A reaction–diffusion coupled kinetic model for hydrothermal acid pretreatment of wheat straw

Hydrothermal acid pretreatment is a promising method to overcome the recalcitrance of lignocellulosic biomass for subsequent efficient enzymatic hydrolysis and biofuel production. However, little is known about heterogeneous catalysis reactions involving the proton diffusion in the pore of lignocellulosic biomass coupled with the hydrolysis of hemicellulose and cellulose catalyzed by proton. In this study, a reaction–diffusion coupled kinetic model for hydrothermal acid pretreatment of wheat straw was developed based on the visualization of particle geometry and pore features. The increase rate of average proton concentration in the pores is higher at a higher temperature or a smaller particle size. A mathematical model was successfully developed to describe the time courses of average proton concentration dictated by initial acid concentration and an unsteady diffusion fitting parameter. The kinetic parameters of each reaction step for hydrothermal acid pretreatment of wheat straw were obtained by fitting experimental data. The activation energies for the hydrolysis of slow-hydrolyzing cellulose, fast-hydrolyzing cellulose, and hemicellulose were determined of 937.8 kJ·mol−1, 90.7 kJ·mol−1, and 39.8 kJ·mol−1, respectively, indicating the temperature dependence of slow-hydrolyzing cellulose with a high crystalline index is strongest. The prediction accuracy of this model can be further improved at higher stirring speeds and initial acid concentrations. Additionally, the model demonstrates high prediction accuracy across three different particle sizes. Generally, this model can gratifyingly correlate data of formation and degradation of monosaccharides and furfural in the hydrothermal acid pretreatment of wheat straw with fair accuracy.