• Korean Chemical Engineering Research
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• v.55 no.3
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• pp.353-357
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• 2017

In this study, the inclusion phenomena of tetrahydrofuran + 3-hydroxytetrahydrofuran + $CH_4$ clathrate hydrates were explored via thermodynamic and spectroscopic approaches. The phase equilibria of the double hydrates - THF + $CH_4$ and 3-OH THF + $CH_4$ clathrate hydrates - were determined by pressure-temperature trace during hydrate formation and dissociation, and the result revealed that the equilibrium pressures were shifted to lower pressure region compared to pure $CH_4$ hydrate. The powder X-ray diffraction patterns revealed that the double hydrates of THF + 3-OH THF formed structure II type clathrate hydrates with $CH_4$. The dispersive Raman spectra of the double clathrate hydrates also exhibited that $CH_4$ can be trapped in both $5^{12}6^4$ and $5^{12}$ cages whereas THF and 3-OH THF were encaged in $5^{12}6^4$ cage.

• Proceedings of the KSME Conference
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• 2007.05b
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• pp.2471-2475
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• 2007

Clathrate compound is the material that host in hydrogen bond forms cage and guest is included into it and combined. Crystallization of hydrate is generated at higher temperature than that of ice from pure water. And physical properties according to temperature are stable and congruent melting phenomenon is occurred without phase separation. But clathrate compound still had supercooling problem occurred in the course of phase change and supercooling should be minimized because it affects efficiency of equipment very much. Therefore, various studies on additives to restrain this or heat storage methods are needed. In this study was investigated the cooling characteristics of the TMA-water clathrate compound including TMA (Tri-methyl-amine, $(CH_3)_3N)$ of 20${\sim}$25 wt% as a low temperature latent heat storage material. And ethanol$(CH_3CH_2OH)$ was added and its cooling characteristics were studied experimentally to restrain supercooling of TMA-water clathrate compound.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.19 no.5
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• pp.228-236
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• 2009

In this study, we investigated morphological characteristics of $SF_6$ clathrate hydrate crystals to understand its formation and growth mechanism. $SF_6$ clathrate hydrate crystals were formed in high-pressure reaction cell charged with pure water and $SF_6$ gas at constant pressure and temperature. Two-phase ($SF_6$ gas/aqueous solution) and three-phase ($SF_6$ gas/aqueous solution/$SF_6$ liquid) conditions were investigated, In both conditions, dendritic shape hydrate crystals were grown as like fibriform crystals along upward growth direction at the gas/aqueous solution interface. In the case of the reaction process of three-phase condition, when the $SF_6$ gas bubbles which were generated in $SF_6$ liquid phase due to the reduction of reaction cell pressure stuck to the gas/aqueous interfaces, the hydrate phase were appeared at the surface of the bubbles. This paper presents the detail growth characteristics of $SF_6$ hydrate crystals including crystal nucleation, migration, growth and interference.

• 한국신재생에너지학회:학술대회논문집
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• 2011.11a
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• pp.122.2-122.2
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• 2011

Sulfur hexafluoride ($SF_6$), one of the most potent greenhouse gases, is known as a hydrate former and has been studied at the high pressure up to 1.3 GPa with gas mixtures and with aqueous surfactant. Since we regard $SF_6$ as a potential promoter molecule that can stabilize hydrate structure more effectively compare to the other promoters, further investigation is required to verify the stabilizing ability of $SF_6$ in the hydrate structure. However, the insoluble nature of $SF_6$ in water or gases hinders fine scale analyses. This work discusses the data obtained by using molecular dynamics simulations of structure II (sII) clathrate hydrates containing $SF_6$ and $H_2$. The simulations were performed using the TIP4P/Ice model for water molecule and a previously reported $SF_6$ molecular model (optimized at the pure $SF_6$ single phase system (Olivet and Vega, 2007)), and a $H_2$ molecular model (adapted from the THF+$H_2$ hydrate system (Alavi et al., 2006)). The simulations are performed to observe the stability of $SF_6$ and $H_2$ in the sII clathrate hydrate system with varying temperature and pressure conditions and occupancies of $SF_6$ and $H_2$, which cannot be easily tuned experimentally. We observe that stability of H2 enclathrated in the hydrate structure more affected by the occupancy of $SF_6$ molecules and temperature than pressure, which ranges from 1 to 100 bar.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.216.1-216.1
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• 2010

본 연구는 최근 하이드레이트와 유사한 형태인 semi-clathrate 형성을 통해 열역학적 촉진제로서 주목받고 있는 TBAF(Tetra-n-butyl ammonium fluoride)의 가스 하이드레이트 형성에 작용하는 영향을 알아보았다. TBAF를 10, 33.8, 45 wt%의 농도로 $CH_4+H_2O$, $CO_2+H_2O$, $N_2+H_2O$계에 첨가하여 가스 하이드레이트 3상 평형점(하이드레이트(H) - 물(Lw) - 기상(V)) 측정을 하였다. TBAF가 첨가된 경우 순수한 $CH_4$, $CO_2$, $N_2$ 가스 하이드레이트보다 평형조건이 더 높은 온도와 더 낮은 압력 영역에서 나타났으며 기체의 종류와 무관하게 TBAF의 농도가 33.8 wt%일 때 10, 45 wt%보다 뛰어난 촉진효과를 갖고 있음을 확인할 수 있었다. 이를 통해 양론비인 TBAF의 농도 33.8 wt% 이상에서는 반응을 하지 않고 남아있는 TBAF가 하이드레이트 생성반응에 방해요소로 작용하는 것을 알 수 있었다. 본 실험에서 얻어진 결과 TBAF를 촉진제로서 사용하는 가스 하이드레이트 공정이라면 33.8 wt% 농도의 사용이 가장 효과적일 것으로 사료된다.

• Korean Chemical Engineering Research
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• v.45 no.4
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• pp.400-409
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• 2007

Morphology of methane/propane clathrate hydrate crystal was investigated under different undercooling conditions. After the water pressurized with compound guest gas was fully saturated by agitation, medium within the vessel was rapidly undercooled and maintained at the constant temperature while the visual observations using microscope revealed detailed features of subsequent crystal nucleation, migration, growth and interference occurring within liquid pool. The growth of hydrate was always initiated with film formations at the bounding surface between bulk gas and liquid regions under all tested experimental conditions. Then a number of small crystals ascended, some of which settled beneath the hydrate film. When undercooling was relatively small, 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 within liquid pool 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 growth characteristics of floating crystals are reported focused on the influences caused by undercooling and memory effect.

• The Korean Journal of Petroleum Geology
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• v.7 no.1_2 s.8
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• pp.13-18
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• 1999

Methane hydrate is an ice-like solid material and it has a structure which water molecules enclose gas molecules. For low temperature and high pressure, hydrocarbon gas forms hydrate and due to this condition, it is existed in the arctic region or deep sea. Presently, the amount of methane hydrate is unpredictable, but it is assumed that the amount will be enormous. For this reason, it is expected that it will play a major role as natural gas resources in the future. However, the production technologies are stayed on the low level and the economical technology was not developed yet. Also, emission of natural gas from methane hydrate will cause global warming and thus it is considered as a critical environmental problem. In this paper, the state of the art of the production technologies and environmental effects of methane hydrate were summarized.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.711-711
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• 2009

Global warming has been widely recognized as a serious problem threatening the future of human beings. It is caused by the buildup in the atmosphere of greenhouse gases, such as carbon dioxide, methane, hydrofluorocarbons (HFCs), and sulfur hexafluoride (SF6). Particularly, SF6 has extremely high global warming potential compare to those of other global warming gases. One option for mitigating this greenhouse gas is the development of an effective process for capturing and separating these gases from anthropogenic sources. In general, gas hydrates can be formed under high pressure and low temperature. However, SF6 gas is known to form hydrate under relatively milder conditions. Therefore, technological and economical effects could be expected for the separation of SF6 gas from waste gas mixtures. In this study, we carried out morphological study for the SF6 hydrate crystals to understand its formation and growth mechanisms. The observations were made in high-pressure optical cell charged with liquid water and SF6 gas at constant pressure and temperature. Initially SF6 hydrate formed at the surface between gas and liquid regions, and then subsequent dendrite crystals grew at the wall above the gas/water interface. The visual observations of crystal nucleation, migration, growth and interference were reported. The detailed growth characteristics of SF6 hydrate crystals were discussed in this study.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.691-694
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• 2009

TBAB (Tetra-n-butyl ammonium bromide)는 상압에서 semi-clathrate를 형성하는 물질로서 최근 열역학적 촉진제 및 기체 저장 물질로서 주목받고 있다. 본 연구에서는 가스 하이드레이트 형성 시TBAB가 열역학적 촉진제로서 미치는 영향을 알아보기 위해 다양한 농도 (5, 10, 40, 60 wt%)의 TBAB를 $CH_4\;+\;H_2O$계, $CO_2\;+\;H_2O$계, $N_2\;+\;H_2O$계에 첨가하여 가스 하이드레이트 3상 평형 (H - LW - V)을 측정 하였다. 실험 결과 TBAB의 조성에 따른 촉진경향은 각 계가 유사하지만, 촉진 정도는 $N_2\;+\;H_2O$ 계가 앞의 두계에 비해 월등히 큰 것을 알 수 있었다. 또한, TBAB 농도가 40 wt% 일때 촉진효과가 가장 크게 나타났으며, 그 이상의 농도에서는 반대로 촉진효과가 감소하는 것을 알 수 있었다. 이는 혼합 하이드레이트 형성에 참여하지 못한 TBAB가 가스 하이드레이트 형성을 억제하기 때문으로 사료된다. 결과적으로 가스하이드레이트 공정에 TBAB를 열역학적 촉진제로서 적용할 경우 촉진효과가 가장 큰 40 wt% 범위의 농도로 사용하는 것이 가장 적절할 것으로 사료된다. 본 실험에서 얻어진 결과는 가스 하이드레이트 형성을 이용한 천연가스 수송/저장법을 위한 연구뿐만 아니라 기체 분리 공정 개발과 관련된 연구의 중요한 기초 자료가 될 것이다.

• Korean Chemical Engineering Research
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• v.57 no.3
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• pp.378-386
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• 2019

In the present paper we report the calculation results of operation energy consumption for dissolved ions concentration technologies using vacuum evaporation (VE) and hydrate formation. Calculations were conducted assuming the tenfold concentration of saline water (0.35 wt% NaCl solution) of 1 mol/s at room temperature and atmospheric pressure employing vacuum evaporation at $69^{\circ}C$ and 30 kPa and hydrate-based concentration using $CH_4$, $CO_2$ and $SF_6$ as guest molecules. Operation energy consumption of VE-based concentration resulted in 47 kJ/mol, whereas those of hydrate-based concentration were 43, 32, and 28 kJ/mol for $CH_4$, $CO_2$ and $SF_6$ hydrates, respectively. We observe that hydrate-based concentration can a competitive option for dissolved ions recovery from energy consumption standpoint. However, the selection of guest gas is very critical, since it accordingly determines the hydration number, the hydrate formation energy, gas compression energy, etc. The selection of guest gas, separation of concentrated brine and water phases, and the enhancement of hydrate formation rate are the key factors for the commercialization of hydrated-based technology for concentrating dissolved ions.