New trends in modelling of breakthrough curves to remove pollutants using adsorption on advanced monoliths geometries.

This work proposes a rigorous mathematical model capable of reproducing the adsorption process in dynamic regime on advanced monoliths geometries. For this, four bed geometries with axisymmetric distribution of channels and similar solid mass were proposed. In each geometry a different distribution of channels was suggested, maintaining constant the bed dimensions of 15 cm high and 5 cm radius. The mathematical modeling includes mass and momentum transfer phenomena, and it was solved with the COMSOL Multiphysics software using mass transfer parameters published in the literature. The overall performance of the column was evaluated in terms of breakthrough (CA/CA0 = 0.1) and saturation times (CA/CA0 = 0.9). The mass and velocity distributions obtained from the proposed model show good physical consistency with what is expected in real systems. In addition, the model proved to be easy to solve given the short convergence times required (2-4 h). Modifications were made to the bed geometry to achieve a better use of the adsorbent material which reached up to 80%. The proposed bed geometries allow obtaining different mixing distributions, in such a way that inside the bed a thinning of the boundary layer is caused, thus reducing diffusive effects at the adsorbent solid-fluid interface, given dissipation rates of about 323 × 10-11 m2/s3. The bed geometry composed of intersecting rings deployed the best performance in terms of usage of the material adsorbent, and acceptable hydrodynamical behavior inside the channels (maximum fluid velocity = 35.4 × 10-5 m/s and drop pressure = 0.19 Pa). Based on these results, it was found that it is possible to reduce diffusional effects and delimit the mass transfer zone inside the monoliths, thus increasing the efficiency of adsorbent fixed beds.

Synthesis and characterization of hydrochar from industrial Capsicum annuum seeds and its application for the adsorptive removal of methylene blue from water.

Chili seeds (CS) represent one of the most abundant residues in Mexico due to the high production and consumption. In this work, CS were used as raw material for the production of low-cost adsorbents for the removal of methylene blue from water. The adsorbents were synthesized from a hydrothermal treatment (based on a surface response experiment design) and characterized texturally by assessing changes in their properties. The mass yield (%R), carbon content (%C), and the second order adsorption rate constant (k2) were derived in relation to a list of input variables (e.g., the reaction temperature, residence time, and water/biomass ratio). Accordingly, those output variables were affected most sensitively by temperature and/or residence time, while changes of the water/biomass ratio were insignificant. Besides, an increase in the reaction temperature favored the degradation of the lignocellulosic material with increases in the carbon fixation. The adsorption capacity of methylene blue (MB) by the hydrochars depended drastically on the oxygen/carbon ratio. As such, the maximum adsorption capacity value of 145 mg g-1 was attained at the initial MB concentration of ~3000 µM (optimal oxygen/carbon value of 0.43). On the other hand, the maximum partition coefficient (KD) was estimated as 2.96 µM-1 mg g-1 with the initial/equilibrium concentrations of 20.5/6.93 µM. The performance evaluation between different studies, when made in terms of KD, suggests that the tested hydrochar should be one of the best adsorbents to treat methylene blue, especially at near-real environmental conditions (e.g., below micromolar levels).

Modeling and experimental analysis of CO2 methanation reaction using Ni/CeO2 monolithic catalyst.

In this study, the effect of the cell density of monolithic catalysts was investigated and further mathematically modeled on cordierite supports used in CO2 methanation. Commercial cordierite monoliths with 200, 400, and 500 cpsi cell densities were coated by immersion into an ethanolic suspension of Ni/CeO2 active phase. SEM-EDS analysis confirmed that, owing to the low porosity of cordierite (surface area < 1 m2 g-1), the Ni/CeO2 diffusion into the walls was limited, especially in the case of low and intermediate cell density monoliths; thus, active phase was predominantly loaded onto the channels' external surface. Nevertheless, despite the larger exposed surface area in the monolith with high cell density, which would allow for better distribution and accessibility of Ni/CeO2, its higher macro-pore volume resulted in some introduction of the active phase into the walls. As a result, the catalytic evaluation showed that it was more influenced by increments in volumetric flow rates. The low cell density monolith displayed diffusional control at flow rates below 500 mL min-1. In contrast, intermediate and high cell density monoliths presented this behavior up to 300 mL min-1. These findings suggest that the interaction reactants-catalyst is considerably more affected by a forced non-uniform flow when increasing the injection rate. This condition reduced the transport of reactants and products within the catalyst channels and, in turn, increased the minimum temperature required for the reaction. Moreover, a slight diminution of selectivity to CH4 was observed and ascribed to the possible formation of hot spots that activate the reverse water-gas shift reaction. Finally, a mathematical model based on fundamental momentum and mass transfer equations coupled with the kinetics of CO2 methanation was successfully derived and solved to analyze the fluid dynamics of the monolithic support. The results showed a radial profile with maximum fluid velocity located at the center of the channel. A reactive zone close to the inlet was obtained, and maximum methane production (4.5 mol m-3) throughout the monolith was attained at 350 °C. Then, linear streamlines of the chemical species were developed along the channel.