Influences of fractional separation on the structure and reactivity of wheat straw cellulose for producing 5-hydroxymethylfurfural

doi:10.1016/j.cjche.2024.05.005

Abstract

Abstract: High-efficient production of 5-hydroxymethylfurfural (HMF), a “sleeping giant” in sustainable chemistry, from cellulose depends significantly on the effective separation of cellulose from lignocellulosic biomass. Herein, we report the fractional separation of wheat straw cellulose (WSC) from wheat straw under solvothermal conditions using a mixed solvent of γ-valerolactone (GVL) and H₂O as the separating solvent, wherein the impacts of fractional separation parameters (solvent composition, temperature, and time) on removals of lignin and hemicellulose as well as purity and recovery of cellulose were studied by a Box-Behnken Design of response surface method. The optimization of the solvothermal parameters enabled an optimal fractional separation condition (V_GVL: ~60.0%, T: 205 ℃, t: ~1.7 h) that led to a higher purity (89.4%) and recovery (86.7%) of cellulose in WSC. A further correlation of the removals of lignin and hemicellulose as well as purity and recovery of cellulose with the yield of HMF excluded an independent influence of the above factors. Instead, a comprehensive contribution of high fractional separation efficiency (defined as the product of cellulose purity and recovery) and low crystallinity of WSC was found to improve the HMF yield. However, the heat- and freeze-dryings of WSC after the solvothermal separation were found to lower the HMF molar yield because it re-improved the crystallinity of WSC. A high HMF molar yield of 58.6% was achieved after reacting wet-WSC in a mixed solvent of 1,4-dioxane and H₂O at 180 ℃ for 20 min, which was 1.5 fold higher than that from microcrystalline cellulose. This work highlights the importance of enhancing the fractional separation efficiency of cellulose from lignocellulosic biomass while avoiding the drying process for future HMF biorefinery.

Key words: Biomass, Separation, Drying, Crystallinity, Wheat straw cellulose, 5-Hydroxymethylfurfural

摘要： High-efficient production of 5-hydroxymethylfurfural (HMF), a “sleeping giant” in sustainable chemistry, from cellulose depends significantly on the effective separation of cellulose from lignocellulosic biomass. Herein, we report the fractional separation of wheat straw cellulose (WSC) from wheat straw under solvothermal conditions using a mixed solvent of γ-valerolactone (GVL) and H₂O as the separating solvent, wherein the impacts of fractional separation parameters (solvent composition, temperature, and time) on removals of lignin and hemicellulose as well as purity and recovery of cellulose were studied by a Box-Behnken Design of response surface method. The optimization of the solvothermal parameters enabled an optimal fractional separation condition (V_GVL: ~60.0%, T: 205 ℃, t: ~1.7 h) that led to a higher purity (89.4%) and recovery (86.7%) of cellulose in WSC. A further correlation of the removals of lignin and hemicellulose as well as purity and recovery of cellulose with the yield of HMF excluded an independent influence of the above factors. Instead, a comprehensive contribution of high fractional separation efficiency (defined as the product of cellulose purity and recovery) and low crystallinity of WSC was found to improve the HMF yield. However, the heat- and freeze-dryings of WSC after the solvothermal separation were found to lower the HMF molar yield because it re-improved the crystallinity of WSC. A high HMF molar yield of 58.6% was achieved after reacting wet-WSC in a mixed solvent of 1,4-dioxane and H₂O at 180 ℃ for 20 min, which was 1.5 fold higher than that from microcrystalline cellulose. This work highlights the importance of enhancing the fractional separation efficiency of cellulose from lignocellulosic biomass while avoiding the drying process for future HMF biorefinery.

关键词: Biomass, Separation, Drying, Crystallinity, Wheat straw cellulose, 5-Hydroxymethylfurfural

Di Wu, Ping Hu, Hui Li, Zhidan Xue, Hang Lv, Yimeng Guo, Changwei Hu, Liangfang Zhu. Influences of fractional separation on the structure and reactivity of wheat straw cellulose for producing 5-hydroxymethylfurfural[J]. Chinese Journal of Chemical Engineering, 2024, 73(9): 154-162.

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