Simulations of the impact of co-injected gases on CO2 storage, the SIGARRR
project: processes and geochemical approaches for gas-water-salt interactions
modeling
Jérôme Corvisier1 Martha Hajiw2 Elise El Ahmar2 Christophe Coquelet2 Jérôme Sterpenich3
Romain Privat4 Jean-Noël Jaubert4 Karine Ballerat-Busserolles5 Jean-Yves Coxam5
Pierre Cézac6 François Contamine6 Jean-Paul Serin6 Véronique Lachet7 Benoit Creton7
Marc Parmentier8 Joachim Tremosa8 Philippe Blanc8 Laurent André8 Louis de Lary8
Eric C. Gaucher9
1
MINES ParisTech, PSL Research University, Centre de Géosciences, 35 rue Saint-Honoré 77305
Fontainebleau – France
2
MINES ParisTech, PSL Research University, Centre Thermodynamique des Procédés, 35 rue
Saint-Honoré 77305 Fontainebleau – France
3
Université de Lorraine, GéoRessources UMR CNRS 7359, BP70239 Faculté des Sciences et
Technologies 54506 Vandoeuvre-lès-Nancy – France
4
Université de Lorraine, LRGP-ENSIC UMR CNRS 7274, BP 20451 1 rue Granville 54001 Nancy
– France
5
Université Blaise Pascal Clermont-Ferrand 2, ICCF UMR CNRS/UBP 6296, 24 avenue des
Landais 63177 Aubière – France
6
Université de Pau et des Pays de l’Adour, ENSGTI LaTEP EA 1932, BP7511 rue Jules Ferry
64075 Pau – France
7
IFP Energies Nouvelles, 1 et 4 avenue de Bois-Préau 92852 Rueil-Malmaison – France
8
BRGM, 3 avenue Claude Guillemin BP 36009 45060 Orléans cedex 2 – France
9
TOTAL, CSTJF, avenue Larribau F-64018 Pau – France
Abstract
An important part of the induced cost of Carbon Capture, Transport and Storage (CCTS) comes
from the separation step when CO2 is separated from other gaseous compounds. The composition of
the captured gaseous mixture may considerably vary both qualitatively and quantitatively
depending on the sources, the selected technologies for purification... Many other compounds could
be co-captured at various concentration levels [1] and their potential co-storage along with CO2 is
considered. If acceptable, an increase of the impurities concentrations can significantly reduce
capture costs and consequently contributes to a faster deployment of CCTS technologies.
Nevertheless, some of these impurities could be toxic regarding environment or even human health
and/or could chemically react with water, mineral phases or materials involved on storage sites.
These compounds and their induced reactions may change the behavior of the CO2 rich mixture [2],
may affect the permeability of the cap rock and then potentially contaminate surrounding
environments.
Operators of the whole CCTS chain therefore wait for clear recommendations in terms of
admissible concentration levels for the various co-injected impurities while regulators need tools
allowing them to formulate these recommendations. Testing scenarios with accurate reactivetransport codes, validated and calibrated regarding laboratory experiments, should enable to
propose these awaited precise recommendations.
1
The main thrust of purpose of the “SIGARRR” project, funded by the ANR, started in late 2013, is
to be able to conduct precise geochemical simulations to model the long-term behavior of coinjected gases within CO2 storage sites focusing on the:
§ Impact of CO2 and co-injected gases (SO2, NO, O2) on the minerals and reservoir (silicates
+ clay minerals) geochemistry,
§ Possible inferences on the environment in case of leak.
Within the frame of the SIGARRR project, recent improvements in geochemical codes allow to
deal with non-ideal gas mixtures and to reproduce rather accurately existing solubility
measurements for CO2 and even mixtures [3,4]. However, the quality of such numerical simulations
obviously depends on available thermodynamic data (gas solubility in water or brine). The
SIGARRR project proposes thus to combine experimental and numerical approaches, to ensure the
reliability of numerical simulations.
Acquisition of new experimental data
A part of the project consists naturally in experimental (using various technical approaches) or
pseudo-experimental (i.e. molecular simulation) acquisition of thermodynamic data (vapor-liquid
equilibrium properties) for CO2 rich systems with increasing complexity: gas mixtures, gas
mixtures+water, gas mixtures+brine and gas mixtures+brine+rock [5].
EOS development/parametrization
Then, adapted Equations of State (EoS) needed to be developed and parameterized on relevant data
[6], and consequently implemented in geochemical and reactive-transport codes, with a particular
concern paid to the electrolyte part.
Numerical simulations
Developed numerical codes could handle gas mixtures+water or brine equilibrium calculations and
allow us to compare experimental data with various processes approaches PPR78 (such as
Predictive Peng-Robinson) or GC-PR-CPA [7] (Cubic Plus Association using Peng-Robinson EOS
and the Group Contribution method) and geochemical codes CHESS or PHREEQC (fig.1). A
B
Figure 1. Aqueous molar fraction A/ CO2 and B/ SO2 vs. pressure for CO2-SO2-H2O system (95%. CO2 and
5%. SO2). Symbols correspond to new measurements, thin solid lines to GC-PR-CPA model, thin dotted
lines to PPR78 model and bold solid lines to CHESS simulations.
This approach should enable us to handle more complex gas mixture-brine-rock systems to validate
our models and to reach the final phases of our projects: site-scaled simulations of leakage scenarios
involving complex gas mixtures and the associated risk analysis, which could also lead to the
formulation of first recommendations in terms of geochemically admissible CO2 flux composition.
This paper will present both the project itself, its selected experimental and numerical
methodologies and its more recent results as well.
This work was supported by the ANR grant SIGARRR (ANR-13-SEED-0006).
2
[1] IEAGHG 2011, Effects of impurities on geological storage of CO2, Technical report, 2011/04.
[2] Creton, B.; de Bruin, T.; Le Roux, D.; Duchet-Suchaux, P. & Lachet, V. 2014, Impact of
associated gases on equilibrium and transport properties of an injected CO2 stream: Molecular
simulation and experimental studies, International Journal of Thermophysics, 35(2), 256-276.
[3] Corvisier, J. 2013 Modeling water-gas-rock interactions using CHESS/HYTEC, Goldschmidt
Conference,Florence – Italy.
[4] Corvisier, J.; El Ahmar, E.; Coquelet, C.; Sterpenich, J.; Privat, R.; Jaubert, J.-N.; BalleratBusserolles, K.; Coxam, J.-Y.; Cézac, P.; Contamine, F.; Serin, J.-P.; Lachet, V.; Creton, B.;
Parmentier, M.; Blanc, P.; André, L.; de Lary, L. & Gaucher, E.C. 2014, Simulations of the Impact
of Co-injected Gases on CO2 Storage, the SIGARRR Project: First Results on Water-gas
Interactions Modeling, Energy Procedia (GHGT-12), 63, 3160–3171.
[5] Caumon, M.-C.; Sterpenich, J.; Randi, A. & Pironon, J. submitted, New data of mutual
solubility in the H2O-CO2 system measured by in-situ Raman spectroscopy up to 200 bar at 65 and
200°C, Fluid Phase Equilibria.
[6] Xu, X.; Privat, R. & Jaubert, J.-N. 2015, Addition of the sulfur dioxide group (SO2), the oxygen
group (O2), and the nitric oxide group (NO) to the E-PPR78 model, Industrial & Engineering
Chemistry Research, 54, 9494-9504.
[7] Hajiw, M.; Chapoy, A. & Coquelet, C. 2015, Hydrocarbons – water phase equilibria using the
CPA equation of state with a group contribution method, The Canadian Journal of Chemical
Engineering, 93, 432-442.
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