• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.150.2-150.2
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• 2011

Unlike non-ionic clathrate hydrates stably formed by van der Waals interaction between a guest molecule and a surrounding host framework, ionic clathrate hydrates are stabilized by ionic interaction between an ionic guest molecule and the host water-framework. Here, we firstly described the stable entrapment of the superoxide ions in ${\gamma}$-irradiated $Me_4NOH+O_2$ hydrate. Owing to peculiar direct guest-guest ionic interaction, the lattice structure of ${\gamma}$-irradiated $Me_4NOH+O_2$ hydrate shows significant change of lattice contraction behavior even at relatively high temperature(120K). Particularly, we note that ionic-induced dimensional change is much greater than thermal-induced change. Such findings are expected to provide useful information for a better understanding of unrevealed nature of clathrate hydrate fields.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.150.1-150.1
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• 2011

Structure-II hydrate has been highlighted due to its higher gas storage capacity and favorable thermodynamic conditions. In this study, we introduce a new structure-II hydrate former, tert-butyl hydroperoxide (TBHP) and confirm the structural characteristics through High-Resolution Powder Diffraction (HRPD), $^{13}C$ solide-state NMR and Ramanspectroscopy. Here,we also investigated the thermodynamic stability of binary(TBHP+gaseous) clathrate hydrates. The experimental data were generated using an isochoric pressure-search method. The dissociation data for (TBHP +gaseous) clathrate hydrates are compared with the other hydrocarbon hydrate and pure gaseous hydrate.

• Korean Chemical Engineering Research
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• v.46 no.6
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• pp.1095-1099
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• 2008

In this study, we investigated that hydrate formation and phase behavior of the $THF+H_2$ binary clathrate hydrates. In order to confirm the binary clathrate hydrate formation we employed the Raman and NMR spectroscopies that are known to be quite powerful tools, particularly for examining the cage occupancy pattern of guest molecules. In addition, we traced the P-T profiles from clathrate hydrate formation and dissociation process, which made it possible for the resulting phase equilibrium boundary to be clearly established. In the binary clathrate hydrate matrix we further identified that the relatively large THF molecules can only occupy the large $5^{12}6^4$ cavities, while the small $H_2$ molecules are entrapped in the empty $5^{12}$ cavities in structure-II, making the hydrate to be stable above 273 K even at relatively low pressure condition. Considering that pure $H_2$ hydrate can be produced at the extreme pressures higher that 1,000 bar, we can conclude that the water-soluble second guest inclusion induces $H_2$ storage and transportation to be readily achievable under much milder conditions.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.146.2-146.2
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• 2011

Molecular behaviors and crystal structures of the binary hydrates of $CH_4$ and ethanol were identified by means of 13C solid-state NMR and powder XRD methods at various concentrations of ethanol. In addition, NMR peak areas were used to calculate cage occupancies for both guest species. Obtained results showed that more $CH_4$ molecules are captured into hydrate phase per unit mass of ethanol molecules because $CH_4$ molecule can occupy sII large cages more, and pure $CH_4$ hydrate can form more as well at lower ethanol concentrations. Even though tuning phenomenon was already reported for some aqueous hydrate promoters such as THF, aqueous ethanol solutions are found to play the same tuning role in the binary clathrate hydrates in this study.

• Korean Chemical Engineering Research
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• v.49 no.3
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• pp.367-371
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• 2011

TBAB (tetra-n-butyl ammonium bromide) forms a semi-clathrate with water under atmospheric pressure conditions and recently has attracted great attention due to its usage as a thermodynamic promoter in gas storage and separation process using gas hydrate formation. In this study, we measured the three-phase (hydrate (H) - liquid water ($L_{w}$)-vapor (V)) equilibria of the ternary $CH_{4}$+TBAB+water and $CO_{2}$+TBAB+water mixtures at the TBAB concentrations of 5 and 32 wt% to investigate promoting characteristics of TBAB. The greater promotion effect of TBAB was observed at 32 wt% than at 5 wt%. This result was in good agreement with that from pure TBAB semi-clathrate phase diagram under atmospheric pressure conditions. Through $^{13}C$ NMR analysis of the $CH_{4}$+TBAB semi-clathrate, it was found that $CH_{4}$ molecules are enclathrated in the cages of the double semi-clathrate and the position of resonance peak from encaged $CH_{4}$ molocules in the double semi-clathrate is the same as that from encaged $CH_{4}$ molocules in the pure $CH_{4}$ hydrate of structure I.

• 한국신재생에너지학회:학술대회논문집
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• 2010.11a
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• pp.153.1-153.1
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• 2010

가스 하이드레이트는 낮은 온도와 높은 압력에서 물과 천연가스 분자가 물리적으로 안정한 결합을 하고 있는 결정질의 화합물이다. 현재 130개 이상의 가스분자들이 물분자와 결합하여서 Clathrate 하이드레이트를 형성하는 것으로 보고 되어 있다. 수소의 경우 하이드레이트를 형성하기 위해서 약 200MPa 이상의 높은 압력이 필요하다. TBAB는 semi-clathrate 하이드레이트를 형성하는 첨가제로 알려져 있으며 수소 하이드레이트의 형성 압력을 완화시키기 위한 촉진제로서 많은 연구가 수행되고 있다. Wataru Shimada는 XRD 패턴을 사용하여 semi-clathrate 하이드레이트의 특수한 결정 모델을 분석하였다. 이 모델의 경우, 대기압 하에서 TBAB와 물분자의 화학 양론적 비를 1:38로 제시하였다. 이는 처음으로 TBAB 하이드레이트 결정구조를 밝혀냈지만, 분자 동역학적 부문에서는 그 데이터가 정확히 정의 되지 않았다. 본 연구는 Wataru Shimada 모델을 수소 TBAB 하이드레이이트의 분자 동역학 연구에 적용시켰으며, 실험에서 나온 데이터를 바탕으로 RDF(Radial Distribution Function)와 MSD(Mean Square Displacement)를 측정했다.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.391-394
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• 2006

Growth characteristics of methane-propane clathrate hydrate, growing under different undercooling conditions, was investigated. After the water within pressurized vessel was fully saturated with guest gas molecules by agitation, medium was rapidly undercooled and maintained at the constant temperature. The growth of hydrate was always Initiated with film formations at the upper bounding surface of liquid pool. The visual observation using microscope revealed detailed features of subsequent crystal nucleation, migration, growth and interference occurring within liquid pool. A number of small crystals ascended and settled at the hydrate film. When undercooling was small $({\Delta}T=3.2K)$, some of the settled crystals slowly grew into faceted columns. As the undercooling increased, the downward growth of crystals underneath the hydrate film became dendritic and occurred with greater rate and with finer arm spacing. The shapes of the floating crystals were diverse and included octahedron and triangular or hexagonal platelet When the undercooling was small, the octahedral crystals were found dominant. As the undercooling increased, the shape of the floating crystals also became dendritic. The detailed characteristics of floating crystals were reported in this study.

• Proceedings of the KSME Conference
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• 2003.04a
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• pp.1663-1666
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• 2003

TMA clathrate that is used by PCM of ice storage system in this research creates hydrate crystallization at higher temperature than pure water, and application is expected as PCM because having comparative big dormant temperature without phase separation phenomenon. In case this research uses TMA clathrate by PCM, choose admixture by purpose to control or remove subcooling of TMA clathrate and evaluated experimentally. Subcooling is improved and can expect contraction of freezing machine running time and increase of coefficient of performance as that add admixture to TMA clathrate conclusively. Also, may supply thermal storage system that apply low temperature potential heat thermal storage material that subcooling is improved more extensively laying stress on medium size building and small size building, can expect allowance through localization of ice storage system.

• Korean Chemical Engineering Research
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• v.61 no.3
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• pp.394-400
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• 2023

In this study, the tuning phenomena, gas storage capacity, and thermal expansion behaviors of binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates were investigated for the potential applications of clathrate hydrates to gas storage. To understand the tuning behaviors of binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates, ¹³C solid-state NMR spectroscopy was used, and the results confirmed that maximum tuning factors for the binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates were achieved at 0.5 mol% and 1.0 mol% of guest concentration, respectively. The gas storage capacity of binary (cyclopentylamine + CH₄) and (cyclopropylamine + CH₄) clathrate hydrates were also checked, and the results showed the CH₄ capacity of our hydrate systems was superior to that of binary (tetrahydrofuran + CH₄) and (cyclopentane + CH₄) clathrate hydrates. The synchrotron diffraction patterns of these hydrates collected at 100, 150, 200, and 250 K confirmed the formation of a cubic Fd-3m hydrate. In addition, the lattice constant of clathrate hydrates with cyclopentylamine and methane were larger than that with cyclopropylamine and methane due to the effects of molecular size and shape.

• Proceedings of the KSME Conference
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• 2003.11a
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• pp.250-255
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• 2003

TMA clathrate that is used as PCM of low temperature thermal storage system in this research creates hydrate crystallization at higher temperature then pure water, and its application is expected as PCM because of comparatively big latent heat without phase separation phenomenon. Acetone, Ethylen Glycol, and Ethanol is used as additive and evaluated experimentally for the purpose of the improvement in subcooling of TMA clathrate. In view of the results so far achieved subcooling is improved, the running time of the refrigerator is reduced. Thus the results are expected to use for the increase of coefficient of performance of low temperature thermal storage system in the building.