Four Ni catalysts and one Mo–Ni catalyst supported on montmorillonite were synthesized, characterized by various techniques and evaluated, under solvent-free conditions, for the production of green diesel from waste cooking oil. The optimum Ni content was found to be 20 wt.%. The addition of 2 wt.% Mo to the catalyst resulted in a considerable increase in the amount of green diesel hydrocarbons. The Mo species, moreover, led to a decrease in the (C15 + C17)/(C16 + C18) ratio, which is beneficial from the viewpoint of carbon atom economy. The promoting action of Mo was mainly attributed to the synergy between the oxygen vacancies on the surface of the well-dispersed Mo(V) and Mo(VI) oxides and the neighboring Ni0 sites. The optimum reaction conditions, for achieving a proportion of liquid product in the green diesel hydrocarbons (C15–18) equal to 96 wt.%, were found to be 350 °C, 3 g of catalyst per 100 mL of waste cooking oil and 13 h reaction time. These conditions correspond to an LHSV of 2.5 h−1, a value that is considered quite reliable from the viewpoint of industrial applications. Thus, the cheap and abundant mineral montmorillonite is proved a promising support for developing efficient Ni–Mo catalysts for green diesel production.
The efficiency of Ni/TiO2 catalysts for renewable diesel production was evaluated in the present study. Two series of catalysts were synthesized and characterized using various physicochemical techniques (N2 physisorption, XRD, SEM, XPS, H2-TPR, and NH3–TPD). In the first series of catalysts, successive dry impregnations (SDI) were used for depositing 10, 20, 30, 50, and 60 wt.% Ni. The yield towards renewable diesel is maximized over the catalyst with 50 wt.% Ni loading. Selecting this optimum loading, a second series of catalysts were synthesized via three additional preparation methods: wet impregnation (WI) and deposition–precipitation using either ammonia (DP-NH3) or urea (DP-Urea) as the precipitation agent. The catalysts’ efficiency in the production of green diesel is influenced by the preparation method following the order: DP-Urea > DP-NH3 > WI ≈ SDI. The metallic surface area and the balanced acidity mainly determine the performance of the catalysts.
Nickel-based catalysts promoted by Mo-oxo species have been proven to be quite promising for transformation of triglycerides into green diesel. The selection of the support for such catalysts is crucial. In the present study, pyrolyzed rice husk subjected to acid and/or alkaline post-treatment was studied as support for the aforementioned catalysts. Biochar produced by slow pyrolysis of raw material at 850 °C for 5 h under limited-oxygen conditions exhibited the most promising textural characteristics. These were substantially improved by alkaline post-treatment. Thus, the corresponding MoNi catalysts proved the most efficient for upgrading used cooking oil (UCO) to green diesel via a solvent-free hydrotreatment process, performed in a semi-batch reactor (at 310 °C, 40 bar, 100 mL/min H2, 100 mL UCO and 1 g of catalyst). The enhanced catalytic performance (complete conversion of UCO and 32 wt.% green diesel yield) of MoNi catalysts supported on biochar subjected at least to an alkaline post-treatment step has been attributed to their high SSA, suitable pore size distribution (enhanced mesoporosity), and acidity (enhanced population of acid sites with moderate strength), as well as to the high dispersion of the active phase.
22 December 2024 in Biomass Conversion and Biorefinery
There has been a recent increasing interest in Zn–air batteries as an alternative to Li-ion batteries. Zn–air batteries possess some significant advantages; however, there are still problems to solve, especially related to the tuning of the properties of the air–cathode which should carry an inexpensive but efficient bifunctional oxygen reduction (ORR) and oxygen evolution (OER) reaction electrocatalyst. Biochar can be an alternative, since it is a material of low cost, it exhibits electric conductivity, and it can be used as support for transition metal ions. Although there is a significant number of publications on biochars, there is a lack of data about biochar from raw biomass rich in hemicellulose, and biochar with a small number of heteroatoms, in order to report the pristine activity of the carbon phase. In this work, activated biochar has been made by using corncobs. The biomass was first dried and minced into small pieces and pyrolyzed. Then, it was mixed with KOH and pyrolyzed for a second time. The final product was characterized by various techniques and its electroactivity as a cathode was determined. Physicochemical characterization revealed that the biochar had a hierarchical pore structure, moderate surface area of 92 m2 g−1, carbon phase with a relatively low sp2/sp3 ratio close to one, and a limited amount of N and S, but a high number of oxygen groups. The graphitization was not complete while the biochar had an ordered structure and contained significant O species. This biochar was used as an electrocatalyst for ORR and OER in Zn–air batteries where it demonstrated a satisfactory performance. More specifically, it reached an open-circuit voltage of about 1.4 V, which was stable over a period of several hours, with a short-circuit current density of 142 mA cm−2 and a maximum power density of 55 mW cm−2. Charge–discharge cycling of the battery was achieved between 1.2 and 2.1 V for a constant current of 10 mA. These data show that corncob biochar demonstrated good performance as an electrocatalyst in Zn–air batteries, despite its low specific surface and low sp2/sp3 ratio, owing to its rich oxygen sites, thus showing that electrocatalysis is a complex phenomenon and can be served by biochars of various origins.
Nickel catalysts promoted with Mo and supported on silica were studied for renewable diesel production from triglyceride biomass, through the selective deoxygenation process. The catalysts were prepared by wet co-impregnation of the SiO2 with different Ni/(Ni + Mo) atomic ratios (0/0.84/0.91/0.95/0.98/1) and a total metal content equal to 50%. They were characterized by XRD, XPS, N2 physisorption, H2-TPR, and NH3-TPD. Evaluation of the catalysts for the transformation of sunflower oil to renewable (green) diesel took place in a high-pressure semi-batch reactor, under solvent-free conditions. A very small addition of Mo, namely the synergistic Ni/(Ni + Mo) atomic ratio equal to 0.95, proved to be the optimum one for a significant enhancement of the catalytic performance of the metallic Ni/SiO2 catalyst, achieving 98 wt.% renewable diesel production. This promoting action of Mo has been attributed to the significant increase of the metallic Ni active phase surface area, the suitable regulation of surface acidity, the acceleration of the hydro-deoxygenation pathway (HDO), the creation of surface oxygen vacancies, and the diminution of coke formation provoked by Mo addition.