Geochemistry of Water and Gases in the Frio Brine Pilot Test: Baseline Data and Changes During and Post CO 2 Injection

Transcription

1 Geochemistry of Water and Gases in the Frio Brine Pilot Test: Baseline Data and Changes During and Post CO 2 Injection GCCC Digital Publication Series #5-4l Y. Kharaka D. Cole W. Gunter K. Knauss S. Nance Keywords: Grass-Water-Rock Interactions, Mineral Dissolution Kinetics, Open Hole Logs, Mineral-Water-Gas Interactions, Field Sampling Cited as: Kharaka, Y., Cole, D., Gunter, W., Knauss, K., and Nance, S., Geochemistry of water and gases in the Frio Brine Pilot test: baseline data and changes during and post CO2 injection: presented at the National Energy Technology Laboratory Fourth Annual Conference on Carbon Capture and Sequestration, Alexandria, Virginia, May 2-5, 25. GCCC Digital Publication Series #5-4l, pp

2 Fourth Annual Conference on Carbon Capture & Sequestration Developing Potential Paths Forward Based on the Knowledge, Science and Experience to Date Geologic - Frio Brine Field Project (1) Geochemistry of Water and Gases in the Frio Brine Pilot Test: Baseline Data and Changes During and Post CO2 Injection Yousif Kharaka* (USGS), David Cole (ONL), William Gunter (ARC), Kevin Knauss (LLNL), Seay Nance (BEG) Financial support from DOE-NETL (Sheila Hedges) May 2-5, 25, Hilton Alexandria Mark Center, Alexandria Virginia

3 Frio Brine Pilot Research Team Funded by US DOE National Energy Technology Lab: Sheila Hedges, Karen Cohen Bureau of Economic Geology, Jackson School, The University of Texas at Austin: Susan Hovorka, Mark Holtz, Shinichi Sakurai, Seay Nance, Joseph Yeh, Paul Knox, Khaled Faoud Lawrence Berkeley National Lab, (Geo-Seq): Larry Myer, Tom Daley, Barry Freifeld, Rob Trautz, Christine Doughty, Sally Benson, Karsten Pruess, Curt Oldenburg, Jennifer Lewicki, Ernie Major, Mike Hoversten, Mac Kennedy, Don Lippert Oak Ridge National Lab: Dave Cole, Tommy Phelps Lawrence Livermore National Lab: Kevin Knauss, Jim Johnson Alberta Research Council: Bill Gunter, B. Kadatz, John Robinson Texas American Resources: Don Charbula, David Hargiss Sandia Technologies: Dan Collins, Spud Miller, David Freeman; Phil Papadeau BP: Charles Christopher, Mike Chambers Schlumberger: T. S. Ramakrishna and others SEQUIRE National Energy Technology Lab: Curt White, Rod Diehl, Grant Bromhall, Brian Stratizar, Art Wells University of West Virginia: Henry Rausch USGS: Yousif Kharaka, Bill Evans, Evangelos Kakauros, Jim Thordsen, Bob Rosenbauer Praxair: Joe Shine, Dan Dalton Australian CO2CRC (CSRIO): Kevin Dodds Core Labs: Paul Martin and others Hovorka et al., 24

4 Topics Discussed Composition of water and gases in the Frio Baseline, during and post injection results. How are such data obtained and why are they important to CO 2 sequestration? Water-mineral-CO 2 interactions in the Frio. Environmental implications of post injection results. Future plans and concluding remarks.

5 Frio CO 2 Field sampling Drilling & test water tagged with dye tracers Date Site Sampling info Sample series June 3, 24 injection well MDT tool 4FCO 2-1 Jul 23-Aug 2, 24 injection well, monitoring well surface sampling (N 2 ), Kuster, submers.pump 4FCO 2-2 & gw wells Oct 4-7, 24 monitoring well U-tube 4FCO 2-3 Oct 29-Nov 3, 24 monitoring well U-tube 4FCO 2-4 April 4-6, 25 injection well surface sampling (N 2 ) 5FCO 2-1 & monitoring well & Kuster

6 A national produced-water geochemistry database James K. Otton George N. Breit Yousif K. Kharaka Cynthia A. Rice internet at:

7 Use of water isotopes and chemistry to determine mixing with drilling water 14, Frio brines Electrical Conductance ( υs/cm) 12, 1, 8, 6, 4, 2, shallow monitoring wells 11, δ 18 O (permil)

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9 Open Hole logs Top A ss Injection well Observation well Top B ss Top C ss Proposed injection zone Hovorka et al., 24

10 Salinity and normalized conc. of major cations and anions 4-FCO2-28 (injection well) Na HCO 3 4FCO2-218 (monitoring well, C-sand) Na HCO 3 Ca SO 4 Ca SO 4 Mg ph = 6.86; TDS = 91,5 mg/l Cl Mg ph = 6.7; TDS = 93,8 mg/l Cl 4FCO2-337 (monitoring well; post injection) Na HCO 3 seawater Na HCO 3 Ca SO 4 Ca SO 4 Mg ph = 6.3; TDS = 92,6 mg/l Cl Mg ph = 8.2; TDS = 36,9 mg/l Cl [milliequivalents/liter, normalized to 1%]

11 Selected chemical data from monitoring well during CO2 injection 6.9 ph HCO3 35 ph EC Alkalinity HCO 3 (mg/l); EC (x1 ms/cm) Oct-4 5-Oct-4 6-Oct-4 7-Oct-4 8-Oct-4

12 Frio CO2 (6/4-4/5) ph injection w ell ph Shlumberger injection w ell ph monitoring w ell C-sand ph monitoring w ell B-sand 6.5 ph Jun-4 Aug-4 Oct-4 Dec-4 Feb-5 Apr-5

13 Frio CO2 (6/4-4/5) HCO3 (mg/l) HCO3 injection w ell HCO3 Schlumberger injection w ell HCO3 monitoring w ell C-sand HCO3 monitoring w ell B-sand EC injection w ell EC Shlumberger injection w ell EC monitoring w ell C-sand EC monitoring w ell B-sand E. Conductance ( µs/cm) 5 2 Jun-4 Aug-4 Oct-4 Dec-4 Feb-5 Apr-5

14 Frio Cl & Ca (6/4-11/4) Cl injection well Cl MDT injection well Cl monitoring well C-sand Ca injection well Ca MDT injection well Ca monitoring well C-sand Cl (mg/l) Ca (mg/l) Ca (mg/l) 26 1/5 1/6 1/7 1/8 Jun-4 Jul-4 Aug-4 Sep-4 Oct-4 Nov-4 Dec-4 18

15 Frio CO2 (6/4-11/4) Mg (mg/l), Cl (x 1-2 mg/l) Mg injection w ell Mg MDT injection w ell Mg monitoring w ell C-sand Cl injection w ell Cl MDT injection w ell Cl monitoring w ell C-sand Ca injection w ell Ca MDT injection w ell Ca monitoring w ell C-sand Ca (mg/l) 2 Jun-4 Jul-4 Aug-4 Sep-4 Oct-4 Nov-4 Dec-4 18

16 Frio CO2 (6/4-11/4) 12 Fe injection well 2 Fe (mg/l) Fe MDT injection well Fe monitoring well C-sand Mn injection well Mn MDT injection well Mn monitoring well C-sand Zn monitoring well C-sand Mn (mg/l), Zn (mg/l) 2 4 Jun-4 Jul-4 Aug-4 Sep-4 Oct-4 Nov-4 Dec-4

17 Frio CO2 (1/5/4-1/7/4) Fe (mg/l) Fe monitoring well C-sand Mn monitoring well C-sand Zn monitoring well C-sand Mn (mg/l), Zn (mg/l) 2 4 1/5/4 1/6/4 1/7/4 1/8/4

18 Br-Cl as indicator of origin of solutes (* Frio value) Kharaka & Hanor, 24

19 Frio Brine Pilot Injection interval Oil production Injection interval: 24-m-thick, mineralogically complex Oligocene reworked fluvial sandstone, porosity 24%, Permeability 2-3 Darcys Seals numerous thick shales, small fault block Depth 1,5 m Brine-rock system, no hydrocarbons 67 C; 15 bar Hovorka et al., 24

20 ph Surface T & P Eq. calcite calcite ### albite, low dolomite ### goethite ### siderite ### G (kcal/mole) 3 ph pco 2 (bars)

21 Computed ph and saturated states of selected minerals at T & P ph calcite albite, low dolomite goethite siderite G (kcal/mole) 3 ph pco 2 (bars)

22 Idealized carbonate speciation H 2 CO 3 HCO 3 - CO % ph

23 Chemical Composition of Frio Gases Frio formation water at saturation with CH 4

24 Solubility of CH 4 in Aqueous Solutions Duan et al., 1992

25 Solubility of CO 2 in water as f (t, P & chemical composition) Drummond (1981); Rosenbauer et al., (5 C) 5 CaCl 2 (7%) CO 2 (wt %) CO 2 (wt %) NaCl (1%) Pressure (bar)

26 Isotope data- H 2 O, CH 4 & DIC Dissolved Inorganic Carbon -5 1/5 Base line DIC Post-injection DIC δ 13 C DIC (per mil) /6 (after breakthrough) 11/3 δd CH 4 (per mil) Base line methane Post-injection methane δ 13 C CH 4 (per mil) δd H 2 O (per mil) Days After CO 2 Injection Frio baseline brines Brines after injection Meteoric water line δ 18 O H 2 O (per mil)

27 KINETICS OF MINERAL DISSOLUTION AND PRECIPITATION dm dt Ei n i i j RT, = [ i j SA Aie ai, j f ( G r )] The surface area is SA (m 2 ), A is the Arrhenius pre-exponential factor (mol m -2 s -1 ), E is the activation energy (J mol -1 ), T is the temperature (K), R is the gas constant, a i,j is the activity of the j th species in the i th reaction mechanism, and n i,j is the reaction order. The term f ( G r ) is a dimensionless function of the chemical affinity to account for slowing of reactions as equilibrium is approached: f ( G r ) = (1 Ω p i ) q i = Omega (Ω = Q/K) is the mineral saturation index where Q is the activity product, and K is the equilibrium constant. The parameters p i and q i are empirical and dimensionless, although p i can be predicted from transition state theory. (1 Q K p i ) q i dm dt = SA 25 k + k C acid e 25 C base Eacid R( T ) e a Ebase R( T ) n 1a + H a a n H n 3 + 1b 3+ Fe (1 Ω (1 Ω p 3 ) p 1 q 3 ) q 1 + k + k 25 C HCO 25 C neut 3 e e Eneut R( T ) Ebase R( T ) a (1 Ω n 4 HCO 3 p 2 ) q 2 (1 Ω p 4 ) q 4

28 Important Mineral-Water-Gas Interactions in Frio CO 2 (gas) + H 2 O H 2 CO o (1) H 2 CO 3o HCO 3- + H (2) CO 2 (gas) + H 2 O + CaCO 3 Ca HCO (3) H + + CaCO 3 Ca ++ + HCO (4) H + + FeCO 3 Fe ++ + HCO (5) 4Fe ++ + O 2 + 1H 2 O 4Fe(OH) 3 + 8H (6) 2H + + CaMg(CO 3 ) 2 Ca ++ + Mg HCO (7) 4.8H + + Ca.2 Na.8 Al 1.2 Si 2.8 O H 2 O.2Ca Na Al H 4 SiO (8)

29 CO 2 Sequestration: Theoretical studies (Palandri, Kharaka, 24) Compilation of a database of rate parameters for mineral dissolution and precipitation for use in geochemical modeling: Prediction of rates of water/ rock/gas interaction Example simulation: CO 2 sequestration in Ca-bearing arkose Log Mass (kg) Log Molality quartz kaolinite anorthite.5 Years annite K-feldspar dolomite albite siderite calcite 33 Years illite -1 H 2 CO 3 - HCO Mg Fe Time (Log Years) FeCl + a H + = - ph Ca 2+

30 Summary and Conclusions 1- The Frio brine is saturated with CH 4 has a salinity of ~93, mg/l TDS, and is a Na-Ca- Cl type water; composition of formation water that determines CO 2 interactions in sedimentary basins is highly variable TDS=2,-46, mg/l. 2- Though useful parameters may be obtained from electrical logs and the National Geochemical Database, careful sampling & analysis of brine samples are necessary to study interactions. 3- Alkalinity and ph determinations are excellent and rapid field methods for tracking injected CO The low ph values resulting from CO 2 injection could have important environmental implications: a)-dissolution of minerals, esp. iron oxyhdroxides could mobilize toxic components; b) dissolution of minerals may create pathways for CO 2 and brine leakage. 5- Where residual oil and other organics are present, CO 2 may mobilize organic compounds; some may be toxic.