• Korean Journal of Air-Conditioning and Refrigeration Engineering
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• v.25 no.5
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• pp.233-239
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• 2013

The Thermophysical properties of thermal conductivity, viscosity, and heat capacity for $CO_2$ slurry ($CO_2$ gas and $CO_2$-hydrate mixture) having a high gas phase volume fraction were predicted using the conventional mixture models and the TRAPP model under hydrate formation conditions. Based on the calculated thermophysical properties, the heat transfer coefficient and pressure drop of the $CO_2$ slurry in the tube were predicted. The thermal conductivity of $CO_2$ slurry ranged from 0.02 to 0.2 W/m-K, and the mixture viscosity was larger than that of pure $CO_2$ by 1.9~2.7 times. The heat capacity of $CO_2$ slurry ranged from 63 to 68% of that for pure $CO_2$. The predicted heat transfer coefficient of $CO_2$ slurry was 6 times higher than that of pure $CO_2$. In the separate model, the estimated pressure drop increased with an increase of $CO_2$-hydrate mole fraction, and was 60% of that of pure $CO_2$.

• Korean Journal of Materials Research
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• v.18 no.12
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• pp.650-654
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• 2008

The emission of carbon dioxide from the burning of fossil fuels has been identified as a major contributor to green house emissions and subsequent global warming and climate changes. For these reasons, it is necessary to separate and recover $CO_2$ gas. A new process based on gas hydrate crystallization is proposed for the $CO_2$ separation/recovery of the gas mixture. In this study, gas hydrate from $CO_2/H_2$ gas mixtures was formed in a semi-batch stirred vessel at a constant pressure and temperature. This mixture is of interest to $CO_2$ separation and recovery in Integrated Coal Gasification (IGCC) plants. The impact of tetrahydrofuran (THF) on hydrate formation from the $CO_2/H_2$ was observed. The addition of THF not only reduced the equilibrium formation conditions significantly but also helped ease the formation of hydrates. This study illustrates the concept and provides the basic operations of the separation/recovery of $CO_2$ (pre-combustion capture) from a fuel gas ($CO_2/H_2$) mixture.

• 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.

• Korean Journal of Air-Conditioning and Refrigeration Engineering
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• v.29 no.7
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• pp.341-349
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• 2017

Formation and transportation of $CO_2$-hydrate slurry was conducted by circulating saturated water with $CO_2$ through a double-tube type heat exchanger which was cooled down by brine. The inner diameter and circulation length of the heat exchanger were 1 inch and 20 m, respectively. Water in tank was supersaturated by injected $CO_2$ and the operation pressure was maintained at 3,000 to 4,000 kPa with fluid-temperature of less than $9^{\circ}C$. $CO_2$ hydrate mass fraction was calculated based on density of $CO_2$-hydrate slurry mixture. Results showed that the $CO_2$-hydrate slurry could be circulated without blockage for 1 hr. Circulation status of the $CO_2$-hydrate slurry was also visualized.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.2
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• pp.171-181
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• 2008

There are several methods for the gas hydrate production such as spraying water with countercurrent gas flow, stirring water-gas mixture, and flowing water with micro-bubble, etc. These days it has been widely studied for the gas hydrate production method, having low energy consumption and high efficiency. In this paper, patents in the gas hydrate production method were gathered and analyzed. The search range was limited to the open patents of USA, European Union (EP), Japan (JP), and Korea (KR) from 1991 to 2007. Patents were gathered by using keywords searching and filtered by crucial criteria. The trends of the patents were analyzed by the years, countries, companies, and technologies.

• Korean Chemical Engineering Research
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• v.48 no.2
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• pp.232-243
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• 2010

Gas hydrates are crystalline solids composed of water and gas molecules. Water molecules are linked through hydrogen bonding and create cavities(host lattice) that can capture a large variety of guest molecules under appropriate conditions, generally high pressure and low temperature. Recently, many researchers try to apply gas hydrates to industrial processes to capture greenhouse gases due to the facts that the process is eco-friendly and target gas molecules can be preferentially captured. In this paper, we introduced recent studies on $CO_2$ and $CO_2-N_2$ mixture hydrates to evaluate the feasibility of industrial application of gas hydrate technology to $CO_2$ capture process. Specifically, we put emphasis on the technical feasibility of $CO_2$ separation in steel industry using gas hydrate formation principles.

• Journal of the Korean Ceramic Society
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• v.27 no.2
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• pp.211-218
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• 1990

CA2-based clinker with highly activated surface and hydraulic properties was synthesized at a comparatively lowr temperature than that of conventional synthesis by "hydration-burning method". This consists of calcining the mixture of CaCO3 and Al2O3 to obtain a primary clinker, hydrating the primary clinker and reburning the hydrates to obtain final clinker. Burning of primary clinker above 1200℃ was necessary to eliminate free CaO in it and to obtain it's solid hydrate. However, rising the burning temperature above 1300℃ is ineffective due to the decrease in hydraulic properties of the primary clinker with the temperature. Hydration of primary clinker at the elevated temperature(>35℃) was required to obtain the hydrate with more porous structure and final clinker with more active surface. CA2 was formed and increased with temperature at above 1150℃, finally became a primary phase of the final clinker. However, burning at the temperature above 1300℃ resulted in reverse effect on the hydraulic properties of the final clinker due to rapid decrease in it's surface area with the temperature.

• Clean Technology
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• v.19 no.4
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• pp.476-480
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• 2013

The growth behavior of $CH_4$ and $SF_6$ mixture gas hydrate has been investigated by a combined approach of Raman spectroscopy and molecular modeling. Raman spectroscopy results presented that when $CH_4$ is used only, $CH_4$ guest molecule is inserted first into the large cavity of the host structure built by $H_2O$ molecules and then into the small cavity to stabilize the whole gas hydrate structure. In the other hand, when $SF_6$ is mixed together, $SF_6$ is favored over (or competing with) $CH_4$ in being inserted into the large cavity and the small cavity still prefers $CH_4$ insertion. The calculations of binding energies clearly supported this. While $SF_6$ has a binding energy of -26.9 kcal/mol a little lower than -24.2 kcal/mol of $CH_4$ in the large cavity, $SF_6$ and $CH_4$ has 1.2 kcal/mol and -22.0 kcal/mol, respectively, in the small cavity. It indicates that the sizable $SF_6$ is not preferred in the small cavity but has a relative energetic advantage over $CH_4$ in the large cavity.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.710-710
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• 2009

$SF_6$ 가스는 높은 절연 특성으로 인해 산업공정에서 순수 또는 $N_2$ 나 $CO_2$ 가스를 혼합시켜 광범위하게 사용되고 있다. 그러나 $SF_6$ 가스의 지구온난화지수는 $CO_2$ 대비 23,900배로 환경에 치명적인 영향을 줄 수 있으므로, $SF_6$ 가스에 대한 분리 및 처리에 관한 연구가 필요하다. 본 연구에서는 조성에 따른 $SF_6-N_2$ 혼합기체의 3상평형(물-하이드레이트-기체)점을 측정하였다. 측정결과 $N_2$가 더 많이 첨가된 혼합기체일수록 순수 $SF_6$의 상평형 조건보다 더 높은 압력, 더 낮은 온도에서 형성됨을 알 수 있었고 라만분석으로 실제 만들어진 하이드레이트 내에 혼합기체를 확인하였다. 또한 하이드레이트 형성속도 및 회수기체의 조성을 측정하여 분리 및 회수의 효율을 살펴보았다. 본 실험에서 얻어진 결과는 $SF_6$ 혼합기체의 분리 및 처리에 관한 연구의 중요한 기초 자료가 될 것이다.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.218.2-218.2
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• 2010

저분자량의 가스와 물이 물리적 결합으로 이루어진 가스 하이드레이트는 상대적으로 많은 양의 가스가 포집될 수 있다는 특성을 이용하여 다양한 분야에서 활발한 연구가 진행되고 있다. 본 연구에서는 매립지에서 발생되는 매립가스를 하이드레이트의 원리를 이용하여 효율적으로 저장 및 수송하기위한 공정에 적용하기위해 필요한 매립지 가스 하이드레이트의 상평형에 대한 특성을 분석하고자한다. 일반적으로 매립지 가스에는 메탄이 약 50%, 이산화탄소가 약 35%, 질소가 약 6% 포함되어 있으며 그 밖에 산소, 수분, 암모니아 황화수소 메르캅탄 등 할로겐 계통을 포함한 탄화수소계화합물 수십여종이 포함되어 있다. 이러한 매립지가스를 하이드레이트화 하기위해서는 매립지가스에 포함된 다양한 성분들이 하이드레이트 형성에 미치는 영향을 알아볼 필요가 있다. 특히 황화수소의 경우 독성이 있으며, 실제 플랜트에서 장비의 부식등 악영향을 미치므로 이와 관련한 기초 연구가 필요하다. 따라서 본 연구에서는 메탄, 이산화탄소, 황화수소가 각각 49.9%, 50.05%, 500ppm의 조성으로 이루어진 혼합가스를 이용하여 하이드레이트 생성 및 해리 시 거동을 측정하고 그 상평형 영역을 기존데이터와 비교분석 하였다. 25bar, 36bar에서 측정한 상평형 데이터는 한국해양대학교 에서 측정한 결과와 마찬가지로 실제 상평형 영역이 CSMHYD 프로그램으로 예측한 것보다 하이드레이트의 안정영역이 약 2bar 정도 높게 형성되는 것을 확인하였으며, $CH_4+CO_2+H_2S$ 혼합가스 하이드레이트의 생성 시 mol consumption은 $CH_4+CO_2$ 혼합가스 하이드레이트와 유사하게 나타났다. 이 결과로 유추하건대, 황화수소의 첨가는 하이드레이트의 형성 압력을 높이지만, 하이드레이트 형성률에는 크게 영향을 미치지 않는다고 할 수 있다.