Salinity Effect on the Equilibria and Kinetics of the Formation of CO2 and R-134a Gas Hydrates in Seawater

Lianna Johanna; A Ram Kim; Guk Jeong; Jea-Keun Lee; Tae Yun Lee; Jun-Heok Lim; Yong Sun Won

Korean Journal of Materials Research, Vol.26, No.7, 382-387, July, 2016

DOI10.3740/MRSK.2016.26.7.382 Export Citation

Salinity Effect on the Equilibria and Kinetics of the Formation of CO2 and R-134a Gas Hydrates in Seawater

Lianna Johanna, A Ram Kim, Guk Jeong, Jea-Keun Lee¹, Tae Yun Lee¹, Jun-Heok Lim^†, and Yong Sun Won^†

Department of Chemical Engineering, Pukyong National University, 365, Sinseon-ro, Nam-gu, Busan 48547, Republic of Korea
¹Department of Environmental Engineering, Pukyong National University, 45, Yongso-ro, Nam-gu, Busan 48513, Republic of Korea

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Gas hydrates are crystalline solids in which gas molecules (guests) are trapped in water cavities (hosts) that are composed of hydrogen-bonded water molecules. During the formation of gas hydrates in seawater, the equilibria and kinetics are then affected by salinity. In this study, the effects of salinity on the equilibria of CO2 and R134-a gas hydrates has been investigated by tracing the changes of operating temperature and pressure. Increasing the salinity by 1.75% led to a drop in the equilibrium temperature of about 2 ℃ for CO2 gas hydrate and 0.38 ℃ for R-134a gas hydrate at constant equilibrium pressure; in other words, there were rises in the equilibrium pressure of about 1 bar and 0.25 bar at constant equilibrium temperature, respectively. The kinetics of gas hydrate formation have also been investigated by time-resolved in-situ Raman spectroscopy; the results demonstrate that the increase of salinity delayed the formation of both CO2 and R134-a gas hydrates. Therefore, various ions in seawater can play roles of inhibitors for gas hydrate formation in terms of both equilibrium and kinetics.

Keywords:gas hydrate;CO2;R-134a;salinity;kinetics

[References]

Fingar CT, Global Trends 2025: A Transformed World, Superintendent of Documents, US Government Printing Office, Washington D.C., USA (2008).
Fiorenza G, Sharma VK, Braccio G, Energy Conv. Manag., 44(14), 2217 (2003)
IDA and GWI, IDA Worldwide Desalting Plant Inventory Report No. 20 in MS Excel Format, Media Analytics Ltd., Oxford, UK (2008).
Escobar IC, Schafer AI, Sustain. Sci. Eng., 2, 1 (2010)
Karagiannis IC, Soldatos PG, Desalination, 223(1-3), 448 (2008)
GWI, Desalination Markets 2007, A Global Industry Forecast (CD ROM), Global Water Intelligence, Media Analytics Ltd., Oxford, UK (2007).
Parrish WR, Prausnitz JM, Ind. Eng. Chem. Process Des. Dev., 11, 26 (1972)
Holder GD, Corbin G, Papadopoulos KD, Ind. Eng. Chem. Fundam., 19, 282 (1980)
Diamond LW, Geochim. Cosmochim. Acta, 56, 273 (1992)
Nakano S, Moritoki M, Ohgaki K, J. Chem. Eng. Data, 43(5), 807 (1998)
Youssef Z, Barreau A, Mougin P, Jose J, Mokbel I, Ind. Eng. Chem. Res., 48(8), 4045 (2009)
Lirio CFS, Pessoa FLP, Chem. Eng. Trans., 32, 577 (2013)
Liang DQ, Guo KH, Wang RH, Fan SS, Fluid Phase Equilib., 187-188, 61 (2001)
Hashimoto S, Makino T, Inoue Y, Ohgaki K, J. Chem. Eng. Data, 55(11), 4951 (2010)
Oowa M, Nakaiwa M, Akiya T, Fukuura H, Suzuki K, Ohsuka M, Energy Conversion Engineering Conference, Proceedings of the 25th Intersociety, 4, 269 (1990)
Liu N, Gong G, Liu D, Xie Y, Proceeding of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, Canada (2008).
Tang C, Dai X, Du J, Li D, Zang X, Yang X, Liang D, Scientia Sinica Chimica, 41, 145 (2011)
Deaton WM, Frost EM, Gas Hydrates and Their Relation to the Operation of Natural-Gas Pipe Lines, Helium Research Center, Bureau of Mines, Amarillo, Texas, USA (1946).
Vlahakis JG, Chen HS, Suwandi MS, Barduhn AJ, The Growth Rate of Ice Crystals: Properties of Carbon Dioxide Hydrate, a Review of Properties of 51 Gas Hydrates, Syracuse University Research and Development Report, p.830 (1972).
Larson SD, Phase Studies of the Two Component Carbon Dioxide-water System Involving the Carbon Dioxide Hydrate, University of Illinois, Urbana, USA (1955).

[Referenced By]

[1] Fingar CT, Global Trends 2025: A Transformed World, Superintendent of Documents, US Government Printing Office, Washington D.C., USA (2008).

[2] Fiorenza G, Sharma VK, Braccio G, Energy Conv. Manag., 44(14), 2217 (2003)

[3] IDA and GWI, IDA Worldwide Desalting Plant Inventory Report No. 20 in MS Excel Format, Media Analytics Ltd., Oxford, UK (2008).

[4] Escobar IC, Schafer AI, Sustain. Sci. Eng., 2, 1 (2010)

[5] Karagiannis IC, Soldatos PG, Desalination, 223(1-3), 448 (2008)

[6] GWI, Desalination Markets 2007, A Global Industry Forecast (CD ROM), Global Water Intelligence, Media Analytics Ltd., Oxford, UK (2007).

[7] Parrish WR, Prausnitz JM, Ind. Eng. Chem. Process Des. Dev., 11, 26 (1972)

[8] Holder GD, Corbin G, Papadopoulos KD, Ind. Eng. Chem. Fundam., 19, 282 (1980)

[9] Diamond LW, Geochim. Cosmochim. Acta, 56, 273 (1992)

[10] Nakano S, Moritoki M, Ohgaki K, J. Chem. Eng. Data, 43(5), 807 (1998)

[11] Youssef Z, Barreau A, Mougin P, Jose J, Mokbel I, Ind. Eng. Chem. Res., 48(8), 4045 (2009)

[12] Lirio CFS, Pessoa FLP, Chem. Eng. Trans., 32, 577 (2013)

[13] Liang DQ, Guo KH, Wang RH, Fan SS, Fluid Phase Equilib., 187-188, 61 (2001)

[14] Hashimoto S, Makino T, Inoue Y, Ohgaki K, J. Chem. Eng. Data, 55(11), 4951 (2010)

[15] Oowa M, Nakaiwa M, Akiya T, Fukuura H, Suzuki K, Ohsuka M, Energy Conversion Engineering Conference, Proceedings of the 25th Intersociety, 4, 269 (1990)

[16] Liu N, Gong G, Liu D, Xie Y, Proceeding of the 6th International Conference on Gas Hydrates (ICGH 2008), Vancouver, Canada (2008).

[17] Tang C, Dai X, Du J, Li D, Zang X, Yang X, Liang D, Scientia Sinica Chimica, 41, 145 (2011)

[18] Deaton WM, Frost EM, Gas Hydrates and Their Relation to the Operation of Natural-Gas Pipe Lines, Helium Research Center, Bureau of Mines, Amarillo, Texas, USA (1946).

[19] Vlahakis JG, Chen HS, Suwandi MS, Barduhn AJ, The Growth Rate of Ice Crystals: Properties of Carbon Dioxide Hydrate, a Review of Properties of 51 Gas Hydrates, Syracuse University Research and Development Report, p.830 (1972).

[20] Larson SD, Phase Studies of the Two Component Carbon Dioxide-water System Involving the Carbon Dioxide Hydrate, University of Illinois, Urbana, USA (1955).