Deep Oxidative Desulfurization of Planar Compounds Over Functionalized Metal-Organic Framework UiO-66(Zr): An Optimization Study.

This study aims to determine the catalytic activity and stability of ligand-modified UiO-66 with different functional groups (-NO2, -OH) in deep oxidative desulfurization from a model fuel (MF). The planar sulfur compounds included dibenzothiophene (DBT), 2-methylbenzothiazole (2-MB), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in n-dodecane as the fuel phase. The synthesized functionalized metal-organic framework (MOF) samples were characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FTIR), proton nuclear magnetic resonance (1H NMR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), nitrogen adsorption-desorption analysis, and microwave plasma-atomic emission spectrometer (MP-AES). The experiment assessment and desulfurization reaction optimization were carried out by the central composite design methodology. Response surface methodology and analysis of variance were employed to evaluate the individual process factors, their interactions, and sulfur removal responses. The responses showed that the oxidation of the planar compounds declined following the sequence DBT > 2-MB ≫ 4,6-DMDBT for all the MOFs. The findings revealed that at 66.7 °C, 3.0 equiv of oxidative agent over sulfur and 9.7 of MOF over sulfur by weight achieved the highest removal efficiency of 98.68% DBT, 93.23% 2-MB, and 69.32% 4,6-DMDBT for UiO-66-NO2 as a catalyst from the model fuel. It was also observed that UiO-66-NO2 had a higher efficiency in deep oxidative desulfurization when compared to other UiO-66-based catalysts used in the current study. Under optimal conditions, all the MOFs showed acceptable catalytic activity and reusability after four runs, although gradual loss of activity was observed.

Process Optimization for Catalytic Oxidation of Dibenzothiophene over UiO-66-NH2 by Using a Response Surface Methodology.

This research investigates the catalytic performance of a metal-organic framework (MOF) with a functionalized ligand-UiO-66-NH2-in the oxidative desulfurization of dibenzothiophene (DBT) in n-dodecane as a model fuel mixture (MFM). The solvothermally prepared catalyst was characterized by XRD, FTIR, 1H NMR, SEM, TGA, and MP-AES analyses. A response surface methodology was employed for the experiment design and variable optimization using central composite design (CCD). The effects of reaction conditions on DBT removal efficiency, including temperature (X 1), oxidant agent over sulfur (O/S) mass ratio (X 2), and catalyst over sulfur (C/S) mass ratio (X 3), were assessed. Optimal process conditions for sulfur removal were obtained when the temperature, O/S mass ratio, and C/S mass ratio were 72.6 °C, 1.62 mg/mg, and 12.1 mg/mg, respectively. Under these conditions, 89.7% of DBT was removed from the reaction mixture with a composite desirability score of 0.938. From the results, the temperature has the most significant effect on the oxidative desulfurization reaction. The model F values gave evidence that the quadratic model was well-fitted. The reusability of the MOF catalyst in the ODS reaction was tested and demonstrated a gradual loss of activity over four runs.

Co-Pyrolysis of Estonian Oil Shale with Polymer Wastes.

Recycling of polymeric wastes is important for both energy recovery and raw material processing. In light of the EU Green Deal, the oil shale industry is looking for new opportunities to use its production potential. As an intermediate stage, the co-pyrolysis of oil shale with waste plastic and tires will be considered acceptable. The article presents the kinetics of pyrolysis of Estonian oil shale, the main polymer components of municipal waste, and their mixtures with oil shale by the thermogravimetric analysis method. The influence of each component separately on the process of sample weight loss during co-pyrolysis was also studied. It is shown that when plastics are added to oil shale, the experimental and calculated data coincide according to the principle of the additive contribution of each component. Kinetic parameters were calculated according to the Coats-Redfern integral method and show that during the co-pyrolysis of mixtures of oil shale with polymer wastes, the value of the activation energy increases in comparison with the pyrolysis of oil shale. Based on the experimental data, it was determined that there is a manifestation of a synergistic effect in the form of an increase in the yield of liquid products during the co-pyrolysis of oil shale and polymer wastes.