Hamdy Farag

Assessment of limitations and potentials for improvement in deep desulfurization through detailed kinetic analysis of mechanistic pathways

Abstract Utilizing an improved method for the assignment of the rate constants to the complicated network of reaction pathways in the hydrodesulfurization (HDS) of polyaromatic sulfur compounds (PASCs), new understanding has been obtained concerning the intrinsic limitations to achieving the new distillate fuels standards. Establishing the relative rates for hydrogenation of the parent sulfur compound and its desulfurized products, and considering thermodynamic limitations on hydrogenated intermediates are critical to these improved kinetics. With this new approach, it has been possible to more accurately assess the differences in performance of different catalysts such as Co–MoSx/Al2O3, Ni–MoSx/Al2O3 and analogous catalysts supported on carbons, the basic causes of selectivity change with temperature, and the mechanistic consequences of inhibitors on the HDS product distributions. Ni promoted catalysts were found to possess much higher hydrogenation activities than comparable Co promoted catalysts. Carbon supported catalysts appear to have potential for HDS at high temperatures. Inhibition by H2S affects both hydrogenation and direct sulfur extraction HDS routes, but, secondary hydrogenation of desulfurized aromatic products was found to be the most sensitive to inhibition. Naphthalene inhibits all hydrogenation reactions but has little effect on direct HDS.

A comparative kinetic study on ultra-deep hydrodesulfurization of pre-treated gas oil over nanosized MoS2, CoMo-sulfide, and commercial CoMo/Al2O3 catalysts

Unsupported nanosized MoS(2) and CoMo-sulfide catalysts were synthesized, and their catalytic performances for the deep hydrodesulfurization (HDS) of treated gas oil were investigated as compared with that of a CoMo/Al(2)O(3) catalyst. The HDS reactions were carried out in a batch autoclave reactor at 340 °C and 3 MPa H(2). The CoMo-sulfide catalyst shows the highest activity and can reduce the sulfur content to less than 10 ppm. The decrease in total sulfur content as a function of reaction time was found to follow pseudo-second order kinetics (empirical form). The change in the concentration of some individual representative sulfur-containing species in gas oil as a function of time was found to follow pseudo-first-order kinetics. However, the change in combined concentration of these species in the gas oil during HDS with the reaction time was found to corroborate pseudo-second-order kinetics. A kinetic model approach was proposed from which an estimation of the intrinsic kinetic data can be achieved. The model fitted the obtained data reasonably well, suggesting its potential for better assessment of the catalytic activity in the HDS of real feedstock. The study reveals that ranking of catalyst activities using model refractory sulfur-containing compounds does not necessarily imply a typical rank in case of investigating the real feedstocks.

Textural characterizations and catalytic properties of quasispherical nanosized molybdenum disulfide

Synthesis of sphere nanostructured MoS(2) is reported. Characterization of the synthesized MoS(2) was investigated by X-ray diffraction, nitrogen adsorption, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the obtained MoS(2) is composed of layers that bend to form mostly spheres, with an average diameter of approximately 180 nm. The growth in crystallinity is mainly due to the increased number of the round-stacked layers of MoS(2). The catalytic activity and selectivity of the synthesized nanostructured MoS(2) for the dibenzothiophene hydrodesulfurization were investigated. The closed-circle MoS(2) layers exhibited a high selectivity for the direct sulfur removal.

Highly Active Low Cobalt Content-Based Bulk MoS2 Hydrodesulfurization Catalysts with a Unique Impact of H2S

A series of unsupported MoS2, Co9S8, and Co-promoted MoS2 catalysts have been synthesized by tuned impregnation and successive thermal annealing methods using a continuous flow of a mixture of H2 and H2S gases. The resulting catalysts were evaluated in terms of their activity and selectivity for the hydrodesulfurization of dibenzothiophene (DBT) both in the absence and the presence of H2S. The inclusion of Co onto MoS2 affected both the hydrogenation and direct desulfurization reactions, with the latter (production of biphenyl) being magnified to a much greater degree than the former. Interestingly, low cobalt/molybdenum ratio of ca. 0.05 of the catalyst exhibited outstanding promotion efficiency in the hydrodesulfurization reaction. However, as cobalt is added, the synergy effect drastically decreased. H2S in the reaction mixture led to a remarkable step up in the product from the direct desulfurization reaction route with the most notable increases occurring for the product from the hydrogenation reaction pathway. The HDS activity of such catalysts was much higher than that of the commercial CoMo/Al2O3. The promotion by H2S was discussed.

Preparation of alkaline polymer catalyst by radiation induced grafting for transesterification of triacetin under neural network optimized conditions

ABSTRACT A simple and flexible method was used to develop new alkaline polymer catalyst through radiation induced grafting of glycidylmethacrylate (GMA) onto polyethylene/polypropylene (PE/PP) nonwoven sheet followed by amination reaction and alkalisation. The chemical structure and morphology of catalyst was evaluated by Fourier transform-infrared (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermal gravimetric analyzer (TGA). The catalyst was examined for the transesterification of triacetin/methanol mixtures in a batch mode and the obtained methyl ester was detected by GC-MS. In order to optimize the reaction parameters towards getting the higher yield, an artificial neural network (ANN) was used to develop a non-linear model correlating the four independent reaction parameters including catalyst dosage, triacetin/methanol molar ratio, reaction time and temperature. The maximum conversion obtained via the simulated annealing (SA) algorithm was 86.2% at the optimal conditions of 5.01 wt% catalyst dosage, triacetin/methanol 1:12 molar ratio, 8 h reaction time and 62.8°C temperature. Upon using these optimal conditions in the experimental reaction, the conversion of as high as 85% was achieved. These results suggest that the simply modified low cost PE/PP fibrous sheet has a potential to catalyze biodiesel production. Moreover, the combined ANN-SA modelling method is highly effective in predicting the conversion of transesterification reaction and optimizing its parameters.