Synthesis and Characterization of NiMo Catalysts Supported on Fine Carbon Particles for Hydrotreating: Effects of Metal Loadings in Catalyst Formulation

The by-products collected during the synthesis of carbon nanohorns via the arc discharge synthesis method is comprised of other carbon particles (OCP). At a hydrotreating operating temperature of 370°C, preliminary investigations using a bimetallic catalyst with support originating from the fine fractions of other carbon particles (OCPf) and containing 13 wt% Mo and 2.5 wt% Ni resulted in an HDS and HDN conversion of 78 and 25%, respectively. Variation of metal compositions in catalyst formulation and its impact on hydrotreating activity was therefore considered in this study to enhance the hydrotreating activity of OCPf–supported catalyst, and to determine if the best NiMo/OCPf catalyst achieved from this study could be a viable catalyst for hydrotreating applications. The co-incipient wetness impregnation was used in preparing series of hydrotreating catalysts with Ni and Mo loadings within the range of (2.5–5.0 wt%) and (13–26 wt%) respectively. Overall, the catalyst samples with maximum Ni loading of 5.0 wt% and Mo loadings of either 13 or 19 wt% showed higher dispersion and the ability to form a Type II Ni-Mo-S phase with enhanced activity. The effects of metal compositions on both HDS and HDN activities were correlated with their physicochemical properties.

Hydrodesulfurization of 4,6-Dimethyldibenzothiophene and the Diesel Oil Fraction on NiMo Catalysts Supported over Proton-Exchanged AlMCM-41 and TiMCM-41 Extrudates

NiMo catalysts supported on mesoporous MCM-41 type materials shaped with binder were tested for activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene (4,6-DMDBT) and the diesel fuel fraction (0.92 wt% of sulfur). The aim of the investigation was to evaluate the effect of ion exchange with protons of Al- or Ti-substituted MCM-41 mesoporous supports. The subjected catalytic systems were NiMo/HAlMCM-41 and NiMo/HTiMCM-41, and for comparison purposes NiMo/AlMCM-41 and NiMo/TiMCM-41. The samples were characterized by N2 sorption (at 77 K), XRD, TEM, XPS, SEM and Py–IR. It was found that the functionalization of AlMCM-41 and TiMCM-41 with protons increased the conversion of 4,6-DMDBT and the pseudo-first-order rate constant. Correspondingly, 4,6-DMDBT HDS reactions over the NiMo/HTiMCM-41 catalyst proceeded to a similar extent via hydrogenation and direct desulfurization, whereas over the NiMo/HAlMCM-41 they proceeded mainly via direct desulfurization. Furthermore, the ion-exchanged catalysts displayed two-fold higher efficiency in direct desulfurization than their non-modified counterparts. The NiMo/HTiMCM-41 catalyst exhibited the highest catalytic efficiency in the HDS of 4,6-DMDBT and the diesel oil fraction. The high activity of the NiMo/HTiMCM-41 catalyst is mainly attributed to its appropriate acidity, as well as the metal–support interaction providing both the high dispersion of the active phase and the desirable multilayered stacking morphology of the active phase slabs.

Effect of Different Catalyst Supports on the Quality, Yield and Morphology of Carbon Nanotubes Produced from Waste Polypropylene Plastics

The role of the effect of the support on the reactivity of heterogeneous catalysts cannot be over-emphasized. Therefore, the study documented in this article investigated the effect of different metal oxide supports (MgO, CaO and TiO2) and mixed oxide supports (CaTiO3) on the performance of a bimetallic NiMo catalyst prepared via the sol–gel method during the catalytic growth of carbon nanotubes (CNTs) from waste polypropylene (PP). Waste PP was pyrolyzed at 700 °C in a single-stage chemical vapor deposition reactor and off-gas was utilized in-situ as a cheap carbon feedstock for the growth of CNTs under similar conditions for all the prepared NiMo catalysts (supported and unsupported). The structures of the prepared catalysts and deposited carbon were extensively characterized using X-ray diffraction (XRD), temperature-programmed reduction (TPR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), etc. The catalytic performance of NiMo supported and unsupported catalysts was evaluated in terms of the yield, purity, and morphology of synthesized CNTs. The results revealed that the stabilizing role of supports is fundamental in preventing nanoparticle agglomeration and aggregation, thereby resulting in improved yield and quality of CNTs. Supported NiMo catalysts produced better aligned graphitic and high-quality CNTs. The NiMo/CaTiO3 catalyst produced the highest carbon of 40.0%, while unsupported NiMo produced low-quality CNTs with the lowest carbon yield of 18.4%. Therefore, the type of catalyst support and overall stability of catalytic materials play significant roles in the yield and quality of CNTs produced from waste PP.

Catalytic Conversion of Lignin in an Isopropanol/formic Acid Medium With Nimo Catalyst Promoted by W Species

Background: Large amounts of enzymatic hydrolysis lignin (EHL) are generated with the production of cellulosic bioethanol. Efficient degradation and upgrading of EHL is significant for the sustainable and stable development of energy supply.Results: In this study, hydrodeoxygenation (HDO) of EHL to biofuels was carried out promoted by the in situ hydrogen donor produced from the decomposition of formic acid over NiMo catalysts. Results showed that active sites (derived from the support SiO2, W, and NiMo species) had remarkable effect on lignin conversion, and the highest oil yield (57.2 wt%) was gained over NiMo/W-SiO2 catalyst. Conclusions: The product evolution demonstrated that active metal sites (derived from NiMo species) favored hydrogenolysis and deoxygenation via leading in situ hydrogen to attack C-O-C bonds, while acid sites (derived from the support) adsorbed and activated chemical bonds in lignin, resulting in the linkage cleavage caused by the heating program. The obtained bio-oil was rich in alkyl guaiacols (6.7 wt%), containing stable chemical properties and high quality.

Efficient depolymerization of lignins to alkylphenols using phosphided NiMo catalysts

Greening up the chemical industry by using waste biomass streams as feed is a topic of high relevance. Residual lignins from for example the pulp and paper industry and second-generation...

Synthesis of Ni-Modified ZSM-5 Zeolites and Their Catalytic Performance in n-Octane Hydroconversion

Ni-modified ZSM-5 zeolites with different nickel contents were successfully prepared by the in situ synthesis method and the impregnation method. The synthesized samples were characterized by XRD, SEM, N2 adsorption–desorption isothermals, and Py-FTIR. The characterization results show that both the textural properties and crystallization of Ni-modified ZSM-5 zeolites were preserved well, and their acidic properties can be modulated after nickel modification. The corresponding NiMo catalysts supported on Ni-modified ZSM-5 zeolites were prepared by the incipient wetness co-impregnation method, and their catalytic performances were evaluated in n-octane hydroconversion. Compared to the those modified by the in situ synthesis method, ZSM-5 zeolite-supported catalysts modified by the impregnation method exhibit higher stability and higher isomerization selectivity. This is due to the synergistic effect between Brønsted acid sites and Lewis acid sites on the Ni-modified ZSM-5 zeolites, especially for the NiMo/1Ni-Z5 catalyst.