1 Can functionalized nanoparticles be used as reservoir
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 of phase-partitioning tracers to determine interwell water-contactable average remaining oil saturation in the swept volume: Focus on chemical molecular compounds Focus on nano-particles, in particular C-dots. Subtask 5. 2: Development of new tracers for single-well push-and-pull operations to dermine residual oil in the near-well zone (5 -10 m from wellbore): Focus on reacting (mainly ester-based) chemical compounds which converts parts of a partitioning tracer into a water tracer in situ Focus on nano-particles which carry a partitioning and a passive tracer simultaneously into some depth from the wellbore Determine the effect of EOR-operations by measuring the oil saturation before and after an EOR –injection in a single-well push-and-pull test. Post. doc 2 • New esterbased tracers • New nanoparticles 2015 Extent. as RS RS+eng. • New nanoparticles RS+eng. 2016 2017 2018 Single-well pilot 2019 2020 Ph. D-student Post. doc 1 a Nano-part. = C-dots Progress report Thesis or final conclusion Final product Interwell pilot Phase-part. molecules RS+eng. Ph. D + RS Planning interwell pilot Post. doc 1 b Nano-part. = C-dots RS Planning singlewell pilot Tor Bjørnstad Single-well EORpilot + single-well tracer test pilot Additional: • Tracer modelling and the reservoir model • Combination of production data, tracer and 4 D seismics 2022
7 Carbon quantum dots = C-dots Tor Bjørnstad
8 Properties of C-dots 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
9 C-dot synthesis Citric acid OH Ethanol amine OH NH -H 2 O 180 C Tor Bjørnstad HO Mix at room temperature NH NH + 3 • Dry • Pyrolyze at 200°C for 8 hrs
10 Size of C-dots based on citric acid Tor Bjørnstad
Size distribution - effect of surfactant – Intensity aged dispersion After surfactant treatment Before surfactant treatment Size (nm) Tor Bjørnstad 11
C-dots in DI and 50 m. M Ca. Cl 2 through acid washed fine and coarse silica sand 1. 2 Saturated medium sand 1 1 100 % recovery 99. 7 % recovery 0. 8 90% recovery 79% recovery C/C 0 0. 8 C/C 0 saturated fine sand 0. 6 0. 4 0. 2 0 0 0 1 2 3 4 Pore volume 5 6 7 8 0 1 2 3 4 5 6 7 8 9 10 11 12 Pore volume Hassanpour (2016) Counter to the result of Li et al. (2014) for M-dots 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
14 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. Courtesy Larry Catles, from Kanj, Rashid and Gianelis, 2011, SPE 142592 -PP • 86% recovery. Tor Bjørnstad
Successful test in quartzite, Altona NY Iodide C-Dot Yushi Zhou, 2014 Cornell Ph. D Thesis Tor Bjørnstad
Field tracer tests in Colorado under planning Possible Schedule • Prepare fall 2017 • Execute summer shallow 2018 Multi-tracer test deep in fractured reservoir Tor Bjørnstad 16
17 Fluorescence of Rare Earth Compounds Fluorescence spectra of selected rare earths Fluorescence colors of selected rare earths Tor Bjørnstad
18 Intensity Fluorescent Ln-complexes Tb-DOTA = Ln-DTPA Intensity Wave length (nm) Eu-DOTA Wave length (nm) Tor Bjørnstad
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 PCRmethod. Was the possible use of DNA just a wet dream? Tor Bjørnstad 19
20 DNA in silica shell structure Si. O 2 TMAPS Si. O 2 ds. DNA Si. O 2 TMAPS TEOS + H 2 O Si. O 2 Modified, from Yuran Zhang: DNA-Encapsulated Silica Nanoparticle Tracers for Fractured Reservoir Characterization, SGP-TR-207, 2015 Tor Bjørnstad
21 More detailed Coulombic bonds… Si. O 2 Modified, from Daniela Paunescu, Nature Protocols 8, 2440– 2448 (2013) Tor Bjørnstad
22 Release of DNA NH 4 FHF Si. O 2 NH 4 F Free DNA ready for PCR analysis Tor Bjørnstad
23 Doped with a fluophor… Fluorophor 2 Fluorophor 1 Si. O 2 Tor Bjørnstad
24 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 (> 50100 darcy) NB! Such particles may be unique tools for well tracing and reservoir fracture detection Tor Bjørnstad
25 Thanks for listening Tor Bjørnstad
26 PCR = Polymerase Chain Reaction Doubles the number of present double-stranded DNA (ds. DNA) fragments for each multiplication cycle n into a detectable number: 1 2 4 8 16 ……… 2 n Tor Bjørnstad
27 Tetraethylorthosilicate - TEOS 77 L Tor Bjørnstad
28 Concentrations The «oil phase» = 1. 5 g Triton X-100 7. 4 m. L cyclohexane 1. 6 m. L 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 Na. OH 10 m. L ethanol was added to induce precipitation of the microemulsion Tor Bjørnstad
29 Aqueous pool in silver microemulsion… 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 1 m. M 4 -mercaptobenzoic acid (total volume = 680 μL) Tor Bjørnstad
30 DOPS Tor Bjørnstad
31 DOTAP Tor Bjørnstad
32 Triton X-100 Tor Bjørnstad
33 Tetraethoxysilane = TEOS Tor Bjørnstad
34 (3 -aminopropyl)triethoxysilane = APTES CH 3 Tor Bjørnstad
35 Rhodamine Skeleton Tor Bjørnstad
36 Rhodamine B Tor Bjørnstad
37 Sodium-2 -mercaptoethanesulfonate = MES Tor Bjørnstad
38 Polyethylene glycol = PEG Tor Bjørnstad
39 Back-up slides follow…. Tor Bjørnstad
40 Synthesis of nanoparticle with hydrophilic surface, - an example Tor Bjørnstad
41 Preparation of Nano-Tracer: Example Goal: A functionalized nanoparticle tracer with a metal (Au) core. Red sphere: Green/blue dots: Light grey: Black lines: Au core Fluorophores Silica matrix Surface functionalization Tor Bjørnstad
42 Chemical Agents Organic liquid: 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
43 Forming Metallic Cores + Au 3+ + MES + Na. BH 4 + NH 3 Core of reduced metal (Au 0) Procedure by Brichart et al. , Univ. of Lyon Tor Bjørnstad
44 Particle Functionalization (1) APTES + fluorescent dye TEOS + fluorescent dye + NH 3 Hydrolysis starts Procedure by Brichart et al. , Univ. of Lyon Tor Bjørnstad
45 ) Particle Functionalization (2) ( ) ( PEG ) ( ) ( ( ( ) ) Procedure by Brichart et al. , Univ. of Lyon Tor Bjørnstad
46 ) Emulsion Breaking ( ) ( ) ( ( ) ) + ethanol/ isopropanol ( ) ) ( ) ( ( ) ) Hydrophilic functionalized nanoparticle tracer ) ( ( ( Procedure by Brichart et al. , Univ. of Lyon Tor Bjørnstad
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