化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3347-3358.DOI: 10.16085/j.issn.1000-6613.2023-0859
• 资源与环境化工 • 上一篇
谢国平1(), 谭雪松2, 刘鹏1, 苗长林2, 许光文1, 庄新姝2(
)
收稿日期:
2023-05-25
修回日期:
2023-09-15
出版日期:
2024-06-15
发布日期:
2024-07-02
通讯作者:
庄新姝
作者简介:
谢国平(1997—),男,硕士研究生,研究方向为有机溶剂预处理。E-mail:2559884479@qq.com。
基金资助:
XIE Guoping1(), TAN Xuesong2, LIU Peng1, MIAO Changlin2, XU Guangwen1, ZHUANG Xinshu2(
)
Received:
2023-05-25
Revised:
2023-09-15
Online:
2024-06-15
Published:
2024-07-02
Contact:
ZHUANG Xinshu
摘要:
木质纤维素类生物质是地球上最丰富的可再生资源,但纤维素、半纤维素、木质素三组分之间复杂的键合结构限制了其有效的转化利用。有机溶剂预处理是消除这种顽抗性的有效方法,其能有效拆解三组分、提高纤维素酶水解性能,并回收高纯木质素组分。随着对溶剂绿色和可持续性的要求,预处理有机溶剂正逐渐向生物基衍生溶剂方向发展,近期已有多种新型的生物基衍生溶剂预处理的报道。本文系统综述了基于Hansen溶度参数理论和CHEM21绿色溶剂指南的有机溶剂预处理体系设计,分别归类为均相体系、两相体系和多元相转化体系,归纳了生物基衍生预处理有机溶剂应用的研究进展,在此基础上探论了生物基衍生溶剂预处理面临的挑战和应用前景,以期为木质纤维素类生物质的有机溶剂预处理体系的设计和选择提供参考。
中图分类号:
谢国平, 谭雪松, 刘鹏, 苗长林, 许光文, 庄新姝. 基于生物基衍生有机溶剂的木质纤维素预处理研究进展[J]. 化工进展, 2024, 43(6): 3347-3358.
XIE Guoping, TAN Xuesong, LIU Peng, MIAO Changlin, XU Guangwen, ZHUANG Xinshu. Research progress of lignocellulosic pretreatment based on bio-based derived organic solvents[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3347-3358.
溶剂 | Hansen溶解度参数 | 相对能差(RED) | ||
---|---|---|---|---|
色散分量 | 极性分量 | 氢键分量 | ||
乙醇 | 15.8 | 8.8 | 19.4 | 1.37 |
甲苯 | 18.0 | 1.4 | 2.0 | 1.53 |
四氢呋喃 | 16.8 | 5.7 | 8.0 | 1.06 |
戊内酯 | 15.5 | 4.7 | 6.6 | 1.38 |
昔兰尼 | 18.8 | 10.5 | 7.0 | 0.89 |
二甲基异山梨醇 | 17.6 | 7.1 | 7.5 | 1.06 |
乙二醇 | 17.0 | 11.0 | 26.0 | 1.00 |
二甲基四氢呋喃 | 16.9 | 5.0 | 4.3 | 1.34 |
甲基异丙基酮 | 15.1 | 6.1 | 4.1 | 1.48 |
苯氧乙醇 | 17.0 | 6.1 | 12.3 | 0.93 |
丁醇 | 16.0 | 5.7 | 15.8 | 1.06 |
戊醇 | 15.1 | 5.7 | 15.9 | 1.16 |
表1 生物基衍生溶剂预处理的溶解度参数和与木质素的相对能差
溶剂 | Hansen溶解度参数 | 相对能差(RED) | ||
---|---|---|---|---|
色散分量 | 极性分量 | 氢键分量 | ||
乙醇 | 15.8 | 8.8 | 19.4 | 1.37 |
甲苯 | 18.0 | 1.4 | 2.0 | 1.53 |
四氢呋喃 | 16.8 | 5.7 | 8.0 | 1.06 |
戊内酯 | 15.5 | 4.7 | 6.6 | 1.38 |
昔兰尼 | 18.8 | 10.5 | 7.0 | 0.89 |
二甲基异山梨醇 | 17.6 | 7.1 | 7.5 | 1.06 |
乙二醇 | 17.0 | 11.0 | 26.0 | 1.00 |
二甲基四氢呋喃 | 16.9 | 5.0 | 4.3 | 1.34 |
甲基异丙基酮 | 15.1 | 6.1 | 4.1 | 1.48 |
苯氧乙醇 | 17.0 | 6.1 | 12.3 | 0.93 |
丁醇 | 16.0 | 5.7 | 15.8 | 1.06 |
戊醇 | 15.1 | 5.7 | 15.9 | 1.16 |
溶剂 | 沸点/℃ | 闪点/℃ | 绿色溶剂等级 | |||
---|---|---|---|---|---|---|
安全 | 健康 | 环境 | CHEM21 | |||
乙醇 | 78.3 | 14 | 4 | 3 | 3 | 推荐 |
甲苯 | 110.6 | 4 | 5 | 6 | 3 | 有问题 |
四氢呋喃 | 66 | -14 | 6 | 7 | 5 | 有问题 |
戊内酯 | 205 | 81 | 1 | 5 | 7 | 有问题 |
昔兰尼 | 226 | 108 | 1 | 2 | 7 | 有问题 |
二甲基异山梨醇 | 93~95 | 120 | 1 | 2 | 3 | 推荐 |
乙二醇 | 198 | 111 | 1 | 2 | 5 | 推荐 |
二甲基四氢呋喃 | 80 | -11 | 6 | 5 | 3 | 有问题 |
甲基异丙基酮 | 94 | -7.9 | 5 | 3 | 3 | 推荐 |
苯氧乙醇 | 245 | 105 | 1 | 4 | 3 | 推荐 |
丁醇 | 118 | 35 | 3 | 4 | 3 | 推荐 |
戊醇 | 137 | 49 | 3 | 7 | 4 | 有问题 |
表2 生物基衍生溶剂的物理性质和绿色特征参数
溶剂 | 沸点/℃ | 闪点/℃ | 绿色溶剂等级 | |||
---|---|---|---|---|---|---|
安全 | 健康 | 环境 | CHEM21 | |||
乙醇 | 78.3 | 14 | 4 | 3 | 3 | 推荐 |
甲苯 | 110.6 | 4 | 5 | 6 | 3 | 有问题 |
四氢呋喃 | 66 | -14 | 6 | 7 | 5 | 有问题 |
戊内酯 | 205 | 81 | 1 | 5 | 7 | 有问题 |
昔兰尼 | 226 | 108 | 1 | 2 | 7 | 有问题 |
二甲基异山梨醇 | 93~95 | 120 | 1 | 2 | 3 | 推荐 |
乙二醇 | 198 | 111 | 1 | 2 | 5 | 推荐 |
二甲基四氢呋喃 | 80 | -11 | 6 | 5 | 3 | 有问题 |
甲基异丙基酮 | 94 | -7.9 | 5 | 3 | 3 | 推荐 |
苯氧乙醇 | 245 | 105 | 1 | 4 | 3 | 推荐 |
丁醇 | 118 | 35 | 3 | 4 | 3 | 推荐 |
戊醇 | 137 | 49 | 3 | 7 | 4 | 有问题 |
溶剂体系 | 原料 | 催化剂 | 预处理条件 | 纤维素保留率/% | 半纤维素去除率/% | 木质素去除率/% | 纤维素酶解率/% | 参考文献 |
---|---|---|---|---|---|---|---|---|
玉米芯 | 220℃,30min | 68.2 | 83.4 | 97.5 | [ | |||
高粱秸秆 | 200℃,60min | 87.4 | 97.1 | 91.4 | 92.8 | [ | ||
GVL/H2O | 银叶草 | 170℃,120min | 82.2 | 87.7 | 75.9 | 96.5 | [ | |
GVL/H2O | 桉树 | 120℃,60min | 77.1 | 96.1 | 81.6 | 89.1 | [ | |
GVL/H2O | 桉树 | HCl | 100℃,60min | 93.2 | 80 | 68 | 65 | [ |
GVL/H2O | 桉树 | 120℃,30min | 83.5 | 97.2 | 86.2 | 75.4 | [ | |
GVL/H2O | 桉树 | 167℃,10min | 86 | 91 | [ | |||
Cyrene/H2O | 杨木 | 120℃,60min | 72.5 | [ | ||||
Cyrene/TsOH | 竹 | TsOH | 120℃,60min | 79.1 | 90.6 | [ | ||
DMI/H2O | 桉树 | 120℃,60min | 80 | 98 | 91.6 | 82.1 | [ | |
EG/H2O | 甘蔗渣 | HCl | 120℃,60min | 71.4 | 83.5 | 61.2 | 80.4 | [ |
EG | 甘蔗渣 | HCl | 120℃,60min | 96.9 | 78.8 | 48.5 | 85.6 | [ |
EG/H2O | 玉米秸秆 | 120℃,60min | 84.7 | 81.3 | 80.3 | 70.6 | [ | |
EG/H2O | EPB | 80℃,45min | 90.4 | 81.5 | 75.1 | [ | ||
EG/H2O | 甘蔗渣 | 170℃,60min | 93 | 74.3 | 71.2 | [ | ||
EG/H2O | 甘蔗渣 | 120℃,60min | 96.9 | 84.6 | 47.5 | 82.1 | [ | |
EG/H2O | 杨木 | 120℃,10min | 42.7 | 56.9 | 94.5 | [ |
表3 均相体系预处理木质纤维素类生物质
溶剂体系 | 原料 | 催化剂 | 预处理条件 | 纤维素保留率/% | 半纤维素去除率/% | 木质素去除率/% | 纤维素酶解率/% | 参考文献 |
---|---|---|---|---|---|---|---|---|
玉米芯 | 220℃,30min | 68.2 | 83.4 | 97.5 | [ | |||
高粱秸秆 | 200℃,60min | 87.4 | 97.1 | 91.4 | 92.8 | [ | ||
GVL/H2O | 银叶草 | 170℃,120min | 82.2 | 87.7 | 75.9 | 96.5 | [ | |
GVL/H2O | 桉树 | 120℃,60min | 77.1 | 96.1 | 81.6 | 89.1 | [ | |
GVL/H2O | 桉树 | HCl | 100℃,60min | 93.2 | 80 | 68 | 65 | [ |
GVL/H2O | 桉树 | 120℃,30min | 83.5 | 97.2 | 86.2 | 75.4 | [ | |
GVL/H2O | 桉树 | 167℃,10min | 86 | 91 | [ | |||
Cyrene/H2O | 杨木 | 120℃,60min | 72.5 | [ | ||||
Cyrene/TsOH | 竹 | TsOH | 120℃,60min | 79.1 | 90.6 | [ | ||
DMI/H2O | 桉树 | 120℃,60min | 80 | 98 | 91.6 | 82.1 | [ | |
EG/H2O | 甘蔗渣 | HCl | 120℃,60min | 71.4 | 83.5 | 61.2 | 80.4 | [ |
EG | 甘蔗渣 | HCl | 120℃,60min | 96.9 | 78.8 | 48.5 | 85.6 | [ |
EG/H2O | 玉米秸秆 | 120℃,60min | 84.7 | 81.3 | 80.3 | 70.6 | [ | |
EG/H2O | EPB | 80℃,45min | 90.4 | 81.5 | 75.1 | [ | ||
EG/H2O | 甘蔗渣 | 170℃,60min | 93 | 74.3 | 71.2 | [ | ||
EG/H2O | 甘蔗渣 | 120℃,60min | 96.9 | 84.6 | 47.5 | 82.1 | [ | |
EG/H2O | 杨木 | 120℃,10min | 42.7 | 56.9 | 94.5 | [ |
溶剂体系 | 原料 | 催化剂 | 预处理条件 | 纤维素 保留率/% | 半纤维素 去除率/% | 木质素 去除率/% | 纤维素 酶解率/% | 参考文献 |
---|---|---|---|---|---|---|---|---|
2-MeTHF/H2O | 桦木 | 180℃,60min | — | — | — | 77.09 | [ | |
2-MeTHF/H2O | 小麦秸秆 | TsOH | 140℃,180min | 95.69 | — | 77.49 | — | [ |
2-MeTHF/H2O | 玉米秸秆 | 170℃,60min | — | — | — | 78.9 | [ | |
MIBK/H2O | 桉树 | 180℃,60min | — | 100 | 65.82 | 97.54 | [ | |
EPH/H2O | 稻草 | 120℃,180min | — | 75.83 | 72.69 | 88.06 | [ | |
EPH/H2O | 稻草 | 140℃,90min | 73.74 | 100 | 88.43 | — | [ | |
EPH/H2O | 稻草 | 120℃,30min | 79.76 | 45.9 | 82.2 | 71.26 | [ | |
Butanol/H2O | 甜菜浆 | 180℃,200min | — | 100 | 80 | 96 | [ | |
Pentanol/H2O | 金合欢木 | 170℃,30min | — | — | 70.27 | 92.14 | [ | |
Pentanol/H2O | 白杨 | 160℃,60min | 91.1 | 91 | 85 | 96 | [ |
表4 双相生物质衍生溶剂木质纤维素类预处理
溶剂体系 | 原料 | 催化剂 | 预处理条件 | 纤维素 保留率/% | 半纤维素 去除率/% | 木质素 去除率/% | 纤维素 酶解率/% | 参考文献 |
---|---|---|---|---|---|---|---|---|
2-MeTHF/H2O | 桦木 | 180℃,60min | — | — | — | 77.09 | [ | |
2-MeTHF/H2O | 小麦秸秆 | TsOH | 140℃,180min | 95.69 | — | 77.49 | — | [ |
2-MeTHF/H2O | 玉米秸秆 | 170℃,60min | — | — | — | 78.9 | [ | |
MIBK/H2O | 桉树 | 180℃,60min | — | 100 | 65.82 | 97.54 | [ | |
EPH/H2O | 稻草 | 120℃,180min | — | 75.83 | 72.69 | 88.06 | [ | |
EPH/H2O | 稻草 | 140℃,90min | 73.74 | 100 | 88.43 | — | [ | |
EPH/H2O | 稻草 | 120℃,30min | 79.76 | 45.9 | 82.2 | 71.26 | [ | |
Butanol/H2O | 甜菜浆 | 180℃,200min | — | 100 | 80 | 96 | [ | |
Pentanol/H2O | 金合欢木 | 170℃,30min | — | — | 70.27 | 92.14 | [ | |
Pentanol/H2O | 白杨 | 160℃,60min | 91.1 | 91 | 85 | 96 | [ |
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