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Collège doctoral N° attribué par la bibliothèque ||||||||||

Collège doctoral N° attribué par la bibliothèque |__|__|__|__|__|__|__|__|__|__| T H E S E pour obtenir le grade de Docteur de l’Ecole des Mines de Paris Spécialité “Génie des Procédés” présentée et soutenue publiquement par Antonin CHAPOY Le 26 Novembre 2004 PHASE BEHAVIOUR IN WATER/HYDROCARBON MIXTURES INVOLVED IN GAS PRODUCTION SYSTEMS ETUDE DES EQUILIBRES DES SYSTEMES : EAU-HYDROCARBURES-GAZ ACIDES DANS LE CADRE DE LA PRODUCTION DE GAZ Directeur de thèse : Dominique RICHON Jury : M. Jürgen GMEHLING ...................................................................President M. Jean-Michel HERRI.................................................................Rapporteur M. Gerhard LAUERMANN........................................................Examinateur M. Francois MONTEL................................................................Examinateur M. Dominique RICHON.............................................................Examinateur M. Bahman TOHIDI .....................................................................Rapporteur 2 3 A ma Misstinguette, 4 5 Remerciements Dans un premier temps, je voudrais exprimer ma sincère gratitude au Professeur Dominique Richon d’avoir été mon Directeur de Thèse durant ces trois années passées au sein du laboratoire TEP et qui m’a fait confiance pour réaliser ce travail. Ich bin Herrn Jürgen Gmehling außerordentlich dankbar, den Vorsitz des Prüfungsausschusses für diese Dissertation angenommen zu haben. Je remercie très sincèrement M. Jean-Michel Herri et M. Bahman Tohidi d’avoir accepté d’être rapporteurs de cette thèse et de participer au jury chargé de son examen. Je tiens également à remercier M. Gerhard Lauermann et M. Francois Montel d’avoir eu la gentillesse de s’intéresser à ce travail et pour leur participation au jury d’examen. Ce travail est, pour une grande partie un travail expérimental et il matérialise les efforts et la participation de toute l’équipe du laboratoire. Pour cela je tiens à remercier Alain Valtz, Albert Chareton et Pascal Théveneau pour leurs conseils sur le plan expérimental ainsi que David Marques et Hervé Legendre pour leurs aides techniques. Sans aucun doute, les résultats de ce travail tiennent la marque d’une série de discussions très fructueuses avec l’ensemble des doctorants et post- doctorants. Je garderai également un très bon souvenir des différents membres du laboratoire que j’ai pu côtoyer au cours de ces trois années: Christophe, Fabien, Cathy, Jeannine, Armelle, Vania, Samira, Salim, Wael, Duc. I also would like to thank Professor Bahman Tohidi from the Centre of Gas Hydrate, for welcoming me in his team. It has been very helpful time to discuss problems with him, during my stay at the Heriot Watt Petroleum Institute. A big thank you goes to his Ph. D. students, A. H. Mohammadi and Zahidah Md Zain for all the help they provided me during my stay, for 6 welcoming me in their office and for very fruitful discussions. I wish also to thank Rod Burgass, Ross Anderson, Alastair Reid, Colin Flockhart and Jim Pantling for their experimental expertise and the maintenance of the experimental set up. I wish also to acknowledge the European Infrastructure for Energy Reserve Optimization (EIERO) for their financial support providing me the opportunity to work with the hydrate team. Further I am grateful to Professor Adrian Todd for helping me to get through the EIERO application process. 7 Table of Contents 1. INTRODUCTION AND INDUSTRIAL CONTEXT.......................................... 17 2. STATE OF THE ART, BIBLIOGRAPHY REVIEW ........................................ 25 2.1. Properties and Characteristics of Water................................................................... 25 2.2. Gas Hydrates ............................................................................................................ 31 2.3. Experimental Data.................................................................................................... 33 2.3.1. Water Content in the Gas Phase....................................................................... 34 2.3.1.1. Water Content in the Gas Phase of Binary Systems ................................ 34 2.3.1.2. Water Content in Natural Gas Systems.................................................... 37 2.3.2. Hydrocarbon Solubility in Water ..................................................................... 38 2.3.3. Hydrate Forming Conditions............................................................................ 45 3. THERMODYNAMIC MODELS FOR FLUID PHASE EQUILIBRIUM CALCULATION ............................................................................................ 53 3.1. Approaches for VLE Modelling............................................................................... 53 3.1.1. Virial Equations................................................................................................ 54 3.1.2. Cubic Equations of State.................................................................................. 55 3.1.2.1. van der Waals Equation of State .............................................................. 56 3.1.2.2. RK and RKS Equation of State................................................................ 57 3.1.2.3. Peng-Robinson Equation of State ............................................................ 58 3.1.2.4. Three-Parameter Equation of State .......................................................... 59 3.1.2.5. Temperature Dependence of Parameters.................................................. 63 3.1.2.6. EoS Extension for Mixture Application................................................... 66 3.1.3. The γ – Φ approach .......................................................................................... 67 3.1.4. Activity Coefficient.......................................................................................... 70 3.1.4.1. NRTL Model............................................................................................ 71 3.1.4.2. UNIQUAC Model.................................................................................... 72 3.1.4.3. UNIFAC and Modified UNIFAC ............................................................ 73 3.2. Hydrate Phase Equilibria.......................................................................................... 75 3.2.1. Empirical Determination........................................................................................ 75 3.2.2. van der Waals-Platteeuw Model (Parrish and Prausnitz Development) ................ 77 3.2.3. Modifications of the vdW-P Model ....................................................................... 80 3.2.3.1. Classical Modifications................................................................................... 80 3.2.3.2. Chen and Guo Approach................................................................................. 81 4 EXPERIMENTAL STUDY ................................................................................................... 87 4.1 Literature Survey of Experimental Techniques and Apparatus ............................... 87 4.1.1 Synthetic Methods............................................................................................ 88 4.1.2 Analytical Methods .......................................................................................... 90 8 4.1.3 Stripping Methods, Measurement of Activity Coefficient and Henry’s Constant at Infinite Dilution............................................................................................................ 91 4.1.4 Review of the Experimental Set-Ups for Determination of the Water Contents. .......................................................................................................................... 93 4.1.4.1 Direct Methods............................................................................................. 93 4.1.4.2 Indirect Methods ......................................................................................... 95 4.1.5 Review of the Experimental Set-ups for Determination of Gas Solubilities . 100 4.2 Description of the Apparati for Measurement of the Water Content and Gas Solubilities.......................................................................................................................... 100 4.2.1 The Experimental Set-ups for Determination of the Water Content and Gas Solubilities...................................................................................................................... 101 4.2.1.1 Chromatograph........................................................................................... 104 4.2.1.2 Calibration of Measurement Devices and GC Detectors ........................... 105 4.2.1.2.1 Calibration of Pressure Measurement Sensors........................................ 105 4.2.1.2.2 Calibration of Temperature Measurement Devices ................................ 107 4.2.1.3 Determination of the Composition in the Vapour Phase............................ 109 4.2.1.3.1 Calibration of the FID with Hydrocarbons (Vapour Phase) .................. 109 4.2.1.3.2 Calibration of the TCD with Water (Vapour Phase).............................. 111 4.2.1.3.2.1 Estimation of the Water Content......................................................... 111 4.2.1.3.2.2 Calibration Method .............................................................................. 112 4.2.1.3.3 Optimization of the Calibration Conditions............................................ 115 4.2.1.3.3.1 Optimization of the Chromatographic Conditions............................... 115 4.2.1.3.3.2 Calibration Results............................................................................... 118 4.2.1.3.4 Experimental Procedure for determination of the vapour phase composition .................................................................................................................................... 119 4.2.1.4 Determination of the Composition in the Aqueous Phase ......................... 119 4.2.1.4.1 Calibration of the TCD with Water........................................................ 119 4.2.1.4.2 Calibration of the TCD and FID with the gases..................................... 121 4.2.1.4.3 Experimental procedure for determination of the aqueous phase composition ................................................................................................................ 122 4.2.2 The Experimental Set-ups for Determination of Gas Solubilities.................. 123 4.2.2.1 Apparatus based on the PVT techniques.................................................... 123 4.2.2.1.1 Principle ............................................................................................... 123 4.1.2.2.2 Experimental Procedures...................................................................... 124 4.2.2.2 Apparatus based on the static method (HW University)............................ 125 4.2.2.2.1 Principle .................................................................................................. 125 4.2.2.2.2 Experimental Procedures......................................................................... 126 5 MODELLING AND RESULTS........................................................................................ 131 5.1 Pure Compound Vapour Pressure .......................................................................... 131 5.1.2 Temperature Dependence of the Attractive Parameter .................................. 132 5.1.3 Comparison of the α-function abilities........................................................... 133 5.2 Modelling by the φ - φ Approach........................................................................... 139 5.3 Modelling by the γ - φ Approach............................................................................ 141 6 EXPERIMENTAL AND MODELLING RESULTS......................................... 147 6.1 Water Content in Vapour Phase............................................................................. 147 6.1.1 Methane-Water System.................................................................................. 147 9 6.1.2 Ethane-Water System..................................................................................... 156 6.1.3 Water Content in the Water with -Propane, -n-Butane, -Nitrogen, -CO2, -H2S Systems ........................................................................................................................ 158 6.1.5 Mix1- Water-Methanol System...................................................................... 167 6.1.6 Mix1- Water-Ethylene Glycol System........................................................... 170 6.1.7 Comments and Conclusions on Water Content Measurements ..................... 171 6.2 Gas Solubilities in Water and Water-Inhibitor Solutions....................................... 172 6.2.1 Gas Solubilities in Water................................................................................ 172 6.2.1.2 Ethane – Water System .............................................................................. 175 6.2.1.3 Propane – Water System ............................................................................ 177 6.2.1.4 Mix1 – Water System................................................................................. 179 6.2.1.5 Carbon Dioxide –Water System................................................................. 180 6.2.1.5.1 Data generated with the PVT apparatus.................................................. 180 6.2.1.5.1 Data generated with the Static analytic apparatus................................... 182 6.2.1.6 Hydrogen Sulphide–Water System ............................................................ 185 6.2.1.7 Nitrogen –Water System ............................................................................ 188 6.2.2 Gas Solubilities in Water and Ethylene Glycol Solution............................... 190 7 CORRELATIONS...................................................................................................................... 197 7.1 Water Content Models and Correlations............................................................... 198 7.1.1 Correlation and Charts ......................................................................................... 198 7.1.1.1 Sweet and Dry Gas in Equilibrium with Liquid Water.......................... 198 7.1.1.2 Acid Gas in Equilibrium with Liquid Water.............................................. 203 7.1.1.3 Gas in Equilibrium with Ice or Hydrate..................................................... 204 7.1.1.4 Comments................................................................................................... 205 7.1.2 Semi – Empirical Correlation......................................................................... 206 7.1.2.1 Approach for Sweet and Dry Gas .............................................................. 206 7.1.2.2 Gravity Correction Factor .......................................................................... 209 7.1.2.3 Acid and Sour Gas Correction Factor ........................................................ 209 7.1.2.4 Salt Correction Factor ................................................................................ 210 7.1.3 Comments and discussions............................................................................. 210 7.2 Gas Solubilities and Henry’s Law Correlations.................................................... 212 8 CONCLUSION AND PERSPECTIVES .................................................................... 215 8.1 En français.............................................................................................................. 215 8.2 In English ............................................................................................................... 216 9 REFERENCES.............................................................................................................................. 219 APPENDIX A: PROPERTIES OF SELECTED PURE COMPOUNDS .......................................... 241 APPENDIX B: PUBLISHED PAPERS AND PROJECTS DONE DURING THE PHD................. 242 APPENDIX C: THERMODYNAMIC RELATIONS FOR FUGACITY COEFFICIENT CALCULATIONS USING RK, RKS OR PR-EOS. ...................................................................................... 244 10 APPENDIX D: CALCULATION OF FUGACITY COEFFICIENT USING AN EOS AND THE NDD MIXING RULES..................................................................................................................................... 247 APPENDIX E: BIPS FOR THE VPT EOS .......................................................................................... 248 APPENDIX F: DATA USED FOR THE WATER CONTENT CORRELATION........................... 249 APPENDIX G: ARTIFICIAL NEURAL NETWORK FOR GAS HYDRATE PREDICTIONS.... 253 11 List of Symbols Abreviations AAD Average absolute deviation AD Absolute deviation BIP Binary interaction parameter EG Ethylene glycol EOR Enhanced oil recovery FID Flame ionization detector FOB Objective function GC Gas Chromatography MC Mathias-Copeman alpha function MW Micro wave NDD Non density dependent mixing rules NIR Near infrared NRTL Non random two liquids PVT Pressure – volume – temperature PR - EoS Peng Robinson equation of state ppt Part per trillion ppm Part per million RK- EoS Redlich and Kwong equation of state RKS- EoS Soave modification of Redlich and Kwong equation of state ROLSI Rapid online sampler injector RTD Resistance Thermometer Devices TB Trebble – Bishnoi alpha function TCD Thermal conductivity detector TDLAS Tunable diode laser absorption spectroscopy UNIFAC Universal quasi chemical UNIQUAC Universal quasi chemical model Functional activity coefficient model VHE Vapour – hydrate equilibrium VLE Vapour – liquid equilibrium VLLE uploads/Geographie/ water-content-in-gas.pdf