聚酰亚胺增强木质纤维素纳米纤丝气凝胶制备及其油水分离性能研究

doi:10.11949/0438-1157.20240985

化工学报 ›› 2025, Vol. 76 ›› Issue (5): 2169-2185.DOI: 10.11949/0438-1157.20240985

聚酰亚胺增强木质纤维素纳米纤丝气凝胶制备及其油水分离性能研究

李家顺¹(), 李旺¹, 秦祖赠¹, 苏通明¹, 谢新玲¹(), 纪红兵¹^,²

^1.广西大学化学化工学院，广西石化资源加工及过程强化技术重点实验室，广西南宁 530000
^2.浙江工业大学化学工程学院，浙江杭州 310014

收稿日期:2024-09-02 修回日期:2024-12-10 出版日期:2025-05-25 发布日期:2025-06-13
通讯作者: 谢新玲
作者简介:李家顺（2003—），男，本科生，2168351466@qq.com
基金资助:
国家自然科学基金项目(22168011);广西重点研发计划项目(2023AB38126);广西石油化工资源加工与过程强化技术重点实验室主任基金项目(2023Z008);广西八桂学者资助项目

Preparation of polyimide-reinforced lignocellulosic nanofibril aerogel and its oil-water separation performance

Jiashun LI¹(), Wang LI¹, Zuzeng QIN¹, Tongming SU¹, Xinling XIE¹(), Hongbing JI¹^,²

^1.Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530000, Guangxi, China
^2.College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China

Received:2024-09-02 Revised:2024-12-10 Online:2025-05-25 Published:2025-06-13
Contact: Xinling XIE

摘要/Abstract

摘要：

木质纤维素纳米纤丝(LCNF)气凝胶具有高孔隙率、低密度、原料可再生及可重复利用等优点，但力学性能不足限制了其在油水分离领域的应用。通过冷冻干燥和化学气相沉积法制备了LCNF/聚酰亚胺(PI)复合气凝胶。结果表明，PI与LCNF之间的强氢键作用赋予了气凝胶良好的力学和油水分离性能，其弹性模量为9.69~11.88 kPa，吸油倍率为73.0~103.4 g∙g^-1。相较M-LCNF气凝胶，M-LCNF/PI气凝胶的弹性模量提升了1.459~2.015倍，吸油倍率提升了1.6~21.0 g∙g^-1。M-LCNF/PI-1.00气凝胶保持了低密度(8.66 g∙cm^-3)、优异的疏水性(水接触角达140.6°)、高热稳定性(最大分解速率温度达363.1℃)及良好的隔热性能(热导率0.04436 W∙m^-1∙K^-1)。M-LCNF/PI-1.00对真空泵油的吸附更符合准二级动力学模型。M-LCNF/PI-1.00挤压吸附无水乙醇5次后，仍保持原吸附倍率的79.1%，表现出良好的可重复使用性，为制备高性能吸油材料提供了新策略。

关键词: 木质纤维素纳米纤丝, 聚酰亚胺, 气凝胶, 分离, 隔热, 动力学模型, 循环利用

Abstract:

Lignocellulosic nanofibril (LCNF) aerogels have the advantages of high porosity, low density, renewable and reusable raw materials, but their insufficient mechanical properties limit their application in the field of oil-water separation. To address this issue, LCNF/polyimide (PI) composite aerogels were created using freeze-drying and chemical vapor deposition. The results show that the strong hydrogen bond between PI and LCNF endowed aerogels with good mechanical and oil-water separation performance, with elasticity modulus ranging from 9.69 to 11.88 kPa and oil-absorption multiplicity ranging from 73.0 to 103.4 g·g^-1. Compared with M-LCNF aerogels, the elastic modulus of M-LCNF/PI aerogels increased by 1.459—2.015 times, and the adsorption capacity for a variety of organic solvents and oils increased by 1.6—21.0 g∙g^-1. M-LCNF/PI-1.00 aerogels maintained low density (8.66 g∙cm^-3), excellent hydrophobicity (water contact angle of 140.6°), good thermal stability (maximum decomposition rate temperature up to 363.1℃) and excellent thermal insulation performance of 0.04436 W∙m^-1∙K^-1. The adsorption of vacuum pump oil by M-LCNF/PI-1.00 was more consistent with a quasi-secondary kinetic model. The M-LCNF/PI-1.00 still retained 79.1% of the original adsorption capacity after 5 times of extrusion adsorption of anhydrous ethanol, showing good reusability and providing a new strategy for preparing high-performance oil-absorbing materials.

Key words: lignocellulosic nanofibril, polyimide, aerogel, separation, heat insulation, kinetic modeling, recycling

中图分类号:

TQ 353.9

李家顺, 李旺, 秦祖赠, 苏通明, 谢新玲, 纪红兵. 聚酰亚胺增强木质纤维素纳米纤丝气凝胶制备及其油水分离性能研究[J]. 化工学报, 2025, 76(5): 2169-2185.

Jiashun LI, Wang LI, Zuzeng QIN, Tongming SU, Xinling XIE, Hongbing JI. Preparation of polyimide-reinforced lignocellulosic nanofibril aerogel and its oil-water separation performance[J]. CIESC Journal, 2025, 76(5): 2169-2185.

图/表 17

图1 LCNF/PI复合气凝胶的制备过程

Fig.1 Preparation process of LCNF/PI composite aerogel

表1 疏水气凝胶的组成成分

Table 1 Composition of hydrophobic aerogels

样品	V_LCNF/ml	V_PI/ml	m_LCNF：m_PI
M-LCNF	10.00	0	—
M-LCNF/PI-0.25	9.75	0.25	39∶1
M-LCNF/PI-0.50	9.50	0.50	38∶2
M-LCNF/PI-0.75	9.25	0.75	37∶3
M-LCNF/PI-1.00	9.00	1.00	36∶4

图2 气凝胶的制备示意图

Fig.2 Schematic diagram of the construction of aerogel

图3 原料和气凝胶的红外光谱图

Fig.3 FTIR spectra of raw materials and aerogels

图4 气凝胶的宏观形貌和物理结构参数

Fig.4 Macroscopic morphology and physical structure parameters of aerogel

图5 气凝胶的扫描电镜图

Fig.5 SEM images of aerogels

图6 原料和气凝胶的孔结构

Fig.6 Pore structure of raw materials and aerogels

表2 气凝胶的孔结构参数

Table 2 Pore structure parameters of aerogels

样品	比表面积/ (m²∙g^-1)	孔体积/ (cm³∙g^-1)	平均孔直径/ nm
LCNF	2.27	0.0091	32.49
PI	7.50	0.0335	28.61
M-LCNF	2.89	0.0065	16.74
M-LCNF/PI-1.00	26.29	0.0622	11.97

图7 气凝胶的力学性能

Fig.7 Mechanical properties of aerogels

图8 气凝胶的疏水性能

Fig.8 Hydrophobic properties of aerogels

图9 气凝胶的热稳定性

Fig.9 Thermal stability of aerogels

表3 气凝胶的热参数

Table 3 Thermal parameters of aerogel

样品	最大分解速率温度/℃	最大分解速率/(%·℃^-1)	残留量/%	水含量/%
M-LCNF	362.5	-2.053	6.204	5.513
M-LCNF/PI-1.00	363.1	-1.970	6.590	5.644

图10 M-LCNF和M-LCNF/PI-1.00的吸油性能

Fig.10 Oil absorption properties of M-LCNF and M-LCNF/PI-1.00

图11 气凝胶的吸油速率和循环使用性能

Fig.11 Oil absorption rate and recycling performance of aerogels

表4 M-LCNF/PI-1.00吸附真空泵油的动力学参数

Table 4 Kinetic parameters of vacuum pump oils adsorbed by M-LCNF/PI-1.00

q_e,exp/

(g·g^-1)

准一级动力学模型

准二级动力学模型

k₁/s^-1

q_e,cal/(g·g^-1)

r 12

k₂/(g·g^-1∙s^-1)

q_e,cal/(g·g^-1)

r 22

表4 M-LCNF/PI-1.00吸附真空泵油的动力学参数

Table 4 Kinetic parameters of vacuum pump oils adsorbed by M-LCNF/PI-1.00

q_e,exp/

(g·g^-1)

准一级动力学模型

准二级动力学模型

k₁/s^-1

q_e,cal/(g·g^-1)

r 12

k₂/(g·g^-1∙s^-1)

q_e,cal/(g·g^-1)

r 22

79.36

0.01327

119.4

0.8406

4.637×10^-5

81.22

0.9795

图12 利用M-LCNF/PI-1.00模拟油水分离

Fig.12 Simulation of oil-water separation by M-LCNF/PI-1.00

图13 M-LCNF/PI-1.00气凝胶油水分离的机理

Fig.13 Mechanism of oil-water separation of M-LCNF/PI-1.00 aerogel

参考文献 45

1	Cherukupally P, Sun W, Williams D R, et al. Wax-wetting sponges for oil droplets recovery from frigid waters[J]. Science Advances, 2021, 7(11): eabc7926.
2	Tian G D, Duan C, Lu W L, et al. Cellulose acetate-based electrospun nanofiber aerogel with excellent resilience and hydrophobicity for efficient removal of drug residues and oil contaminations from wastewater[J]. Carbohydrate Polymers, 2024, 329: 121794.
3	Qiao A H, Huang R L, Penkova A, et al. Superhydrophobic, elastic and anisotropic cellulose nanofiber aerogels for highly effective oil/water separation[J]. Separation and Purification Technology, 2022, 295: 121266.
4	Fan B J, Bao X M, Pan S S, et al. High capillary effect and solar dual-drive nanofibrillated cellulose aerogels for efficient crude oil spill cleanup[J]. Chemical Engineering Journal, 2024, 480: 148149.
5	Miao Y, Liang Y P, Wang E F, et al. Magnetic superhydrophobic cellulose nanofibril based aerogel with rope-ladder like structure incorporating both superelasticity and excellent oil absorption[J]. Journal of Environmental Management, 2024, 358: 120909.
6	Xu H, Zhang Z, Jiang W, et al. Multifunctional amphibious superhydrophilic-oleophobic cellulose nanofiber aerogels for oil and water purification[J]. Carbohydrate Polymers, 2024, 330: 121774.
7	Liu Z S, Sheng Z Z, Bao Y Q, et al. Ionic liquid directed spinning of cellulose aerogel fibers with superb toughness for weaved thermal insulation and transient impact protection[J]. ACS Nano, 2023, 17(18): 18411-18420.
8	Sivaraman D, Nagel Y, Siqueira G, et al. Additive manufacturing of nanocellulose aerogels with structure-oriented thermal, mechanical, and biological properties[J]. Advanced Science, 2024, 11(24): 2307921.
9	Rafieian F, Hosseini M, Jonoobi M, et al. Development of hydrophobic nanocellulose-based aerogel via chemical vapor deposition for oil separation for water treatment[J]. Cellulose, 2018, 25(8): 4695-4710.
10	Zhang M L, Jiang S, Han F Y, et al. Anisotropic cellulose nanofiber/chitosan aerogel with thermal management and oil absorption properties[J]. Carbohydrate Polymers, 2021, 264: 118033.
11	Chen B Y, Hu Y C. Hierarchical aerogels based on cellulose nanofibers and long-chain polymers for enhancing oil-water separation efficiency[J]. Materials Today Nano, 2024, 26: 100469.
12	Chen X Y, Yang M Y, Cai X D, et al. Fabrication of wheat straw-based lignin containing nanofibril aerogels as recyclable absorbents for oil-water separation[J]. Cellulose, 2024, 31(1): 497-514.
13	Tang R, Xu S Q, Hu Y, et al. Multifunctional nano-cellulose aerogel for efficient oil-water separation: vital roles of magnetic exfoliated bentonite and polyethyleneimine[J]. Separation and Purification Technology, 2023, 314: 123557.
14	李明星, 谢慧红, 李帅, 等. 高疏水型纤维素纳米纤/聚乳酸杂化气凝胶用于高效油水分离[J]. 高分子材料科学与工程, 2022, 38(8): 104-112.
	Li M X, Xie H H, Li S, et al. Highly hydrophobic cellulose nanofiber/polylactic acid hybrid aerogel for efficient oil-water separation[J]. Polymer Materials Science & Engineering, 2022, 38(8): 104-112.
15	Liaw D J, Wang K L, Huang Y C, et al. Advanced polyimide materials: syntheses, physical properties and applications[J]. Progress in Polymer Science, 2012, 37(7): 907-974.
16	高端辉, 肖卫强, 高峰, 等. 聚酰亚胺基气凝胶材料的制备与应用[J]. 化工学报, 2022, 73(7): 2757-2773.
	Gao D H, Xiao W Q, Gao F, et al. Preparation and application of polyimide-based aerogels[J]. CIESC Journal, 2022, 73(7): 2757-2773.
17	Zheng R N, Hu J Y, Lin Z C, et al. Anisotropic polyimide/cellulose nanofibril composite aerogels for thermal insulation and flame retardancy[J]. ACS Applied Polymer Materials, 2023, 5(6): 4180-4189.
18	Wu T T, Dong J, Gan F, et al. Low dielectric constant and moisture-resistant polyimide aerogels containing trifluoromethyl pendent groups[J]. Applied Surface Science, 2018, 440: 595-605.
19	谢新玲, 李旺, 秦祖赠, 等. 一种疏水改性木质纤维素纳米纤丝及其制备方法: 116463873A[P]. 2023-07-21.
	Xie X X, Li W, Qin Z Z, et al. A hydrophobically modified lignocellulosic nanofibril and its preparation method: 116463873A[P]. 2023-07-21.
20	Fan B J, Wu L L, Ming A X, et al. Highly compressible and hydrophobic nanofibrillated cellulose aerogels for cyclic oil/water separation[J]. International Journal of Biological Macromolecules, 2023, 242: 125066.
21	刘会娥, 黄扬帆, 马雁冰, 等. 石墨烯基气凝胶对有机物的饱和吸附能力[J]. 化工学报, 2019, 70(1): 280-289.
	Liu H E, Huang Y F, Ma Y B, et al. Saturated adsorption capacities of graphene aerogels on organics[J]. CIESC Journal, 2019, 70(1): 280-289.
22	Chen W W, Zhou X M, Wan M M, et al. Recent progress on polyimide aerogels against shrinkage: a review[J]. Journal of Materials Science, 2022, 57(28): 13233-13263.
23	Tang R, Hu Y, Yan J Y, et al. Multifunctional carboxylated cellulose nanofibers/exfoliated bentonite/Ti₃C₂ aerogel for efficient oil adsorption and recovery: the dual effect of exfoliated bentonite and MXene[J]. Chemical Engineering Journal, 2023, 473: 145412.
24	Vimonses V, Lei S M, Jin B, et al. Kinetic study and equilibrium isotherm analysis of Congo Red adsorption by clay materials[J]. Chemical Engineering Journal, 2009, 148(2/3): 354-364.
25	Liu Y X, Wei H X, Liu Z W, et al. Ultrafast and energy-saving extraction of cellulose nanocrystals[J]. Green Chemistry, 2022, 24(18): 6823-6829.
26	Ji H, Xiang Z Y, Qi H S, et al. Strategy towards one-step preparation of carboxylic cellulose nanocrystals and nanofibrils with high yield, carboxylation and highly stable dispersibility using innocuous citric acid[J]. Green Chemistry, 2019, 21(8): 1956-1964.
27	Wang N N, Wang H, Wang Y Y, et al. Robust, lightweight, hydrophobic, and fire-retarded polyimide/MXene aerogels for effective oil/water separation[J]. ACS Applied Materials & Interfaces, 2019, 11(43): 40512-40523.
28	Wang Y M, Zeng X Y, Wang W, et al. Superhydrophobic polyimide/cattail-derived active carbon composite aerogels for effective oil/water separation[J]. Separation and Purification Technology, 2023, 308: 122994.
29	Luo B, Cai C C, Liu T, et al. Multiscale structural nanocellulosic triboelectric aerogels induced by hofmeister effect[J]. Advanced Functional Materials, 2023, 33(42): 2306810.
30	Zhu P H, Yu Z Y, Sun H, et al. 3D printed cellulose nanofiber aerogel scaffold with hierarchical porous structures for fast solar-driven atmospheric water harvesting[J]. Advanced Materials, 2024, 36(1): 2306653.
31	Yang X, Jiang P J, Xiao R, et al. Elastic agarose nanowire aerogels for oil-water separation and thermal insulation[J]. ACS Applied Nano Materials, 2022, 5(9): 12423-12434.
32	Li Y Z, Grishkewich N, Liu L L, et al. Construction of functional cellulose aerogels via atmospheric drying chemically cross-linked and solvent exchanged cellulose nanofibrils[J]. Chemical Engineering Journal, 2019, 366: 531-538.
33	Wang Y X, He T J, Liu M Y, et al. Fast and efficient oil-water separation under harsh conditions of the flexible polyimide aerogel containing benzimidazole structure[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 581: 123809.
34	Liao Y R, Zhang S Z, Yu S, et al. Microstructural evolution of bio-based chitosan aerogels for thermal insulator with superior moisture/fatigue resistance and anti-thermal-shock[J]. International Journal of Biological Macromolecules, 2024, 278: 134681.
35	Apostolopoulou-Kalkavoura V, Munier P, Bergström L. Thermally insulating nanocellulose-based materials[J]. Advanced Materials, 2021, 33(28): 2001839.
36	Li C J, Guo J X, Xu P K, et al. Facile preparation of superior compressibility and hydrophobic reduced graphene oxide@cellulose nanocrystals/EPDM composites for highly efficient oil/organic solvent adsorption and enhanced electromagnetic interference shielding[J]. Separation and Purification Technology, 2023, 307: 122775.
37	Sankhla S, Neogi S. Ambient-dried, scalable and biodegradable cellulose nanofibers aerogel for oil-spill cleanup[J]. Journal of Environmental Chemical Engineering, 2024, 12(3): 112745.
38	Lyu P, Xia L J, Liu X, et al. Self-cleaning superhydrophobic aerogels from waste hemp noil for ultrafast oil absorption and highly efficient PM removal[J]. Separation and Purification Technology, 2023, 306: 122503.
39	Mei J F, Ding Z L, Sun X Y, et al. A solvent-template ethyl cellulose-polydimethylsiloxane crosslinking sponge for rapid and efficient oil adsorption[J]. International Journal of Biological Macromolecules, 2023, 244: 125399.
40	Peng D, Zhao J, Liang X J, et al. Corn stalk pith-based hydrophobic aerogel for efficient oil sorption[J]. Journal of Hazardous Materials, 2023, 448: 130954.
41	Hou Y S, Liao J M, Li L, et al. A novel eco-friendly lightweight cellulose-based foam with superior resilience and hydrophobicity for selective oil/water separation[J]. Cellulose, 2024, 31(7): 4409-4420.
42	Huang B J, Jiang J C. Construction of super-hydrophobic lignocellulosic nanofibrils aerogels as speedy oil absorbents[J]. Applied Biochemistry and Biotechnology, 2024, 196(1): 220-232.
43	Guan Y H, Qiao D, Dong L M, et al. Efficient recovery of highly viscous crude oil spill by superhydrophobic ocean biomass-based aerogel assisted with solar energy[J]. Chemical Engineering Journal, 2023, 467: 143532.
44	Feng J D, Nguyen S T, Fan Z, et al. Advanced fabrication and oil absorption properties of super-hydrophobic recycled cellulose aerogels[J]. Chemical Engineering Journal, 2015, 270: 168-175.
45	Dilamian M, Noroozi B. Rice straw agri-waste for water pollutant adsorption: relevant mesoporous super hydrophobic cellulose aerogel[J]. Carbohydrate Polymers, 2021, 251: 117016.

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聚酰亚胺增强木质纤维素纳米纤丝气凝胶制备及其油水分离性能研究

Preparation of polyimide-reinforced lignocellulosic nanofibril aerogel and its oil-water separation performance

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