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Item type:Publication, Bifunctional WOx/SiO2 catalysts for hydrogen-free upgrading of B100 and bio-ethylene to SAF and green diesel precursors via olefin metathesis and deoxygenation(2026-09-15) ;Solehudin, Mochamad ;Wengwirat, Kanokwan ;Promchana, Pratya ;Poo-arporn, YingyotLimphirat, WanwisaThis work presents a hydrogen-free catalytic route for upgrading palm-derived biodiesel (B100) into olefinic precursors for sustainable aviation fuel (SAF) and green diesel (GD) using bifunctional WO<inf>x</inf>/SiO<inf>2</inf> catalysts under atmospheric pressure. The catalysts integrate olefin cross-metathesis, mediated by surface W CH<inf>2</inf> species, with deoxygenation via Lewis-acidic W O sites, enabling selective C C bond exchange and C O bond cleavage without external hydrogen or noble metals. Detailed mechanistic studies revealed that methyl oleate (MO) rapidly undergoes cross-metathesis with ethylene to yield SAF-range C<inf>9</inf>–C<inf>14</inf> precursors, while methyl palmitate (MP) contributes primarily to GD (C<inf>15</inf>–C<inf>18</inf>) through ketene intermediates and decarbonylation–hydrogen transfer pathways. Contact time and temperature experiments confirmed that MO conversion is kinetically favored at milder conditions, whereas MP-derived pathways dominate at higher temperatures and extended residence times. Catalyst loading studies show that the 3 and 5 wt% WO<inf>x</inf>/SiO<inf>2</inf> catalysts are dominated by highly dispersed isolated and polymeric WO<inf>x</inf> species, which exhibit higher accessible acidity and consequently promote secondary cracking reactions. In contrast, the 8 wt% WO<inf>x</inf>/SiO<inf>2</inf> catalyst contains a higher fraction of bulk crystalline WO<inf>3</inf> domains, resulting in reduced surface acidity and suppressed cracking. Overall, 8 wt% WO<inf>x</inf>/SiO<inf>2</inf> delivers reasonable rates with high selectivity toward SAF/GD precursors, while minimizing secondary cracking. It can be regenerated and recycled with substantial recovery of catalytic performance, establishing a robust, low-pressure, and hydrogen-free pathway for scalable renewable fuel production from B100. - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Hydrogen-Free Production of Green Diesel from Deoxygenation of Methyl Palmitate via Cross-Metathesis with Bio-Ethylene Using Supported WO3 Catalyst(2025-06-02) ;Solehudin, Mochamad ;Wengwirat, Kanokwan ;Promchana, Pratya ;Poo-arporn, YingyotLimphirat, WanwisaTraditional green diesel production from used cooking oils faces challenges in H<inf>2</inf> supply and carbon loss as CO<inf>2</inf>. This study presents a novel hydrogen-free deoxygenation process via cross-metathesis between fatty acids/FAMEs and bio-ethylene under atmospheric pressure as an alternative sustainable solution. The carboxyl end group was removed as CO and blue hydrogen, bearing the hydrocarbons as green diesel, sustainable aviation fuel (SAF), and bio-naphtha. Bifunctional WO<inf>3</inf>/SiO<inf>2</inf> was prepared and characterized by XRD, XANES, EXAFS, DR-UV, and Raman. Lewis site (W = O) promotes the formation of ketene intermediate that undergoes cross-metathesis with ethylene over tungsten carbene (WCH<inf>2</inf>) sites, yielding a C16-ene majority with trace amounts of C17-ene. Smaller hydrocarbons (<C15) are obtained as minor components from decarbonylation, hydrogen transfer, and cracking. The increased contact time (27–106 g h/mol) at 460 °C results in increased conversion (30%–87 %), green diesel (12%–57%), SAF (3.5%–12.7%), and bio-naphtha (1.3%–5.3%). Optimal green diesel production of 2.92 h⁻¹ with 73% selectivity can be achieved at 480 °C. SAF and bio-naphtha yields can be tuned by varying temperature from 460 to 500 °C. This provides a sustainable pathway for renewable liquid fuels without an external hydrogen supply.
