Kharrat, Mamdouh (2004) Study of formation and stability conditions of gas hydrates in drilling fluids. PhD thesis Génie des Procédés, ENSMP.

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Abstract

Drilling fluids are complex media, in which solid particles are in suspension in a water-in-oil emulsion. The formation of gas hydrates in these fluids during off shore drilling operations has been suspected to be the cause of serious accidents. The purpose of this thesis is the study of the formation conditions as well as the stability of gas hydrates in complex fluids containing water-in-oil emulsions.
The technique of high-pressure differential scanning calorimetry was used to characterise the conditions of hydrates formation and dissociation. Special attention has first been given to the validation of thermodynamic measurements in homogeneous solutions, in the pressure range 4 to 12 Mpa; the results were found to be in good agreement with literature data, as well as with modelling results. The method was then applied to water-in-oil emulsion, used as a model for real drilling fluids. It was proven that thermodynamics of hydrate stability are not significantly influenced by the state of dispersion of the water phase. On the other hand, the kinetics of formation and the amount of hydrates formed are highly increased by the dispersion. Applying the technique to real drilling fluids confirmed the results obtained in emulsions. Results interpretation allowed giving a representation of the process of hydrate formation in emulsion.
Empirical modelling was developed to compute the stability limits of methane hydrate in the presence of various inhibitors, at pressures ranging from ambient to 70 MPa. Isobaric phase diagrams were constructed, that allow predicting the inhibiting efficiency of sodium chloride and calcium chloride at constant pressure, from 0,25 to 70 MPa.

References

Références bibliographiques
[1] Hammerschmidt E. G., "Formation of Gas Hydrates in Natural Gas Transportation Lines‿,
Ind. Eng. Chem., 26 (1934), 851-855
[2] Nixdorf, J. et Oellrich L. R. "Experimental determination of hydrate equilibrium conditions for pure gases, binary and ternary mixtures and natural gases‿, Fluid Phase Equilibria, Volume 139, Issues 1-2, December 1997, Pages 325-333.
[3] Barker J.W. et R.K. Gomez, "Formation of Hydrates During Deepwater Drilling Operations‿, J. Pet. Technol. 1989, 297-301.
[4] Hodder M. "Drilling Fluids Design for Deepwater Wells‿, Hart's Petroleum Engineer International, mars 1998, pp. 25-32.
[5] Bureau N. "Interactions entre fluides de gisement et fluides de forage‿, Thèse de doctorat de l'université Claude-Bernard - Lyon 1, présentée à l'IFP le 23 Septembre 2002.
[6] Ouar, H.; Cha, S. B.; Wildeman, T. R. and Sloan E. D. "The formation of Natural Gas Hydrates in Water-Based Drilling Fluids‿ Trans IChemE, Vol 70, Part A, Jan. 1992.
[7] Grigg, R.B. and Lynes, G.L.: "Oil-Base Mud as a Gas-Hydrates Inhibitor‿, SPE (March 1992) 32-38.
[8] Larsen, R.; C. A. Knight and E.D. Sloan "Clathrate Growth and inhibition‿, Fluid Phase Equilibria, 150-151, pp 353-360.
[9] Fidel-Dufour, A.; D.N. Hong and J. M. Herri "Formation and Dissociation of Hydrate Plugs in a Water in Oil Emulsion‿, The Proceedings of the Fourth International Conference on Gas Hydrates‿, 938-941, Yokohama, Japan, May 19-23, 2002.
[10] Claussen W.F. "Suggested Structures of Water in Inert Gas Hydrates‿, J. Chem. Phys., 19, 259-260, 1951a.
[11] Claussen W.F. "A Second Water Structure for Inert Gas Hydrates‿, J. Chem. Phys., 19, 1425-1426, 1951b.
[12] Claussen W.F., Erratum: "Suggested Structures of Water in Inert Gas Hydrates‿, J. Chem. Phys., 19, 662, 1951c.
[13] Von Stackelberg, M. et H.R. Müller "On the Structure of Gas Hydrates‿, J. Chem. Phys., 1319-1320, 1951a.
[14] Von Stackelberg, M. et H.R. Müller "Zur Struktur der Gashydrate‿, Naturwissenschaften, 456, 1951b.
[15] Pauling, L. et R.E. Marsh, "The Structure of Chlorine Hydrate‿, Proc. Natl. Acad. Sci. U.S.A. 38, 112-118, 1952.
[16] Muller H.R. et M. von Stackelberg, "Zur struktur der gashydrate‿, Naturwissenschaften, 39, 20-21, 1952.
[17] Ripmeester J.A., J.S. Tse, C.I. Ratcliffe et B.M. Powell, "A New Clathrate Hydrate Structure‿, Nature, 325, 135-136, 1987.
[18] Ripmeester J. A., C. I. Ratcliffe et G.E. McLaurin, "The Role of Heavier Hydrocarbons in Hydrate Formation‿, AIChE Spring Meeting, Session 44, Hydrates in the Gas Industry, April 1991.
[19] Sloan E.D., "Gas Hydrates: Review of Physical/Chemical Properties‿, Energy & Fuels, Vol. 12, No. 2, 1998.
[20] Mehta A.P., T.Y. Makogon, R.C. Burruss, R.F. Wendlandt et E. D. Sloan "A composite phase diagram of structure H hydrates using Schreinemakers' geometric approach‿, Fluid Phase Equilibria, Volume 121, Issues 1-2, 15 July 1996, Pages 141-165.
[21] Lai D. T. et A. K. Dzialowski (1989) "Investigation of natural gas hydrates in various drilling fluids ‿, SPE/IADC 18637, SPE/IADC Drilling Conference, New Orleans, Louisiane, 28 Fev-3 Mars 1989.
[22] Sloan E. J. D. "Clathrate Hydrate of Natural Gases‿, Marcel Dekker, New York, 1990.
[23] Roberts O. L., E. R. Brownscombe et L.S. Howe "Methane and ethane hydrates‿, Oil&Gas J., 39(30), 37 (1940).
[24] Deaton, W. M. et E.M. Frost, J. "Gas hydrates and their relation to the operation of natural gas pipe lines‿, U.S. Bureau of Mines Monograph 8, 1946.
[25] Kobayashi R. et D.L. Katz, "Methane hydrate at high pressures‿, Petroleum Transactions , AIME, 186, 66 (1949).
[26] Mc Leod, H.D. et J.M. Campbell, "Natural gas hydrates at pressures to 10,000 psia‿, J. Petrol. Tech., 13, 590, 1961.
[27] Marshall D.R., S. Saito et R. Kobayashi, "Hydrates at High Pressures. Methane-Water and Argon-Water Systems‿, AIChE Journal, 10, 202, 723, 1964.
[28] Jhaveri J. et D.B. Robinson, "Hydrates in the methane-nitrogen system‿, Can. J. Chem. Eng. 43, 75, 1965.
[29] Galloway T.J., W. Ruska, P.S. Chappelear et R. Kobayashi, "Experimental measurements of hydrate numbers for methane and ethane and comparison with theoretical values‿, Ind. Eng. Chem. Fundam., 9, 237, 1970.
[30] Falabella, B.J. "A study of Nartural Gas Hydrates‿, Dissertation, U. Mass., 1975, Univ. Microfilms. No. 76-5849, Ann Arbor, MI.
[31] Verma, V.K., "Gas Hydrate from Liquid Hydrocarbon-Water Systems‿, Ph.D. Thesis, University of Michigan, 1974, Univ. Microfilms No. 75-10, 324, Ann arbour, MI.
[32] Aoyagi K., K.Y. Song, R. Kobayashi, E.D. Sloan et P.B. Dharmawardhana, "The Water Content and Correlation of the Water Content of Methane in Equilibrium with Hydrates, and (II) Water Content of a High Carbon Dioxide Simulated Prudhoe Bay Gas in Equilibrium with Hydrates‿, Gas Processors Assgn. Res. Rpt. No. 45, Tulsa, Ok, Décembre 1980.
[33] De Roo, J. L., G. L. Peters, R. N. Lichtenthaler and G. A. M. Diepen "Occurrence of Methane Hydrate in Saturated and Unsaturated Solutions of Sodium Chloride and Water in Dependence of Temperature and Pressure‿, AIChE Journal 1983, 29(4), 651-657.
[34] Jager M.D. et E.D. Sloan, "The effect of pressure on methane hydration in pure water and sodium chloride solutions‿, Fluid Phase Equilibria, Volume 185, Issues 1-2, 30 July 2001, Pages 89-99.
[35] Thakore J.L. et G.D. Holder, "Solid vapor azeotropes in hydrate-forming systems‿, Ind. Eng. Chem. Res., 26, 462 (1987).
[36] Reamer H.H., F.T. Selleck et B.H. Sage, J. Petrol. Tech., 4(8), 197, 1952.
[37] Holder G.D. et G.C. Grigoriou, "Hydrate dissociation pressures of (methane + ethane + water) existence of a locus of minimum pressures‿, J. Chem. Therm., 12, 1093, 1980.
[38] Holder G.D. et J.H. Hand, "Multiple-phase equilibria in hydrates from methane, ethane, propane and water mixtures‿, AIChE J., 28, 440-447, 1982.
[39] Ng H. J. et D.B. Robinson, "Hydrate formation in systems containing methane, ethane, propane, carbon dioxide or hydrogen sulfide in the presence of methanol‿, Fluid Phase Equilibria, 21, 145-155, 1985.
[40] Sloan E.D., K.A. Sparks et J.J. Jhonson, "Two-phase liquid hydrocarbon-hydrate equilibrium for ethane and propane‿, Ind. Eng Chem. Res. 26, 1173-1179, 1987.
[41] Avlonites, D. "Multiphase Equilibria in oil-Water Hydrates Forming Systems‿, M. Sc. Thesis, Heriot-Watt University, Edinburgh, Scotland, 1988.
[42] Miller B. et E.R. Strong, Proc. Am. Gas. Assoc., 27, 80, 1945.
[43] Wilcox, W.I., D.B. Carson et D.L. Katz, "Natural gas hydrates‿ Ind. Eng. Chem., 33, 662, 1941.
[44] Robinson D.B. et B.R. Mehta, J. Can. Petr. Tech., 10, 33-35, 1971.
[45] Holder G.D. et S.P. Godbole, AIChE J.,‿Measurement and prediction of dissociation pressures of isobutane and propane hydrates below the ice point‿ 28 (6), 930-934, 1982.
[46] Patil S.L., "Measurement of Multiphase Gas Hydrate Phase Equilibria: Effect of Inhibitors and Heavier Hydrocarbon Components‿, M.Sc. Thesis, U. Alaska, Fairbanks, AL, 1987.
[47] Schneider G.R. et J. Farrar, U.S. Dept. of Interior, Rsch. Dev. Rpt. No. 292, p37, January 1968.
[48] Rouher O.S. et A.J. Barduhn, "Hydrates of Iso and Normal Butane and their mixtures‿ Desalination, 6, 57, 1969.
[49] Wu B.J., D.B. Robinson et H.J. Ng, "Three and four-phase hydrate forming conditions in methane + isobutane + water ‿ J. Chem. Therm., 8, 461, 1976.
[50] Unruh, C.H., Katz, D.L. "Gas hydrates of carbon dioxide - methane mixtures‿ Petroleum Transactions; AIME, 186, p 83, 1949.
[51] Larson S.D., "Phase Studies of the Two-Component Carbon-Dioxide-Water System‿, Involving the Carbon Dioxide Hydrate, Univ. Illinois, 1955.
[52] Miller S.L. et W.D. Smythe, "Carbon dioxide clathrate in the Martian ice Cap‿, Science, 170, 531-533, 1970.
[53] Song K.Y. et R. Kobayashi, "Water Content of CO2 in Equilibrium with Liquid Water and/or Hydrates‿, Society of Petroleum Engineers Formation Evaluation, 2, 500-508, Décembre 1987.
[54] Van Cleeff A. et G.A.M. Diepen, "Gas hydrates of nitrogen and oxygen‿ Rec. Trav. Chim., 79, 582-586, 1960.
[55] Bond D.C. et N.B. Russell, Trans. AIME, 179, 192, 1949.
[56] Selleck F.T., L.T. Carmichael et B.H. Sage, "Phase behaviour in the Hydrogen Sulfide -Water System‿, Ind. Eng. Chem. 44, 2219-2226, 1952.
[57] Kobayashi R., H.J. Withrow, G.B. Williams et D.L. Katz, "Gas hydrate formation with brine and ethanol solutions‿, Proc. Du 30ème Ann. Convention. Natural Gasoline Assoc. Amer., 27-31 (1951).
[58] Ng H.J. et D.B. Robinson, Gas Proc. Assn. Rsch. Rpt. 66, Avril 1983.
[59] Ng H.J. et D.B. Robinson, Gas Proc. Assn. Rsch. Rpt. 74, Mars 1983.
[60] Robinson D.B. et H.J. Ng, J. Can. Petrol. Tech., 26, Juillet-Août, 1986.
[61] Ng H.J., C.J. Chen et D.B. Robinson, Gas Proc. Assn. Rsch. Rpt. 87, Mars 1985.
[62] Ng H.J., C.J. Chen et D.B. Robinson, Gas Proc. Assn. Rsch. Rpt. 92, Septembre 1985.
[63] Ng H.J., C.J. Chen et D.B. Robinson, Gas Proc. Assn. Rsch. Rpt. 106, Avril 1987b.
[64] Paranjpe S.G., S.L. Patil, V.A. Kamath et S.P. Godbole, "Hydrate formation in crude oils and phase behaviour of hydrates in mixtures of methane, propane, isobutene and n-butane‿, Papier présenté au troisième congrès de l'Amérique du Nord, Toronto, Canada, 5-10 Juin, 1988.
[65] Benzler H., "Kälteerzeugung durch Auflösen von Eis in Sole‿, Kältetechnick, 7, p. 66, 1955.
[66] Vinh. V.Q. "Modélisation des Conditions de Stabilité des Systèmes d'Hydrates de Méthane en Présence de Mélange de Méthanol-Sels à l'aide d'une Equation d'Etat d'Electrolytes ‿, Thèse de doctorat (Spécialité, Génie des Procédés), Ecole Nationale Supérieure des Mines de Paris, 25 janvier 2001.
[67] Van der Waals, J. H. et J.C. Platteeuw, "Clathrate Solutions‿, Adv. Chem. Phys. 2(1), 1-57, 1959.
[68] Makogon Y.F., F.A. Trebin, A.A. Trofimuk, V.P. Tsarev et N.V. Chersky, "Detection of Natural Gas in a Solid (Hydrate Gas) State‿. Dokl. Acad. Sci. USSR-Earth Sci. Select. 1972, 196, 197-200 (publié à l'origine en Russe, 1971).
[69] Englezos, P., "Clathrate Hydrates‿, invited review, Ind. & Eng. Chem. Res. 32(7), 1251-1274, 1993.
[70] Knox W. G., M. Hess, G.E. Jones et H.B. Smith, "The Clathrate Process‿, Chem. Eng. Progr., 57 (2), 66 (1961)
[71] Mc Naughton J. L. et C.T. Mortimer, "La calorimétrie Différentielle à Balayage‿, (traduit de l'anglais par G. Garrabe) IRS: Physical Chemistry Serie 2, 1975, Vol. 10.
[72] Gray A.P., In analytical Calorimetry, Vol. 1, (R. J. Porter et J. F. Johnson, editors- New York: Plenum Press ), 1968,pp. 209.
[73] Richardson, M. J. "Quantitative aspects of differential scanning calorimetry‿, Thermochimica Acta 300 (1997) 15-28.
[74] Chikos J. S. "Reference materials for measurement of phase change enthalpies‿, dans "Reference materials for calorimetry and differential thermal analysis‿, Sabbah R. (Ed.), Thermochimica Acta (special issue), 1999, 331 (2), 121-166.
[75] ASTM Standard E967, Standard Practice for the Temperature Calibration of Differential Scanning Calorimeters and Differential Thermal Analyzers.
[76] Handa Y.P., "Calorimetric determinations of the compositions, enthalpies of dissociation, and heat capacities in the range 85 to 270 K for clathrate hydrates of xenon and krypton‿, J. Chem. Thermodyn. 1986a, 18, 891-902.
[77] Handa Y.P., "Compositions, enthalpies of dissociation, and heat capacities in the range 85 to 270 K for clathrate hydrates of methane, ethane, and propane, and enthalpy of dissociation of isobutane hydrate as determined by heat-flow calorimeter‿ J. Chem. Thermodyn. 1986b, 18, 915-921.
[78] Handa Y.P., R.E. Hawkins et J.J. Murray, "Calibration and testing of a Tian-Calvet heat-flow calorimeter Enthalpies of fusion and heat capacities for ice and tetrahydrofuran hydrate in the range 85 to 270 K‿, J. Chem. Thermodyn. 1984, 16, 623-632.
[79] Handa Y.P., "A calorimetric study of naturally occurring gas hydrates‿ Ind. Eng. Chem. Res. 1988, 27, 872-874.
[80] Handa Y.P., O. Yamamuro, M. Oguni et H. Suga, "Low-temperature heat capacities of xenon and krypton clathrate hydrates‿ J. Chem. Thermodyn. 1989, 21,1249-1262.
[81] Rueff R.M., E.D. Sloan et V.F. Yesavage, "Heat Capacity and Heat of Dissociation of Methane Hydrates‿, AIChE Journal, 1988, 34 (9), 1468-1476.
[82] Lievois J.S., R. Perkins, R.J. Martin et R. Kobayashi, "Development of an automated, high pressure heat flux calorimeter and its application to measure the heat of dissociation and hydrate numbers of methane hydrate ‿, Fluid Phase Equilibria, 1990, 59, 73-97.
[83] Kang S. P., Lee H. et Ryu B. J., "Enthalpies of dissociation of clathrate hydrates‿, Journal of Chemical Thermodynamics, 2001, 33 (5), 513-521.
[84] Koh C.A., R.E. Westacott, Hurachand K., Zugic M., Zhang W. et Savidge J.L., Proc. Intern. Gas. Res. Conf., San Diego (USA), 1998, vol I, 194-200.
[85] Devarakonda S., A. Groysman et S. Myerson, "THF-water hydrate crystallization: an experimental investigation‿, Journal of Crystal Growth, 204 (1999) 525-538.
[86] Fouconnier B. "Etude par calorimétrie de la formation de l'hydrate de trichlorofluorométhane en émulsion: système modèles pour l'étude des hydrates de gaz‿, Thèse Génie des Procédés Industriels, Université de Technologie de Compiègne, 18 Juillet 2002.
[87] Fouconnier B., Manissol Y., Dalmazzone D., Clausse D., "Study of Trichlorofluoromethane Hydrate Formation in W/O Emulsions: Dissociation Energy and Equilibria with Salt + Water Solutions‿, 7èmes Journées Européennes Thermodynamique Contemporaine. Mons, Belgique, 27-31 août 2001.
[88] Fouconnier B., Manissol Y., Dalmazzone D., Clausse D., "Determination of Trichlorofluoromethane Hydrate Dissociation Energy Using the Shell Model‿, Entropie, 38(239/240), 2002, 72-77.
[89] Fouconnier B., Legrand V., Komunjer L., Clausse D., Bergflodt L., Sjöblom J., " Formation of trichlorofluoromethane hydrate in w/o emulsions studied by differential scanning calorimetry ‿, Progress in Colloid and Polymer Sciences, 1999, 112, 105—108.
[90] Kuustra V. A. et Hammerschaimb E.C., Handbook of Gas Hydrate Properties and Occurrence, DOE/MC/19239, National Technical Information Service, U.S. Department of Commerce, 1983.
[91] Fouconnier B., Clausse D., Habchi K., Dalmazzone D., Dalmazzone C., "Kinetics of Methane Hydrate Formation in Water in Oil Emulsions. A Calorimetry Study‿, 2nd International Conference on Petroleum Behavior and Fouling. Copenhague, Danemark, August 28—30, 2000.
[92] Clausse D., Dalmazzone D., Fouconnier B., Kharrat M., "Etude de la cinétique de formation de divers hydrates dans les émulsions eau dans huile‿, Congrès Mondial des Emulsions, Lyon, France, 24-27 septembre 2002.
[93] Dalmazzone D., Lachet V., Clausse D., "Caractérisation des équilibres de dissociation des hydrates dans les milieux complexes par les techniques PVT et DSC‿, 32èmes Journées de Calorimétrie et d'Analyse Thermique. Hammamet, Tunisie, 12-14 mai 2001.
[94] Dalmazzone D., Kharrat M., Lachet V., Fouconnier B., Clausse D., "DSC and PVT measurements of methane and trichlorofluoromethane hydrate dissociation equilibria in highly concentrated calcium chloride solutions and water-in-oil emulsions‿, Journal of Thermal Analysis and Calorimetry, 70, 2002, 493-505.
[95] Dalmazzone D., Kharrat M., Clausse D., Fouconnier B., "Thermodynamic study of several hydrates in dispersed systems using Differential Scanning Calorimetry‿, 4th Intl. Conf. On Gas Hydrates, Yokohama, Japon, 19-23 mai 2002.
[96] Dalmazzone D., Kharrat M., Lachet V., "Etude des hydrates de méthane et de gaz naturel dans les émulsions eau dans huile par PVT et DSC‿, Colloque sur l'apport de l'analyse thermique et de la calorimétrie dans les industries chimiques, pharmaceutiques et cosmétiques. Lyon, France, 14-16 novembre 2001.
[97] Kharrat M., Dalmazzone D. "Experimental determination of stability conditions of methane hydrate in aqueous calcium chloride solutions using high pressure differential scanning calorimetry‿, Journal of Chemical Thermodynamics, 2003, 35, 1489—1505.
[98] Dalmazzone C., Dalmazzone D., Herzhaft B., "Differential Scanning Calorimetry: A New Technique to Characterize Hydrate Formation in Drilling Muds‿, Society of Petroleum Engineers Annual Technical Conference and Exhibition. Dallas, Texas, October 1-4, 2000.
[99] Dalmazzone C., Herzhaft B., Dalmazzone D., "Characterization of hydrate formation in drilling muds using Differential Scanning Calorimetry (DSC)‿, 4th Intl. Conf. On Gas Hydrates, Yokohama, Japon, 19-23 mai 2002.
[100] Dalmazzone C., Hertzhaft B., Dalmazzone D., Clausse D., "Etude par DSC de la formation d'hydrates de gaz dans les fluides de forage à base d'huile‿, Congrès Mondial des Emulsions, Lyon, France, 24-27 septembre 2002.
[101] Dalmazzone D., Dalmazzone C., Herzhaft B., "Differential Scanning Calorimetry: A New Technique to Characterize Hydrate Formation in Drilling Muds‿, SPE Journal, June 2002, 196-202.
[102] Dalmazzone C., Hertzhaft B., Rousseau L., Le Parlouer P., Dalmazzone D., "Prediction of Gas Hydrates Formation With DSC Technique‿, SPE Annual Technical Conference and Exhibition, 2003, 5 - 8 October, Denver, Colorado.
[103] Roozeboom, H.W.B., " Experimentelle und theoretische Studien über die Gleich-gewichtsbedingungen zwischen festen and flüssigen Verbindungen von Wasser mit Salzen, bespnders mit dem Chlorcalcium‿, Zeit. Phys. Chemie, 4 (1889), 31-65.
[104] Rodebush, W.H., "The freezing points of concentrated solutions and the free energy of solutions of salts‿, J. Amer. Chem. Soc., 40 (1918), 1204-1213.
[105] Yanatieva, O.K., "Polythermal solubilities in the systems CaCl2-MgCl2-H2O and CaCl2-NaCl-H2O‿. Zh. Priklad. Khim. 19, 709-722, 1946 (en Russe).
[106] Parrish W.R. et J.M. Prausnitz, "Dissociation Pressures of Gas Hydrates Formed by Gas Mixtures‿, Ind. Eng. Chem. Process. Des. Develop. 11 (1) (1972) 26-34.
[107] Von Stackelberg M. et H.R. Müller, "Feste Gashydrate II. Struktur und Raumchemie " Elektrochem., 58, 25-39 (1954).
[108] Munck J, S. Skjold-Jorgensen et P. Rasmussen P, "Computations of the formation of gas hydrates‿, Chemical Engineering Data, 27, 22-24, 1988.
[109] Holder G.D., S.P. Zetts et N. Pradhan, "Phase Behaviour in Systems Containing Clathrate Hydrates‿, Rev. Chem. Eng.,5, 1-4, 1988.
[110] Weast, R. C., Ed., "Handbook of Chemistry and Physics,‿ Chemical Rubber Co., Cleveland, Ohio, 48th ed., 1968, p D-95.
[111] Sortland L. D. et D.B. Robinson, Can. J . Chem. Eng., 42, 38, 1964.
[112] Pitzer K.S. et G. Mayorga, "Thermodynamics of electrolytes. II. Activity and osmotic coefficients for strong electrolytes with one or both ions univalent‿ Journal of Physical Chemistry Vol. 77, No. 19: September 13, 1973 , pp 2300 - 2308.
[113] Bradley D.J. et Pitzer K.S. "Thermodynamics of electrolites. 12. dielectric properties of water and Debye-Huckel parameters to 350°C and 1 kbar‿, Journal of Physical Chemistry, 83, 1599-1603,1979.
[114] Silvester L. F. et Pitzer K.S. "Thermodynamics of Electrolytes. 8. High-Temperature Properties, Including Enthalpy and Heat Capacity, with Application to Sodium Chloride‿, The Journal of Physical Chemistry, Vol. 81, No. 19, 1977.
[115] Phutela R.C. et Pitzer K.S. "Thermodynamics of Aqueous Magnesium Chloride, Calcium Chloride, and Sodium Chloride at Elevated Temperatures‿ J. Chem. Eng. Data 32, 76-80, 1987.
[116] Dalmazzone C., Clausse D. " Microcalorimetry ‿, dans Sjöblom J. (Ed.) " Encyclopedic Handbook of Emulsion Technology ‿, chapitre 14, 327—347, 2000, Marcel Dekker Inc., New York.
[117] Turner D., Sloan E.D. "Hydrate phase equilibria measurements and prediction in sediments‿, 4th Intl. Conf. On Gas Hydrates, Yokohama, Japon, 19-23 mai 2002.
[118] Breton A.-M. Thèse de doctorat en Sciences Physiques. Université de Pau, France, 17 Juin1967.
[119] Hirata, M.; S. Ohe et K. Nagahama, " Computed Aided Data Book of Vapor-Liquid Equilibria ‿, Kodansha Limited Elsevier Scientific Publishing Company, Tokyo, 1975.
[120] Peng, D.Y. et D.B. Robinson, " A new Two-Constant Equation of State‿, Ind. Eng. Chem. Fundam., Vol. 15, No. 1, 1976.
[121] Kanno, H. et C.A. Angell, " Homogeneous Nucleation and Glass Formation in Aqueous Alkali Halide Solutions at high Pressures‿ The Journal of Physical Chemistry, Vol 81, No 26, 1977.
[122] Adams, L.H. et R.E. Gibson, " The melting curve of sodium chloride dihydrate. An experimental study of incongruent melting at pressures up to twelve thousand atmospheres‿, J. Am. Chem. Soc., 52, p. 4252, 1930.
[123] Jänecke E., "Über das inkongruente Schmelzen von Salzhydraten bis zum Aufreten von Eis VI, inbesondere von NaCl∙2H2O" Z. Elektrochem., 53, pp. 251 (249).
[124] Wagman D.D.; Evans W.H.; Parker V.B.; Schumm R.H.; Halow I; Bailey S.M.; Churney K.L.; Nuttall R.L. " The NBS tables of chemical thermodynamic properties‿, J. Phys. Chem. Ref. Data, Vol. 11, Suppl. 2, 1982.
Autres ouvrages consultés
Calvet E., "Microcalorimetry of slow phenomena‿, dans "Experimental Thermochemistry‿, Rossini F. D. (Ed.), 1956, Interscience, New York, pp. 237—286.
Calvet E., "Recent progress in microcalorimetry‿, dans "Experimental Thermochemistry‿, vol. II, Skinner H. A. (Ed.), 1962, Interscience, New York, pp. 385—410.
"CRC Handbook of Chemistry and Physics‿, 67th edition, 1986—87, Weast R. C. (Ed.), CRC Press Inc., Boca Raton, Florida, USA.

Table of content

Sommaire
Introduction - 1
Chapitre 1: Contexte de l'étude - 3
1. Le contexte industriel - 3
1.1 Les hydrates de gaz dans l'industrie pétrolière - 3
1.2 Les fluides de forage - 4
1.2.1 Fonctions des fluides de forage - 4
1.2.2 Formulation des boues de forage - 5
1.3 Prévention de la formation d'hydrates - 6
2. Revue bibliographique - 7
2.1 Structure et composition des hydrates de gaz - 7
2.2 La thermodynamique des hydrates de gaz - 8
2.2.1 Mesure des conditions de stabilité - 8
2.2.2 Effet de la structure et de la composition - 9
2.2.3 Effet des solutés - 10
2.2.4 Diagramme de phase hydrate-eau-inhibiteur - 11
2.2.5 Calcul des équilibres des hydrates - 13
2.3 Perspectives d'exploitation des hydrates naturels et artificiels - 14
3. L'Analyse Calorimétrique Différentielle: théorie et applications - 15
3.1 Présentation de l'Analyse Calorimétrique Différentielle (ACD) - 15
3.1.1 Principe technique - 15
3.1.2 Applications de l'ACD - 16
3.2 Théorie de l'ACD - 17
3.2.1 Hypothèses et notations - 18
3.2.2 Bilan thermique - 18
3.2.3 Equation fondamentale de l'ACD - 19
3.3 Etalonnage et précautions de mesure - 21
4. Applications de la calorimétrie dans l'étude des hydrates - 23
4.1 Etudes par microcalorimétrie - 23
4.2 Etudes par analyse calorimétrique différentielle - 26
4.2.1 Etudes cinétiques - 26
4.2.2 Etudes sur les conditions d'équilibre des hydrates en phase dispersé - 26
Chapitre 2: Application de l'Analyse Calorimétrique Différentielle sous pression à la détermination des conditions de stabilité des hydrates de gaz en solution continue - 28
1. Montage expérimental et matériaux - 28
1.1 Description du montage expérimental - 28
1.2 Matériaux - 30
2. Validations - 31
2.1 Contrôle des concentrations par densimétrie - 31
2.2 Validation de l'étalonnage du DSC 111 - 31
2.3 Signaux thermiques associés à la formation et à la dissociation de l'hydrate - 32
2.4 Mesure des température d'équilibre de dissociation des hydrates: principe et validation - 33
3. Détermination des points d'équilibre de l'hydrate de méthane dans les solutions de chlorure de sodium et de chlorure de calcium - 37
3.1 Analyse des thermogrammes - 37
3.1.1 Solutions de chlorure de sodium - 37
3.1.2 Solutions de chlorure de calcium - 38
3.1.3 Interprétation - 38
3.2 Mise en œuvre du modèle de Van der Waals et Platteuuw - 40
3.2.1 Ecriture des conditions d'équilibre - 40
3.2.2 Le modèle de van der Waals et Platteeuw - 41
3.2.3 Développement thermodynamique de - 43
3.2.4 Modèle de Pitzer - 45
3.2.5 Calcul de la fugacité du méthane - 47
3.3 Comparaison entre mesures et calculs - 48
3.3.1 Solutions de chlorure de sodium - 48
3.3.2 Solutions de chlorure de calcium - 49
4. Application aux hydrates de gaz naturel - 52
4.1 L'eau pure - 52
4.2 Solutions de chlorure de sodium - 54
4.3 Solutions de chlorure de calcium - 57
4.4 Tentatives d'interprétation - 58
5. Conclusion - 59
Chapitre 3: Application de l'A.C.D. sous pression à l'étude des hydrates de gaz dans les fluides hétérogènes - 60
1. Systèmes étudiés - 60
1.1 Formulation - 60
1.2 Granulométrie - 61
1.3 Caractérisation de la stabilité des émulsions - 63
2. Caractéristiques de la formation et de la dissociation des hydrates de gaz en phase aqueuse dispersée - 66
2.1 Formation - 66
2.1.1 Hydrates de méthane - 66
2.1.2 Hydrates de gaz naturel - 68
2.2 Dissociation - 69
2.2.1 Interprétation des thermogrammes de dissociation - 69
2.2.2 Conditions d'équilibre des hydrates de méthane en milieu dispersé - 70
2.2.3 Effets de sursaturation - 71
2.2.4 Cas des hydrates de gaz naturel - 72
2.3 Equilibres invariants - 74
2.3.1 Mise en évidence - 74
2.3.2 Mesure des équilibres quadruples - 77
2.3.3 Quantité d'hydrates formés - 79
2.4 Effet des hydrates de gaz sur la stabilité des émulsions - 80
2.5 Interprétation du phénomène de cristallisation des hydrates de gaz en émulsion - 82
3. Etude des boues à l'eau - 85
3.1 Formation et dissociation des hydrates dans les boues à l'eau - 85
3.2 Influence du dosage du mélange d'inhibiteurs - 88
4. Conclusion - 88
Chapitre 4: Modélisation - 91
1. Développement d'une méthode simple de calcul des données d'équilibres de l'hydrate de méthane - 91
1.1 Modélisation de l'activité de l'eau dans l'hydrate de méthane - 91
1.2 Application à la prédiction des conditions d'équilibre de l'hydrate de méthane en présence d'inhibiteurs - 95
1.2.1 Mise en œuvre de la méthode prédictive - 95
1.2.2 Calcul des points d'équilibre dans l'eau pure - 95
1.2.3 Calcul des points d'équilibre en présence de chlorure de calcium - 95
1.2.4 Calcul des points d'équilibre en présence d'alcools - 97
2. Diagrammes de phases des systèmes (CH4 + H2O + NaCl) et (CH4 + H2O + CaCl2) - 99
2.1 Principe de construction des diagrammes de phases ternaires - 99
2.1.1 Hypothèses - 99
2.1.2 Points remarquables - 99
2.2 Diagrammes de phases binaires - 100
2.2.1 Binaire (NaCl + H2O) - 100
2.2.2 Binaire (CaCl2 + H2O) - 105
2.3 Diagrammes de phases ternaires (CH4 + H2O + NaCl) - 105
2.3.1 Point quintuple {NaCl•2H2O (s) + H2O (s) + H (s) + L + V} - 106
2.3.2 Points quadruples {H (s) + H2O (s) + L + V} - 106
2.3.3 Points quadruples {H (s) + NaCl•2H2O (s) + L + V} - 107
2.3.4 Point quintuple {NaCl•2H2O (s) + NaCl (s) + H (s) + L + V} - 109
2.3.5 Points quadruples {H (s) + NaCl (s) + L + V} - 109
2.3.6 P <1,285 MPa - 110
2.3.7 P = 1,285 MPa - 111
2.3.8 1,285 MPa <P <2,543 MPa - 111
2.3.9 P = 2,543 MPa - 111
2.3.10 2,543 MPa <P <37,041 MPa - 113
2.3.11 P = 37,041 MPa - 113
2.3.12 P >37,041 MPa - 113
2.4 Diagrammes de phases ternaires CH4-H2O-CaCl2 - 113
2.4.1 Point quintuple {CaCl2•6H2O (s) + H2O (s) + H (s) + L + V} - 115
2.4.2 Points quadruples {H (s) + H2O (s) + L + V} - 115
2.4.3 Points quadruples {H (s) + CaCl2•6H2O (s) + L + V} - 116
2.4.4 P <0,457 MPa - 118
2.4.5 P = 0,457 MPa - 118
2.4.6 0,457 MPa <P <2,543 MPa - 120
2.4.7 P = 2,543 MPa - 120
2.4.8 P >2,543 MPa - 121
Conclusion - 123
Références bibliographiques - 125

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