Abstract
The processes of methane hydrate formation from 50 mass% water-in-oil emulsion from the Mamontovskoe, Sovetskoe, Van-Eganskoe, and Vakhskoe oil deposits (East Siberia) were studied using differential scanning calorimetry. It was shown that different types of thermal effects may be observed in curves corresponding to the formation of hydrate (and/or ice) in different emulsions. In particular on the curves, we observed the appearance of a single asymmetric thermal effect or a set of a large number of separate small thermal effects. The analysis of the results allowed us to conclude that hydrate formation (ice freezing) in the studied emulsions occurs as a collective process, which involves a lot of water droplets in the emulsions. This process occurs in some space inside the emulsion sample. The volume of this space determines the type of curve recorded in experiment. Secondary nucleation (nucleation of the solid phase due to the contact of a drop of water with the neighboring hydrate or ice particle) enables fast formation of gas hydrate in all droplets inside this space.
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References
Sloun ED, Koh CA. Clathrate hydrates of natural gases. 3rd ed. Boca Rator, New-York: CRC Press; 2008.
Sum AK, Koh CA, Sloan ED. Clathrate hydrates: From laboratory science to engineering practice. Ind Eng Chem Res. 2009;48:7457–65.
Milkov AV. Global estimates of hydrate-bound gas in marine sediments: How much is really out there? Earth Sci Rev. 2004;66(3–4):183–97.
Sloan ED. Hydrate engineering. Vol. 21, SPE H.L. Doherty series. In: J.B. Bloys. Richardson: Society of Petroleum Engineers Inc.; 2000.
Zerpa LE, Salager J-L, Koh CA, Sloan ED, Sum AK. Surface chemistry and gas hydrates in flow assurance. Ind Eng Chem Res. 2011;50:188–97.
Sum AK, Koh CA, Sloan ED. Developing a comprehensive understanding and model of hydrate in multiphase flow: from laboratory measurements to field applications. Energy Fuels. 2012;26:4046–52.
Creek JL. Efficient hydrate plug prevention. Energy Fuels. 2012;26:4112–6.
Sjöblom J, Øvrevoll B, Jentoft G, Lesaint C, Palermo T, Sinquin A, Gateau P, Barré L, Subramanian S, Boxall J, Davies S, Dieker L, Greaves D, Lachance J, Rensing P, Miller K, Sloan ED, Koh CA. Investigation of the hydrate plugging and non-plugging properties of oils. J Disp Sci Technol. 2010;31(8):1100–19.
Kelland MA. History of the development of low dosage hydrate inhibitors. Energy Fuels. 2006;20:825–47.
Manakov AYu, Aladko LS, Ogienko AG, Ancharov AI. Hydrate formation in the system n-propanol–water. J Therm Anal Calorim. 2013;111:885–90.
Mayoufi N, Dalmazzone D, Furst W, Elghoul L, Seguatni A, Delahaye A, Fournaison L. Phase behavior of tri-n-butylmethylammonium chloride hydrates in the presence of carbon dioxide. J Therm Anal Calorim. 2012;109:481–6.
Gatiatulin A, Ziganshin M, Gorbatchuk VV. Selective preparation of beta-cyclodextrine clathrates by solid-phase exchange of included tetrahydrofurane for volatile guests in absence of water. J Therm Anal Calorim. 2014;. doi:10.1007/s10973-014-3800-9.
Tohidi B. Novel Hydrate based system, US Patent US20090124520 A1, 14 may 2009.
Moradpour H, Chapoy A, Tohidi B. Transportability of hydrate particles at high water cut systems and optimization of anti-agglomerant concentration. In Proceedings 7th International Conference on Gas Hydrates (ICGH 2011), Edinburgh, 17–21 July 2011.
Turner DJ, Miller KT, Sloan ED. Methane hydrate formation and an inward growing shell model in water-in-oil dispersions. Chem Eng Sci. 2009;64:3996–4004.
Aichele CP, Chapman WG, Rhyne LD, Subramani HJ, Montesi A, Creek JL, House W. Nuclear magnetic resonance analysis of methane hydrate formation in water-in-oil emulsions. Energy Fuels. 2009;23(1):835–41.
Moudrakovski IL, McLaurin GE, Ratcliffe CI, Ripmeester JA. Methane and carbon dioxide hydrate formation in water droplets: spatially resolved measurements from magnetic resonance microimaging. J Phys Chem B. 2004;108:17591–5.
Moudrakovski IL, Ratcliffe CI, McLaurin GE, Simard B, Ripmeester JA. Hydrate layers on ice particles and superheated ice: A 1H NMR microimaging study. J Phys Chem A. 1999;103:4969–72.
Turner DJ, Miller KT, Sloan ED. Direct conversion of water droplets to methane hydrate in crude oil. Chem Eng Sci. 2009;64:5066–72.
Leba H, Cameirao A, Herri J-M, Darbouret M, Peytavy J-L, Gle´nat P. Chord length distributions measurements during crystallization and agglomeration of gas hydrate in a water-in-oil emulsion: simulation and experimentation. Chem Eng Sci. 2010;65:1185–200.
Dalmazzone D, Kharrat M, Lachet V, Fouconnier B, Clausse D. DSC and PVT measurements—Methane and trichlorofluoromethane hydrate dissociation equilibria. J Therm Anal Calorim. 2002;70(2):493–505.
Dalmazzone D, Hamed N, Dalmazzone C, Rousseau L. Application of high pressure DSC to the kinetics of formation of methane hydrate in water-in-oil emulsion. J Therm Anal Calorim. 2006;85:361–8.
Dalmazzone D, Hamed N, Dalmazzone C. DSC measurements and modelling of the kinetics of methane hydrate formation in water-in-oil emulsion. Chem Eng Sci. 2009;64:2020–6.
Dalmazzone C, Noik C, Clausse D. Application of DSC for emulsified system characterization. Oil & Gas Sci Technol Rev IFP. 2009;64(5):543–55.
Clausse D, Gomez F, Dalmazzone C, Noik C. A method for the characterization of emulsions, thermogranulometry: application to water-in-crude oil emulsions. J Colloid Interface Sci. 2005;287:694–703.
Davies SR, Hester KC, Lachance JW, Koh CA, Sloan ED. Studies of hydrate nucleation with high pressure differential scanning calorimetry. Chem Eng Sci. 2009;64(2):370–5.
Kashchiev D, Firoozabadi A. Induction time in crystallization of gas hydrates. J Cryst Growth. 2003;250(3–4):499–515.
Lachance JW, Sloan ED, Koh CA. Determining gas hydrate kinetic inhibitor effectiveness using emulsions. Chem Eng Sci. 2009;64:180–4.
Davies SR, Lachance JW, Sloan ED, Koh CA. High-pressure differential scanning calorimetry measurements of the mass transfer resistance across a methane hydrate film as a function of time and subcooling. End Eng Chem Res. 2010;49:12319–26.
Ohno H, Susilo R, Gordienko R, Ripmeester JA, Walker VK. Interaction of antifreeze proteins with hydrocarbon hydrates. Chem Eur J. 2010;16:10409–17.
Colombel E, Gateau P, Barre L, Gruy F, Palermo T. Discussion of agglomeration mechanisms between hydrate particles in water in oil emulsions. Oil&Gas Sci Technol Rev IFP. 2009;64:629–36.
Gafonova OV, Yarranton HW. The stabilization of water-in-hydrocarbon emulsions by asphaltenes and resins. J. Colloid Interface Sci. 2001;241:469–78.
Taylor CJ, Miller KT, Koh CA, Sloan ED. Macroscopic investigation of hydrate film growth at the hydrocarbon/water interface. Chem Eng Sci. 2007;62(23):6524–33.
Acknowledgements
DSC studies presented in this work were supported by Siberian Branch of the Russian Academy of Sciences, Integration Project No 19 (2012–2014). Measurements carried out with a thermal imaging camera were financially supported by the grants of RF Government for the state support of research conducted under the guidance of leading scientists No. 14.B25.31.0030 (the leading scientist—Yoshiyuki Kawazoe, S. S. Kutateladze Institute of Thermal Physics SB RAS), under the guidance of leading scientists in Russian universities No. 11.G34.31.0046 (the leading scientist—K. Hanjalich, NSU).
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Semenov, M.E., Manakov, A.Y., Shitz, E.Y. et al. DSC and thermal imaging studies of methane hydrate formation and dissociation in water emulsions in crude oils. J Therm Anal Calorim 119, 757–767 (2015). https://doi.org/10.1007/s10973-014-4203-7
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DOI: https://doi.org/10.1007/s10973-014-4203-7