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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]

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]

Most of the implemented marine gas hydrate test exploitation in the world adopt the depressurization method to break down the hydrate in the reservoir into natural gas and then extract it, but because the gas production results are still a certain distance away from the commercial exploitation, and it mainly stays in the stage of theoretical research and trial exploitation. Based on two trial productions in the Shenhu area of the South China Sea, this study established a model for hydrate exploitation and investigated the impact of different well types on the recovery rates of hydrates and free gas in different development layers during depressurization. For the Class 1 hydrate reservoirs, horizontal wells are the optimal solution to extract hydrate and free gas simultaneously when exploiting the hydrate three-phase layer. Meanwhile, the effect of different well spacing in vertical wells on the recovery rate of hydrate and free gas was studied. It is found that the best recovery efficiency is achieved when the spacing between two wells is 80 m. The lower the bottom flow pressure of the well, the higher the production capacity, but its influence is limited. [ABSTRACT FROM AUTHOR]

The heat transfer and stability of methane hydrate in reservoirs have a direct impact on the drilling and production efficiency of hydrate resources, especially in complex stress environments caused by formation subsidence. In this study, we investigated the thermal transport and structural stability of methane hydrate under triaxial compression using molecular dynamics simulations. The results suggest that the thermal conductivity of methane hydrate increases with increasing compression strain. Two phonon transport mechanisms were identified as factors enhancing thermal conductivity. At low compressive strains, a low-frequency phonon transport channel was established due to the overlap of phonon vibration peaks between methane and water molecules. At high compressive strains, the filling of larger phonon bandgaps facilitated the opening of more phonon transport channels. Additionally, we found that a strain of −0.04 is a watershed point, where methane hydrate transitions from stable to unstable. Furthermore, a strain of −0.06 marks the threshold at which the diffusion capacities of methane and water molecules are at their peaks. At a higher strain of −0.08, the increased volume compression reduces the available space, limiting the diffusion ability of water and methane molecules within the hydrate. The synergistic effect of the strong diffusion ability and high probability of collision between atoms increases the thermal conductivity of hydrates during the unstable period compared to the stable period. Our findings offer valuable theoretical insights into the thermal conductivity and stability of methane hydrates in reservoir stress environments. [ABSTRACT FROM AUTHOR]

This document is a summary of a special issue titled "Macroscopic and Microscopic Thermodynamics: From Fundamentals to Present Applications, 2nd Edition." It explores the broad field of thermodynamics and its applications in various scientific disciplines. The article discusses the historical development of thermodynamics and its expansion into fields such as cosmology, information science, and social sciences. It also highlights the importance of molecular thermodynamics in chemical engineering and the use of computational methods in solving thermodynamic problems. The document provides a list of the contributions included in the special issue, which cover topics such as vapor-liquid equilibrium, clathrate hydrates, binary mixtures, and surface tension. The authors emphasize the importance of thermodynamics in addressing theoretical and practical problems and highlight its potential for further research in fields like process engineering, human health, and environmental preservation. [Extracted from the article]

The degree and amount of sand production in hydrate reservoirs is related to the selection of stable production processes, but there is currently a lack of quantitative sand production prediction research using real logging data and formation samples from hydrate reservoirs. To reveal the dynamic change characteristics of in-situ reservoirs during hydrate decomposition, and explore quantitative prediction methods for guiding production practice, it is conducted a series of numerical simulations and quantitative prediction experiments. The numerical simulations are carried out using different sand-out prediction methods by using hydrate logging data during drilling, while quantitative prediction experiments of water production and sand-out are carried out based on in-situ reservoir samples. Our experiments indicate that hydrate mining is facing a serious risk of sand-out. The particle transport in the reservoir changes from "large-channel seepage" to "umbrella seepage" and then to "uniform fine flow" as the replacement flow rate decreases. A quantitative prediction model for water and sand production is also established. As a result, our study can provide support for the advancement of technology for long-term stable production and sand control of hydrates, laying the groundwork for developing a stable production plan for natural gas hydrates in offshore areas and determining the optimal depressurisation method. [ABSTRACT FROM AUTHOR]

Due to high energy density, clean combustion products and abundant resources, natural gas hydrates (NGHs) have been regarded as an important clean energy source with the potential for large-scale development and utilization. However, pilot tests in NGHs show that their production rates are far below commercial needs. Multilateral well technology may lead to a solution to this problem because it can dramatically expand the drainage area of production wells. This paper presents the practical rate transient analysis for multilateral horizontal wells in NGHs. In developing solution to the diffusivity equation of multilateral horizontal wells in NGHs, the superposition principle and reciprocity are applied. We wrote the governing equation in cylindrical coordinates to describe the NGH flow process. We used the moving boundaries and dissociation coefficients to model the solid-to-gas transition process in hydrates. To obtain solutions for flow in hydrate reservoirs, we used Laplace transforms and the Stehfest numerical inversion method. Superposition principle and Gaussian elimination are applied to obtain the desired solution for multilateral horizontal wells. We validated our proposed model with a commercial numerical simulator. By performing sensitivity analyses, effects on production behavior of the number of branches, dissociation coefficient, radius of the region with dissociated hydrate, and dispersion ratio are determined. A synthetic case study is conducted to show the typical production behaviors. [ABSTRACT FROM AUTHOR]

Accurate estimation of gas hydrate formation condition is crucial for many reasons. In one hand, the gas hydrate formation is a promising approach for gas separation, cold energy storage, seawater desalination, etc. On the other hand, in some industries, this phenomenon may cause some challenges, such as pipelines blockage. The current study was undertaken to develop trustworthy predictive tools for methane hydrate formation temperature (MHFT) in the presence of brines. To achieve this target, 1051 experimental data pertinent to the methane hydrate equilibrium in 26 single and multiple brines over an extensive range of operating conditions were amassed from published studies. Four simple factors, including pressure, brine concentration, salt molecular weight and salt melting temperature were defined as the input variables, and the black-box intelligent techniques, including gaussian process regression (GPR), multilayer perceptron (MLP) and radial basis function (RBF) were employed to link MHFT to the mentioned factors. A plethora of graphical and statistically-based assessments were performed to determine the accuracy level of the proposed models. While all intelligent models had excellent performances, the one established by the GPR method showed the best agreements with experimental data, and gave the AARE and R2 values of 0.14% and 99.17%, respectively, in the testing step. The foregoing model was capable of predicting MHFT over a broad range of conditions with relative deviations mostly below 0.10%. Additionally, it showed an excellent performance in describing the physical variations of MHFT versus operating factors. The authority of the analyzed databank and the presented model was asserted via the William's plot investigation. Moreover, a sensitivity analysis was undertaken in order to determine the most fundamental factors in controlling MHFT. Eventually, a simple mathematical correlation was also derived based on the white-box intelligent approach of gene expression programming (GEP), which allowed the accurate estimation of MHFT with an AARE of 0.56%. [Display omitted] • Smart predictive models were presented for methane hydrate formation condition. • 1051 methane hydrate equilibrium data in the presence of 26 brines were analyzed. • The GPR method presented the best predictions with the testing AARE of 0.14%. • The models favorably described the physical variations of MHFT. • A simple and accurate MHFT correlation was derived by the GEP approach. [ABSTRACT FROM AUTHOR]

From December 2021 to January 2022, MH21-S conducted an exploratory drilling campaign using logging-while-drilling tools to confirm the methane hydrate concentrated zone (MHCZ) for future offshore production tests. In a preliminary screening study using seismic survey data, methane hydrate (MH) prospects have been extracted in The Hyuganada Sea, offshore Kyushu. In the exploration drilling site, a previous study had reported that MH prospects were inferred from four indices. We have selected two MH prospects: one with an anticlinal structure and another with a planus structure. As a result of drilling, a resistivity value higher than 3 Ω·m, which was a criterion for interpreting MHCZs from log data, was confirmed at a depth of 336–376 mBSF in the prospect with an anticlinal structure. The MH saturation calculated using Archie's formula was 12–95% (average saturation of 70%). The average density porosity at the same depth was 52%. P-wave velocities were faster than the upper layers. Compared with those of the MHCZ at Daini Atsumi Knoll, the MH saturation is expected to be higher, the spread of some strong-amplitude reflectors has been interpreted from seismic survey data, and the potential MH resources in this area can be sufficiently expected. [ABSTRACT FROM AUTHOR]

In this paper, a one-dimensional model of gas–water two-phase productivity for hydrate depressurization is established, which takes into account permeability variation and gas–water two-phase flow. By solving the coupled algebraic equations of dissociation front position, equilibrium temperature, and pressure in an iterative scheme, the movement law of the hydrate dissociation front and the evolution process of temperature and pressure near the well were obtained, and the effects of bottom hole pressure, reservoir temperature, and hydrate saturation on productivity were analyzed. The results show that the hydrate reservoir is divided into a decomposed zone and an undecomposed zone by the dissociation front, and the temperature and pressure gradients of the former are greater than those of the latter. Reducing bottom hole pressure, increasing reservoir temperature, and increasing hydrate saturation all lead to an increase in temperature and pressure gradient in the decomposed zone. Methane gas production is a sensitive function of bottom hole pressure, reservoir temperature, and hydrate saturation. The lower the bottom hole pressure, the higher the reservoir temperature, the lower the hydrate saturation (within a certain range), and the higher the gas production rate. The trend of the water production curve is the same as that of gas, but the value is 3–4 orders of magnitude smaller, which may be due to the large difference in the viscosity of gas and water, and the gas seepage speed is much larger than that of water. [ABSTRACT FROM AUTHOR]

The aim of this study was to determine the influence of four inorganic salts, KCl, NaCl, KBr and NaBr, on the thermodynamic conditions of methane hydrate formation. In order to achieve this, the vapor–liquid water-hydrate (VLWH) equilibrium conditions of methane (CH4) hydrate were measured in the temperature range of 274.15 K–282.15 K by the isothermal pressure search method. The results demonstrated that, in comparison with deionized water, the four inorganic salts exhibited a significant thermodynamic inhibition on CH4 hydrate. Furthermore, the inhibitory effect of Na+ on methane hydrate is more pronounced than that of K+, where there is no discernible difference between Cl− and Br−. The dissociation enthalpy ( ∆ H d i s s ) of CH4 hydrate in the four inorganic salt solutions is comparable to that of deionized water, indicating that the inorganic salt does not participate in the formation of hydrate crystals. The Chen–Guo hydrate model and N–NRTL–NRF activity model were employed to forecast the equilibrium conditions of CH4 hydrate in electrolyte solution. The absolute relative deviation (AARD) between the predicted and experimental values were 1.24%, 1.08%, 1.18% and 1.21%, respectively. The model demonstrated satisfactory universality and accuracy. This study presents a novel approach to elucidating the mechanism and model prediction of inorganic salt inhibition of hydrate. [ABSTRACT FROM AUTHOR]

The thermodynamic effect of octyl-β-D-glucopyranoside (OGP) on the formation of methane-1,3-dimethylcyclohexane (DMCH) hydrate was studied in this work. The thermodynamic equilibrium hydrate formation pressures between 275.15 K and 283.15 K were measured by the isothermal pressure search method. Different OGP aqueous solutions (0, 0.1, and 1 wt%) were used in this work. The experimental results show that OGP had no obvious thermodynamic inhibition on methane-DMCH hydrate formation when its concentration was low (0.1 wt%), whereas it had an inhibition on methane-DMCH hydrate formation when its concentration was high (1 wt%). The phase equilibrium hydrate formation pressure of the methane-DMCH-OGP system is about 0.1 MPa higher than that of the methane-DMCH system. The dissociation enthalpies of methane hydrate in different solutions remained uniform, which indicates that OGP was not involved in methane-DMCH hydrate formation. This phenomenon is explained from the perspective of the molecular structure of OGP. As a renewable and biological nonionic surfactant, the concentration of OGP in the liquid phase is low, so OGP can be added to the methane-DMCH system without significant thermodynamic inhibition. [ABSTRACT FROM AUTHOR]

Understanding the acoustic characteristics of hydrates in various sediments is crucial for hydrate resource detection and safe and efficient exploitation, as hydrate occurrence patterns vary greatly in different sediments. In this work, sediments with different bentonite contents, water saturations, and types were prepared to investigate the characteristics of P-wave velocity (reflecting the magnitude of hydrate saturation in the sediment) and amplitude (reflecting the degree of hydrate-sediment cementation) during hydrate formation and depressurization. During hydrate formation, the P-wave velocity and amplitude have similar trends. As clay content increases, the P-wave velocity increase rates quickened. On the other hand, the increased rate of P-wave velocity slows down with the increase of water saturation in the clay-bearing sediments. Comparing various types of sediment shows that the water absorption and swelling of bentonite reduce the pore space, speeding up the cementation of the hydrate with the sediment and increasing P-wave velocity at a faster rate. Correspondence between P-wave velocity and hydrate saturation is strongly related to sediment type, clay content, and water saturation. The rapidly decreasing amplitude in the early stage of hydrate depressurization indicates that hydrate in clay-bearing sediments is weakly cemented to the sediments, which is prone to stratigraphic instability. The findings of this study offer guidance for hydrate resource assessments in clay-bearing sediments as well as geologic risk estimations during hydrate mining. [ABSTRACT FROM AUTHOR]

Recently, it was found that mud flocculates, or flocs, coexist with methane hydrate within turbidite layers off the Japanese coast. There is a concern that mud flocs may be broken down by the flow of pure water generated from the dissociation of methane hydrate, causing sand troubles in the production wells. To clarify the characteristics of the flocs, in this study, the samples of mud flocs collected from natural cores having contained methane hydrate were observed before and after sonication in a pure-water ultrasonic bath. Then, these flocs were placed in distilled water flow to investigate their mechanical stability. As a result, it was confirmed that the flocs mainly consist of silt together with a little clay and fine sand. In addition, these flocs were found to be stable for flow rates on the order of magnitude of 10−3 m/s, which is expected inside the strata during gas production from methane hydrate. However, it was also found that, after the distilled water flow experiments, the flocs were decomposed into silt and clay particles when pressed with a handheld needle in the air, suggesting that the floc might be a source of the fine particles as underground stress conditions change, although not many flocs are likely to be immersed in pure water alone. [ABSTRACT FROM AUTHOR]

Natural gas hydrate is widely distributed, shallow-buried, clean, and pollution-free and has enormous reserves, it is regarded as the alternative clean energy source in the oil and gas field with the most potential. Pressure coring is the only way to drill for gas hydrate core on the surface under in situ conditions, which is of great value for analyzing its occurrence conditions and reserves comprehensively. Based on this, a new wireline pressure coring system (WPCS) with a ball valve seal was designed and developed in this paper; it was applied in the deep sea for the first time in the South China Sea hydrate survey voyage of the Guangzhou Marine Geological Survey (GMGS). A total of 15 runs of deep-sea gas hydrate drilling and coring applications were carried out, and they tested well. The experimental water depth was 1700–1800 m, and the coring depth below the seafloor was about 100–150 m. The formation consisted of sandy hydrate and argillaceous hydrate. The results showed the following. (1) The success rate of ball valve turn-over could reach almost 100% in the argillaceous hydrate reservoir, although there are some isolated cases of pressure relief. Meanwhile, drilling in the sandy hydrate reservoir, the success rate was only 54.55%. (2) When drilling in the argillaceous hydrate reservoir, the core recovery rate could reach 80%, while in the sandy hydrate reservoir, it was almost 0%. In practice, the sandy formation with gas hydrate is stiff to drill compared to the performance in argillaceous formations. After our analysis, it was believed that the ball valve and core tube could be easily plugged by sand debris during the sampling of sandy hydrate formation. Moreover, the sandy core is easily plugged into the core liner because of the high friction of sand grains in clearance. (3) The pressure-holding effect of the core drilling tool was related to the formation of hydrate, the sealing form of the ball valve, and the environmental pressure. Sandy hydrate formations often caused the ball valve to jam, while the muddy hydrate formation did not. The research results of this paper have reference value for the further optimization of the WPCS structure, the optimization of drilling parameters, and the design parameters of the ball valve structure, which could be better used for the pressure coring of gas hydrate and subsequent research work in the future. [ABSTRACT FROM AUTHOR]

Natural gas hydrate is a kind of low-carbon and clean new energy, so research on its efficient extraction in terms of theory and technology is particularly important. Combined thermal injection and depressurization is an effective method for extracting natural gas hydrate. In this study, the classical local heat equilibrium model was modified, and a pore-scale fully coupled unsteady heat transfer model for hydrate reservoirs was set up by considering multiple forms of heat flow accompanying hydrate's decomposition and gas–liquid flow. Based on this model and the basic geological information of the X2 hydrate reservoir in the western Pacific Ocean, a numerical model of gas hydrate extraction using combined heat injection and depressurization was constructed to simulate the production performance of the hydrate reservoir. The results were fully compared with the results obtained by the depressurization method alone. The results indicated the hydrate extraction via a combined heat injection and depressurization would have a cumulative gas production of 31.609 million m3 and a cumulative water production of 1.5219 million m3, which are 72.57% higher and 31.75% lower than those obtained by depressurization alone, respectively. These study results can provide theoretical support for the industrial extraction of gas hydrate in seas. [ABSTRACT FROM AUTHOR]

The problem of hydrate plug, low efficiency of hydrate dissociation and short production time in hydrate exploitation processes have significantly hindered the commercial viability of gas hydrate extraction. This study investigated the inhibitory effects of ethylene glycol (EG), EG + polyvinyl pyrrolidone (PVP), and EG + PVP + sodium chloride (NaCl) on methane hydrate formation through experiment. The hydrate inhibitory performance is evaluated by using differential of pressure curve, the amount of hydrate, and pressure drop values, and the effects of different temperatures, pressures, inhibitors, and injection time on hydrate dissociation are further studied. The experiment results indicate that the rank of inhibitors combination in terms of effectiveness is 5%EG + 0.5 wt%PVP + 3 wt%Nacl > 10%EG + 1 wt%PVP > 30% EG. At low-temperature conditions, 30% EG exhibits good inhibition of hydrate synthesis but poor dissociation efficiency. As temperature increases, the hydrates dissociation rate with 30% EG also increases. For the combination inhibitor system of EG, PVP, and NaCl, PVP will reduce the dissociation efficiency of hydrates, while EG and Nacl will improve the hydrate dissociation performance. For low production pressure, it is found that 10% EG + 10% NaCl have a good promotion effect on hydrate dissociation, whereas under high production pressure, 20% EG + 10% NaCl is more effective. Furthermore, injecting the inhibitors earlier enhances the dissociation of hydrates more effectively. [ABSTRACT FROM AUTHOR]

The biological and technological importance of anion-mediated processes has made the development of improved methods for the selective recognition of anions one of the most relevant research topics today. The hydration sphere of anions plays an important role in the functions performed by anions by forming a variety of cluster complexes. Here we describe a supramolecular capsule that recognizes hydrated anion clusters. These clusters are most likely composed of three ions that form hydrated C3 symmetry complexes that are entrapped within the supramolecular capsule of the same symmetry. The capsule is made of self-assembled α,γ-cyclic peptide containing amino acid with by five-membered rings and equipped with a tris(triazolylethyl)amine cap. To recognise the hydrated anion clusters, the hexapeptide capsule must disassemble to entrap them between its two subunits. Due to the biological and technological importance of anion-mediated processes, the development of selective recognition methods which account for the hydration sphere of anions is highly relevant. Here, the authors describe a supramolecular capsule that recognizes hydrated anion clusters by disassembling to trap them between its two subunits. [ABSTRACT FROM AUTHOR]

As the understanding of natural gas hydrates as a vast potential resource deepens, their importance as a future clean energy source becomes increasingly evident. However, natural gas hydrates trend towards secondary generation during extraction and transportation, leading to safety issues such as pipeline blockages. Consequently, developing new and efficient natural gas hydrate inhibitors has become a focal point in hydrate research. Kinetic hydrate inhibitors (KHIs) offer an effective solution by disrupting the nucleation and growth processes of hydrates without altering their thermodynamic equilibrium conditions. This paper systematically reviews the latest research progress and development trends in KHIs for natural gas hydrates, covering their development history, classification, and inhibition mechanisms. It particularly focuses on the chemical properties, inhibition effects, and mechanisms of polymer inhibitors such as polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap). Studies indicate that these polymer inhibitors provide an economical and efficient solution due to their low dosage and environmental friendliness. Additionally, this paper explores the environmental impact and biodegradability of these inhibitors, offering guidance for future research, including the development, optimization, and environmental assessment of new inhibitors. Through a comprehensive analysis of existing research, this work aims to provide a theoretical foundation and technical reference for the commercial development of natural gas hydrates, promoting their safe and efficient use as a clean energy resource. [ABSTRACT FROM AUTHOR]

In situ electric heating is an important method used to increase production capacity during the extraction of natural gas hydrates. This work numerically evaluated the sensitivity of different heating parameters on gas production behavior with a vertical well depressurization in the Shenhu Sea area hydrate reservoir, the production pressure difference of 4 MPa, and continuous depressurization for 1080 days. The results showed that the in situ electric heating method can effectively enhance production capability by promoting hydrate dissociation and eliminating secondary hydrates. Compared with scenarios without heating, implementing whole wellbore heating (100 W/m) increases cumulative gas production (Vg) by 118.56%. When intermittent heating is applied to the local wellbore (15 m) located in the three-phase layer (with an interval of 30 days) and stops heating in advance at 480 days, there is no significant difference in Vg compared to the whole wellbore heating case, and the cumulative heat input is only 4.76%. We recommend considering intermittent heating of the local wellbore and stopping heating in advance during vertical well depressurization as this approach significantly reduces heating energy consumption while simultaneously improving production capacity. [ABSTRACT FROM AUTHOR]

This work includes the synthesis of new pyrazoline derivatives 6-20 over two steps. The first step included a condensation between vanillin and various aromatic ketones (acetophenone, p-nitroacetophenone, p-chloroacetophenone, pbromoacetophenone, and 2-acetylnaphthalene) to provide the corresponding chalcone derivatives 1-5 in high yields (up to 93%). The second step involved a reaction of 1- 5 with hydrazine hydrate, phenyl hydrazine, and p-nitrophenyl hydrazine, which gave the desired products 6-20 in yields ranging from 60 to 85%. The structures of the prepared compounds were confirmed by FT-IR and 1H NMR spectroscopy. A few of the produced compounds were tested for antibacterial and antioxidant properties. [ABSTRACT FROM AUTHOR]

Hydrate-based CO2 sequestration is a novel approach that can not only realize permanent CO2 sequestration but can also form an artificial cap to prevent its upward migration. In this work, a self-developed large-scale 3D apparatus was employed to investigate hydrate formation characteristics in hydrate-based CO2 sequestration at a constant liquid CO2 injection rate through a vertical well for the first time. Temperature and pressure evolutions in the sediment were analyzed in detail. Key indicators, including cumulative sequestered CO2, CO2 in hydrate and liquid phases, the instantaneous hydrate conversion, and liquid CO2 retention rates, were calculated. The results show that hydrate continuously forms with increased CO2 injection and exhibits strong heterogeneity due to the variation in hydrate formation rate and quantity. Severe liquid CO2 heterogeneous figuring phenomena occur since hydrate deteriorates the effective pore structure and topology, resulting in relatively small cumulative sequestered CO2 when a large amount of CO2 is released from the outlet. Meanwhile, the instantaneous hydrate conversion and liquid CO2 retention rates have large fluctuations owing to water consumption and variation in the effective contact area between liquid CO2 and water. However, hydrate formation does not cause blockage of wellbore and formation nearby under given experimental conditions, which is beneficial for hydrate formation in deeper sediment. This study provides insights into hydrate formation and liquid CO2 immigration regularity during hydrate-based CO2 sequestration and demonstrates its feasibility at a field scale. [ABSTRACT FROM AUTHOR]

This research discovered that carboxylated cellulose nanofibrils (CNF) with cations of various structures can significantly reduce the number of nucleation sites for methane hydrate formation when compared to distilled water. The electrokinetic potential of CNF in water slightly affects the concentration of hydrate crystallization centers, but it does alter the work of their formation. The energy barrier increases as the absolute value of the electrokinetic potential of nanoparticles decreases. The study of the effect of various CNF salts on the kinetics of methane hydrate formation expands our understanding of the inhibition mechanism of hydrate formation. It's assumed that a significant negative charge prevents the adsorption of like-charged hydrate nucleation centers on CNF. A decrease in the absolute value of zeta potential of CNF due to a change in cation facilitates this process. As a result, nuclei sorbed on colloidal CNF particles are stabilized on the surface, complicating their coalescence and crystal growth. The design of cellulose-based nanoparticles with varying zeta potential will allow the development of a colloid theory for controlling the formation of gas hydrates. [ABSTRACT FROM AUTHOR]

The synthesis and dissociation of methane hydrate and carbon dioxide hydrate were studied. Nonflammable gas hydrates can be used to extinguish flames in confined spaces. To increase the extinguishing efficiency, it is necessary to increase the dissociation rate (gas release rate) by using surfactant. The work investigates gas hydrates synthesized using sodium dodecyl sulfate (SDS). Experimental studies were carried out in wide ranges of surfactant concentration, the number of the stirrer revolutions and the initial water volume. To achieve the maximum rate of synthesis and dissociation, optimization of the specified parameters was performed. The influence of the key parameters on the dissociation rate was investigated experimentally and theoretically. The novelty of the work lies in solving a complex of interrelated tasks on the synthesis and dissociation of gas hydrate. It is shown that in order to achieve the maximum dissociation rate of carbon dioxide hydrate, it is necessary to optimize the following parameters: the diameter of the particles and their porosity, the porosity of the layer and the external heat flux. [ABSTRACT FROM AUTHOR]

This study proposed a novel development mode combining boundary sealing and hot water injection to address the challenges of gas leakage, limited reservoir sensible heat, boundary water intrusion, and low productivity faced by challenging hydrate extraction, and the stimulation effect was numerically investigated with Shenhu hydrates as the geological background. The results showed that lower boundary permeability facilitated pressure propagation and achieved volumetric dissociation of hydrates, whereas insufficient formation energy resulted in substantial gas retention. Hot water injection was effective for stimulation, but open boundaries could not maintain the high injection pressure, leading to massive hot water losses and gas escapes. However, their combination achieved a synergistic stimulation like "1 + 1 > 2" because a piston water drive similar to secondary recovery in oil and gas development was formed. Relative to three-spot well patterns, the five-spot shortened the extraction cycle by 680 days and enhanced the gas-to-water ratio by 17%. Increasing injection pressure enhanced water yield more significantly while the improvement of gas yield was more significant by increasing hot water temperature. Overall, high-pressure and high-temperature injection was suggested for gas enhancement and water control. These findings provide important guidance for advancing the commercial development of challenging hydrates. [ABSTRACT FROM AUTHOR]

The paper presents a mathematical model of injecting liquid sulfur dioxide in a porous bed saturated with methane and water in a flat-dimensional approximation. The formulation of the problem under consideration implies the formation of SO2 hydrate on the frontal surface separating the region saturated with sulfur dioxide and its hydrate and also with methane and water. An investigation has been made into the effects of the pressure and temperature of the sulfur dioxide being injected, of the initial temperature and also of the permeability of the system on the specific features of the formation of SO2 hydrate. Based on numerical calculations, it has been shown that in the case of low injection pressure values, the formation of sulfur dioxide hydrate can occur in a regime with the formation of an additional region containing methane and its gas hydrate. It has also been shown that in the case of high values of injection temperature and of the bed′s initial temperature, and also of the bed permeability, the formation of sulfur dioxide hydrate occurs without the formation of a region containing methane and its gas hydrate. The critical injection temperature whose exceedance results in the occurrence of a regime without the formation of a region containing methane and its gas hydrate has been shown related to the SO2 injection pressure. Based on the analysis of this dependence, it has been shown that the regime with the formation of a region saturated with methane and its gas hydrate is characteristic of the case of low injection temperature and pressure values. [ABSTRACT FROM AUTHOR]

Composition, structure, energy parameters, and existence regions of hydrate complexes formed in the HClO4–H2O system are studied by IR spectroscopy and quantum chemical methods. Three concentration-structural regions are determined. The HClO4–H2O solutions diluted to the 1:13.3 molar ratio of components contain and solvate-separated ions, each hydrated by four water molecules. More concentrated solutions (1:13.3-1:5) contain hydrated ion pairs that are contact ion pairs if the [HClO4]:[H2O] ratio falls within the region 1:9-1:5. As the acid concentration increases further up to the transition of the HClO4–H2O system into the solid phase, pair complexes are formed. The structure of the latter is formed by a cycle of two contact ion pairs connected by two H-bonds. The solid phase consists of interacting polymer chains formed by and ion pairs. [ABSTRACT FROM AUTHOR]

Multi‐walled carbon nanotubes (MWCNTs) are an excellent hydrate promoter, with their own Brownian motion of nanoparticles effectively shortening hydrate nucleation and accelerating hydrate formation. In this work, the properties of methane hydrate formation in a complex system of MWCNTs, sodium dodecyl sulphate (SDS) and NaCl were investigated. It was shown that the compounding system effectively enhanced the kinetics of methane hydrate formation, and the gas consumption of the reaction reached 0.38 MPa at 100 ppm MWCNTs, an increase of 865.8% compared to the pure water system, effectively promoting methane hydrate. In the complexed system, NaCl significantly enhanced the dispersion of MWCNTs, with 1000 ppm NaCl showing the best kinetic promotion effect. SDS not only increases the gas–liquid contact area through the wall attachment effect, but also enhances the dispersion of MWCNTs by adsorbing on the surface of carbon nanotubes and forming an electronic layer with NaCl. MWCNTs not only improve the mass transfer of the system through Brownian motion, but their large heat transfer coefficients can also effectively conduct the heat generated by the system. However, MWCNTs become agglomerated with increasing concentration, making the kinetic promotion effect weaker and the solution less stable, resulting in shorter shelf life. This study confirmed the effective promotion of hydrate formation by MWCNTs under the ultrasonic compounding system, and also provided a reference for related studies on the compounding of MWCNTs with NaCl. [ABSTRACT FROM AUTHOR]

We investigate the effect of pressure on the carbon dioxide (CO2) hydrate–water interfacial free energy along its dissociation line using advanced computer simulation techniques. In previous works, we have determined the interfacial energy of the hydrate at 400 bars using the TIP4P/Ice and TraPPE molecular models for water and CO2, respectively, in combination with two different extensions of the Mold Integration technique [J. Colloid Interface Sci. 623, 354 (2022) and J. Chem. Phys. 157, 134709 (2022)]. Results obtained from computer simulation, 29(2) and 30(2) mJ/m2, are found to be in excellent agreement with the only two measurements that exist in the literature, 28(6) mJ/m2 determined by Uchida et al. [J. Phys. Chem. B 106, 8202 (2002)] and 30(3) mJ/m2 determined by Anderson et al. [J. Phys. Chem. B 107, 3507 (2002)]. Since the experiments do not allow to obtain the variation of the interfacial energy along the dissociation line of the hydrate, we extend our previous studies to quantify the effect of pressure on the interfacial energy at different pressures. Our results suggest that there exists a correlation between the interfacial free energy values and the pressure, i.e., it decreases with the pressure between 100 and 1000 bars. We expect that the combination of reliable molecular models and advanced simulation techniques could help to improve our knowledge of the thermodynamic parameters that control the interfacial free energy of hydrates from a molecular perspective. [ABSTRACT FROM AUTHOR]

In this paper, the solubility of carbon dioxide (CO2) in water along the isobar of 400 bar is determined by computer simulations using the well-known TIP4P/Ice force field for water and the TraPPE model for CO2. In particular, the solubility of CO2 in water when in contact with the CO2 liquid phase and the solubility of CO2 in water when in contact with the hydrate have been determined. The solubility of CO2 in a liquid–liquid system decreases as the temperature increases. The solubility of CO2 in a hydrate–liquid system increases with temperature. The two curves intersect at a certain temperature that determines the dissociation temperature of the hydrate at 400 bar (T3). We compare the predictions with T3 obtained using the direct coexistence technique in a previous work. The results of both methods agree, and we suggest 290(2) K as the value of T3 for this system using the same cutoff distance for dispersive interactions. We also propose a novel and alternative route to evaluate the change in chemical potential for the formation of hydrates along the isobar. The new approach is based on the use of the solubility curve of CO2 when the aqueous solution is in contact with the hydrate phase. It considers rigorously the non-ideality of the aqueous solution of CO2, providing reliable values for the driving force for nucleation of hydrates in good agreement with other thermodynamic routes used. It is shown that the driving force for hydrate nucleation at 400 bar is larger for the methane hydrate than for the carbon dioxide hydrate when compared at the same supercooling. We have also analyzed and discussed the effect of the cutoff distance of dispersive interactions and the occupancy of CO2 on the driving force for nucleation of the hydrate. [ABSTRACT FROM AUTHOR]

Clathrate hydrates are crystalline inclusion compounds wherein a water framework encages small guest atoms/molecules within its cavities. Among the others, methane clathrates are the largest fossil fuel resource still available. They can also be used to safely transport gases and can also form spontaneously under suitable conditions plugging pipelines. Understanding the crystallization mechanism is very important, and given the impossibility of experimentally identifying the atomistic path, simulations played an important role in this field. Given the large computational cost of these simulations, in addition to all-atom force fields, scientists considered coarse-grained water models. Here, we have investigated the effect of coarse-graining, as implemented in the water model mW, on the crystallization characteristics of methane clathrate in comparison with the all-atom TIP4P force field. Our analyses revealed that although the characteristics directly depending on the energetics of the water models are well reproduced, dynamical properties are off by the orders of magnitude. Being crystallization a non-equilibrium process, the altered kinetics of the process results in different characteristics of crystalline nuclei. Both TIP4P and mW water models produce methane clathrate nuclei with some amount of the less stable (in the given thermodynamic conditions) structure II phase and an excess of pentagonal dodecahedral cages over the tetrakaidecahedral ones regarding the ideal ratio in structure I. However, the dependence of this excess on the methane concentration in solution is higher with the former water model, whereas with the latter, the methane concentration in solution dependence is reduced and within the statistical error. [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]

In this work, we shall estimate via computer simulations the homogeneous nucleation rate for the methane hydrate at 400 bars for a supercooling of about 35 K. The TIP4P/ICE model and a Lennard-Jones center were used for water and methane, respectively. To estimate the nucleation rate, the seeding technique was employed. Clusters of the methane hydrate of different sizes were inserted into the aqueous phase of a two-phase gas–liquid equilibrium system at 260 K and 400 bars. Using these systems, we determined the size at which the cluster of the hydrate is critical (i.e., it has 50% probability of either growing or melting). Since nucleation rates estimated from the seeding technique are sensitive to the choice of the order parameter used to determine the size of the cluster of the solid, we considered several possibilities. We performed brute force simulations of an aqueous solution of methane in water in which the concentration of methane was several times higher than the equilibrium concentration (i.e., the solution was supersaturated). From brute force runs, we infer the value of the nucleation rate for this system rigorously. Subsequently, seeding runs were carried out for this system, and it was found that only two of the considered order parameters were able to reproduce the value of the nucleation rate obtained from brute force simulations. By using these two order parameters, we estimated the nucleation rate under experimental conditions (400 bars and 260 K) to be of the order of log10 (J/(m3 s)) = −7(5). [ABSTRACT FROM AUTHOR]

The interactions between molecules and electrode surfaces play a key role in electrochemical processes and are a subject of extensive research, both experimental and theoretical. In this paper, we address the water dissociation reaction on a Pd(111) electrode surface, modeled as a slab embedded in an external electric field. We aim at unraveling the relationship between surface charge and zero-point energy in aiding or hindering this reaction. We calculate the energy barriers with dispersion-corrected density-functional theory and an efficient parallel implementation of the nudged-elastic-band method. We show that the lowest dissociation barrier and consequently the highest reaction rate take place when the field reaches a strength where two different geometries of the water molecule in the reactant state are equally stable. The zero-point energy contributions to this reaction, on the other hand, remain nearly constant across a wide range of electric field strengths, despite significant changes in the reactant state. Interestingly, we show that the application of electric fields that induce a negative charge on the surface can make nuclear tunneling more significant for these reactions. [ABSTRACT FROM AUTHOR]

Methane hydrates are important from a scientific and industrial perspective, and form by nucleation and growth from a supersaturated aqueous solution of methane. Molecular simulation is able to shed light on the process of homogeneous nucleation of hydrates, using straightforward molecular dynamics or rare event enhanced sampling techniques with atomistic and coarse grained force fields. In our previous work [Arjun, T. A. Berendsen, and P. G. Bolhuis, Proc. Natl. Acad. Sci. U. S. A. 116, 19305 (2019)], we performed transition path sampling (TPS) simulations using all atom force fields under moderate driving forces at high pressure, which enabled unbiased atomistic insight into the formation of methane hydrates. The supersaturation in these simulations was influenced by the Laplace pressure induced by the spherical gas reservoir. Here, we investigate the effect of removing this influence. Focusing on the supercooled, supersaturated regime to keep the system size tractable, our TPS simulations indicate that nuclei form amorphous structures below roughly 260 K and crystalline sI structures above 260 K. For these temperatures, the average transition path lengths are significantly longer than in our previous study, pushing the boundaries of what can be achieved with TPS. The temperature to observe a critical nucleus of certain size was roughly 20 K lower compared to a spherical reservoir due to the lower concentration of methane in the solution, yielding a reduced driving force. We analyze the TPS results using a model based on classical nucleation theory. The corresponding free energy barriers are estimated and found to be consistent with previous predictions, thus adding to the overall picture of the hydrate formation process. [ABSTRACT FROM AUTHOR]

Accurate control of natural gas flow and pressure is essential to achieving multi-gas combined production of the natural gas hydrates. In this study, a downhole stratification control tool for controlling natural gas flow rate and pressure with a multi-stage throttling structure was innovatively proposed. The multi-stage throttling structure combined an adjustable cage sleeve and a fixed nozzle. The numerical model of the internal flow field of the downhole stratification control tool was established. Through the computer fluid dynamics numerical simulation, the flow field change law inside the spool module of the downhole stratification control tool under different spool structures, different outlet pressures, and different spool openings was analyzed. Moreover, the spool module prototype was processed, and the indoor experiment of the spool's performance of reducing pressure and regulating production was carried out. The results show that the multi-stage throttling structure has the advantages of adjustable spool opening and moderate cooling range and the mass flow of gas inside the spool changes linearly with the opening of the spool. The spool module can accurately control the mass flow of natural gas under high-pressure conditions, and meet the needs of the downhole stratification control tool for accurate gas control. • A DSCT with multi-stage throttling structure is proposed. • The throttling structure composed of a cage sleeve and a fixed nozzle. • The flow field of multi-stage throttling structure is analyzed. • The DSCT can precisely control the gas mass flow under high-pressure conditions. • The pressure drop performance of the multi-stage throttling structure is the best. [ABSTRACT FROM AUTHOR]

Solar water evaporation offers a promising solution to address global water scarcity, utilizing renewable energy for purification and desalination. Transition-metal selenite hydrates (specifically nickel and cobalt) have shown potential as solar absorbers with high evaporation rates of 1.83 and 2.34 kg∙m−2∙h−1, but the reported discrepancy in evaporation rate deserves further investigation. This investigation aims to clarify their thermal stability for applications and determine the underlying mechanisms responsible for the differences. Nickel and cobalt selenite hydrate compositions were synthesized and investigated via thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy to assess their temperature-induced structural and compositional variations. The results reveal distinct phase transitions and structural alterations under various temperature conditions for these two photothermal materials, providing valuable insights into the factors influencing water transportation and evaporation rates. [ABSTRACT FROM AUTHOR]

Macroscopic geomechanical properties of methane hydrate-bearing sands (MHBSs) have attracted much scholarly attention. But the associated particle-level mechanisms often rely on assumptions. In this paper, triaxial compression tests and numerical simulations using discrete element method (DEM) are combined to study the unique mechanical properties of MHBS at the particle scale. The triaxial compression tests understand the basic mechanical properties of MHBS, and the experiments results are used for DEM modeling and parameter calibration. Small cementing particles are used to simulate methane hydrate, showing dispersion and coalescence distributions in sediments to simulate different hydrate spatial distributions. The simulation results show that in MHBS samples, the increasing hydrate saturation enhances the cementation network as well as the hydrate-related micro-force chains, and the particles in the cementation network jointly share the loading. The hydrate cementation is restricted by the high effective confining pressure as the cementation network was subjected to an ultimate strength. For hydrate cementation failure, the high effective confining pressure increases the proportion of shear breakage, but tensile breakage is the dominant failure form. The sample with hydrate coalescence distribution behaves strain hardening, while the sample with hydrate dispersion distribution yields later and shows strain softening with a higher peak strength. Finally, the stress-induced anisotropy in microstructure fabrics is observed, and the development of radial fabrics is hindered by hydrates, especially the coalesced hydrates. [ABSTRACT FROM AUTHOR]

The results of mathematical and experimental modeling of dissociation of pore methane hydrate in ice- and gas-bearing sediments with a decrease in the external pressure below equilibrium are presented. The described model of pore gas hydrate dissociation at negative temperatures, along with the experiment, makes it possible to calculate the kinetics of this process. A comparative analysis of the results is conducted. The proposed mathematical model confirms the trend of decreasing hydrate saturation of frozen soil in the form of obtained previously in experiments. These experiments have made it possible to calculate the coefficients A and n, while the mathematical modeling shows how these coefficients depend on the problem parameters. The theoretically estimated properties of the coefficient fully confirm the experimental data. The results of experimental and mathematical modeling have implications for key factors that determine the self-preservation of pore methane hydrates in frozen sediments. [ABSTRACT FROM AUTHOR]