As a natural renewable biomass, the tea oil fruit hull (TOFH) mainly consists of lignocellulose, together with some bioactive substances. Our earlier work constructed a two-stage solvent-based process, including one aqueous ethanol organosolv extraction and an atmospheric glycerol organosolv (AGO) pretreatment, for bioprocessing of the TOFH into diverse bioproducts. However, the AGO pretreatment is not as selective as expected in removing the lignin from TOFH, resulting in the limited delignification and simultaneously high cellulose loss. In this study, acetic acid organosolv (AAO) pretreatment was optimized with experimental design to fractionate the TOFH selectively. Alkaline hydrogen peroxide (AHP) pretreatment was used for further delignification. Results indicate that the AAO–AHP pretreatment had an extremely good selectivity at component fractionation, resulting in 92% delignification and 88% hemicellulose removal, with 87% cellulose retention. The pretreated substrate presented a remarkable enzymatic hydrolysis of 85% for 48 h at a low cellulase loading of 3 FPU/g dry mass. The hydrolyzability was correlated with the composition and structure of substrates by using scanning electron microscopy, confocal laser scanning microscopy, and X-ray diffraction. The mild AAO–AHP pretreatment is an environmentally benign and advantageous scheme for biorefinery of the agroforestry biomass into value-added bioproducts.

Cellulose is the most abundant natural biopolymer, with unique properties such as biodegradability, biocompability, nontoxicity, and so on. However, its extensive application has actually been hindered, because of its insolubility in water and most solvents. Herein, highly efficient cellulose solvents were developed by coupling diallylimidazolium methoxyacetate ([A₂im][CH₃OCH₂COO]) with polar aprotic solvents dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA). Attractively, these solvents showed extraordinarily powerful dissolution performance for cellulose (e.g., 26.1 g·100g⁻¹) in [A₂im][CH₃OCH₂COO]/DMSO(R_DMSO = 1.01 solvent even at 25 °C), which is much more advantageous over previously reported solvents. To our knowledge, such powerful cellulose solvents have not been reported before. The cellulose dissolution mechanism is proposed to be of three combined factors: (1) The hydrogen bond interactions of the H2, H4 and H6 in [A₂im]⁺ and the carboxyl O atom in [CH₃OCH₂COO]⁻, along with the hydroxyl H atom and O atom in cellulose, are main driving force for cellulose dissolution; (2) the dissociation of [A₂im][CH₃OCH₂COO] by DMF increases the anion and cation concentrations and thus promotes cellulose dissolution; (3) at the same time, DMF also stabilizes the dissolved cellulose chains. Meanwhile, the porous cellulose material with a varying morphologic structure could be facially fabricated by modulating the cellulose solution concentration. Additionally, the dissolution of cellulose in the solvents is only a physical process, and the regenerated cellulose from the solvents retains sufficient thermostability and a chemical structure similar to the original cellulose. Thus, this work will provide great possibility for developing cellulose-based products at ambient temperatures or under no extra heating/freezing conditions.