From Hydrothermal Extraction to Catalytic Conversion: Mesoporous ZrO2-Assisted Valorization of Wheat Bran Sugars and Polysaccharides

Wheat bran (WB) is an abundant agro-industrial residue rich in starch and structural polysaccharides, representing an attractive feedstock for sustainable biorefinery applications. In this work, an integrated strategy combining mild hydrothermal extraction and catalytic hydrothermal conversion was proposed to promote sugar recovery from unmilled WB and its subsequent transformation into organic acids. Conventional (HE-CH) and microwave-assisted hydrothermal extraction (HE-MW) were compared at 80–100 °C and 5–30 min. Under these soft conditions, total sugar recoveries of up to 6.45 g/100 g WB (5 min) and 8.71 g/100 g WB (30 min) were achieved, with a clear predominance of bound sugars and preferential extraction of hemicellulosic (C5) fractions, without formation of degradation products. Microwave-assisted extraction enhanced sugar recovery and selectivity by improving access to the wheat bran cell wall through volumetric heating and enhanced mass transfer. The resulting liquid extracts were subsequently converted at 180 °C and 40 bar (N2) using a mesoporous hydrated ZrO2 catalyst. In the absence of a catalyst, the system exhibited autothermal behavior but low efficiency (X < 20%). In contrast, catalytic conversion led to total sugar conversions above 75% at 90 min, with high lactic acid yields and LA/GA ratios consistently above unity, particularly for HE-MW-derived extracts. Overall, this work demonstrates that coupling microwave-assisted extraction under mild conditions with heterogeneous catalysis enables efficient access to WB cell-wall carbohydrates and their selective upgrading into value-added organic acids, offering a low-severity and sustainable route for wheat bran valorization.