Low-Hydrophilic HKUST-1/Polymer Extrudates for the PSA Separation of CO2/CH4.

HKUST-1 is an MOF adsorbent industrially produced in powder form and thus requires a post-shaping process for use as an adsorbent in fixed-bed separation processes. HKUST-1 is also sensitive to moisture, which degrades its crystalline structure. In this work, HKUST-1, in the form of crystalline powder, was extruded into pellets using a hydrophobic polymeric binder to improve its moisture stability. Thermoplastic polyurethane (TPU) was used for that purpose. The subsequent HKUST-1/TPU extrudate was then compared to HKUST-1/PLA extrudates synthesized with more hydrophilic polymer: polylactic acid (PLA), as the binder. The characterization of the composites was determined via XRD, TGA, SEM-EDS, and an N2 adsorption isotherm analysis. Meanwhile, the gas-separation performances of HKUST-1/TPU were investigated and compared with HKUST-1/PLA from measurements of CO2 and CH4 isotherms at three different temperatures, up to 10 bars. Lastly, the moisture stability of the composite materials was investigated via an aging analysis during storage under humid conditions. It is shown that HKUST-1's crystalline structure was preserved in the HKUST-1/TPU extrudates. The composites also exhibited good thermal stability under 523 K, whilst their textural properties were not significantly modified compared with the pristine HKUST-1. Furthermore, both extrudates exhibited larger CO2 and CH4 adsorption capacities in comparison to the pristine HKUST-1. After three months of storage under atmospheric humid conditions, CO2 adsorption capacities were reduced to only 10% for HKUST-1/TPU, whereas reductions of about 25% and 54% were observed for HKUST-1/PLA and the pristine HKUST-1, respectively. This study demonstrates the interest in shaping MOF powders by extrusion using a hydrophobic thermoplastic binder to operate adsorbents with enhanced moisture stability in gas-separation columns.

Thermodynamic data of adsorption reveal the entry of CH4 and CO2 in a smectite clay interlayer.

The ability of smectite clays to incorporate gases in their interlayers is shown to be conditioned by interlayer spacing, depending, in turn, on phyllosilicate layer composition and effective size of the charge-balancing cations. As illustrated by earlier in situ X-ray diffraction and spectroscopic characterization of the gas/clay interface, most smectites with small-size charge-balancing cations, such as Na+ or Ca2+, accommodate CO2 and CH4 in their interlayers only in a partially hydrated state resulting in the opening of the basal spacing, above a certain critical value. In the present study CH4 and CO2 adsorption isotherms were measured for Na- and Mg-exchanged montmorillonite up to 9 MPa using a manometric technique. The process of dehydration of these clays was thoroughly characterized by thermogravimetric analysis and powder X-ray diffraction. A dramatic decrease in specific surface area and methane and carbon dioxide adsorption capacities for fully dehydrated samples in comparison to partially dehydrated ones is assigned to the shrinkage of interlayer spacing resulting in its inaccessibility for the entry of CH4 and CO2 molecules. This observation is direct evidence of CH4 and CO2 adsorption capacity variation depending on the opening of smectite clay interlayer spacing.

Optimization of Washing Processes in Solvothermal Synthesis of Nickel-Based MOF-74.

Solvothermal synthesis is the most preferable preparation technique of metal-organic frameworks (MOFs) that consists of reactants mixing, ultrasonication, solvothermal reaction, product washing, and solvent evacuation. Owing to fast reaction kinetics in solvothermal reaction, this technique allows for production of uniform MOF particles with high crystallinity, high phase purity, and small particle sizes. However, it exhibits some difficulties of washing processes that may involve the blockage of pores due to incomplete removal of reactive medium from MOF products. The present study proposes an improvement of washing processes by introducing centrifugal separations with optimized parameters at two different stages: after reaction and after product washing. Nickel­based MOF­74 was synthesized as the experimental material for this purpose. The quality of the produced sample was evaluated by gas adsorption performance using CO2 at 1 bar and 25 °C. The final sample of the optimized synthesis routes was able to adsorb 5.80 mmol/g of CO2 uptake, which was competitive with literature data and significantly higher than the sample of the basic synthesis. Fourier­transform infrared spectroscopy (FTIR) and powder X­ray diffraction (PXRD) analysis revealed that the sample displayed much higher crystallinity structure and was clean from impurities after centrifugations. The outcome indicated the success of separation between MOF products and reactive medium during washing processes, leading to the effective pore activation of MOFs.

Smectite fraction assessment in complex natural clay rocks from interlayer water content determined by thermogravimetric and thermoporometry analysis.

The smectite content is a key parameter to be determined for various applications of clays and clay-rich rocks. The quantity of interlayer water characteristic of swelling domains can be used to assess the smectite content in clays. We propose in this study to use a simple approach to determine water distribution in clays (mainly between pores and interlayers) by means of thermoporometry and thermogravimetric analysis. Provided the interlayer water does not freeze at low temperature upon thermoporometry experiments, the difference between water quantities determined by the two techniques is assigned to interlayer water. Single-phase model clays and complex natural clay rocks and their composites in water-saturated state are characterized by this approach. The open question is the application of available thermoporometry models developed for simple pore geometry to characterize the complex pore network of clays. Depending on the approach used, different pore sizes were obtained highlighting the limit of a simplified model to describe the complex porous network. The results are more coherent when quantifying the amount of interlayer water, further used for smectite content estimation. Good agreement was obtained between smectite fraction contents deduced from the results of thermal analysis and those measured by conventional mineralogical techniques.