Part 2: What s a caprock? «From the mineral to the basin scale: sealing and confinement functions»

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1 Part 2: What s a caprock? 1 µm «From the mineral to the basin scale: sealing and confinement functions» CEPAC PUCRS Porto Alegre 23/09/2008 1

2 O que é um selo? «Uma rocha argilosa ou salina de baixa permeabilidade localizada acima de um reservatório e que impede o escape de fluidos (gás, solução, óleo)» IPCC, 2005 O selo tem uma função de confinamento do CO 2 e uma função selante É a tampa da nossa garrafa de água (reservatório) com gás (CO 2 )! CEPAC PUCRS Porto Alegre 23/09/2008 2

3 Clayey caprock and its mineralogy CLAYS QUARTZ CARBONATES = CIMENT And other minerals CEPAC PUCRS Porto Alegre 23/09/2008 3

4 Expected properties of clayey caprock Slow reactivity (geochemistry) Low permeability (10-11 até m².s -1 ) (hydrogeology) Homogeneity (geology) Clay minerals: low permeability, high sorption and ionic exchange capacity, swelling properties, elasticity CEPAC PUCRS Porto Alegre 23/09/2008 4

5 Caprock sealing and confinement functions Geochemical control Limitation of CO 2 migration Geomechanical control (elasticity) => Natural barrier against fluids migration CEPAC PUCRS Porto Alegre 23/09/2008 5

6 Geological contexts and caprock composition Carbonate (limestone ( limestone) Sandstone Cap-rock composition: 40-70%: Carbonates 10-40%: Clay minerals & accessory minerals Paris Basin Weyburn Reservoir composition: 60-90%: Carbonates 10-20%: Clay minerals & accessory minerals Cap-rock composition: 40-60%: Clay minerals 40-60%: Quartz, feldspar Fe-Mn oxides & accessory minerals Colorado, Parana Basin Sleipner,, In Salah Reservoir composition: 10-30%: Clay minerals 60-90%: Quartz, feldspar Fe-Mn oxides & accessory minerals CEPAC PUCRS Porto Alegre 23/09/2008 6

7 Potential migrations of CO 2 through the caprock Caprock Properties: Low reactivity, low permeability, good homogeneity, =>supported by clay minerals Functions for the storage: CO 2 confinement and long-term sealing Initial caprock: Heterogeneities of structure and composition CO 2 injection: plume migration until the upper level of the reservoir, pressure exerced on the caprock Sources of failure of the system for the Performance and Safety Assessment => Study focused on the potential geochemical reactivity and reactive transport Connectivity Continuity Aqueousdi ffusion From João Lampreia (UFRJ) Fails Heterogeneity Fractures Plume Migration (capillarity) Dilatation Elasticity Fracturation Injection pressure CEPAC PUCRS Porto Alegre 23/09/2008 8

8 The geochemical components at CO 2 /Caprock interface Caprock Wells Supercritical CO 2 Acidified Solution CO + H O 2 2 HCO 3- + H + Depth: > 800 m T > 40 C P > 80 bars Reservoir acidified solution Plume CEPAC PUCRS Porto Alegre 23/09/2008 9

9 What s the scientific demarch? Aims: Feasability and safety of geological CO2 storage: Caprock integrity and clay minerals reactivity CEPAC PUCRS Porto Alegre 23/09/

10 1 2 Experimental Identification of the reactive phenomena Feasability and safety of geological CO 2 storage: Caprock integrity and clay minerals reactivity 3 Modeling of caprock reactivity Example of Colorado case study Acquisition of experimental kinetics and thermodynamics parameters Reactive transport scenarios Homogeneous caprock + Diffusion of CO 2 Fractured caprock + Advection of CO 2 Safety assessment Presentation on the afternoon CEPAC PUCRS Porto Alegre 23/09/

11 Colorado cap-rock: a sandstone context Cap-rock rock: Chinle (clay-rich Triassic layer) Reservoir: White Rim (Permian layer) Active geothermal zone: industrial extraction of CO 2 Minerals g/g rock Quartz 40-60% Clays 30-60% Calcite 0-20% Fe oxides 10% Benedicte Blanchet (Ph-D IFP - CEA, ) 2008) studies on Natural Analogs of Colorado Haszeldine et al. (2005) Natural geochemical analogues for carbon dioxide storage in deep geological porous reservoirs,, a UK perspective. Rauzi (1999). Carbon dioxide in the St Johns-Springerville area, Apache County,, Arizona, AZGS. CEPAC PUCRS Porto Alegre 23/09/

12 Paris Basin cap-rock: a carbonaceous context Cap-rock rock: : Marl of Massingy (Callovo-Oxfordian layer) Reservoir: : Dogger saline aquifer French National Research Program (Framework) on CO2 storage: ANR «Geocarbone-Integrity» ( ) 2008) Potential French «pilote site» for CCS? Minerals g/g rock Calcite 45% I/S + Illite 15% Kaolinite 10% Quartz 10% Fe-dolomite 5% Gypsum 5% Pyrite 5% Others phases 5% Source: Brosse et al (from Matray et al. 1989) CEPAC PUCRS Porto Alegre 23/09/

13 1 Experimental identification of the reactive phenomena Feasability and safety of geological CO 2 storage: Caprock integrity and clay minerals reactivity CEPAC PUCRS Porto Alegre 23/09/

14 Experimental identification of the reactive phenomena Argillaceous caprock: Chinle-Colorado; COx- Paris Basin; Paraná Basin 0-D experiments : Solid + NaCl Solution T = 80 C / 150 C Atmospheric pco2 0-D experiments : Solid + NaCl Solution T = 80 C / 150 C pco2 = 150 bars Closed reactor Studied effects: pco 2, CO 2(SC), long-term experiments (1 year) CEPAC PUCRS Porto Alegre 23/09/

15 Experimental identification of the reactive phenomena SEM After G = 10,000 After G = 10,000 Case study of Charmotte + NaCl Solution 0,1M + pco 2 = 150 bars + T = 80 C Gypsum/ anhydrite precipitation after 3 months with CO 2(SC) Substitued dolomite dissolution after 3 months with CO 2(SC) XRD Input phenomena for simulations Preferentially carbonated minerals dissolution Sulfate minerals precipitation in the short-term Impacts on the caprock transport properties Input phenomena for reactive transport modeling CEPAC PUCRS Porto Alegre 23/09/

16 Mineralogical Analysis of Paranã Samples J. RAYNAL CEA Cadarache - DEC / SPUA / LCU M. JULLIEN A. CREDOZ CEA Cadarache DTN / SMTM / LMTE CEPAC PUCRS Porto Alegre 23/09/

17 Methods X-Ray Diffraction Bruker D8 advance Thermal Analysis with Coupled Mass Spectrometry Netzsch STA 409 with Pfeiffer Thermostar 300 Infra-Red Fourier Transform (not presented here) Thermo Nicolet Nexus Interpretation still in progress CEPAC PUCRS Porto Alegre 23/09/

18 Sample Pt 1-Br07-04: Rio Bonito (reservoir) 100 TG /% DSC /(uv/mg) exo 0.30 Gypsum Illite Smectite or I/S Chlorite? Kaolinite Calcite Quartz Albite Organic Carbon CEPAC PUCRS Porto Alegre 23/09/

19 Sample Pt 3-Br07-06: Rio Bonito (reservoir) Quartz Kaolinite Gypsum Smectite or I/S Goethite 100 TG /% DSC /(uv/mg) exo CEPAC PUCRS Porto Alegre 23/09/

20 Sample Pt 4-Br07-01: Rio Bonito (reservoir) Quartz Minor phases 102 TG /% DSC *10-2 /(uv/mg) exo CEPAC PUCRS Porto Alegre 23/09/

21 Sample Pt 6-Br07-07: Palermo (transition area) TG /% DSC /(uv/mg) exo 0.05 Quartz Illite Anatase Smectite I/S Kaolinite or K/S Carbonate (substitued calcite) CEPAC PUCRS Porto Alegre 23/09/

22 Sample Pt 7-Br07-09: Irati (caprock) Quartz Illite Smectite or Chlorite Kaolinite or K/S or Chlor. Analcime Albite TG /% DSC /(uv/mg) exo CEPAC PUCRS Porto Alegre 23/09/

23 Sample Pt 9-Br07-12: Serra alta (caprock) TG /% DSC /(uv/mg) exo Quartz Calcite Illite Smectite Kaolinite or K/S Analcime Albite CEPAC PUCRS Porto Alegre 23/09/

24 Sample Pt 10-Br07-19: Rio do Rastro (caprock) TG /% DSC *10-2 /(uv/mg) exo Calcite Quartz Illite? Smectite I/S Kaolinite Albite Analcime Carbonate? Unidentified phase(s) CEPAC PUCRS Porto Alegre 23/09/

25 Feasability and safety of geological CO 2 storage: Caprock integrity and clay minerals reactivity 1 2 Experimental Identification of the reactive phenomena Acquisition of experimental kinetics and thermodynamics parameters CEPAC PUCRS Porto Alegre 23/09/

26 Acquisition of experimental kinetics and thermodynamics parameters 2 clay minerals: I/S (Chinle-Colorado) and Smectite (MX80) 1-D experiments: Solid + NaCl Solution T = 80 C pco 2 = 0 à 150 bars Percolation and automatic sampling 0-D experiments: Solid + NaCl Solution T = 80 C / 150 C ph = 3 to 7 Dissolved Carbonates: (0 à 0,05M) Studied effects: pco 2, CO 2(SC), Discriminated effects of CO 2 : ph (3 to 7), Dissolved carbonates CEPAC PUCRS Porto Alegre 23/09/

27 Acquisition of experimental kinetics and thermodynamics parameters Case study of Smectite + NaCl Solution 0,1M + pco 2 = 30 bars Experiment Concentration SiO2(aq) (mmol/l) Modeling R(Si) = -q. 1/n. [Si(aq)]tot/s Determination of the kinetics parametrized law by CO 2 effects (acidity and dissolved carbonates) R(Clay) = k. A. a(h+). a(hco3). [1 - (Q/K)] Temps (jours) Adaptated input data for modeling studies CEPAC PUCRS Porto Alegre 23/09/

28 1 2 Experimental Identification of the reactive phenomena Feasability and safety of geological CO 2 storage: Caprock integrity and clay minerals reactivity 3 Modeling of caprock reactivity Example of Colorado case study Acquisition of experimental kinetics and thermodynamics parameters Reactive transport scenarios Homogeneous caprock + Diffusion of CO 2 Fractured caprock + Advection of CO 2 Safety assessment Michel Jullien presentation CEPAC PUCRS Porto Alegre 23/09/

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