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Thickening supercritical CO2 at high temperatures with rod-like reverse micelles

Masanobu Sagisaka Orcid Logo, Yuuki Sato, Sajad Kiani, Shirin Alexander Orcid Logo, Tretya Ardyani Orcid Logo, Azmi Mohamed, Robert M. Enick, Sarah E. Rogers, Christopher Hill Orcid Logo, Julian Eastoe

Colloids and Surfaces A: Physicochemical and Engineering Aspects, Volume: 686

Swansea University Author: Shirin Alexander Orcid Logo

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DOI (Published version): 10.1016/j.colsurfa.2024.133302

Abstract

Earlier studies demonstrated the ability of some fluorinated surfactants to form rod-like reverse micelles with the ability to thicken water/supercritical CO2 (scCO2) mixtures at temperatures below 45 ºC [Langmuir 26 (2010) 83–88. Soft Matter 8 (2012) 7044–7055. Colloids and Surfaces B, 168 (2018),...

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Published in: Colloids and Surfaces A: Physicochemical and Engineering Aspects
ISSN: 0927-7757
Published: Elsevier BV 2024
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URI: https://cronfa.swan.ac.uk/Record/cronfa65642
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Such viscosity enhancement of scCO2 is known to increase sweep efficiency for oil recovery with CO2 flooding. However, temperatures of up to ∼100 ºC in conventional reservoirs are much higher than those employed in laboratory studies, and tend to weaken inter- and intra-molecular interactions between surfactant molecules, discouraging rod-like reverse micelle formation. With the aim of designing surfactants which form rod-like reverse micelles and thicken CO2 at high temperatures, this study examined phase behavior, nanostructures of reverse micelles and thickening ability of double ω-hydroperfluorocarbon-tail anionic surfactants in W/scCO2 mixtures at temperatures of 35 - 75 ºC and pressure of 80 - 400 bar with different water-to-surfactant molar ratios (W0). The measured CO2 viscosity increased by 1.9–2.2 × for double-chain surfactants M(di-HCF6)x (counterion Mx+ = Ni2+ and Co2+) at 40 mM, over the experimental temperature range. On the other hand, the shorter chain H(CF2)4CH2 twin-tail surfactants M(di-HCF4)x and Na(di-HCF6) gave only 1.1–1.5 × viscosity enhancements. The maximum thickening ability of M(di-HCF6)2 was at W0 = 10 in the W0 range of 5–20 75 ºC and 350 bar. High pressure and high temperature small-angle neutron scattering (SANS) was used determine the micellar structure in these systems, and rod micelles of aspect ratios of 4.5–6.5 were found. The results clearly suggest that ω-hydroperfluorohexyl-tails and divalent counterions induce the formation of rod-like reverse micelles in W/CO2 mixtures, even at high temperatures commensurate with in-reservoir conditions.</abstract><type>Journal Article</type><journal>Colloids and Surfaces A: Physicochemical and Engineering Aspects</journal><volume>686</volume><journalNumber/><paginationStart/><paginationEnd/><publisher>Elsevier BV</publisher><placeOfPublication/><isbnPrint/><isbnElectronic/><issnPrint>0927-7757</issnPrint><issnElectronic/><keywords>Supercritical CO2ω-hydroperfluorocarbon, Viscosity, Rod-like reverse micelle, Small-angle neutron scattering</keywords><publishedDay>5</publishedDay><publishedMonth>4</publishedMonth><publishedYear>2024</publishedYear><publishedDate>2024-04-05</publishedDate><doi>10.1016/j.colsurfa.2024.133302</doi><url/><notes/><college>COLLEGE NANME</college><department>Chemical Engineering</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>CHEG</DepartmentCode><institution>Swansea University</institution><apcterm/><funders>This project was supported by JSPS [KAKENHI, Grant-in-Aid for Scientific Research (B), No. 23H01750 and 19H02504, and International Exchanges 2021 Cost Share (JSPS) award 1845272]. We also acknowledge STFC for the allocation of beam time, travel, and consumables grants at ISIS. The authors acknowledge Shared Facility Center for Science and Technology, Hirosaki University (SFCST) for 1H NMR and FT-IR spectra measurements and elemental analysis. 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spelling v2 65642 2024-02-15 Thickening supercritical CO2 at high temperatures with rod-like reverse micelles 0773cc55f7caf77817be08806b8b7497 0000-0002-4404-0026 Shirin Alexander Shirin Alexander true false 2024-02-15 CHEG Earlier studies demonstrated the ability of some fluorinated surfactants to form rod-like reverse micelles with the ability to thicken water/supercritical CO2 (scCO2) mixtures at temperatures below 45 ºC [Langmuir 26 (2010) 83–88. Soft Matter 8 (2012) 7044–7055. Colloids and Surfaces B, 168 (2018), 201–210.]. Such viscosity enhancement of scCO2 is known to increase sweep efficiency for oil recovery with CO2 flooding. However, temperatures of up to ∼100 ºC in conventional reservoirs are much higher than those employed in laboratory studies, and tend to weaken inter- and intra-molecular interactions between surfactant molecules, discouraging rod-like reverse micelle formation. With the aim of designing surfactants which form rod-like reverse micelles and thicken CO2 at high temperatures, this study examined phase behavior, nanostructures of reverse micelles and thickening ability of double ω-hydroperfluorocarbon-tail anionic surfactants in W/scCO2 mixtures at temperatures of 35 - 75 ºC and pressure of 80 - 400 bar with different water-to-surfactant molar ratios (W0). The measured CO2 viscosity increased by 1.9–2.2 × for double-chain surfactants M(di-HCF6)x (counterion Mx+ = Ni2+ and Co2+) at 40 mM, over the experimental temperature range. On the other hand, the shorter chain H(CF2)4CH2 twin-tail surfactants M(di-HCF4)x and Na(di-HCF6) gave only 1.1–1.5 × viscosity enhancements. The maximum thickening ability of M(di-HCF6)2 was at W0 = 10 in the W0 range of 5–20 75 ºC and 350 bar. High pressure and high temperature small-angle neutron scattering (SANS) was used determine the micellar structure in these systems, and rod micelles of aspect ratios of 4.5–6.5 were found. The results clearly suggest that ω-hydroperfluorohexyl-tails and divalent counterions induce the formation of rod-like reverse micelles in W/CO2 mixtures, even at high temperatures commensurate with in-reservoir conditions. Journal Article Colloids and Surfaces A: Physicochemical and Engineering Aspects 686 Elsevier BV 0927-7757 Supercritical CO2ω-hydroperfluorocarbon, Viscosity, Rod-like reverse micelle, Small-angle neutron scattering 5 4 2024 2024-04-05 10.1016/j.colsurfa.2024.133302 COLLEGE NANME Chemical Engineering COLLEGE CODE CHEG Swansea University This project was supported by JSPS [KAKENHI, Grant-in-Aid for Scientific Research (B), No. 23H01750 and 19H02504, and International Exchanges 2021 Cost Share (JSPS) award 1845272]. We also acknowledge STFC for the allocation of beam time, travel, and consumables grants at ISIS. The authors acknowledge Shared Facility Center for Science and Technology, Hirosaki University (SFCST) for 1H NMR and FT-IR spectra measurements and elemental analysis. CH acknowledges JSPS for support as a JSPS International Research Fellow (Graduate School of Science and Technology, Hirosaki University). 2024-04-03T16:23:47.9548372 2024-02-15T15:05:55.6147750 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Masanobu Sagisaka 0000-0001-9685-7524 1 Yuuki Sato 2 Sajad Kiani 3 Shirin Alexander 0000-0002-4404-0026 4 Tretya Ardyani 0000-0001-7290-105x 5 Azmi Mohamed 6 Robert M. Enick 7 Sarah E. Rogers 8 Christopher Hill 0000-0002-9257-5244 9 Julian Eastoe 10 65642__29555__dd8785862bc14be2a59e5dd046a954eb.pdf 65642.pdf 2024-02-15T15:11:34.8605128 Output 850565 application/pdf Accepted Manuscript true Author accepted manuscript document released under the terms of a Creative Commons CC-BY licence using the Swansea University Research Publications Policy (rights retention). true eng https://creativecommons.org/licenses/by/2.0/deed.en
title Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
spellingShingle Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
Shirin Alexander
title_short Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
title_full Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
title_fullStr Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
title_full_unstemmed Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
title_sort Thickening supercritical CO2 at high temperatures with rod-like reverse micelles
author_id_str_mv 0773cc55f7caf77817be08806b8b7497
author_id_fullname_str_mv 0773cc55f7caf77817be08806b8b7497_***_Shirin Alexander
author Shirin Alexander
author2 Masanobu Sagisaka
Yuuki Sato
Sajad Kiani
Shirin Alexander
Tretya Ardyani
Azmi Mohamed
Robert M. Enick
Sarah E. Rogers
Christopher Hill
Julian Eastoe
format Journal article
container_title Colloids and Surfaces A: Physicochemical and Engineering Aspects
container_volume 686
publishDate 2024
institution Swansea University
issn 0927-7757
doi_str_mv 10.1016/j.colsurfa.2024.133302
publisher Elsevier BV
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
document_store_str 1
active_str 0
description Earlier studies demonstrated the ability of some fluorinated surfactants to form rod-like reverse micelles with the ability to thicken water/supercritical CO2 (scCO2) mixtures at temperatures below 45 ºC [Langmuir 26 (2010) 83–88. Soft Matter 8 (2012) 7044–7055. Colloids and Surfaces B, 168 (2018), 201–210.]. Such viscosity enhancement of scCO2 is known to increase sweep efficiency for oil recovery with CO2 flooding. However, temperatures of up to ∼100 ºC in conventional reservoirs are much higher than those employed in laboratory studies, and tend to weaken inter- and intra-molecular interactions between surfactant molecules, discouraging rod-like reverse micelle formation. With the aim of designing surfactants which form rod-like reverse micelles and thicken CO2 at high temperatures, this study examined phase behavior, nanostructures of reverse micelles and thickening ability of double ω-hydroperfluorocarbon-tail anionic surfactants in W/scCO2 mixtures at temperatures of 35 - 75 ºC and pressure of 80 - 400 bar with different water-to-surfactant molar ratios (W0). The measured CO2 viscosity increased by 1.9–2.2 × for double-chain surfactants M(di-HCF6)x (counterion Mx+ = Ni2+ and Co2+) at 40 mM, over the experimental temperature range. On the other hand, the shorter chain H(CF2)4CH2 twin-tail surfactants M(di-HCF4)x and Na(di-HCF6) gave only 1.1–1.5 × viscosity enhancements. The maximum thickening ability of M(di-HCF6)2 was at W0 = 10 in the W0 range of 5–20 75 ºC and 350 bar. High pressure and high temperature small-angle neutron scattering (SANS) was used determine the micellar structure in these systems, and rod micelles of aspect ratios of 4.5–6.5 were found. The results clearly suggest that ω-hydroperfluorohexyl-tails and divalent counterions induce the formation of rod-like reverse micelles in W/CO2 mixtures, even at high temperatures commensurate with in-reservoir conditions.
published_date 2024-04-05T16:23:44Z
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