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WO2025136759A1 - Capture et libération électrochimiques de co2 au moyen de matériaux sorbants inorganiques - Google Patents

Capture et libération électrochimiques de co2 au moyen de matériaux sorbants inorganiques Download PDF

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Publication number
WO2025136759A1
WO2025136759A1 PCT/US2024/059551 US2024059551W WO2025136759A1 WO 2025136759 A1 WO2025136759 A1 WO 2025136759A1 US 2024059551 W US2024059551 W US 2024059551W WO 2025136759 A1 WO2025136759 A1 WO 2025136759A1
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WIPO (PCT)
Prior art keywords
electrolyte
capture
inorganic oxide
electrode
snch
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PCT/US2024/059551
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English (en)
Inventor
Marcel Schreier
Guangjing Li
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Wisconsin Alumni Research Foundation
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Wisconsin Alumni Research Foundation
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Publication of WO2025136759A1 publication Critical patent/WO2025136759A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • Carbamate and protonated amine pairs or bicarbonates are formed after the CO2 absorption process, followed by regeneration through application of both heat and vacuum.
  • the thermal energies required for regeneration are around 100 to 180 kJ mol' 1 , but inefficiencies in the plant design decrease the efficiency by 20 to 25 %.
  • the amines are prone to decomposition under typical operating temperatures as well as forming carcinogenic products when reacting with contaminants in the CO2 gas streams, such as NO X and SO X . See Chen et al., Emerging N-nitrosamines and N- nitramines from amine-based post-combustion CO2 capture-a review. Chemical Engineering Journal 2018, 335, 921-935.
  • the system includes a porous inorganic oxide electrode (e.g., T1O2) disposed in a non-aqueous solution comprising a dissolved electrolyte (e g, tetrabutylammonium hexafluorophosphate (TBAPFe)).
  • a gaseous input comprising CO2 is introduced whereupon it saturates the electrolyte with CO2.
  • a negative voltage is applied to the electrode to generate nucleophilic sites on the surface of the inorganic oxide electrode which subsequently adsorbs the CO2 from the electrolyte solution.
  • the adsorbed CO2 is desorbed from the electrode by applying a positive voltage.
  • a voltage sweep of -1.7 V to 0.6 V was sufficient to adsorb and desorb the CO2.
  • a method of adsorbing CO2 in a gaseous input comprising: contacting the gaseous input with a non-aqueous solution comprising a dissolved electrolyte and having disposed therein a working electrode comprising a porous inorganic oxide, and a counter electrode; and applying a negative voltage across the electrodes wherein at least a portion of the CO2 in the gaseous input is adsorbed to the working electrode.
  • the inorganic oxide comprises at least one reducible oxide.
  • suitable reducible oxides include T1O2. WO3, SnCh. Sb-SnCh, In-SnCh, and the like.
  • the inorganic oxide comprises T1O2.
  • the electrolyte may comprise TBAPFg.
  • the electrolyte may comprise TBAPFe and 1 -ethyl -3-methylimidazolium tetrafluoroborate (EMIMBF4).
  • EMIMBF4 1 -ethyl -3-methylimidazolium tetrafluoroborate
  • the negative voltage applied to the electrode to adsorb CO2 ranges from about -1.2 to about -1.8 V. Voltages above and below this range are explicitly within the scope of the disclosed method.
  • the method may further comprise sparging the electrolyte with a noble gas after applying the negative voltage.
  • the method may further comprise applying a positive voltage across the electrodes to desorb the CO2.
  • the positive voltage can be applied by a positive sweep of potential from the negative voltage.
  • a system configured to adsorb and desorb CO2, the system comprising: a working electrode comprising a porous inorganic oxide; a counter electrode: and a non-aqueous solution comprising a dissolved electrolyte.
  • the inorganic oxide of the working electrode comprises at least one reducible oxide.
  • the inorganic oxide comprises one or more of TiCh, WO3, SnCh, Sb-SnCh, and In-SnO2.
  • the inorganic oxide comprises TiCh.
  • the electrolyte may comprise TBAPFg.
  • the electrolyte may comprise TBAPFg and EMIMBF4.
  • the method and system described herein address both the efficiency and stability challenges associated with current CO2 capture systems (e g., energy intensive desorption processes and degradation of organic materials via radical formation). Instead of applying substantial amounts of heat, the present method relies on the application of current at select voltages.
  • reducible inorganic oxides as electrosorbents (e g., TiCh) addresses both the energy and stability limitations described above.
  • an electrochemical approach has the potential to be agnostic to the CO2 concentration in the source gas. The method can also be run entirely on renewable electricity, thereby avoiding C'Ch-generating externalities.
  • Fig. 1 A schematic illustration of the electrochemical adsorption and desorption process of CO2 on TiO2 as described herein.
  • Fig. 2 A scanning electron microscopic image of porous TiO2.
  • Fig.3 A graph showing the current caused by CO2 desorption by running a CV scan from -1.7 V to 0.6 V.
  • Fig. 4 A GC chromatogram showing signals of CO2 desorbed from a porous TiCh electrode after an oxidative cyclovoltammetry scan from -1.5 V to 0.6 V vs Ag/AgCl (10), and signals of CO2 remaining in acetonitrile solution after Ar sparging but before the oxidative desorption (12).
  • Fig. 5 A histogram showing maximum (white) and minimum (black) energies required to capture 1 mol of CO2 under flue gas conditions.
  • GM NPQ glyco-modified naphthoquinone
  • MCDI membrane capacitive deionization
  • PCET proton-coupled electron transfer
  • BPMED bipolar membrane electrodialysis
  • EMAR electrochemically mediated amine regeneration
  • Co-SAC PSE cobalt single atom catalyst porous solid electrolyte
  • GM NPQ glyme-modified naphthoquinone
  • PAQ-CNT Polyanthraquinone carbon nanotubes.
  • Fig. 6 Cyclic voltammetry scans of porous TiCh electrode after holding potentials in saturated CO2 acetonitrile, 0.1 M TBAPFe (2000 seconds) at -1.7 V (26), -1.6 V (22) and -1.5 V (18).
  • the dashed lines 24 (-1.7 V), 20 (-1.6 V), and 16 (-1.5 V) are cyclic voltammetry scans performed under the corresponding potential conditions but under saturated CO2 solutions for 800 seconds, then followed by 1200 seconds of argon sparging while maintaining the potential hold.
  • the solid line 14 is the cyclic voltammetry scan of argon-saturated solution.
  • Fig. 8 Cyclic voltammetry scans of porous TiCh after holding potentials (—1.7 V, 600 seconds) in CO2 saturated acetonitrile, 0.1 M TBAPFg and 0.02 M EMIMBF4 concentrations. Cyclic voltammetry scans of porous TiCh electrode, placed in the same electrolyte concentrations and holding potential value, but for 600 seconds in saturated CO2 solution and 1200 seconds under argon sparging. The cyclic voltammetry scan of argon-saturated solution is shown in the solid “Ar” line at bottom.
  • ATO Antimony-doped Tin Oxide (Sb-SnO2).
  • EMIMBF4 l-Ethyl-3-methylimidazolium tetrafluoroborate.
  • ITO Indium tin oxide (In-SnO2).
  • TBAPFg Tetrabutylammonium hexafluorophosphate.
  • Non-aqueous solvent is used broadly herein to denote solvents other than water.
  • Nonaqueous polar aprotic solvents are generally preferred, including but not limited to acetone, acetonitrile, dichloromethane, dimethylformamide, dimethyl sulfoxide, ethyl acetate, pyridine, sulfolane, tetrahydrofuran, and the like.
  • carbonate solvents may also be used, including, but not limited to ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, vinylene carbonate, and the like.
  • Halogenated benzenes such as fluorobenzenes, may also be used.
  • Ionic liquids such as imidazoles and their cations (imidzaoliums) may also be used - e g., ethylmethylimidazolium, dimethylimidazolium, etc.
  • stable anions such as tetrafluorborate, perchlorate, and the like.
  • halogenated acids such as trifluoromethanesulfonic acid.
  • the methods of the present disclosure can comprise, consist of, or consist essentially of the essential elements and limitations of the method described herein, as well as any additional or optional ingredients, components, or limitations described herein or otherwise useful in electrochemistry.
  • the disclosure provided herein may be practiced in the absence of any element or step which is not specifically disclosed herein.
  • Disclosed herein is a novel electrochemical method to adsorb and desorb carbon dioxide molecules on porous inorganic oxide electrodes.
  • the method achieves better energy efficiency and far greater stability than the conventional organic sorbents.
  • the method disclosed herein uses titanium dioxide (T1O2) as a model compound inorganic oxide electrode. This is for brevity only.
  • the method can be easily implemented using other reducible oxides.
  • Non-limiting examples of the reducible oxides that can be used include WO3, SnCE, Sb-SnCh (ATO), In-SnCh (ITO), etc.
  • the present method rests on the property of TiO2 (and other reducible inorganic oxides) to form nucleophilic sites upon reduction. These nucleophilic sites serve as adsorption sites for CO2. Electrochemical reduction of TiO2, transforms some Ti 4+ sites to Ti 3+ , which possess nucleophilic character. In the presence of H + or Li + , for example, the charge on these reduced Ti centers is compensated by cation intercalation. This effect is used in some Li-ion batteries for energy storage (“LTO anodes”), where Li-intercalation and deintercalation can be carried out for thousands of cycles. This phenomenon confirms the robust stability of TiCL-based electrodes.
  • Li-ion batteries for energy storage (“LTO anodes”)
  • T1O2 is shown herein to be an equally efficient and stable sorbent material for the electrochemical capture and release of CO2.
  • the designed system involves the use of anon-aqueous solution (e.g., acetonitrile) with dissolved electrolytes as a medium for CO2 capture, a surface of porous titania as the working electrode, a counter electrode, a reference electrode, and a potentiostat.
  • Mesoporous T1O2 was prepared by deposition of a titania paste dispersed in ethanol, which was subsequently calcined at 500 °C for 30 minutes.
  • the surface morphology of the porous TiCh surface is shown in Fig. 2, compared the morphology- of the polished TiCh surface, the “rough"’ surface of the porous material is expected to accommodate adequate amount of CO2 adsorption.
  • the Ag/AgCl electrode was a “leakless electrode” acquired commercially from eDAQ Pty Ltd, Denistone East, NSW, Australia) While still applying the same potential, CO2 was subsequently removed by sparging the electrolyte with argon. This step was followed by a positive sweep of the potential from -1.7 V to 0.6 V at 100 mV sec" 1 . During this sweep, a cunent was observed corresponding to the desorption of CO2, demonstrating that T1O2 surfaces can be employed as an inorganic electrochemical CO2 capture medium as shown in Fig. 3.
  • line 10 shows the released CO2 dissolved in 1 mL of acetonitrile after adsorbing CO2 at - 1.5 V vs Ag/AgCl followed by sparging the solvent with Ar to remove excess CO2 in the solution.
  • the amount of captured CO2 is calculated to be 1.15 pmol from a 0.20 cm 2 TiCh surface.
  • the total number of charges passing through the electrode during the adsorption process is 144 mC, thus if assuming CO2 adsorption is a one electron process, the Faradaic efficiency is 90 %.
  • the potential gap between the onsets of desorption and adsorption should be as small as possible since this voltage difference represents a loss in energy between the potential at which adsorption takes place and the one at which CO2 can be desorbed.
  • the method demonstrates the onset of CO2 adsorption is at slightly below -1.4 V. As the adsorption of CO2 mostly occurred by holding the electrode under -1.7 V and the onset of desorption is at approximately 60 mV more positive or 6 kJ mol" 1 , this is less than the 16 kJ mol" 1 energy loss for the best sorbent material known to date, which is 4,4'-azopyridine. Even more, since the electrosorbent is an inorganic solid, it features substantially better stability- than existing adsorbent materials. For example, a test was performed for 210 cycles; a capacity fade of only 3% was observed.
  • Electrochemical CO2 capture/release on inorganic oxides offers the ability to control the nucleophilicity of the electrode surface. Defining the difference of the onset potential at the desorption peak and the negative potential at which the electrode was held at during adsorption of CO2, then the energy of releasing the captured low-binding energy CO2 is calculated to be approximately 6 kJ mol for when CO2 was captured at -1.7 V. This energy is lower than that for typical pressure, temperature swings, and systems using quinones. Also, the present method and system does not require the membranes that are required when using organic compounds in electrochemical CO2 capturing processes. Electrochemically mediated amine regeneration and proton-coupled electron transfer-mediated CO2 capture requires such membranes to function.
  • the system disclosed herein can be used as a device to electrochemically capture CO2 under ambient conditions.
  • the method has a substantially smaller energy gap between the adsorption and desorption potential.
  • the adsorbent material is entirely inorganic and can thus be expected to feature substantially higher stability than the commonly used organic sorbents which are notoriously unstable.
  • the system disclosed herein can be used as a component in enclosed spaces that require scrubbing of CO2 from the local atmosphere, such as in high-altitude aircraft, spacecraft, and submarines. It can also be used to remove CO2 from flue gas.
  • the system disclosed herein will play a crucial part in the effort of using cheap and renewable electricity to capture and store CO2, hence leaving investment opportunities for companies that wish to earn carbon credits or to avoid emission penalties.

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

L'invention concerne un procédé électrochimique et un système associé d'adsorption et de désorption de CO2. Le système comprend une électrode à base d'oxyde inorganique poreux et une solution non aqueuse comprenant un électrolyte dissous. Le procédé comprend la mise en contact de l'électrode avec une entrée gazeuse comprenant du CO2, le CO2 saturant l'électrolyte, et l'application d'une tension négative, le CO2 étant adsorbé sur l'électrode. Une fois saturé, la désorption du CO2 de l'électrode à base d'oxyde inorganique est obtenue par application d'une tension positive.
PCT/US2024/059551 2023-12-18 2024-12-11 Capture et libération électrochimiques de co2 au moyen de matériaux sorbants inorganiques Pending WO2025136759A1 (fr)

Applications Claiming Priority (2)

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US202363611459P 2023-12-18 2023-12-18
US63/611,459 2023-12-18

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160293985A1 (en) * 2013-03-15 2016-10-06 Exxonmobil Research And Engineering Company Integration of Molten Carbonate Fuel Cells in Fischer-Tropsch Synthesis
WO2023094487A1 (fr) * 2021-11-25 2023-06-01 Vito Nv Système et procédé de capture intégrée du co2 et production d'hydrogène

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160293985A1 (en) * 2013-03-15 2016-10-06 Exxonmobil Research And Engineering Company Integration of Molten Carbonate Fuel Cells in Fischer-Tropsch Synthesis
WO2023094487A1 (fr) * 2021-11-25 2023-06-01 Vito Nv Système et procédé de capture intégrée du co2 et production d'hydrogène

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LIU HAI, MIAO BAIYU, CHUAI HONGYUAN, CHEN XIAOYI, ZHANG SHENG, MA XINBIN: "Nanoporous tin oxides for efficient electrochemical CO2 reduction to formate", GREEN CHEMICAL ENGINEERING, vol. 3, no. 2, 1 June 2022 (2022-06-01), pages 138 - 145, XP093331814, ISSN: 2666-9528, DOI: 10.1016/j.gce.2021.11.001 *
TUFA RAMATO ASHU; CHANDA DEBABRATA; MA MING; AILI DAVID; DEMISSIE TAYE BEYENE; VAES JAN; LI QINGFENG; LIU SHANHU; PANT DEEPAK: "Towards highly efficient electrochemical CO2 reduction: Cell designs, membranes and electrocatalysts", APPLIED ENERGY, vol. 277, 12 August 2020 (2020-08-12), GB , XP086287377, ISSN: 0306-2619, DOI: 10.1016/j.apenergy.2020.115557 *

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