Freshwater Recovery and Removal of Cesium and Strontium from Radioactive Wastewater by Methane Hydrate Formation.

As human society has advanced, nuclear energy has provided energy security while also offering low carbon emissions and reduced dependence on fossil fuels, whereas nuclear power plants have produced large amounts of radioactive wastewater, which threatens human health and the sustainability of water resources. Here, we demonstrate a hydrate-based desalination (HBD) technology that uses methane as a hydrate former for freshwater recovery and for the removal of radioactive chemicals from wastewater, specifically from Cs- and Sr-containing wastewater. The complete exclusion of radioactive ions from solid methane hydrates was confirmed by a close examination using phase equilibria, spectroscopic investigations, thermal analyses, and theoretical calculations, enabling simultaneous freshwater recovery and the removal of radioactive chemicals from wastewater by the methane hydrate formation process described in this study. More importantly, the proposed HBD technology is applicable to radioactive wastewater containing Cs+ and Sr2+ across a broad concentration range of low percentages to hundreds of parts per million (ppm) and even subppm levels, with high removal efficiency of radioactive chemicals. This study highlights the potential of environmentally sustainable technologies to address the challenges posed by radioactive wastewater generated by nuclear technology, providing new insights for future research and development efforts.

Recovery of N2O: Energy-Efficient and Structure-Driven Clathrate-Based Greenhouse Gas Separation.

N2O has 300 times more global warming potential than CO2 and is also one of the main stratospheric ozone-depleting substances emitted by human activities such as agriculture, industry, and the combustion of fossil fuels and solid waste. We present here an energy-efficient clathrate-based greenhouse gas-separation (CBGS) technology that can operate at room temperature for selectively recovering N2O from gas mixtures. Clathrate formation between α-form/ß-form hydroquinone (α-HQ/ß-HQ) and gas mixtures reveals guest-specific and structure-driven selectivity, revealing the preferential capture of N2O in ß-HQ and the molecular sieving characteristics of α-HQ. With a maximum gas storage capacity and cage occupancy of 54.1 cm3 g-1 and 0.86, respectively, HQ clathrate compounds including N2O are stable at room temperature and atmospheric pressure and thus can be easily synthesized, treated, and recycled via commercial CBGS processes. High selectivity for N2O recovery was observed during ß-HQ clathrate formation from N2O/N2 gas mixtures with N2O concentrations exceeding 20%, whereas α-HQ traps only N2 molecules from gas mixtures. Full characterization using X-ray diffraction, scanning electron microscopy, Raman spectroscopy, solid-state nuclear magnetic resonance, and compositional analysis and the formation kinetics of HQ clathrates was conducted to verify the peculiar selectivity behavior and to design the conceptual CBGS process. These results provide a new playground on which to tailor host-guest materials and develop commercial processes for the recovery and/or sequestration of greenhouse gases.

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N2O-N2) binary gas hydrates formed from N2O/N2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N2O-N2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N2O-N2 binary gas hydrate formed from N2O/N2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N2O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N2O molecules for the N2O-N2 binary gas hydrate formed from the N2O/N2 (20/80 mol %) gas mixture, indicating that N2O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N2O-N2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N2O molecules rather than N2 molecules in the hydrate cages, leading to a possible process for separating N2O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N2O-N2 binary gas hydrates are discussed in detail.

Equilibrium, Kinetics, and Spectroscopic Studies of SF6 Hydrate in NaCl Electrolyte Solution.

Many studies have focused on desalination via hydrate formation; however, for their potential application, knowledge pertaining to thermodynamic stability, formation kinetics, and guest occupation behavior in clathrate hydrates needs to be determined. Herein, the phase equilibria of SF6 hydrates in the presence of NaCl solutions (0, 2, 4, and 10 wt %) were monitored in the temperature range of 277-286 K and under pressures of up to 1.4 MPa. The formation kinetics of SF6 hydrates in the presence of NaCl solutions (0, 2, and 4 wt %) was also investigated. Gas consumption curves of SF6 hydrates showed that a pure SF6 hydrate system allowed fast hydrate growth as well as high conversion yield, whereas SF6 hydrate in the presence of NaCl solutions showed retarded hydrate growth rate as well as low conversion yield. In addition, structural identification of SF6 hydrates with and without NaCl solutions was performed using spectroscopic tools such as Raman spectroscopy and X-ray diffraction. The Raman spectrometer was also used to evaluate the temperature-dependent release behavior of guest molecules in SF6 and SF6 + 4 wt % NaCl hydrates. The results indicate that whereas SF6 hydrate starts to decompose at around 240 K, the escape of SF6 molecules in SF6 + 4 wt % NaCl hydrate is initiated rapidly at around 205 K. The results of this study can provide a better understanding of guest-host interaction in electrolyte-containing systems.

Thermodynamic stability, spectroscopic identification, and gas storage capacity of CO2-CH4-N2 mixture gas hydrates: implications for landfill gas hydrates.

Landfill gas (LFG), which is primarily composed of CH(4), CO(2), and N(2), is produced from the anaerobic digestion of organic materials. To investigate the feasibility of the storage and transportation of LFG via the formation of hydrate, we observed the phase equilibrium behavior of CO(2)-CH(4)-N(2) mixture hydrates. When the specific molar ratio of CO(2)/CH(4) was 40/55, the equilibrium dissociation pressures were gradually shifted to higher pressures and lower temperatures as the mole fraction of N(2) increased. X-ray diffraction revealed that the CO(2)-CH(4)-N(2) mixture hydrate prepared from the CO(2)/CH(4)/N(2) (40/55/5) gas mixture formed a structure I clathrate hydrate. A combination of Raman and solid-state (13)C NMR measurements provided detailed information regarding the cage occupancy of gas molecules trapped in the hydrate frameworks. The gas storage capacity of LFG hydrates was estimated from the experimental results for the hydrate formations under two-phase equilibrium conditions. We also confirmed that trace amounts of nonmethane organic compounds do not affect the cage occupancy of gas molecules or the thermodynamic stability of LFG hydrates.

Structural transformation and guest dynamics of methanol-loaded hydroquinone clathrate observed by temperature-dependent Raman spectroscopy.

The structural transformations and guest dynamics of methanol-loaded ß-form hydroquinone (HQ) clathrate were investigated using temperature-dependent Raman spectroscopy. Methanol-loaded ß-form HQ clathrate was obtained by recrystallization and characterized by elemental analysis, synchrotron X-ray diffraction, solid-state (13)C NMR spectroscopy, and Raman spectroscopy. Temperature-dependent Raman spectra of methanol-loaded ß-form HQ clathrate were measured in the temperature range 300-412 K at increments of 4 K. Although no significant changes were evident in the temperature range 300-376 K, abrupt changes in the relative intensity and shape of the Raman bands were observed between 380 and 412 K indicating the structural transition from methanol-loaded ß-form HQ clathrate to pure α-form HQ. Methanol molecules were gradually released from the ß-form HQ clathrate in the range 364-380 K. Upon returning to ambient conditions, the crystal structure of the HQ sample remained identical to that of pure α-form HQ. Therefore, the temperature-induced structural transition of methanol-loaded HQ clathrate is completely irreversible and α-form HQ is more stable at ambient conditions.

Probing structural transition and guest dynamics of hydroquinone clathrates by temperature-dependent terahertz time-domain spectroscopy.

The structural transition from hydroquinone clathrates to crystalline α-form hydroquinone was observed up to the range of 3 THz frequency as a function of temperatures. We found that all three hydroquinone clathrates, CO(2)-, CH(4)-, and CO(2)/CH(4)-loaded hydroquinone clathrates, transform into the α-form hydroquinone at around 102 ± 7 °C. The resonance peak of the CO(2)-loaded hydroquinone clathrate at 2.15 THz decreases with increasing temperature, indicating that CO(2) guest molecules are readily released from the host framework prior to the structural transformation. This reveals that the hydroquinone clathrates may transform into the stable α-form hydroquinone via the metastable form of guest-free clathrate, which depends on guest molecules enclathrated in the cages of the host frameworks. A strong resonance of the α-form hydroquinone at 1.18 THz gradually shifts to the low frequency with increasing temperature and shifts back to the high frequency with decreasing temperature.

Hydrogen molecules trapped in interstitial host channels of alpha-hydroquinone.

Easy come, easy go: Hydroquinone forms a channel structure of cages with hydrogen-bonded hexagons. These may provide an ideal route for the fast inclusion and facile release of hydrogen molecules (see figure), which can lead to reversible hydrogen storage under mild conditions.

High pressure investigation of alpha-form and CH4-loaded beta-form of hydroquinone compounds.

The high pressure compression behaviors of two hydroquinone compounds have been investigated using a combination of in situ synchrotron x-ray powder diffraction and Raman spectroscopy up to ca. 7 GPa. The structural integrity of the alpha-form hydroquinone clathrate is maintained throughout the pressure range, whereas the CH(4)-loaded beta-form hydroquinone clathrate decomposes and transforms to a new high pressure phase near 5 GPa. The bulk modulus (K) and its pressure derivative (K(')) of the alpha-form and the CH(4)-loaded beta-form hydroquinones are measured to be 8.2(3) GPa and 8.4(4), and 10(1) GPa and 9(2), respectively, representing one of the most compressible classes of crystalline solids reported in the literature. The corresponding axial compression behaviors, however, show greater contrast between the two hydroquinone compounds; the elastic anisotropy of the alpha-form is only marginal, being K(a):K(c) = 1.08:1, whereas that of the CH(4)-loaded beta-form is rather drastic, being K(a):K(c) = 11.8:1. This is attributed to the different dimensionality of the hydrogen bonding networks between the two structures and might in turn explain the observed structural instability of the beta-form, compared to the alpha-form.

Relationship between metabolic syndrome categorized by newly recommended by International Diabetes Federation criteria with plasma homocysteine concentration.

Plasma total homocysteine (tHcy) is an independent risk factor for cardiovascular disease and increased tHcy levels have been reported to be a novel risk factor of atherosclerotic disease. The aim of this study was to assess the association of the metabolic syndrome components with plasma (tHcy) level. Total 722 participants (284 men, 438 women) from the medical checkup program were enrolled in this study. The clinical characteristics and biochemical parameters of the subjects were assessed and the tHcy levels were compared according to the components of metabolic syndrome diagnosed by Adult Treatment Panel (ATP) III guideline and International Diabetes Federation (IDF) criteria. Among the components, groups with larger waist circumference and higher fasting blood glucose levels showed significantly higher tHcy level than the counterparts. Although statistically insignificant, mean concentrations of tHcy was higher in subjects with metabolic syndrome defined by both criteria. In multiple regression analysis, age, sex and systolic blood pressure were the independent determinants of tHcy level. In conclusion, tHcy level was not associated with metabolic syndrome defined by either criteria in Korean subjects.

Highly selective encaging of carbon dioxide molecules in the mixed carbon dioxide and nitrogen hydrate at low temperatures.

The structural identification and guest compositions of the mixed CO(2) and N(2) hydrates at low temperature conditions were investigated by both theoretical predictions and experimental measurements. From the model calculations, at very low temperatures, the highly CO(2)-concentrated hydrates over 95 mol % CO(2) on the basis of water-free concentration could coexist with the gas mixtures of low CO(2) concentrations in equilibrium. X-ray diffraction measurements of the hydrates formed with the gas mixture of 3.16 mol % CO(2) and balanced N(2) indicate that the formed hydrates at all conditions considered in this study were identified as structure I, whereas the model predicts a structural transition to structure II around 220 K. However, it was also found that the formed hydrate samples contain a considerable amount of hexagonal ice resulting from incomplete conversion of ice to the hydrates. The compositional analysis suggests that a favorable encaging of CO(2) in the mixed hydrate can be obtained by the hydrate formation at low temperatures and relative amount of CO(2) molecules in the mixed hydrates increases with a decrease of temperature.

Pressure-dependent release of guest molecules and structural transitions in hydroquinone clathrate.

Structural phase transitions of N2-loaded and guest-free hydroquinone (HQ) clathrates have been investigated as a function of pressure using synchrotron X-ray diffraction and Raman spectroscopy. The N2-loaded ß-form HQ clathrate reveals a structural transition to a new high pressure phase near 4 GPa and exhibits gradual N2 release from the hydrogen-bonded organic framework (HOF) cage with a further increase in pressure. Upon reducing the pressure to ambient conditions, the crystal structure reverts to the original ß-form HQ clathrate, indicating that the pressure-induced structural transition is fully reversible. In contrast, around 0.4 GPa, the guest-free ß-form HQ clathrate undergoes an irreversible phase transition to the nonporous α-form HQ, which is retained at ambient conditions. These results suggest that HOF encaged guest molecules play an important role in the structural transitions under high pressure.

Gas-phase synthesis and characterization of CH4-loaded hydroquinone clathrates.

A CH(4)-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the alpha-form of crystalline HQ and CH(4) gas at 12 MPa and room temperature. Solid-state (13)C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH(4) molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH(4) molecules, that is, 0.69 CH(4) per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH(4)-loaded HQ clathrate adopts the beta-form of HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 A and c = 5.5038 A. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH(4)-loaded HQ clathrate is stable up to 368 K and gradually transforms to the alpha-form by releasing the confined CH(4) gases between 368-378 K. Using solid-state (13)C CP/MAS NMR, the reaction kinetics between the alpha-form HQ and CH(4) gas is qualitatively described in terms of the particle size of the crystalline HQ.