In a context of international reduction of greenhouse gases emissions, CCS (ce{CO2} Capture and Storage) appears as a particularly interesting midterm solution. Indeed, geological storage capacities may raise to several millions of tons of ce{CO2} injected per year, allowing to reduce substantially the atmospheric emissions of this gas. One of the most interesting targets for the development of this solution are the deep saline aquifers. These aquifers are geological formations containing brine whose salinity is often higher than sea water's, making it unsuitable for human consumption. However, this solution has to cope with numerous technical issues, and in particular, the precipitation of salt initially dissolved in the aquifer brine. Consequences of this precipitation are multiple, but the most important is the modification of the injectivity i.e. the injection capacity. Knowledge of the influence of the precipitation on the injectivity is particularly important for both the storage efficiency and the storage security and durability. The aim of this PhD work is to compare the relative importance of negative (clogging) and positive (fracturing) phenomena following ce{CO2} injection and salt precipitation. Because of the numerous simulations and modelling results in the literature describing the clogging of the porosity, it has been decided to focus on the mechanical effects of the salt crystallization and the possible deformation of the host rock. A macroscopic and microscopic modelling has then been developed, taking into account two possible modes of evaporation induced by the spatial distribution of residual water, in order to predict the behavior of a porous material subjected to the drying by carbon dioxide injection. Results show that crystallization pressure created by the growth of a crystal in a confined medium can reach values susceptible to locally exceed the mechanic resistance of the host rock, highlighting the importance of these phenomena in the global mechanical behavior of the aquifer. At the experimental level, the study of a rock core submitted to the injection of supercritical carbon dioxide has been proceeded on a new reactive percolation prototype in order to obtain the evolution of permeabilities in conditions similar to these of a deep saline aquifer
Authors
- Bibliographic Reference
- Florian Osselin. Thermochemical-based poroelastic modelling of salt crystallization, and a new multiphase flow experiment : how to assess injectivity evolution in the context of CO2 storage in deep aquifers. Other. Université Paris-Est, 2013. English. ⟨NNT : 2013PEST1136⟩. ⟨tel-00958697v2⟩
- HAL Collection
- ['Bureau de Recherches Géologiques et Minières', 'PASTEL - ParisTech', 'ParisTech', 'Ecole des Ponts ParisTech', 'CNRS - Centre national de la recherche scientifique', 'Laboratoire Navier', 'Milieux poreux', 'STAR - Dépôt national des thèses électroniques', 'Ifsttar', 'Université Gustave Eiffel', "Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux"]
- HAL Identifier
- 977430
- Institution
- ["Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux", 'École des Ponts ParisTech']
- Laboratory
- Laboratoire Navier
- Published in
- France
Table of Contents
- Remerciements 4
- Résumé 6
- Abstract 8
- Contents 10
- List of Figures 18
- List of Tables 24
- List of symbols 26
- General introduction 34
- I Injection of supercritical carbon dioxide in deep saline aquifers 36
- 1 Context of the study 38
- 1.1 Carbon dioxide and greenhouse effect 39
- 1.2 Political decisions and solutions 41
- 1.2.1 International conferences and political decisions 41
- 1.2.2 The different ways to decrease carbon dioxide emissions 41
- 2 Problem at stake: injectivity and permeability evolution 44
- II Thermo-Hydro-Chemical behavior of the aquifer 46
- 3 Hydrodynamic behavior of the aquifer 48
- 3.1 Porosities and phase saturations 49
- 3.1.1 Definitions 49
- 3.1.2 Diagenesis and the formation of natural porous media 50
- 3.2 Mass balance and fluid velocity 51
- 3.2.1 Mass Balance 51
- 3.2.2 Fluid velocity: Darcy's law and relative permeabilities 52
- 3.2.3 Displacement of dissolved species: diffusion 53
- 3.2.4 Klinkenberg effect 53
- 3.3 Surface energy and consequences 54
- 3.3.1 Interfacial energy and wettability 54
- 3.3.2 Capillary pressure 56
- 3.4 Hydrodynamic regimes 58
- 4 Chemical behavior of the aquifer 62
- 4.1 Carbon dioxide/brine partitioning 63
- 4.1.1 Thermodynamics of mixtures 63
- 4.1.2 Molar quantities of reaction 67
- 4.1.3 Laws for CO2/H2O partitioning 69
- 4.1.4 Activity and fugacity coefficients 71
- 4.1.5 Kinetics of evaporation and simplifications 73
- 4.2 Chemical reactions induced by carbon dioxide dissolution (mineral trapping) 74
- 4.2.1 Carbon dioxide dissolution and pH evolution 74
- 4.2.2 Mineral reactions and carbon dioxide trapping 75
- 4.2.3 Kinetics of mineral reactions: nucleation and crystal growth 77
- 4.2.4 Porosity and permeability variations induced from dissolution/precipitation 83
- 5 Thermal behavior of the aquifer 86
- 5.1 Joule-Thomson expansion 87
- 5.2 Heat of reaction 87
- 5.3 Thermal diffusion 88
- 5.4 Importance of the different phenomena 89
- 6 Summary of the THC behavior of the aquifer 90
- 6.1 TOUGH, an intensively used family of codes 91
- 6.2 Presentation of different simulations 92
- 6.3 Summary of the simulations: the THC Behavior 92
- III Modellings and simulations 96
- 7 Basics of poromechanics 98
- 7.1 Fundamental hypothesis 99
- 7.1.1 Presentation and definitions 99
- 7.1.2 Frame of the Study and Constitutive Hypothesis 99
- 7.2 Constitutive equations of unsaturated poroelasticity 100
- 7.3 Application of the equations to the CCS case 102
- 8 Thermodynamics of in-pore crystallization 106
- 8.1 Ostwald-Freundlich equation and Wulff theorem 107
- 8.1.1 Chemical equilibrium of a crystal in solution 107
- 8.1.2 Ostwald-Freundlich equation for small crystallite 108
- 8.1.3 Wulff theorem and equilibrium shape 109
- 8.1.4 Non-flat surfaces 110
- 8.2 Interaction energy between two solid surfaces 111
- 8.2.1 Equilibrium of a crystal surface close to the pore wall 111
- 8.2.2 Expression of the interaction energy 115
- 8.3 In-pore growth of a single crystal and crystallization pressure 117
- 8.3.1 First case: crystallization pressure in a cylindrical pore 117
- 8.3.2 Second case: crystallization pressure in a spherical pore with small entry channels 118
- 8.3.3 Crystallization pressure and Wulff shape 121
- 8.3.4 Thickness and interaction forces 124
- 8.3.5 Effectively transmitted stress 125
- 8.4 Final remark 126
- 9 Estimation of crystallization pressure in the case of CCS 128
- 9.1 Macroscopic behavior: poromechanics at the REV scale 129
- 9.1.1 Modelling at constant concentration 129
- 9.1.2 Simulation of a REV submitted to carbon dioxide evaporation 139
- 9.1.3 Comparison of the two modellings 148
- 9.2 Microscopic behavior: nucleation and stress creation at the pore level 150
- 9.2.1 Evolution of the salt quantity in the corner 150
- 9.2.2 Algorithm 155
- 9.2.3 Results of the simulation 158
- 9.2.4 Nucleation and crystal growth 160
- 9.2.5 Upscaling and poromechanics 163
- 9.3 Conclusion on the modellings 168
- IV Experimentation of reactive percolation 170
- 10 General purpose of the experiments 172
- 11 Description of the set-up and characteristics 174
- 11.1 Description and sketch of the prototype 175
- 11.1.1 Material 175
- 11.1.2 Description of the different parts of the set-up 178
- 11.2 Dead volumes measurement 185
- 11.2.1 Method 186
- 11.2.2 Results 186
- 12 Rock cores and sintered glass 190
- 12.1 Rock cores 191
- 12.1.1 Pierre de Lens 191
- 12.1.2 Grès des Vosges 191
- 12.1.3 Rocks from the Dogger aquifer of the Paris Basin 191
- 12.2 Sintered glass beads 193
- 12.2.1 Sintering temperature and duration 193
- 12.2.2 Moulding of the material 193
- 12.2.3 Shrinkage and density profile 196
- 12.3 Mercury Intrusion Porosimetry of the different cores 197
- 12.3.1 Principle of the measurement 197
- 12.3.2 Material and methods 197
- 12.3.3 Results 198
- 13 Intrinsic and relative permeability measurement 200
- 13.1 Intrinsic permeability 201
- 13.1.1 Method 201
- 13.1.2 Results 201
- 13.2 Relative permeability 204
- 13.2.1 Methods 204
- 13.2.2 Results 208
- 13.3 Capillary pressure measurement 211
- 13.3.1 Method 211
- 13.3.2 Results 211
- 13.4 Issues and solutions 213
- 13.4.1 Carbon dioxide pressure and leakage 213
- 13.4.2 BPV oscillations 214
- 13.4.3 Meniscus and sensor in the separator 215
- 13.4.4 Precipitation in the gasometer 216
- 14 Drying-out measurement 218
- 14.1 Purpose 219
- 14.2 Issues and solutions 219
- 14.3 Addendum 220
- General conclusion 224
- Bibliography 226
- Appendices 238
- A Pitzer model and fugacity coefficient calculation 240
- A.1 Pitzer's model for activity coefficients 240
- A.2 Fugacities 244
- B Wulff construction and Wulff theorem 248
- C Correlation of the equilibrium constant 254
- D Capillary pressure curve estimation from mercury intrusion porosimetry 258
- E Correlation between maximum pore radius and water saturation 262
- F Analysis of the Grès des Vosges (BRGM) 266
- G Communication and presentations 274