The use of H-ZSM-5 with various binders (Al2O3, SiO2, and kaolinite, 10 wt% on catalyst formulation) for the catalytic conversion of glycerol to bio-based aromatics (GTA) was investigated in a continuous bench-scale unit at a pyrolysis temperature of 450 °C, catalytic upgrading temperature of 500 °C, WHSV of pure glycerol of 1 h−1, and atmospheric pressure, and their performance was compared to H-ZSM-5 (SiO2/Al2O3 molar ratio of 28). The latter gave a peak BTX carbon yield of ca. 31.1C.%, a life-time of ca. 220 min, and a total BTX productivity of ca. 312 mg BTX g−1H-ZSM-5. The introduction of binders affects catalyst performance, which is the most profound and promising for the H-ZSM-5/Al2O3 catalyst. It shows a prolonged catalyst life-time of ca. 320 min and a higher total BTX productivity of ca. 518 mg BTX g−1H-ZSM-5, compared to the H-ZSM-5 without a binder. Catalyst characterization studies show that the addition of the binder does not have a major effect on the specific surface area, total pore volume, and total acidity. Other relevant properties were affected, though, such as micropore volume (SiO2), a reduced Brønsted acidity (Al2O3, and SiO2), and reduced crystallinity (SiO2). Coke formation causes severe catalyst deactivation, ultimately leading to an inactive catalyst for BTX formation. Catalyst characterization studies after an oxidative regeneration showed that the textural properties of the regenerated catalysts were close to those of the original catalysts. However, some dealumination of H-ZSM-5 occurs, resulting in decreased crystallinity and acidity, causing irreversible deactivation, which needs attention in future catalyst development studies.
The catalytic conversion of oleic acid to aromatics (benzene, toluene, and xylenes, BTX) over a granular H-ZSM-5/Al2O3 catalyst (ϕ 1.2–1.8 mm, 10 g loading) was investigated in a continuous bench-scale fixed-bed reactor (10 g oleic acid h–1). A peak carbon yield of aromatics of 27.4% was obtained at a catalyst bed temperature of 550 °C and atmospheric pressure. BTX was the major aromatics formed (peak carbon yield was 22.7%), and a total BTX production of 1000 mg g–1 catalyst was achieved within a catalyst lifetime of 6.5 h for the fresh catalyst. The catalyst was deactivated due to severe coke deposition (ca. 22.1 wt % on the catalyst). The used catalyst was reactivated by an ex situ oxidative regeneration at 680 °C in air for 12 h. The regenerated catalyst was subsequently recycled, and in total, 7 cycles of reaction-regeneration were performed. A gradual decrease in the peak carbon yield of BTX was observed with reaction-regeneration cycles (e.g., to 16.3% for the catalyst regenerated for 6 times). However, the catalyst lifetime was remarkably prolonged (e.g., >24 h), leading to a significantly enhanced total BTX production (e.g., 3000 mg g–1 catalyst in 24 h). The fresh, used, and regenerated catalysts were characterized by N2 and Ar physisorption, XRD, HR-TEM-EDX, 27Al, and 29Si MAS ssNMR, NH3-TPD, TGA, and CHN elemental analysis. Negligible changes in textural properties, crystalline structure, and framework occurred after one reaction-regeneration cycle, except for a slight decrease in acidity. However, dealumination of the H-ZSM-5 framework was observed after 7 cycles of reaction-regeneration, leading to a decrease in microporosity, crystallinity, and acidity. Apparently, these changes are not detrimental for catalyst activity, and actually, the lifetime of the catalyst increases, rationalized by considering that coke formation rates are retarded when the acidity is reduced.