Catastrophic growth of gas hydrates in the presence of kinetic hydrate inhibitors.

The effect of the concentration of kinetic hydrate inhibitors, polyvinylpyrrolidone (PVP), and polyvinylcaprolactam (PVCap) on the onset and growth of synthetic natural gas hydrates is investigated by measuring the hydrate onset time and gas consumption rate. Although the hydrate onset time is extended by increasing the concentration from 0.5 to 3.0 wt % for both PVP and PVCap, the growth rate of hydrates shows that the different tendency depends on the type of kinetic hydrate inhibitor and its concentration. For PVCap solution, the hydrate growth was slow for more than 1000 min after the onset at the concentration of 0.5 and 1.5 wt %. However, the growth rate becames almost 8 times faster at the concentration of 3.0 wt %, representing the catastrophic growth of hydrate just after the hydrate onset. (13)C NMR spectra of hydrates formed at 3.0 wt % of PVP and PVCap indicate the existence of both structures I and II. Cage occupancy of methane in large cages of structure II decreases significantly when compared to that for pure water. These results suggest that increasing the concentration of KHI up to 3.0 wt % may induce the earlier appearance of catastrophic hydrate growth and the existence of metastable structure I; thus, there needs to be an upper limit for using KHI to manage the formation of gas hydrates.

Spectroscopic identification on cage occupancies of binary gas hydrates in the presence of ethanol.

Ethanol has been widely used for inhibiting gas hydrate formation due to its cost and efficiency. However, recent research showed that ethanol can act as a hydrate former when coguested with CH(4) molecules at various ethanol concentrations. Herein, we report tuning phenomenon of the gas hydrate in the presence of ethanol by means of spectroscopic measurements. On the basis of the experimental results, it is verified that ethanol molecules cannot inhibit hydrate formation effectively, but enhance the gas storage in the hydrate phase when a much less amount of the inhibitor than the stoichiometric concentration is used. The cage occupancies of binary hydrate systems in the presence of a thermodynamic inhibitor, showing similar guest behaviors in the presence of a promoter such as tetrahydrofuran (THF), can provide useful information on the molecular behaviors of guest species.

Tuning ionic liquids for hydrate inhibition.

Pyrrolidinium cation-based ionic liquids were synthesized, and their inhibition effects on methane hydrate formation were investigated. It was found that the ionic liquids shifted the hydrate equilibrium line to a lower temperature at a specific pressure, while simultaneously delaying gas hydrate formation.

Formation characteristics of synthesized natural gas hydrates in meso- and macroporous silica gels.

Phase equilibria and formation kinetics of the natural gas hydrate in porous silica gels were investigated using the natural gas composition in the Korean domestic natural gas grid. The hydrate-phase equilibria in the porous media are found to shift to the inhibition area than that in the bulk phase. The measured phase equilibrium data, combined with the Gibbs-Thomson equation, were used to calculate the hydrate-water interfacial tension. The value was estimated to be 59.74 +/- 2 mJ/m(2) for the natural gas hydrate. In addition, the inhibition effect is observed to be more significant in the meso-sized pore than the macro-sized one. In the formation kinetics, it was found that the hydrate formation reached the steady-state in a short period of time without mechanical stirring. Furthermore, the formation rate was found to be faster at 275.2 K than 273.2 K even though the driving force at 273.2 K is larger than that of 275.2 K. Even though the porous silica gels have smaller volume than other methods for gas storage, the gas consumption was found to be significantly enhanced in this study (for example, 120 vol/vol for the silica gels and 97 vol/vol for wet activated carbon). In this regard, using porous silica gels can be a potential alternative for gas storage and transportation as a nonmechanical stirring method. Although this investigation was performed with the natural gas composition in the Korean domestic grid, the results can also be expanded for designing or operating any hydrate-based process using various gas compositions.

Inhibition of natural gas hydrates in the presence of liquid hydrocarbons forming structure H.

The effects of LMGS (large molecule guest substance) amount on the thermodynamics of natural gas hydrates, as well as structural characteristics of mixed hydrates of LMGS and natural gas, have been studied. The addition of 1.7 wt % neohexane (NH) to water induced inhibition of natural gas hydrates, and this inhibition effect increased with increased addition of NH up to 7.8 wt %. However, the hydrate equilibrium condition changed slightly when the concentration of NH further increased from 7.8 to 14.5 wt %. Investigations on structural characteristics were carried out by analyzing (13)C NMR spectra of mixed hydrates formed from the mixture of natural gas and NH. They indicate that two hydrate structures of II and H coexist simultaneously, and the ratio of structure H to II decreased from 0.97 to 0.43 when the NH concentration decreased from 14.5 to 7.8 wt %. In addition, it was confirmed that ethane, propane, and iso-butane gas molecules do not participate in the formation of structure H and only enclathrated in large cages of structure II. These results indicate the existence of multiple hydrate structures, which must be considered in many industrial applications when mixed hydrates are formed from multicomponent gas mixtures and liquid hydrocarbons.

Structure and composition analysis of natural gas hydrates: 13C NMR spectroscopic and gas uptake measurements of mixed gas hydrates.

Gas hydrates are becoming an attractive way of storing and transporting large quantities of natural gas, although there has been little effort to understand the preferential occupation of heavy hydrocarbon molecules in hydrate cages. In this work, we present the formation kinetics of mixed hydrate based on a gas uptake measurement during hydrate formation, and how the compositions of the hydrate phase are varied under corresponding formation conditions. We also examine the effect of silica gel pores on the physical properties of mixed hydrate, including thermodynamic equilibrium, formation kinetics, and hydrate compositions. It is expected that the enclathration of ethane and propane is faster than that of methane early stage hydrate formation, and later methane becomes the dominant component to be enclathrated due to depletion of heavy hydrocarbons in the vapor phase. The composition of the hydrate phase seems to be affected by the consumed amount of natural gas, which results in a variation of heating value of retrieved gas from mixed hydrates as a function of formation temperature. 13C NMR experiments were used to measure the distribution of hydrocarbon molecules over the cages of hydrate structure when it forms either from bulk water or water in silica gel pores. We confirm that 70% of large cages of mixed hydrate are occupied by methane molecules when it forms from bulk water; however, only 19% of large cages of mixed hydrate are occupied by methane molecules when it forms from water in silica gel pores. This result indicates that the fractionation of the hydrate phase with heavy hydrocarbon molecules is enhanced in silica gel pores. In addition when heavy hydrocarbon molecules are depleted in the vapor phase during the formation of mixed hydrate, structure I methane hydrate forms instead of structure II mixed hydrate and both structures coexist together, which is also confirmed by 13C NMR spectroscopic analysis.