• Korean Chemical Engineering Research
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• 제50권5호
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• pp.890-893
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• 2012

가스 하이드레이트란 물이 형성하는 수소 결합의 격자 구조 내로 저분자량의 기체 분자가 포집되며 형성하는 결정성 화합물이다. 가스 하이드레이트는 작은 고체 부피 내에 막대한 양의 기체 분자를 저장할 수 있다는 특징으로 인해 에너지 가스의 수송/저장 매체로 주목받고 있다. 또한 심해저와 영구 동토지역에 천연적으로 형성되어 부존되어 있는 막대한 양의 천연가스 하이드레이트를 미래 청정 에너지원으로 활용하기 위한 연구도 진행 중에 있다. 본 연구에서는 천연가스의 수송/저장 매체로 가스 하이드레이트의 활용 가능성을 확인하기 위하여, 메탄, 에탄, 프로판이 각각 90.0, 7.0, 3.0 mol% 포함된 합성 천연가스를 사용하여 가스 하이드레이트 형성과 형성시의 거동 변화를 측정하였다. 268 K 및 50 bar의 조건에서 형성된 천연가스 하이드레이트 시료에 대해 고체상 NMR 및 고분해능 분말 XRD 분석을 통하여 시료의 결정 구조 확인 및 미세 분자 거동을 확인하였다. 실험 결과를 통해 형성된 천연가스 하이드레이트는 구조-II인 것을 확인하였으며, 구조-II의 두 가지 동공 중 작은 동공은 메탄이, 그리고 큰 동공은 메탄, 에탄, 프로판 모든 성분들이 포집되어 있음을 알 수 있었다. 또한 NMR 분광 분석법과 기체 크로마토그래피를 사용하여 기체 및 고체 조성을 분석한 결과, 천연가스의 성분별 포집도에 차이가 있는 것을 알 수 있었는데, 순수한 기체를 기준으로 하였을 때 가스 하이드레이트를 더 잘 형성할 수 있는 프로판, 에탄, 메탄의 순으로 포집 경향이 나타남을 알 수 있었다.

• Journal of Korean Society for Atmospheric Environment
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• 제23권E1호
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• pp.10-15
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• 2007

The gas hydrates are probably most sensitive to climate change since they are stable only under specific conditions of high pressure and low temperature. One of the main factors responsible for formation of gas hydrates is the saturation of the gases with water vapor. Quantitative phase equilibrium data and understanding of the roles of water component in the phase behavior of the heterogeneous water-hydrocarbon-hydrate mixture are of importance and of engineering value. In this study, the water content of ethylene gas in equilibrium with hydrate and water phases were analyzed by theoretical and experimental methods at temperatures between 274.15 up to 291.75 K and pressures between 593.99 to 8,443.18 kPa. The experimental and theoretical enhancement factors (EF) for the water content of ethylene gas and the fugacity coefficients of water and ethylene in gas phase were determined and compared with each other over the entire range of pressure carried out in this experiment. In order to get the theoretical enhancement factors, the modified Redlich-Kwong equation of state was used. The Peng-Robinson equations and modified Redlich-Kwong equations of state were used to get the fugacity coefficients for ethylene and water in the gas phase. The results predicted by both equations agree very well with the experimental values for the fugacity coefficients of the compressed ethylene gas containing small amount of water, whereas, those of water vapor do not in the ethylene rich gas at high temperature for hydrate formation locus.

• 한국해양공학회지
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• 제34권5호
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• pp.342-350
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• 2020

In this study, a hydrate inhibition system is investigated for shallow water gas fields. Mono-ethylene glycol (MEG) injection has been used as a typical method for inhibiting hydrate formation in gas fields; therefore, most offshore platforms are equipped with MEG injection and regeneration processes. A recent application of a kinetic hydrate inhibitor (KHI) has reduced the total volume of MEG injection and hence reduce the operating cost. Experiments are designed and performed to evaluate and verify the KHI performance for inhibiting hydrate formation under shallow water conditions. However, the shut-in and restart operation may require the injection and regeneration of MEG. For this operation, the MEG concentration must be optimized while considering the cost of MEG regeneration. The obtained results suggest that decreasing MEG concentration from 80 wt% to 70 wt% can reduce the life cycle cost (LCC) of MEG regeneration process by approximately 5.98 million USD owing to reduced distillation column cost. These results suggest that the hydrate inhibition system must be evaluated through well-designed experiments and process simulations involving LCC analysis.

• 한국가스학회지
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• 제6권1호
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• pp.38-45
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• 2002

가스 하이드레이트는 메탄, 에탄, 프로판, 부탄 등과 같은 천연가스-성분이 물에 의해 포획된 얼움형태의 고체연료로서, 세계적으로 가스 하이드레이트 추정 매장량은 기존 화석연료 매장량에 비해 약 2배 이상인 것으로 예측되어 미래의 신 에너지 자원으로 기대되고 있다. 그러나 이러한 에너지 자원측면과는 반대로 파이프라인을 통한 가스 수송과정에서 형성된 하이드레이트는 유동저해나 배관손상을 유발 할 수 있는 요인으로 영구동토지연인 시베리아는 물론이고 북해와 멕시코만 등의 여러 유전이나 가스전에서 심각한 문제를 발생시키고 있다. 해저 가스 파이프라인이나 동토지역을 통과하는 가스 파이프라인에서는 관내 압력과 온도에 따라 하이드레이트가 생성될 수 있으며, 특히 송출압력을 높게 할 경우에는 파이프라인 안에 하이드레이트가 생성될 가능성은 더욱 높아져, 플러깅 형성에 의한 유동저해 및 배관손상이 예상된다. 본 연구에서는 실제 파이프라인 내부에서 하이드레이트로 인한 플러깅 생성 메카니즘을 규명하고 이에 대한 형성조건을 측정함으로써, 그 방지기준 및 방지책을 선정하는데 활용하고자 실험실 규모의 환상형 파이프라인 실험장치를 개발하려다. 개발된 실험장치를 통해 파이프라인에서의 하이드레이트 평형조건을 도출하고, 다양한 속도 및 압력 조건하에서 하이드레이트 플러깅 형성온도를 측정하였다 이를 통해 유통속도 및 압력, 온도에 관한 상관관계를 파악하고 그 경향을 도출함으로써 실제 가스 파이프라인에의 하이드레이트 플러깅 형성조건을 파악할 수 있었다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 추계학술대회
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• pp.54-57
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• 2006

Structure H formation experiments were conducted in a semi-batch stirred vessel using methane as the small guest substance and neohexane(NH), tert-butylmethylether(TBME) and methylcyclohexane(MCH) as the large molecule guest substance (LMGS). The results indicate that the rates of gas uptake and induction times are generally dependent on the magnitude of the driving force. When tert-butyl methyl ether is used as the LMGS rapid hydrate formation, much smaller induct ion time and rapid decomposition can be achieved. Liquid-liquid equilibrium (LLE) data for the above LMGS with water have been measured under atmospheric pressure at 275.5, 283.15K, and 298.15K. It was found that TBME is the most water soluble followed by NM and MCH. The solubility of water in the non-aqueous liquid was found to increase in the following order: MCH

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2005년도 춘계학술대회
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• pp.618-621
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• 2005

In this study, the phenomena of hydrate formation and inhibition were investigated according to varying the concentrations using methanol and ethylene glycol as chemical additives. The results reveal that the used additives display better inhibition effects compared to pure water by decreasing the formation temperature and the inhibition performance of methanol is superior to that of ethylene glycol. As a conclusion, the plugging phenomena of flowline in natural gas product ion. subsea and frozen field pipelines can be predicted by examining the hydrate formation and inhibition conditions. Specifically, the results of this study can be applied to the selection of the prevention criteria and method of hydrate formation.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2008년도 춘계학술대회 논문집
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• pp.588-590
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• 2008

The thermal signature of nucleation process is characterized by the induction time, the degree of supercooling, and the equilibrium temperature depression. The initiation of nucleation presents stochastic characteristics. The factors that affect nucleation are mechanical impact, ionic concentration, mineral surface characters, and pore size. Hydrate-bearing sediments behave mechanically like other cemented sediments. The data set has important implications for the calibration and interpretation of geophysical measurements and downhole logs collected in gas hydrate provinces, providing particular insight for the interpretation of P- and S-wave data and resistivity logs. In addition, laboratory formation history and ensuing pore-scale spatial distribution likely have a more pronounced effect on the macroscale mechanical properties of hydrate-bearing sediments

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 추계학술대회 초록집
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• pp.122.1-122.1
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• 2011

The motivation for this work was the potential of hydrophobic amino acids such as glycine, L-alanine, and L-valine to be applied as thermodynamic hydrate inhibitors (THIs). To confirm their capabilities in inhibiting the formation of gas hydrates, three-phase (liquid-hydrate-vapor) equilibrium conditions for carbon dioxide hydrate formation in the presence of 0.1 to 3.0 mol% amino acid solutions were determined in the range of 273.05 to 281.45 K and 14.1 to 35.2 bar. From quantitative analyses, the inhibiting effects of the amino acids (on a mole concentration basis) decreased in the following order: L-valine > L-alanine > glycine. The application of amino acids as THIs has several potential advantages over conventional methods. First, the environmentally friendly nature of amino acids as compared to conventional inhibitors means that damage to ecological systems and the environment could be minimized. Second, the loss of amino acids in recovery process would be considerably reduced because amino acids are non-volatile. Third, amino acids have great potential as a model system in which to investigate the inhibition mechanism on the molecular level, since the structure and chemical properties of amino acids are well understood.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2007년도 추계학술대회 논문집
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• pp.585-589
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• 2007

Gas hydrate is a special kind of inclusion compound that can be formed by capturing gas molecules to water lattice in high pressure and low temperature conditions. When referred to standard conditions, $1m^3$ solid hydrates contain up to $172Nm^3$ 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. In this study, three-phase equilibrium conditions for forming methane hydrate were theoretically obtained in aqueous single electrolyte solution containing 3wt% Nacl. The results show that Nacl acts as a inhibitor, but help gases such as ethan, propane, i-butane, and n-butane reduce the hydrate formation pressure at the same temperature.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2005년도 춘계학술대회
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• pp.663-666
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• 2005

Gas hydrates are ice-like compounds that form at the low temperature and high pressure conditions common in shallow marine sediments at water depths greater than 300-500 m when concentrations of methane and other hydrocarbon gases exceed saturation. Estimates of the total mass of methane carbon that resides in this reservoir vary widely. While there is general agreement that gas hydrate is a significant component of the global near-surface carbon budget, there is considerable controversy about whether it has the potential to be a major source of fossil fuel in the future and whether periods of global climate change in the past can be attributed to destabilization of this reservoir. Also essentially unknown is the interaction between gas hydrate and the subsurface biosphere. ODP Leg 204 was designed to address these questions by determining the distribution, amount and rate of formation of gas hydrate within an accretionary ridge and adjacent basin and the sources of gas for forming hydrate. Additional objectives included identification of geologic proxies for past gas hydrate occurrence and calibration of remote sensing techniques to quantify the in situ amount of gas hydrate that can be used to improve estimates where no boreholes exist. Leg 204 also provided an opportunity to test several new techniques for sampling, preserving and measuring gas hydrates. During ODP Leg 204, nine sites were drilled and cored on southern Hydrate Ridge, a topographic high in the accretionary complex of the Cascadia subduction zone, located approximately 80km west of Newport, Oregon. Previous studies of southern Hydrate Ridge had documented the presence of seafloor gas vents, outcrops of massive gas hydrate, and a pinnacle' of authigenic carbonate near the summit. Deep-towed sidescan data show an approximately $300\times500m$ area of relatively high acoustic backscatter that indicates the extent of seafloor venting. Elsewhere on southern Hydrate Ridge, the seafloor is covered with low reflectivity sediment, but the presence of a regional bottom-simulating seismic reflection (BSR) suggests that gas hydrate is widespread. The sites that were drilled and cored during ODP Leg 204 can be grouped into three end-member environments basedon the seismic data. Sites 1244 through 1247 characterize the flanks of southern Hydrate Ridge. Sites 1248-1250 characterize the summit in the region of active seafloor venting. Sites 1251 and 1252 characterize the slope basin east of Hydrate Ridge, which is a region of rapid sedimentation, in contrast to the erosional environment of Hydrate Ridge. Site 1252 was located on the flank of a secondary anticline and is the only site where no BSR is observed.