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

中国化学工程学报 ›› 2024, Vol. 73 ›› Issue (9): 154-162.DOI: 10.1016/j.cjche.2024.05.005

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

Di Wu, Ping Hu, Hui Li, Zhidan Xue, Hang Lv, Yimeng Guo, Changwei Hu, Liangfang Zhu

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China

收稿日期:2024-04-25 修回日期:2024-05-08 接受日期:2024-05-10 出版日期:2024-11-21 发布日期:2024-05-21
通讯作者: Liangfang Zhu,E-mail:zhulf@scu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (22378277), the 111 project (B17030), and the Basal Research Fund of the Central University (2016SCU04B06).

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

Di Wu, Ping Hu, Hui Li, Zhidan Xue, Hang Lv, Yimeng Guo, Changwei Hu, Liangfang Zhu

Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China

Received:2024-04-25 Revised:2024-05-08 Accepted:2024-05-10 Online:2024-11-21 Published:2024-05-21
Contact: Liangfang Zhu,E-mail:zhulf@scu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (22378277), the 111 project (B17030), and the Basal Research Fund of the Central University (2016SCU04B06).

摘要/Abstract

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

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

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]. 中国化学工程学报, 2024, 73(9): 154-162.

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

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

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