Recent improvements in the differential scanning calorimetry methods applied to the study of gas hydrates

André, Rémi

Le parlouer, Pierre

Marlin, Laurent

Plantier, Frédéric

Torré, Jean-Philippe

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    OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible Any correspondence concerning this service should be sent  to the repository administrator: tech-oatao@listes-diff.inp-toulouse.fr This is an author’s version published in: http://oatao.univ-toulouse.fr/21951  To cite this version:  Plantier, Frédéric and Torré, Jean-Philippe  and Marlin, Laurent and André, Rémi and Le parlouer, Pierre Recent improvements in the differential scanning calorimetry methods applied to the study of gas hydrates. (2014) In: 20th European Conference on Thermophysical Properties, 31 August 2014 - 4 September 2014 (Porto, Portugal). (Unpublished)  Open  Archive  Toulouse  Archive  Ouverte a Laboratoire des Fluides Complexeset leurs RéservoirsUPPA - TOTAL – CNRSPau (France)ECTP 2014 20th European Conference on Thermophysical Properties – August 31st - 2014 – Porto, Portugalb SETARAM Instrumentation Caluire, FranceTechnical details of the prototypeContact: (*) Frédéric Plantier (LFCR): Univ. Pau & Pays Adour, LFCR, BP1155, PAU, F-64013, France ; frederic.plantier@univ-pau.fr ; +335 59 57 44 17Conclusions• A novel high pressure calorimetric cell equipped with a mechanical agitation and a dynamic pressure control has been developed and tested.• The temperature and enthalpy calibrations have been performed ; the precision and the sensitivity constant have been determined.• the cell prototype has been used to obtain equilibrium data and phase change enthalpy of the CO2 hydrate• The experimental results obtained are in good agreement with literature data, and demonstrate the potentialities of this novel equipmentReferences• [1] Larson, D., 1955. PhD Thesis, University of Illinois, Urbana, Illinois, USA.• [2] Adisasmito S. et al. (1991). J. Chem. Eng. Data 36(1), 68-71• [3] Fan S. and Guo T.-M. (1999). J. Am. Chem. Soc. 44, 829-832 • [4] Sloan, E.D and Koh, C.A., 2008. Clathrate hydrates of natural gases. 3rd edition. CRCPress, New York.• [5] Uchida et al. (1995). Direct Ocean Disposal of Carbon Dioxide. Terra Sci. Publish., 45-61• [6] Sabil et al. (2010). Fluid Phase Equilibria 290 (2010) 109–114Thermodynamic properties of gas hydrates (e.g. phase equilibrium data, phase change enthalpies, specific heat, etc.) can be obtained by using high pressure calorimetric techniques.However, in some cases, one of the major drawback to existing devices is the absence of in-situ agitation leading to problems such as efficient gas solubilization, long induction times, formation of an hydrate crust covering the gas/liquid interface,low hydrate to water conversion, etc.) OutlineImage from  Lenny Martinez (LAL), MSc thesisDevelopment, tests and validation in our laboratory (LFCR, France) of a novel type of calorimetric cell for BT 2.15 and C80 SETARAM calorimeters :Patent number WO2014016414 (A1)Patent Cooperation Treaty applicationDynamic control of the pressureAgitation motorLink between the motor and the agitator shaftWellheadHigh pressure measuring cellGeneral views The mechanical agitation in the measuring cell is provided by a removable rotaryshaft on which star washers have been welded (N < 200 RPM). The link between the wellhead and the measuring cell is provided by two concentric tubes allowing the agitator shaft to rotate freely in the middle of the tubes.  The space let between the agitator shaft and the first tube is used for the admission of the fluids into the cell, while the annular space between the two concentric tubes allows flowing the fluids to the outlet.   The direction of the fluid flow is completely reversible and the pressure inside the cell can be dynamic controlled during the experiment.(A) Circulation du fluide vers la cellule de mesure. (B)(C)(A) Picture of the prototype (B) High pressure cell and its agitation system(C) Prototype installed on a SETARAM BT 2.15 calorimeterfluidinletFluid outletExperimental resultsCalibration of the prototype in temperature and enthalpySensitivity constant:  κ = (3,46 ± 0,05).10-5 J.µV-1.s1Application to CO2 hydratesP = 3.05 ± 0.05 MPaComparison of our results to literature data• Teq.EXP (PCO2 = 3.05 ± 0.05 MPa) = 7.6 ± 0.2 °CPrecision in temperature : ± 0.2 °C {-10 < T (°C) < 18 }• the presence of the in-situ agitation triggers the crystallization (rupture of the metastability, reduction of the induction time) • the stirring process no creates noise/perturbation of the calorimetric signal • a good reproducibility in the results is obtained• ∆HdissoEXP (PCO2 = 3.05 ± 0.05 MPa) :y = 3.4595E-05xR2 = 9.9873E-010501001502002503003504000.E+00 2.E+06 4.E+06 6.E+06 8.E+06 1.E+07signal calo ( µV.s/g)Enthalpie de fusion (J/g)Cyclohexanen-C12n-C14n-C16H2OY  4.4 95 10-5 XR2 = 0.998735101520253035404550-2 3 8 13T (°C)P (bar)our data (CO2 hydrate)Larson et al. (1955) [1]Adisasmito et al. (1991) [2]Fan and Guo (1999) [3]CSMGem Model from Sloan andKoh (2008) [4] Good agreement !-800-600-400-20002004006008000 40000 80000 120000 160000 200000Temps (s)Flux (mW)051015202530Température (°C)avec agitationsans agitation20 °C0.9 °C25 °CHydrate CrystallizationStart of hydrate dissociationwithout agitationwith agitation ∆HdissoEXP = 62  ± 3 (kJ / molCO2)Assumptions:• NH = hydration number (CO2 – NH .H20 ) equal to 7.3 ± 0.13 [5]• the water to hydrate conversion is total (η = 100 %)OK !RECENT IMPROVEMENTS IN THE HIGH PRESSURE DIFFERENTIAL SCANNING CALORIMETRY METHOD APPLIED TO THE STUDY OF GAS HYDRATESFrédéric Plantier a,*, Jean-Philippe Torré a, Laurent Marlin a, André Rémib, Le Parlouer PierrebCirculation of fluids through annular spacesMechanical agitator located inside the measuring cellFluid flow from inlet to outlet (through the measuring cell) Benefits: measurements under pressure(P < 20 Mpa) in-situ mechanical agitation dynamic control of the pressure inside the cell designed for BT 2.15 and C 80 SETARAM calorimetersRéférences [6] T (°C ) ∆H (kJ/mol)Vlahakis et al. (1972) 0 59.9Kamath (1984) -- 80.1Long (1994) -- 73Skovborg and Rasmussen (1994) 0.5 68.71Uchida et al. (1995) 0.5 65.22Yoon et al. (2003) quadruple point Q1 57.66Anderson (1983) 9.0 - 1.0 58.2 - 62.5Dalahaye et al. (2006) 7.1 65.22Sabil et al. (2010) 7.6 (P = 3.0 MPa) 62.48Tfusion _ref (°C) Tfusion _exp (°C) Water 0,00 ± 0,05 0.1 ± 0.1 Cyclohexane 6.5 ± 0.3 6.7 ± 0.2 n-C12 - 9,7 ± 0,3 - 9,9 ± 0.2n-C14 5.6 ± 0.9 5.3 ± 0.2 n-C16 18 ± 1 18,1 ± 0,2 reference (NIST)Tdisso (°C) ∆Hdisso (J/geau)Test 1 7,5 ± 0,2 480 ± 10 Test 2 7,6 ± 0,2 480 ± 10 Test 3 7,7 ± 0,2 460 ± 10 Réf 7,1 CSMGEMindustrialized and commercialized by SETARAM Instrumentation

Recent improvements in the differential scanning calorimetry methods applied to the study of gas hydrates.

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Recent improvements in the differential scanning calorimetry methods applied to the study of gas hydrates.

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