Filippo Maccioni

Dissociation Rate of THF-methane Hydrates

Abstract A number of papers and research projects suggest that stranded natural gas can be transported in a solid hydrate state at higher temperatures or lower pressures compared to conventional transportation systems (LNG and CNG). The self-preservation effect of methane hydrate can probably be improved by the use of a third component besides CH4 and water. Tetrahydrofuran (THF) is a promoter that greatly reduces the required formation pressures. In the present work the influence of THF on the decomposition kinetics of mixed THF-CH4 hydrates was studied to evaluate the THF stabilization effect. The experimental work, carried out with the help of a reaction calorimeter, has revealed that the dissociation rate of mixed THF hydrates is lower (on average by one order of magnitude) than that of simple methane hydrates. Mixed hydrates can also be stored for short periods at temperatures over 0°C. However, the best preservation conditions (among the experimented ones) are realized at −1°C and 3 MPa. (about 66 days required for complete dissociation).

FORMATION AND DISSOCIATION OF CO2 AND CO2 – THF HYDRATES COMPARED TO CH4 AND CH4 - THF HYDRATES

. This work is part of a research project sponsored by the Italian Electricity Agency for CO2 disposal in form of hydrate. The dissociation behavior of CH4 hydrate was taken as a reference for the study of the CO2 hydrate preservation. The formation and dissociation of CO2 and CO2–THF mixed hydrates, compared to CH4 and CH4 – THF mixed hydrates, has been considered. The experimental tests were performed in a 2 liter reaction calorimeter at pressures between 0.1 and 0.3 MPa. The dissociation has been followed at temperatures from -3 °C to 0 °C for CO2 and CH4 hydrates, and from -3 °C to 10 °C for THF mixed hydrates. More than pressure, which is very important for methane hydrates, temperature affects the preservation of CO2 and CO2–THF mixed hydrates. Subcooling after formation is important for methane hydrate preservation, but it does not substantially affect CO2 hydrate stability. In the studied P, T range, CO2 hydrate does not present any anomalous self-preservation effect. The mixtures containing more ice show a slower dissociation rate. Methane hydrate requires less energy to dissociate than CO2 hydrate and, therefore, is less stable. On the contrary, the mixed CO2 – THF hydrates are less stable than the mixed methane hydrates. Modulated differential scanning calorimetry (MDSC) has been used for hydrate characterization: both CH4 and CO2 hydrates include two decomposition peaks, the first due to the melting of the ice and the second to the decomposition of the hydrate. The higher temperature of the decomposition peak of CO2 hydrate confirms its higher stability respect to CH4 hydrate.

Characterization of Gas Hydrates by Modulated Differential Scanning Calorimetry

Abstract Modulated Differential Scanning Calorimetry (MDSC) has been applied to the study of methane, ethane, and propane hydrates at different hydrate and ice concentrations. The reversing thermodynamical component of the MDSC curves, makes it possible to characterize such hydrates. Methane and ethane hydrates show the melting-decomposition peak at a temperatures higher than the ice contained in the sample, while propane hydrate melts and decomposes at a lower temperature than the ice present in the sample. The hydrate peaks tend to disappear if the hydrate is stored at atmospheric pressure. Guest size and cavity occupation fix the heat of dissociation and stability of the hydrates, as confirmed by parallel tests on tetrahydrofurane hydrates.

A HIGH YIELD PROCESS FOR HYDRATE FORMATION

A new procedure was studied to obtain concentrated methane hydrates in bulk, at medium-low pressure, avoiding the use of the spray process. Methane hydrate was formed at about 5 MPa and 2 °C in a reaction calorimeter with the volume of two liters. The clathrate concentration was about 30% and the final reactor pressure was 2.7 MPa. Any further repressurization at 2 °C had no noticeable effect on the hydrate formation. However, by repressurizing the vessel again to 4 MPa and increasing the temperature near the decomposition value (about 6° C) more clathrate was formed. Repressurizing again the reactor at 4 MPa and controlling the temperature at the same level, a concentration of 88% hydrate in the bulk was reached. Respect to the hydrate produced by the spray process, this procedure takes more time, but it can be sped up and made continuous by using teo reaction vessels, one for hydrate formation and the other for hydrate concentration. The advantage is the production of concentrated hydrates, by a simple equipment, working at relatively low pressures.