• Korean Chemical Engineering Research
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• v.51 no.4
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• pp.500-505
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• 2013

In this study, we investigated the kinetics of gas hydrate formation in the presence of ionic liquid (IL). Hydroxyethyl-methyl-morpholinium chloride (HEMM-Cl) was chosen as a material for the promotion effect test. Phase equilibrium curve for $CH_4$ hydrate with aqueous IL solution was obtained and its induction time and consumed amount of $CH_4$ gas were also measured. Aqueous solutions containing 20~20,000 ppm of HEMM-Cl was prepared and studied at 70 bar and 274.15 K. To compare the measured results to those of the conventional promoter, sodium dodecyl sulfate was also tested at the same condition. Result showed that the hydrate equilibrium curve was shifted toward higher pressure and lower temperature region. In addition, the induction time on $CH_4$ hydrate formation in the presence of IL was not shown. The amount of consumed $CH_4$ was increased with the whole range of tested concentration of IL and the highest consumption of $CH_4$ happened at 1,000 ppm of HEMM-Cl. HEMM-Cl induced and enhanced the $CH_4$ hydrate formation with a small amount of addition. Obtained result is expected to be applied for the development of technologies such as gas storage and transport using gas hydrates.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.27 no.2
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• pp.251-258
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• 2003

Natural gas hydrates typically contain 85 wt.% water and 15 wt.% natural gas, and commonly belongs to cubic structure I and II. When referred to standard conditions, 1㎥ solid hydrates contain up to 172N㎥ of methane gas, depending on the pressure and temperature of production. Such large volumes make natural gas hydrates can be used to store and transport natural gas. So, the tests were performed on the formation of natural gas hydrate is governed by the pressure, temperature, gas composition etc. The results show that the formation pressure of structure II is lower about 65% and the solubility is higher about 3 times than that of structure I.

• Korean Chemical Engineering Research
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• v.55 no.5
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• pp.704-710
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• 2017

Although the desalination technique using gas hydrate formation is at a development stage compared to the commercially well-established reverse osmosis (RO), it still draws attention because of its simplicity and moderate operational conditions especially when using refrigerants for guest gases. In this study, DFT (density functional theory)-based molecular modeling was employed to explain the energetics of the gas hydrate formation using HFC (hydrofluorocarbon) and HCFC (hydrochlorofluorocarbon) refrigerants. For guest gases, R-134a, R-227ea, R-236fa, and R-141b were selected and three cavity structures ($5^{12}$, $5^{12}6^2$, and $5^{12}6^4$) composed of water molecules were constructed. The geometries of guest gas, cavity, and cavity encapsulating guest gas were optimized by molecular modeling respectively and their located energies were then used for the calculation of binding energy between the guest gas and cavity. Finally, the comparison of binding energies was used to propose which refrigerant is more favorable for the gas hydrate formation energetically. In conclusion, R-236fa was the best choice in terms of thermodynamic spontaneity, less toxicity, and low solubility in water.

• Journal of the Korean Institute of Gas
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• v.6 no.4 s.18
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• pp.8-16
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• 2002

Since hydrate has been discovered on the earth, many numbers of experimental studies have been conducted for characterizing the fundamental properties of hydrates, such as equilibrium conditions, thermodynamic properties, structures, kinetics, etc. It is considered naturally occurred hydrates in porous rocks have a great potential as a future of unconventional energy resources, and the investigations of formation and dissociation of hydrates in porous media are required. In this study, an experimental apparatus was designed to perform experiments of hydrates in porous core. With the apparatus developed, firstly, isochoric experiments were conducted to find hydrate equilibrium conditions in porous media, and the results were compared with reference data to verify experimental apparatus and methods in this study. Secondly, experiment of formation was examined by observing the behaviors of pressure and electrical resistance and the effects of initial water saturation on formation were analysed.

• 한국신재생에너지학회:학술대회논문집
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• 2006.06a
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• pp.419-423
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• 2006

Basic studies on natural gas hydrates in the East Sea were been carried out by the Korea Institute of Geoscience and Mineral Resources (KIGAM) from 2000 to 2004 involving 2D multichannel seismic lines and piston coring. 27 piston cores recovered from the deed-water Ulleung Basin of the East Sea were analyzed in this study. In piston cores cracks generally developed parallel to bedding suggest significant gas content. The core analyses showed high total organic carbon (TOC) content, sedimentation rate and heat flow of sediments. The cores recovered from the southern study area show also high residual hydrocarbon gas concentrations for the formation of natural gas hydrates. This study indicates that there is the potential for the generation of biogenic gas and the formation of natural gas hydrates in the near seafloor sediments of the study area.

• Clean Technology
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• v.15 no.4
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• pp.258-264
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• 2009

Thermodynamic measurements were performed to show the possibility of recovering $CO_2$ from fuel gas (the mixture of $CO_2$ and $H_2$) by forming gas hydrates with water where water was dispersed in the pores of silica gel particles having nominal 100 nm of pore diameter. The hydrate-phase equilibria for the ternary $CO_2+H_2$+water in pores were measured and $CO_2$ concentrations in vapor and hydrate phase were determined under the hydrate-vapor two phase region at constant 274.15 K. It was shown that the inhibition effect appeared due to silica gel pores, and the corresponding equilibrium dissociation pressures became higher than those of bulk water hydrates at a specific temperature. In addition, direct measurement of $CO_2$ content in the hydrate phase showed that the retrieved gas from the dissociation of hydrate contained more than 95 mol% of $CO_2$ when 42 mol% of $CO_2$ and balanced Hz mixture was applied. Compared with data obtained in case of bulk water hydrates, which showed just 83 mol% of $CO_2$ where 2-stage hydrate slurry reactor was intended to utilize this property, the hydrate formation in porous silica gel has enhanced the feasibility of $CO_2$ separation process. Hydrate formation as not for slurry but solid particle makes it possible to used fixed bed reactor, and can be a merit of well-understood technologies in the industrial field.

• 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.

• Clean Technology
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• v.22 no.3
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• pp.154-160
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• 2016

For any conceivable desalination process using the gas hydrate formation, the kinetics has to be one of the most important parameters from the economic point of view. We thus were to improve the kinetics of the R-134a (also known as HFC-134a) gas hydrate formation by using promoters and three different kinds of edible surfactants were selected for the desalination process targeted to produce potable water; κ-carrageenan, lecithin, and polysorbate 80 among anionic, amphoteric, and nonionic surfactants, respectively. Then, the kinetics change of the R-134a hydrate formation was monitored by varying the surfactant concentration. Experimental results demonstrated that the rate of R-134a hydrate formation increases with the addition of edible surfactants in general and the effect as a promotor has an order of polysorbate 80 > κ-carrageenan > lecithin. As a supportive measure, the atomic charges of each surfactant were calculated by using a DFT (density functional theory)-based molecular modeling and the results showed a positive relationship between the promotor effect of each surfactant and the number of oxygens available for hydrogen bonding and the negativity of their atomic charge values.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.30 no.2C
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• pp.109-117
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• 2010

Gas hydrate dissociation can generate large amounts of gas and water in gas hydrate bearing sediments, which may eventually escape from a soil skeleton and form voids within the sediments. The loss of fine particles between coarse particles or collapse of cementation due to water flow during heavy or continuous rainfall may form large voids within soil structure. In this study, the effect of void formation resulting from gas hydrate dissociation or loss of some particles within soil structure on the strength of soil is examined. Glass beads with uniform gradation were used to simulate a gas hydrate bearing or washable soil structure. Glass beads were mixed with 2% cement ratio and 7% water content and then compacted into a cylindrical sample with five equal layers. Empty capsules for medicine are used to mimic large voids, which are bigger than soil particle, and embedded into the middle of five equal layers. The number, direction, and length of capsules embedded into each layer vary. After two days curing, a series of unconfined compression tests is performed on the capsule-embedded cemented glass beads. Unconfined compressive strength of cemented glass beads with capsules depends on the volume, direction and length of capsules. The volume and cross section formed by voids are most important factors in strength. An unconfined compressive strength of a specimen with large voids decreases up to 35% of a specimen without void. The results of this study can be used to predict the strength degradation of gas hydrate bearing sediments in the long term after dissociation and loss of fine particles within soil structure.

• Economic and Environmental Geology
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• v.38 no.2 s.171
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• pp.165-176
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• 2005

Natural gas in deep sediment may occur in three phases based on the physical and chemical conditions. If the concentration of gas in pore water is less than the solubility, gas is dissolved. If the concentration of gas is greater than its solubility (water is saturated or supersaturated with gas), gas occurs as a fee gas below the gas hydrate stability Lone (GHSZ) and is present as solid hydrate within the GHSZ. The knowledge of gas concentration in deep sediment appears critical to determine the phase of natural gases and to understand the formation and distribution of gas hydrate. However, reliable data on gas concentration are usually available only from the upper section of marine sediment by the headspace gas technique, which is widely used for sampling of gases from the sediments. The headspace gas technique represents only a fraction of gases present in situ because sediments release most of the gases during recovery and sampling. The PCS (Pressure Core Sampler) is a downhole tool developed to recover a nominal $1{\cal}m$ long, $4.32{\cal}cm$ diameter core containing $1,465cm^3$ of sediment, pore water and gas at in situ pressure up to 68.9 MPa. During Leg 204, the PCS was deployed at 6 Sites. In situ methane gas concentration and distribution of gas hydrate was measured by using PCS tool. Characteristics of methane concentration and distribution is different from site to site. Distribution of gas hydrate in the study area is closely related to characteristics of in situ gas concentration measured by PCS.