Oxabicyclic Guest Compounds as sII Promoters: Spectroscopic Investigation and Equilibrium Measurements.

In this study, we investigate three oxabicyclic compounds, 3,6-dioxabicyclo[3. 1.0]hexane (C4H6O2, ETHF), 7-oxabicyclo[2.2.1]heptane (C6H10O, 14ECH), and 7-oxabicyclo[4.1.0]heptane (C6H10O, 12ECH) as novel promoters for gas hydrates. According to the outcomes of powder X-ray diffraction (PXRD) and synchrotron high-resolution powder diffraction (HRPD), all CH4 hydrates formed with ETHF, 14ECH, and 12ECH were identified to be sII (Fd-3m) hydrates with corresponding lattice parameters of 17.195, 17.330, and 17.382 Å, respectively. It was also clearly demonstrated that CH4 molecules are accommodated in the sII-S cages through solid-state 13C NMR and Raman spectra. Consequently, we clarified that the three compounds observed are large guest molecules (LGMs) that occupy the sII-L cages. Moreover, the thermodynamic stability of each LGM + CH4 (and N2) hydrate system was remarkably improved compared to that of the simple CH4 (and N2) hydrate. In particular, 14ECH manifested several unique features compared to the other two promoters. First, the 14ECH + CH4 hydrate did not dissociate up to room temperature (298 K), even at a moderate pressure of approximately 60 bar. At a given pressure, 14ECH increased the dissociation temperature of the CH4 hydrate by ~18 K, indicating that its promotion capability is as strong as that of tetrahydrofuran (THF), currently considered to be the most powerful promoter. Second, more interestingly, it was revealed by further PXRD, NMR, and Raman analyses that 14ECH forms a simple sII hydrate in the absence of help gases. According to differential scanning calorimetry (DSC) outcomes, we revealed that the simple 14ECH hydrate dissociates at 270~278 K under ambient pressure. In addition to the thermodynamic stability, we also note that the 14ECH + CH4 hydrate presented a sufficiently high temperature of formation, requiring little additional cooling. Given these promising features, we expect that the 14ECH hydrate system can be adopted to realize hydrate-based technologies. We also believe that the LGMs introduced here have considerable potential to serve as alternates to conventional promoters and that they can be widely utilized in both engineering and scientific research fields.

Epoxycyclopentane hydrate for sustainable hydrate-based energy storage: notable improvements in thermodynamic condition and storage capacity.

We suggest epoxycyclopentane (ECP) as a novel guest compound for hydrate-based energy storage. All of the key properties of the ECP hydrate, including the thermodynamic stability, storage capacity, and formation condition, are notably superior to those of hydrates containing tetrahydrofuran (THF) and cyclopentane (CP), currently considered to be the most powerful promoters.

Thermoresponsive Microcarriers for Smart Release of Hydrate Inhibitors under Shear Flow.

The hydrate formation in subsea pipelines can cause oil and gas well blowout. To avoid disasters, various chemical inhibitors have been developed to prevent or delay the hydrate formation and growth. Nevertheless, direct injection of the inhibitors results in environmental contamination and cross-suppression of inhibition performance in the presence of other inhibitors against corrosion and/or formation of scale, paraffin, and asphaltene. Here, we suggest a new class of microcarriers that encapsulate hydrate inhibitors at high concentration and release them on demand without active external triggering. The key to the success in microcarrier design lies in the temperature dependence of polymer brittleness. The microcarriers are microfluidically created to have an inhibitor-laden water core and polymer shell by employing water-in-oil-in-water (W/O/W) double-emulsion drops as a template. As the polymeric shell becomes more brittle at a lower temperature, there is an optimum range of shell thickness that renders the shell unstable at temperature responsible for hydrate formation under a constant shear flow. We precisely control the shell thickness relative to the radius by microfluidics and figure out the optimum range. The microcarriers with the optimum shell thickness are selectively ruptured by shear flow only at hydrate formation temperature and release the hydrate inhibitors. We prove that the released inhibitors effectively retard the hydrate formation without reduction of their performance. The microcarriers that do not experience the hydration formation temperature retain the inhibitors, which can be easily separated from ruptured ones for recycling by exploiting the density difference. Therefore, the use of microcarriers potentially minimizes the environmental damages.

Recovery of methane from gas hydrates intercalated within natural sediments using CO(2) and a CO(2)/N(2) gas mixture.

The direct recovery of methane from massive methane hydrates (MHs), artificial MH-bearing clays, and natural MH-bearing sediments is demonstrated, using either CO(2) or a CO(2)/N(2) gas mixture (20 mol % of CO(2) and 80 mol % of N(2), reproducing flue gas from a power plant) for methane replacement in complex marine systems. Natural gas hydrates (NGHs) can be converted into CO(2) hydrate by a swapping mechanism. The overall process serves a dual purpose: it is a means of sustainable energy-source exploitation and greenhouse-gas sequestration. In particular, scant attention has been paid to the natural sediment clay portion in deep-sea gas hydrates, which is capable of storing a tremendous amount of NGH. The clay interlayer provides a unique chemical-physical environment for gas hydrates. Herein, for the first time, we pull out methane from intercalated methane hydrates in a clay interlayer using CO(2) and a CO(2)/N(2) gas mixture. The results of this study are expected to provide an essential physicochemical background required for large-scale NGH production under the seabed.

Atomic hydrogen production from semi-clathrate hydrates.

Atomic hydrogen has received recent attention because of its potential role in energy devices, silicon devices, artificial photosynthesis, hydrogen storage, and so forth. Here, we propose a highly efficient route for producing atomic hydrogen using semi-clathrate hydrates. Two major hydrogen radical sources, derived from guest/host materials, are closely examined.