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.

Different families of volatile organic compounds pollution control by microporous carbons in temperature swing adsorption processes.

In this research work, the three different VOCs such as acetone, dichloromethane and ethyl formate (with corresponding families like ketone, halogenated-organic, ester) are recovered by using temperature swing adsorption (TSA) process. The vapors of these selected VOCs are adsorbed on a microporous activated carbon. After adsorption step, they are regenerated under the same operating conditions by hot nitrogen regeneration. In each case of regeneration, Factorial Experimental Design (FED) tool had been used to optimize the temperature, and the superficial velocity of the nitrogen for achieving maximum regeneration efficiency (R(E)) at an optimized operating cost (OP(€)). All the experimental results of adsorption step and hot nitrogen regeneration step had been validated by the simulation model PROSIM. The average error percentage between the simulation and experiment based on the mass of adsorption of dichloromethane was 3.1%. The average error percentages between the simulations and experiments based on the mass of dichloromethane regenerated by nitrogen regeneration were 4.5%.

Global statistical predictor model for characteristic adsorption energy of organic vapors-solid interaction: use in dynamic process simulation.

Adsorption of Volatile Organic Compounds (VOCs) is one of the best remediation techniques for controlling industrial air pollution. In this paper, a quantitative predictor model for the characteristic adsorption energy (E) of the Dubinin-Radushkevich (DR) isotherm model has been established with R(2) value of 0.94. A predictor model for characteristic adsorption energy (E) has been established by using Multiple Linear Regression (MLR) analysis in a statistical package MINITAB. The experimental value of characteristic adsorption energy was computed by modeling the isotherm equilibrium data (which contain 120 isotherms involving five VOCs and eight activated carbons at 293, 313, 333, and 353 K) with the Gauss-Newton method in a statistical package R-STAT. The MLR model has been validated with the experimental equilibrium isotherm data points, and it will be implemented in the dynamic adsorption simulation model PROSIM. By implementing this model, it predicts an enormous range of 1200 isotherm equilibrium coefficients of DR model at different temperatures such as 293, 313, 333, and 353K (each isotherm has 10 equilibrium points by changing the concentration) just by a simple MLR characteristic energy model without any experiments.

Recovery comparisons--hot nitrogen Vs steam regeneration of toxic dichloromethane from activated carbon beds in oil sands process.

The regeneration experiments of dichloromethane from activated carbon bed had been carried out by both hot nitrogen and steam to evaluate the regeneration performance and the operating cost of the regeneration step. Factorial Experimental Design (FED) tool had been implemented to optimize the temperature of nitrogen and the superficial velocity of the nitrogen to achieve maximum regeneration at an optimized operating cost. All the experimental results of adsorption step, hot nitrogen and steam regeneration step had been validated by the simulation model PROSIM. The average error percentage between the simulation and experiment based on the mass of adsorption of dichloromethane was 2.6%. The average error percentages between the simulations and experiments based on the mass of dichloromethane regenerated by nitrogen regeneration and steam regeneration were 3 and 12%, respectively. From the experiments, it had been shown that both the hot nitrogen and steam regeneration had regenerated 84% of dichloromethane. But the choice of hot nitrogen or steam regeneration depends on the regeneration time, operating costs, and purity of dichloromethane regenerated. A thorough investigation had been made about the advantages and limitations of both the hot nitrogen and steam regeneration of dichloromethane.

Hazardous dichloromethane recovery in combined temperature and vacuum pressure swing adsorption process.

Organic vapors emitted from solvents used in chemical and pharmaceutical processes, or from hydrocarbon fuel storage stations at oil terminals, can be efficiently captured by adsorption onto activated carbon beds. To recover vapors after the adsorption step, two modes of regeneration were selected and could be possibly combined: thermal desorption by hot nitrogen flow and vacuum depressurization (VTSA). Because of ignition risks, the conditions in which the beds operate during the adsorption and regeneration steps need to be strictly controlled, as well as optimized to maintain good performances. In this work, the optimal conditions to be applied during the desorption step were determined from factorial experimental design (FED), and validated from the process simulation results. The regeneration performances were compared in terms of bed regeneration rate, concentration of recovered volatile organic compounds (VOC) and operating costs. As an example, this methodology was applied in case of dichloromethane. It has been shown that the combination of thermal and vacuum regeneration allows reaching 82% recovery of dichloromethane. Moreover, the vacuum desorption ended up in cooling the activated carbon bed from 93°C to 63°C and so that it significantly reduces the cooling time before starting a new cycle.

Modeling the heat and mass transfers in temperature-swing adsorption of volatile organic compounds onto activated carbons.

A theoretical model was built to simulate the adsorption of volatile organic compounds (VOCs) onto activated carbons in a fixed bed. This model was validated on a set of experimental data obtained for the adsorption of acetone, ethyl formate, and dichloromethane onto five commercial activated carbons. The influence of operating conditions was modeled with various VOC contents atthe inlet of the adsorber and superficial velocities of the gas-phase from 0.14 to 0.28 m.s(-1). Breakthrough times and maximum temperature rises were computed with a coefficient of determination of 0.988 and 0.901, respectively. The simulation was then extended to the adsorption of mixtures of VOCs. From the comparison of simulation and experimental results, the advantage of accounting for dispersions of heat and mass is shown and the importance in taking into account the temperature effect on the equilibrium data is demonstrated.