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Received April 2, 2013
Accepted May 20, 2013
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이온성 액체를 이용한 메탄 하이드레이트 생성 촉진효과 연구
Study on the Promotion Effect of Ionic Liquid on CH4 Hydrate Formation
1한양대학교 화학공학과, 133-791 서울특별시 성동구 왕십리로 222 2한국에너지기술연구원 온실가스연구단, 305-343 대전광역시 유성구 가정로 152 3한국교통대학교 화공생물공학과, 380-702 충북 충주시 대학로 50
1Department of Chemical Engineering, Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 133-791, Korea 2Greenhouse Gas Department, Korea Institute of Energy Research, 152 Gajeong-ro, Yuseong-gu, Daejeon 305-343, Korea 3Chemical and Biological Engineering, Korea National University of Transportation, 50 Daehak-ro, Chungju 380-702, Korea
spkang@kier.re.kr
Korean Chemical Engineering Research, August 2013, 51(4), 500-505(6), 10.9713/kcer.2013.51.4.500 Epub 24 July 2013
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Abstract
본 연구에서는 가스 하이드레이트 생성 시 첨가된 이온성 액체가 미치는 생성속도의 향상효과를 조사하였다. 이온성 액체로는 Hydroxyethyl-methyl-morpholinium chloride (HEMM-Cl)을 사용하였다. 메탄 하이드레이트의 상평형 곡선을 구하고 생성유도시간과 메탄가스의 소모량을 측정하였다. 20~20,000 ppm의 HEMM-Cl을 준비하여 하이드레이트가 생성될 수 있는 70 bar, 274.15 K 조건에서 실험을 수행하였다. 하이드레이트 생성 속도에 대한 비교를 위해 순수한 물과 대표적인 촉진제인 sodium dodecyl sulfate를 같은 조건에서 실험하였다. 실험 결과, 이온성 액체인 HEMMCl은 상평형 곡선을 더 높은 압력과 낮은 온도 쪽으로 이동시켰다. 이온성 액체의 첨가 시에는 메탄 하이드레이트의 생성유도시간이 거의 나타나지 않는 것을 알 수 있었다. 메탄가스의 소모량은 모든 농도에서 향상되었고 1,000 ppm에_x000D_
서 가장 많은 양의 가스를 흡수하는 것으로 나타났다. 이온성 액체는 가스 하이드레이트 생성 촉진을 유도하는 것으로 나타났으며 가스저장, 수송 등의 응용기술 개발에 적용이 기대된다._x000D_
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 CH4 hydrate with aqueous IL solution was obtained and its induction time and consumed amount of CH4 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 CH4 hydrate formation in the presence of IL was not shown. The amount of consumed CH4 was increased with the whole range of tested concentration of IL and the highest consumption of CH4 happened at 1,000 ppm of HEMM-Cl. HEMM-Cl induced and enhanced the CH4 hydrate_x000D_
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.
Keywords
References
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Seol J, Lee H, Korean J. Chem. Eng., 30(4), 771 (2013)
Lee JH, Kang SP, Korean Chem. Eng. Res., 50(4), 690 (2012)
Clarke MA, Bishnoi PR, Chem. Eng. Sci., 56(16), 4715 (2001)
Handa Y, J. Chem.Thermodyn., 18(9), 891 (1986)
Gudmundsson JS, Khodakar AA, Parlaktuna M, “Storage of Natural Gas as Frozen Hydrate,” The 67th Annual Technical Conference and Exhibition of SPE, October, Washington DC (1992)
Daimaru T, Yamasaki A, Yanagisawa Y, Chem. Eng. Sci., 56(1-3), 89 (2007)
Vysniauskas A, Bishnoi PR, Chem. Eng. Sci., 38(7), 1061 (1983)
Narita H, Uchida T, “Studies on Formation/Dissociation Rates of Methane Hydrates,” Second International Conference on NGH, Toulouse, France (1996)
Ohmura R, Kashiwazaki S, Shiota S, Tsuji H, Mori YH, Energy Fuels, 16(5), 1141 (2002)
Kalogerakis N, Jamaluddin AKM, Dholabhai, P. D. and Bishnoi PR, “Effect of Surfactants on Hydrate Formation Kinetic,” SPE International Symposium on Oilfield Chemistry, New Orleans, LA (1993)
Khokhar AA, Gudmundsson JS, Sloan ED, Fluid Phase Equilib., 151-152, 383 (1998)
Han X, Wang S, Chen X, Liu F, “Surfactant Accelerates Gas Hydrate Formation,” 4th International Conference on Gas Hydrates, Yokohama, Japan (2002)
Guo Y, Fan S, Guo K, Chen Y, “Storage Capacity of Methane in Hydrate Using Calcium Hypochlorite as Additive,” 4th International Conference on Gas Hydrates, Yokohama, Japan (2002)
Sun ZG, Wang RZ, Ma RS, Guo KH, Fan SS, Energy Conv. Manag., 44(17), 2733 (2003)
Zhang CS, Fan SS, Liang DQ, Guo KH, Fuel, 83(16), 2115 (2004)
Ganji H, Manteghian M, Zadeh KS, Omidkhah MR, Mofrad HR, Fuel, 86(3), 434 (2007)
Daimaru T, Yamasaki A, Yanagisawa Y, J. Petrol. Sci. Eng., 56(1-3), 89 (2007)
Chen Q, Yu Y, Zeng P, Yang W, Liang Q, Peng X, Liu Y, Hu Y, J. Nat. Gas Chem., 17(3), 264 (2008)
Makino T, Matsumoto Y, Sugahara T, Ohgaki K, Masuda H, “Effect of Ionic Liquid on Hydrate Formation Rate in Carbon Dioxide Hydrates,” 7th International Conference on Gas Hydrates, Edinburgh, UK (2011)
Zhong Y, Rogers RE, Chem. Eng. Sci., 55(19), 4175 (2000)
Kwona YA, Park JM, Jeong KE, Kim CU, Kim TW, Chae HJ, Jeong SY, Yim JH, Park YK, Lee J, J. Ind. Eng. Chem., 17(1), 120 (2011)
Deaton WM, Frost EM, “Gas Hydrates and Their Relation to the Operation of Natural Gas Pipelines,” Monograph, American Gas Association (1946)
