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Basin-Specific Geochemistry to Promote Unconventional Efficiency John Bargar Aug 26, 2019 Comprehensive Approach to Geochemical Optimization

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Basin-Specific Geochemistry to Promote Unconventional Efficiency John Bargar Aug 26, 2019 Comprehensive Approach to Geochemical Optimization Marcellus Midland Basin-specific geochemistry to promote unconventional efficiency John Bargar Aug 26, 2019 Comprehensive approach to geochemical optimization Measure basin-specific shale alteration processes FY19 – Identify chemical controls over mineral scale Modeling to extract reactions, rates Investigation 2 Comprehensive approach to geochemical optimization Measure basin-specific shale alteration processes FY19 – Identify chemical controls over mineral scale Modeling to extract reactions, rates Investigation Use model to explore Verify &optimize Verify alternative stimulation chemistry to: Mitigation Mitigate SCALE Optimize POROSITY to Industrial maximize flow partner testing out of matrix 3 Comprehensive approach to geochemical optimization Measure basin-specific What chemical parameters control scale shale alteration processes in different basins? FY19 – How can we mitigate Can we monitor scale Identify chemical controls unconventional and fractures over mineral scale scale? simultaneously? Modeling to extract reactions, rates Investigation Use model to explore Verify &optimize Verify alternative stimulation chemistry to: Mitigation Mitigate SCALE Optimize Wachtmeister et al (2017) Nat. Resour.Res POROSITY to Industrial maximize flow Can we manipulate reactions to improve partner testing out of matrix flow through altered zone? 4 Geochemistry Drivers Improve efficiency and recovery factors Improve water reuse • National energy security Mineral Scale Matrix access • Environmental footprint • Water security • Economics of production Task 2 Task 3 Ryan Flynn, executive director of the New Mexico Oil and Gas Association, a trade group representing up to 900 oil and gas operators in New Mexico, said water reuse is the industry’s “No. 1” priority, as fresh water becomes scarce, and the industry looks to cut back on its environmental impact. Carlsbad Current-Argus, May 19, 2019 5 Geochemistry varies across basins Marcellus Field labs HFTS MSEEL Permian Oil Gas • Mineralogy, rock microstructure • Injection sequence, fluid chemistry, water supply (fresh vs reuse) • Universal problems: Iron scale, low recovery • Play specific scale problems • Strontium- Permian • Barium/Radium- Marcellus Industrial partners Permian / Midland Marcellus / Utica 7 Collaborations, partnerships, and acknowledgements • NETL • LBNL • LLNL • Pioneer Natural Resources • Equinor 8 Geochemistry? • Geochemistry controls permeability permeability (under explored) • Dissolution (general): means to increase permeability, and to initiate massive chemical reactions • Precipitation (general):Technical carbonates, sulfates, status iron-bearing minerals oxides • Ppt reduces permeability by occluding fracture apertures and by coating fracture surfaces • Fe redox: can be driven by DO and pH changes 9 TaskGeochemistry? 2: Scale Geochemistry • Geochemistry controls permeability permeability (under explored)2.1 Scale prediction • WhatDissolution chemical (general): parameters means to increase control permeability, scale and in to initiatedifferent massive chemical reactions • Precipitation (general): carbonates,basins? sulfates, iron-bearing minerals oxides • Ppt reduces permeability by occluding fracture apertures and by coating fracture surfaces • Fe redox: can be driven2.2 by Scale DO and mitigationpH changes Develop chemical strategies to mitigate scale. 2.3 In-situ scale monitoring Can we monitor scale and fractures simultaneously? 10 TaskGeochemistry? 2: Scale Geochemistry • Geochemistry controls permeability permeability (under explored)2.1 Scale prediction • WhatDissolution chemical (general): parameters means to increase control permeability, scale and in to initiatedifferent massive chemical reactions • Precipitation (general): carbonates,basins? sulfates, iron-bearing minerals oxides • Ppt reduces permeability by occluding fracture apertures and by coating fracture Jewsurfaces Li Spielman-Sun Noël • Fe redox: can be driven by DO and pH changes 11 Result 1. Iron scale precipitation in Altered Zone The problem: Scale precipitation in altered zone chokes hydrocarbon production μm? cm? Altered Unaltered matrix zone The questions: • Reaction penetration Gas/Oil Fracture fluid Fracture depth? Fluid • Controlling factors? • How are matrix permeability & diffusivity affected? 12 Result 1. Iron scale precipitation time lapse XRF chemical mapping Fe Fe TIME • Time-lapse reactors cover wide range of chemical conditions. • Complements NETL work • Characterization: Fe • Fe(III)-oxide scale thickens over time in spite of persistent acidic conditions (first time observed!) Unaltered matrix Fluid zone • Fe-rich clay mineral scale Altered precipitated (first time observed!) 13 Result 1. Iron scale precipitation time lapse XRF chemical mapping Fe Fe TIME • Time-lapse reactors cover wide range of chemical conditions. • Complements NETL work • Characterization: Fe • Fe(III)-oxide scale thickens over time in spite of persistent acidic conditions (first time observed!) • Fe-rich clay mineral scale precipitated (first time observed!) 14 Result 2. Iron scale: Reactive transport modeling Advection HCl (fast) Diffusion (slow) Simulated Reaction Fe2+ Fe3+ (fast) by model Li et al. URTeC, 2019 Fluid Shale Marcellus w/ bitumen (match with observation) 3+ Fe 2+ No bitumen leaching Fe from shale Fe(III) Fe scale Shale Marcellus Fluid 100 μm 15 Result 2. Iron scale: Reactive transport modeling Advection HCl (fast) • Bitumen increases Fe(III) scale precipitation Diffusion (slow) • Predicted mitigation: Guar gum in frac fluid Fe2+ Fe3+ (fast) Reaction can adsorb Fe and reduce scaling Fluid Shale Marcellus Eagle Ford w/ bitumen (match with observation) 3+ w/ bitumen Fe (match with observation) 2+ No bitumen leaching Fe from shale No bitumen leaching from shale 100 μm Fe(III) Fe(III) Fe scale Shale Shale Eagle Marcellus Fluid Fluid Ford 100 μm 100 μm 16 Result 3. Barite scale: Reactive transport modeling Marcellus Eagle Ford Acidic pH Neutral pH Predicted Predicted barite scale barite scale precipitation precipitation Pores Barite Barite CT pores imaging • pH strongly affects rates – fast at acidic conditions • Neutral pH: only slower rates can match with observations • Barite suppressed by chemicals in the frac fluid 17 Geochemistry? • Geochemistry controls permeability permeability (under explored) • Dissolution (general): means to increase permeability, and to initiate massiveReaction chemical reactions rates extremely important • Precipitation (general): carbonates, sulfates, iron-bearing minerals oxides • Ppt reduces permeability by occluding fracture apertures and by coating…controlled fracture surfaces by pH, fluid composition • Fe redox: can be driven by DO and pH changes 18 TaskGeochemistry? 2: Scale Geochemistry • Geochemistry controls permeability permeability (under explored)2.1 Scale prediction • WhatDissolution chemical (general): parameters means to increase control permeability, scale and in to initiatedifferent massive chemical reactions • Precipitation (general): carbonates,basins? sulfates, iron-bearing minerals oxides • Ppt reduces permeability by occluding fracture apertures and by coating fracture surfaces • Fe redox: can be driven2.2 by Scale DO and mitigationpH changes Develop chemical strategies to mitigate scale. Emphasize incremental optimization 2.3 In-situ scale monitoring Can we monitor scale and fractures simultaneously? 19 Result 4: Acid swap to control barite scale The problem: Ba release from mud Jew et al. URTeC, 2019 • Drilling mud is rich in barium • Ba dissolved by HCl can precipitate in reservoir X • NaCl promotes barite dissolution The solution: acid swap X • Modeling: H2SO4 should shut down Ba leaching at the source X Barite Precipitation in dissolution fracture system Ba transport to fractures • But: need to control CaSO4 precipitation: Citrate should work 20 Result 4. Lab tests suggest incremental acid swap works Jew et al. URTeC, 2019 Is Ba leaching reduced? HCl 1000000 850-fold H2SO4 • Yes!; 850-fold decrease in decrease HCl + Citrate Ba leaching! 100000 H2SO4 + Citrate Field test scheduled 10000August/September Does Citrate control Ca? with Equinor North1000 America for • Yes! • Doesn’t promoteUtica Ba play 100in Ohio Barium released (mg/L) release 10 1 Can we predict with models? • Yes! 21 Model-based iron scale mitigation in 2020 Model–guided sensitivity analyses: ID most important parameters Use the model to optimize scale inhibitor usage Verify in laboratory experiments Continue basin-specific experimental observations 22 TaskGeochemistry? 2: Scale Geochemistry • Geochemistry controls permeability permeability (under explored)2.1 Scale prediction • WhatDissolution chemical (general): Vanorioparameters means to increaseDing control permeability, scaleClark and in to initiatedifferent massive chemical reactions • Precipitation (general): carbonates,basins? sulfates, iron-bearing minerals oxides • Ppt reduces permeability by occluding fracture apertures and by coating fracture surfaces • Fe redox: can be driven2.2 by Scale DO and mitigationpH changes Develop chemicalStanford strategies Geophysics to mitigate scale. 2.3 In-situ scale monitoring Can we monitor scale and fractures simultaneously? 23 Next generation shale geochemistry needs: The Vision: In the field, in real time: Monitor and mitigate scale precipitation … and optimize porosity and permeability The problem: Currently no way to monitor these properties in the field! The solution: Develop new acoustic-based technologies for shale geochemistry 24 S-wave velocity: Sensitive
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