Search

In this work, Co-promoted MoS2 catalysts supported on Al-modified mesoporous silica (HMS and SBA-16) have been prepared by the decomposition of ammonium tetrathiomolybdate and cobalt nitrate precursors in a H2S/H2 gas mixture. The effects of the support morphology and Al incorporation method (one-pot synthesis vs. support's grafting) on the catalyst activity were investigated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) conducted in a high-pressure batch reactor at 350 °C and total H2 pressure of 3.3 MPa. The physical and chemical characterization of the oxide precursors and spent catalysts was studied by a variety of several techniques (N2 adsorption–desorption, XRD, SEM, EDS, 27Al MAS NMR, Raman, TG/DTA and DRS UV–vis). The MoS2 phase of all catalysts exhibits similar size (about 2.8 nm) and stacking layers (4). Activity tests showed that CoAT/HMS-Al was most active and selective toward direct desulfurization (DDS) reaction pathway among the catalysts studied. Its catalytic response was similar to that of CoMo/γ-Al2O3 catalyst activated by reductive sulfiding. A linear correlation was found between DBT conversion at a reaction time of 5 h and the specific surface area and mean pore diameter of the catalysts. The best DBT HDS activity showed CoAT/HMS-Al catalyst having the best textural properties among the catalysts studied. Modification of SBA-16 with Al3+ ions by the one-step synthesis method rendered the catalyst more active in the HDS reaction than its modification by grafting. [ABSTRACT FROM AUTHOR]

In this work, novel trimetallic catalysts based on transition metal sulphides (Ru, Mo and Ni) supported on SBA-15 were synthesized. Citric acid (CA) was used as chelating agent in order to enhance the dispersion of the active phase and minimize the metal-support interaction. Sulfided catalysts were evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) at 320 °C and 54.5 atm of total H2 pressure. The effects of different Ru/(Ni + Mo) atomic ratios on the active phase were studied. The catalysts were characterized using Micro-Raman spectroscopy, DRIFTS, XRD, XPS, HR-TEM and SEM techniques. Results have shown that there was a better dispersion of the metallic phases, which improves the physicochemical properties of the catalysts, increasing the catalytic activity. The trimetallic RuxMoNi catalyst with the lowest atomic ratio, have shown superior catalytic activity compared to their higher atomic ratio counterparts. The interaction of the chelating agent improved the catalytic activity, which was superior to that observed for NiMo based catalysts, considered one of the most active hydrotreating catalysts. [ABSTRACT FROM AUTHOR]

Abstract: This research compares the hydrodesulphurization (HDS) activity of supported Co(Ni)-Mo-W ternary catalysts with respect to the nature of the support (hexagonal mesoporous silica (HMS) versus SBA-16 material having cage-like mesoporous structure), the type of promoter (Co vs. Ni) and the nature of Al species formed after support modification with Al. Both Al-HMS and Al-SBA-16 mesoporous silica substrates were prepared by the one-pot sol–gel synthesis method via the neutral templating pathway using dodecylamine and Pluronic F127 as surfactants, respectively. The oxide precursors were characterized by a variety of techniques (N2 adsorption–desorption isotherms, XRD, DRS UV–vis spectroscopy and 27Al NMR), whereas sulphided catalysts were characterized by XPS and HRTEM, and tested in the HDS of DBT conducted in a high-pressure batch reactor at T =350°C and P =3.1MPa. The activity results revealed that NiMoW/Al-HMS catalyst was more active than all Co-promoted catalysts (including a commercial CoMo/Al2O3 catalyst). The HDS activity was found to be markedly influenced by the textural properties of support and the dispersion of the active phases on the catalyst surface. It has been hypothesised that the presence of extraframework AlNO3 phases on the surface of CoMoW/Al-SBA16 compromises its HDS activity because of the formation of a less active “onion-type” Mo(W)S2 structure. [Copyright &y& Elsevier]

Abstract: Phosphate-loaded mesoporous SBA-15 and SBA-16 materials were used as supports of novel ternary Co-Mo-W hydrodesulfurization catalysts. The effects of support morphology (SBA-15 against SBA-16) and its modification with variable amounts of phosphorus were studied. The sulfided catalysts were tested in a reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT) at 350°C and 3.1MPa of total H2 pressure. The calcined, fresh sulfided and spent catalysts were characterized by a variety of techniques (N2 adsorption–desorption isotherms, XRD, TPR, TPD-NH3, DRS UV–vis, micro-Raman spectroscopy, XPS, HRTEM and TPO/TGA). Regardless of the support, it was found that the presence of phosphorous inhibited the HDS activity, and the catalytic response of both SBA-15- and SBA-16-based systems did not depend on the support morphology. In terms of the reaction rate constants (k), both CoMoW/SBA-15 and CoMoW/SBA-16 catalysts were more active than a CoMo/Al2O3 commercial catalyst containing a small amount of phosphorous in its formulation. In general, the spent CoMoW/(x)P-SBA-16 catalysts showed a lower coke formation than their SBA-15-based counterparts because the phosphate incorporation to the SBA-16 material led to decrease in coke formation in the final catalysts, as opposite to the behavior of SBA-15-based counterparts. [Copyright &y& Elsevier]

NiMoS/TiMg and NiWS/TiMg nanocatalysts were synthesized, characterized by various techniques and tested in the hydrodesulphurization (HDS) of dibenzothiophene (DBT). TiMg mixed oxides containing 5, 10 or 15 wt% of MgO were prepared by sol–gel and then used as catalyst supports. A constant atomic ratio of Ni/(Ni + M) = 0.5 was kept for all the catalysts (M = Mo or W). The catalysts were first prepared by sequential-wet impregnation. Then, after an ex-situ sulfidation process, they were characterized by high resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and physisorption of N2 following the BET method. The presence of MgO in the NiMoS/TiMg and NiWS/TiMg catalysts resulted in an enhancement in the HDS activity of DBT. In addition, their HDS activities were higher than those observed in the NiMoS/Ti and NiWS/Ti catalysts. Furthermore, higher HDS activity was found for the NiMoS/TiMg compared with their NiWS/TiMg catalysts counterpart. [ABSTRACT FROM AUTHOR]

This article is focused on the problem of the inhibition of the hydrodeoxygenation (HDO) reaction by competitive adsorption of the S-containing compounds on the active sites. The phosphorous effect during co-processing of pyrolysis bio-oils and S-content model compounds over sulfide NiMo/P/HMS-Al catalysts was investigated. A series of NiMo catalysts supported on mesoporous P (x) /HMS-Al materials were prepared and characterized by several techniques. Guaiacol (GUA) was considered as a pyrolysis bio-oils model compound, while the dibenzothiophene (DBT) was used as a model molecule of S-content. The activity test revealed that support modification with 1.1 wt% of P (NM-P1.1) decreased the inhibition of HDO reaction by co-adsorption of DBT on the active sites. With the most active NM-P1.1 catalyst, the formation of a less susceptible to coke formation product (phenol) was favored. The main superiority of sulfided NM-P1.1 catalyst comes from the support decoration with P 2 O 5 nanoparticles leading to its highest Brønsted acidity, the surface enrichment with metal sulfide species as well as with the diminishing of Al leaching from the framework of support during the HDO reaction. The activity tests demonstrated that support modification with phosphorous is an efficient method to solve the problem of the HDS inhibition by the HDO reaction. Unlabelled Image • The NiMoP/HMS-Al 1.1 wt% of P loaded exhibited the best HDO activity and stability during simultaneous HDO and HDS reactions • P loaded is effective method for diminishing the inhibition of HDO reaction by co-adsorption of S-containing compound • Surface P 2 O 5 nanoparticles decoration is effective for lowering Al leaching from the support framework during HDO reaction [ABSTRACT FROM AUTHOR]

A group of hydrodesulfurization (HDS) catalysts, based on transition metal sulfides (Co-Mo-W) and supported on mechanically-mixed mesoporous silicas (SBA-15 and SBA-16), have been synthesized and characterized by physicochemical methods (DRS-UV–vis, Micro Raman spectroscopy, XRD, SEM, HRTEM, EDS and catalytic activity). It has been demonstrated that the use of a mixture of silicas with two different porous structures has an advantage with respect to the use of the SBA-15 and SBA-16 separately for the preparation of supported catalysts for hydrodesulfurization reactions of refractory sulfur compounds, such as dibenzothiophene. This is because the presence of different porous structures has a positive effect over the diffusion processes of the precursors of the active phases on the support, and the whole result is a higher catalytic activity for the HDS reactions of dibenzothiophene, even more than that of the commercial catalyst used as a comparative model; this activity is also related with the stage of the synthesis process in which the mixture is done. [ABSTRACT FROM AUTHOR]

A series of trimetallic Ni–Mo–W catalysts supported on cubic mesoporous silica (SBA-16) modified with Ti were prepared with the aim to study the effect of Ti incorporation method (sol-gel against pore volume post-synthesis impregnation) on the physical and chemical properties of the synthetized materials. The catalytic behavior of the sulfided catalysts was evaluated in the reaction of hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalyst characterization by variety of techniques demonstrated that one-pot synthesis led to Ti ions incorporation into SBA-16 structure and an increase of acidity whereas the post-synthesis method led to formation of octahedral Ti species decorating support's surface. The catalytic behavior was closely linked with the characteristics of their oxide precursors. The catalysts prepared by sol-gel method demonstrated to be more effective toward S-removal from DBT than the catalyst modified by post-synthesis method. The initial HDS activity of the best NiMoW/S16–Ti catalyst doubled that of NiMoW/SBA-16 and a commercial NiMo/γ-Al 2 O 3 which was linked with its better textural properties, acidity and adequate active phases dispersion. The main effect of the support modification with Ti was the enhancement of selectivity toward HYD route products. The best hydrogenation selectivity was archived by Ti incorporation via post-synthesis method which was linked to the formation of curved Mo(W)S 2 layers having a large amount of "brim" HYD sites. Image 1 • HDS activity of NiMoW catalysts was enhanced by Ti incorporation into SBA-16 framework. • The post-synthesis support's decoration with TiO 2 enhanced HYD selectivity. • The bent Mo(W)S 2 layers are formed around of TiO 2 nanoparticles. [ABSTRACT FROM AUTHOR]