Ice-Shielding Models for Self-Preservation of Gas Hydrates

The self-preservation of methane hydrate is a key process in its engineering applications because the hydrate can survive for a significant period under atmospheric pressure and moderate temperature. Some experiments have predicted that the shielding ice formed on the hydrate surface after initial dissociation of the hydrate plays an important role in the self-preservation effect. We propose ice-shielding models of gas hydrates to investigate the dissociation rates quantitatively, including the self-preservation process, at temperatures below the ice-melting point and at atmospheric pressure. Three general models are constructed for two temperature ranges The rate-determining process for the lower temperature range is hydrate dissociation, and those for the higher range are gas diffusion through ice or hydrate layers, which depend on the thickness of the shielding-ice layer. Our models suggest that the extent of self-preservation depends on temperature, original hydrate size, and guest substances, which can explain the experimental results.

A covering liquid method to intensify self-preservation effect for safety of methane hydrate storage and transportation

In this work,experiments and comprehensive insights into the proposed covering liquid method to intensify self-preservation effect for methane(CH_(4))storage are presented.The CH_(4)hydrate decomposition percentage was 17.6%with the pressure of 0.61 MPa after 12 h at 266.0 K without a covering liquid,which can be reduced to 12.4%,13.8%,13.0%,and 8.3%with the pressure of 0.26 MPa,0.33 MPa,0.51 MPa,and 0.37 MPa by covering with tetrahydrofuran(THF),cyclopentane(CP),cyclohexane,and n-tetradecane,respectively.When the temperature for CH_(4)hydrate decompositionwas 274.2 K,covering with THF,CP,cyclohexane,and n-tetradecane failed to inhibit CH_(4)hydrate decomposition.The results suggested that the covering liquid may form a new solid layer(a hydrate layer or other solidified layer)around the CH_(4)hydrate,which inhibit CH_(4)transfer below the freezing point of water.However,the new solid layer cannot resist the fast transfer of CH_(4)from decomposed CH_(4)hydrate above the freezing point of water.The same phenomenon was also observed in a sodium dodecyl sulfonate(SDS)-dry solution CH_(4)hydrate formation system.Therefore,the covering method can only intensify the self-preservation effect below the freezing point of water,but cannot generate a self-preservation effect.

Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15 K

It is known that salt ions are abundant in the natural environment where natural gas hydrates are located;thus,it is essential to investigate the self-preservation effect of salt ions on methane hydrates.The dissociation behaviors of gas hydrates formed from various NaCl concentration solutions in a quartz sand system at 268.15 K were investigated to reveal the microscopic mechanism of the self-preservation effect under different salt concentrations.Results showed that as the salt concentration rises,the initial rate of hydrate decomposition quickens.Methane hydrate hardly shows self-preservation ability in the 3.35%(mass)NaCl and seawater systems at 268.15 K.Combined the morphology of hydrate observed by the confocal microscope with results obtained from in situ Raman spectroscopy,it was found that during the initial decomposition stage of gas hydrate below the ice point,gas hydrate firstly converts into liquid water and gas molecules,then turns from water to solid ice rather than directly transforming into solid ice and gas molecules.The presence of salt ions interferes with the ability of liquid water to condense into solid ice.The results of this study provide an important guide for the mechanism and application of the self-preservation effect on the storage and transport of gas and the exploitation of natural gas hydrates.

Molecular dynamics simulation for surface melting and self-preservation effect of methane hydrate

The surface melting process of structure sI methane hydrate is simulated at T = 240, 260, 280, and 300 K using NVT molecular dynamics method. The simulation results show that a quasi-liquid layer will be formed during the melting process. The density distribution, translation, orientation, and dynamic properties of water molecules in the quasi-liquid layer are calculated as a function of the distance normal to the interface, which indicates the performance of quasi-liquid layer exhibits a continuous change from crystal-like to liquid-like. The quasi-liquid layer plays as a resistance of mass transfer restraining the diffusion of water and methane molecules during the melting process. The resistance of quasi-liquid layer will restrain methane molecules diffuse from hydrate phase to gas phase and slow the melting process, which can be considered as a possible mechanism of self-preservation effect. The performance of quasi-liquid layer is more crystal-like when the temperature is lower than the melt- ing-point of water, which will exhibit an obvious self-preservation. The self-preservation will weaken while the temperature is higher than the melting-point of water because of the liquid-like performance of the quasi-liquid layer.

Metastable state of gas hydrate during decomposition: A novel phenomenon

Natural gas hydrates are solid compounds with cage-like structures formed by gas and water.An intriguing phenomenon that gas hydrates can dissociate at a low rate below the ice freezing point has been viewed as the metastability of hydrate.The mechanisms of hydrate metastability have been widely studied,and many mechanisms were proposed involving the self-preservation effect,supercooled water-gas-hydrate metastable equilibrium,and supersaturated liquid-gas-hydrate system etc.The metastable state of hydrate could be of crucial significance in the kinetics of hydrate formation and decomposition,heat and mass transfer during gas production processes,and the application of hydrate-based technique involving desalination,energy storage and transportation,and gas separation and sequestration.Few researches have systematically considered this phenomenon,and its mechanism remains unclear.In this work,various mechanisms and hypothesis explaining the metastable state of gas hydrates were introduced and discussed.Further studies are still required to reveal the intrinsic nature of this metastable state of gas hydrate,and this work could give some implications on the existing theory and current status of relevant efforts.

Estimation of ultra-stability of methane hydrate at 1 atm by thermal conductivity measurement

Thermal conductivity of methane hydrate was measured in hydrate dissociation self-preservation zone by means of the transient plane source（TPS） technique developed by Gustafsson.The sample was formed from 99.9%（volume ratio） methane gas with 280 ppm sodium dodecyl sulfate（SDS） solution under 6.6 MPa and 273.15 K.The methane hydrate sample was taken out of the cell and moved into a low temperature chamber when the conversion ratio of water was more than 90%.In order to measure the thermal conductivity,the sample was compacted into two columnar parts by compact tool at 268.15 K.The measurements are carried out in the temperature ranging from 263.15 K to 271.15 K at atmospheric pressure.Additionally,the relationship between thermal conductivity and time is also investigated at 263.15 K and 268.15 K,respectively.In 24 h,thermal conductivity increases only 5.45% at 268.15 K,but thermal conductivity increases 196.29% at 263.15 K.Methane hydrates exhibit only minimal decomposition at 1 atm and the temperature ranging from 263.15 K to 271.15 K.At 1 atm and 268.15 K,the total gas that evolved after 24 h was amounted to less than 0.71% of the originally stored gas,and this ultra-stability was maintained if the test was lasted for more than two hundreds hours before terminating.

THE NEW METHOD OF SOLVING VELOCITY CORRELATION FUNCTIONS AND APPLICATION TO THE PLANE TURBULENT WAKE

The results of plane turbulent wake given by Chou Peiyuan are considered as the first order ap- proximation and put into the equations of turbulent fluctuation.The equations are solved numerically within the range of micro-scale by means of spectrum method.The double,triple and quadruple fluctuating velocity correlations are obtained by computation.They are in good agreement with experimental results.

The Identity of nds in Ancient Egypt

nds as a civilian group,completed the formation of the group through self-identity and the public recognition was as an external feedback of their self-awareness awakening.The life-or-death moment promoted the nds s group cohesion and inspired their group survival consciousness.Therefore,the study of nds can be a good breakthrough and reference for the study of other commoner groups in ancient Egypt.

Two-component Brownian coagulation: Monte Carlo simulation and process characterization

The compositional distribution within aggregates of a given size is essential to the functionality of com- posite aggregates that are usually enlarged by rapid Brownian coagulation, There is no analytical solution for the process of such two-component systems, Monte Carlo method is an effective numerical approach for two-component coagulation, In this paper, the differentially weighted Monte Carlo method is used to investigate two-component Brownian coagulation, respectively, in the continuum regime, the free-molecular regime and the transition regime. It is found that （1） for Brownian coagulation in the continuum regime and in the free-molecular regime, the mono-variate compositional distribution, i.e., the number density distribution function of one component amount （in the form of volume of the component in aggregates） satisfies self-preserving form the same as particle size distribution in mono-component Brownian coagulation; （2） however, for Brownian coagulation in the transition regime the mono-variate compositional distribution cannot reach self-similarity; and （3） the bivariate compositional distribution, i.e., the combined number density distribution function of two component amounts in the three regimes satisfies a semi self-preserving form. Moreover, other new features inherent to aggregative mixing are also demonstrated; e.g., the degree of mixing between components, which is largely controlled by the initial compositional mass fraction, improves as aggregate size increases.