scholarly journals Raman Spectroscopic Study on a CO2-CH4-N2 Mixed-Gas Hydrate System

2021 ◽  
Vol 9 ◽  
Author(s):  
Liu Chuanhai ◽  
Chen Ran ◽  
Zhang Baoyong ◽  
Wu Qiang ◽  
Zhang Qiang ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Gas Separation ◽  
Gas Hydrate ◽  
Raman Band ◽  
Accurate Determination ◽  
Type I ◽  
Mixed Gas ◽  
Large Cage ◽  
Guest Molecules ◽  
Band Area

Accurate determination of the characteristics of coal mine gas separation products is the key for gas separation applications based on hydrate technology. Gas hydrates are synthesized from gases with two types of compositions (CO2-CH4-N2). The separation products were analyzed by in situ Raman spectroscopy. The crystal structure of the mixed-gas hydrate was determined, and the cage occupancy and hydration index were calculated based on the various vibrational modes of the molecules according to the “loose cage-tight cage” model and the Raman band area ratio combined with the van der Waals-Platteeuw model. The results show that the two mixed-gas hydrate samples both have a type I structure. Large cages of mixed-gas hydrate are mostly occupied by guest molecules, with large cage occupancies of 98.57 and 98.52%; however, small cages are not easy to occupy, with small cage occupancies of 29.93 and 33.87%. The average cage occupancies of these two hydrates are 81.41 and 82.36%, and the stability of the crystal structure of the mixed-gas hydrate in the presence of 75% CO2 is better than that of the mixed-gas hydrate in the presence of 70% CO2. The hydration indices of the two hydrate gas samples are 7.14 and 6.98, which are greater than the theoretical value of structure l.

scholarly journals Exploiting weak supramolecular interactions to assemble organic cage materials

2014 ◽  
Vol 70 (a1) ◽  
pp. C632-C632
Author(s):  
Samantha Chong ◽  
Tom Hasell ◽  
Jamie Culshaw ◽  
Marc Little ◽  
Marc Schmidtmann ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Gas Separation ◽  
Crystal Engineering ◽  
Weak Interactions ◽  
Bulk Material ◽  
Gain Control ◽  
Supramolecular Assembly ◽  
Supramolecular Interactions ◽  
Guest Molecules ◽  
Supramolecular Motifs

Intensive research into microporous materials has been driven by potential applications in areas such as catalysis, gas separation, storage, and sensing. Recently, a new class of purely organic molecular cage materials has emerged, which can exhibit significant porosity arising from the internal molecular cavity as well as extrinsic porosity from packing in the crystal structure [1]. Unlike extended frameworks, porous molecular materials lack strongly directional interactions to drive their assembly, complicating the crystal engineering possible for isoreticular metal-organic frameworks [2], for example. Our work has focused on covalent imine-linked cages, which exhibit diverse crystal chemistry. The connectivity of the pore network is derived from the cage packing: Therefore, the crystal structure directly affects the observed porosity. The imine cages synthesised so far lack strongly hydrogen bonding groups. Thus, the solid state supramolecular assembly of cage molecules is governed by the aggregate of weak interactions, such as van der Waals forces. By identifying robust `tectons', that is, regularly occurring supramolecular motifs, progress toward designing the crystal structure and therefore controlling the physical properties of organic cage materials becomes possible. Here, we report exploiting robust supramolecular motifs, comprising either cage modules or host and guest molecules to gain control over the porosity of the bulk material. We demonstrate how formation of a desired void network topology can be driven by hosting a specific guest in preferred sites which maximise weak host-guest interactions [3]. Subsequent guest removal can produce stable polymorphs, one of which exhibited double the Brunauer-Emmett-Teller surface area with respect to the originally observed polymorph. We also examine how the interaction between gas phase guests and cage host is important in the application of porous organic cages in rare gas separation.

scholarly journals Hydrogen Inter-Cage Hopping and Cage Occupancies inside Hydrogen Hydrate: Molecular-Dynamics Analysis

2020 ◽  
Vol 11 (1) ◽  
pp. 282
Author(s):  
Yogeshwaran Krishnan ◽  
Mohammad Reza Ghaani ◽  
Arnaud Desmedt ◽  
Niall J. English
Keyword(s):  
Molecular Dynamics ◽  
Energy Barrier ◽  
Guest Molecule ◽  
Arrhenius Equation ◽  
Dynamics Simulation ◽  
Type Ii ◽  
Large Cage ◽  
Guest Molecules ◽  
Simulation Time ◽  
Average Occupancy

The inter-cage hopping in a type II clathrate hydrate with different numbers of H2 and D2 molecules, from 1 to 4 molecules per large cage, was studied using a classical molecular dynamics simulation at temperatures of 80 to 240 K. We present the results for the diffusion of these guest molecules (H2 or D2) at all of the different occupations and temperatures, and we also calculated the activation energy as the energy barrier for the diffusion using the Arrhenius equation. The average occupancy number over the simulation time showed that the structures with double and triple large-cage H2 occupancy appeared to be the most stable, while the small cages remained with only one guest molecule. A Markov model was also calculated based on the number of transitions between the different cage types.

scholarly journals Integration of Stable Ionic Liquid-Based Nanofluids into Polymer Membranes. Part II: Gas Separation Properties toward Fluorinated Greenhouse Gases

Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 582
Author(s):  
Fernando Pardo ◽  
Sergio V. Gutiérrez-Hernández ◽  
Carolina Hermida-Merino ◽  
João M. M. Araújo ◽  
Manuel M. Piñeiro ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Gas Separation ◽  
Value Added ◽  
Gas Permeation ◽  
Mixed Matrix Membranes ◽  
Separation Performance ◽  
Mixed Gas ◽  
Neat Polymer ◽  
Stable Suspension ◽  
Base Polymer

Membrane technology can play a very influential role in the separation of the constituents of HFC refrigerant gas mixtures, which usually exhibit azeotropic or near-azeotropic behavior, with the goal of promoting the reuse of value-added compounds in the manufacture of new low-global warming potential (GWP) refrigerant mixtures that abide by the current F-gases regulations. In this context, the selective recovery of difluorometane (R32, GWP = 677) from the commercial blend R410A (GWP = 1924), an equimass mixture of R32 and pentafluoroethane (R125, GWP = 3170), is sought. To that end, this work explores for the first time the separation performance of novel mixed-matrix membranes (MMMs) functionalized with ioNanofluids (IoNFs) consisting in a stable suspension of exfoliated graphene nanoplatelets (xGnP) into a fluorinated ionic liquid (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate ([C2C1py][C4F9SO3]). The results show that the presence of IoNF in the MMMs significantly enhances gas permeation, yet at the expense of slightly decreasing the selectivity of the base polymer. The best results were obtained with the MMM containing 40 wt% IoNF, which led to an improved permeability of the gas of interest (PR32 = 496 barrer) with respect to that of the neat polymer (PR32 = 279 barrer) with a mixed-gas separation factor of 3.0 at the highest feed R410A pressure tested. Overall, the newly fabricated IoNF-MMMs allowed the separation of the near-azeotropic R410A mixture to recover the low-GWP R32 gas, which is of great interest for the circular economy of the refrigeration sector.

scholarly journals A Molecular Simulation Study of Silica/Polysulfone Mixed Matrix Membrane for Mixed Gas Separation

Polymers ◽  
2021 ◽  
Vol 13 (13) ◽  
pp. 2199
Author(s):  
Khadija Asif ◽  
Serene Sow Mun Lock ◽  
Syed Ali Ammar Taqvi ◽  
Norwahyu Jusoh ◽  
Chung Loong Yiin ◽  
...  
Keyword(s):  
Transport Properties ◽  
Molecular Simulation ◽  
Gas Separation ◽  
Membrane Separation ◽  
Gas Transport ◽  
Mixed Matrix ◽  
Mixed Gas ◽  
Gas Transport Properties ◽  
Simulation Results ◽  
Mixed Gases

Polysulfone-based mixed matrix membranes (MMMs) incorporated with silica nanoparticles are a new generation material under ongoing research and development for gas separation. However, the attributes of a better-performing MMM cannot be precisely studied under experimental conditions. Thus, it requires an atomistic scale study to elucidate the separation performance of silica/polysulfone MMMs. As most of the research work and empirical models for gas transport properties have been limited to pure gas, a computational framework for molecular simulation is required to study the mixed gas transport properties in silica/polysulfone MMMs to reflect real membrane separation. In this work, Monte Carlo (MC) and molecular dynamics (MD) simulations were employed to study the solubility and diffusivity of CO2/CH4 with varying gas concentrations (i.e., 30% CO2/CH4, 50% CO2/CH4, and 70% CO2/CH4) and silica content (i.e., 15–30 wt.%). The accuracy of the simulated structures was validated with published literature, followed by the study of the gas transport properties at 308.15 K and 1 atm. Simulation results concluded an increase in the free volume with an increasing weight percentage of silica. It was also found that pure gas consistently exhibited higher gas transport properties when compared to mixed gas conditions. The results also showed a competitive gas transport performance for mixed gases, which is more apparent when CO2 increases. In this context, an increment in the permeation was observed for mixed gas with increasing gas concentrations (i.e., 70% CO2/CH4 > 50% CO2/CH4 > 30% CO2/CH4). The diffusivity, solubility, and permeability of the mixed gases were consistently increasing until 25 wt.%, followed by a decrease for 30 wt.% of silica. An empirical model based on a parallel resistance approach was developed by incorporating mathematical formulations for solubility and permeability. The model results were compared with simulation results to quantify the effect of mixed gas transport, which showed an 18% and 15% percentage error for the permeability and solubility, respectively, in comparison to the simulation data. This study provides a basis for future understanding of MMMs using molecular simulations and modeling techniques for mixed gas conditions that demonstrate real membrane separation.

scholarly journals Raman Sensor for the Determination of Gas Solubility

Physchem ◽  
2021 ◽  
Vol 1 (2) ◽  
pp. 176-188
Author(s):  
Gregor Lipinski ◽  
Markus Richter
Keyword(s):  
Carbon Dioxide ◽  
Gas Separation ◽  
Accurate Determination ◽  
Measurement Techniques ◽  
Screening Tools ◽  
Measuring System ◽  
Separation Processes ◽  
Use Of Resources ◽  
Gas Solubilities

Efficient and environmentally responsible use of resources requires the development and optimization of gas separation processes. A promising approach is the use of liquids that are designed for specific tasks, e.g., the capture of carbon dioxide or other greenhouse gases. This requires an accurate determination of gas solubilities for a broad range of temperatures and pressures. However, state of the art measurement techniques are often very time consuming or exhibit other pitfalls that prevent their use as efficient screening tools. Here, we show that the application of Raman spectroscopy through a compact measuring system can simplify data acquisition for the determination of gas solubilities in liquids. To demonstrate that this approach is expedient, we determined gas solubilities of carbon dioxide in water for three isotherms T = (288.15, 293.15, 298.15) K over a pressure range from p = (0.5–5) MPa and in three imidazolium-based ionic liquids for one isotherm T = 298.15 K at pressures from p = (0.1–5) MPa. When compared to data in the literature, all results are within the reported uncertainties of the measurement techniques involved. The developed analysis method eliminates the need for a lengthy volume or mass calibration of the sample prior to the measurements and, therefore, allows for fast screening of samples, which can help to advance gas separation processes in scientific and industrial applications.

Crystal structure of magnesium chromium vanadate Mg2CrV3O11, a member of the A2BV3O11 vanadate family

2007 ◽  
Vol 22 (3) ◽  
pp. 246-252 ◽  
Author(s):  
A. Worsztynowicz ◽  
S. M. Kaczmarek ◽  
W. Paszkowicz ◽  
R. Minikayev
Keyword(s):  
Crystal Structure ◽  
Rietveld Method ◽  
Ion Pairs ◽  
Exchange Constant ◽  
Type I ◽  
Type Ii ◽  
Paramagnetic Resonance ◽  
Interatomic Distances ◽  
Electron Paramagnetic ◽  
Full Occupancy

The crystal structure of recently discovered chromium (III) dimagnesium trivanadate (V) Mg2CrV3O11 was refined using the Rietveld method. The crystal system of Mg2CrV3O11 is triclinic with space group P1− (Mg1.7Zn0.3GaV3O11 type) and lattice parameters a=6.4057(1) Å, b=6.8111(1) Å, c=10.0640(2) Å, α=97.523(1)°, β=103.351(1)°, γ=101.750(1)°, and Z=2. The characteristic feature of compounds in the A2BV3O11 (A=Mg, Zn and B=Ga, Fe, Cr) family is a strong tendency to share the octahedral M(1) and M(2) sites by both divalent A and trivalent B atoms, and the bipyramidal M(3) sites occupied by divalent A ions. In the present refinement, the only constraint assuming full occupancy of the M(1), M(2), and M(3) sites leads to the following Cr/(Cr+Mg) ratios: 0.70(2) at M(1), 0.24(2) at M(2), and 0.03(2) at M(3). These occupancies are discussed and compared to those of isotypic compounds. The values of interatomic distances are found to be comparable with those reported by R. D. Shannon in 1976. Electron paramagnetic resonance has been also analyzed. Two absorption lines with g≈2.0 (type I) and g≈1.98 (type II) have been recorded in the EPR spectra, and attributed to V4+ ions and Cr3+–Cr3+ ion pairs, respectively. The exchange constant J between Cr3+ ions has been calculated.

Synthesis, Crystal Structure, and Physical Properties of the Type-I Clathrate Ba8−δNix□ySi46–x–y

2012 ◽  
Vol 51 (8) ◽  
pp. 4730-4741 ◽  
Author(s):  
U. Aydemir ◽  
C. Candolfi ◽  
A. Ormeci ◽  
H. Borrmann ◽  
U. Burkhardt ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Physical Properties ◽  
Type I

Xenon recovery from natural gas by hybrid method based on gas hydrate crystallisation and membrane gas separation

2021 ◽  
Vol 86 ◽  
pp. 103740
Author(s):  
Maria S. Sergeeva ◽  
Nikita A. Mokhnachev ◽  
Dmitry N. Shablykin ◽  
Andrey V. Vorotyntsev ◽  
Dmitriy M. Zarubin ◽  
...  
Keyword(s):  
Natural Gas ◽  
Gas Separation ◽  
Hybrid Method ◽  
Gas Hydrate ◽  
Membrane Gas Separation

Disorder-Induced Low-Frequency Raman Band Observed in Deposited MoS2 Films

1994 ◽  
Vol 48 (6) ◽  
pp. 733-736 ◽  
Author(s):  
N. T. McDevitt ◽  
J. S. Zabinski ◽  
M. S. Donley ◽  
J. E. Bultman
Keyword(s):  
Crystal Structure ◽  
Thin Films ◽  
Raman Band ◽  
Low Frequency ◽  
Pulsed Laser ◽  
Laser Deposition ◽  
First Order ◽  
Order Spectrum ◽  
History Of ◽  
Frequency Feature

Crystalline disorder in thin films plays an important role in determining their properties. Disorder in the crystal structure of MoS2 films prepared by magnetron sputtering and pulsed laser deposition was evaluated with the use of Raman spectroscopy. The peak positions and bandwidths of the first-order Raman bands, in the region 100 to 500 cm−1, were used as a measure of crystalline order. In addition, a low-frequency feature was observed at 223 cm−1 that is not part of the normal first-order spectrum of a fully crystalline specimen. Data presented here demonstrate that this band is characteristic of crystalline disorder, and its intensity depends on the annealing history of the film. This behavior seems to be analogous to the disorder found in graphite thin films.

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