Phase Equilibrium and Cage Occupancy of Binary Gas Hydrates: Its Application to the Gas Hydrate Refrigeration System

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2009 Vol.46, Issue 2 Preview Page Next Page

Phase Equilibrium and Cage Occupancy of Binary Gas Hydrates: Its Application to the Gas Hydrate Refrigeration System 가스하이드레이트 냉동기 응용을 위한 하이드레이트 상평형 및 포집률 변이에 관한 연구: 임준혁, 이윤제, 한규원, 윤지호
Jun-Hyuck Im, Yun-Je Lee, Kyu-Won Han and Ji-Ho Yoon

30 April 2009. pp. 171-181

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Abstract

Gas hydrate is formed by a physical reaction between relatively small guest molecules and host water molecules under high pressure and low temperature conditions. Gas hydrates have been used in a variety of industrial fields not only as a large energy resource but also as a target medium for various technologies using its physicochemical characteristics. There are a lot of practical applications such as separation processes, natural gas storage-transportation and carbon dioxide sequestration. In particular, the refrigeration system using properties of gas hydrate is expected to be environment-friendly coolants. It is a non-toxic and energy saving process which can be used to replace CFCs which are well known as a main reason of destroying the ozone layer. In this study, the phase equilibrium and cage occupancy of the multi-guest hydrate systems including methane and carbon dioxide are observed to investigate the applicability of gas hydrates to the refrigeration system. To test and prove the validity and reproducibility of a newly designed experimental apparatus, the dissociation pressures of pure methane hydrates are measured at the range of 268～285 K and 2.0～7.5 MPa and compared with the literature values. The three-phase equilibrium conditions of methane + acetone, carbon dioxide + acetone, methane + tert-butyl methyl ether (TBME), carbon dioxide + TBME, and carbon dioxide + tetrahydrofuran hydrates are measured over a wide range of temperatures and pressures. To obtain the heat of dissociation of gas hydrate, the cage occupancy of relatively small guests are estimated using the van der Waals-Platteeuw model.

Keywords

Gas hydrate

Methane

Carbon Dioxide

Refrigeration system

Phase Equilibrium

Cage Occupancy

가스하이드레이트(gas hydrate)는 물 분자(host)가 메탄, 에탄, 이산화탄소 같은 저분자가스(guest)와 고압, 저온의 평형상태에서 포접화합물을 형성하는 것으로 규명되어져 있다. 가스하이드레이트는 에너지 자원으로써의 활용 가치뿐만 아니라 그것의 물리화학적 특성을 이용한 여러 응용 기술 분야에 걸쳐 다양하게 활용되고 있는 실정이다. 분리공정 기술, 에너지 가스의 수송 및 저장 기술, 이산화탄소 격리 기술 등이 대표적인 응용기술이라고 할 수 있다. 특히 가스하이드레이트 냉동기 시스템은 기존의 냉각제로써 오존층 파괴의 주범으로 널리 알려진 CFC(chlorofluorocarbon)-형, HFC(hydrofluorocarbone)-형 냉각제들을 대체할 수 있는 친환경적인 냉각제로 이용될 것으로 기대되고 있다. 본 연구에서는 하이드레이트 냉동기 시스템에 적용하기 위해서 메탄과 이산화탄소를 이용한 다중객체 하이드레이트에 대한 상평형 및 포집률 변이 연구를 실시하였다. 새로 고안된 장치의 적합성을 테스트하기 위해서 268～285 K의 온도범위와 2.0～7.5 MPa의 압력범위에서 순수 메탄 하이드레이트에 대한 상평형 연구를 실시하였고 기존 문헌의 값과 비교하였다. 또한 methane + acetone, carbon dioxide + acetone, methane + tert-butyl methyl ether(TBME), carbon dioxide + TBME, and carbon dioxide + tetrahydrofuran의 3상 상평형 데이터를 측정하였고, 가스하이드레이트의 해리열을 계산하기 위해 van der Waals-Platteeuw 모델을 이용하여 포집률을 예측하였다.

키워드

가스하이드레이트

메탄

이산화탄소

냉동기 시스템

상평형

포집률

References

이흔, 이철수, 강주명, 2003, “가스 하이드레이트를 이용한 이산화탄소의 심해저장,” 한국화학공학회지, 제 41권, 2호, pp. 135-146.
Anthony, D., Laurence, F., Sandrine, M., Imen, C., Jean-Pierre, P., Didier, D. and Walter, F., 2006, “Effect of THF on equilibrium pressure and dissociation enthalpy of CO2 hydrates applied to secondary refrigeration,” Ind. ENg. Chem. Res., Vol. 45, No. 1, pp. 391-397.
Fischer, K. and Gmehling, J., 1995, “Further development, status and results of the PSRK method for the prediction of vapor-liquid equilibria and gas solubilities,” Fluid Phase Equilibria, Vol. 112, pp. 1-22.
Gmehling, J., 1995, “From UNIFAC to modified UNIFAC to PSRK with the help of DDB,” Fluid Phase Equilibria, Vol. 107, pp. 1-29.
Hammershmidt, E. G., 1934, “Formation of Gas Hydrates in natural gas transmission lines,” Int. Eng. Chem., 26 (8), pp. 851-855.
Holderbaum, T. and Gmehling, J., 1991, “PSRK : A group contribution equation of state based on UNIFAC,” FluidPhase Equilibria, Vol. 70, pp. 251-265.
Imen, C., Anthony, D., Laurence, F. and Jean-Pierre, P., 2005, “Benefits and drawbacks of clathrate hydrates : a review of their areas of interest,” Energy Conversion and Management, 46, pp. 1333-1343.
Komai, T., Kang, S. P., Yoon, J. H., Yamamoto, Y., Kawamura, T. and Ohtake, M., 2004, “In situ Raman spectroscopy investigation of th dissociation of methane hydrate at temperatures just below the ice point,” J. Phys. Chem. B, Vol. 108, No. 23, pp. 8062-8068.
Mark, T. C. F. and McMullen, R. K., 1965, “Polygedral clathrate hydrate X : Structure of the double hydrate of tetrahydrofuran and hydrogen sulteide,” J. Chem. Phys., Vol. 43, pp. 2725-2732.
Matsumoto, R., Aoki, Y. and Okuda, Y., 1994, “Methane Hydrate,” Nikkei Sience.
McMullen, R. K. and Jeffery, G. A., 1965, “Polyhedral clathrate hydrate XVI : The structure of ethylene oxide hydrate,” J. Chem. Phys., Vol. 43, pp. 2725-2732.
Ohmura, R., Takeya, S., Uchida, T., Ikeda, I. Y., Ebinuma, T. and Narita, H., 2004, “Clathrate hydrate formation in the system methane + 3-methyl-1-butanol + water : equilibrium data and crystallographic structures of hydrates,” Fluid Phase Equilibria, Vol. 221, pp. 151-156.
Park, Y. J., Cha, M. J., Shin, W. C., Cha, J. H. and Lee, H., 2008, “Thermodynamic and spectroscopic analysis of tert-Butyl Alcohol hydrate : Application for the methane gas storage and transportation,” Proceedings of the 6th International Conference on Gas Hydrates (ICGH2008).
Ripmeester, J. A., Tse, J. S., Ratcliffe, C. I., and Powell, B. M., 1987, “A new clathrate hydrate structure,” Nature, Vol. 325, No. 135, pp. 135-136.
Robert, S. R., John, M. P. and Bruce, E. P., 1988, “The Properties of Gases & Liquids,” McGRAW-Hill International Editions, pp. 314-332.
Shin, H. J., Lee, Y. J., Im, J. H., Han, K. W and Yoon, J. H., 2008, “Thermodynamic stability, spectroscopic identification and molecular composition of binary CO2 clathrate hydrates,” Proceedings of the 6th International Conference on Gas Hydrates (ICGH2008).
Sloan, E. D., 1998, “Clathrate hydrates of natural gases,” Marcel Dekker inc., New York.
Takeshi, S., Shu, M., Shunsuke, H., and Kazunari, O., 2005, “Phase equilibria for H2+CO2+H2O system containing gas hydrate,” Fluid Phase Equilibria, Vol. 233, pp. 190-193.
Uchida, T., Takagi, A., Mae, S., and Kawabata, J., 1997, “Dissolution mechanisms of CO2 molecules in water containing CO2 hydrate,” Energy converse, Vol. 38, pp. 307-312.
Yoon, J. H., Chun, M. K. and Lee, H., 2002, “Generalized model for predicting phase behavior of Clathrate Hydrate,” AIChE Journal, Vol. 48, No. 6, pp. 1317-1330.
Yoon, J. H., Yoshitaka, Y., Takeshi, K. and Hironori, H., 2003, “Rigorous approach to the prediction of the heat of dissociation of gas hydrates,” Ind. Eng. Chem. Res., Vol. 42, No. 5, pp. 1111-1114.
Yoon, J. H., Yoshitaka, Y., Takeshi, K. and Taro, K., 2004, “PSRK method for gas hydrate equilibria,” AIChE Journal, Vol. 50, No. 1, pp. 203-214.
Yoon, J. H., Han, J., Park, J. S., Choi, S. J., Yeon, S. H. and Lee, H., 2007, “Spectroscopic identification, thermodynamic stability and molecular composition of hydrogen and 1,4-dioxane binary clathrate hydrate,” J. Phys. Chem. Solids. Vol. 69, pp. 1432-1435.

Information

Publisher :The Korean Society of Mineral and Energy Resources Engineers
Publisher(Ko) :한국자원공학회
Journal Title :Journal of the Korean Society for Geosystem Engineering
Journal Title(Ko) :한국지구시스템공학회지
Volume : 46
No :2
Pages :171-181

[1] 이흔, 이철수, 강주명, 2003, “가스 하이드레이트를 이용한 이산화탄소의 심해저장,” 한국화학공학회지, 제 41권, 2호, pp. 135-146.

[2] Anthony, D., Laurence, F., Sandrine, M., Imen, C., Jean-Pierre, P., Didier, D. and Walter, F., 2006, “Effect of THF on equilibrium pressure and dissociation enthalpy of CO2 hydrates applied to secondary refrigeration,” Ind. ENg. Chem. Res., Vol. 45, No. 1, pp. 391-397.

[3] Fischer, K. and Gmehling, J., 1995, “Further development, status and results of the PSRK method for the prediction of vapor-liquid equilibria and gas solubilities,” Fluid Phase Equilibria, Vol. 112, pp. 1-22.

[4] Gmehling, J., 1995, “From UNIFAC to modified UNIFAC to PSRK with the help of DDB,” Fluid Phase Equilibria, Vol. 107, pp. 1-29.

[5] Hammershmidt, E. G., 1934, “Formation of Gas Hydrates in natural gas transmission lines,” Int. Eng. Chem., 26 (8), pp. 851-855.

[6] Holderbaum, T. and Gmehling, J., 1991, “PSRK : A group contribution equation of state based on UNIFAC,” FluidPhase Equilibria, Vol. 70, pp. 251-265.

[7] Imen, C., Anthony, D., Laurence, F. and Jean-Pierre, P., 2005, “Benefits and drawbacks of clathrate hydrates : a review of their areas of interest,” Energy Conversion and Management, 46, pp. 1333-1343.

[8] Komai, T., Kang, S. P., Yoon, J. H., Yamamoto, Y., Kawamura, T. and Ohtake, M., 2004, “In situ Raman spectroscopy investigation of th dissociation of methane hydrate at temperatures just below the ice point,” J. Phys. Chem. B, Vol. 108, No. 23, pp. 8062-8068.

[9] Mark, T. C. F. and McMullen, R. K., 1965, “Polygedral clathrate hydrate X : Structure of the double hydrate of tetrahydrofuran and hydrogen sulteide,” J. Chem. Phys., Vol. 43, pp. 2725-2732.

[10] Matsumoto, R., Aoki, Y. and Okuda, Y., 1994, “Methane Hydrate,” Nikkei Sience.

[11] McMullen, R. K. and Jeffery, G. A., 1965, “Polyhedral clathrate hydrate XVI : The structure of ethylene oxide hydrate,” J. Chem. Phys., Vol. 43, pp. 2725-2732.

[12] Ohmura, R., Takeya, S., Uchida, T., Ikeda, I. Y., Ebinuma, T. and Narita, H., 2004, “Clathrate hydrate formation in the system methane + 3-methyl-1-butanol + water : equilibrium data and crystallographic structures of hydrates,” Fluid Phase Equilibria, Vol. 221, pp. 151-156.

[13] Park, Y. J., Cha, M. J., Shin, W. C., Cha, J. H. and Lee, H., 2008, “Thermodynamic and spectroscopic analysis of tert-Butyl Alcohol hydrate : Application for the methane gas storage and transportation,” Proceedings of the 6th International Conference on Gas Hydrates (ICGH2008).

[14] Ripmeester, J. A., Tse, J. S., Ratcliffe, C. I., and Powell, B. M., 1987, “A new clathrate hydrate structure,” Nature, Vol. 325, No. 135, pp. 135-136.

[15] Robert, S. R., John, M. P. and Bruce, E. P., 1988, “The Properties of Gases & Liquids,” McGRAW-Hill International Editions, pp. 314-332.

[16] Shin, H. J., Lee, Y. J., Im, J. H., Han, K. W and Yoon, J. H., 2008, “Thermodynamic stability, spectroscopic identification and molecular composition of binary CO2 clathrate hydrates,” Proceedings of the 6th International Conference on Gas Hydrates (ICGH2008).

[17] Sloan, E. D., 1998, “Clathrate hydrates of natural gases,” Marcel Dekker inc., New York.

[18] Takeshi, S., Shu, M., Shunsuke, H., and Kazunari, O., 2005, “Phase equilibria for H2+CO2+H2O system containing gas hydrate,” Fluid Phase Equilibria, Vol. 233, pp. 190-193.

[19] Uchida, T., Takagi, A., Mae, S., and Kawabata, J., 1997, “Dissolution mechanisms of CO2 molecules in water containing CO2 hydrate,” Energy converse, Vol. 38, pp. 307-312.

[20] Yoon, J. H., Chun, M. K. and Lee, H., 2002, “Generalized model for predicting phase behavior of Clathrate Hydrate,” AIChE Journal, Vol. 48, No. 6, pp. 1317-1330.

[21] Yoon, J. H., Yoshitaka, Y., Takeshi, K. and Hironori, H., 2003, “Rigorous approach to the prediction of the heat of dissociation of gas hydrates,” Ind. Eng. Chem. Res., Vol. 42, No. 5, pp. 1111-1114.

[22] Yoon, J. H., Yoshitaka, Y., Takeshi, K. and Taro, K., 2004, “PSRK method for gas hydrate equilibria,” AIChE Journal, Vol. 50, No. 1, pp. 203-214.

[23] Yoon, J. H., Han, J., Park, J. S., Choi, S. J., Yeon, S. H. and Lee, H., 2007, “Spectroscopic identification, thermodynamic stability and molecular composition of hydrogen and 1,4-dioxane binary clathrate hydrate,” J. Phys. Chem. Solids. Vol. 69, pp. 1432-1435.

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