An Efficient Strategy for Electroreduction Reactor Outlet Fractioning into Valuable Products.

In this work, two industrial dual-step pressure swing adsorption (PSA) processes were designed and simulated to obtain high-purity methane, CO2, and syngas from a gas effluent of a CO2 electroreduction reactor using different design configurations. Among the set of zeolites that was investigated using Monte Carlo and molecular dynamics simulations, NaX and MFI were the ones selected. The dual-PSA process for case study 1 is only capable of achieving a 90.5% methane purity with a 95.2% recovery. As for case study 2, methane is obtained with a 97.5% purity and 95.3% recovery. Both case studies can produce CO2 with high purity and recovery (>97 and 95%, respectively) and syngas with a H2/CO ratio above 4. Although case study 2 allows methane to be used as domestic gas, a much higher value for its energy consumption is observed compared to case study 1 (64.9 vs 29.8 W h molCH4-1).

Metaheuristic Framework for Material Screening and Operating Optimization of Adsorption-Based Heat Pumps.

The current methods applied to material screening for adsorption-based heat pumps are based on a fixed set of temperatures or their independent variation, providing a limited, insufficient, and unpractical evaluation of different adsorbents. This work proposes a novel strategy for the simultaneous optimization and material screening in the design of adsorption heat pumps by implementing a meta-heuristic approach, particle swarm optimization (PSO). The proposed framework can effectively evaluate variable and broad operation temperature intervals to search for viable zones of operation for multiple adsorbents at once. The criteria for selecting the adequate material were the maximum performance and the minimum heat supply cost, which were considered the objective functions of the PSO algorithm. First, the performance was assessed individually, followed by a single-objective approximation of the multi-objective problem. Next, a multi-objective approach was also adopted. With the results generated during the optimization, it was possible to find which adsorbents and temperature sets were the most suitable according to the main objective of the operation. The Fisher-Snedecor test was applied to expand the results obtained during PSO application and a feasible operating region built around the optima, enabling the arrangement of close-to-optima data into practical design and control tools. This approach allowed for a fast and intuitive evaluation of multiple design and operation variables.

Bovine serum albumin and myoglobin separation by size exclusion SMB.

The separation of the proteins Bovine Serum Albumin (BSA) and Myoglobin (Mb) was achieved by Size-Exclusion Simulated Moving Bed (SE-SMB) and performed experimentally in the FlexSMB® unit, an SMB unit designed and built in the Laboratory of Separation and Reaction Engineering. Before accomplishing the separation experiments in the mentioned unit, separation regions were computed by simulation based on a phenomenological mathematical model to determine appropriate operating conditions. The developed model was validated in advance, against fixed-bed dynamic adsorption experimental results, for pure component and binary mixtures. Then the SMB experiments were carried out, and purities of the Mb on the extract and BSA on the raffinate streams were 98% and 96%, respectively. The achieved recoveries were 80% of Mb on the extract and 94% of BSA on the raffinate. Lastly, productivities of 6.4 gprotein⋅lads-1⋅day-1 for the extract and 28.8 gprotein⋅lads-1⋅day-1 for the raffinate were obtained.

Separation of tartronic and glyceric acids by simulated moving bed chromatography.

The SMB unit developed by the Laboratory of Separation and Reaction Engineering (FlexSMB-LSRE®) was used to perform tartronic acid (TTA) and glyceric acid (GCA) separation and to validate the mathematical model in order to determine the optimum operating parameters of an industrial unit. The purity of the raffinate and extract streams in the experiments performed were 80% and 100%, respectively. The TTA and GCA productivities were 79 and 115 kg per liter of adsorbent per day, respectively and only 0.50 cubic meters of desorbent were required per kilogram of products. Under the optimum operating conditions, which were determined through an extensive simulation study based on the mathematical model developed to predict the performance of a real SMB unit, it was possible to achieve a productivity of 86 kg of TTA and 176 kg of GCA per cubic meter of adsorbent per day (considering the typical commercial purity value of 97% for both compounds) with an eluent consumption of 0.30 cubic meters per kilogram of products.

Gas-phase simulated moving bed: Propane/propylene separation on 13X zeolite.

In the last years several studies were carried out in order to separate gas mixtures by SMB technology; however, this technology has never been implemented on an industrial scale. In the present work, a gas phase SMB bench unit was built and tested for the separation of propane and propylene mixtures, using 13X zeolite extrudates as adsorbent and isobutane as desorbent. Three experiments were performed to separate propane/propylene by gas phase SMB in the bench scale unit with a 4-2-2 configuration, i.e., open loop circuit by suppressing section IV (desorbent regeneration followed by a recycle). Consequently, all the experiments were conducted using an external supply of pure isobutane as desorbent. Parameters such as switching time, extract and raffinate stream flow rates were changed to improve the efficiency of the process. Experimental results have shown that it is feasible to separate propylene from propane by gas phase SMB at a bench scale and that this process is a potential candidate to replace the conventional technologies for the propane/propylene separation. The performance parameters obtained are very promising for future development of this technology, since propylene was obtained in the extract stream with a purity of 99.93%, a recovery of 99.51%, and a productivity of [Formula: see text] . Propane was obtained in the raffinate stream with a purity of 98.10%, a recovery of 99.73% and a productivity of [Formula: see text] . The success of the above mentioned bench scale tests is a big step for the future implementation of this technology in a larger scale.

Sieving di-branched from mono-branched and linear alkanes using ZIF-8: experimental proof and theoretical explanation.

We study the adsorption equilibrium isotherms and differential heats of adsorption of hexane isomers on the zeolitic imidazolate framework ZIF-8. The studies are carried out at 373 K using a manometric set-up combined with a micro-calorimeter. We see that the Langmuir model describes well the isotherms for all four isomers (n-hexane, 2-methylpentane, 2,2-dimethylbutane and 2,3-dimethylbutane). The linear and mono-branched isomers adsorb well, but 2,2-dimethylbutane is totally excluded. Plotting the differential heat of adsorption against the loading shows an initial plateau for n-hexane and 2-methylpentane. This is followed by a slow rise, indicating adsorbate-adsorbate interactions. For the di-branched isomers the differential heat of adsorption decreases with loading. To gain further insight, we ran molecular simulations using the grand-canonical Monte Carlo approach. Comparing the simulation and the experimental results shows that the ZIF framework model requires blocking of the cages, since 2,2-dimethylbutane cannot fit through the sodalite-type windows. Practically speaking, this means that ZIF-8 is a highly promising candidate for enhancing gasoline octane numbers at 373 K, as it can separate 2,2-dimethylbutane and 2,3-dimethylbutane from 2-methylpentane. Our results prove the potential of ZIF-8 as a new adsorbent that can be employed in the upgrade of the Total Isomerization Process for the production of high octane number gasoline, by blending di-branched alkanes in the gasoline.

Reverse shape selectivity in the liquid-phase adsorption of xylene isomers in zirconium terephthalate MOF UiO-66.

Powder, agglomerates, and tablets of the microporous zirconium(IV) terephthalate metal-organic framework UiO-66 were evaluated for the selective adsorption and separation of xylene isomers in the liquid phase using n-heptane as the eluent. Pulse experiments, performed at 313 K in the presence of n-heptane, revealed the o-xylene preference of this material, which was further confirmed by binary and multicomponent breakthrough experiments in the presence of m- and p-xylene, resulting in selectivities at 313 K of 1.8 and 2.4 with regards to m-xylene and p-xylene, respectively. Additionally, because p-xylene is the less retained isomer, UiO-66 presents a selectivity pattern that is reverse of that of the xylenes' molecular dimension with respect to shape selectivity. The shaping of the material as tablets did not significantly change its selectivity toward the o-xylene isomer or toward p-xylene, which was the less retained isomer, despite a loss in capacity. Finally, the selectivity behavior of UiO-66 in the liquid n-heptane phase makes it a suitable material for o-xylene separation in the extract (heavy product) or p-xylene separation in the raffinate (light product) by simulated moving bed technology.

Toward understanding the influence of ethylbenzene in p-xylene selectivity of the porous titanium amino terephthalate MIL-125(Ti): adsorption equilibrium and separation of xylene isomers.

The potential of the porous crystalline titanium dicarboxylate MIL-125(Ti) in powder form was studied for the separation in liquid phase of xylene isomers and ethylbenzene (MIL stands for Materials from Institut Lavoisier). We report here a detailed experimental study consisting of binary and multi-component adsorption equilibrium of xylene isomers in MIL-125(Ti) powder at low (≤0.8 M) and bulk (≥0.8 M) concentrations. A series of multi-component breakthrough experiments was first performed using n-heptane as the eluent at 313 K, and the obtained selectivities were compared, followed by binary breakthrough experiments to determine the adsorption isotherms at 313 K, using n-heptane as the eluent. MIL-125(Ti) is a para-selective material suitable at low concentrations to separate p-xylene from the other xylene isomers. Pulse experiments indicate a separation factor of 1.3 for p-xylene over o-xylene and m-xylene, while breakthrough experiments using a diluted ternary mixture lead to selectivity values of 1.5 and 1.6 for p-xylene over m-xylene and o-xylene, respectively. Introduction of ethylbenzene in the mixture results however in a decrease of the selectivity.

Inline monitoring of butane isomers adsorption on MFI using near-infrared spectroscopy: drift correction in time based experiments.

Near-infrared (NIR) spectroscopy is used to monitor online a large variety of processes. Hydrocarbons with their strong NIR spectral signature are good candidate analytes. For this work, the sorption data are measured in a manometric setup coupled with online NIR spectroscopy, to monitor the bulk composition. The assessment of time based results faces a baseline stability problem. The goal of this article is to study the robustness of different spectral preprocessing methods when dealing with time based data. In this study, it was found that for time based experiments it is necessary to perform drift correction on the spectra combined with a water band correction. For the calibration experiments, which only last few seconds, offset correction and drift correction performed equally well.