Spectroscopic Identification on CO2 Separation from CH4 + CO2 Gas Mixtures Using Hydroquinone Clathrate Formation

The formation of hydroquinone (HQ) clathrate and the guest behaviors of binary (CH4 + CO2) gas mixtures were investigated by focusing on an application to separate CO2 from landfill gases. Spectroscopic measurements show that at two experimental pressures of 20 and 40 bar, CO2 molecules are preferentially captured in HQ clathrates regardless of the gas composition. In addition, preferential occupation by CO2 is observed more significantly when the formation pressure and the CH4 concentration are lower. Because the preferential occupation of CO2 is found with binary (CH4 + CO2) gas mixtures regardless of the composition of the feed gas, a clathrate-based process can be applied to CO2 separation or concentration from landfill gases or (CH4 + CO2) mixed gases.

Migration and storage of methane in the Martian crust

<p>Several detections of methane in the Martian atmosphere have been reported from Earth-based and Mars orbit instruments with abundances ranging up to tens of ppbv, while in-situ measurements performed by the MSL rover at Gale crater showed some peaks up to 7 ppbv. A variety of methane formation mechanisms occurring in the subsurface have been proposed such as abiotic synthesis through Fischer-Tropsch Type (FTT) reactions. After its generation at depth, Martian methane can migrate upwards and be either directly released at the surface or trapped in subsurface reservoirs, such as clathrate hydrates, where it could accumulate over long time before being episodically liberated during destabilizing events. When ascending through stratigraphic layers, methane can move via one or several transport mechanisms. Seepage can occur through advection, the main CH<sub>4</sub> transport process on Earth, driven by pressure gradients and permeability and generally associated to fracture networks. Another transport mechanism is diffusion, which is mainly controlled by concentration gradient. This process is not efficient on short timescales and short-lived methane plumes related to diffusion should therefore originate from very shallow depths.</p><p>In this work, we model the subsurface transport of methane on Mars and its subsequent trapping in clathrate hydrates. For the latter, the effect of the clathrate formation pressure is especially examined, while methane subsurface transport is studied considering adsorption onto, advection and diffusion through the regolith.</p>

Unraveling nucleation pathway in methane clathrate formation

Methane clathrates are widespread on the ocean floor of the Earth. A better understanding of methane clathrate formation has important implications for natural-gas exploitation, storage, and transportation. A key step toward understanding clathrate formation is hydrate nucleation, which has been suggested to involve multiple evolution pathways. Herein, a unique nucleation/growth pathway for methane clathrate formation has been identified by analyzing the trajectories of large-scale molecular dynamics (MD) simulations. In particular, ternary water-ring aggregations (TWRAs) have been identified as fundamental structures for characterizing the nucleation pathway. Based on this nucleation pathway, the critical nucleus size and nucleation timescale can be quantitatively determined. Specifically, a methane hydration layer compression/shedding process is observed to be the critical step in (and driving) the nucleation/growth pathway, which is manifested through overlapping/compression of the surrounding hydration layers of the methane molecules, followed by detachment (shedding) of the hydration layer. As such, an effective way to control methane hydrate nucleation is to alter the hydration layer compression/shedding process during the course of nucleation.

Guest Partitioning and High CO2 Selectivity in Hydroquinone Clathrates Formed from Ternary (CO + CO2 + H2) Gas Mixtures

Clathrate formation and guest behaviors in hydroquinone (HQ) clathrates were investigated for the first time using ternary (CO + CO2 + H2) gas mixtures. Two gas compositions (low and high CO2 concentrations) were used to simulate synthesis gases generated from various sources. After reaction at 2.0, 4.0, and 6.0 MPa, the conversion yield of pure HQ to the clathrate form reached >90% if the CO2 partial pressure was 0.7 MPa or higher. In addition, CO2 was the most abundant occupant, whereas CO was only detectable at higher CO concentrations and experimental pressures. The separation efficiency values expressed as molar ratios of CO2 to CO in the solid clathrate form were found to be 12.7 and 23.9 MPa at 4.0 and 6.0 MPa, respectively. The experimental and the calculated results in this study provide information useful for the design of a clathrate-based separation process for synthesis gases from various sources (i.e., synthesis gases with various compositions).

Numerical modelling of permafrost spring discharge and open-system pingo formation induced by basal permafrost aggradation

In the high Arctic valley of Adventdalen, Svalbard, sub-permafrost groundwater feeds several pingo springs distributed along the valley axis. The driving mechanism for groundwater discharge and associated pingo formation is enigmatic because wet-based glaciers in the adjacent highlands and the presence of continuous permafrost seem to preclude recharge of the sub-permafrost groundwater system by either a sub-glacial source or a precipitation surplus. Since the pingo springs enable methane that has accumulated underneath the permafrost to escape directly to the atmosphere, our limited understanding of the groundwater system brings significant uncertainty to the understanding of how methane emissions will respond to changing climate. We address this problem with a new conceptual model for open-system pingo formation wherein pingo growth is sustained by sub-permafrost pressure effects during millennial scale basal permafrost aggradation. We test the viability of this mechanism for generating groundwater flow with decoupled heat (1D-transient) and groundwater (2D-steady-state) transport modelling experiments. Our results show that the pingos in lower Adventdalen easily conform to this conceptual model. Simulations suggest that the generally low-permeability hydrogeological units cause groundwater residence times that exceed the duration of the Holocene. The likelihood of such pre-Holocene groundwater ages is also supported by the hydrogeochemistry of the pingo springs, which demonstrate a sea-wards freshening of groundwater, potentially supplied by paleo-subglacial melting during the Weichselian. Such waters form a sub-permafrost fresh water wedge that progressively thins inland, where the duration of permafrost aggradation is longest. The mixing ratio of the underlying marine waters therefore increases in this direction because less unfrozen freshwater is available for mixing. Although this unusual hydraulic system is most likely governed by permafrost aggradation, the potential for additional pressurization is also explored. We conclude that methane production and methane clathrate formation may also affect hydraulic the pressure in sub-permafrost aquifers, but additional research is needed to fully establish their influence.

Crystal structures of three hexakis(fluoroaryloxy)cyclotriphosphazenes

The syntheses and crystal structures of three cyclotriphosphazenes, all with fluorinated aryloxy side groups that generate different steric characteristics, viz. hexakis(pentafluorophenoxy)cyclotriphosphazene, N3P3(OC6F5)6, 1, hexakis[4-(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H4(CF3)]6, 2 and hexakis[3,5-bis(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H3(CF3)2]6 3, are reported. Specifically, each phosphorus atom bears either two pentafluorophenoxy, 4-trifluoromethylphenoxy, or 3,5-trifluoromethylphenoxy groups. The central six-membered phosphazene rings display envelope pucker conformations in each case, albeit to varying degrees. The maximum displacement of the `flap atom' from the plane through the other ring atoms [0.308 (5) Å] is seen in 1, in a molecule that is devoid of hydrogen atoms and which exhibits a `wind-swept' look with all the aromatic rings displaced in the same direction. In 3 an intramolecular C—H(aromatic)...F interaction is observed. All the –CF3 groups in 2 and 3 exhibit positional disorder over two rotated orientations in close to statistical ratios. The extended structures of 2 and 3 are consolidated by C—H...F interactions of two kinds: (a) linear chains, and (b) cyclic between molecules related by inversion centers. In both 1 and 3, one of the six substituted phenyl rings has a parallel-displaced aromatic π–π stacking interaction with its respective symmetry mate with slippage values of 2.2 Å in 1 and 1.0 Å in 3. None of the structures reported here have solvent voids that could lead to clathrate formation.

Experimental Investigation of the Effect of Nanofluid on Thermal Energy Storage System Using Clathrate

Climatic change illustrates the need to new policy of load management. In this research, a special design of thermal energy storage (TES) system, with an appropriate storage medium that is suitable for residential and commercial buildings has been constructed and commissioned. Direct contact heat transfer is a significant factor to enhance the performance of TES. Numerous experimental runs were conducted to investigate the clathrate formation and the characteristics of the proposed TES cooling system; in addition, the effect of using nanofluid particles Al2O3 on the formation of clathrate under different operating parameters was evaluated. The experiments were conducted with a fixed amount of water 15 kg, mass of refrigerant to form clathrate of 6.5 kg, nanofluid particles concentration ranged from 0.5% to 2% and the mass flux of refrigerant varied from 150 to 300 kg/m2 s. The results indicate that there is a significant effect of using nanoparticles concentration on the charging time of the clathrate formation. The percentage of reduction in charging time of about 22% was achieved for high nanoparticles concentration. In addition, an enhancement in charging time by increasing the refrigerant flow rate reaches 38% when the mass flux varied from 200 to 400 kg/m2 s. New correlation describing the behavior of the temperatures with the charging time at different nanoparticles concentrations is presented.