非水溶剂预处理木质纤维原料研究进展

doi:10.16085/j.issn.1000-6613.2021-1969

摘要/Abstract

摘要：

木质纤维素是目前中国最丰富的可再生资源，但由于其交织的复杂结构阻碍了内部纤维素和半纤维素的后续转化，这促使研究者们去寻求有效的预处理方法以解决目前的困境。近年来，随着预处理溶剂不断被发现和新型溶剂的快速涌现，非水溶剂预处理作为一种新兴的预处理方式在木质纤维素生物炼制中展现出良好的效果和应用前景。本文在系统介绍了各种非水溶剂理化性质和特点的基础上，综述了各种非水溶剂对木质纤维素预处理的作用原理、半纤维素和木质素的去除效果以及对纤维素酶解性能的影响，同时总结归纳了不同非水溶剂预处理的主要优缺点，并对非水溶剂预处理面临的挑战和未来的发展方向进行了展望，以期对未来绿色、低廉、高效的预处理方法提供借鉴和指导。

关键词: 木质纤维素, 预处理, 非水溶剂, 醇类, 有机酸, 离子液体

Abstract:

Lignocellulose is the most abundant renewable resource in China. However, the intertwined complex structures prevent further conversion of cellulose and hemicellulose inside, which makes researchers seek effective pretreatment methods to solve the current problem. With the continuous discovery of solvents for biomass pretreatment and the emergence of new solvents, non-aqueous solvent pretreatment as an emerging pretreatment method has shown good effects and application prospects in the biorefinery of lignocellulosic raw materials. In this paper, based on introducing the physicochemical properties of various non-aqueous solvents, recent advances on the effect of these solvents on the pretreatment of lignocellulose, including the performance for hemicellulose and lignin removal and their influence on enzymatic hydrolysis are reviewed. The main advantages and disadvantages of different non-aqueous solvent pretreatment are also summarized. Furthermore, the challenges and future development directions of non-aqueous solvent pretreatment are proposed, which would provide references and guidance for future green, low-cost and efficient pretreatment methods.

Key words: lignocellulose, pretreatment, non-aqueous solvent, alcohols, organic acid, ionic liquid

中图分类号:

韩明阳, 乔慧, 付佳铭, 马泽雯, 王妍, 欧阳嘉. 非水溶剂预处理木质纤维原料研究进展[J]. 化工进展, 2022, 41(8): 4086-4097.

HAN Mingyang, QIAO Hui, FU Jiaming, MA Zewen, WANG Yan, OUYANG Jia. Research progress of non-aqueous solvents on the pretreatment of lignocellulose[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4086-4097.

图/表 6

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溶剂	化学式	介电常数（ε_r）	Hildebrand溶解参数/MPa^1/2	极性参数E_T(30)/kcal·mol^-1	沸点/℃	闪点/℃
乙醇	C₂H₆O	24.55	26.5	0.654	78.3	12
甲醇	CH₄O	32.66	29.6	0.762	64.5	11.1
丙三醇	C₃H₈O₃	47	36.1	0.817	290	176
乙二醇	C₂H₆O₂	37.7	32.9	0.79	197.3	111.1
甲酸	CH₂O₂	58.5（16℃）	24.9	0.833	100.6	69
乙酸	C₂H₄O₂	6.17（20℃）	21.4	0.648	117.9	39
丙酮	C₃H₆O	20.56	20	0.355	56.5	-20
甲基异丁基酮	C₆H₁₂O	13.11（20℃）	17.4	0.179	116.5	13.3
γ-戊内酯	C₅H₈O₂	—	—	—	207	81
甲基四氢呋喃	C₅H₁₀O	6.97	—	—	80	-11

溶剂	化学式	介电常数（ε_r）	Hildebrand溶解参数/MPa^1/2	极性参数E_T(30)/kcal·mol^-1	沸点/℃	闪点/℃
乙醇	C₂H₆O	24.55	26.5	0.654	78.3	12
甲醇	CH₄O	32.66	29.6	0.762	64.5	11.1
丙三醇	C₃H₈O₃	47	36.1	0.817	290	176
乙二醇	C₂H₆O₂	37.7	32.9	0.79	197.3	111.1
甲酸	CH₂O₂	58.5（16℃）	24.9	0.833	100.6	69
乙酸	C₂H₄O₂	6.17（20℃）	21.4	0.648	117.9	39
丙酮	C₃H₆O	20.56	20	0.355	56.5	-20
甲基异丁基酮	C₆H₁₂O	13.11（20℃）	17.4	0.179	116.5	13.3
γ-戊内酯	C₅H₈O₂	—	—	—	207	81
甲基四氢呋喃	C₅H₁₀O	6.97	—	—	80	-11

溶剂（体积分数）	催化剂（质量分数）	底物	预处理条件	半纤维素去除率/%	木质素去除率/%	纤维素酶解得率/%	参考文献
40%乙醇	—	甘蔗渣	195℃，30min	66.25	47.79	92.2	［15］
50%乙醇	—	甘蔗渣	190℃，45min	72.1	50.1	90.83	［16］
60%乙醇	—	甘蔗渣	190℃，45min	56.3	44.6	92.50	［16］
70%乙醇	—	甘蔗渣	190℃，45min	42.3	42.8	46.04	［16］
80%乙醇	—	甘蔗渣	190℃，45min	24.7	21.2	33.09	［16］
50%乙醇	—	桉树	170℃，10min	18.9	21.1	8.1	［17］
50%乙醇	1% H₂SO₄	桉树	140℃，10min	90.2	70.0	55.6	［17］
50%乙醇	1% H₂SO₄	桉树	150℃，10min	96.6	74.0	62.1	［17］
50%乙醇	1% H₂SO₄	桉树	160℃，10min	98.3	83.3	77.5	［17］
50%乙醇	1% H₂SO₄	桉树	170℃，10min	99.2	80.7	75.8	［17］
60%乙醇	—	甘蔗渣	120℃，60min	13.4	2.5	23.6	［18］
60%乙醇	5%NaOH	甘蔗渣	120℃，60min	22.6	17.9	72.0	［18］
60%乙醇	5% NaOH	甘蔗渣	180℃，30min	92.9	71.8	93.0	［19］
60%乙醇	正丙胺	玉米秸秆	140℃，40min	78.9	81.7	83.2	［20］
50%甲醇	碱性液体	甘蔗渣	120℃，180min	—	82.75	92.82	［21］
50%甲醇	2% NaOH	菜花废弃物	80℃，90min	—	86.7	97.9	［22］

溶剂（体积分数）	催化剂（质量分数）	底物	预处理条件	半纤维素去除率/%	木质素去除率/%	纤维素酶解得率/%	参考文献
40%乙醇	—	甘蔗渣	195℃，30min	66.25	47.79	92.2	［15］
50%乙醇	—	甘蔗渣	190℃，45min	72.1	50.1	90.83	［16］
60%乙醇	—	甘蔗渣	190℃，45min	56.3	44.6	92.50	［16］
70%乙醇	—	甘蔗渣	190℃，45min	42.3	42.8	46.04	［16］
80%乙醇	—	甘蔗渣	190℃，45min	24.7	21.2	33.09	［16］
50%乙醇	—	桉树	170℃，10min	18.9	21.1	8.1	［17］
50%乙醇	1% H₂SO₄	桉树	140℃，10min	90.2	70.0	55.6	［17］
50%乙醇	1% H₂SO₄	桉树	150℃，10min	96.6	74.0	62.1	［17］
50%乙醇	1% H₂SO₄	桉树	160℃，10min	98.3	83.3	77.5	［17］
50%乙醇	1% H₂SO₄	桉树	170℃，10min	99.2	80.7	75.8	［17］
60%乙醇	—	甘蔗渣	120℃，60min	13.4	2.5	23.6	［18］
60%乙醇	5%NaOH	甘蔗渣	120℃，60min	22.6	17.9	72.0	［18］
60%乙醇	5% NaOH	甘蔗渣	180℃，30min	92.9	71.8	93.0	［19］
60%乙醇	正丙胺	玉米秸秆	140℃，40min	78.9	81.7	83.2	［20］
50%甲醇	碱性液体	甘蔗渣	120℃，180min	—	82.75	92.82	［21］
50%甲醇	2% NaOH	菜花废弃物	80℃，90min	—	86.7	97.9	［22］

溶剂	催化剂	底物	预处理条件	半纤维素去除率/%	木质素去除率/%	纤维素酶解得率/%	参考文献
100%甘油	—	麦草	240℃，4h	—	70	90	［40］
100%甘油	0.02% H₂SO₄	甘蔗渣	160℃，30min	67	28	—	［40］
100%甘油	0.04% H₂SO₄	甘蔗渣	160℃，30min	83	31	—	［40］
100%甘油	0.06% H₂SO₄	甘蔗渣	200℃，15min	82	52	70	［40］
80%乙二醇	—	玉米秸秆	120℃，60min	7.5	27.7	—	［43］
80%乙二醇	0.6% H₂SO₄	玉米秸秆	120℃，60min	81.3	80.3	70.6	［43］
90%乙二醇	—	甘蔗渣	150℃，60min	6.5	3.6	29.8	［44］
90%乙二醇	1mol/L HCl	甘蔗渣	150℃，60min	99.3	67.1	80.1	［44］
90%乙二醇	1mol/L NaOH	甘蔗渣	150℃，60min	28.8	90.9	90.0	［44］
90%乙二醇	0.006mol/L AlCl₃	稻草	150℃，30min	0.2	35.0	—	［45］
90%乙二醇	0.028mol/L AlCl₃	稻草	150℃，30min	82.4	83.5	—	［45］
90%乙二醇	0.055mol/L AlCl₃	稻草	150℃，30min	90.1	87.7	94	［45］