高疏水纳米纤维素-壳聚糖/膨润土气凝胶的构建及其高效油水分离的应用

徐诗琪; 周洲; 汤睿; 江露莹; 王俊辉; 金学群; 张菁玮; 廖丹葵; 童张法; 张寒冰

doi:10.13801/j.cnki.fhclxb.20230912.003

高疏水纳米纤维素-壳聚糖/膨润土气凝胶的构建及其高效油水分离的应用

doi: 10.13801/j.cnki.fhclxb.20230912.003

1.
广西大学　资源环境与材料学院，南宁 530004
2.
崇左南方水泥有限公司，广西钙基材料协同创新中心，崇左 532200
3.
广西大学　化学化工学院，广西钙基材料协同创新中心，南宁 530004

基金项目: 国家自然科学基金项目(52263029)；广西自然科学基金项目(2021GXNSFAA220035；2020GXNSFAA297036)；广西石化资源加工及过程强化技术重点实验室主任基金(2022Z005)；钙基材料协同创新中心横向科研项目(GJZX2022-2)

详细信息

通讯作者:
张寒冰，博士，副教授，研究方向为环保材料制备及水污染修复　E-mail: 24346260@qq.com

中图分类号: X703.1；TB332
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出版历程
- 收稿日期: 2023-07-08
- 修回日期: 2023-08-16
- 录用日期: 2023-08-25
- 网络出版日期: 2023-09-13
- 刊出日期: 2024-03-01

Construction of highly hydrophobic nanocellulose-chitosan/bentonite aerogel and its application of efficient oil-water separation

1.
School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China
2.
Guangxi Cooperative Innovation Centre for Calcium-Based Materials (GCICCM), Chongzuo South Cement CO. LTD., Chongzuo 532200, China
3.
Guangxi Cooperative Innovation Centre for Calcium-Based Materials (GCICCM), School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China

Funds: National Natural Science Foundation of China (52263029); Natural Science Foundation of Guangxi (2021GXNSFAA220035; 2020GXNSFAA297036); Petrochemical Resources Processing and Process Reinforcement Technology Key Laboratory Project of Guangxi Province (2022Z005); Calcium-based Materials Co-innovation Center Horizontal Research Project (GJZX2022-2)

摘要

摘要: 气凝胶具有高孔隙率和高吸附性的特点，因此在含油废水处理领域是一种具有前景的候选材料。目前，所报道的气凝胶仍存在机械强度不足、制作工艺复杂、制备成本高等问题，限制了气凝胶在油水分离领域的应用。膨润土(Bentonite，BT)具有价格低、来源丰富、机械性能优良等特点，能够有效地改善气凝胶的机械性能。本文通过简单的冷冻干燥-常温浸渍法，在羧基纤维素纳米纤维(Carboxycellulose nanofibres，CNF-C)与壳聚糖(Chitosan，CS)的交联网络上引入剥离膨润土(Exfoliated bentonite，BTex)，合成了疏水的纳米纤维素-壳聚糖/剥离膨润土气凝胶(CNC/BTex)。制备出的CNC/BTex气凝胶表现出优异的疏水性能(水接触角高达133°)；经过挤压后在5 s内可恢复形变，具有良好的力学性能；对不同油品(正己烷、环己烷、二氯甲烷、食用油和发动机油)的吸附容量为18.48~40.20 g·g⁻¹不等。以二氯甲烷和环己烷为主要研究对象，经过5次循环使用后依然保持稳定的吸油性能(维持在原始吸附量的90%)。本文的工作为制备低成本、高性能的油水分离吸附材料提供了参考。
- 油水分离 /
- 气凝胶 /
- 纤维素 /
- 壳聚糖 /
- 剥离膨润土
Abstract: Due to the high porosity and high absorption characteristics, aerogel has been a promising candidate material in the field of oily wastewater treatment. However, the reported aerogels were still suffering from insufficient mechanical strength, complicated fabrication process and high preparation cost, which limited the application of aerogels in the field of oil-water separation. Bentonite (BT) has the characteristics of low price, abundant source and excellent mechanical properties, which can effectively improve the mechanical properties of aerogels. In this paper, hydrophobic nanocellulose-chitosan/exfoliated bentonite aerogels (CNC/BTex) were synthesized by introducing exfoliated bentonite (BTex) onto a cross-linked network of carboxycellulose nanofibres (CNF-C) and chitosan (CS) by a simple freeze-drying and ambient temperature impregnation method. The prepared CNC/BTex aerogel exhibited excellent hydrophobic properties (water contact angle 133°), recovered deformation within 5 s after extrusion and showed good mechanical properties. The adsorption capacities for different oils (hexane, cyclohexane, dichloromethane, cooking oil and engine oil) ranged from 18.48-40.20 g·g⁻¹. Using dichloromethane and cyclohexane as the main research objects, the oil adsorption performance remained stable (90% of the original adsorption capacity) after five cycles of use. In summary, the present work provides a reference for the preparation of low-cost and high-performance adsorbent materials for oil-water separation.
- oil-water separation /
- aerogel /
- cellulose /
- chitosan /
- exfoliated bentonite

HTML全文

图 1 剥离膨润土(BTex)、羧基纤维素纳米纤维(CNF-C)、壳聚糖(CS)及纳米纤维素-壳聚糖/剥离膨润土气凝胶 (CNC/BTex)的XRD图谱

Figure 1. XRD patterns of exfoliated bentonite (BTex), carboxycellulose nanofibers (CNF-C), chitosan (CS) and nanocellulose-chitosan/exfoliated bentonite aerogels (CNC/BTex)

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图 2 BTex、CNF-C、CS及CNC/BTex的FTIR图谱

Figure 2. FTIR spectra of BTex, CNF-C, CS and CNC/BTex

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图 3 CNF-C (a)、CS (b)、BTex (c)和CNC/BTex ((d)~(f))的SEM图像

Figure 3. SEM images of CNF-C (a), CS (b), BTex (c) and CNC/BTex ((d)-(f))

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图 4 CNC/BTex的N₂吸附-脱附等温曲线(a)和孔径分布(b)

STP—Standard temperature and pressure

Figure 4. N₂ adsorption-desorption isothermal curves (a) and pore width distribution (b) of CNC/BTex

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图 5 油(用油红O染成红色)和水(用亚甲基染成蓝色)液滴在原始CNC/BTex (a)和CNC/BTex (b)气凝胶表面上的照片及CNC/BTex气凝胶的表面(c)和内部(d)的水接触角(WCA)

Figure 5. Photographs of oil (dyed red with Oil Red O) and water (dyed blue with methylene) droplets on the surface of original CNC/BTex (a) and CNC/BTex aerogel (b); Water contact angle (WCA) on the surface (c) and the interior (d) of CNC/BTex aerogel

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图 6 CNC/BTex在20%、40%及60%应变下(a) 及其在60%应变下20个循环的应力-应变曲线(b)

Figure 6. Stress-strain curves of CNC/BTex at 20%, 40% and 60% strain (a) and at 60% strain for 20 cycles (b)

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图 7 CNC/BTex受外力挤压(a)和去除外力回弹后的照片(b)

Figure 7. Photographs of CNC/BTex after extrusion (a) and rebound after removal of external forces (b)

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图 8 通过CNC/BTex气凝胶(用油红O染成红色的正己烷)去除水表面的机油

Figure 8. Removal of n-hexane on the surface of water by CNC/BTex aerogel (n-hexane dyed red with Oil Red O)

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图 9 CNC/BTex对各种油的吸附能力和挤压后的油残留量

Figure 9. Adsorption capacities of CNC/BTex for various oils and the residual amount of oil after squeezing

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图 10 通过手动挤压CNC/BTex释放正己烷((a), (b))和撤去外力后CNC/BTex回弹的照片(c)

Figure 10. Photographs of releasing n-hexane by hand squeezing CNC/BTex ((a), (b)) and CNC/BTex rebound after removal of external forces (c)

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图 11 CNC/BTex气凝胶对二氯甲烷和环己烷的循环使用性

Figure 11. Recyclability of CNC/BTex aerogels to dichloromethane and cyclohexane

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表 1 CNC/BTex与文献报道的多孔材料的比较

Table 1. Comparison of CNC/BTex with porous materials reported in the literature

Material	Preparation method	Adsorption capacity/(g·g^–1)	Ref.
Kapok/cellulose aerogel	Freeze-drying	141.9	[12]
Graphene oxide decorated polyacrylonitrile nanofiber/ carbon nanotubes (PANF/CNTs) composite aerogel	Freeze-drying and heat crosslinking	36.07-65.09	[35]
Cellulose nanofiber-polydimethylsiloxane aerogel	Directional freeze-drying, solution immersion and heat treatment	24-48	[36]
Graphene/chitosan composite aerogel	Directional freeze-drying	18-45	[37]
Stem fiber/chitosan composite aerogel	Freeze-drying	12.34-21.85	[38]
Chitosan-enhanced hydrophobic silica aerogel	Sol-gel method and atmospheric drying method	5-9	[39]
Polydimethylsiloxane/SiO₂ superhydrophobic rock wool	Dipping	8-13	[40]
CNC/BTex aerogel	Freeze-drying	18.48-40.20	This study

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