Methane Molecules Research Articles

Selective Monoborylation of Methane by a Mono Bipyridyl‐Nickel(II) Hydride Catalyst

We report the development of an earth‐abundant metal catalyst for methane C‒H borylation. The post‐synthetic metalation of bipyridine‐functionalized zirconium metal−organic framework (MOF) with NiBr2, followed by treatment of NaEt3BH affords MOF‐supported monomeric bipyridyl‐nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 ºC using pinacolborane (HBpin) to afford CH3Bpin in 61% yield with a turnover number (TON) up to 1388. The confinement of the active NiH2‐species within the uniformly porous MOF allows selective monoborylation of methane via shape‐selective catalysis by preventing the formation of sterically encumbered overborylated products. Unlike MOF‐Ni catalyst, its homogeneous control is almost inactive in methane borylation due to its intermolecular decomposition. Our mechanistic investigation, including spectroscopic, kinetic, and control experiments, as well as DFT calculations, revealed that stabilizing mononuclear bipyridyl‐nickel dihydride and diboryl species by MOF is crucial for achieving efficient methane borylation via turnover‐limiting σ‐bond metathesis. This work shows promise in designing MOF‐based abundant metal catalysts for the chemoselective functionalization of methane and other inert molecules into valuable chemicals.

Selective Monoborylation of Methane by a Mono Bipyridyl-Nickel(II)Hydride Catalyst.

We report the development of an earth-abundant metal catalyst for methane C‒H borylation. The post-synthetic metalation of bipyridine-functionalized zirconium metal-organic framework (MOF) with NiBr2, followed by treatment of NaEt3BH affords MOF-supported monomeric bipyridyl-nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 ºC using pinacolborane (HBpin) to afford CH3Bpin in 61% yield with a turnover number (TON) up to 1388. The confinement of the active NiH2-species within the uniformly porous MOF allows selective monoborylation of methane via shape-selective catalysis by preventing the formation of sterically encumbered overborylated products. Unlike MOF-Ni catalyst, its homogeneous control is almost inactive in methane borylation due to its intermolecular decomposition. Our mechanistic investigation, including spectroscopic, kinetic, and control experiments, as well as DFT calculations, revealed that stabilizing mononuclear bipyridyl-nickel dihydride and diboryl species by MOF is crucial for achieving efficient methane borylation via turnover-limiting σ-bond metathesis. This work shows promise in designing MOF-based abundant metal catalysts for the chemoselective functionalization of methane and other inert molecules into valuable chemicals.

Analytical simulation of the simultaneous adsorption process of methane and water vapor in shales

ABSTRACT Investigations on the diffusion – adsorption of methane and water vapour in shale nanopores are essential for developing shale gas extraction. A kinetic model considering diffusion and different adsorption mechanisms was proposed. An analytical solution to the model was obtained through the integral transformation method and used to predict the distributions of methane and water within a shale particle. The results suggest that the reversible adsorption caused by the dispersion force is not the only adsorption mechanism; irreversible adsorption caused by hydrogen bonding or other types of intermolecular forces is more prominent, lengthening the delay to reach equilibrium. The presence of water strongly affects shale, considerably decreasing the diffusivity and adsorption capacity as well as the swelling of the shale matrix caused by the increase in the methane pressure. The diffusion and adsorption process expands to the shale particle surface after the pores near the particle centre are filled. The transport and storage of water vapour are more sensitive to the pore structure than those of methane. In the initial stage of the methane diffusion‒adsorption process, a large number of water molecules enter the particles, and the adsorbed water hinders methane molecules from contacting the shale surface.

Microscopic study on the memory effect of methane hydrate in the presence of silica nanoparticles: Ⅱ. Residual structure hypothesis & impurity imprinting hypothesis

Based on the hydrate dissociation mechanism and guest supersaturation hypothesis studied in the first part of this series, methane hydrate reformation characteristics affected by memory effect regarding the residual structures hypothesis and impurity imprints hypothesis is further studied to clarify the microscopic mechanism of methane hydrate memory effect during combustible ice exploitation. The initial molecular dynamics simulation configurations containing hydrate residual structures and silica nanoparticles were captured from hydrate dissociation simulation. By analyzing the distribution and transportation of methane molecules, hydrate clusters, and silica nanoparticles, the macroscopically recognized three-stage process of induction-growth-equilibrium for methane hydrate reformation has been verified from microscopic insight. Besides, the orderly arrangement of methane molecules around hydrate residual structures has been found to be essential to promote the growth of hydrate clusters. Moreover, the mutual adsorption between silica nanoparticles-guest nanobubbles and the mutual aggregation between silica nanoparticles-hydrate clusters both affect hydrate reformation process. Combined with the main conclusions derived from the first part of this series, it is found that hydrate memory effect diminishes as hydrate dissociation equilibriums. Thence, the microscopic analysis indicated that the methane hydrate reformation memory effect is influenced by multiple factors, where residual structures are the basis, supersaturated guest is the driving force, and silica nanoparticles are potential threats to form aggregates plugging.

Preparation of zwitterionic polymer and its application for dual-functional inhibition in deepwater drilling

During deep-water drilling operations, due to the conditions with low temperature and high pressure in the wellbore, methane hydrate can be easily formed in the presence of methane and plug the wellbore. In addition, the deep-water sediments are dominated by clay-silty with weak cementation, so well instability may be occurred due to clay hydration. In order to inhibit hydrate formation and clay hydration in deepwater drilling, a zwitterionic polymer AADV was synthesized through quaternary copolymerization of AM/AMPS/DMDAAV/VAC. The hydrate inhibition performance of AADV was evaluated in a high-pressure reactor chamber, and the results showed that AADV can delay the hydrate formation time from 330 min in pure water to 2204 min, indicating an excellent inhibition effect of hydrate formation. Meanwhile, 1 % AADV can significantly reduce the linear swelling rate of the calcium-based bentonite to 3.69 % for 10 h and increase the rolling recovery rate to 94.7 %, suggesting an excellent inhibition effect on clay hydration. The mechanism of dual-functional inhibition of AADV was further analyzed. The zwitterionic group in AADV and the hydrophilic amide group can strongly adsorb the water molecules through a strong hydration effect and the hydrogen bonding effect, respectively, which contributes to destroy the water molecules cage structure, and thus to suppress the hydrate formation. Besides, AADV can effectively obstruct mass transfer of methane molecules by increasing the viscosity of the aqueous phase and absorbing on the hydrate surface, leading to hydrate formation inhibition. For the inhibition of clay hydration, the SEM and XRD results proved that AADC inhibits the clay hydration through the film-forming effect. In addition, the contact angle of Na-Bent/AADC composite reached to 55.68° when the polymer concentration increased to 2 %, suggesting that the hydrophobicity of Na-Bent surface can be enhanced after AADC treatment. AADV can wrap around clay particles and form hydrophobic film through adsorption and intercalation, preventing the intrusion of external fluids and inhibiting clay hydration.

Microscopic study on the memory effect of methane hydrate in the presence of silica nanoparticles: Ⅰ. Dissociation mechanism & guest supersaturated hypothesis

As a key issue emerged in the exploitation of combustible ice resources, the memory effect inducing hydrate reformation in sand-containing dissociated-water system is still ambiguous. Among them, methane hydrate dissociation kinetics and guest supersaturated hypothesis for methane hydrate reformation are the primary issues to be addressed. A molecular dynamics simulation system where methane hydrate interacts with surface-hydroxylated silica nanoparticles was established to simulate dissociation process, which is necessary to construct hydrate reformation systems for further microscopic study on hydrate memory effect. The transportation mechanism of methane during hydrate dissociation in sand-containing aqueous system was elucidated. Based on this, hydrate-dissociated systems with methane supersaturated were captured, and molecular dynamics simulations were carried out to further study hydrate reformation mechanism regarding the guest supersaturated hypothesis. By analyzing the distribution and transportation of methane, hydrate clusters, and silica nanoparticles, it can be concluded that the hydrate-like orderly arrangement of methane that are dissolved in the solution or on the surface of nanobubbles are necessary to trigger hydrate memory effect by inducing the reformation of hydrate clusters, while the silica nanoparticles can inhibit the reformation of hydrate clusters by disturbing the arrangement of methane molecules and water molecules. Thence, the microscopic analysis indicated that supersaturated guest molecules is vital to the occurrence of hydrate memory effect and its effect varies between the supersaturated states.

Study on the formation process of methane hydrates on the surface of wax crystals with pour point depressant

Molecular dynamics simulations were applied to clarify the kinetic pathways and mechanism in the process of methane hydrate formation on the wax crystal surface with ethylene–vinyl acetate copolymer (EVA). The simulation results showed that methane molecules near the surfaces would adsorb on the surfaces of wax-EVA eutectic, while hydrates formed in the bulk of the solution away from the surfaces. The VA side chains on the wax crystal surface inhibit/promote the growth of hydrates by influencing the growth and re-dissolution process of methane nano-bubbles on eutectic surface. When a small amount of VA side chains was introduced on the wax crystal surface, as the simulation proceeded, the generated hydrates would gradually decompose. However, when more VA side chains distribute on the surface of wax crystals, the growth rate of hydrates would increase. In addition, hydrates and wax crystals could connect through a semi-cage structure, in which the VA side chain served as the guest of this semi-cage, making the eutectic and hydrates form a whole and increasing the risk of co-deposition of wax crystals and hydrates.

Kinetics of methane hydrate formation in a 1200 ml unstirred reactor for natural gas storage

Solidified natural gas (SNG) technology via clathrate hydrates, enhanced by promoters such as tetrahydrofuran (THF), promises large-scale natural gas storage due to its high volumetric capacity and mild storage conditions. Despite its potential for industrial scale-up, limited research exists on methane hydrate formation behaviors in large reactors (>1000 cm3), which is crucial for evaluating practical storage performance. In this study, methane hydrate formation kinetics were investigated in a scaled-up unstirred reactor (1200 cm3) at 288.15 K and 283.15 K, and 5.0 MPa. Methane uptake, system pressure, gas and liquid phase temperatures, and hydrate morphologies were analyzed to describe the dynamic hydrate formation process. Results reveal three effects of increased reactor size in contrast to smaller reactors: (i) heterogeneous distribution of THF-rich and methane-rich hydrates; (ii) hydrate bulk show a hollow inner structure with a cavity due to the wall-climbing behavior of hydrate growth; (iii) optimal THF concentration no longer always agrees with stoichiometric 5.56 mol%, which is case-dependent. These effects are attributed to higher diffusion resistances for methane molecules and more intensive heat accumulation. These findings provide some insight into the kinetics of methane hydrate formation in industrial reactors, which is critical for the commercialization of SNG technology.

Comparisons between full molecular dynamics simulation and Zhang's multiscale scheme for nanochannel flows.

In a very small surface separation, the fluid flow is actually multiscale consisting of both the molecular scale non-continuum adsorbed layer flow and the intermediate macroscopic continuum fluid flow. Classical simulation of this flow often takes over large computational source and is not affordable owing to using molecular dynamics simulation (MDS) to model the adsorbed layer flow, if the flow field size is on the engineering size scale such as of 0.01-10mm or even bigger like occurring in micro or macro hydrodynamic bearings. The present paper uses full MDS to validate Zhang's multiscale flow model, which yields the closed-form explicit flow equations respectively for the adsorbed layer flow and the intermediate continuum fluid flow. Here, full MDS was carried out for the pressure-driven flow of methane in the nano slit pore made of silicon respectively with the channel heights 5.79nm, 11.57nm, and 17.36nm. According to the number density distribution, the flow areas were respectively discriminated as the adsorbed layer zone and the intermediate fluid zone. The values of the characteristic parameters for Zhang's multiscale scheme were extracted from full MDS and input to Zhang's multiscale flow equations respectively for calculating the flow velocity profile and the volume flow rates of the adsorbed layers and the intermediate fluid. It was found that for these three channel heights, the flow velocity profiles calculated from Zhang's model approximate those calculated from full MDS, while the total flow rates through the channel calculated from Zhang's model are close to those calculated from full MDS. The accuracy of Zhang's multiscale flow model is improved with the increase of the channel height. The recent modification of the optimized potential for liquid simulation (MOPLS) model was used to calculate the interaction force between two methane molecules. In order to calculate the interaction force between the wall atoms and the methane molecules accurately, our previous non-equilibrium multiscale MDS was used. The interaction forces between the methane molecule and the wall atom were obtained from the coupled potential function by the L-B mixing rule when the fluid molecules arrived at near wall. The methane molecule diameter was obtained from the radial distribution function by using equilibrium MDS under the same initial conditions. The local viscosities across the adsorbed layer were obtained from the local velocity profile by using the Poiseuille flow method. The motion equation of the methane molecule was solved by the leapfrog method. The temperature of the simulation system was checked by Bhadauria's method, i.e., the system temperature was rectified by the velocities in the y- and z-directions. The flow velocity distributions across the channel height and the volume flow rates through the channel were also calculated from Zhang's closed-form explicit flow equations respectively for the adsorbed layer flow and the intermediate fluid flow. The results respectively obtained from full MDS and Zhang's multiscale flow equations were then compared.

Enhanced conversion of methane to liquid-phase oxygenates via hollow ferrite nanotube@horseradish peroxidase based photoenzymatic catalysis

A novel photoenzymatic catalytic system employing hollow ferrite nanotubes and horseradish peroxidase (HRP) has been developed to significantly enhance the conversion of methane to liquid-phase oxygenates. The 1.5 % HRP-Fe3O4 HNTs demonstrated an exceptional liquid product yield of 177.87 μmol g−1 h−1 and exhibited reusability for methane photo-oxidation under ambient conditions. The physicochemical characterization revealed that the immobilization of HRP enhanced the visible light absorption and charge carrier separation efficiency. The Fe3O4 HNTs facilitated methane (CH4) molecule adsorption, while photogenerated electrons and H2O2 participated in the Fe2+-porphyrin and Fe3+-porphyrin cycle of HRP, enabling continuous generation of hydroxyl radicals, which activated CH4 to methyl radicals. In situ EPR and FTIR results indicated that CH3OH and CH3CH2OH were produced via the formation and consumption of •CH3O and •CH2 intermediates. This work presents an efficient strategy and provides new insights into the direct photo-oxidation of methane reaction through a photoenzyme catalytic system.

Physical and practical constraints on atmospheric methane removal technologies

Abstract Despite their apparent utility in mitigating climate change, technologies for removing methane from air are in early stages of development. Here we evaluate the limiting physical constraints, for three types of systems: two- and three-dimensional infrastructure and atmospheric oxidation enhancement, focusing on removing low ( x CH4 < 1000 ppm) and ambient ( x CH4 < 2 ppm) methane from air. With the space velocities and removal efficiencies of current three-dimensional technologies, volumes of 7–350 km3 are required to remove 1 Tg CH4 yr−1. Two-dimensional solutions are limited by the transport rate of methane to a surface. If every molecule of methane that collides with the surface is removed, an area of 1130 km2 is needed to remove 1 Tg CH4 yr−1 at ambient concentration. However, research shows that per-collision reaction probabilities are < 10−8 requiring a surface area of 1010–1015 km2. Finally, we examine atmospheric oxidation enhancement, where 4.8 Tg yr−1 of Cl ⋅ or 8.8 Tg yr−1 of OH ⋅ is required to remove 1 Tg CH4 yr−1, with precursors such as H2O2 or O3. However, limitations arise concerning multiple environmental impacts. We conclude that the physical and practical constraints are considerable, and identify the main barriers that must be addressed.

Depressurization-induced production of shale gas in organic-inorganic shale nanopores: A kinetic Monte Carlo simulation

Methane gas production from unconventional reservoirs, such as shale formations, is in high demand due to the global energy needs. However, maximizing production remains challenging due to the ultra-tight porosity, heterogeneity, and complex nature of shale rocks under high pressure. To address this issue, we employ a novel kinetic Monte Carlo (kMC) simulation to investigate the molecular-level behavior of shale gas in both homogeneous and heterogeneous organic-inorganic shale nanopores. This approach not only provides accurate computations of shale gas under high pressure but also aims to uncover the mechanisms of shale gas storage at reservoir pressure and production during pressure drawdown. Our findings indicate that organic shale ultramicropores (pore width < 0.7 nm) contribute significantly to the highest storage capacity of shale gas but pose challenges for production capacity solely through depressurization. In contrast, the free gas zone is the primary source of shale gas production from mesoporous shales, which has a high recovery efficiency but a low production capacity due to less pronounced interaction effects from the shale surface. The heterogeneous nature of shale surfaces leads to asymmetric distributions of density and potential energy across pore widths, with methane molecules favoring locations near organic pore walls due to stronger attractive interactions, while inorganic pore walls facilitate shale gas migration. Interestingly, the optimal ultramicropore size yields the highest recovery efficiency of shale gas via depressurization, characterized by a transition from near-commensurate to incommensurate molecular packing between reservoir and post-drawdown pressures. Based on these detailed molecular simulations, further research is necessary to develop innovative techniques for enhancing shale gas recovery, especially in micropores.

Synergistic effect of oxygen vacancies and functionalized ligands selectively enhanced the photocatalytic oxidation of methane to carbon monoxide

The titanium-based metal–organic framework MIL-125(Ti) has been widely investigated in photocatalytic carbon dioxide reduction and water splitting, but rarely studied in photocatalytic methane conversion by employing only water as an oxidant under mild conditions. Simultaneously controlling products with high yield and selectivity is highly challenging in methane conversion. Herein, we develop a series of functionalized titanium metal–organic frameworks via a facile organic ligand exchange process. The abundant Ti3+ active sites induced by oxygen vacancies and functionalized ligands synergistically facilitate the adsorption and activation of methane molecules. The carbon monoxide yield over NH2-MIL-125(Ti) increased to 198.6 μmol·gcat−1·h−1 with a high selectivity of 87.1 % under simulated solar illumination. Combined with in-situ characterizations and density functional theoretical calculations, the results confirmed that Ti3+ active sites induced by oxygen vacancies and amino functional groups synergistically enhanced the photocatalytic conversion of methane and elucidate CH4-to-CO conversion mechanism. This study does not only provide insights into the rational design of metal–organic frameworks with copious oxygen vacancies and functional groups, but also provides some significant cognition for photocatalytic methane conversion.

Calculation of coal cleats spacing for methane degassing by image processing

Coal bed methane is one of the clean energy sources in the world. Methane molecules are confined inside the pores of coals and when the gas drainage wells are drilled into the coal seams, due to the resulted pressure difference. Coal cleats are spread all over the coal seam as face and butt cleats and play an essential role in the methane gas drainage operation from coal mines. Calculating the coal cleats spacing makes great help in modeling the amount of emitted gas followed by calculating the spacing of gas suction wells. Furthermore, the time required for gas drainage will be determined. Computer-based image processing technique has been utilized to identify the cleats spacing. In this study, three-dimensional computed tomography scan images were prepared for coal samples from Tabas Coal Mine in Iran. Computer-based image processing technology was conducted to determine the coal cleats. Their spacing was then calculated. Based on the results obtained using image processing with computer, the average distance between face cleats was 20 to 30 mm and the distance between butt cleats was 15 to 25 mm. The results of this study are used to modeling the amount of methane gas in the coal cleats. Based on this modeling, the amount of released gas and the distance between the wells can be designed.

Study on the Synergistic Effect of SiO2 and H2O on Oxidative Coupling of Methane over Mn-Na2WO4/SiO2 Catalyst.

Mn-Na2WO4-based catalysts with different supports were prepared using the incipient wetness impregnation method and evaluated for their oxidative coupling of methane (OCM) reaction performance. The results demonstrated that the SiO2- supported catalyst exhibited the best catalytic performance, and the introduction of H2O further enhanced its activity. Under the conditions of a feed gas mixture of CH4/O2/H2O = 6:1:24 at 800 °C and atmospheric pressure, the CH4 conversion and C2+ selectivity over the Mn-Na2WO4/SiO2 catalyst increased from 28.4% and 77.4% (without H2O) to 33.2% and 84.9%, respectively. In contrast, the catalytic activity using TiO2 and MgO supports drastically declined. Characterizations using X-ray diffraction (XRD), in situ infrared spectroscopy (In-situ IR), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), and oxygen temperature-programmed desorption (O2-TPD) revealed that the introduction of steam not only served as a diluent to decrease the partial pressures of the reactants CH4 and O2, thereby reducing deep oxidation reactions in the gas phase, but also interacted with surface oxygen species (O2 2-) and silica to form adjacent surface-bonded disilanol free radicals Si-OIH. This interaction facilitated the dehydrogenation and coupling of two methane molecules on the catalyst surface, resulting in the generation of C2+ products, significantly enhancing the catalytic activity and selectivity of OCM.

Cryogenic Ion Vibrational Spectroscopy of Protonated Valine: Messenger Tag Effects.

We report the infrared photodissociation spectrum of tagged protonated valine in the range 1000-1900 cm-1, prepared in a cryogenic ion trap. Comparison of experimental results with calculated infrared spectra based on density functional theory shows that the hydroxyl group of the carboxylic acid functionality and the protonated amine group adopt a trans configuration. Nitrogen and methane molecules were used as messenger tags with optimal tagging temperatures of 30 K for N2 and 60 K for CH4. While the calculated infrared spectra of the tagged ion suggest only a weak influence of the messenger tag on the frequency positions of ValH+, the measured intensities for N2-tagged ValH+ appear strongly suppressed for all but the highest frequency feature at 1773 cm-1. We trace this behavior to the binding energy of the N2 tag, which is significantly higher than that of CH4, based on density functional and coupled cluster calculations and rate estimates for photoinduced unimolecular dissociation from statistical theory.

Transport Properties of Aqueous Methane Solutions and Blocking Behavior of Intelligent-Responsive Temporary Plugging Agent in a Switchable Nano-channel: A Dissipative Particle Dynamics Simulation Study.

Intelligent-responsive temporary plugging agents (TPAs) have great potential in the field of oil and gas resource extraction due to their self-adaptability to the environment. However, the transport mechanism of oil and gas molecules, such as aqueous methane solution in intelligent-responsive TPA-modified nano-channels and the blocking behavior of TPA, have not been verified yet. In this work, dissipative particle dynamics simulations (DPD) are conducted to investigate the velocity distribution and the force characteristics of aqueous methane solutions under different driving velocities, as well as the blocking effect of TPA to the flow of solution. Simulation results indicate that aqueous methane solution primarily concentrates in theuncovered area of the TPA and diffuses into the TPA-covered area when the nano-channel is closed. The velocity distribution of the flowing solution in the open nano-channel follows a subparabolic pattern. Methane molecules in the closed nano-channel show sharp oscillations in velocity and force profiles, which can be mitigated by increasing the methane concentration. The designed TPA effectively blocks fluid flow but its head and tail are vulnerable to the shear forces from the fluid. This study enhances the understanding of the nanoflows in the wellbores during the extraction of oil and natural gas resources.

Modelling of physical and chemical properties of activated carbons which affect methane adsorption mechanisms

Effect of important physical and chemical properties of activated carbons which affect the way methane adsorbs were studied. The Grand Canonical Monte Carlo (GCMC) simulations were used to study how the curvature and size of the platelets affect the mechanisms of methane adsorption process; and which role is played by the amount of oxygen present in activated carbons. Furthermore, Molecular dynamic (MD) simulations were carried out to study the effect of those properties on motion behavior of methane molecules during adsorption. The two simulations are very vital because they were able to exploit mechanisms which are difficult to obtain by using experiments alone. It was found that oxygen content, degree of curvature of platelets and size of basic structural units affected the availability of suitable methane binding sites in activated carbons and hence total methane adsorbed amount. Furthermore, the studied parameters were found to have impacts to the energy of interaction between activated carbons and methane, methane diffusion characteristics and amount of heat generated during adsorption process. It is concluded that the studied activated carbon properties hugely affect the way methane adsorbs and should be given attention during designing of the optimal adsorbent for methane adsorption.

Design of eco-friendly antifreeze peptides as novel inhibitors of gas-hydration kinetics.

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.

Liquefaction efficiency study of heterogeneous condensation of methane-ethane binary gas mixtures with different component contents

Natural gas is a mixture of hydrocarbons. During the liquefaction of natural gas, the mixed gas undergoes heterogeneous condensation on the surface of the heat exchanger. Currently, the heterogeneous condensation mechanism of mixed gases is not fully understood, and the influence of component content on the liquefaction efficiency is not clear. Therefore, the molecular dynamics simulation was employed to investigate the heterogeneous condensation process of methane-ethane binary mixed gas on a solid surface. The characteristics of condensation nucleation cluster growth was explored and the variations in temperature, density, heat flux, and liquefaction rate were analyzed. The impact of ethane on methane condensation was also discussed. The results indicate that increasing wettability enhances surface nucleation quantity and shortens nucleation time, resulting in a 3.6- times increase in heat flux. The addition of ethane gas in the system promotes condensation nucleation, which increases the liquefaction rate by 60 % when x = 20 % compared to the pure methane system. However, for methane gas, ethane only benefits the liquefaction of methane molecules in the initial nucleation stage. As the mixture in the system enters the cluster growth stage, component migration in the mixed gas leads to a lower liquefaction rate compared to pure methane gas.