Molecular dynamics simulations for the growth of CH_4-CO_2 mixed hydrate

Molecular dynamics simulations are performed to study the growth mechanism of CH4-CO2 mixed hydrate in xCO2= 75%, xCO2= 50%, and xCO2= 25% systems at T = 250 K, 255 K and 260 K, respectively. Our simulation results show that the growth rate of CH4-CO2 mixed hydrate increases as the CO2 concentration in the initial solution phase increases and the temperature decreases. Via hydrate formation, the composition of CO2 in hydrate phase is higher than that in initial solution phase and the encaging capacity of CO2 in hydrates increases with the decrease in temperature. By analysis of the cage occupancy ratio of CH4 molecules and CO2 molecules in large cages to small cages, we find that CO2 molecules are preferably encaged into the large cages of the hydrate crystal as compared with CH4 molecules. Interestingly, CH4 molecules and CO2 molecules frequently replace with each other in some particular cage sites adjacent to hydrate/solution interface during the crystal growth process. These two species of guest molecules eventually act to stabilize the newly formed hydrates, with CO2 molecules occupying large cages and CH4 molecules occupying small cages in hydrate.     

Molecular dynamics simulations for the growth of CH4-CO2 mixed hydrate

Molecular dynamics simulations are performed to study the growth mechanism of CH4-CO2 mixed hydrate in xco2 = 75%, xco2 = 50%, and zco2 = 25% systems at T = 250 K, 255 K and 260 K, respectively. Our simulation results show that the growth rate of CH4-CO2 mixed hydrate increases as the CO2 concentration in the initial solution phase increases and the temperature decreases. Via hydrate formation, the composition of CO2 in hydrate phase is higher than that in initial solution phase and the encaging capacity of CO2 in hydrates increases with the decrease in temperature. By analysis of the cage occupancy ratio of CH4 molecules and CO2 molecules in large cages to small cages, we find that CO2 molecules are preferably encaged into the large cages of the hydrate crystal as compared with CH4 molecules. Interestingly, CH4 molecules and CO2 molecules frequently replace with each other in some particular cage sites adjacent to hydrate/solution interface during the crystal growth process. These two species of guest molecules eventually act to stabilize the newly formed hydrates, with CO2 molecules occupying large cages and CH4 molecules occupying small cages in hydrate.     

水合物CH4-CO2置换的双重机理:空位辅助与竞争

过去的CO2置换甲烷水合物的微观机理研究,主要集中在客体分子(CH4、CO2)之间的交换、占据状态,孤立地研究分解过程或生成过程,忽视主体-客体之间的作用、主体分子(H2O)的空位辅助和客体分子的多重竞争通道。本文基于水合物分解的过冷水及其水空位辅助,以及水合物生成的串滴链及其客体分子竞争的研究,进一步评论水合物CH4-CO2置换的双重机理。然后,对微观机理的动态性和未来研究的相关问题进行讨论。通过综述和评论,文章得出以下初步结果:过冷水通过水空位推动客体分子的跳跃、扩散,实现置换过程的自组装;CO2分子在分解前沿形成一个有序结构的CO2串滴链,其动态性伴随水的组织到获取包合物笼的结构,以及非晶形包合物转变成晶形包合物的生长过程;CO2和CH4在中晶穴中必然产生竞争,并且存在多种竞争类型;成核过程中,不稳定簇导致竞争结构,且有多重竞争通道。最后,结果表明水合物的CH4-CO2置换机理具有双重性,即主体分子的空位辅助和客体分子的竞争,是分解过程和生成过程的自然统一。     

Kinetics and stability of CH4-CO2 mixed gas hydrates during formation and long-term storage.

The formation of CH4-CO2 mixed gas hydrates was observed by measuring the change of vapor-phase composition using gas chromatography and Raman spectroscopy. Preferential consumption of carbon dioxide molecules was found during hydrate formation, which agreed well with thermodynamic calculations. Both Raman spectroscopic analysis and the thermodynamic calculation indicated that the kinetics of this mixed gas hydrate system was controlled by the competition of both molecules to be enclathrated into the hydrate cages. However, the methane molecules were preferentially crystallized in the early stages of hydrate formation when the initial methane concentration was much less than that of carbon dioxide. According to the Roman spectra, pure methane hydrates first formed under this condition. This unique phenomenon suggested that methane molecules play important roles in the hydrate formation process. These mixed gas hydrates were stored at atmospheric pressure and 190 K for over two months to examine the stability of the encaged gases. During storage, CO2 was preferentially released. According to our thermodynamic analysis, this CO2 release was due to the instability of CO2 in the hydrate structure under the storage conditions.     

Structure transition and tuning pattern in the double (tetramethylammonium hydroxide + gaseous guests) clathrate hydrates

In this study, we present an extraordinary structural transition accompanying the occurrence of more than two coexisting clathrate hydrate phases in the double (CH4 + tetramethylammonium hydroxide (Me(4)NOH)) and (H2 + Me(4)NOH) ionic clathrate hydrates using solid-state NMR spectroscopy (high-powered decoupling and CP/MAS) and powder X-ray diffraction. It was confirmed that structure-I (sI) and structure-II (sII) hydrates coexist as the water concentration increases. In the Me(4)NOH-depleted region, the unique tuning phenomenon was first observed at a chemical shift of -8.4 ppm where relatively small gaseous CH4 molecules partly occupy the sII large cages (sII-L), pulling out large cationic Me(4)N+ that is considered to be strongly bound with the surrounding host lattices. Moreover, we note that, while pure Me(4)NOH.16H(2)O clathrate hydrates melted at 249 K under atmospheric pressure conditions, the double (CH4 + Me(4)NOH) clathrate hydrate maintained a solid state up to approximately 283 K under 120 bar of CH4 with a conductivity of 0.065 S cm(-1), suggesting its potential use as a solid electrolyte. The present results indicate that ionic contributions must be taken into account for ionic clathrate hydrate systems because of their distinctive guest dynamic behavior and structural patterns. In particular, microscopic analyses of ionic clathrate hydrates for identifying physicochemical characteristics are expected to provide new insights into inclusion chemistry.     

Raman spectroscopic studies on methane + tetrafluoromethane mixed-gas hydrate system

Raman spectra of intramolecular vibration mode for each guest species in the methane + tetrafluoromethane (CF₄) mixed-gas hydrate crystal have been measured at 291.1 K. Both of pure guest species generate the structure-I hydrate in the present pressure ranges. Isothermal phase-equilibrium curve exhibits two discontinuous points around the equilibrium methane compositions (water-free) in the gas phase of 0.3 and 0.8. At the above points, the Raman spectra of both guest molecules have been drastically changed. One of the most important findings is that the crystal of methane + tetrafluoromethane mixed-gas hydrate shows the structural phase-transition (from the structure-I to the structure-II and back to the structure-I) caused by composition changes.     

The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations

Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.     

Sorption equilibria of CO2/CH4 mixture on activated carbon in presence of water

The sorption isotherms of CO2 + CH4 mixtures on an activated carbon were collected in the presence of water at a temperature suitable for hydrate formation. The equilibrium composition of both phases was determined. The initial concentration of CO2 in mixtures was set at 33, 38 and 42%, and the total pressure was up to 10 MPa. CO2 hydrates were firstly formed following the increase of total pressure, and CO2 dominates the sorbed phase composition. CO2 concentration in the sorbed phase begins to decrease when the partial pressure of methane allows for the formation of methane hydrates. Competition for hydrate cavities was observed between CO2 and CH4 as reflected in the isotherm shape and phase composition at equilibrium. The formation pressure of hydrates is lower for mixtures than for pure gases, and the highest sorption capacity of each gas decreased in the mixture sorption either.     

Clathrate hydrate formation in (methane + water + methylcyclohexanone) systems: the first phase equilibrium data

The present study experimentally demonstrated clathrate hydrate formation in the systems of (methane + water + each of the three methylcyclohexanone isomers, i.e., 2-methylcyclohexanone, 3-methylcyclohexanone, and 4-methylcyclohexanone) and measured the first data of the quadruple (water rich liquid + hydrate + methylcyclohexanone rich liquid + methane rich vapor) equilibrium pressure and temperature conditions in these systems over the temperatures from T=273 K to T=281 K. In the three systems with methylcyclohexanone, the measured equilibrium pressure at each given temperature is ∼1.3 MPa lower than that in a structure-I hydrate forming (methane + water) system without any methylcyclohexanone, which suggests the formation of structure-H hydrates with methylcyclohexanones as large-molecule guest substances. Among the three systems, 3-methylcyclohexanone provides the highest equilibrium pressure, and 2-methylcyclohexanone, the lowest.     

Crystal lattice size and stability of type H clathrate hydrates with various large-molecule guest substances

To gain a better understanding of the effects of guest molecules on the lattice and stability of type H hydrates, we performed powder X-ray diffraction (PXRD) measurements and semiempirical molecular orbital calculations. The unit cell parameters and cohesive energies of various type H hydrates that contain methane (CH4) were analyzed. PXRD measurements indicated that an increase in the large-molecule guest volume caused the unit cell volume to increase. It was also indicated that a large-molecule guest substance caused the a-axis-direction of the unit cell to increase with little decrease in the c-axis direction. Calculations of cohesive energy by means of a semiempirical molecular orbital method indicated that the functional group and configuration of large-molecule guest substances affects the stability of type H hydrates. It was concluded that the icosahedron (5(12)6(8)) cages do not easily increase in length along the c-axis direction when larger guest molecules are used to form the hydrate, but the 5(12)6(8) cage and the layer of dodecahedron (5(12)) cages can easily increase in length along the a-axis direction due to interactions of the guest-host molecule.     

Thermodynamic stability of structure-H hydrates of methylcyclopentane and cyclooctane helped by methane

The four-phase equilibria were measured for the methylcyclopentane+methane+H₂O hydrate system (274.28–287.40 K, 1.75–9.34 MPa) and the cyclooctane+methane+H₂O hydrate system (274.08–288.57 K, 1.60–9.33 MPa). Each structure-H hydrate has the lower equilibrium pressure than the pure methane structure-I hydrate in the temperature range of the present work. The isothermal equilibrium pressures of both methylcyclopentane and cyclooctane hydrates are slightly higher than that of methylcyclohexane hydrate.     

Thermal expansivity for sI and sII clathrate hydrates

Knowledge of thermal expansivity can aid in the understanding of both microscopic and macroscopic behavior of clathrate hydrates. Diffraction studies have shown that hydrate volume changes significantly (as much as 1.5% over 50 K) as a function of temperature. It has been demonstrated previously via statistical mechanics that a minor change in hydrate volume (e.g., a 1.5% change in volume or 0.5% change in lattice parameter) can lead to a major change in the predicted hydrate formation pressure (e.g., >15% at >100 MPa for methane). Because of this sensitivity, hydrate thermal expansivity measurements, for both Structures I and II with various guests, are needed help quantify volume distortions in hydrate lattices to ensure accurate hydrate phase equilibria predictions. In addition to macroscopic phase equilibria, the thermal expansion of different hydrates can give information about the interactions between the guest molecules and the host lattice. In this work, the hydrate lattice parameters for four Structure I (C2H6, CO2, 47% C2H6 + 53% CO2, and 85% CH4 + 15% CO2) and seven Structure II (C3H8, 60% CH4 + 40% C3H8, 30% C2H6 + 70% C3H8, 18% CO2 + 82% C3H8, 87.6% CH4 + 12.4% i-C4H10, 95% CH4 + 5% C5H10O, and a natural gas mixture) systems were measured as a function of temperature. The lattice parameter measurements were combined with existing literature values. Both sI and sII hydrates, with a few exceptions, had a common thermal expansivity, independent of hydrate guest. Many guest-dependent correlations for linear thermal expansivity have been proposed. However, we present two guest-independent, structure-dependent correlations for sI and sII lattices, which have been developed to express the normalized hydrate lattice parameters (and therefore volume) as a function of temperature.     

Theoretical Investigation of the Fusion Process of Mono-Cages to Tri-Cages with CH4/C2H6 Guest Molecules in sI Hydrates

Owing to a stable and porous cage structure, natural gas hydrates can store abundant methane and serve as a potentially natural gas resource. However, the microscopic mechanism of how hydrate crystalline grows has not been fully explored, especially for the structure containing different guest molecules. Hence, we adopt density functional theory (DFT) to investigate the fusion process of structure I hydrates with CH₄/C₂H₆ guest molecules from mono-cages to triple-cages. We find that the volume of guest molecules affects the stabilities of large (5¹²6², L) and small (5¹², s) cages, which are prone to capture C₂H₆ and CH₄, respectively. Mixed double cages (small cage and large cage) with the mixed guest molecules have the highest stability and fusion energy. The triangular triple cages exhibit superior stability because of the three shared faces, and the triangular mixed triple cages (large-small-large) structure with the mixed guest molecules shows the highest stability and fusion energy in the triple-cage fusion process. These results can provide theoretical insights into the growth mechanism of hydrates with other mono/mixed guest molecules for further development and application of these substances.     

Free-energy calculation of structure-H hydrates

A molecular-dynamics (MD) simulation of structure-H hydrates was performed under constant pressure and temperature with 6120 TIP4P water molecules, 900 OPLS-UA methane molecules, and 180 large molecular guest substance (LMGS) molecules. The LMGS molecules were represented in the form of a one-site Lennard-Jones (LJ) model using the LJ parameters sigma and epsilon. In order to clarify the thermodynamic stability of structure-H hydrates, we calculated the free-energy difference, changing on the sigma and epsilon only of the LMGS molecules. In this simulation, stable crystals of structure-H hydrates and a minimum value of DeltaG were obtained at sigma approximately 6.2 A and large values of epsilon. All simulations were performed using the special-purpose computer hardware MDGRAPE-2.     

Highly selective encaging of carbon dioxide molecules in the mixed carbon dioxide and nitrogen hydrate at low temperatures

The structural identification and guest compositions of the mixed CO(2) and N(2) hydrates at low temperature conditions were investigated by both theoretical predictions and experimental measurements. From the model calculations, at very low temperatures, the highly CO(2)-concentrated hydrates over 95 mol % CO(2) on the basis of water-free concentration could coexist with the gas mixtures of low CO(2) concentrations in equilibrium. X-ray diffraction measurements of the hydrates formed with the gas mixture of 3.16 mol % CO(2) and balanced N(2) indicate that the formed hydrates at all conditions considered in this study were identified as structure I, whereas the model predicts a structural transition to structure II around 220 K. However, it was also found that the formed hydrate samples contain a considerable amount of hexagonal ice resulting from incomplete conversion of ice to the hydrates. The compositional analysis suggests that a favorable encaging of CO(2) in the mixed hydrate can be obtained by the hydrate formation at low temperatures and relative amount of CO(2) molecules in the mixed hydrates increases with a decrease of temperature.     

Guest gas enclathration in semiclathrates of tetra-n-butylammonium bromide: stability condition and spectroscopic analysis

In this study, guest gas enclathration behavior in semiclathrates of tetra-n-butylammonium bromide (TBAB) was closely investigated through phase equilibrium measurement and spectroscopic analysis. The three-phase equilibria of semiclathrate (H), liquid water (L(W)), and vapor (V) for the ternary CH(4) + TBAB + water and CO(2) + TBAB + water mixtures with various TBAB concentrations were experimentally measured to determine the stability conditions of the double TBAB semiclathrates. Equilibrium dissociation temperatures for pure TBAB semiclathrate were also measured at the same concentrations under atmospheric conditions. The dissociation temperature and dissociation enthalpy of pure TBAB semiclathrate were confirmed by differential scanning calorimetry. The experimental results showed that the double CH(4) (or CO(2)) + TBAB semiclathrates yielded greatly enhanced thermal stability when compared with pure CH(4) (or CO(2)) hydrate. The highest stabilization effect was observed at the stoichiometric concentration of pure TBAB semiclathrate, which is 3.7 mol%. From the NMR and Raman spectroscopic studies, it was found that the guest gases (CH(4) and CO(2)) were enclathrated in the double semiclathrates. In particular, from the cage-dependent (13)C NMR chemical shift, it was confirmed that CH(4) molecules were captured in the 5(12) cages of the double semiclathrates.     

13C NMR studies of hydrocarbon guests in synthetic structure H gas hydrates: experiment and computation

(13)C NMR chemical shifts were measured for pure (neat) liquids and synthetic binary hydrate samples (with methane help gas) for 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylpentane, 3-methylpentane, methylcyclopentane, and methylcyclohexane and ternary structure H (sH) clathrate hydrates of n-pentane and n-hexane with methane and 2,2-dimethylbutane, all of which form sH hydrates. The (13)C chemical shifts of the guest atoms in the hydrate are different from those in the free form, with some carbon atoms shifting specifically upfield. Such changes can be attributed to conformational changes upon fitting the large guest molecules in hydrate cages and/or interactions between the guests and the water molecules of the hydrate cages. In addition, powder X-ray diffraction measurements revealed that for the hexagonal unit cell, the lattice parameter along the a-axis changes with guest hydrate former molecule size and shape (in the range of 0.1 ?) but a much smaller change in the c-axis (in the range of 0.01 ?) is observed. The (13)C NMR chemical shifts for the pure hydrocarbons and all conformers were calculated using the gauge invariant atomic orbital method at the MP2/6-311+G(2d,p) level of theory to quantify the variation of the chemical shifts with the dihedral angles of the guest molecules. Calculated and measured chemical shifts are compared to determine the relative contribution of changes in the conformation and guest-water interactions to the change in chemical shift of the guest upon clathrate hydrate formation. Understanding factors that affect experimental chemical shifts for the enclathrated hydrocarbons will help in assigning spectra for complex hydrates recovered from natural sites.     

A molecular dynamics study of ethanol-water hydrogen bonding in binary structure I clathrate hydrate with CO2

Guest-host hydrogen bonding in clathrate hydrates occurs when in addition to the hydrophilic moiety which causes the molecule to form hydrates under high pressure-low temperature conditions, the guests contain a hydrophilic, hydrogen bonding functional group. In the presence of carbon dioxide, ethanol clathrate hydrate has been synthesized with 10% of large structure I (sI) cages occupied by ethanol. In this work, we use molecular dynamics simulations to study hydrogen bonding structure and dynamics in this binary sI clathrate hydrate in the temperature range of 100-250 K. We observe that ethanol forms long-lived (>500 ps) proton-donating and accepting hydrogen bonds with cage water molecules from both hexagonal and pentagonal faces of the large cages while maintaining the general cage integrity of the sI clathrate hydrate. The presence of the nondipolar CO(2) molecules stabilizes the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The distortions of the large cages from the ideal form, the radial distribution functions of the guest-host interactions, and the ethanol guest dynamics are characterized in this study. In previous work through dielectric and NMR relaxation time studies, single crystal x-ray diffraction, and molecular dynamics simulations we have observed guest-water hydrogen bonding in structure II and structure H clathrate hydrates. The present work extends the observation of hydrogen bonding to structure I hydrates.     

The mobility of water molecules through gas hydrates

Crystal growth simulations of gas hydrates have suggested that hydrate cages may occasionally be occupied by H(2)O rather than guest molecules, leaving interstitial defects within the hydrate crystal. Further inspection of the behavior of these interstitial H(2)O molecules has revealed that they are relatively highly mobile entities within a gas hydrate. In this paper, we report these observations and examine the molecular mechanisms responsible for the transport of these interstitial molecules through hydrate crystals. Four distinct pathways for the H(2)O molecule transport between cages are found, each facilitated by the presence of empty cages. The relative richness of the observed behavior of interstitial defects suggests that interstitial diffusion could be an important mechanism for the mass transport of H(2)O molecules through gas hydrates.     

Communication: quantitative Fourier-transform infrared data for competitive loading of small cages during all-vapor instantaneous formation of gas-hydrate aerosols

A simple method has been developed for the measurement of high quality FTIR spectra of aerosols of gas-hydrate nanoparticles. The application of this method enables quantitative observation of gas hydrates that form on subsecond timescales using our all-vapor approach that includes an ether catalyst rather than high pressures to promote hydrate formation. The sampling method is versatile allowing routine studies at temperatures ranging from 120 to 210 K of either a single gas or the competitive uptake of different gas molecules in small cages of the hydrates. The present study emphasizes hydrate aerosols formed by pulsing vapor mixtures into a cold chamber held at 160 or 180 K. We emphasize aerosol spectra from 6 scans recorded an average of 8 s after "instantaneous" hydrate formation as well as of the gas hydrates as they evolve with time. Quantitative aerosol data are reported and analyzed for single small-cage guests and for mixed hydrates of CO(2), CH(4), C(2)H(2), N(2)O, N(2), and air. The approach, combined with the instant formation of gas hydrates from vapors only, offers promise with respect to optimization of methods for the formation and control of gas hydrates.