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Authors: Cantucci, B.* 
Montegrossi, G.* 
Vaselli, O.* 
Pizzino, L.* 
Quattrocchi, F.* 
Title: An approach to the geochemical modelling of the Weyburn oil brines before and during the first 3 years of CO2 injection for Enhanced Oil Recovery by using experimental data and monitoring
Issue Date: 21-Sep-2005
Keywords: CO2 Geological Storage Monitoring;
EOR Weyburn oil field brines
fluid geochemistry
reaction path modeling
Subject Classification03. Hydrosphere::03.01. General::03.01.01. Analytical and numerical modeling 
Abstract: EnCana’s CO2 injection EOR project at Weyburn (Saskatchewan, Canada) is the focal point of a multi-faceted research program, sponsored by IEA GHG R&D and numerous international industrial and government partners including the European Community (BGS, BRGM, INGV and GEUS research providers), to find co-optimization of “CO2-EOR Production” and “CO2 -Geological Storage”, addressed to environmental purposes, in the frame of the Kyoto Agreement Policies. The Weyburn oil-pull is recovered from Midale Beds (at the depth of 1300-1500 m). This formation consists of Mississipian shallow marine carbonate-evaporites that can be subdivided into two units: i) the dolomitic “Marly” and ii) the underlying calcitic “Vuggy”, sealed by an anhydrite cap. Presently, around 3 billions mc of supercritical CO2 have been injected into the “Phase A1”injection area that includes around 90 oil producers, 30 water injectors and 30 CO2 injection wells, build up since September 2000. INGV has carried out a geochemical monitoring programme -approximately thrice yearly from pre-injection (“Baseline” trip, August 2000) to September 2004- performing trace element and dissolved gas analysis along with fluids sampling surveys, the latter being performed by the Canadian partners. The experimental data are the base of a geochemical modelling, i.e. the main goal of the present study. In the past, assumptions and gap-acceptance have been made in the literature in the frame of the geochemical modelling of CO2 geological storage, in order to reconstruct the reservoir conditions (pressure, pH and boundary conditions). As these parameters of deep fluids cannot be measured in-situ, all this information must be computed by a a posteriori procedure involving the analytical data. In this work we applied a geochemical model to: i) reconstruct the in-situ reservoir chemical composition (including pH) and ii) evaluate the boundary conditions (pCO2, pH2S), necessary to implement the reaction path modelling. This is the starting point to assess the geochemical impact of CO2 into the oil reservoir and, as main target, to quantify water-gas-rock reactions. Our geochemical modelling procedure is based on the available data such as: a) bulk mineralogy of the Marly and Vuggy zones; b) gas-cap composition and c) pre-and post-CO2 injection selected water samples from Midale Beds. The PRHEEQC (V2.11) Software Package was used to reconstruct the in-situ reservoir composition by calculating the chemical equilibrium among the various phases at reservoir temperature (60°C) and pressure (150 bars) conditions by suitable thermodynamic corrections to code database. Then, we identified possible compositions of the initially reservoir liquid phases, always taking into account the case histories of the Marly and Vuggy units. Finally, we modelled the geochemical impact of CO2 injection on Weyburn reservoir subjected to both local equilibrium and kinetically controlled reactions. The inverse modelling simulation (IMS) was then performed in order to calculate the amounts of mass transfer of liquid, gas and solid phases that accounted for changes in the water chemistry between the 2000 and 2003 data-sets. IMS calculations suggest that the reservoir underwent mineralogical changes, such as precipitation of chalcedony, gypsum and kaolinite and dissolution of anhydrite and k-feldspar. Calcite dissolution is predicted, but the precipitation of others carbonates (dolomite, dawsonite and siderite) can also occur. All experimental data and geochemical modelling confirm that “solubility trapping” is prevailing in this early stage of CO2 injection. Further and detailed studies are necessary until all the kinetic parameters will fully be identified. Thermo-kinetic modeling of the evolution of the CO2-rich Weyburn brine interacting with host rock minerals over 1000 years is one of main aims of this study in the framework of a PhD programme between the INGV of Rome and the Department of Earth Sciences of Florence.
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