Search Results (11)

The fast growth of the aviation sector has intensified the need for sustainable alternatives to conventional fossil-based jet fuels. Sustainable aviation fuel (SAF) has emerged as one of the most promising strategies to reduce greenhouse gas emissions while remaining compatible with existing aviation infrastructure. Among the different feedstocks explored for SAF production, lipid-based resources such as vegetable oils, animal fats, and waste cooking oil have received considerable attention due to their high content of triglycerides and free fatty acids. Additionally, the increasing generation of plastic waste has stimulated interest in its catalytic valorization as an alternative carbon source for hydrocarbon fuel production. This mini-review summarizes recent advances in catalytic pathways for producing jet-fuel-range hydrocarbons (C₈–C₁₆) from lipid-based feedstocks and polyolefins. Particular emphasis is given on hydroprocessing reactions, including deoxygenation, cracking, and isomerization, which are essential to adjust fuel properties and meet aviation specifications. In this context, bifunctional heterogeneous catalysts play a crucial role, particularly regarding the influence of the metal phase and catalyst support on catalytic activity and stability. Different support classes, including metal oxides, mesoporous silicas, and zeolites, are discussed. Carbon-based materials, especially carbon nanotubes (CNT), are also highlighted due to their outstanding chemical and textural properties. Full article

Co and Mo mono- and bimetallic catalysts supported on CNT-H-ZSM-5 composites were prepared and characterized using various techniques. The catalysts were evaluated for the conversion of sunflower oil (SO) into sustainable aviation fuel (SAF) hydrocarbons in the C₈–C₁₆ range. The effects of reduction temperature and metal loading were the main parameters investigated in this study. The catalyst reduced at 600 °C promoted the formation of Mo₂C species, resulting in high SO conversion (84%), complete deoxygenation, and enhanced isomerization within the C₈–C₁₆ fraction. Optimal metal loadings (2.5 wt% Co and 8 wt% Mo) and the bimetallic configuration led to superior performance compared with monometallic catalysts and physical mixtures, clearly highlighting a synergistic effect between Co and Mo species. In contrast, when waste cooking oil was used as feedstock, lower conversion and reduced selectivity toward SAF-range hydrocarbons were observed, which were attributed to the higher complexity and impurity content of this residue feedstock. Full article

Green diesel is a high-quality biofuel obtained through the transformation of triglycerides into linear alkanes. In order to obtain green diesel, this study investigates the impact of impregnation pH on the surface species of NiMo/Al₂O₃ catalysts in the hydroprocessing of soybean oil. NiMo catalysts supported on Al₂O₃ were synthesized at different pH values (pH = 7 and 9). In the oxide state, solids were characterized by UV-Vis diffuse reflectance, Raman, and FT-IR spectroscopies, and, in the sulfide state, they were characterized by HR-TEM. The results show that the pH of impregnation significantly determines the surface species formed. An impregnation at pH = 7 favors the formation of Ni²⁺_(Oh) and Ni²⁺_(Oh-dis) interacting with non-crystalline molybdenum trioxide, while the formation of Ni²⁺/Al₂O₃, Ni_2+(Oh-dis), and MoO₃ species is favored at pH = 9. These surface species play a fundamental role in the hydrogenolysis and deoxygenation steps. Catalyst impregnated at pH = 7 shows higher activity due to the formation of shorter MoS₂ slabs. This study emphasized the importance of controlling impregnation conditions for optimizing catalyst performance. Full article

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. Full article

Phonolite material has shown to be promising catalyst support for the deoxygenation of triglycerides. In this work, we continue with our previous research by synthesising and testing three acid-treated phonolite-supported Co-Mo, Ni-Mo and Ni-W catalysts for the hydrotreating of atmospheric gas oil and co-processing with rapeseed oil at industrial operating conditions (350–370 °C, WHSV 1–2 h⁻¹, 5.5 MPa) in the continuous regime for more than 270 h. The phonolite-supported catalysts showed hydrotreating activity comparable with commercial catalysts, together with a complete conversion of triglycerides into n-alkanes. During co-processing, the Ni-promoted catalyst showed strong stability, with similar activity previous to the rapeseed oil addition. Our results enable us to evaluate the suitability of phonolite as catalyst support for the development of plausible alternatives to conventional hydrotreating catalysts for the co-processing of middle distillates with vegetable oils. Full article

The catalytic deoxygenation of coconut oil was performed in a continuous-flow reactor over bimetallic NiCo/silicoaluminophosphate-11 (SAPO-11) nanocatalysts for hydrocarbon fuel production. The conversion and product distribution were investigated over NiCo/SAPO-11 with different applied co-reactants, i.e., water (H₂O) or glycerol solution, performed under nitrogen (N₂) atmosphere. The hydrogen-containing co-reactants were proposed here as in-situ hydrogen sources for the deoxygenation, while the reaction tests under hydrogen (H₂) atmosphere were also applied as a reference set of experiments. The results showed that applying co-reactants to the reaction enhanced the oil conversion as the following order: N₂ (no co-reactant) < N₂ (H₂O) < N₂ (aqueous glycerol) < H₂ (reference). The main products formed under the existence of H₂O or glycerol solution were free fatty acids (FFAs) and their corresponding C_n−1 alkanes. The addition of H₂O aids the triglyceride breakdown into FFAs, whereas the glycerol acts as hydrogen donor which is favourable to initiate hydrogenolysis of triglycerides, causing higher amount of FFAs than the former case. Consequently, those FFAs can be deoxygenated via decarbonylation/decarboxylation to their corresponding C_n−1 alkanes, showing the promising capability of the NiCo/SAPO-11 to produce hydrocarbon fuels even in the absence of external H₂ source. Full article

Bio-hydrogenated diesel (BHD), derived from vegetable oil via hydrotreating technology, is a promising alternative transportation fuel to replace nonsustainable petroleum diesel. In this work, a novel Pt-based catalyst supported on N-doped activated carbon prepared from polypyrrole as the nitrogen source (Pt/N-AC) was developed and applied in the palm oil deoxygenation process to produce BHD in a fixed bed reactor system. High conversion rates of triglycerides (conversion of TG > 90%) and high deoxygenation percentage (DeCO_x% = 76% and HDO% = 7%) were obtained for the palm oil deoxygenation over Pt/N-AC catalyst at optimised reaction conditions: T = 300 °C, 30 bar of H₂, and LHSV = 1.5 h⁻¹. In addition to the excellent performance, the Pt/N-AC catalyst is highly stable in the deoxygenation reaction, as confirmed by the XRD and TEM analyses of the spent sample. The incorporation of N atoms in the carbon structure alters the electronic density of the catalyst, favouring the interaction with electrophilic groups such as carbonyls, and thus boosting the DeCO_x route over the HDO pathway. Overall, this work showcases a promising route to produce added value bio-fuels from bio-compounds using advanced N-doped catalysts. Full article

The objective of this work was to study the fast pyrolysis of a diglyceride intermediate compound during the conversion of triglycerides to fatty acids, esters and/or hydrocarbons. Dilaurin was selected as a model compound. Pyrolysis was conducted in a micro-pyrolyzer coupled to GC-MS equipment at 500, 550 and 600 °C for 15 s in the presence of sodium carbonate (Na₂CO₃) as the catalyst. Results were compared to pyrolysis data using γ-Al₂O₃ as a catalyst. At 600 °C with Na₂CO₃ almost total conversion of diglyceride was obtained, with the formation of 41.3% hydrocarbons (C3 to C13). In the same conditions using alumina as a catalyst 68.5% of hydrocarbons were obtained. Na₂CO₃ presented itself as an efficient feedstock modifier, allowing pre-cracking and partial deoxygenation of the load. The use of the Na₂CO₃ and γ-Al₂O₃ conjugated system in layers reduced the fatty acid content in the products, increasing both the reagent conversion and the hydrocarbon variety (C3 to C23). This work suggests that the use of a double bed catalytic reactor is suitable for performing a deoxygenating pretreatment and producing hydrocarbons compatible with current liquid fuels, being potentially useful for more complex raw materials such as those from biomass treatments. Full article

Pt represents an effective promoter of supported Ni catalysts in the transformation of tristearin to green diesel via decarbonylation/decarboxylation (deCO_x), conversion increasing from 2% over 20% Ni/Al₂O₃ to 100% over 20% Ni-0.5% Pt/Al₂O₃ at 260 °C. Catalyst characterization reveals that the superior activity of Ni-Pt relative to Ni-only catalysts is not a result of Ni particle size effects or surface area differences, but rather stems from several other phenomena, including the improved reducibility of NiO when Pt is present. Indeed, the addition of a small amount of Pt to the supported Ni catalyst dramatically increases the amount of reduced surface metal sites, which are believed to be the active sites for deCO_x reactions. Further, Pt addition curbs the adsorption of CO on the catalyst surface, which decreases catalyst poisoning by any CO evolved via decarbonylation, making additional active sites available for deoxygenation reactions and/or preventing catalyst coking. Specifically, Pt addition weakens the Ni-CO bond, lowering the binding strength of CO on surface Ni sites. Finally, analysis of the spent catalysts recovered from deCO_x experiments confirms that the beneficial effect of Pt on catalyst performance can be partially explained by decreased coking and fouling. Full article

Waste cooking oil with a high-acid-value (28.7 mg-KOH/g-oil) was converted to bio-hydrogenated diesel by a hydrotreatment process over supported Ru catalysts. The standard reaction temperature, H₂ pressure, liquid hourly space velocity (LHSV), and H₂/oil ratio were 350 °C, 2 MPa, 15.2 h^–1, and 400 mL/mL, respectively. Both the free fatty acids and the triglycerides in the waste cooking oil were deoxygenated at the same time to form hydrocarbons in the hydrotreatment process. The predominant liquid hydrocarbon products (98.9 wt%) were n-C₁₈H₃₈, n-C₁₇H₃₆, n-C₁₆H₃₄, and n-C₁₅H₃₂ when a Ru/SiO₂ catalyst was used. These long chain normal hydrocarbons had high melting points and gave the liquid hydrocarbon product over Ru/SiO₂ a high pour point of 20 °C. Ru/H-Y was not suitable for producing diesel from waste cooking oil because it formed a large amount of C₅–C₁₀ gasoline-ranged paraffins on the strong acid sites of HY. When Al-polyoxocation-pillared montmorillonite (Al₁₃-Mont) was used as a support for the Ru catalyst, the pour point of the liquid hydrocarbon product decreased to −15 °C with the conversion of a significant amount of C₁₅–C₁₈ n-paraffins to iso-paraffins and light paraffins on the weak acid sites of Al₁₃-Mont. The liquid product over Ru/Al₁₃-Mont can be expected to give a green diesel for current diesel engines because its chemical composition and physical properties are similar to those of commercial petro-diesel. A relatively large amount of H₂ was consumed in the hydrogenation of unsaturated C=C bonds and the deoxygenation of C=O bonds in the hydrotreatment process. A sulfided Ni-Mo/Al₁₃-Mont catalyst also produced bio-hydrogenated diesel by the hydrotreatment process but it showed slow deactivation during the reaction due to loss of sulfur. In contrast, Ru/Al₁₃-Mont did not show catalyst deactivation in the hydrotreatment of waste cooking oil after 72 h on-stream because the waste cooking oil was not found to contain sulfur-containing compounds. Full article