Raman Micro-Imaging of the Coexistence of sⅠ and sⅡ Hydrates Formed from a Mixed Methane-Propane Gas in a Confined Space

Natural gas hydrate contains a specific amount of heavy hydrocarbons, such as ethane, propane, etc., aside from the primary guest gas of methane. Although the coexistence of two or even three hydrate structures has been discovered at several hydrate sites, the requisite formation mechanism is still not well understood. In-situ observation of the formation process of mixed methane-propane hydrate in a confined space was conducted using confocal Raman imaging microscopy. The Raman imaging results reveal that sI methane hydrate and sII mixed methane-propane hydrate are formed and coexist in the reaction system. In the confined space, the sI hydrate originates from the dissolved gas in water, while the sII hydrate is formed from free gas. The results obtained can help explain the coexistence of sI and sII hydrates found in natural hydrate samples, as well as providing insights into a possible dynamic scenario of hydrate reservoirs in geological history.

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 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.

Effect of hydration on the surface basicity and catalytic activity of Mg-rare earth mixed oxides for aldol condensation

Magnesium and rare earth mixed oxides（Mg3 REOx（RE=La, Y. Ce）） were prepared and characterized by Xray diffraction（XRD）, N_2 adsorption-desorption, infrared spectra and microcalorimetry of CO_2. The results reveal that the Mg_3 CeO_x catalyst is present in the form of Mg-Ce-O solid solution,while the Mg3 LaOx and Mg_3 YO_x catalysts are probably rare earth oxides dispersed on MgO surface. As a result, among the calcined Mg_3 REO_x catalysts, the Mg_3 CeO_x catalyst presents the highest rate constant for acetone aldolization, which is well correlated to its more homogeneous distribution of basic sites. In contrary, the Mg_3 YO_x catalyst exhibit the lowest catalytic activity for acetone aldolization. Upon hydration pre-treatment, the basic properties on the surface of the Mg_3 REO_x catalysts were changed markedly. The Mg_3 YO_x catalyst after hydration treatment shows the highest amount of basic sites on catalyst surface, and then exhibits the highest activity among the hydrated Mg_3 REO_x catalysts. These results make it possible to fine-tune basic sites for acetone aldolization.