Molecule-based Kinetic Modeling of Residue Desulfurization

摘要

A molecule-based kinetic model simulating main reaction behavior in residue desulfurization (RDS) was developed based on detailed composition data of heavy oils obtained from Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). In this study, a kinetic modeling approach was applied to quantitatively demonstrate the reaction pathways of heavy oils based on the structural attributes (cores, side chains and bridges) of heavy oils. Reaction behavior of cores, an important factor for RDS, was analyzed using the structure/composition data of cores during RDS as obtained from FT-ICR-MS. From the analysis, 1233 types of cores were selected as main reaction species, and a reaction network of the cores is proposed consisting of 2107 reaction pathways (hydrosulfurization/hydrodenitrogenation/aromatic-ring saturation). Activation energies of the reaction pathways of the cores were estimated from both the standard enthalpy of reaction in the cores and the quantitative structure reactivity relationship (QSRR). The side chains and bridges of heavy oils were also modeled, and a molecule based kinetic model was developed for RDS reaction simulation. In addition, the relationship between catalyst activities and physical properties was investigated by comparison of the kinetic models constructed for two types of catalysts.