Entropy‐Driven Chemisorption of NO<sub><i>x</i></sub> on Phosphotungstic Acid

Heylen, Steven; Joos, Lennart; Parac‐Vogt, Tatjana N.; Speybroeck, Véronique Van; Kirschhock, Christine; Martens, Johan A.

doi:10.1002/anie.201205636

Cited by 4 publications

(3 citation statements)

References 30 publications

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“…34,35 At high temperature, NO x molecules are chemisorbed in the crystal structure of the acid, substituting the H 2 O molecules that were present in the crystal structure before. The NO x moieties are released only at low temperature and in the presence of H 2 O.…”

Section: Introductionmentioning

confidence: 99%

“…In this paper, we propose an alternative operation of the carbon capture process that circumvents the high energy penalty for the CO 2 /N 2 separation in the presence of H 2 O. CO 2 adsorption is performed at high temperature (400 K), whereas the release of CO 2 happens at low temperature, through saturation of the absorbent with H 2 O. Inspiration for the proposed methodology was found in the chemisorption of NO x on phosphotungstic acid. 34,35 At high temperature, NO x molecules are chemisorbed in the crystal structure of the acid, substituting the H 2 O molecules that were present in the crystal structure before. The NO x moieties are released only at low temperature and in the presence of H 2 O.…”

Section: Introductionmentioning

confidence: 99%

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Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Joos

Lejaeghere

Huck

et al. 2015

Energy Environ. Sci.

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Carbon capture & sequestration (CCS) could reduce CO 2 emissions from large fossil-fuel power plants on the short term, but the high energy penalty of the process hinders its industrial deployment. Moreover, the utility of nanoporous materials, known to be selective for the CO 2 /N 2 separation, is drastically reduced due to the competitive adsorption with H 2 O. Taking advantage of the power plant's waste heat to perform CCS while at the same time surmounting the negative effect of H 2 O is therefore an attractive idea. We propose an upside-down approach for CCS in nanoporous materials, high-temperature adsorption & low-temperature desorption (HALD), that exploits the temperature-dependent competitive adsorption of CO 2 and H 2 O. First, we provide a theoretical background for this entropy-driven behavior and demonstrate under what conditions competitive adsorption can be in favor of CO 2 at high temperature and in favor of H 2 O at low temperature. Then, molecular simulations in all-silica MFI provide a proof of concept. The International Zeolite Association database is subsequently screened for potential candidates and finally, the most promising materials are selected using a post-Pareto search algorithm. The proposed post-Pareto approach is able to select the material that shows an optimal combination of multiple criteria, such as CO 2 /H 2 O selectivity, CO 2 /N 2 selectivity, CO 2 uptake and H 2 O uptake. As a conclusion, this work provides new perspectives to reduce the energy requirement for CCS and to overcome the competitive adsorption of H 2 O. Broader contextUtilizing the residual heat of a power plant's flue gas to capture the CO 2 from this CO 2 /N 2 /H 2 O mixture could drastically reduce the energy requirement of carbon capture and sequestration (CCS). The novel approach to CCS presented here, high-temperature adsorption & low-temperature desorption (HALD) of CO 2 in zeolites, exploits the temperature-dependent competitive adsorption of CO 2 and H 2 O. A theoretical model demonstrates that differences in the adsorption enthalpy and entropy for CO 2 and H 2 O can favor CO 2 adsorption at high temperature and H 2 O uptake at low temperature. Using Grand Canonical Monte Carlo simulations, we perform a screening of the existing zeolite topologies to assess their adsorption properties. Afterwards, a post-Pareto analysis identifies the most promising materials. The proposed HALD behavior can be used in a temperature-swing process, which would not require the input of energy for regeneration, but instead would recover the CO 2 by saturating the material with water. In addition, the deeper understanding of the entropy-driven competitive adsorption of CO 2 and H 2 O opens new perspectives to overcome the detrimental effect of water.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Joos

Lejaeghere

Huck

et al. 2015

Energy Environ. Sci.

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“…31 In the newly proposed "High-temperature Adsorption and Low-temperature Desorption" (HALD) set-up, the temperature-dependent competitive adsorption of CO 2 and H 2 O is exploited to overcome the high energy requirement. 22,32 At high temperatures, the competitive adsorption of CO 2 and H 2 O is in favor of CO 2 , so adsorption at higher temperatures (without rst cooling the exhaust gases) improves the selectivity towards CO 2 . As the competition is in favor of H 2 O at low temperatures, CO 2 can be desorbed at low temperatures, by cooling and saturating the absorbent with H 2 O.…”

Section: Alternative Technologiesmentioning

confidence: 99%

Cutting the cost of carbon capture: a case for carbon capture and utilization

et al. 2016

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A significant part of the cost for carbon capture and storage (CCS) is related to the compression of captured CO to its supercritical state, at 150 bar and typically 99% purity. These stringent conditions may however not always be necessary for specific cases of carbon capture and utilization (CCU). In this manuscript, we investigate how much the parasitic energy of an adsorbent-based carbon capture process may be lowered by utilizing CO at 1 bar and adapting the final purity requirement for CO from 99% to 70% or 50%. We compare different CO sources: the flue gases of coal-fired or natural gas-fired power plants and ambient air. We evaluate the carbon capture performance of over 60 nanoporous materials and determine the influence of the initial and final CO purity on the parasitic energy of the carbon capture process. Moreover, we demonstrate the underlying principles of the parasitic energy minimization in more detail using the commercially available NaX zeolite. Finally, the calculated utilization cost of CO is compared with the reported prices for CO and published costs for CCS.

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A new approach of kinetic modeling: Kinetically consistent energy profile and rate expression analysis

Wang

Yang

et al. 2022

Chemical Engineering Journal

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Entropy‐Driven Chemisorption of NO_x on Phosphotungstic Acid

Abstract: Free-energy calculations indicated that the NO(x) adsorption process on heteropolyacids is entropy-driven, as more gas molecules are released than adsorbed by substitution of H(5)O(2)(+) with NO(+) species. P yellow, W light blue, O red, H pink, N small dark blue spheres.

Cited by 4 publications

References 30 publications

Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Cutting the cost of carbon capture: a case for carbon capture and utilization

A new approach of kinetic modeling: Kinetically consistent energy profile and rate expression analysis

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Entropy‐Driven Chemisorption of NOx on Phosphotungstic Acid

Abstract: Free-energy calculations indicated that the NO(x) adsorption process on heteropolyacids is entropy-driven, as more gas molecules are released than adsorbed by substitution of H(5)O(2)(+) with NO(+) species. P yellow, W light blue, O red, H pink, N small dark blue spheres.

Cited by 4 publications

References 30 publications

Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Carbon capture turned upside down: high-temperature adsorption & low-temperature desorption (HALD)

Cutting the cost of carbon capture: a case for carbon capture and utilization

A new approach of kinetic modeling: Kinetically consistent energy profile and rate expression analysis

Contact Info

Product

Resources

About

Entropy‐Driven Chemisorption of NO_x on Phosphotungstic Acid