CO<sub>2</sub>–Hydroquinone Clathrate: Synthesis, Purification, Characterization and Crystal Structure

Torré, Jean-Philippe; Coupan, Romuald; Chabod, Mathieu; Péré, Eve; Labat, Stéphane; Khoukh, Abdel; Brown, Ross; Sotiropoulos, Jean‐Marc; Gornitzka, Heinz

doi:10.1021/acs.cgd.6b00834

Cited by 30 publications

(69 citation statements)

References 49 publications

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“…Moreover, Raman spectroscopy made it possible to clearly identify the presence of CO 2 and CH 4 guest molecules in the HQ clathrates. In the case of the CO 2 molecules, the symmetrical CO stretching bands were observed at 1272 and 1380 cm −1 , 29,32,33 and in the case of the CH 4 molecules, the symmetrical C−H stretching bands were at 2905 cm −1 . 34 It is worth noting that, based on the analysis of the equimolar CO 2 /CH 4 mixture ( Figure 2c), CO 2 could be detected at 1287 and 1390 cm −1 and CH 4 at 2915 cm −1 .…”

Section: ■ Results and Discussionmentioning

confidence: 95%

New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity

et al. 2017

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Hydroquinone (HQ) is known to form organic clathrates with different gaseous species over a wide range of pressures and temperatures. However, the enclathration reaction involving HQ is not fully understood. This work offers new elements of understanding HQ clathrate formation and dissociation mechanisms. The kinetics and selectivity of the enclathration reaction were also investigated. The focus was placed on HQ clathrates formed with CO and CH as guest molecules for potential use in practical applications for the separation of a CO/CH gas mixture. The structural transition from the native form (α-HQ) to the clathrate form (β-HQ), as well as the reverse process, were tracked using in situ Raman spectroscopy. The clathrate formation was conducted at 323 K and 3.0 MPa, and the dissociation was conducted at 343 K and 1.0 kPa. The experiments with CH confirmed that a small amount of gas can fill the α-HQ before the phase transition from α- to β-HQ begins. The dissociation of the CO-HQ clathrates highlighted the presence of a clathrate structure with no guest molecules. We can therefore conclude that HQ clathrate formation and dissociation are two-step reactions that pass through two distinct reaction intermediates: guest-loaded α-HQ and guest-free β-HQ. When an equimolar CO/CH gas mixture is put in contact with either the α-HQ or the guest-free β-HQ, the CO is preferentially captured. Moreover, the guest-free β-HQ can retain the CO quicker and more selectively.

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Section: ■ Results and Discussionmentioning

confidence: 95%

New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity

et al. 2017

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“…The initial coordinates of the HQ lattice are obtained from experimental crystallographic data acquired by X-ray diffraction analysis. 8 The simulation boxes for the β-HQ clathrates are shown in Figure 1. The initial cell parameters of β-HQ are taken from the experimental values a = b = 1620.7 ± 0.6 pm, c = 578.0 ± 0.2 pm.…”

Section: ■ Numerical Methodsmentioning

confidence: 99%

Insights into the Crystal Structure and Clathration Selectivity of Organic Clathrates Formed with Hydroquinone and (CO₂ + CH₄) Gas Mixtures

et al. 2019

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Organic clathrates, particularly those formed by hydroquinone (HQ) and gas mixtures, have been far less studied than other inclusion compounds, such as gas hydrates. In this study, experiments and molecular dynamics simulations were performed on mixed (CO 2 + CH 4)−HQ clathrates. Single crystals were synthesized using gas mixtures with different compositions, ranging from pure CO 2 to pure CH 4. The crystal structure, the guest occupancy in the clathrates, and the variation of the crystal lattice parameters according to clathrate composition were obtained by X-ray diffraction measurements. In addition, molecular dynamics simulations were performed on the same systems, with state-of-the-art molecular models and force fields. The experimental results obtained and the molecular dynamics simulation estimations were in good agreement. The clathration selectivity was also calculated on the basis of experimental results, and the composition of the solid phase was correlated with the composition of the gas phase at equilibrium. These new insights into these structures will be useful from both a fundamental and a practical point of view, particularly for further developing innovative gas separation techniques using HQ clathrates.

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“…A very limited number of studies involving or ganic clathrates is available in literature, in comparison to common gas hydrates. For example, the precise molecular structure of the simple CO 2 HQ clathrate was reported only recently by Torré et al [22] showing that much remains to be done even at the fundamental level to increase our understanding of such compounds. The stoichiometry of the HQ clathrate (β HQ) is 3:1 (i.e.…”

Section: Introductionmentioning

confidence: 99%

Hydroquinone clathrate based gas separation (HCBGS): Application to the CO2/CH4 gas mixture

Coupan

Dicharry

Torré

2018

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Hydroquinone (HQ) clathrates have recently been identified as promising candidates for selective gas capture and storage processes. This study evaluates the effectiveness of HQ clathrates in the separation of CO 2 from CO 2 / CH 4 gas mixtures, through direct gas/solid reactions in a fixed-bed reactor. The influence of the process operating parameters (i.e. reaction time, pressure, temperature and feed gas composition) on the CO 2 capture kinetics, selectivity towards CO 2 , and transient storage capacity were investigated. The experiments were performed using either pure HQ or HQ-based composite materials, with temperatures ranging from about 283 to 343 K, pressures from 3.0 to 9.0 MPa, and CO 2 mole fraction in the gas mixture ranging from 0.2 to 1. The experimental results show that over the range of gas composition investigated, the enclathration reaction is selective to CO 2. This preferential CO 2 capture is enhanced at high CO 2 mole fractions, low temperatures and high pressures. Regarding gas capture kinetics, it was confirmed that the composite material is much more efficient than pure HQ crystals. The CO 2 enclathration rate increases with temperature, pressure and CO 2 fraction in the feed gas. For the first time, the feasibility of such gas separation techniques using HQ clathrates was demonstrated at bench scale.

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CO₂–Hydroquinone Clathrate: Synthesis, Purification, Characterization and Crystal Structure

Cited by 30 publications

References 49 publications

New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity

New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity

Insights into the Crystal Structure and Clathration Selectivity of Organic Clathrates Formed with Hydroquinone and (CO₂ + CH₄) Gas Mixtures

Hydroquinone clathrate based gas separation (HCBGS): Application to the CO2/CH4 gas mixture

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CO2–Hydroquinone Clathrate: Synthesis, Purification, Characterization and Crystal Structure

Cited by 30 publications

References 49 publications

New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity

New Insights on Gas Hydroquinone Clathrates Using in Situ Raman Spectroscopy: Formation/Dissociation Mechanisms, Kinetics, and Capture Selectivity

Insights into the Crystal Structure and Clathration Selectivity of Organic Clathrates Formed with Hydroquinone and (CO2 + CH4) Gas Mixtures

Hydroquinone clathrate based gas separation (HCBGS): Application to the CO2/CH4 gas mixture

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CO₂–Hydroquinone Clathrate: Synthesis, Purification, Characterization and Crystal Structure

Insights into the Crystal Structure and Clathration Selectivity of Organic Clathrates Formed with Hydroquinone and (CO₂ + CH₄) Gas Mixtures