Articles de journaux
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T. Dufour; H.M. Hoang; J. Oignet; V. Osswald; P. Clain; L. Fournaison; A. Delahaye Impact of pressure on the dynamic behavior of CO2 hydrate slurry in a stirred tank reactor applied to cold thermal energy storage Article de journal Applied Energy, 204 , p. 641-652, 2017. BibTeX @article{clain2017a,
title = {Impact of pressure on the dynamic behavior of CO2 hydrate slurry in a stirred tank reactor applied to cold thermal energy storage},
author = {T. Dufour and H.M. Hoang and J. Oignet and V. Osswald and P. Clain and L. Fournaison and A. Delahaye},
year = {2017},
date = {2017-10-15},
journal = {Applied Energy},
volume = {204},
pages = {641-652},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
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J; Oignet; A. Delahaye; J.-P.Torré; C. Dicharry; H.M. Hoang; P. Clainand; V. Osswald; Z. Youssef; L. Fournaison Rheological study of CO2 hydrate slurry in the presence of Sodium Dodecyl Sulfate in a secondary refrigeration loop Article de journal Chemical Engineering Science, 158 , p. 294-303, 2017. BibTeX @article{clain2017b,
title = {Rheological study of CO2 hydrate slurry in the presence of Sodium Dodecyl Sulfate in a secondary refrigeration loop},
author = {J; Oignet and A. Delahaye and J.-P.Torré and C. Dicharry and H.M. Hoang and P. Clainand and V. Osswald and Z. Youssef and L. Fournaison},
year = {2017},
date = {2017-06-14},
journal = {Chemical Engineering Science},
volume = {158},
pages = {294-303},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
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Jérémy Oignet; Anthony Delahaye; Jean-Philippe Torré; Christophe Dicharry; Hong Minh Hoang; Pascal Clain; Véronique Osswald; Ziad Youssef; Laurence Fournaison Rheological study of CO2 hydrate slurry in the presence of Sodium Dodecyl Sulfate in a secondary refrigeration loop Article de journal Chemical Engineering Science, 158 , p. 294 - 303, 2016. Résumé | Liens | BibTeX @article{Oignet2017294,
title = {Rheological study of CO2 hydrate slurry in the presence of Sodium Dodecyl Sulfate in a secondary refrigeration loop},
author = {Jérémy Oignet and Anthony Delahaye and Jean-Philippe Torré and Christophe Dicharry and Hong Minh Hoang and Pascal Clain and Véronique Osswald and Ziad Youssef and Laurence Fournaison},
url = {http://www.sciencedirect.com/science/article/pii/S0009250916305486},
doi = {http://dx.doi.org/10.1016/j.ces.2016.10.018},
year = {2016},
date = {2016-12-13},
journal = {Chemical Engineering Science},
volume = {158},
pages = {294 - 303},
abstract = {Abstract Secondary refrigeration and thermal energy storage are promising solutions to enhance the performance of refrigeration systems and reduce the impact of refrigerants on the environment. To improve the energy efficiency of secondary refrigeration loops, phase change material (PCM) slurries with a high energy density, such as CO2 hydrate slurries, can be used as a secondary refrigerant. In addition, hydrate-based processes could be an innovative option to capture CO2 from flue gas. In both applications, the rheological properties of the CO2 hydrate slurry have to be controlled. In the present study, CO2 hydrate slurry in the presence of Sodium Dodecyl Sulfate (SDS) was studied in a dynamic flow loop. The results show that SDS used at concentrations of 1500–2000 ppm significantly decreases agglomeration and improves the flow properties of the slurry. Moreover, SDS helps decrease the viscosity of the CO2-hydrate slurry at high fraction (>10 vol%) and therefore could be suitable for use in industrial applications such as secondary refrigeration, in which hydrate slurries must be easy to handle.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Abstract Secondary refrigeration and thermal energy storage are promising solutions to enhance the performance of refrigeration systems and reduce the impact of refrigerants on the environment. To improve the energy efficiency of secondary refrigeration loops, phase change material (PCM) slurries with a high energy density, such as CO2 hydrate slurries, can be used as a secondary refrigerant. In addition, hydrate-based processes could be an innovative option to capture CO2 from flue gas. In both applications, the rheological properties of the CO2 hydrate slurry have to be controlled. In the present study, CO2 hydrate slurry in the presence of Sodium Dodecyl Sulfate (SDS) was studied in a dynamic flow loop. The results show that SDS used at concentrations of 1500–2000 ppm significantly decreases agglomeration and improves the flow properties of the slurry. Moreover, SDS helps decrease the viscosity of the CO2-hydrate slurry at high fraction (>10 vol%) and therefore could be suitable for use in industrial applications such as secondary refrigeration, in which hydrate slurries must be easy to handle. |
Pascal Clain; Fatou-Toutie Ndoye; Anthony Delahaye; Laurence Fournaison; Wei Lin; Didier Dalmazzone Particle size distribution of TBPB hydrates by focused beam reflectance measurement (FBRM) for secondary refrigeration application Article de journal International Journal of Refrigeration, 50 , p. 19-31, 2015. Résumé | Liens | BibTeX @article{CNDFLD14,
title = {Particle size distribution of TBPB hydrates by focused beam reflectance measurement (FBRM) for secondary refrigeration application},
author = { Pascal Clain and Fatou-Toutie Ndoye and Anthony Delahaye and Laurence Fournaison and Wei Lin and Didier Dalmazzone},
url = {http://labs.esilv.fr/publications/public/2014/CNDFLD14},
year = {2015},
date = {2015-01-01},
journal = {International Journal of Refrigeration},
volume = {50},
pages = {19-31},
abstract = {The present work investigates TBPB(tetra-n-butylphosphonium bromide) hydrate slurries based on focused beam reflectance measurement (FBRM) method. Hydrates can be used as phase change materials (PCM) for thermal energy storage due to their high latent heat of melting. In this study, hydrates were formed from TBPB-water mixtures, suitable for air-conditioning applications. Moreover, hydrate slurries, composed of hydrate-particles dispersed in liquid, are appropriate solutions for cold distribution. Nevertheless, flow properties of hydrate slurries, depending on hydrate crystallization kinetics, must be controlled. In this work, FBRM was used for analysing TBPB-hydrate-particle size distribution. This work showed that FBRM can detect system phase changes (nucleation, growth, agglomeration). In addition, a bimodal distribution of particles was observed. This work could be useful to understand rheological behaviour of hydrate slurry, not only for secondary refrigeration applications, but also for natural gas hydrate transportation, pipeline plugging prevention, and gas capture.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present work investigates TBPB(tetra-n-butylphosphonium bromide) hydrate slurries based on focused beam reflectance measurement (FBRM) method. Hydrates can be used as phase change materials (PCM) for thermal energy storage due to their high latent heat of melting. In this study, hydrates were formed from TBPB-water mixtures, suitable for air-conditioning applications. Moreover, hydrate slurries, composed of hydrate-particles dispersed in liquid, are appropriate solutions for cold distribution. Nevertheless, flow properties of hydrate slurries, depending on hydrate crystallization kinetics, must be controlled. In this work, FBRM was used for analysing TBPB-hydrate-particle size distribution. This work showed that FBRM can detect system phase changes (nucleation, growth, agglomeration). In addition, a bimodal distribution of particles was observed. This work could be useful to understand rheological behaviour of hydrate slurry, not only for secondary refrigeration applications, but also for natural gas hydrate transportation, pipeline plugging prevention, and gas capture. |
Wei Lin; Pascal Clain; Didier Dalmazzone; Walter Fürst; Anthony Delahaye; Laurence Fournaison Thermodynamic properties of semiclathrate hydrates formed from the TBAB+TBPB+water and CO2+TBAB+TBPB+water systems Article de journal Fluid Phase Equilibria, 372 , p. 63–68, 2014. Résumé | Liens | BibTeX @article{LCDFDF14,
title = {Thermodynamic properties of semiclathrate hydrates formed from the TBAB+TBPB+water and CO2+TBAB+TBPB+water systems},
author = { Wei Lin and Pascal Clain and Didier Dalmazzone and Walter Fürst and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2014/LCDFDF14},
year = {2014},
date = {2014-01-01},
journal = {Fluid Phase Equilibria},
volume = {372},
pages = {63--68},
abstract = {Semiclathrate hydrates formed from binary systems of tetra-n-butylammonium bromide (TBAB) + water and tetra-n-butylphosphonium bromide (TBPB) + water have been investigated for their promising application in the refrigeration system. In the present work, semiclathrate hydrates in the ternary system of TBAB + TBPB + water were studied for the first time, in the presence and absence of CO2 pressure. Using DSC technique, the dissociation temperatures of semiclathrate hydrates were determined at the mass fraction of salt mixture ranges from 0.05 to 0.60 with variable composition from pure TBAB to pure TBPB. At any salt concentration tested, the dissociation temperature of semiclathrate hydrates increased regularly with TBAB composition increase. Applying CO2 pressure in the TBAB + TBPB + water system resulted in further increase of dissociation temperature due to the gas enclathration in the mixed hydrate structure. The phase transition enthalpy of semiclathrate hydrates were investigated at wsalts = 0.40 and variable TBPB compositions, without CO2 and with p CO 2 = 1.0 ? MPa . It was found that the dissociation enthalpies of CO2-free and CO2-containing semiclathrate hydrates are almost independent of the TBPB salt composition. From our current results, TBAB + TBPB + CO2 hydrates appear as valuable phase change materials to be used as hydrate slurries for cold storage and transportation in applications requiring variable working temperatures.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Semiclathrate hydrates formed from binary systems of tetra-n-butylammonium bromide (TBAB) + water and tetra-n-butylphosphonium bromide (TBPB) + water have been investigated for their promising application in the refrigeration system. In the present work, semiclathrate hydrates in the ternary system of TBAB + TBPB + water were studied for the first time, in the presence and absence of CO2 pressure. Using DSC technique, the dissociation temperatures of semiclathrate hydrates were determined at the mass fraction of salt mixture ranges from 0.05 to 0.60 with variable composition from pure TBAB to pure TBPB. At any salt concentration tested, the dissociation temperature of semiclathrate hydrates increased regularly with TBAB composition increase. Applying CO2 pressure in the TBAB + TBPB + water system resulted in further increase of dissociation temperature due to the gas enclathration in the mixed hydrate structure. The phase transition enthalpy of semiclathrate hydrates were investigated at wsalts = 0.40 and variable TBPB compositions, without CO2 and with p CO 2 = 1.0 ? MPa . It was found that the dissociation enthalpies of CO2-free and CO2-containing semiclathrate hydrates are almost independent of the TBPB salt composition. From our current results, TBAB + TBPB + CO2 hydrates appear as valuable phase change materials to be used as hydrate slurries for cold storage and transportation in applications requiring variable working temperatures. |
Wei Lin; Pascal Clain; Didier Dalmazzone; Walter Fürst; Anthony Delahaye; Laurence Fournaison Accurate DSC measurement of the phase transition temperature in the TBPB–water system Article de journal The Journal of Chemical Thermodynamics, 61 , p. 132–137, 2013. Résumé | Liens | BibTeX @article{LCDFDF13a,
title = {Accurate DSC measurement of the phase transition temperature in the TBPB–water system},
author = { Wei Lin and Pascal Clain and Didier Dalmazzone and Walter Fürst and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2013/LCDFDF13a},
year = {2013},
date = {2013-01-01},
journal = {The Journal of Chemical Thermodynamics},
volume = {61},
pages = {132--137},
abstract = {There is some disagreement in the literature on the phase transition temperatures of salt semi-clathrates, which melt incongruently due to the change of salt concentration in the liquid phase. By using differential scanning calorimetry (DSC), the phase transition temperatures of tetrabutylphosphonium bromide (TBPB) hydrates were investigated at 0.10 < wTBPB < 0.37 and atmospheric pressure. The freezing point of ice with the presence of NaCl was also studied as a reference. In this work, two DSC procedures were employed: dynamic and stepwise schemes, characterized by the maximum peak temperature Tpeak and inflection point temperature Tend, and final step temperature Tstep, respectively. The stepwise DSC scheme was validated by the measurement of the ice freezing point at wNaCl = 0.10, 0.15 and 0.18. For the dynamic scheme, we developed and tested a method to estimate the melting temperature of TBPB hydrates. This method, though having a higher uncertainty, was more efficient than the stepwise scheme. The phase transition temperatures of TBPB hydrates are presented with the accuracy of 0.1 K and compared with literature data.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
There is some disagreement in the literature on the phase transition temperatures of salt semi-clathrates, which melt incongruently due to the change of salt concentration in the liquid phase. By using differential scanning calorimetry (DSC), the phase transition temperatures of tetrabutylphosphonium bromide (TBPB) hydrates were investigated at 0.10 < wTBPB < 0.37 and atmospheric pressure. The freezing point of ice with the presence of NaCl was also studied as a reference. In this work, two DSC procedures were employed: dynamic and stepwise schemes, characterized by the maximum peak temperature Tpeak and inflection point temperature Tend, and final step temperature Tstep, respectively. The stepwise DSC scheme was validated by the measurement of the ice freezing point at wNaCl = 0.10, 0.15 and 0.18. For the dynamic scheme, we developed and tested a method to estimate the melting temperature of TBPB hydrates. This method, though having a higher uncertainty, was more efficient than the stepwise scheme. The phase transition temperatures of TBPB hydrates are presented with the accuracy of 0.1 K and compared with literature data. |
Pascal Clain; Fatou-Toutie Ndoye; Anthony Delahaye; Laurence Fournaison Comportamiento de flujo y equilibrio de fases de las suspensiones de hidratos de TBPB (bromuro de tetra-n-butilfosfonio) en medios porosos para aplicaciones de refrigeracion Article de journal Frio Calor Aire Acondicionado, 41 (460), p. 3–10, 2013. Résumé | Liens | BibTeX @article{CNDF13,
title = {Comportamiento de flujo y equilibrio de fases de las suspensiones de hidratos de TBPB (bromuro de tetra-n-butilfosfonio) en medios porosos para aplicaciones de refrigeracion},
author = { Pascal Clain and Fatou-Toutie Ndoye and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2013/CNDF13},
year = {2013},
date = {2013-01-01},
journal = {Frio Calor Aire Acondicionado},
volume = {41},
number = {460},
pages = {3--10},
abstract = {The present work investigates the use of hydrates, as appropriate media for cold storage and distribution in refrigeration applications. Previous studies showed that these hydrates are able to trap molecules of carbon dioxide resulting in mixed hydrates. Hydrate can be used as phase change material (PCM) for thermal energy storage and hydrate slurries could be a good solution for industrial issues of cold distribution at various temperature levels. In fact, hydrates formed from tetra-n-butylphosphonium bromide (TBPB) + water mixtures have equilibrium conditions required for air-conditioning applications, with melting temperature at 281 K at atmospheric pressure. Calorimetry devices were used for determining dissociation enthalpies of salt hydrates under vari-ous stability conditions and salt concentrations in bulk and porous media. The results reveal that TBPB hydrates formed in porous media at lower temperature than in bulk conditions for a constant pressure due to capillary forces. In order to characterize the flow behavior of hydrate slurries for cold distribution, a rheological study was carried out in a dynamic loop by the Ostwald method. Finally, FBRM probe was used for a particle size analysis of TBPB hydrate and showed a bimodal distribution which could be confirmed in further work in order to define a potential relation between hydrate particle size and rheological behavior of hydrate slurry.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present work investigates the use of hydrates, as appropriate media for cold storage and distribution in refrigeration applications. Previous studies showed that these hydrates are able to trap molecules of carbon dioxide resulting in mixed hydrates. Hydrate can be used as phase change material (PCM) for thermal energy storage and hydrate slurries could be a good solution for industrial issues of cold distribution at various temperature levels. In fact, hydrates formed from tetra-n-butylphosphonium bromide (TBPB) + water mixtures have equilibrium conditions required for air-conditioning applications, with melting temperature at 281 K at atmospheric pressure. Calorimetry devices were used for determining dissociation enthalpies of salt hydrates under vari-ous stability conditions and salt concentrations in bulk and porous media. The results reveal that TBPB hydrates formed in porous media at lower temperature than in bulk conditions for a constant pressure due to capillary forces. In order to characterize the flow behavior of hydrate slurries for cold distribution, a rheological study was carried out in a dynamic loop by the Ostwald method. Finally, FBRM probe was used for a particle size analysis of TBPB hydrate and showed a bimodal distribution which could be confirmed in further work in order to define a potential relation between hydrate particle size and rheological behavior of hydrate slurry. |
Wei Lin; Pascal Clain; Didier Dalmazzone; Walter Fürst; Anthony Delahaye; Laurence Fournaison Thermodynamic Studies of CO2 + TBAB + Water System: Experimental Measurements and Correlations Article de journal Journal of Chemical & Engineering Data, 58 (8), p. 2233–2239, 2013. Résumé | Liens | BibTeX @article{LCDFDF13,
title = {Thermodynamic Studies of CO2 + TBAB + Water System: Experimental Measurements and Correlations},
author = { Wei Lin and Pascal Clain and Didier Dalmazzone and Walter Fürst and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2013/LCDFDF13},
year = {2013},
date = {2013-01-01},
journal = {Journal of Chemical & Engineering Data},
volume = {58},
number = {8},
pages = {2233--2239},
abstract = {Thermodynamic properties of TBAB + CO2 + water system are important for using TBAB + CO2 semiclathrate hydrates in some promising hydrate-based techniques. This work is an experimental and modeling study of two fundamental properties in vapor?liquid phase equilibrium of TBAB + CO2 + water, that is, CO2 solubility in TBAB solution and density of CO2-saturated TBAB solution. With the use of a PVT system, CO2 solubility was measured; thus, Henry?s constant was obtained at temperatures from 288.1 K to 303.1 K and TBAB mass fraction from 0.10 to 0.40. Our results showed that CO2 is either salted-in or salted-out by the presence of TBAB, depending upon the temperature and TBAB concentration. For the density, we present experimental data for TBAB + water system at T = 283.15 K to 303.15 K with pressures up to 5 MPa. The density of CO2-saturated TBAB aqueous solution was calculated with the help of Duan?s model, which takes into account the effect of pressure and temperature to calculate the apparent molar volume of dissolved CO2 in pure water.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Thermodynamic properties of TBAB + CO2 + water system are important for using TBAB + CO2 semiclathrate hydrates in some promising hydrate-based techniques. This work is an experimental and modeling study of two fundamental properties in vapor?liquid phase equilibrium of TBAB + CO2 + water, that is, CO2 solubility in TBAB solution and density of CO2-saturated TBAB solution. With the use of a PVT system, CO2 solubility was measured; thus, Henry?s constant was obtained at temperatures from 288.1 K to 303.1 K and TBAB mass fraction from 0.10 to 0.40. Our results showed that CO2 is either salted-in or salted-out by the presence of TBAB, depending upon the temperature and TBAB concentration. For the density, we present experimental data for TBAB + water system at T = 283.15 K to 303.15 K with pressures up to 5 MPa. The density of CO2-saturated TBAB aqueous solution was calculated with the help of Duan?s model, which takes into account the effect of pressure and temperature to calculate the apparent molar volume of dissolved CO2 in pure water. |
Pascal Clain; Anthony Delahaye; Laurence Fournaison; Nadia Mayoufi; Didier Dalmazzone; Walter Fürst Rheological properties of tetra-n-butylphosphonium bromide hydrate slurry flow Article de journal Chemical Engineering Journal, 193-194 , p. 112-122, 2012. Résumé | Liens | BibTeX @article{CDFMDF12,
title = {Rheological properties of tetra-n-butylphosphonium bromide hydrate slurry flow},
author = { Pascal Clain and Anthony Delahaye and Laurence Fournaison and Nadia Mayoufi and Didier Dalmazzone and Walter Fürst},
url = {http://labs.esilv.fr/publications/public/2012/CDFMDF12},
year = {2012},
date = {2012-01-01},
journal = {Chemical Engineering Journal},
volume = {193-194},
pages = {112-122},
abstract = {Clathrate hydrate slurries can be considered as two-phase refrigerants due to their high energy densities. The heat of formation of many clathrate hydrates is higher than that observed for other phase change materials used in this field. The present work investigates the use of semiclathrate hydrates, formed from tetra-n-butylphosphonium bromide (TBPB) + water mixtures, as appropriate media for cold storage and distribution in refrigeration applications. Indeed, TBPB hydrates crystallize under atmospheric pressure and at temperatures around 281 K, which are suitable conditions for air-conditioning or refrigeration applications. In the present study, we focus on the rheological behaviour of TBPB hydrate slurry studied thanks to a dynamic loop and the application of Ostwald method. Volumetric flow rates and pressure drops are measured for hydrate fractions between 0 and 28.2 vol.%. The rheological properties deduced from these measurements were modelled using a semi-empirical Ostwald-de Waele law taking into account hydrate slurry fraction. Finally, the apparent viscosity of TBPB hydrate slurry was estimated from the model and a good agreement was found between our data and literature.},
keywords = {},
pubstate = {published},
tppubtype = {article}
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Clathrate hydrate slurries can be considered as two-phase refrigerants due to their high energy densities. The heat of formation of many clathrate hydrates is higher than that observed for other phase change materials used in this field. The present work investigates the use of semiclathrate hydrates, formed from tetra-n-butylphosphonium bromide (TBPB) + water mixtures, as appropriate media for cold storage and distribution in refrigeration applications. Indeed, TBPB hydrates crystallize under atmospheric pressure and at temperatures around 281 K, which are suitable conditions for air-conditioning or refrigeration applications. In the present study, we focus on the rheological behaviour of TBPB hydrate slurry studied thanks to a dynamic loop and the application of Ostwald method. Volumetric flow rates and pressure drops are measured for hydrate fractions between 0 and 28.2 vol.%. The rheological properties deduced from these measurements were modelled using a semi-empirical Ostwald-de Waele law taking into account hydrate slurry fraction. Finally, the apparent viscosity of TBPB hydrate slurry was estimated from the model and a good agreement was found between our data and literature. |
Laurence Fournaison; Anthony Delahaye; Salem Jerbi; Pascal Clain Etudes des cinétiques de formation des coulis d hydrates de CO2 et de leurs écoulements en présence d additifs Article de journal Revue Générale du Froid et du Conditionnement d air, (112), p. 50–56, 2011. Liens | BibTeX @article{FDJC11,
title = {Etudes des cinétiques de formation des coulis d hydrates de CO2 et de leurs écoulements en présence d additifs},
author = { Laurence Fournaison and Anthony Delahaye and Salem Jerbi and Pascal Clain},
url = {http://labs.esilv.fr/publications/public/2011/FDJC11},
year = {2011},
date = {2011-01-01},
journal = {Revue Générale du Froid et du Conditionnement d air},
number = {112},
pages = {50--56},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
|
Nadia Mayoufi; Didier Dalmazzone; Anthony Delahaye; Pascal Clain; Laurence Fournaison; Walter Fürst Experimental Data on Phase Behavior of Simple Tetrabutylphosphonium Bromide (TBPB) and Mixed CO2 + TBPB Semiclathrate Hydrates Article de journal Journal of Chemical & Engineering Data, 56 (6), p. 2987–2993, 2011. Résumé | Liens | BibTeX @article{MDDCFF11,
title = {Experimental Data on Phase Behavior of Simple Tetrabutylphosphonium Bromide (TBPB) and Mixed CO2 + TBPB Semiclathrate Hydrates},
author = { Nadia Mayoufi and Didier Dalmazzone and Anthony Delahaye and Pascal Clain and Laurence Fournaison and Walter Fürst},
url = {http://labs.esilv.fr/publications/public/2011/MDDCFF11},
year = {2011},
date = {2011-01-01},
journal = {Journal of Chemical & Engineering Data},
volume = {56},
number = {6},
pages = {2987--2993},
abstract = {The phase behavior of simple and mixed semiclathrate hydrates formed from CO2 + tetrabutylphosphonium bromide (TBPB) + water mixtures was investigated by pressure-controlled differential scanning calorimetry (DSC) at TBPB concentrations in the range of 0 to 0.073 mole fraction and at CO2 pressure in the range of (0 to 2.0) MPa. In a previous article we demonstrated that TBPB + CO2 mixed hydrates present high dissociation enthalpies and could be used as phase change material, covering the range of temperature from (284.6 to 289.0) K, for secondary refrigeration applications. The present work investigates a broader domain of compositions, resulting in x?T phase diagrams at atmospheric conditions and at various CO2 pressures. These data are required to model the potential latent heat of hydrate slurries as a function of gas pressure and aqueous phase composition over the whole range of interest for refrigeration purposes. The results presented show that adding TBPB to the water at low concentration (0.0058 mole fraction) decreases the pressure of formation of CO2 hydrates to 0.5 MPa at 281.6 K, instead of 3.5 MPa at the same temperature in the absence of a promoter. Crystallization of CO2 + TBPB hydrate could therefore offer an attractive means of capture for CO2.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The phase behavior of simple and mixed semiclathrate hydrates formed from CO2 + tetrabutylphosphonium bromide (TBPB) + water mixtures was investigated by pressure-controlled differential scanning calorimetry (DSC) at TBPB concentrations in the range of 0 to 0.073 mole fraction and at CO2 pressure in the range of (0 to 2.0) MPa. In a previous article we demonstrated that TBPB + CO2 mixed hydrates present high dissociation enthalpies and could be used as phase change material, covering the range of temperature from (284.6 to 289.0) K, for secondary refrigeration applications. The present work investigates a broader domain of compositions, resulting in x?T phase diagrams at atmospheric conditions and at various CO2 pressures. These data are required to model the potential latent heat of hydrate slurries as a function of gas pressure and aqueous phase composition over the whole range of interest for refrigeration purposes. The results presented show that adding TBPB to the water at low concentration (0.0058 mole fraction) decreases the pressure of formation of CO2 hydrates to 0.5 MPa at 281.6 K, instead of 3.5 MPa at the same temperature in the absence of a promoter. Crystallization of CO2 + TBPB hydrate could therefore offer an attractive means of capture for CO2. |
Conférences
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Osswald V.; Boufares A.; Clain P.; Provost E.; Dalmazzone D.; Delahaye A.; Fournaison L. Etude expérimentale de la cinétique de cristallisation des hydrates deCO2 en présence ou non d’additif chimique 5500 - 5599 Conférence 16th Congrès de la Société Française de Génie des Procédés, Nancy, 2017. BibTeX @conference{clain2017g,
title = {Etude expérimentale de la cinétique de cristallisation des hydrates deCO2 en présence ou non d’additif chimique},
author = {Osswald V. and Boufares A. and Clain P. and Provost E. and Dalmazzone D. and Delahaye A. and Fournaison L. },
year = {2017},
date = {2017-11-10},
booktitle = {16th Congrès de la Société Française de Génie des Procédés, Nancy},
keywords = {},
pubstate = {published},
tppubtype = {conference}
}
|
Boufares, A.; Provost, E.; Osswald, V.; Clain, P.; Delahaye, A.; Fournaison, L.; Dalmazzone, D. Détermination de la concentration du CO2 moléculaire en phase aqueuse par spectroscopie infrarouge : application à la cristallisation des hydrates de CO2 5500 - 5599 Conférence SFGP, Nancy, France, 11-13 juillet, 2017. BibTeX @conference{clain2017d,
title = {Détermination de la concentration du CO2 moléculaire en phase aqueuse par spectroscopie infrarouge : application à la cristallisation des hydrates de CO2},
author = {Boufares, A. and Provost, E. and Osswald, V. and Clain, P. and Delahaye, A. and Fournaison, L. and Dalmazzone, D. },
year = {2017},
date = {2017-07-15},
booktitle = {SFGP, Nancy, France, 11-13 juillet},
keywords = {},
pubstate = {published},
tppubtype = {conference}
}
|
Inproceedings
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Boufares, A.; Provost, E.; Osswald, V.; Clain, P.; Delahaye, A.; Fournaison, L.; Dalmazzone, D. Effect of additives on the kinetic study of CO2 hydrates during crystallization for secondary refrigeration applications using FTIR/ATR spectroscopy inproceedings ICGH9, Denver, Colorado, USA, 25-30 juin, 2017. BibTeX @inproceedings{clain2017c,
title = {Effect of additives on the kinetic study of CO2 hydrates during crystallization for secondary refrigeration applications using FTIR/ATR spectroscopy},
author = {Boufares, A. and Provost, E. and Osswald, V. and Clain, P. and Delahaye, A. and Fournaison, L. and Dalmazzone, D. },
year = {2017},
date = {2017-06-14},
booktitle = {ICGH9, Denver, Colorado, USA, 25-30 juin},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Clain P.; Lesperance W.; Dufour T.; Osswald V.; Delahaye A.; Fournaison L. Heat and mass transfer modeling approach of Differential Thermal Analysis – Case study of CO2 hydrates formation inproceedings 9 th International Conference of Gas Hydrates, Denver, Colorado, USA, 25-30 juin, 2017. BibTeX @inproceedings{clain2017e,
title = {Heat and mass transfer modeling approach of Differential Thermal Analysis – Case study of CO2 hydrates formation},
author = {Clain P. and Lesperance W. and Dufour T. and Osswald V. and Delahaye A. and Fournaison L. },
year = {2017},
date = {2017-06-14},
booktitle = {9 th International Conference of Gas Hydrates, Denver, Colorado, USA, 25-30 juin},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Osswald, V.; Clain, P.; Boufares, A.; Dalmazzone, D.; Delahaye, A.; Fournaison, L. Impact of chemical additives on CO2 hydrate formation kinetics in a stirred tank reactor inproceedings ICGH9, Denver, Colorado, USA, 25-30 juin, 2017. BibTeX @inproceedings{clain2017f,
title = {Impact of chemical additives on CO2 hydrate formation kinetics in a stirred tank reactor},
author = {Osswald, V. and Clain, P. and Boufares, A. and Dalmazzone, D. and Delahaye, A. and Fournaison, L. },
year = {2017},
date = {2017-06-14},
booktitle = {ICGH9, Denver, Colorado, USA, 25-30 juin},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Pichon, B.; Clain,P and, Hoang, H.M and, Dufour, T.; Delahaye, A.; Fournaison, L. Review of Thermal Energy Storage technologies integration in Smart-Grid inproceedings CYSENI, Kaunas, Lithuania, 25-26 mai, 2017. BibTeX @inproceedings{clain2017h,
title = {Review of Thermal Energy Storage technologies integration in Smart-Grid},
author = {Pichon, B. and Clain,P and, Hoang, H.M and, Dufour, T. and Delahaye, A. and Fournaison, L. },
year = {2017},
date = {2017-05-15},
booktitle = {CYSENI, Kaunas, Lithuania, 25-26 mai},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Salehy, Y.; Clain, P.; Boufares, A.; Osswald, V.; Delahaye, A.; Fournaison, L. Rheological study on CO2 hydrate slurries inproceedings CYSENI, Kaunas, Lithuania, 25-26 mai, 2017. BibTeX @inproceedings{clain2017i,
title = {Rheological study on CO2 hydrate slurries},
author = {Salehy, Y. and Clain, P. and Boufares, A. and Osswald, V. and Delahaye, A. and Fournaison, L. },
year = {2017},
date = {2017-05-15},
booktitle = {CYSENI, Kaunas, Lithuania, 25-26 mai},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Jérémy Oignet; Anthony Delahaye; Thomas Dufour; Hong-Minh Hoang; Pascal Clain; Laurence Fournaison Energy study of CO2 hydrate slurries formation in a tank reactor inproceedings 24rd IIR International Congress of Refrigeration (ICR 2015), Aug 16-22 Yokohama, Japan, 2015. BibTeX @inproceedings{Oignet2015,
title = {Energy study of CO2 hydrate slurries formation in a tank reactor},
author = {Jérémy Oignet and Anthony Delahaye and Thomas Dufour and Hong-Minh Hoang and Pascal Clain and Laurence Fournaison},
year = {2015},
date = {2015-08-16},
booktitle = {24rd IIR International Congress of Refrigeration (ICR 2015)},
address = {Yokohama, Japan},
organization = {Aug 16-22},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Pascal Clain; Véronique Osswald; Olivier Spiga; Anthony Delahaye; Laurence Fournaison A new formation kinetics study method of TBPB and CO2 hydrates based on DTA inproceedings 24rd IIR International Congress of Refrigeration (ICR 2015), Aug 16-22 Yokohama, Japan, 2015. BibTeX @inproceedings{Clain2015,
title = {A new formation kinetics study method of TBPB and CO2 hydrates based on DTA},
author = {Pascal Clain and Véronique Osswald and Olivier Spiga and Anthony Delahaye and Laurence Fournaison},
year = {2015},
date = {2015-08-16},
booktitle = {24rd IIR International Congress of Refrigeration (ICR 2015)},
address = {Yokohama, Japan},
organization = {Aug 16-22},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Pascal Clain; Jeremy Oignet; Anthony Delahaye; Laurence Fournaison Experimental and thermodynamic of a cold storage hydrate slurries process inproceedings Société Française des Génies des Procédés, Lyon, France, 2013. Liens | BibTeX @inproceedings{CODF13,
title = {Experimental and thermodynamic of a cold storage hydrate slurries process},
author = { Pascal Clain and Jeremy Oignet and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2013/CODF13},
year = {2013},
date = {2013-01-01},
booktitle = {Société Française des Génies des Procédés},
address = {Lyon, France},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Jeremy Oignet; Pascal Clain; Salem Jerbi; Anthony Delahaye; Laurence Fournaison Study of a secondary refrigeration loop hydrate slurries inproceedings Société Française des Génies des Procédés, Lyon, France, 2013. Liens | BibTeX @inproceedings{OCJDF13,
title = {Study of a secondary refrigeration loop hydrate slurries},
author = { Jeremy Oignet and Pascal Clain and Salem Jerbi and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2013/OCJDF13},
year = {2013},
date = {2013-01-01},
booktitle = {Société Française des Génies des Procédés},
address = {Lyon, France},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Pascal Clain; Anthony Delahaye; Laurence Fournaison DTA and DSC characterization of TBPB and TBPB+CO2 hydrates in porous media inproceedings Calorimetry and thermal effects in catalysis, Lyon, France, 2012. Liens | BibTeX @inproceedings{CDF12,
title = {DTA and DSC characterization of TBPB and TBPB+CO2 hydrates in porous media},
author = { Pascal Clain and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2012/CDF12},
year = {2012},
date = {2012-01-01},
booktitle = {Calorimetry and thermal effects in catalysis},
address = {Lyon, France},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Pascal Clain; Fatou-Toutie Ndoye; Anthony Delahaye; Laurence Fournaison Flow behavior and phase equilibrium of TBPB hydrate slurry in porous media for refrigeration application inproceedings IIR conference on Phase-change materials and slurries for refrigeration and air-conditioning, IIR, Kobe, Japan, 2012. Résumé | Liens | BibTeX @inproceedings{CNDF12,
title = {Flow behavior and phase equilibrium of TBPB hydrate slurry in porous media for refrigeration application},
author = { Pascal Clain and Fatou-Toutie Ndoye and Anthony Delahaye and Laurence Fournaison},
url = {http://labs.esilv.fr/publications/public/2012/CNDF12},
year = {2012},
date = {2012-01-01},
booktitle = {IIR conference on Phase-change materials and slurries for refrigeration and air-conditioning},
publisher = {IIR},
address = {Kobe, Japan},
abstract = {The present work investigates TBPB(tetra-n-butylphosphonium bromide) hydrate slurries based on focused beam reflectance measurement (FBRM) method. Hydrates can be used as phase change materials (PCM) for thermal energy storage due to their high latent heat of melting. In this study, hydrates were formed from TBPB-water mixtures, suitable for air-conditioning applications. Moreover, hydrate slurries, composed of hydrate-particles dispersed in liquid, are appropriate solutions for cold distribution. Nevertheless, flow properties of hydrate slurries, depending on hydrate crystallization kinetics, must be controlled. In this work, FBRM was used for analysing TBPB-hydrate-particle size distribution. This work showed that FBRM can detect system phase changes (nucleation, growth, agglomeration). In addition, a bimodal distribution of particles was observed. This work could be useful to understand rheological behaviour of hydrate slurry, not only for secondary refrigeration applications, but also for natural gas hydrate transportation, pipeline plugging prevention, and gas capture.},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
The present work investigates TBPB(tetra-n-butylphosphonium bromide) hydrate slurries based on focused beam reflectance measurement (FBRM) method. Hydrates can be used as phase change materials (PCM) for thermal energy storage due to their high latent heat of melting. In this study, hydrates were formed from TBPB-water mixtures, suitable for air-conditioning applications. Moreover, hydrate slurries, composed of hydrate-particles dispersed in liquid, are appropriate solutions for cold distribution. Nevertheless, flow properties of hydrate slurries, depending on hydrate crystallization kinetics, must be controlled. In this work, FBRM was used for analysing TBPB-hydrate-particle size distribution. This work showed that FBRM can detect system phase changes (nucleation, growth, agglomeration). In addition, a bimodal distribution of particles was observed. This work could be useful to understand rheological behaviour of hydrate slurry, not only for secondary refrigeration applications, but also for natural gas hydrate transportation, pipeline plugging prevention, and gas capture. |
Pascal Clain; Anthony Delahaye; Laurence Fournaison; Salem Jerbi; Nadia Mayoufi; Didier Dalmazzone; Walter Fürst Characterization of mixed CO2 + TBPB hydrates for refrigeration applications inproceedings International conference on gas hydrates, Edinburgh, Scotland, 2011. Liens | BibTeX @inproceedings{CDFJMDF11,
title = {Characterization of mixed CO2 + TBPB hydrates for refrigeration applications},
author = { Pascal Clain and Anthony Delahaye and Laurence Fournaison and Salem Jerbi and Nadia Mayoufi and Didier Dalmazzone and Walter Fürst},
url = {http://labs.esilv.fr/publications/public/2011/CDFJMDF11},
year = {2011},
date = {2011-01-01},
booktitle = {International conference on gas hydrates},
address = {Edinburgh, Scotland},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Salem Jerbi; Anthony Delahaye; Laurence Fournaison; Pascal Clain; Philippe Haberschill CO2 hydrate formation kinetics and modelling of the available enthalpy of CO2 hydrate slurry in tank reactor inproceedings IIR International congress of refrigeration, Prague, Czech Republic, 2011. Liens | BibTeX @inproceedings{JDFCH11,
title = {CO2 hydrate formation kinetics and modelling of the available enthalpy of CO2 hydrate slurry in tank reactor},
author = { Salem Jerbi and Anthony Delahaye and Laurence Fournaison and Pascal Clain and Philippe Haberschill},
url = {http://labs.esilv.fr/publications/public/2011/JDFCH11},
year = {2011},
date = {2011-01-01},
booktitle = {IIR International congress of refrigeration},
address = {Prague, Czech Republic},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Pascal Clain; Anthony Delahaye; Laurence Fournaison; Salem Jerbi; Ziad Youssef; Carlos Zambrana; Didier Dalmazzone Study on the hydrate slurries for the storage and transport of cold inproceedings Société Française des Génies des Procédés, Lille, France, 2011. Liens | BibTeX @inproceedings{CDFJYZD11,
title = {Study on the hydrate slurries for the storage and transport of cold},
author = { Pascal Clain and Anthony Delahaye and Laurence Fournaison and Salem Jerbi and Ziad Youssef and Carlos Zambrana and Didier Dalmazzone},
url = {http://labs.esilv.fr/publications/public/2011/CDFJYZD11},
year = {2011},
date = {2011-01-01},
booktitle = {Société Française des Génies des Procédés},
address = {Lille, France},
keywords = {},
pubstate = {published},
tppubtype = {inproceedings}
}
|
Thèses
|
Pascal Clain Couplage entre le stockage et la distribution de froid par coulis d hydrates Thèse de doctorat Université Pierre et Marie Curie, 2014. Résumé | Liens | BibTeX @phdthesis{Cla14,
title = {Couplage entre le stockage et la distribution de froid par coulis d hydrates},
author = { Pascal Clain},
url = {http://labs.esilv.fr/publications/public/2014/Cla14},
year = {2014},
date = {2014-01-01},
school = {Université Pierre et Marie Curie},
abstract = {The use of hydrate slurries as two-phase secondary refrigerants (FFD) reduces the environmental impact of refrigeration systems because these fluids have a high energy density. They can be used for cold storage will be a solution at an industrial problem of cold distribution at various temperature levels (air-conditioning, cooling process or preservation temperature). In this work, we study the coupling between a storage device and a cold distribution system by hydrate slurries. For achieve this objective, a two-stage reactor has been built for simulate the process. Equilibrium conditions studies for single and mixed hydrate showed an equilibrium temperature shift in porous media without deterioration of latent heat fusion. Hydrates formation/dissociation kinetics have been studied according to crystallization classical theories and an empirical model was obtained. Rheological studies of hydrate slurries emphasized a shear-thinning behavior for both, but a high propensity for agglomeration for mixed hydrate slurry. Particle size analysis showed the slurry has bimodal crystals distribution. Experimental set-up characterization showed process parameters effect in induction time. A 2D numerical tool integrating various empirical relations was developed for modelling temperature profile in the reactor and was validated in a first approach},
keywords = {},
pubstate = {published},
tppubtype = {phdthesis}
}
The use of hydrate slurries as two-phase secondary refrigerants (FFD) reduces the environmental impact of refrigeration systems because these fluids have a high energy density. They can be used for cold storage will be a solution at an industrial problem of cold distribution at various temperature levels (air-conditioning, cooling process or preservation temperature). In this work, we study the coupling between a storage device and a cold distribution system by hydrate slurries. For achieve this objective, a two-stage reactor has been built for simulate the process. Equilibrium conditions studies for single and mixed hydrate showed an equilibrium temperature shift in porous media without deterioration of latent heat fusion. Hydrates formation/dissociation kinetics have been studied according to crystallization classical theories and an empirical model was obtained. Rheological studies of hydrate slurries emphasized a shear-thinning behavior for both, but a high propensity for agglomeration for mixed hydrate slurry. Particle size analysis showed the slurry has bimodal crystals distribution. Experimental set-up characterization showed process parameters effect in induction time. A 2D numerical tool integrating various empirical relations was developed for modelling temperature profile in the reactor and was validated in a first approach |
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