Adsorption-induced deformation in porous materials is the structural change due to specific interactions between adsorbents and adsorbates. For many systems, this effect can be neglected because the ...variation in pore volume is practically zero. This fact allowed the hypothesis of a rigid structure of pores that led to many adsorption models for zeolites, carbonaceous, and silicate materials. However, for many new porous materials, such as MOFs and PAFs, the effects of these deformations are significant for multicomponent adsorption, heat determination, and process separation. As a consequence, these adsorption-induced deformations need to be well described. In this context, the classical density functional theory models (cDFT) are an excellent tool to describe inhomogeneous fluids and predict adsorption in micro or mesoporous. Here, we calculate the adsorption stress exerted on the cavity surface by adsorbed molecules by applying the classical density functional theory for nitrogen and hydrocarbons. Unlike the literature that uses the Rosenfeld FMT for the residual free energy term for the hard-sphere contribution and a mean-field term for the dispersive forces, we extend the approach to more complex hydrocarbons and their mixtures using PC-SAFT classical density functional theory to predict the stresses in the pores induced by fluid adsorption to describe how these stresses affect the material.
Hydrotreating stands as a critical facet in oil refining to meet stringent environmental norms, facilitating the production of ultra-low sulfur fuels. This study delves into the concurrent ...hydrodesulfurization of DBT and 4,6-DMDBT utilizing a NiMoP/Al2O3 catalyst. Through 27 experiments, parameters such as temperature, pressure, concentrations, and WHSV were scrutinized to derive kinetic insights. Employing five power law (PL) models, encompassing both global and individual HDS variations, parameter estimation employed weighted least squares optimization techniques like particle swarm and Gauss-Newton methods. Rigorous statistical analyses underlined model performance nuances. While the ‘global HDS of 4,6-DMDBT’ model met the chi-squared test, the ‘global HDS of DBT’ revealed complexities beyond PL modeling. Notably, the negative hydrogenation order for DBT implied significant adsorption effects. Apparent activation energies, approximately 117 kJ mol−1 for DBT and 124 kJ mol−1 for 4,6-DMDBT, were discerned using global models.
•Deep hydrodesulfurization of DBT and 4,6-DMDBT was evaluated in fixed-bed reactor.•Estimation and statistical evaluation of kinetic parameters were performed.•A power-law model considering individual DBT routes fits the experimental data well.•The reparameterization technique and Arrhenius equation optimization reduced parametric correlation.
