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

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 CO2 from CO2/CH4 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 CO2 capture kinetics, selectivity towards CO2, 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 CO2 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 CO2. This preferential CO2 capture is enhanced at high CO2 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 CO2 enclathration rate increases with temperature, pressure and CO2 fraction in the feed gas. For the first time, the feasibility of such gas separation techniques using HQ clathrates was demonstrated at bench scale

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

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 CO2 and CH4 as guest molecules for potential use in practical applications for the separation of a CO2/CH4 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 CH4 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 CO2–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 CO2/CH4 gas mixture is put in contact with either the α-HQ or the guest-free β-HQ, the CO2 is preferentially captured. Moreover, the guest-free β-HQ can retain the CO2 quicker and more selectively

Kinetics of CO2 Capture by Hydroquinone Clathrates

Organic clathrates formed by combining hydroquinone (HQ) and CO2 could offer very interesting prospects in the near future, particularly in the field of CO2 capture and storage. However, one of the main limitations hindering the large-scale deployment of this type of clathrate-based technology is the slow enclathration kinetics. Our experiments, performed at different pressures (1.5, 3.0, and 4.5 MPa) and temperatures (298, 323, and 348 K), with HQ in different forms (HQ powder, HQ pellets, and HQ–silica composites, each different in nature and in terms of pore size and HQ content) demonstrated that (i) an increase in both pressure and temperature enhances the enclathration rate, (ii) the textural properties of HQ significantly impact kinetics, and composite materials remain the most efficient for improving HQ clathrate formation kinetics

Phase equilibrium properties of CO 2 /CH 4 mixed gas hydroquinone clathrates: Experimental data and model predictions

Hydroquinone (HQ) clathrates seem to be promising inclusion compounds for selective CO2 capture from gas mixtures. However, to date no phase equilibrium data are known in literature for mixed-gas HQ clathrates. This study presents experimental equilibrium pressures obtained within a range of 298–343 K for different CO2/CH4 gas mixtures. The clathrate composition is given for each equilibrium point. The capture selectivity is calculated from the molar composition of the CO2/CH4 gas mixture in the clathrate and in the gas phase. The results obtained reveal that CH4 molecules in the CO2/CH4 mixtures are preferentially captured at equilibrium conditions. Our experimental data are compared against numerical predictions obtained from thermodynamic modeling using the Conde’s model. Very good agreement is found between the calculated and experimental data in terms of clathrate phase equilibria

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

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 (CO2 + CH4)–HQ clathrates. Single crystals were synthesized using gas mixtures with different compositions, ranging from pure CO2 to pure CH4. 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

CO2 Capture and Storage by Hydroquinone Clathrate Formation: Thermodynamic and Kinetic Studies

Hydroquinone (HQ) can form a gas clathrate in specific pressure and temperature conditions in the presence of CO2 molecules. This study presents experimental data of clathrate phase equilibrium and storage capacity for the CO2-HQ system in the range of temperature from about 288 to 354 K. Intercalation enthalpy and entropy are determined using the obtained equilibrium data and the Langmuir adsorption model. On a kinetic point of view, CO2-HQ clathrate formation by solid/gas reaction revealed a non-negligible effect of textural parameters on enclathration rate

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

Organic clathrate compounds, particularly those formed between hydroquinone (HQ) and gases, are supramolecular entities recently highlighted as promising alternatives for applications such as gas storage and separation processes. This study provides new insights into CO2–HQ clathrate, which is a key structure in some of the proposed future applications of these compounds. We present a novel synthesis and purification of CO2–HQ clathrate monocrystals. Clathrate crystals obtained from a single synthesis and native HQ are characterized and compared using Raman/Fourier transform infrared/NMR spectroscopies, optical microscopy, and thermogravimetric analysis coupled to mass spectrometry. The molecular structure of the clathrate has been resolved by X-ray diffraction analysis, and detailed crystallographic information is presented for the first time

Experimental Determination of Phase Equilibria and Occupancies for CO2, CH4, and N2 Hydroquinone Clathrates

Hydroquinone (HQ) forms organic clathrates in the presence of various gas molecules in specific thermodynamic conditions. For some systems, clathrate phase equilibrium and occupancy data are very scarce or inexistent in literature to date. This work presents experimental results obtained for the CO2–HQ, CH4–HQ, and N2–HQ clathrates, in an extended range of temperature from about 288 to 354 K. Formation/dissociation pressures, and occupancies at the equilibrium clathrate forming conditions, were determined for these systems. Experiments showing the influence of the crystallization solvent, and the effect of the gas pressure on HQ solubility, were also presented and discussed. A good agreement is obtained between our experimental results and the already published experimental and modeling data. Our results show a clear dependency of the clathrate occupancy with temperature. The equilibrium curves obtained for CO2–HQ and CH4–HQ clathrates were found to be very close to each other. The results presented in this study, obtained in a relatively large temperature range, are new and important to the field of organic clathrates with potential impact on gas separation, energy storage, and transport

Creating innovative composite materials to enhance the kinetics of CO 2 capture by hydroquinone clathrates

This study addresses both the preparation of a reactive medium composed of porous particles impregnated with hydroquinone (HQ), an organic compound capable of forming gas clathrates, and an evaluation of the kinetic performance of these composite materials for CO2 capture. Two types of porous silica particles of different sizes and pore diameters were tested. The porous particles were impregnated with HQ by a dry impregnation (DI) method in a fluidized bed, and by a wet impregnation (WI) method. The impregnation effectiveness of the two methods is discussed, and the reactivity of the composite materials formed in terms of CO2 capture and storage capacity is studied experimentally. The experimental results showed that the HQ adheres well on the silica without any chemical modification of the deposit’s structure. We demonstrated that the impregnation technique plays a very important role in the kinetics of CO2 capture. A series of experiments performed using a magnetic suspension balance at 3.0 MPa and 323 K showed that the silica-based impregnated particles reversibly capture and store CO2, and that the CO2 capture kinetics are significantly enhanced compared to the results obtained with pure powdered HQ. Finally, we demonstrated that CO2 capture is faster with dry-impregnated particles

Characterization Study of CO2, CH4, and CO2/CH4 Hydroquinone Clathrates Formed by Gas–Solid Reaction

Hydroquinone (HQ) is known to form organic clathrates with some gaseous species such as CO2 and CH4. This work presents spectroscopic data, surface and internal morphologies, gas storage capacities, guest release temperatures, and structural transition temperatures for HQ clathrates obtained from pure CO2, pure CH4, and an equimolar CO2/CH4 mixture. All analyses are performed on clathrates formed by direct gas–solid reaction after 1 month’s reaction at ambient temperature conditions and under a pressure of 3.0 MPa. A collection of spectroscopic data (Raman, FT-IR, and 13C NMR) is presented, and the results confirm total conversion of the native HQ (α-HQ) into HQ clathrates (β-HQ) at the end of the reaction. Optical microscopy and SEM analyses reveal morphology changes after the enclathration reaction, such as the presence of surface asperities. Gas porosimetry measurements show that HQ clathrates and native HQ are neither micro- nor mesoporous materials. However, as highlighted by TEM analyses and X-ray tomography, α- and β-HQ contain unsuspected macroscopic voids and channels, which create a macroporosity inside the crystals that decreases due to the enclathration reaction. TGA and in situ Raman spectroscopy give the guest release temperatures as well as the structural transition temperatures from β-HQ to α-HQ. The gas storage capacity of the clathrates is also quantified by means of different types of gravimetric analyses (mass balance and TGA). After having been formed under pressure, the characterized clathrates exhibit exceptional metastability: the gases remain in the clathrate structure at ambient conditions over time scales of more than 1 month. Consequently, HQ gas clathrates display very interesting properties for gas storage and sequestration applications