. At a concentration of 10 wt%, the formation of hydrates is completely inhibited. ② From the perspective of kinetics analysis, methanol has no effect on the decomposition of hydrate, but can effectively inhibit the secondary formation of hydrate. ③ The salt ions in simulated seawater have hydration and salt-expulsion effects, which continuously reduce the solubility of methane, leading to an extended growth period of hydrate and inhibiting the formation of hydrate. ④ The molecular simulation results show that when the simulation step size lasts for 30 ns, methane gas exhibits different existential states in simulated seawater and fresh water. The former shows obvious gas-liquid stratification, and the latter appears in the form of nanobubbles, and an increase in methanol concentration will prolong the formation time of methane nanobubbles. ⑤ According to the simulation results from the perspective of molecular dynamics, when methanol molecules enter the crystal cavity of the hydrate, the hydroxyl groups will disturb the formation of the hydrogen bond network of the hydrate, resulting in the inability of the hydrate cage structure to close, which inhibits the formation of the hydrate. The above research results are helpful for field personnel to deepen the understanding of the mechanism of methanol inhibitors. [ABSTRACT FROM AUTHOR]

As a common method for liquid drainage in wave‐shaped pipelines, foam drainage has been used in gas‐gathering pipelines in various oil and gas fields. One of the common problems encountered in wave‐shaped foam drainage pipelines is the inaccurate prediction of the liquid retention rate. This issue makes it difficult to predict liquid accumulation points, which affects gas output efficiency, causes pipeline corrosion, and generates natural gas hydrates. To clarify the liquid‐holding rate law of wavy foam drainage pipelines is studied. In this study, through experiments to verify the accuracy of the numerical simulation method, we investigate the easiest liquid accumulation points and the liquid‐holding rate of wave‐shaped foam drainage pipelines, with factors such as inlet gas velocity, inlet liquid velocity, import and export differential pressure, undulation angle, and inlet temperature change rule. Among them, the error between the numerical simulation results and the experimental results is 4.68%. Finally, after considering the influence of the aforementioned factors on the liquid retention rate of wave‐shaped pipelines, a new liquid retention rate calculation model for wave‐shaped pipelines with foam drainage is established by introducing dimensionless numbers, such as gas‐phase velocity coefficient, liquid‐phase velocity coefficient, and angle correction coefficient. The method is compared with the results of previous research, and the error is within 15%. The model has a simple form and high calculation accuracy, providing a theoretical basis for pipeline inspectors to predict liquid accumulation conditions and reasonably adjust production schedules. [ABSTRACT FROM AUTHOR]

Research progress of carbon dioxide applied for methane exploitation from hydrates is summarized, with a focus on advances in molecular dynamics simulations and their application in understanding the mechanism of carbon dioxide replacement for hydrate exploitation. The potential of carbon dioxide in enhancing energy recovery efficiency and promoting carbon capture and storage is emphasized. An overview is provided of the advancements made in utilizing carbon dioxide for methane hydrate exploitation, highlighting its significance. Subsequently, the theoretical foundations and techniques of molecular dynamics simulations are delved into, encompassing key elements such as statistical ensembles, molecular force fields, and numerical solution methods. Through simulations, various characterization parameters including mean square displacement, radial distribution functions, coordination numbers, angular order parameters, and hydrogen bonds are computed and analyzed, which are crucial for understanding the dynamic changes in hydrate structures and the replacement process. Thorough research and analysis have been conducted on the two possible and widely debated mechanisms involved in the replacement of methane hydrates by carbon dioxide, with a particular emphasis on guest molecular replacement and hydrate reconfiguration. These processes encompass the intricate interactions between carbon dioxide molecules and the cage-like structure of hydrates, as well as the rearrangement and stabilization of hydrate structures. Several key issues surrounding the application of carbon dioxide for methane hydrate exploitation are identified, including the influence of thermodynamic conditions, the selection of auxiliary gases, and other potential factors such as geological conditions and fluid properties. Addressing these issues is crucial for optimizing the extraction process and enhancing economic and environmental benefits. A theoretical foundation and technical reference for the application of carbon dioxide in methane hydrate exploitation are provided, while future research directions and priorities are also outlined. [ABSTRACT FROM AUTHOR]

The geological environment of marine methane hydrate-bearing sediments (MHBS) is highly complex. Mastering the mechanical behavior of MHBS is crucial for analyzing geomechanical hazards and evaluating its stability. The marine sediment in the South China Sea (SCS) contains a significant amount of porous foraminifera shells, which serve as the primary storage space for natural gas hydrates and differ significantly from other sea areas. In the laboratory, porous carbonate sand (CS) and cohesion-less silt were utilized to prepare host sand of methane hydrate. In this paper, based on the analysis of experimental data, a bounding surface model was proposed to describe the mechanical behavior of artificial MHBS. The effect of methane hydrates on the elastic strain, normal consolidation and critical state of host sand is discussed, and corresponding equations for the model parameters are established, taking into consideration the cementing mechanism of hydrates. These equations are defined as functions of hydrate saturation, carbonate sand content (CSC), and initial void ratio. The increase in hydrate saturation significantly reduces the compressibility of the host sand and improves its strength. The proposed model is applied to predict the results of isotropic consolidation and drained triaxial tests on MHBS, demonstrating satisfactory performance. [ABSTRACT FROM AUTHOR]

Low dosage kinetic hydrate inhibitors (KHIs) are a kind of alternative chemical additives to prevent gas hydrate formation in oil & gas production wells and transportation pipelines. In this work, a series of KHIs were experimentally synthesized with N-vinyl caprolactam (N-VCap) and vinyl ether including vinyl ether, vinyl n-butyl ether, vinyl isobutyl ether, triethylene glycol divinyl ether, with the mole ratio ranging from 9:1 to 5:5. The inhibition performance of new-synthesized KHIs on the formation process of methane hydrate were examined and compared with that of commercial N-vinyl caprolactam PVCap. Several ethylenediamine reagents were used as synergists and tested to improve the inhibition capacity of new-synthesized KHIs. The experimental results demonstrate that the introduction of ether groups on PVCap improves the performance of hydrate inhibitors. PVCap-VNBE (N-VCap: vinyl n-butyl ether = 5:5) shows the best inhibition performance for methane hydrate, which could extend the TVO to 1251 min under 6 K subcooling. N,N′ -dimethylethylenediamine shows the best synergistic effect for PVCap-VNBE (5:5), and extends the TVO by 2.75 times at 7 K subcooling. Additionally, the relationship between hydrate inhibition performance and interfacial tension of newly-synthesized KHIs under high pressure were studied. It shows that the lower interfacial tension of KHIs would result in longer onset time, exhibiting better inhibition performance. [ABSTRACT FROM AUTHOR]

The stepwise depressurization method offers substantial advantages in terms of mitigating the risk of pipeline blockages, ensuring production stability, and reducing environmental impact. This study employs a self-developed two-dimensional production simulation test system for natural gas hydrate. It enables precise control of depressurization rates through a servo system, allowing for stepwise depressurization within a single horizontal well at three different rates: high, medium, and low. The experiment investigates the temperature–pressure responses within the reservoir during the production, as well as gas production characteristics, including gas production and gas production rate. The results reveal that choosing a medium depressurization rate significantly increases gas production, achieving a gas production proportion of 59%. However, there is a considerable risk associated, with a peak gas production rate of 8.894 l/min, severely impacting reservoir stability and jeopardizing well control safety in the late-stage production. In the third depressurization stage, there is a relatively weak linear relationship between the normalized multiples of average gas production rate and depressurization rate, with the average gas production rate increasing to 5.78 times and 5.76 times the original rate when the depressurization rate is raised to 1.5 times and 3 times, respectively. [ABSTRACT FROM AUTHOR]

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Laboratory acoustic measurements of hydrate-bearing sediments serve as an important reference for the geological interpretation of seismic exploration data. Tetrahydrofuran (THF) hydrates are relatively easy to form with precise control of hydrate saturation, and they overcome the long time it takes for methane in sediments to form hydrate. However, when THF hydrates are used as a substitute for methane hydrate, their acoustic properties yield different results. This study reports the results of a series of laboratory experiments on the formation of methane and THF hydrate in quartz sand and the evaluation of their acoustic properties. It compares the experimental results with the results of calculations from micro-distribution models of the four hydrates using effective medium theory (EMT). Methane hydrate formed by the excess gas method has higher acoustic velocities than THF hydrate at 0–80% saturation, but at 80–100% saturation, the situation reverses, with THF hydrate having a higher wave velocity. The methane hydrate synthesis process follows a mixed micro-distribution, with grain coating predominating at low saturations, the pore-filling mixing mode dominating at medium saturations, and grain coating dominating at high saturations. In addition, THF hydrate has a slow-velocity growth at low saturation and is dominated by a pore-filling model and a load-bearing model at high saturation. We compared our experimental data with a compilation of similar published results to confirm their reliability and support our conclusions. Both hydrate types exhibit distinct micro-distributions across different saturations. Therefore, when testing the elastic characteristics of hydrate sediments, the distinct hydrate synthesis methods and micro-distribution should be considered, especially when using THF hydrate as an alternative to methane hydrate. [ABSTRACT FROM AUTHOR]

Natural gas hydrates, a promising clean energy resource, hold substantial potential. Porosity plays a crucial role in hydrate systems by influencing formation processes and physical properties. To clarify the effects of porosity on hydrate elasticity, we examined methane hydrate formation and its acoustic characteristics. Experiments were conducted on sediment samples with porosities of 23%, 32%, and 37%. P- and S-wave velocities were measured to assess acoustic responses. Results show that as hydrate saturation increases, sample acoustic velocity also rises. However, high-porosity samples consistently exhibit lower acoustic velocities compared to low-porosity samples and reach a lower maximum hydrate saturation. This behavior is attributed to rapid pore filling in high-porosity samples, which blocks flow pathways and limits further hydrate formation. In contrast, hydrate formation in low-porosity sediments progresses more gradually, maintaining clearer pore channels and resulting in relatively higher hydrate saturation. Higher porosity also accelerates the shift of hydrates from cementing to load-bearing morphologies. These findings underscore porosity's significant influence on hydrate formation and provide insights into observed variations in hydrate saturation and acoustic velocity across different experimental conditions. [ABSTRACT FROM AUTHOR]

Natural gas hydrates have great strategic potential as an energy source and have become a global energy research hotspot because of their large reserves and clean and pollution-free characteristics. Hydrate saturation affecting the electrical and acoustic properties of sediments significantly is one of the important parameters for the quantitative evaluation of natural gas hydrate reservoirs. The accurate calculation of hydrate saturation has guiding significance for hydrate exploration and development. In this paper, experiments regarding methane hydrate formation and dissociation in clay-bearing sediments were carried out based on the Ultrasound Combined with Electrical Impedance (UCEI) system, and the measurements of the joint electrical and acoustic parameters were collected. A machine learning (ML)-based model for evaluating hydrate saturation was established based on electrical–acoustic properties and a neural network ensemble. It was demonstrated that the average relative error of hydrate saturation calculated by the ML-based model is 0.48%, the average absolute error is 0.0005, and the root mean square error is 0.76%. The three errors of the ensemble network are lower than those of the Archie formula and Lee weight equation. The ML-based modeling method presented in this paper provides insights into developing new models for estimating the hydrate saturation of reservoirs. [ABSTRACT FROM AUTHOR]

The three body fragmentation of methane dication has been studied using the technique of cold target recoil ion momentum spectroscopy. The process is initiated by impact of energetic Ar9+ ions on neutral methane and the data is subsequently collected in coincidence with Ar8+ projectile. By analysing the dissociation channels leading to (H + H+ + CH 2 + ) and (H + H 2 + + CH+) fragments, it is concluded that these fragments are formed in a sequential manner via formation of molecular intermediates CH 3 + and CH 2 + respectively. It is shown that these molecular intermediates carry a few eVs as their internal energies, part of which is released when they emit an H-atom with the open possibility that the final detected fragments may still be internally excited. This was accomplished by analysing the two-steps of the sequential process in their own native frames. For a molecular system having three-dimensional structure, our results prove to be an ideal example to highlight the importance of using native frames for correct interpretation of the obtained results. Our results indicate that the dissociation of methane dication can be a major source of production of H-atoms in addition to H+ fragments with the probability of the two being of similar order. [ABSTRACT FROM AUTHOR]

1-propanol/water mixtures over the whole composition range (0 < XV ≤ 1; XV is the 1-propanol volume fraction) are shown to be structurally and dynamically heterogeneous. By combining structural (x-ray diffraction), thermodynamic (differential scanning calorimetry) and dynamical probes (dielectric spectroscopy) we construct the pertinent phase diagram. It consists of liquid 1-propanol, liquid water, hexagonal ice and different hydrates, the latter sharing the same lattice. The phase diagram can be discussed in terms of four regimes, all having in common a droplet arrangement of the minority component. When water droplets are strongly confined by 1-propanol (regime I, 0.92 < XV ≤ 1; "soft" confinement), water is unable to crystallize. It has dynamics reminiscent to the ultra-viscous water phase known as high-density liquid (HDL). When water droplets are moderately confined (regime II, 0.75 < XV ≤ 0.92) water can crystallize via homogeneous nucleation. Strikingly, the homogeneous nucleation temperature is at 205 K, well within "no-man's land." The result is in line with earlier reports that soft confinement is the key to enter into the "no-man's land". When 1-propanol is the minority component (regimes III and IV), the structure and the dynamics are dominated by the 1-propanol/water interface with the formation of hydrates. The corresponding dynamical features suggest a link between hydrate formation and the two metastable phases of ultra-viscous water, HDL and low-density liquid. [ABSTRACT FROM AUTHOR]

The rapid warming of the Arctic-Boreal region has led to the concern that large amounts of methane may be released to the atmosphere from its carbon-rich soils, as well as subsea permafrost, amplifying climate change. In this review, we assess the various sources and sinks of methane from northern high latitudes, in particular those that may be enhanced by permafrost thaw. The largest terrestrial sources of the Arctic-Boreal region are its numerous wetlands, lakes, rivers and streams. However, fires, geological seeps and glacial margins can be locally strong emitters. In addition, dry upland soils are an important sink of atmospheric methane. We estimate that the net emission of all these landforms and point sources may be as much as 48.7 [13.3–86.9] Tg CH4 yr−1. The Arctic Ocean is also a net source of methane to the atmosphere, in particular its shallow shelves, but we assess that the marine environment emits a fraction of what is released from the terrestrial domain: 4.9 [0.4–19.4] Tg CH4 yr−1. While it appears unlikely that emissions from the ocean surface to the atmosphere are increasing, now or in the foreseeable future, evidence points towards a modest increase from terrestrial sources over the past decades, in particular wetlands and possibly lakes. The influence of permafrost thaw on future methane emissions may be strongest through associated changes in the hydrology of the landscape rather than the availability of previously frozen carbon. Although high latitude methane sources are not yet acting as a strong climate feedback, they might play an increasingly important role in the net greenhouse gas balance of the Arctic-Boreal region with continued climate change. [ABSTRACT FROM AUTHOR]

Whether the hydrate layer is stabilized during deepwater cementing operations has a direct impact on the safety of the cementing process and the quality of the cementing. When the cement slurry enters the annular space and waits for solidification, it will be extruded to produce filtrate under the action of formation temperature and pressure. Moreover, the inorganic ions and organic matter contained in the filtrate may penetrate into the formation. However, whether these processes have an effect on the stability of the hydrate layer is not clear at present. In this paper, we initially developed a methane hydrate generation system, termed the water-quartz sand-methane system. This system efficiently produces methane hydrate within a short time and ensures a uniform distribution of the gas-solid phase, which is highly suitable for further research into methane hydrate stability. Subsequently, the primary constituents of the cement slurry filtrate and the principal functional groups of the cement additive were identified. Furthermore, enhancements were made to the existing formula for quantifying methane gas alteration. Additionally, a hydrate testing experimental system was employed to circulate a solution comprising the primary constituents of the cement slurry filtrate over the methane hydrate surface. Ultimately, utilizing the amount of change in the volume of methane gas in the cyclic process as a criterion to evaluate the impact of various components of the cement slurry filtrate on methane hydrate stability, an investigation into the effect of the cement slurry filtrate on methane hydrate stability was conducted. It was confirmed that Ca2+, Na+, Cl− ions within the cement slurry filtrate, along with the pH value, minimally influence methane hydrate stability. Conversely, the cement additive exhibits a discernible disruptive effect on methane hydrate stability, with the retarder demonstrating the most pronounced impact when mass fractions are equated. This study suggests that the adverse effects of amide and carboxyl groups on hydrate stability must be considered in the selection of additives for deepwater cementing slurries. The findings offer guidance for the research and development of additives for deepwater cementing slurries and establish a theoretical foundation for studying cementing slurry systems in hydrate formations. • An improved formula for calculating methane gas changes in this experimental system is presented. • Effects of cement slurry filtrate pH and the inorganic ions it contains on methane hydrate stability are investigated. • Effect of cement additives on methane hydrate stability is investigated. [ABSTRACT FROM AUTHOR]

Argillaceous fine silt hydrate reservoirs have a clay content of 20–25% and a median sand particle size of 10–15 um. Sand control is extremely difficult, restricting the continuous and stable testing of gas hydrate. This paper focuses on the sand production mechanisms, plugging characteristics, and clogging mechanisms of these hydrate reservoirs. Based on the actual characteristics of hydrate reservoirs, it presents an understanding of the sand production mechanism of argillaceous fine silt. The characteristics and properties of three different sand control methods and six kinds of sand control screens are analyzed. Clear design concepts for sand control screens in argillaceous fine silt hydrate reservoirs are proposed. Two types of new sand control screen with metal filter screens and pre-filled screens have been innovatively designed, and the sand control ability and overflow performance of the screens are evaluated using the meter production index conversion method. Sand production simulation and comprehensive experimental evaluation and analysis of the flow performance of seven kinds of screens (themselves from two categories of screens) were carried out using a self-made special experimental testing device. The experimental results show that the newly designed screens have good flow performance and can meet the requirements of a certain gas production rate. Specifically, Class A metal screens (60/70 mesh) and Class B pre-filled screens (40/70 mesh) have excellent sand control capacity and flow performance, with 10 g sand output and 300 L total water output, thus fulfilling the sand control requirements and achieving the purpose of "effective sand control, prevention without plugging, and continuous stable production" of argillaceous fine silt gas hydrate reservoirs. They therefore provide a reference for future research on sand control and new screen designs for argillaceous fine silt hydrate reservoirs. [ABSTRACT FROM AUTHOR]

In this article, surfactants such as cetyl trimethyl ammonium chloride (CTAC) and coconut oil amide propyl betaine (CAB) were compounded (TCJ) and used as a double function with foam drainage and hydrate anti‐polymerization. According to the result it was found that 0.05% of CTAC and 0.7% of CAB exhibited both excellent foam property and hydrate anti‐polymerization property. For further clarifying the stability characteristic of foam, the foam half‐life, drainage process, microcosmic liquid film structure, and stability mechanism were investigated in this article. The high initial foam volume of 415 mL with relatively long half‐life time of 5.5 min under high‐speed agitation at 50°C after 25 min indicated a good temperature resistance. The excellent foam properties still remained even amount of methanol and NaCl was added, which indicated its well stability and salt resistance. Furthermore, it was found that TCJ exhibited high liquid carrying rate of 62.5% at 65°C and good compatibility with poly vinyl pyrrolidone (PVP), which played great potential to the application in oil field. By the results of DSC curves, it can be found that the phase transformation point of hydrate decreases after addition of TCJ, which indicates the inhibition to the formation of hydrate as thermodynamic inhibitors. [ABSTRACT FROM AUTHOR]

Using acrylic acid advanced ester and styrene as raw materials, the long-chain polyester polymer, polyacrylic acid advanced ester-styrene pour point depressant (P-PPD), was synthesized by molecular design, and its structure was characterized by infrared spectroscopy and nuclear magnetic resonance. In addition, this study experimentally investigated the effect of P-PPD on the phase equilibrium and induction time of natural gas hydrate inhibitors in deionized water (DW) and crude oil/water (O/W) systems, respectively. Polyvinylpyrrolidone (PVP) and mono ethylene glycol (EG) were selected as representatives of kinetic hydrate inhibitor (KHIs) and thermodynamic hydrate inhibitor (THIs), respectively. The results exhibit that P-PPD played a sight role in the phase equilibrium of hydrate, while the addition of P-PPD significantly prolonged the induction time of methane hydrate both in O/W + PVP, OW + EG and O/W + PVP + EG system, indicating that the addition of as-synthesized PPD has a synergistic inhibition effect on the nucleation ability of methane hydrate and can prevent hydrate from formatting during oil and gas transport process, and thus guarantee the flow assurance. The findings of this work will provide a data reference for the hybrid use of hydrate inhibitors and pour point depressants in oil and gas transport. [ABSTRACT FROM AUTHOR]

Nucleation and growth of methane clathrate hydrates is an exceptional playground to study crystallisation of multi-component, host-guest crystallites when one of the species forming the crystal, the guest, has a higher concentration in the solid than in the liquid phase. This adds problems related to the transport of the low concentration species, here methane. A key aspect in the modelling of clathrates is the water model employed in the simulation. In previous articles, we compared an all-atom force model, TIP4P/Ewald, with a coarse grain one, which is highly appreciated for its computational efficiency. Here, we perform a complementary analysis considering three all-atoms water models: TIP4P/Ewald, TIP4P/ice and TIP5P. A key difference between these models is that the former predicts a much lower freezing temperature. Intuitively, one expects that to lower freezing temperatures of water correspond to lower water/methane–methane gas–clathrate coexistence ones, which determines the degree of supercooling and the degree of supersaturation. Hence, in the simulation conditions, 250 K (500 atm, and fixed methane molar fraction), one expects computational samples made of TIP4P-ice and TIP5P, with a similar freezing temperature ( $ T_f \sim 273 $ T f ∼ 273 K), to be more supersaturated with respect to the case of TIP4P-Ew ( $ T_f \sim 245 $ T f ∼ 245 K), and crystallisation to be faster. Surprisingly, we find that while the nucleation rate is consistent with this prediction, growth rate with TIP4P-ice and TIP5P is much slower than with TIP4P-Ew. The latter was attributed to the slower reorientation of water molecules in strong supercooled conditions, resulting in a lower growth rate. This suggests that the freezing temperature is not a suitable parameter to evaluate the adequacy of a water model. [ABSTRACT FROM AUTHOR]

Averaged local bond order parameters based on spherical harmonics, also known as Lechner and Dellago order parameters, are routinely used to determine crystal structures in molecular simulations. Among different options, the combination of the $ \bar {q}_{4} $ q ¯ 4 and $ \bar {q}_{6} $ q ¯ 6 parameters is one of the best choices in the literature since distinguishes between solid- and liquid-like particles and between different crystallographic phases, including cubic and hexagonal phases. Recently, Algaba et al. [J. Colloid Interface Sci. 623, 354, (2022)] have used the Lechner and Dellago order parameters to distinguish hydrate- and liquid-like water molecules in the context of determining the carbon dioxide hydrate-water interfacial free energy. According to the results, the preferred combination previously mentioned is not the best option to differentiate between hydrate- and liquid-like water molecules. In this work, we revisit and extend the use of these parameters to deal with systems in which clathrate hydrates phases coexist with liquid phases of water. We consider carbon dioxide, methane, tetrahydrofuran, nitrogen, and hydrogen hydrates that exhibit sI and sII crystallographic structures. We find that the $ \bar {q}_{3} $ q ¯ 3 – $ \bar {q}_{12} $ q ¯ 12 combination is the best option possible between a large number of possible different pairs to distinguish between hydrate- and liquid-like water molecules in all cases. [ABSTRACT FROM AUTHOR]

In the South China Sea, a significant amount of methane hydrate exists in the sediment containing fine-grained soil. Increasing temperature and/or decreasing pore pressure can remarkably degrade the mechanical characteristics of this methane hydrate–bearing fine-grained sediment (HBFS). In this study, several compression tests under triaxial stress condition on HBFS are performed with changing temperature and pore pressure. The experimental results reveal that the HBFS specimen has an enhanced stiffness and failure strength characteristic under lower temperature and/or higher pore pressure conditions. An improved phase state parameter H is presented as a characterization for the temperature and pore pressure condition, which considers the capillary effect for HBFS with wide pore size distribution. The secant modulus and failure strength tend to linearly increase with the rising improved phase state parameter H. The internal friction angle is independent of the temperature and pore pressure, while the cohesion exhibits a significantly linear increase with the rising improved phase state parameter H. In addition, the shear–dilatancy curve shifts to the right with the rising improved state parameter H owing to the enhanced cementing strength of hydrate–soil cluster. These research findings are beneficial for grasping the mechanical behavior of HBFS. Furthermore, this research also provides data support for building the constitutive model of HBFS during methane hydrate recovery. [ABSTRACT FROM AUTHOR]

Materials with low lattice thermal conductivity are essential for various heat-related applications like thermoelectrics, and usual approaches for achieving this rely on specific crystalline structures. Here, we report a strategy for thermal conductivity reduction and regulation via guest rotational dynamics and their couplings with lattice vibrations. By applying pressure to manipulate rotational states, we find the intensified rotor-lattice couplings of compressed methane hydrate MH-III can trigger strong phonon scatterings and phonon localizations, enabling an almost three-fold suppression of thermal conductivity. Besides, the disorder in methane rotational dynamics results in anharmonic interactions and nonlinear pressure-dependent heat transport. The overall guest rotational dynamics and heat conduction changes can be flexibly regulated by the rotor-lattice coupling strength. We further underscore that this reduction mechanism can be extended to a wide range of systems with different structures. The results demonstrate a potentially universal method for reducing or controlling heat transport by developing a hybrid system with tailored molecular rotors. Molecular disorder plays an important role in the thermal conductivity of materials. Using atomistic simulations, the authors show that thermal conductivity can be pressure-regulated in methane hydrates by manipulating disordered guest rotational dynamics. [ABSTRACT FROM AUTHOR]

The chemistry of the pore fluid within clayey sediments frequently changes in various processes. However, the impacts of pore fluid chemistry have not been well included in the hydraulic permeability model, and the physical bases behind the salinity sensitivity of the hydraulic permeability remains elusive. In this study, a theoretical model for the hydraulic permeability of clayey sediments is proposed, and impacts of the pore fluid chemistry are quantitatively considered by introducing electrokinetic flow theory. Available experimental data were used to verify the theoretical model, and the verified model was further applied as a sensitivity analysis tool to explore more deeply how hydraulic permeability depends on pore fluid chemistry under different conditions. Coupling effects of pore water desalination and the effective stress enhancement on the hydraulic permeability of marine sediments surrounding a depressurization wellbore during hydrate production are discussed. Results and discussion show that the hydraulic permeability reduction is significant only when the electric double layer thickness is comparable to the characteristic pore size, and the reduction becomes more obvious when the ion mobility of the saline solution is smaller and the surface dielectric potential of clay minerals is lower. During gas hydrate production in the ocean, the salinity sensitivity of the hydraulic permeability could become either stronger and weaker, depending on whether the original characteristic pore size of marine sediments is relatively large or small. [ABSTRACT FROM AUTHOR]

Methane hydrates is regarded as an important alternative energy in the future. Due to the complexity of marine environment, the mechanical parameters and initial stress state of formation have great uncertainties which can affect the wellbore stability in hydrate exploitation. In this study, a new time-dependent analytical model is proposed, considering the influence of hydrate dissociation on the mechanical properties and the partial coupling among pore pressure/temperature/mechanical field. The analytical solutions are verified and validated by numerical solutions. Based on the analytical solution and Mogi-Coulomb failure criterion, the reliability of wellbore stability during drilling in hydrate exploitation is analyzed by the Response Surface Method. Through the reliability analysis, the probability of wellbore instability increases and the safe drilling fluid pressure window range is narrowed with time, and finally tended to be stable at t = 12 h. Hydrate dissociation would lead to a more narrowed pressure window range, about by −38.75%. The most significant parameter whose uncertainty affects the instability probability is initial in-situ stress, followed by the initial internal friction angle and Biot's coefficient. [ABSTRACT FROM AUTHOR]

The objective of this work is to predict the methane hydrate phase boundary equilibrium temperature in the presence of ionic liquids (ILs) using machine learning techniques to overcome the limitations of the existing empirically proposed models. To achieve the objectives of this work, five deep neural networks (DNN) algorithms; Adadelta, Ftrl, Adagrad, Adam, and RMSProp coupled with six activation functions (elu, leaky relu, sigmoid, relu, tanh, and selu) were used on 610 experimental datasets from literature. The independent variables used to predict the ILs methane hydrate boundary temperature were pressure (2.39–100.43 MPa), concentration (0.10–50 wt.%), and ILs molecular weight (91.11–339.50 gmol−1). The study revealed that Adadelta DNN optimization algorithm and elu activation functions gave the best predictions with an average RMSE of 0.6727 and 0.6989, respectively. The findings suggest that the use of Adadelta coupled with elu accurately predicts the methane hydrate phase boundary condition in the presence of ionic liquids. The excellent performance of Adadelta and elu resides in their ability to predict exponential data trends which is the fundamental behavior of hydrate phase behavior condition. This work pioneered the use of machine learning techniques to predict hydrate behavior conditions in IL systems. Thus, the findings in this work will enhance the development of simple hydrate phase behavior properties predictive software for IL systems. [ABSTRACT FROM AUTHOR]

Hydrate-based gas separation (HBGS) has good potential in the separation of helium from helium-rich natural gas. HBGS should be carried out under a pressure higher than the thermodynamic equilibrium hydrate formation pressure (Peq) to ensure the formation of hydrate so that the accurate prediction of Peq is the basis of the determination of HBGS pressure. In this work, the Peq of the helium-rich natural gases with different helium contents (1 mol%, 10 mol%, and 50 mol%) in gas and different tetrahydrofuran (THF) contents (5 wt%, 10 wt%, and 19 wt%) in liquid at different temperatures were experimentally investigated through the isothermal pressure search method. A new thermodynamic model was proposed to predict the Peq of helium-rich natural gas. This model can quantitatively describe the effects of THF and helium on Peq, and it predicts the Peq of the helium-rich natural gases in this work accurately. The average relative deviation of the model is less than 3%. This model can guide the determination of the operating condition of the HBGS of helium-rich natural gas. [ABSTRACT FROM AUTHOR]