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Étude Par Microscopie Optique De La Nucléation, Croissance Et

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Étude Par Microscopie Optique De La Nucléation, Croissance Et THE`SE ´ecole Ecole´ doctorale des Sciences Exactes et leurs Applications (ED : 211) pr´esent´eeet soutenue publiquement le 19 avril 2018 Abdelhafid Touil pour obtenir le grade de docteur Sp´ecialit´edoctorale “Physique” Optical microscopy investigation of gas hydrate nucleation, growth and dissociation processes Etude´ par microscopie optique de la nucl´eation,croissance et dissociation des hydrates de gaz Jury Pr´esidentdu jurry : Marc Prat Directeur de recherche IMFT, Toulouse Rapporteurs : Bertrand Chazallon Professeur Universit´eLille Lionel Mercury Professeur ISTO/CNRS, Orl´eans Examinateurs : Hannelore Derluyn Charg´eede Recherche LFCR/CNRS Arnaud Desmedt Charg´ede Recherche ISM/CNRS, Bordeaux Noushine Shahidzadeh Professeur University of Amsterdam Directeur de th`ese: Daniel Broseta Professeur UPPA/LFCR Laboratoire des Fluides Complexes et leurs R´eservoirs UMR 5150 CNRS-TOTAL-UPPA Pau, France Remerciements Les travaux pr´esent´esdans ce m´emoireont ´et´er´ealis´esau sein du Laboratoire des Flu- ides Complexes et leurs R´eservoirs(LFCR), et une partie au sein de l’Institut des Sciences Mol´eculairesde Bordeaux (ISM) dans le cadre dune th`eseco-financ´eepar le CNRS et lA- gence Nationale de la Recherche. Je tiens tout dabord `aremercier mon directeur de th`eseDaniel Broseta pour mavoir confi´ece travail de recherches si passionnant, ainsi que pour son encadrement infaillible et son soutien tout le long de la th`ese. Il a ´et´eparticuli`erementpr´esentet `al´ecoutelors de mes nombreuses p´erip´etiesscientifiques. Jai pu travailler dans un cadre particuli`erementagr´eable,grˆace`alensemble des mem- bres du laboratoire LFCR et du l’ISM de Bordeaux. Je pense particuli`erement`aRoss, Ar- naud, Christophe, Guillaume, Hannelore, Manuel, Patrick et Romain qui ont su m’apporter leurs conseils et leurs aides durant ces ann´ees. Je remercie les rapporteurs Bertrand Chazallon et Lionel Mercury pour leurs lec- tures et corrections de mon manuscrit. Je souhaite remercier tout le personnel technique et administratif du laboratoire no- tamment Joseph, Fabrice, Eric,´ Laurent, Bertrand, Djamel, Catherine, V´eronique,Blandine et J. Patrick. Mes remerciements ne seraient pas complets sans une pens´ee`ames coll`eguesdoctor- ants stagiaire et post-doctorants : Abdoul, Daoud, Dyhia, Ez´equiel,Fouad,´ Hacene, Hai, Henry, Julien, Lourdes, Mohamed, Patrick, Romuald, Salem et Yacine. Je remercie aussi tous les membres de ma famille, mon p`ereet sa femme, mes fr`eres et surs, ma tante Zohra et ma cousine Zahia qui ont toujours ´et´e`ames cˆot´es(mˆemede loin) pendant cette th`eseet qui m’ont toujours encourag´e. Pour finir, jexprime tout mon amour et mes remerciements pour la femme de ma vie Nawel qui a su mencourager. Je la remercie aussi pour la patience et le soutien dont elle a fait preuve pendant toute la dur´eede cette th`ese. ¸Cafait du bien de dire merci. Encore merci `aCelui quon oublie trop souvent. Abstract The nucleation, growth and dissociation of gas hydrate across a water – gas meniscus in glass capillaries are investigated by means of video-microscopy and confocal Raman spec- troscopy under controlled temperature, pressure, cooling rate and substrate wettability and geometry. Structure I and II hydrates are examined, with the following guest molecules: CO2, CH4,N2, cyclopentane, and cyclopentane + CO2. By lowering the temperature well below 0 ◦C, i.e., under strong subcooling, all these hydrates but the cyclopentane hy- drate nucleate without forming ice on the liquid water – guest meniscus, which is rapidly covered with a polycrystalline crust. The hydrate then propagates from this meniscus as fast-growing fibers or dendrites in bulk water and as a thin polycrystalline crust, or halo, along the capillary wall. On water-wet substrates, this halo advances on the guest side of the meniscus, fed by a water layer sandwiched between the halo and glass. Symmetrically, on guest-wet (silane-treated) glass, the halo and an underlying guest layer grow on the wa- ter side of the interface. No halo is observed on intermediate-wet glass. The hydrate halo growth and morphology and the thickness of its underlying water (or guest) layer strongly depend on subcooling. Thanks to the small capillary volume and the rapid temperature descent, the metastability limit of CO2 hydrate is approached for various pressures and sub- strate wettabilities. The low subcooling regime is investigated as well: a novel CO2 hydrate morphology is discovered for subcoolings below 0.5 ◦C, which consist of a hollow hydrate crystal originating from the water – guest meniscus and advancing on the guest side along glass, fed by a thick water layer sandwiched between glass and this crystal. A new proce- dure is proposed to determine gas hydrate dissociation conditions in a large temperature and pressure range, including the metastable extension of the three-phase (liquid water – hydrate - guest) down to temperatures well below 0 ◦C. Finally, the mechanisms by which CO2 and cyclopentane synergistically act to form the structure II hydrate are discussed. Keywords: Gas Hydrate, Microthermometry, Microscopy, Raman spectroscopy, Microflu- idic, wettability, Phase equilibria R´esum´e La nucl´eation,la croissance et la dissociation des hydrates de gaz au voisinage d’un menisque eau – gaz dans des capillaires de verre sont ´etudi´eespar vid´eo-microscopieet spectroscopie Raman `atemp´erature,pression, mouillabilit´eet g´eom´etriedu substrat contrˆol´ees.Dans ce travail, deux hydrates simples de structure I (hydrate de CO2 et hydrate de CH4), deux hydrates simples de structure II (N2 et Cyclopentane) et un hydrate double (cyclopentane + CO2) sont examin´es.En baissant la temp´eraturebien au-dessous de 0 ◦C, i.e., sous un fort sous-refroidissement, tous ces hydrates, except´el’hydrate de cyclopentane, nucl´eentsans que la glace soit form´ee.L’hydrate forme d’abord une croˆutepolycristalline sur le m´enisque eau-mol´eculeinvit´ee(guest). Ensuite, il se propage rapidement `apartir de ce m´enisque dans l’eau sous forme de fibres ou dendrites et le long de la paroi capillaire sous forme d’une croˆute fine et polycristalline appel´ee” halo ”. Sur un substrat hydrophile, ce halo avance du cˆot´ede la phase invit´ee,aliment´epar une couche d’eau entre le halo et la paroi interne du capillaire. Sym´etriquement,sur un verre hydrophobe (trait´eau silane), le halo et une couche de la phase invit´eese propagent du cˆot´eeau. Aucun halo n’est observ´esur un substrat de mouillabilit´einterm´ediaire.La croissance et la morphologie du halo d’hydrate et l’´epaisseurde sa couche sous-jacente d’eau (ou de phase invit´ee)d´ependent fortement du sous-refroidissement. Grˆaceau faible volume du capillaire utilis´eet `ala vitesse rapide de re- froidissement, la limite de m´etastabilit´ede l’hydrate de CO2 est approch´eepour diff´erentes pressions et mouillabilit´e.Le r´egimedes faibles sous-refroidissements est ´egalement´etudi´e: une nouvelle morphologie d’hydrate de CO2 est d´ecouvertepour des sous-refroidissements inf´erieurs`a0,5 ◦C, constitu´eed’un cristal creux, g´en´er´eeau niveau du m´enisqueeau – guest et avan¸cantdu cˆot´eguest le long du verre, aliment´epar une ´epaissecouche d’eau prise en sandwich entre le verre et ce cristal. Une nouvelle proc´edureest propos´eepour d´etermina- tion des conditions d’´equilibre des hydrates de gaz dans une large plage de temp´eratureet de pression, y compris l’extension m´etastablede la ligne triphasique (eau liquide – hydrate – guest) jusqu’`ades temp´eraturesbien inf´erieures`a0 ◦C. Enfin, les m´ecanismespar lesquels le CO2 et le cyclopentane agissent en synergie pour former l’hydrate de structure II sont discut´es. Mots-cl´es :Hydrate de gaz , Microthermometrie, Microscopie, Spectroscopie Raman, Mi- crofluidique, Mouillabilit´e, Equilibre´ de phase. Contents Contents I List of Figures V List of Tables XIII 1 Introduction 1 1.1 R´ef´erences ..................................... 6 2 Bibliography on clathrate hydrates 9 Introduction ....................................... 10 2.1 Structural analysis of hydrates .......................... 11 2.2 Some physical quantities (hydrate properties) . 13 2.2.1 Hydration number ............................ 13 2.2.2 Molar volumes ............................... 14 2.2.3 Hydrate density .............................. 14 2.2.4 Enthalpy of dissociation of gas hydrates . 14 2.3 Applications of hydrates ............................. 16 2.3.1 Natural gas supply ............................ 17 2.3.2 Natural Gas storage ........................... 17 2.3.3 Hydrogen storage ............................. 17 2.3.4 Gas separation .............................. 18 2.3.5 CO2 sequestration ............................ 19 2.3.6 Refrigeration ................................ 19 2.3.7 Desalination ................................ 20 2.3.8 Other gas hydrate applications ..................... 21 2.4 Gas Hydrate formation, growth and dissociation . 22 2.4.1 Thermodynamics of crystallization ................... 22 2.4.2 Hydrate nucleation ............................ 25 2.4.2.1 Primary nucleation ...................... 26 2.4.2.2 Secondary nucleation ..................... 29 2.4.3 Hydrate growth .............................. 30 2.5 R´ef´erences ..................................... 32 3 Roles of wettability and supercooling in cyclopentane hydrate spreading over a substrate 41 Abstract .......................................... 42 3.1 Introduction .................................... 43 3.2 Materials and Methods .............................. 47 3.2.1
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