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Can functionalized nanoparticles be used as reservoir tracers?

Can functionalized nanoparticles be used as reservoir tracers?. Tor Bjørnstad Institute for Energy Technology (IFE). Tracers in IOR - Research focus. Development of new tracer methods for reservoir monitoring: Interwell flow monitoring (nano-particles) Interwell SOR determination

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Can functionalized nanoparticles be used as reservoir tracers?

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  1. Can functionalized nanoparticles be used as reservoir tracers? Tor Bjørnstad Institute for Energy Technology (IFE) Tor Bjørnstad

  2. Tracers in IOR - Research focus • Development of new tracer methods for reservoir monitoring: • Interwell flow monitoring (nano-particles) • Interwell SOR determination • Single-well push-and-pull SOR monitoring Tor Bjørnstad

  3. Interwell tracer technology Production well Injection well Impermeable area Tor Bjørnstad

  4. Single-well tracer technology • Single well push-and-pull tracer application (SWCTT) measures SOR in a volume around a well 5-10 m from wellbore. Tor Bjørnstad

  5. TT development roadmap • Subtask 5.1: Development ofphase-partitioningtracers to determine interwell water-contactableaverageremainingoilsaturation in thesweptvolume: • Focusonchemicalmolecularcompounds • Focusonnano-particles, in particular C-dots. • Subtask 5.2: Development ofnewtracers for single-well push-and-pull operations to dermine residual oil in thenear-wellzone (5-10 m from wellbore): • Focusonreacting (mainly ester-based) chemicalcompoundswhichconverts parts of a partitioning tracer into a water tracer in situ • Focusonnano-particleswhichcarry a partitioning and a passive tracer simultaneouslyintosomedepth from thewellbore • Determinetheeffectof EOR-operations by measuringtheoilsaturationbefore and after an EOR –injection in a single-well push-and-pull test. Post.doc 2 •New ester- basedtracers •New nano-particles Extent. as RS •New nano-particles RS+eng. Interwell pilot RS+eng. Single-well pilot                        2016 2018 2020 2022 2015 2017 2019 PhD-student Phase-part. molecules RS+eng. Single-well EOR-pilot + single-well tracer test pilot PhD + RS Planning inter- well pilot Post.doc 1a Nano-part. = C-dots Post.doc 1b Nano-part. = C-dots RS Planning single- well pilot • Additional: • Tracer modelling and thereservoirmodel • Combination ofproduction data, tracer and • 4D seismics • Progress report • Thesis or final conclusion • Final product Tor Bjørnstad

  6. Carbon quantum dots = C-dots Tor Bjørnstad

  7. Properties of C-dots • Stable until 200°C • Passive tracers behaviour • Easy detection • Non toxic • Low cost Analyzed by laser-induced fluorescense • Stable until 200 C • Near-passive tracer behaviour • Easy production • Easy detection • Non-toxic • Low cost Stoke shift Tor Bjørnstad

  8. C-dot synthesis OH OH Citric acid Ethanol amine NH NH NH -H2O + 3 180C HO Mix at room temperature • Dry • Pyrolyze at 200°C for 8 hrs Tor Bjørnstad

  9. Size of C-dots based on citric acid Tor Bjørnstad

  10. Size distribution - effect of surfactant –aged dispersion After surfactant treatment Intensity Before surfactant treatment Size (nm) Tor Bjørnstad

  11. C-dots in DI and 50 mM CaCl2 through acid washed fine and coarse silica sand 100 % recovery 99.7 % recovery 90% recovery 79% recovery C/C0 C/C0 Pore volume Pore volume Counter to the result of Li et al.(2014) for M-dots Hassanpour (2016) Tor Bjørnstad

  12. Preliminary observations • C-dots better than M-dots • C-dots seem to be inert in calcite • C-dots retained in silica sand • Important to control Zeta-potential Tor Bjørnstad

  13. Field test in Ghawar Reservoir Field test 86% recovery • 255 bbl with 130 ppm C-Dot injected at 7090 ft into 50 ft interval of 20% porosity carbonate reservoir at ~100°C and 120,000 TDS pore fluids. • Shut in 2 days. • Produced ~6000 bbl. • 86% recovery. Courtesy Larry Catles, from Kanj, Rashid and Gianelis, 2011, SPE 142592-PP Tor Bjørnstad

  14. Successful test in quartzite, Altona NY • Summer 2016 Test • 90°C thermal injection • microseismic array • Fiber optic DT • C-Dots • Adsorbing tracer • T-degrading “ Iodide C-Dot Iodide C-Dot Yushi Zhou, 2014 Cornell Ph.D Thesis Tor Bjørnstad

  15. Field tracer tests in Colorado under planning • Possible Schedule • Prepare fall 2017 • Execute summer 2018 • Multi-tracer test in fractured reservoir shallow deep Tor Bjørnstad

  16. Fluorescence of Rare Earth Compounds Fluorescencespectraofselected rare earths Fluorescencecolorsofselected rare earths Tor Bjørnstad

  17. Fluorescent Ln-complexes Tb-DOTA Intensity = Ln-DTPA Wave length (nm) Eu-DOTA Intensity Wave length (nm) Tor Bjørnstad

  18. DNA fragments as fluid reservoir tracers Fragments with > 4 base pairs have severely reduced penetration in reservoir rock. Such small fragments cannot be analysed by the PCR-method. Was the possible use of DNA just a wet dream? Tor Bjørnstad

  19. DNA in silica shell structure TMAPS SiO2 SiO2 SiO2 dsDNA SiO2 SiO2 TMAPS TEOS + H2O Modified, from Yuran Zhang: DNA-Encapsulated Silica Nanoparticle Tracers for Fractured Reservoir Characterization, SGP-TR-207, 2015 Tor Bjørnstad

  20. More detailed Coulombic bonds… SiO2 Modified, from Daniela Paunescu, Nature Protocols 8, 2440–2448 (2013) Tor Bjørnstad

  21. Release of DNA NH4FHF SiO2 NH4F Free DNA ready for PCR analysis Tor Bjørnstad

  22. Doped with a fluophor… Fluorophor 2 Fluorophor 1 SiO2 Tor Bjørnstad

  23. Challenges and limitations… Number of base-pairs in a primer nucleotide is normally 15-20 Number of base-pairs in a DNA fragment should be > 50-60 Size of the silica nanoparticle readily becomes > 100-150 nm. Postulate: Nanoparticles based on silica-encapsulated DNA can only be used in reservoir zones with very high permeability (> 50-100 darcy) NB! Such particles may be unique tools for well tracing and reservoir fracture detection Tor Bjørnstad

  24. Thanks for listening Tor Bjørnstad

  25. PCR = Polymerase Chain Reaction Doubles thenumberof present double-stranded DNA (dsDNA) fragments for eachmultiplicationcycleninto a detectablenumber: 1  2  4  8  16 ……… 2n Tor Bjørnstad

  26. Tetraethylorthosilicate - TEOS 77 L Tor Bjørnstad

  27. Concentrations The «oil phase» = 1.5 g Triton X-100 7.4 mL cyclohexane 1.6 mL of 1-hexanol 154 μL of ammonium hydroxide (29.5% solution) 680 μL of 0.1 M ice-cold sodium borohydride prepared in 0.04 M aqueous NaOH 10 mL ethanol was added to induce precipitation of the microemulsion Tor Bjørnstad

  28. Aqueous pool in silvermicroemulsion… Consists of premade iron oxide nano-particles (prepared by the co-precipitation of iron (II) and iron (III) salts) dispersed in 0.1 M silver nitrate and 1mM 4-mercaptobenzoic acid (total volume = 680 μL) Tor Bjørnstad

  29. DOPS Tor Bjørnstad

  30. DOTAP Tor Bjørnstad

  31. Triton X-100 Tor Bjørnstad

  32. Tetraethoxysilane = TEOS Tor Bjørnstad

  33. (3-aminopropyl)triethoxysilane = APTES CH3 CH3 CH3 Tor Bjørnstad

  34. Rhodamine Skeleton Tor Bjørnstad

  35. Rhodamine B Tor Bjørnstad

  36. Sodium-2-mercaptoethanesulfonate = MES Tor Bjørnstad

  37. Polyethylene glycol = PEG Tor Bjørnstad

  38. Back-up slides follow…. Tor Bjørnstad

  39. Synthesisofnanoparticlewithhydrophilicsurface, - an example Tor Bjørnstad

  40. Preparation of Nano-Tracer:Example Goal: A functionalized nano-particle tracer with a metal (Au) core. Red sphere: Au core Green/bluedots: Fluorophores Lightgrey: Silicamatrix Black lines: Surfacefunctionalization Tor Bjørnstad

  41. Chemical Agents Organicliquid: Surfactant: Trition X-100 Co-surfactant: n-hexanol Oil: Cyclohexane + Water Emulsion: Water in oil Procedure by Brichart et al., Univ. of Lyon Tor Bjørnstad

  42. Forming Metallic Cores + Au3+ + MES + NaBH4 + NH3 Coreofreduced metal (Au0) Procedure by Brichart et al., Univ. of Lyon Tor Bjørnstad

  43. Particle Functionalization (1) APTES + fluorescent dye TEOS + fluorescent dye +NH3 Hydrolysis starts Procedure by Brichart et al., Univ. of Lyon Tor Bjørnstad

  44. Particle Functionalization (2) PEG ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) Procedure by Brichart et al., Univ. of Lyon Tor Bjørnstad

  45. Emulsion Breaking + ethanol/ isopropanol Hydrophilic functionalized nanoparticle tracer ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) ( ) Procedure by Brichart et al., Univ. of Lyon Tor Bjørnstad

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