Ammonia permeation of fluorinated sulfonic acid polymer/ceramic composite membranes

Wakimoto, Kotaro; Yan, Weiwei; Moriyama, Norihiro; Nagasawa, Hiroki; Kanezashi, Masakoto; Tsuru, Toshinori

doi:10.1016/j.memsci.2022.120718

Cited by 14 publications

(10 citation statements)

References 30 publications

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“…22 The reduction of local NH 3 pressure will allow the reaction rate to remain high even at a greater conversion of gas species, where the overall yield can maintain elevated values. The use of these techniques also allows for an elimination of equilibrium limitations, 23 as these are governed by gas phase concentrations.…”

Section: In Situ Adsorptionmentioning

confidence: 99%

“…Likewise, membrane reactors have been studied to do the same with an NH 3 selective membrane, 22 although current membrane materials are not operable under conditions for low-temperature NH 3 synthesis. 23 Most in situ NH 3 removal studies focus on equilibrium limitations 23 and likely miss the advantages of reducing NH 3 inhibition. In situ adsorption of NH 3 is most advantageous at moderate temperatures and pressures, 24 matching the conditions for renewable NH 3 synthesis.…”

Section: ■ Introductionmentioning

confidence: 99%

“…There have been several theoretical studies for both in situ adsorption-type NH 3 removal, where an NH 3 sorbent removes the NH 3 from the gas phase and is regenerated to release NH 3 at a later step. Likewise, membrane reactors have been studied to do the same with an NH 3 selective membrane, although current membrane materials are not operable under conditions for low-temperature NH 3 synthesis . Most in situ NH 3 removal studies focus on equilibrium limitations and likely miss the advantages of reducing NH 3 inhibition.…”

Section: Introductionmentioning

confidence: 99%

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Low-Temperature Ammonia Synthesis with an In Situ Adsorber under Regenerative Reaction Cycles Surpassing Thermodynamic Equilibrium

et al. 2023

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Catalytic NH 3 synthesis is a well-studied reaction, but its use in renewable energy storage is difficult due to the need for small-scale production, requiring greatly reduced operating temperatures and pressures. NH 3 inhibition on supported Ru catalysts becomes more prevalent at low temperatures, decreasing the reaction rates. In addition, promoter species are prone to oxidation at lower temperatures, further depressing the reaction rate. In situ NH 3 removal techniques have the potential to enhance NH 3 synthesis under milder conditions to combat both NH 3 inhibition and thermodynamic limitations, while the regeneration of the adsorber can potentially reactivate promoter species. The deactivation event of 5 wt % Ru/CeO 2 (3.9 nm average Ru particle size) was first explored in detail, and it was found that slight oxidation of Ce 3+ promoter species is the major cause of deactivation at lower temperatures, which is easily restored by hightemperature H 2 treatment. Ru/CeO 2 was then mixed with zeolite 4A, a substance showing favorable NH 3 capacity under mild reaction conditions. In situ adsorption of NH 3 significantly increased the reaction rate of Ru/CeO 2 at 200 °C with 5 kPa H 2 and 75 kPa N 2 , where the reaction rate increased from 128 to 565 μmol g −1 h −1 even at low H 2 conversions of 0.25% (average NH 3 yield of 0.01%). The temperature swings that were utilized to measure NH 3 uptake on zeolite 4A were also found to provide a reactivation event for Ru/CeO 2 . In situ NH 3 removal went beyond equilibrium limitations, achieving H 2 conversions up to 98%. This study sheds light on the kinetics of the use of in situ NH 3 removal techniques and provides insight into future designs utilizing similar techniques.

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Section: In Situ Adsorptionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Low-Temperature Ammonia Synthesis with an In Situ Adsorber under Regenerative Reaction Cycles Surpassing Thermodynamic Equilibrium

et al. 2023

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“…Membrane separation has attracted wide attention owing to small footprint, high energy efficiency, and easy operation, and the target gas pairs can be directly separated without desorption. − Although there are some studies have been devoted to membrane materials for gas pairs of NH 3 and H 2 or gas pairs of NH 3 and N 2 , − the separation of NH 3 and CO 2 has rarely been investigated. Additionally, the chemical reaction of CO 2 and NH 3 easily occurs at room temperature; thus, direct separation of NH 3 and CO 2 requires it to be carried out at an elevated temperature.…”

Section: Introductionmentioning

confidence: 99%

Polyimide/Ionic Liquids Hybrid Membranes with NH₃-Philic Channels for Ammonia-Based CO₂ Separation Processes

Jiang,

Li,

Bai

et al. 2023

ACS Appl. Mater. Interfaces

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An efficient separation technology involving ammonia (NH3) and carbon dioxide (CO2) is of great importance for achieving low-carbon economy, environmental protection, and resource utilization. However, directly separating NH3 and CO2 for ammonia-based CO2 capture processes is still a great challenge. Herein, we propose a new strategy for selective separation of NH3 and CO2 by functional hybrid membranes that integrate polyimide (PI) and ionic liquids (ILs). The incorporated protic IL [Bim][NTf2] is confined in the interchain segment of PI, which decreases the fractional free volume and narrows the gas transport channel, benefiting the high separation selectivity of hybrid membranes. At the same time, the confined IL also provides high NH3 affinity for transport channels, promoting NH3 selective and fast transport owing to strong hydrogen bonding interaction between [Bim][NTf2] and NH3 molecules. Thus, the optimal hybrid membrane exhibits an ultrahigh NH3/CO2 ideal selectivity of up to 159 at 30 °C without sacrificing permeability, which is 60 times higher than that of the neat PI membrane and superior to the state-of-the art reported values. Moreover, the introduction of [Bim][NTf2] also reduces the permeation active energy of NH3 and reverses the hybrid membrane toward “NH3 affinity”, as understood by studying the effect of temperature. Also, NH3 molecules are much easier to transport at high temperature, showing great application potential in direct NH3/CO2 separation. Overall, this work provides a promising ultraselective membrane material for ammonia-based CO2 capture processes.

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“…Such quantities, however, are limited by a typical trade-off, defined by Robeson in the late 20th century [23,24], whose upper bound represents still today a suitable tool for the evaluation of the potentiality of membrane materials for a given separation. In this context, many materials have been proposed for such separation, demonstrating a fast and highly selective permeation [10,18,25]. Inorganic (MXene [19], silica [11], zeolite [26]) and polymeric (Nafion, Aquivion [18], Cellulose [27], Polystyrene (PS) [28,29], zeolitic imidazolate frameworks (ZIF) [17], Prussian Blue [30]) membranes have been studied for ammonia separation, revealing that both large values of ammonia permeability and selectivity (with respect to N 2 and H 2 ), can be achieved in different operating conditions.…”

Section: Introductionmentioning

confidence: 99%

Study on Ammonia Transport and Separation in Aquivion® Perfluoro Sulfonated Acid Membranes

Signorini,

Aşkın,

Oldani

et al. 2023

Preprint

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Ammonia permeation of fluorinated sulfonic acid polymer/ceramic composite membranes

Cited by 14 publications

References 30 publications

Low-Temperature Ammonia Synthesis with an In Situ Adsorber under Regenerative Reaction Cycles Surpassing Thermodynamic Equilibrium

Low-Temperature Ammonia Synthesis with an In Situ Adsorber under Regenerative Reaction Cycles Surpassing Thermodynamic Equilibrium

Polyimide/Ionic Liquids Hybrid Membranes with NH₃-Philic Channels for Ammonia-Based CO₂ Separation Processes

Study on Ammonia Transport and Separation in Aquivion® Perfluoro Sulfonated Acid Membranes

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Ammonia permeation of fluorinated sulfonic acid polymer/ceramic composite membranes

Cited by 14 publications

References 30 publications

Low-Temperature Ammonia Synthesis with an In Situ Adsorber under Regenerative Reaction Cycles Surpassing Thermodynamic Equilibrium

Low-Temperature Ammonia Synthesis with an In Situ Adsorber under Regenerative Reaction Cycles Surpassing Thermodynamic Equilibrium

Polyimide/Ionic Liquids Hybrid Membranes with NH3-Philic Channels for Ammonia-Based CO2 Separation Processes

Study on Ammonia Transport and Separation in Aquivion® Perfluoro Sulfonated Acid Membranes

Contact Info

Product

Resources

About

Polyimide/Ionic Liquids Hybrid Membranes with NH₃-Philic Channels for Ammonia-Based CO₂ Separation Processes