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[Display omitted] • Oil-soluble Mo-based ILs were utilized for the in situ generation of MoS 2 catalysts. • The hydroconversion of methyl palmitate gives 1.6 × 102 h−1 of TOF MP and 83 h−1 of TOF HDO. • The hydroconversion of methyl palmitate mainly proceeds through the HDO route. • The reaction route of hydroconversion was proposed and the kinetics was analyzed. • Mo-based ILs can also be used for efficient and solvent-free hydroconversion of palm oil. Dispersed metal sulfides are promising catalysts for the hydroconversion of biolipids to produce second-generation biodiesel. In this work, oil-soluble Mo-based ionic liquids (ILs) were innovatively utilized as the precursors for in situ generation of MoS 2 catalysts for the hydroconversion of biolipids. Taking methyl palmitate as the model compound, the excellent activity of in situ generated MoS 2 from ionic liquid Mo-based precursors was obtained. The turnover frequencies (TOFs) reached up to 1.6 × 102 h−1 for methyl palmitate conversion and 83 h−1 for hexadecane (C 16) yield at 320 °C and 0.5 h (42% conversion) under solvent-dilute conditions. The structures of in situ generated MoS 2 catalysts were characterized to provide explanations for the catalytic results. Based on the product distributions, the pathway of methyl palmitate hydroconversion was proposed, and the kinetics of methyl palmitate hydroconversion was analyzed in further detail. Applying the Mo-based ILs in the hydroconversion of methyl palmitate and palm oil under solvent-free condition also granted high conversions of feeds and selectivities of HDO products. [ABSTRACT FROM AUTHOR]

• A novel in-situ combo Mo-based ionic liquid and SAPO-11 catalyst was designed. • Variable combination of highly dispersed MoS 2 active sites and SAPO-11 acid sites. • Great activity and stability of MoS 2 /SAPO-11 for valorisation of methyl palmitate. • High yield of n -C 15 -C 16 via hydrodeoxygenation and i -C 15 -C 16 via isomerization. The design of novel practical catalysts is critical for the blossoming of biodiesel green-energy, in which Mo-based catalysts are of particular interest. In this work, an in-situ synthesis method was proposed to obtain a combo Mo-based ionic liquid and SAPO-11 catalyst. The catalyst presents both highly dispersed MoS 2 as hydrodeoxygenation active sites and acidic sites for isomerization. MoS 2 with a few fine layers can be identified based on TEM images and the Brønsted acid sites are dominant based on Pyridine-IR analysis. A great performance of MoS 2 /C 8 min-15 %SA can be obtained under optimized reaction conditions with 100 % conversion of methyl palmitate, 75.0 mol% hydrodeoxygenation to n -C 15 -C 16 , and 20.5 mol % isomerization to i -C 15 -C 16. The structure and activity of the catalyst can be retained at least for 4 cycles. Thin layers and high sulfurization, large amount of Brønsted acid sites, and suitable reaction conditions are key points to achieve a significant performance and avoid over cracking and deactivation. On basis of detected intermediates and kinetic data simulations, a complex reaction pathway was proposed and the specific k values for each elementary reaction were provided for the hydrodeoxygenation and isomerization of methyl palmitate. [ABSTRACT FROM AUTHOR]

[Display omitted] • Isomerized biodiesel from biolipid was achieved under solvent-free conditions. • High yields of hydrocarbons were produced by in-situ sulfided MoO 3 /ZrPO x. • Strong synergistic effect between sulfided MoS 2 and acid-modified ZrO 2 exhibited. • The deoxygenation and isomerization reaction occurred in one pot. • The prepared catalyst displays well regenerated and recycling. The catalytic deoxygenation and isomerization of biolipids in one pot is a challenge in the production of high-quality biodiesel. Herein, series of bifunctional catalysts, combining with in-situ sulfided MoO 3 and phosphoric acid modified-ZrO 2 , were fabricated for upgrading of biolipid under solvent-free conditions. It is demonstrated that the bifunctional catalysts exhibit great performance for the hydrotreating of methyl palmitate and raw biolipid, affording up to 90% of total hydrocarbons with 20.3% and 18.7% of isomerized alkanes in diesel range. Among several studied ratios, the catalyst with Mo loading of 12.5% and P/Zr ratio of 1/7 achieves the highest yield of i -alkanes due to a coeffect of MoS 2 and acid sites on the surface based on characterizations. The regenerated catalyst also shows excellent performance with no significant change in the structure. Moreover, a synergy between MoS 2 and phosphoric acid is discussed to elucidate the high activity of biolipid conversion. [ABSTRACT FROM AUTHOR]