Search Results (11)

Clathrate hydrates of carbon dioxide represent a subject of considerable interest in both fundamental science and the development of promising technologies. The phase behavior of CO₂ hydrate in the presence of concentrated aqueous solutions remains poorly understood. In this study, we conducted a comprehensive investigation into the impact of magnesium chloride (0–24 mass%) and methanol (0–40 mass%) on the thermodynamic stability of CO₂ hydrate. New experimental data on the three-phase gas–aqueous solution–gas hydrate equilibrium in the temperature range 243–283 K and pressure range 1–4.5 MPa were obtained. A correlation is proposed for the precise representation of equilibrium pressure–temperature lines. A comparison of the anti-hydrate effect, as indicated by the parameter ∆T_h, of these substances demonstrated that ionic MgCl₂ exhibits a stronger thermodynamic inhibitory effect on CO₂ hydrate formation than nonionic MeOH. The results of measuring the melting point of ice at 0.1 MPa for aqueous solutions of MgCl₂ and MeOH confirmed the thermodynamic consistency of the hydrate equilibrium data. A detailed comparison of the anti-hydrate effect of MgCl₂ and MeOH in a wide concentration range was performed on hydrates of different gases (CO₂ and CH₄). The phase composition of CO₂ hydrate samples obtained from water and aqueous solutions of MgCl₂ and MeOH was examined using powder X-ray diffraction (PXRD) at 133 K. The PXRD results indicate the formation of sI CO₂ hydrate with a cell parameter of 11.86 ± 0.04 Å in all cases. Full article

This paper investigates the different relaxation channels of a single symmetric top NH₃ and a spherical top CH₄ molecule trapped at low temperature in a clathrate hydrate nano-cage in the infrared absorption domain of their vibrational degrees of freedom. The approach utilizes the Born–Oppenheimer approximation and the extended site inclusion model applied to CO₂ in a previous work, which was based on pairwise atom–atom effective interaction potentials. The calculations show that trapping the methane or ammonia molecule is energetically more favorable in a type sI clathrate structure than in an sII one, and entropic considerations show that methane can be released much more easily than ammonia from clathrate hydrate nano-cages. In the small (s) and large (l) nano-cages with the sI structure, the CH₄ molecule exhibits a more or less perturbed rotational motion, while the NH₃ molecule shows a strongly hindered orientational motion that tends to a three-dimension librational motion (oscillation motion) around its orientational equilibrium configuration. The calculated orientational energy level schemes are quite different from those of the molecular free rotation. In the static field inside the cage, degenerate ${\nu }_3$ and ${\nu }_4$ vibrational modes of methane and ammonia molecules are shifted and split. Moreover, for ammonia molecules, the ${\nu }_1$ and ${\nu }_2$ modes are shifted, and the inversion motion is no longer allowed. The non-radiative and radiative relaxation channels of CH₄, NH₃ and CO₂ in clathrate nano-cages are discussed with reference to the matrix isolation spectroscopic results. Upon laser excitation, then, from the energy levels calculated for the different degrees of freedom, NH₃ and CO₂ are expected to fluoresce, while for CH₄, non-radiative relaxation should lead to evaporation at the surface of clathrates. Experimental setups are suggested to localize and study these species underneath ice surfaces on distant planets or planetesimals from mobile detectors such as drones or CubeSats equipped with appropriate laser sources and telescopes with 2D imaging detectors. Full article

Carbon dioxide (CO₂) clathrate hydrate is gaining attention as a promising material for cold thermal energy storage (CTES) due to its high energy storage capacity and low environmental footprint. It shows strong potential in building applications, where space cooling accounts for nearly 40% of total energy use and over 85% of electricity demand in developed countries. CO₂ hydrates are also being explored for use in refrigeration, cold chain logistics, supercomputing, biomedical cooling, and defense systems. With the growing number of applications in mind, this review focuses on the thermal behavior of CO₂ hydrates and their environmental impact. It highlights recent efforts to reduce formation pressure and temperature using chemical promoters and surfactants. This paper also reviews key experimental techniques used to study hydrate properties, including Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), high-pressure differential scanning calorimetry (HP-DSC), and the T-history method. In lifecycle comparisons, CO₂ hydrate systems show better energy efficiency and lower carbon emissions than traditional ice or other phase-change materials (PCMs). This review also discusses current commercialization challenges such as high energy input during formation and promoter toxicity. Finally, practical strategies to move CO₂ hydrate-based CTES from lab-scale studies to real-world cooling and temperature control applications are discussed. Full article

Clathrate hydrate-based technologies are considered promising and sustainable alternatives for the effective management of the climate change risks related to emissions of carbon dioxide produced by human activities. This work presents a combined experimental and computational investigation of the effects of the operational procedures and characteristics of the experimental configuration, on the phase diagrams of CO₂-H₂O systems and CO₂ hydrates’ formation, growth and dissociation conditions. The operational modes involved (i) the incremental (step-wise) temperature cycling and (ii) the continuous temperature cycling processes, in the framework of an isochoric pressure search method. Also, two different high-pressure PVT configurations were used, of which one encompassed a stirred tank reactor and the other incorporated an autoclave of constant volume with magnetic agitation. The experimental results implied a dependence of the subcooling degree, (P, T) conditions for hydrate formation and dissociation, and thermal stability of the hydrate phase on the applied temperature cycling mode and the technical features of the utilized PVT configuration. The experimental findings were complemented by a thermodynamic simulation model and other calculation approaches, with the aim to resolve the phase diagrams including the CO₂ dissolution over the entire range of the applied (P, T) conditions. Full article

A countermeasure to global warming is removing high CO₂ amounts from the atmosphere and locating the emitted CO₂ into long-term stable carbon storage sites. The sequestration technologies must be reliable, long-lasting, and environmentally friendly. An alternative and innovative approach that may meet the sequestration requirements is CO₂ storage as clathrate hydrates in marine environments. Extensive research has been devoted to CO₂-CH₄ replacement in natural gas hydrates. Another option is the direct formation of CO₂ hydrates into deep ocean water or into marine underfloor sediments. This article deals with the positioning of direct hydrate-based CO₂ storage among the other traditional geological options and the discussion of new, by-far, state-of-the-art knowledge required for the development of a hydrate-based CO₂ storage pathway that is reliable, stable, durable, efficient, and environmentally benign. Full article

Natural gas is considered a helpful transition fuel in order to reduce the greenhouse gas emissions of other conventional power plants burning coal or liquid fossil fuels. Natural Gas Hydrates (NGHs) constitute the largest reservoir of natural gas in the world. Methane contained within the crystalline structure can be replaced by carbon dioxide to enhance gas recovery from hydrates. This technical review presents a techno-economic analysis of the full pathway, which begins with the capture of CO₂ from power and process industries and ends with its transportation to a geological sequestration site consisting of clathrate hydrates. Since extracted methane is still rich in CO₂, on-site separation is required. Focus is thus placed on membrane-based gas separation technologies widely used for gas purification and CO₂ removal from raw natural gas and exhaust gas. Nevertheless, the other carbon capture processes (i.e., oxy-fuel combustion, pre-combustion and post-combustion) are briefly discussed and their carbon capture costs are compared with membrane separation technology. Since a large-scale Carbon Capture and Storage (CCS) facility requires CO₂ transportation and storage infrastructure, a technical, cost and safety assessment of CO₂ transportation over long distances is carried out. Finally, this paper provides an overview of the storage solutions developed around the world, principally studying the geological NGH formation for CO₂ sinks. Full article

Clathrate formation and guest behaviors in hydroquinone (HQ) clathrates were investigated for the first time using ternary (CO + CO₂ + H₂) gas mixtures. Two gas compositions (low and high CO₂ concentrations) were used to simulate synthesis gases generated from various sources. After reaction at 2.0, 4.0, and 6.0 MPa, the conversion yield of pure HQ to the clathrate form reached >90% if the CO₂ partial pressure was 0.7 MPa or higher. In addition, CO₂ was the most abundant occupant, whereas CO was only detectable at higher CO concentrations and experimental pressures. The separation efficiency values expressed as molar ratios of CO₂ to CO in the solid clathrate form were found to be 12.7 and 23.9 MPa at 4.0 and 6.0 MPa, respectively. The experimental and the calculated results in this study provide information useful for the design of a clathrate-based separation process for synthesis gases from various sources (i.e., synthesis gases with various compositions). Full article

Treatment of water saturated with CO₂ with low-temperature, low-pressure glow plasma of low-frequency (GP) produced a series of liquids. Their temperature and intensity of thermal effects non-linearly depended on the treatment time. However, the Raman spectra patterns of the treated water pointed to a specific structure of the water treated for 30 min. The spectra of control, non-treated water saturated with CO₂, and such water treated for 15, 60, 90, and 120 min showed that their macrostructure was built mainly by a single donor, and single hydrogen bonded arrangements accompanied, to a certain extent, with free water molecules. The macrostructure of the water treated for 30 min consisted chiefly of tetrahedral and deformed tetrahedral structural units. That water contained long-living free radicals of discussed structure, stabilized in such macrostructure. Full article

Water is a key resource for sustainable development and plays a crucial role in human development. Desalination is one of the most promising technologies to mitigate the emerging water crisis. Thermal desalination and reverse osmosis are two of the most widely employed desalination technologies in the world. However, these technologies are energy intensive. Clathrate-hydrate-based desalination (HyDesal) is a potential energy-efficient desalination technology to strengthen the energy–water nexus. In our previous study, we proposed a ColdEn-HyDesal process utilizing waste Liquefied Natural Gas (LNG) cold energy based on a fixed-bed reactor configuration. In this study, we evaluated the effect of 10% propane in three different gas mixtures, namely, nitrogen (G1), argon (G2), and carbon dioxide (G3), as hydrate formers for the HyDesal process. The achieved water recovery was very low (~2%) in the presence of NaCl in the solution for gas mixtures G1 and G2. However, high water recovery and faster kinetics were achieved with the G3 mixture. To improve the water recovery and kinetics of hydrate formation for the G2 gas mixture, the effect of sodium dodecyl sulfate (SDS) was evaluated. The addition of SDS did improve the kinetics and water recovery significantly. Full article

Clathrate hydrates are ice-like systems in which nanometric water cages encapsulate guest molecules. Functionalizing clathrate hydrates is an important issue, accomplished by playing with their chemical composition and their cage structure. In this issue, the cage occupancy and its kinetics constitute key information for future developments. In many aspects, nitrogen gas hydrate represents an interesting system not only for its applied relevance (e.g., gas separation and methane/carbon dioxide exchange), but also for its fundamental interest (e.g., structural metastability and kinetics). Thanks to the complementarity of neutron diffraction and Raman scattering, the vibrational signatures of the so-called SI and SII clathrate structures of the nitrogen hydrates are reviewed. Moreover, the investigation of the ageing of the SII structure is reported together with its interpretation in the frame of the Langmuir behavior of the cage filling at low temperature. The cage filling is monitored with the help of a time-dependent analysis of the Raman scattering signals (over several months). The SII large cage filling decreases with a kinetic rate of $5.9\pm 3.3\times {10}^{-3}$ h⁻¹ at 77 K and atmospheric pressure, so that equilibrium is reached after ca. eight weeks. Isotherm measurements of the guest Raman signatures lead to revealing a Langmuir constant higher in the small cage than in the large cage at 150 K. Such a behavior might thus be correlated with the nitrogen depletion with time, observed in the large cage of the SII nitrogen hydrate. Full article

This paper analyzes the structural, energetic and mechanical properties of carbon dioxide hydrate clathrates calculated using finite cluster and periodic ab initio density-functional theory methodologies. Intermolecular interactions are described by the exchange-hole dipole moment method. The stability, gas saturation energetics, guest–host interactions, cage deformations, vibrational frequencies, and equation of state parameters for the low-pressure sI cubic phase of the CO₂@H₂O clathrate hydrate are presented. Our results reveal that: (i) the gas saturation process energetically favors complete filling; (ii) carbon dioxide molecules prefer to occupy the larger of the two cages in the sI structure; (iii) blue shifts occur in both the symmetric and antisymmetric stretching frequencies of CO₂ upon encapsulation; and (iv) free rotation of guest molecules is restricted to a plane parallel to the hexagonal faces of the large cages. In addition, we calculate the librational frequency of the hindered rotation of the guest molecule in the plane perpendicular to the hexagonal faces. Our calculated spectroscopic data can be used as signatures for the detection of clathrate hydrates in planetary environments. Full article