Upgrading of Rice Straw Bio-Oil Using 1-Butanol over ZrO2-Fe3O4 Bimetallic Nanocatalyst Supported on Activated Rice Straw Biochar to Butyl Esters

Bio-oil produced via fast pyrolysis, irrespective of the biomass source, faces several limitations, such as high water content, significant oxygenated compound concentration (35–40 wt.%), a low heating value (13–20 MJ/kg), and poor miscibility with fossil fuels. These inherent drawbacks hinder the bio-oil’s desirable properties and usability, highlighting the necessity for advanced processing techniques to overcome these challenges and improve the bio-oil’s overall quality and applicability in energy and industrial sectors. To address the limitations of bio-oil, a magnetic bimetallic oxide catalyst supported on activated rice straw biochar (ZrO2-Fe3O4/AcB), which has not been previously employed for this purpose, was developed and characterized for upgrading rice straw bio-oil in supercritical butanol via esterification. Furthermore, the silica in the biochar, combined with the Lewis acid sites provided by ZrO2 and Fe3O4, offers Brønsted acid sites. This synergistic combination enhances the bio-oil’s quality by facilitating esterification, deoxygenation, and mild hydrogenation, thereby reducing oxygen content and increasing carbon and hydrogen levels. The effects of variables, including time, temperature, and catalyst load, were optimized using response surface methodology (RSM). The optimal reaction conditions were determined using a three-factor, one-response, and three-level Box-Behnken design (BBD). The ANOVA results at a 95% confidence level indicate that the results are statistically significant due to a high Fisher’s test (F-value = 37.07) and a low probability (p-value = 0.001). The minimal difference between the predicted R² and adjusted R² for the ester yield (0.0092) suggests a better fit. The results confirm that the optimal reaction conditions are a catalyst concentration of 1.8 g, a reaction time of 2 h, and a reaction temperature of 300 °C. Additionally, the catalyst can be easily recycled for four reaction cycles. Moreover, the catalyst demonstrated remarkable reusability, maintaining its activity through four consecutive reaction cycles. Its magnetic properties allow for easy separation from the reaction mixture using an external magnet.