Demixing Alkyl piperidines for CO2 capture : A thermodynamic approach
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(18) Acknowledgements / Remercîments Back in 2011 I read a journal article from my main thesis supervisor during my master’s degree. I then had the opportunity to meet her when she visited and little did I know then that I would have the opportunity to be her Ph.D student. Since that time I have now completed my Ph.D at the Université de Blaise Pascal, now Université Clermont Auvergne, as her student. From her I have learned that there are many different points of view in science particularly the way of looking at data and evaluating them. Her energy and intensity are limitless and served as motivation during my studies. My thesis co-supervisor I met in 2013 during my masters during a visit at the laboratory in Guelph. His insight in chemical thermodynamics and theory and data helped me further understand chemical thermodynamics and the relationships between what we observe in the nature of materials. The discussions I have had with him have helped me interpret my data and expand my understanding of molecular interactions. To Dr. Karine Ballerat-Busserolles and Dr. Jean-Yves Coxam, I would like to sincerely thank you both for the three year spent working with you and learning from you, it has been a privilege. The reporters and examiners in my Ph.D defence: Prof. Christophe Coquelet (Centre thermodynamique de Procedee, Dr. Aline Auroux (Ircelyon), Dr. Ilham Mokbel (Univ. Claude Bernard) and Dr. Denis Lourdin (INRA Nates). It was a pleasure to have you examine me and hold me accountable to my work. Your comments and suggestions have giving me insight into the areas which I need to improve my knowledge. None of my time here would have been possible without Dr. Yohann Coulier. I met him back in 2012 as a postdoc and I am happy for his recommendation to the group. He helped me to the best of his ability and I am happy for his efforts and to know him. His ability to focus on complex task is an admirable trait, exemplified by his marathon running. To my fellow student, Barbara Liborio (soon to be Dr. Liborio), sharing this experience with you has been a pleasure. The back and forth help we gave each other help me better understand the problems engineers face and gave me motivation to finish degree. I would also like to give a special thank you to Nicole Nénot, for her cheerful demeanour and encouragement. The boys of CALNESIS, Dr. Mickael Simond and Dr. Jean-Claude Neyt, I would like to thank you both for the early years getting started. In both learning french and learning where to go for a drink and beer, i.e. Nota Bene, the campus bar with the best atmosphere I have been to, run by the best barkeep, Fred Gaume. The few games of pool we had during the first year were great. The TIM group is a fantastic group of scientists and technicians who have helped me in one way or another throughout the program. Some of which have offered advice or a small distraction from work at the after lunch coffee or celebration of a grand achievement. Working with you has been a pleasure: Dr. Jean-Micheal Andanson, Dr. Margarida Costa Gomes, Dr. Alain Dequidt, Julien Devemy, Dr. Florent Gujon, Dr. Passcale Husson, Prof. Patrice Malfreyt, Prof. Agilio Padua, Laure Pison, Dr. Sabine Sarraute. While not part of the TIM group but part of the building I would like to thanks Professor Jean-Pierre Grolier, for sharing the history of chemical thermodynamics between Canada and France. The organic chemists of chemistry 4 with who I would like to thank are Dr. Arnaude Gautier, Dr. Frederico Cisnetti, Dr. Gettano Angelici, Dr. Clémentine Gibrad, Dr. Jacob Hansen, Dr. Egon Heuson, Dr. Geoffrey Dumonteil and most importantly Radhe Shyam. It was a pleasure to meet you and get to know you. You are a great group of organic chemists and beer drinkers. Learning french was both a challenge with you guys and a pleasure. To the bureaux d’Auvergne Société Chimique de France Club Jeunes, Audrey Diouf-Lewis, Dr. Amira Farhaoui and Dr. Yannick Esvan. The club we managed to run produced a few good events for everyone. The Christmas party, le journée scientifique, and student oral competition. It was nice working with you and you are great group of people. To my fellow pre docs and post docs and no doc, who was part of the journey. Many thanks to Emilie Bordes, Thibaud Dreher, Joao Franca, Ludovic Garnier, Kevin Kempfer, Dr. Leila Moura, Dr. Makha Ndao, Dr. Inès Otero Fernandez, Dr. Yarick Grosu, Sven Plappert, Pablo Sanchez, Laura Sivet, Dr. José Solano, Gunjita Singh, Dr. Dusan. .
(19) Stosic, Dr. Joana Szala-Bilnik, Dr. Julian Tay and Darius Yeadon. Many of you are still on your journey I hope you find the end of it soon thank you for the time I got to spend with you. Meeting you was great way to learn of new cultures and new and different sciences. Outside of the ICCF and school I would like to thank Jessica Addley, Chantel Nguyen, David Alberti Morales, David Roberti, AntoineTavin, Meghana Upadhyaya, Nathanael Lampe (soon to be Dr), Martyna Zidonis, Dr. Ben Pesch. Meeting and getting to knowing each of you has been a big enjoyment in my life and the helpful distractions have helped me recover from hard weeks of work to get back into the next week. I would also like to thank the international collaborators Dr. John Carroll, Dr Jenny Cox, Dr. Peter Tremaine, Dr. Olivia Fandiño Torres, and Christine McGregor. Finally my parents, Geoffrey and Linda Lowe, and brothers Andrew and Christopher, thank you for your support over the past few years. I would also family in grandparents Joan and Stanley Lowe, my aunt Barbra Roberts and Mike Roberts for letting me spend the holidays with them in Manchester. As well as my aunts, uncles and cousins in Scotland who I had the opportunity to visit. There are many things in life which add complexity to daily tasks. Balancing work and personal relationships is difficult thing to do. Learning how is even harder, I would like to thank you all very much. Merci beaucoup. I apologise for not writing any acknowledgements in French, for I know I would not be able to full express my gratitude to all of you adequately. Mais encore, merci beaucoup à tout le monde pour trois grandes années.. .
(20) 7DEOHRI&RQWHQWV 0. 1. Résumé en Française .................................................................................................................................. 26 0.1. Équilibre de phase liquide-liquide ................................................................................34. 0.2. Les systèmes aqueux binaires ......................................................................................36. 0.3. Les systèmes aqueux ternaires ....................................................................................37. 0.4. Les propriétés thermodynamiques des solutions aqueuses ..........................................40. 0.5. Enthalpies de solution du dioxyde de carbone dans les solutions aqueuses de 4-MPD et 3-MPD 42. 0.6. Conclusion ...................................................................................................................45. Introduction ................................................................................................................................................ 48 1.1. 1.1.1. Increasing Temperature of the Earth .................................................................................................. 48. 1.1.2. Technological Solutions ....................................................................................................................... 49. 1.2. DACOOTA Project ........................................................................................................52. 1.2.1. The Data to Collect .............................................................................................................................. 53. 1.2.2. Recent Bibliography on Phase-Change Solvent ................................................................................... 55. 1.3. The Alkyl Piperidine Family .........................................................................................56. 1.3.1. Molecular Structure ............................................................................................................................. 57. 1.3.2. Thermodynamic Properties ................................................................................................................. 58. 1.4 2. Environmental Context ................................................................................................48. Thesis Goals ................................................................................................................59. Review of Thermodynamic Theory ............................................................................................................. 59 2.1. Chemical Equilibrium ...................................................................................................59. 2.1.1. Vapour-Liquid Equilibrium ................................................................................................................... 61. 2.1.2. Liquid-Liquid Equilibrium ..................................................................................................................... 63. .
(21) 2.2. Maxwell’s Relations of Thermodynamic Properties .....................................................65. 2.2.1 2.3. 3. Partial Molar Properties and Excess Molar Properties ........................................................................ 66. Thermodynamic Models for Phase Equilibrium. ..........................................................71. 2.3.1. The Kent and Eisenberg Model ............................................................................................................ 72. 2.3.2. Ion interaction model from Pitzer modified by Edwards .................................................................... 72. 2.3.3. Deshmukh-Mather............................................................................................................................... 74. 2.3.4. Electrolyte-Non Random two Liquid Model / E-NRTL ......................................................................... 74. 2.3.5. Extended Universal Quasichemial Model / Extended UNIQUAC ......................................................... 77. Liquid-Liquid Equilibrium of Piperidine ....................................................................................................... 81 3.1. Introduction ................................................................................................................81. 3.2. Experimental ...............................................................................................................81. 3.2.1. Cloud Point Method ............................................................................................................................ 81. 3.2.2. Overview of the Methods .................................................................................................................... 82. 3.2.3. Thar Equilibrium Cell............................................................................................................................ 84. 3.2.4. Sapphire cell ........................................................................................................................................ 86. 3.2.5. Comparison of the Equilibrium Cells ................................................................................................... 88. 3.2.6. Alternative Mixing Method ................................................................................................................. 89. 3.3. Results and Discussion .................................................................................................91. 3.3.1. Cloud Point Visualization ..................................................................................................................... 91. 3.3.2. Liquid-Liquid Equilibrium of Alkyl piperidines ..................................................................................... 92. 3.3.3. Mathematical Regressions for Binary Liquid-Liquid Equilibrium Curves ............................................. 97. 3.3.4. Aqueous Solutions of Alkyl-Piperidine with Carbon Dioxide ............................................................... 98. 3.3.5. Discussion .......................................................................................................................................... 108. 3.4. Conclusions ............................................................................................................... 110. .
(22) 3.5 4. Appendix for Chapter 3 ............................................................................................. 111. Thermodynamic Properties of Alkyl-Piperidines. ...................................................................................... 120 4.1. Introduction .............................................................................................................. 120. 4.2. Chemicals and Solution Preparation .......................................................................... 120. 4.3. Experimental Instrumentation. ................................................................................. 120. 4.3.1. Densities of Amine Solutions ............................................................................................................. 120. 4.3.2. Differential Scanning Calorimeter ..................................................................................................... 123. 4.3.3. Enthalpies of Mixing Experiments ..................................................................................................... 125. 4.3.4. Cell Calibration and Solution Measurement ...................................................................................... 127. 4.4. Results and Discussion ............................................................................................... 129. 4.4.1. Densities and Excess Molar Volumes................................................................................................. 129. 4.4.2. Excess Molar Enthalpies of Methyl Piperidines ................................................................................. 140. 4.4.3. Specific Heat Capacities and Excess Molar Heat Capacities .............................................................. 145. 4.5. Conclusions ............................................................................................................... 150. 4.6. Appendix for Chapter 4 ............................................................................................. 151. 5 Enthalpy of Carbon Dioxide Dissolution in Aqueous 3-methylpiperidine and 4-methylpiperidine; A Solubility Model ............................................................................................................................................................ 177 5.1. Experimental ............................................................................................................. 177. 5.1.1. Technic and Procedure ...................................................................................................................... 177. 5.1.2. Results ............................................................................................................................................... 178. 5.2. Thermodynamic Framework...................................................................................... 182. 5.2.1. Modelling Speciation and Absorption ............................................................................................... 182. 5.2.2. Modelling Enthalpies ......................................................................................................................... 190. 5.2.3. Modelling Strategy ............................................................................................................................ 192. .
(23) 5.2.4. Model Results .................................................................................................................................... 192. 5.3. Conclusions ............................................................................................................... 197. 5.4. Appendix for Chapter 5 ............................................................................................. 198. 6. Conclusions ............................................................................................................................................... 224. 7. Lingering Questions and Future Work ....................................................................................................... 226. 8. Research Acknowledgments ..................................................................................................................... 227. 9. References ................................................................................................................................................ 228. . . .
(24) 7DEOHRI)LJXUHV FIGURE 0-1 SCHEMA DE PRINCIPE D’UNE UNITE DE CAPTAGE POST-COMBUSTION DE DIOXYDE DE CARBONE. ................ 28 FIGURE 0-2: SCHEMA DU PROCEDE UTILISANT LES SOLUTIONS D’AMINES DEMIXANTES (GOMEZ ET AL., 2014) ............... 29 FIGURE 0-3: SCHEMA PHYSICO-CHIMIQUE DU PROCEDE DE CAPTAGE DE CO2 ................................................................... 30 FIGURE 0-4: STRUCTURE DES ALKYL-PIPERIDINES ETUDIEES DANS CE LE PROJET: (A) PIPERIDINE, (B) NMETHYLPIPERIDINE, N-MPD (C) 2-METHYLPIPERIDINE, 2-MPD (D) 3-METHYLPIPERIDINE, 3-MPD (E) 4METHYLPIPERIDINE (F) N-ETHYLPIPERIDINE, N-EPD (G) 2,6-DIMETHYLPIPERIDINE, 2,6-DPD (H) 3,5DIMETHYLPIPERIDINE, 3,5-DP, (I) 2-ETHYLPIPERIDINE, 2-EPD. .................................................................................. 32 FIGURE 0-5: ILLUSTRATION DE LA VISUALISATION DE LA SEPARATION DE PHASE LORS DE L’AUGMENTATION DE TEMPERATURE. ........................................................................................................................................................ 35 FIGURE 0-6: PHOTO DE GAUCHE: L’INSTRUMENT DE THAR INSTRUMENTS ; A DROITE: CELLULE EN SAPHIR (CTP). ........... 35 FIGURE 0-7: DIAGRAMMES DE PHASES DES SYSTEMES BINAIRES ETUDIES :A GAUCHE : AMINES TERTIAIRES : N-MPD ( ,. ) ET N-EPD (. ,. ,. FLASCHNER, 1909;. ,. ) 3,5-DPD ( ,. ,. )(. CE TRAVAILLE,. COULIER Y ET AL. 2010,. FLASCHNER AND MACEWEN, 1908;. STEPHENSON, 1993) ; A DROITE : AMINES SECONDAIRES : 4-MPD, ( ). (. ,. CE TRAVAILLE,. ,. FLASCHNER AND MACEWEN, 1908;. ). 3-MPD, (. FLASCHNER, 1909;. ,. STEPHENSON, 1993)......................................................................................................................................... 37. FIGURE 0-8: LLE EN FONCTION DU TAUX DE CHARGE EN CO2, POUR LES SOLUTIONS AQUEUSES DE 2-MPD (GAUCHE) ET NMPD (DROITE). LES SYMBOLES SONT :. 10 WA%, (. ,. ) 20 WA % ET + 40 WA%, ................................................. 38. FIGURE 0-9: PROPRIETES THERMODYNAMIQUES DES METHYL-PIPERIDINES EN SOLUTION AQUEUSE; (A) VOLUME MOLAIRE D’EXCES A 25°C; (B) ENTHALPIE MOLAIRE D’EXCES A 40°C (C) CAPACITE CALORIFIQUE MOLAIRE D’EXCES A 35°C. ......................................................................................................................................................................... 41 FIGURE 0-10: ENTHALPIES DE SOLUTION PAR MOLE DE CO2 (COURBE DE GAUCHE) ET PAR MOLE D’AMINE (COURBE DE DROITE) EN FONCTION DU TAUX DE CHARGE EN CO2, DANS UNE SOLUTION AQUEUSE DE 4-MPD A 40% EN MASSE, ET POUR TROIS PRESSIONS :. (0.43 MPA),. (0.95 MPA), ET. (1.45 MPA)........................................................ 43. FIGURE 1-1: SCHEMATIC REPRESENTATION OF POST-COMBUSTION PROCESS. ................................................................. 50. .
(25) FIGURE 1-2 : SIMPLIFIED REPRESENTATION OF POST-COMBUSTION CARBON DIOXIDE CAPTURE UNIT............................. 51 FIGURE 1-3: LIQUID-LIQUID PHASE SEPARATION FOR TERNARY SOLUTION {WATER + AMINE + CARBON DIOXIDE}. ......... 52 FIGURE 1-4: SIMPLIFIED SCHEMATIC REPRESENTATION OF THE INDUSTRIAL PROCESS USING A DEMIXING AMINE. (GOMEZ ET AL., 2014) ............................................................................................................................................... 53 FIGURE 1-5: THERMODYNAMIC AND PHYSICO-CHEMICAL REPRESENTATION OF THE PROCESS. ........................................ 54 FIGURE 1-6: STRUCTURES OF THE ALKYL PIPERIDINES INVESTIGATED (A) PIPERERIDINE, (B) N-METHYLPIPERIDINE, N-MPD (C) 2-METHYLPIPERIDINE, 2-MPD (D) 3-METHYLPIPERIDINE, 3-MPD (E) 4-METHYLPIPERIDINE(F) N-ETHYLPIPERIDINE, N-EPD (G) 2,6-DIMETHYLPIPERIDINE, 2,6-DPD(H) 3,5-DIMETHYLPIPERIDINE, 3,5-DPD (I) 2-ETHYLPIPERIDINE, 2-EPD. ................................................................................................................................................................................. 57 FIGURE 2-1: EXAMPLE DIAGRAM OF LIQUID-LIQUID PHASE EQUILIBRIUM. ....................................................................... 64 FIGURE 3-1: OVERALL EXPERIMENTAL SET-UP OF LIQUID-LIQUID EQUILIBRIUM CELLS FOR SOLUTIONS CONTAINING DISSOLVED GAS. .............................................................................................................................................................. 83 FIGURE 3-2 : GENERAL OBERVIEW OF THE SPM 20 THAR EQUILIBRIUM APPARATUS. (1) WATER PUMP; (2) CO2 PUMP (3) INJECTION LOOP; (4) SIX WAY VALVE; (5) INJECTION PORT FOR AQUEOUS AMINE; (6) MIXING UNIT; (7) ISOTHERMAL BATH; (8) MEASUREMENT CELL; (9) PRESSURE GAUGES; (10) THERMOCOUPLE; (11) BUFFER VOLUME AND BACK PRESSURE REGULATOR; (12) WASTE BOTTLE. .............................................................................................. 84 FIGURE 3-3 : SAPPHIRE LIQUID-LIQUID EQUILIBRIUM CELL. (1) TITANIUM BLOCKS; (2) SAPPHIRE CELL; (3) SPHERICAL STIRRER; (4) K-TYPE THERMOCOUPLE; (5) O-RING. ........................................................................................................ 86 FIGURE 3-4 : GENERAL OVERVIEW OF THE LIQUID-LIQUID EQUILIBRIUM SAPPHIRE APPARATUS. (1) WATER PUMP; (2) CO2 PUMP; (3) INJECTION LOOP (4) SIX-WAY VALVE; (5) INJECTION PORT FOR AQUEOUS AMINE; (6) DELAY LOOP; (7) MIXING UNIT; (8) SAPPHIRE EQUILIBRIUM CELL; (9) JACKETED GLASS REACTOR VESSEL; (10) THERMOCOUPLE; (11) PRESSURE GAUGES; (12) BUFFER VOLUME AND BACK PRESSURE REGULATOR; (13) WASTE BOTTLE. ........................ 87 FIGURE 3-5 : GENERAL OVERVIEW OF THE SAMPLE CELL: (1) DIRECTION OF NITROGEN FLOW FROM ISCO PUMP (2) PRESSURE GAUGE (3) 3-WAY BALL VALVE (4) SOURCE OF WATER FLOW FROM ISCO PUMP (5) SAMPLE LOOP (6) SIXWAY VALVE (7) INJECTION PORT FOR SOLUTION. (8) SAMPLE CYLINDER, WITH STIR BAR INSIDE (9) ICE BATH. (10) DIRECTION OF SOLUTION FLOW TO THE THAR CELL. ..................................................................................................... 90. .
(26) FIGURE 3-6 : CCD CAMERA PICTURES OF THE INTERNAL CHAMBER OF THE THAR INSTRUMENT MEASURING CELL. (A) TRANSPARENT HOMOGENOUS SOLUTION; (B) CLOUD POINT; (C) OPAQUE HETEROGENEOUS MIXTURE.................. 91 FIGURE 3-7 : PICTURE OF PHASE TRANSITION IN THE SAPPHIRE EQUILIBRIUM CELL. (A) TRANSPARENT HOMOGENOUS SOLUTION (B) CLOUD POINT (C) DECANTED TWO PHASE MIXTURE. ............................................................................ 92 FIGURE 3-8: COMPARISON OF THE LLE FOR TERTIARY ALKYL PIPERIDINES: N-MPD DATA ( (STEPHENSON,1993) , WORK),. (O.FLASCHNER, 1908),. (STEPHENSON 1993),. (COULIER ET AL 2010),. (SCALING FIT THIS WORK) ) AND N-EPD DATA (. (O.FLASCHNER, 1908),. (SCALING FIT THIS WORK) ) ..................................... 94. FIGURE 3-9: COMPARISON OF THE LLE FOR SECONDARY HINDERED ALKYL PIPERIDINES: LLE OF 2-MPD, ( AL. 2010), WORK),. (STEPHENSON 1993) , (STEPHENSON 1993),. (THIS. FLASCHNER AND MACEWAN 1908), (SCALING FITS) ) AND 2-EPD (. (COULIER ET. (SCALING FITS) ) 2,6-DPD, (. (THIS WORK),. (THIS. (STEPHENSON 1993),. (SCALING FITS)) DATA. ..................................................................................................................................................... 95 FIGURE 3-10: COMPARISON OF THE LLE FOR SECONDARY ALKYL PIPERIDINES: LLE OF 4-MPD, ( (STEPHENSON, 1993) , (STEPHENSON 1993), (STEPHENSON 1993),. (FLASCHNER, 1909), (FLASCHNER, 1909),. (SCALING FIT THIS WORK) ). 3-MPD, (. (THIS WORK), (THIS WORK),. (SCALING FIT THIS WORK) ) 3,5-DPD DATA (. (THIS WORK),. (SCALING FIT THIS WORK)). ................................................................................................. 96. FIGURE 3-11: THE LLE TEMPERATURE WITH RESPECT TO THE INCREASING LOADING CHARGE OF CO2 IN SOLUTIONS OF NMPD USING THE SAPPHIRE CELL. (. 10WA% / XA=0.0198) SOLUTIONS, (. WA% SOLUTIONS AT 2 MPA, (+ 40WA% / XA=0.1080), SOLUTIONS. 20WA% / XA=0.0434) SOLUTIONS,. 20. 20WA% SOLUTIONS MEASURED USING THAR. CELL. THE SOLID LINES ARE POLYNOMIAL FITS FOR A VISUAL AID. THE SIZES OF THE MARKERS REPRESENT THE UNCERTAINTY IN THE TEMPERATURE. ......................................................................................................................... 100 FIGURE 3-12 : LLE TEMPERATURE OF N-MPD WITH INCREASING MOLAR FRACTION OF AMINE IN SOLUTION AT A CONSTANT LOADING CHARGE OF 0.17: SOLUTION,. CO2 LOADED N-MPD SOLUTION,. UNLOADED N-MPD SOLUTION,. POLYNOMIAL FIT TO LOADED. SCALING FIT TO UNLOADED. THE WEIGHT PERCENT OF LOADED. SOLUTION WERE INCREASED 10 WA% STARTING FROM 10 WA% (XA=0.0198) TO 40 WA% (XA=0.1080) ................... 102 FIGURE 3-13: LLE TEMPERATURE VERSUS INCREASING LOADING CHARGE OF CARBON DIOXIDE, IN AQUEOUS 2-MPD SOLUTIONS MEASURED USING THE THAR CELL. (+ 40 WA%/XA=0.1080),(. . 20 WA%/ XA=0.0434). .......................... 103.
(27) FIGURE 3-14: LLE TEMPERATURE OF A 2-MPD SOLUTION VERSUS MOLAR FRACTION WITH A CONSTANT LOADING CHARGE OF 0.2 OF CO2. (. UNLOADED 2-MPD SOLUTIONS), (. SOLUTION LOADED TO 0.20), (. SCALING FIT TO 2-MPD DATA), (. 2-MPD. POLYNOMIAL FIT TO THE LLE DATA). THE WEIGHT PERCENT OF LOADED. SOLUTION INCREASES FROM 10WA% (XA=0.0198) TO 30 WA%(XA=0.0722) INCREASING EVER 5 WA%. THE LAST SQUARE IS 40 WA%(XA=0.1080) ..................................................................................................................................... 104 FIGURE 3-15: LLE TEMPERATURE VERUSUS CO2 LOADING OF 2,6-DPD IN SOLUTION AT A CONSTANT WEIGHT PERCENT MEASURED USING THE SAPPHIRE CELL.. (5WA% / XA=0.0083),. (10WA% / XA=0.0173),. (20WA% / XA=0.0382) SOLUTION MIXED PREPARED USING A STATIC MIXING UNIT,. (20WA% / XA=0.0382),. (30 WA% / XA=0.0959). THE. SOLID LINES ARE POLYNOMIAL FITS TO THE DATA. ..................................................................................................... 105 FIGURE 3-16: LLE TEMPERATURE OF 2,6-DPD VERSUS MOLAR FRACTION OF AMINE AT A CONSTANT LOADING CHARGE 0.21: (. CO2 LOADED AQUEOUS 2,6-DPD SOLUTIONS),(. AQUEOUS 2,6-DPD SOLUTION),(. DATA LINE TO GUIDE THE EYE), (. UNLOADED. SCALING FIT TO UNLOADED DATA). THE CORRESPONDING WEIGHT PERCENT. OF SOLUTION FROM MOLE FRACTION ARE (5WA% / XA=0.0959), (10WA% / XA=0.0959), (20WA% / XA=0.0383), (30WA% / XA=0.0959) ..................................................................................................................................................... 106 FIGURE 3-17: LLE TEMPERATURE OF N-EPD VERSUS CO2 LOADING CHARGE. THE SOLUTIONS ARE PREPARED IN A SAMPLE CYLINDER (. 5 WA%/, XA=0.0083) (. THE FLOW MIXING UNIT IS LABELLED (. 10 WA%/ XA=0.0173), (. 20 WA% XA=0.0959) . THE SOLUTION PREPARED BY. 5 WA%/ XA=0.0083), THE LINES ARE POLYNOMIAL FITS TO THE DATA. THE. SIZE OF THE MARKERS REFLECTS THE UNCERTAINTY IN THE DATA. ........................................................................ 107 FIGURE 3-18: CARBON 13 NMR SPECTRA OF PRECIPITATED 3,5-DIMETHYLPIPERIDINE IN D2O SOLVENT. THE CHEMICAL SHIFTS BETWEEN 10 AND 55 PPM ARE PART OF THE RING STRUCTURE. THE DOWN FIELD SHIFTS BETWEEN 160 AND 170 PPM ARE CARBONATE, BICARBONATE AND CARBAMATE SALTS. .................................................................... 119 FIGURE 4-1: EXAMPLE OF CALIBRATION AND MEASUREMENT OF THE PERIOD OF VIBRATION. ........................................ 121 FIGURE 4-2: DIAGRAM OF THE MIXING CHAMBER WITH ZOOM UP TO THE MIXING POINT. (A) STAINLESS STEEL INJECTION TUBES (B) MIXING POINT OF THE CELL (C) MIXING CHAMBER MADE OF STAINLESS STEEL TUBING. ........................ 126 FIGURE 4-3: COMPARISON OF THE MOLAR VOLUMES OF PURE ALKYL-PIPERIDINES: 3-MPD,. 2-MPD (COULIER ET AL., 2010),. 4-MPD,. N-MPD (COULIER ET AL., 2010),. . PIPERIDINE (AFZAL ET AL., 2008), 3,5-DPD,. N-EPD,.
(28) 2,6-DPD. SOLID LINES ARE POLYNOMIAL FITS. THE SIZE OF THE MARKERS REFLECTS THE UNCERTAINTY OF THE DATA. ............................................................................................................................................................................. 130 FIGURE 4-4 AND FIGURE 4-5: EXCESS MOLAR VOLUMES OF 4-MPD (LEFT) AND 3-MPD (RIGHT) MEASURED AT ATMOSPHERIC PRESSURE, WITH REDLICH KISTERS FITS TO THE DATA. ( , 308.15 K) ( ,. 318.15K) ( ,. 288.15 K) ( ,. 298.15 K) ( ,. 328.15 K). THE SIZES OF THE MARKERS REFLECT THE UNCERTAINTY IN THE. DATA. ............................................................................................................................................................................. 132 FIGURE 4-6 AND FIGURE 4-7: EXCESS MOLAR VOLUMES OF 2,6-DPD (LEFT) AND 3,5-DPD (RIGHT) MEASURED AT ATMOSPHERIC PRESSURE WITH REDLICH KISTERS FITS AND POLYNOMIAL FITS TO THE DATA. ( , 298.15 K) ( ,. 308.15 K) ( ,. 288.15 K) ( ,. 318.15K). THE SIZE OF THE MARKERS REFLECTS THE UNCERTAINTY IN THE. DATA. ............................................................................................................................................................................. 133 FIGURE 4-8: EXCESS MOLAR VOLUMES OF N-EPD MEASURED AT ATMOSPHERIC PRESSURE, WITH POLYNOMIAL FITS TO THE DATA. ( ,. 278.15 K) ( ,. 288.15 K) ( ,. 298.15 K). THE SIZE OF THE MARKERS REFLECTS THE. UNCERTAINTY IN THE DATA. ......................................................................................................................................... 133 FIGURE 4-9: EXCESS MOLAR VOLUMES OF TERTIARY ALKY PIPERIDINES AND PIPERIDINE AT 298.15 K. (AFZAL ET AL., 2008) N-MPD. (COULIER ET AL., 2010) N-EPD. PIPERIDINE. ( 278.15 K). THE SIZE OF THE MARKERS REFLECT THE. UNCERTAINTY OF THE DATA ......................................................................................................................................... 136 FIGURE 4-10: EXCESS MOLAR VOLUMES OF SECONDARY HINDERED ALKYL PIPERIDINES AND PIPERIDINE AT 298.15 K. PIPERIDINE (AFZAL ET AL., 2008),. 2-MPD (COULIER ET AL., 2010),. ,2,6-DPD. THE SIZE OF THE MARKERS REFLECT. THE UNCERTAINTY OF THE DATA .................................................................................................................................. 137 FIGURE 4-11: EXCESS MOLAR VOLUMES OF SECONDARY ALKYL PIPERIDINES AND PIPERIDINE AT 298.15 K. (AFZAL ET AL., 2008),. 4-MPD,. 3-MPD ,. PIPERIDINE. 3,5-MPD . THE SIZE OF THE MARKERS REFLECT THE UNCERTAINTY OF. THE DATA ....................................................................................................................................................................... 138 FIGURE 4-12: EXCESS MOLAR VOLUMES OF 3-MPD AT 303.15 K WITH INCREASING PRESSURE AND REDLICH KISTHER FITS: (ATMOSPHERIC PRESSURE),. (0.5 MPA),. (1.0 MPA). THE SIZE OF THE MARKERS REFLECT THE UNCERTAINTY. OF THE DATA.................................................................................................................................................................. 140. .
(29) FIGURE 4-13: EXCESS MOLAR VOLUMES OF 4-MPD AT 303.15 K WITH INCREASING PRESSURE AND REDLICH KISHTER FITS. (ATMOSPHERIC PRESSURE),. (0.5 MPA). THE SIZE OF THE MARKERS REFLECTS THE UNCERTAINTY OF THE DATA.. ........................................................................................................................................................................................ 140 FIGURE 4-14 AND FIGURE 4-15 : EXCESS MOLAR ENTHALPIES OF 3-MPD (LEFT) AND 4-MPD (RIGHT) MEASURED AT 1.0 MPA ( ,. 303.15 K) ( ,. 313.15 K) ( ,. 323.15K) ( ,. 333.15 K). THE SIZE OF THE MARKERS REFLECTS. THE UNCERTAINTY OF THE DATA. ................................................................................................................................. 141 FIGURE 4-16: EXCESS MOLAR ENTHALPIES OF ALKYL PIPERIDINE AND REDLICH KISTER FITS, 2010),. N-MPD (COULIER ET AL., 2015),. 2-MPD (COULIER ET AL., 2015),. PIPERIDINE (KUL AND LIEU,. 3-MPD,. 4-MPD. THE SIZE OF THE. MARKERS REFLECTS THE UNCERTAINTY OF THE DATA. ............................................................................................... 142 FIGURE 4-17 AND FIGURE 4-18 : REDUCED MOLAR ENTHALPIES OF 3-MPD (LEFT) AND 4-MPD (RIGHT): ( 313.15 K), (. 323.15K), (. 303.15 K), (. 333.15 K). THE SOLID LINES ARE LINEAR REGRESSIONS FOR INFINITE DILUTION. THE SIZE. OF THE MARKERS REFLECTS THE UNCERTAINTY OF THE DATA ................................................................................... 143 FIGURE 4-19: TEMPERATURE DEPENDENT INFINITE DILUTION ENTHALPIES OF ALKYL PIPERIDINES. , 298.15 K (DOHNAL ET AL., 1994), MPD (COULIER ET AL., 2015), (BERTHON ET AL., 1979),. N-MPD (COULIER ET AL., 2015),. 3-MPD,. 2-. 3-MPD AT 298.15 K. 4-MPD AT 298.15 K (BERTHON ET AL., 1979). .............................................. 144. FIGURE 4-20: MOLAR HEAT CAPACITIES OF PURE ALKYL-PIPERIDINE. (COULIER ET AL., 2015),. N-MPD (DOHNAL AND REHAK, 2011),. 2-MPD AT 298.15 K (BERTHON ET AL., 1979),. 4-MPD,. PIPERIDINE AT. N-MPD (CONTI, G ET AL., 1976),. MPD,(3-MPD AND 4-MPD ARE OVERLAPPED). PIPERIDINE (MESSERLY ET AL., 1988),. 2-MPD (MESSERLY ET AL., 1988),. 3-MPD,. N-MPD 4-. 2-MPD (COULIER ET AL., 2015), ,. .................................................. 146. FIGURE 4-21 AND FIGURE 4-22: EXCESS MOLAR HEAT CAPACITIES OF 3-MPD (LEFT) AND 4-MPD (RIGHT) AT ATMOSPHERIC PRESSURE: ( ,. 288.15 K) ( ,. 298.15 K) ( ,. 308.15 K) ( ,. 318.15K) ( ,. 328.15 K) .................. 147. FIGURE 4-23: ZOOM IN OF EXCESS MOLAR HEAT CAPACITIES IN THE CROSSOVER CONCENTRATION. (A) 3-MPD ( , 288.15 K) ( , ,. 298.15 K) ( ,. 298.15 K) ( ,. 308.15 K) ( ,. 308.15 K) ( ,. 318.15K) ( ,. 318.15K) ( ,. 328.15 K), (B) 4-MPD ( ,. 288.15 K) (. 328.15 K). THE LINES IN THE FIGURE ARE POLYNOMIAL. FITS TO THE DATA. THE ARROWS SHOW THE DIRECTION OF INCREASING, BLACK, AND DECREASING, RED, HEAT CAPACITY WITH TEMPERATURE. ................................................................................................................................... 147. .
(30) FIGURE 4-24: EXCESS MOLAR HEAT CAPACITIES OF N-MPD FROM (COULIER ET AL. 2015), ( , 298.15 K), ( ,. 288.15 K), ( ,. 308.15 K). ........................................................................................................................................ 148. FIGURE 4-25: COMPARISON OF EXCESS MOLAR HEAT CAPACITIES AT 318.15 K. MPD (COULIER ET AL., 2015),. 3-MPD,. N-MPD (COULIER ET AL., 2015),. 2-. 4-MPD ..................................................................................................... 149. FIGURE 5-1: SOLUTION ENTHALPIES PER MOLE OF CARBON DIOXIDE FOR A 39.86 WA% 4-MPD SOLUTION. THE DASHED LINES REPRESENT THE DATA SELECTED FOR THE AVERAGE ENTHALPY OF DISSOLUTION FOR CO2 IN SOLUTION. ( (0.43 MPA),. (0.95 MPA),. (1.45 MPA)) .................................................................................................................. 179. FIGURE 5-2: SOLUTION ENTHALPIES PER MOL OF AMINE FOR A 39.86 WA% 4-MPD SOLUTION. THE DASHED LINES REPRESENT THE THREE SEPARATE REGIONS FOR THE SOLUTION ENTHALPIES. (A) THE INITIAL SLOPE. (B) THE SECOND SLOPE REPRESENTING THE CHANGE IN ABSORPTION MECHANISM (C) PLATEAU REPRESENTING THE SATURATION OF THE SOLUTION. THE INTERCEPTS OF SLOPS B AND C REVEAL THE SOLUBILITY LIMITS FOR EACH SOLUTION. ( (0.43 MPA),. (0.95 MPA),. (1.45 MPA)) ........................................................................................ 182. FIGURE 5-3: ILLUSTRATION OF THE DIFFERENT EQUILIBRIUM CONDITIONS AND REACTIONS IN THE SYSTEM TO BE MODELLED. .................................................................................................................................................................... 183 FIGURE 5-4: EXPERIMENTAL SOLUBILITY (S) OF CO2 IN AQUEOUS, (A), 3-MPD AND, (B), 4-MPD SOLUTIONS (WA%=40) VS TOTAL PRESSURE. (○), 318 K AND (□), 338 K. SOLID LINES ARE THE CALCULATED SOLUBILITY AT 318 AND 338 K. .. 193 FIGURE 5-5: ENTHALPIES OF SOLUTION (' 'SOLH / KJ·ܔܗܕ۱۽ െ ) VERSUS CO2 LOADING FOR AQUEOUS SOLUTIONS OF 3MPD AND 4-MPD: ○, EXPERIMENTAL DATA. FROM THE THERMODYNAMIC MODEL: (1), TOTAL ENTHALPY OF SOLUTION; ENTHALPIC CONTRIBUTION FROM EQUILIBRIA: (2), AMINE PROTONATION (EQ 6-4); (3), CARBAMATE FORMATION (EQ 6-5); (4), CO2 VAPOUR – LIQUID EQUILIBRIUM; (5), SECOND IONIZATION OF CO2 (EQ 6-2); (6), FIRST IONIZATION OF CO2 (EQ 6-3). (A): T = 318 K AND W3-MPD%= 40; (B): T = 338 K AND W3-MPD %= 40; (C): T = 318 K AND W4-MPD %=40; (D): T = 338 K AND W4-MPD %=40..................................................................................................... 194 FIGURE 5-6: ACTIVITY COEFFICIENTS (JI) AND LIQUID PHASE COMPOSITION (MI, MOLAL CONCENTRATION) OF AQUEOUS SOLUTIONS OF 3-MPD AND 4-MPD VERSUS GAS LOADING CHARGE AS CALCULATED FROM THE MODEL. (A) AND (B): T = 318 K AND W3-MPD%= 20; (C) AND (D): T=318 K AND W4-MPD%= 20. ................................................................. 195. .
(31) FIGURE 5-7: ENTHALPIES OF SOLUTION PER MOLE OF AMINE (ABOVE) AND PER MOLE OF CO2 (BELOW). 3-MPD CORRESPONDING TO TABLE 6-1 (. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) ................................................................... 217. FIGURE 5-8: ENTHALPIES OF SOLUTION TO PER MOLE OF AMINE (ABOVE) AND PER MOL OF CO2 (BELOW). 3-MPD CORRESPONDING TO TABLE 6-2(. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) .................................................................... 218. FIGURE 5-9: ENTHALPIES OF SOLUTION TO PER MOLE OF AMINE (ABOVE) AND PER MOL OF CO2 (BELOW). 3-MPD CORRESPONDING TO TABLE 6-3 (. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) ................................................................... 219. FIGURE 5-10: ENTHALPIES OF SOLUTION TO PER MOLE OF AMINE (ABOVE) AND PER MOL OF CO2 (BELOW). 4-MPD CORRESPONDING TO TABLE 6-4 (. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) ................................................................... 220. FIGURE 5-11: ENTHALPIES OF SOLUTION TO PER MOLE OF AMINE (ABOVE) AND PER MOLE OF CO2 (BELOW). 4-MPD CORRESPONDING TO TABLE 6-5 (. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) ................................................................... 221. FIGURE 5-12: ENTHALPIES OF SOLUTION PER MOLE OF AMINE (ABOVE) AND PER MOLE OF CO2 (BELOW). 4-MPD CORRESPONDING TO TABLE 6-6 (. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) ................................................................... 222. FIGURE 5-13: ENTHALPIES OF SOLUTION PER MOLE OF AMINE (ABOVE) AND PER MOLE OF CO2 (BELOW). 4-MPD CORRESPONDING TO TABLE 6-7. (. 0.5 MPA), (. 1.0MPA) ( 1.5MPA) .................................................................. 223. .
(32) 7DEOHRI7DEOHV TABLEAU 0-1: LISTE DES AMINES ETUDIEES ET LEURS ACRONYMES ....................................................................................... 32 TABLEAU 0-2: CARACTERISTIQUES DES CELLULES D’EQUILIBRE DE PHASE. ............................................................................ 36 TABLE 3-1 : CHARACTERISTICS OF THE VISUAL CELLS USED FOR CLOUD POINT MEASUREMENTS ........................................ 88 TABLE 3-2: EXPERIMENTAL METHOD USED TO MEASURE THE PHASE EQUILIBRIUM TEMPERATURE. ................................. 99 TABLE 3-3 : MOLE FRACTION AND MEASURED LIQUID-LIQUID EQUILIBRIUM TEMPERATURES OF ALKYL PIPERIDINES .... 112 TABLE 3-4: SCALING LAW PARAMETER FOR AQUEOUS ALKYL PIPERIDINE SOLUTIONS. ...................................................... 114 TABLE 3-5: LLE OF AQUEOUS N-MPD SOLUTIONS WITH CO2 MEASURED WITH THE SAPPHIRE EQUILIBRIUM CELL AND THE THAR INSTRUMENTS EQUILIBRIUM CELL. .................................................................................................................... 115 TABLE 3-6: LLE OF AQUEOUS 2-MPD SOLUTIONS WITH CO2 MEASURED WITH THE THAR INSTRUMENTS EQUILIBRIUM CELL ........................................................................................................................................................................................ 116 TABLE 3-7: LLE OF AQUEOUS 2,6-DPD SOLUTIONS WITH CO2 MEASURED WITH THE SAPPHIRE EQUILIBRIUM CELL ......... 117 TABLE 3-8: LLE OF AQUEOUS N-EPD SOLUTIONS WITH CO2 MEASURED WITH THE STATIC MIXING UNIT AND THAR CELL. ........................................................................................................................................................................................ 118 TABLE 4-1: LIST OF CHEMICALS SUPPLIERS AND PURITIES .................................................................................................... 152 TABLE 4-2: EXPERIMENTAL AND LITERATURE OF MOLAR ISOBARIC HEAT CAPACITIES OF N-OCTANE. .............................. 153 TABLE 4-3: DENSITIES AND EXCESS MOLAR VOLUMES OF AQUEOUS 3-MPD SOLUTIONS AND PURE LIQUID AT ATMOSPHERIC PRESSURE.. A,B,C,D. .................................................................................................................................... 154. TABLE 4-4: DENSITIES AND EXCESS MOLAR VOLUMES OF AQUEOUS 4-MPD SOLUTIONS AND PURE LIQUID AT ATMOSPHERIC PRESSURE.. A,B,C,D. .................................................................................................................................... 156. TABLE 4-5: DENSITIES AND EXCESS MOLAR VOLUMES OF AQUEOUS 2,6-DPD SOLUTIONS AND PURE LIQUID AT ATMOSPHERIC PRESSURE.. A,B,C,D. .................................................................................................................................... 158. TABLE 4-6: DENSITIES AND EXCESS MOLAR VOLUMES OF AQUEOUS 3,5-DPD SOLUTIONS AND PURE LIQUID AT ATMOSPHERIC PRESSURE.. A,B,C,D. .................................................................................................................................... 159. .
(33) TABLE 4-7: DENSITIES AND EXCESS MOLAR VOLUMES OF AQUEOUS N-EPD SOLUTION AND PURE LIQUID AT ATMOSPHERIC PRESSURE.. A,B,C,D. .................................................................................................................................... 160. TABLE 4-8: TEMPERATURE DEPENDENT REDLICH-KISHTER PARAMETERS FOR EXCESS MOLARE VOLUMES OF ALKYL PIPERIDINES. .................................................................................................................................................................. 161 TABLE 4-9: TEMPERATURE DEPENDENT EXCESS PARTIAL INFINITE DILUTION MOLAR VOLUMES AND INFINITE DILUTION PARTIAL MOLAR PROPERTIES OF ALKYL PIPERIDINE. .................................................................................................. 162 TABLE 4-10: MAGNITUDE AND LOCAL MINIMA OF EXCESS MOLAR VOLUMES AT 298.15 K. THE TABLE IS ARRANGED BY DECREASING MAGNITUDE OF THE EXCESS MOLAR VOLUMES. ................................................................................... 162 TABLE 4-11: PRESSURE DEPENDANT REDLICH-KISTER PARAMETERS FOR EXCESS MOLAR VOLUMES AT 303.15 K ............ 163 TABLE 4-12: DENSITIES AND EXCESS MOLAR VOLUMES OF 3-MPD AND 4-METHYLPIPERIDINE AT 303 K AT ATMOSPHERIC PRESSURE, 0.5 MPA AND 1.0 MPA. ............................................................................................................................... 164 TABLE 4-13: EXCESS MOLAR ENTHALPIES OF MIXING WATER AND 3-MPD AT A PRESSURE OF 1.0 MPA ........................... 166 TABLE 4-14: EXCESS MOLAR ENTHALPIES OF MIXING WATER AND 4-MPD AT A PRESSURE OF 1.0 MPA ........................... 168 TABLE 4-15: REDLICH-KISTER PARAMETERS FOR THE EXCESS MOLAR ENTHALPIES ............................................................. 170 TABLE 4-16: MAGNITUDE AND LOCAL MINIMA OF EXCESS MOLAR ENTHALPIES. THE TABLE IS ARRANGED BY DECREASING MAGNITUDE OF THE EXCESS MOLAR VOLUMES. ......................................................................................................... 170 TABLE 4-17: INFINITE DILUTION PARTIAL MOLAR ENTHALPIES OF 3-MPD AND 4-MPD. ..................................................... 170 TABLE 4-18: SPECIFIC HEAT CAPACITIES AND EXCESS MOLAR HEAT CAPACITIES OF AQUEOUS 3-MPD SOLUTION AND PURE LIQUID AT ATMOSPHERIC PRESSURE.. A,B,C,D. .................................................................................................................. 171. TABLE 4-19: SPECIFIC HEAT CAPACITIES AND EXCESS MOLAR HEAT CAPACITIES OF AQUEOUS 4-MPD SOLUTION AND PURE LIQUID AT ATMOSPHERIC PRESSURE ............................................................................................................................ 173 TABLE 4-20: REDLICH-KISTER FITTING PARAMETERS FOR EXCESS MOLAR HEAT CAPACITIES. ............................................ 175 TABLE 4-21: MAGNITUDE AND LOCAL MINIMA OF EXCESS MOLAR HEAT CAPACITIES AT 318.15K. THE TABLE IS ARRANGED BY DECREASING MAGNITUDE OF THE EXCESS VOLUMES. ........................................................................................... 176. .
(34) TABLE 5-1: ENTHALPIES OF SOLUTION FOR CO2 DISSOLUTION AND SOLUBILITY OF CO2 IN AQUEOUS SOLUTIONS OF 3MPD ............................................................................................................................................................................... 181 TABLE 5-2: ENTHALPIES OF SOLUTION FOR CO2 DISSOLUTION AND SOLUBILITY OF CO2 IN AQUEOUS SOLUTIONS OF 4MPD ............................................................................................................................................................................... 181 TABLE 5-3: PARAMETERS FOR EQUILIBRIUM CONSTANTS .................................................................................................... 184 TABLE 5-4: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 3-MPD (WA%=19.36) AT 318 K .................... 198 TABLE 5-5: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 3-MPD (WA%=40.44) AT 318 K .................... 200 TABLE 5-6: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 3-MPD (WA%=40.00) AT 338 K ................... 203 TABLE 5-7: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 4-MPD (WA%=16.57) AT 318 K .................... 206 TABLE 5-8: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 4-MPD (WA%=39.86) AT 318 K ................... 209 TABLE 5-9: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 4-MPD (WA%=20.00) AT 338 K .................... 211 TABLE 5-10: EXPERIMENTAL ENTHALPIES OF SOLUTION OF CO2 IN AQUEOUS 4-MPD (WA%=40.00) AT 338 K ................. 214. . . .
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