碳基复合材料在油水分离领域的研究进展

doi:10.19965/j.cnki.iwt.2024-0717

摘要/Abstract

摘要：

海上石油泄漏和工业含油废水严重威胁着水生环境和人类健康，因此对含油废水的治理已成为一个广泛关注的热点。碳基复合材料因其独特的物理化学性质，在油水分离领域展现出广阔的应用前景。综述了近年来碳基复合材料在油水分离领域的研究进展，首先从表面润湿性的角度阐述了油水分离的理论基础，之后分类评述了不同类型碳基复合材料，如石墨基复合材料、碳纳米管复合材料、碳基气凝胶等在油水分离领域的应用可行性以及改性方式。最后，展望了碳基复合材料在油水分离领域的发展方向，提出未来应侧重于开发具有可切换润湿性以同时吸附多种污染物组分的碳基材料，耐极端环境的高稳定性碳基材料，以及具有自清洁、自修复等特殊功能的碳基材料。

关键词: 碳基复合材料, 油水分离, 石墨基, 碳纳米管, 碳气凝胶, 特殊润湿性

Abstract:

Offshore oil spills and industrial oily wastewater pose a serious threat to the aquatic environment and human health, making the treatment of oily wastewater become a widely concerned hot topic. Carbon based composite materials have shown broad application prospects in the field of oil-water separation due to their unique physical and chemical properties. This paper reviewed the research progress of carbon based composites in the field of oil-water separation in recent years. First, the theoretical basis of oil-water separation was introduced from the perspective of surface wettability. Then, the application feasibility and modification methods of different types of carbon based composites, such as graphite based composites, carbon nanotube composites, carbon based aerogels, in the field of oil-water separation were introduced in detail. Finally, the development direction of carbon based composite materials in the field of oil-water separation was discussed, and it was proposed that the future should focus on developing carbon based materials with switchable wettability to simultaneously adsorb multiple pollutant components, high stability carbon based materials resistant to extreme environments, and carbon based materials with special functions such as self-cleaning and self-healing.

Key words: carbon based composite material, oil-water separation, graphite based, carbon nanotubes, carbon aerogel, special wettability

中图分类号:

X703

韩少勋, 张楠, 殷承玉, 田琳, 陈培鑫. 碳基复合材料在油水分离领域的研究进展[J]. 工业水处理, 2025, 45(6): 127-137.

Shaoxun HAN, Nan ZHANG, Chengyu YIN, Lin TIAN, Peixin CHEN. Research progress of carbon based composite materials in oil-water separation field[J]. Industrial Water Treatment, 2025, 45(6): 127-137.

https://www.iwt.cn/CN/Y2025/V45/I6/127

图/表 5

图1 材料表面润湿性理论

θ Y

、

θ W

、

θ C B

分别表示各模型的接触角；

γ S L

、

γ L V

、

γ S V

分别表示固相与液相、液相与气相、固相与气相的表面张力；r表示粗糙度；r _f表示粗糙因子；f _SL表示水滴下面与固体基底的接触面积占复合面的面积分数。

Fig.1 Theory of surface wettability of materials

图1 材料表面润湿性理论

θ Y

、

θ W

、

θ C B

分别表示各模型的接触角；

γ S L

、

γ L V

、

γ S V

Fig.1 Theory of surface wettability of materials

图2 固体（膜）-油-水三相体系中油滴润湿行为及扩散示意

Fig.2 Schematic diagram of oil droplet wetting behavior and diffusion in solid（membrane）-oil-water three-phase system

图3 GOCCF膜（a）、GO@MS和rGO@MS（b）以及PGT膜（c）制备和乳液分离工艺

Fig.3 Preparation and emulsion separation processes of GOCCF membranes（a），GO@MS and rGO@MS（b），and PGT membranes（c）

图4 PU和MWCNT之间的π-π相互作用示意（a）及超疏水超亲油PU-CNT-PDA-ODA海绵的制备过程

Fig.4 Schematic diagram of π-π interactions between PU and MWCNT（a） and preparation process of superhydrophobic and superoleophilic PU-CNT-PDA-ODA sponges（b）

图5 超轻、各向异性和疏水性CS/CNF气凝胶的设计策略（a）和CCAs的制备（b）

Fig.5 Design strategy for ultralight，anisotropic and hydrophobic CS/CNF aerogels（a），and the preparation of CCAs（b）

参考文献 61

1	MISHRA S， CHAUHAN G， VERMA S，et al. The emergence of nanotechnology in mitigating petroleum oil spills［J］. Marine Pollution Bulletin，2022，178：113609. doi:10.1016/j.marpolbul.2022.113609
2	CHEN Dazhe， LAWRENCE K G， SANDLER D P. Nontraditional occupational exposures to crude oil combustion disasters and respiratory disease risk：A narrative review of literature［J］. Current Allergy and Asthma Reports，2023，23（6）：299-311. doi:10.1007/s11882-023-01078-x
3	WANG Xiao， YU Pengxiang， ZHANG Kangmin，et al. Superhydrophobic/superoleophilic cotton for efficient oil-water separation based on the combined octadecanoyl chain bonding and polymer grafting via surface-initiated ATRP［J］. ACS Applied Polymer Materials，2019，1（11）：2875-2882. doi:10.1021/acsapm.9b00585
4	BENSADOK K， BELKACEM M， NEZZAL G. Treatment of cutting oil/water emulsion by coupling coagulation and dissolved air flotation［J］. Desalination，2007，206（1/2/3）：440-448.
5	WANG Chizhou， WU Shaodi， ZHANG Ning，et al. Efficient oil-water separation by novel biodegradable all cellulose composite filter paper［J］. Green Energy & Environment，2023，8（6）：1673-1682. doi:10.1016/j.gee.2022.03.013
6	GUPTA S， TAI N H. Carbon materials as oil sorbents：A review on the synthesis and performance［J］. Journal of Materials Chemistry A，2016，4（5）：1550-1565. doi:10.1039/c5ta08321d
7	LI Jian， SUN Bohui， ZUO Linxuan，et al. Facile preparation of light-weight and robust carbon aerogel monoliths for high-temperature thermal insulation and oil-water separation［J］. Carbon，2024，218：118734. doi:10.1016/j.carbon.2023.118734
8	JUNAIDI N F D， OTHMAN N H， FUZIL N S，et al. Recent development of graphene oxide-based membranes for oil-water separation：A review［J］. Separation and Purification Technology，2021，258：118000. doi:10.1016/j.seppur.2020.118000
9	LIU Hongzhi， GENG Biyao， CHEN Yufei，et al. Review on the aerogel-type oil sorbents derived from nanocellulose［J］. ACS Sustainable Chemistry & Engineering，2017，5（1）：49-66. doi:10.1021/acssuschemeng.6b02301
10	HU Xiaodong， YANG Bo， HAO Ming，et al. Preparation of high elastic bacterial cellulose aerogel through thermochemical vapor deposition catalyzed by solid acid for oil-water separation［J］. Carbohydrate Polymers，2023，305：120538. doi:10.1016/j.carbpol.2023.120538
11	YU Haiyang， WU Min， DUAN Gaigai，et al. One-step fabrication of eco-friendly superhydrophobic fabrics for high-efficiency oil/water separation and oil spill cleanup［J］. Nanoscale，2022，14（4）：1296-1309. doi:10.1039/d1nr07111d
12	SUTAR R S， LATTHE S S， WU Xinna，et al. One-step candle soot-PDMS dip-coated superhydrophobic stainless steel mesh for oil-water separation［J］. Materials Letters，2024，357：135791. doi:10.1016/j.matlet.2023.135791
13	XIE Shian， GUO Lijun， ZHANG Manbo，et al. Durable hydrophobic ceramics of Al₂O₃-ZrO₂ modified by hydrophilic silane with high oil/water separation efficiency［J］. Journal of Porous Materials，2021，28（4）：1115-1127. doi:10.1007/s10934-021-01055-7
14	LI Wei， SHEN Mao， YU Yunjie，et al. Superhydrophobic covalent organic frameworks prepared via nucleophilic substitution reaction for effective oil/water separation［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2022，655：130239. doi:10.1016/j.colsurfa.2022.130239
15	PHAN N M， KIM J H， KIM J，et al. Durable tetra-scale superhydrophobic coatings with virus-like nanoparticles for oil-water separations［J］. Applied Surface Science，2021，570：151088. doi:10.1016/j.apsusc.2021.151088
16	YOUNG T. An essay on the cohesion of fluids［J］. Philosophical Transactions of the Royal Society of London Series Ⅰ，1805，95：65-87. doi:10.1098/rstl.1805.0005
17	崔久云. 超亲水/水下超疏油PVDF复合膜的制备及油/水乳液分离性能研究［D］. 镇江：江苏大学，2020.
	CUI Jiuyun. Preparation of super hydrophilic/underwater super oleophobic PVDF composite membrane and study on separation performance of oil/water emulsion［D］. Zhenjiang：Jiangsu University，2020.
18	TESHIMA H， KUSUDO H， BISTAFA C，et al. Quantifying interfacial tensions of surface nanobubbles：How far can Young’s equation explain？［J］. Nanoscale，2022，14（6）：2446-2455. doi:10.1039/d1nr07428h
19	WENZEL R N. Resistance of solid surfaces to wetting by water［J］. Industrial & Engineering Chemistry，1936，28（8）：988-994. doi:10.1021/ie50320a024
20	CASSIE A B D， BAXTER S. Wettability of porous surfaces［J］. Transactions of the Faraday Society，1944，40：546-551. doi:10.1039/tf9444000546
21	HUANG Shilin， RAS R H A， TIAN Xuelin. Antifouling membranes for oily wastewater treatment：Interplay between wetting and membrane fouling［J］. Current Opinion in Colloid & Interface Science，2018，36：90-109. doi:10.1016/j.cocis.2018.02.002
22	APLAN M P， GOMEZ E D. Recent developments in chain-growth polymerizations of conjugated polymers［J］. Industrial & Engineering Chemistry Research，2017，56（28）：7888-7901. doi:10.1021/acs.iecr.7b01030
23	PI Peng， REN Zhiying， YANG Yu，et al. A review of various dimensional superwetting materials for oil-water separation［J］. Nanoscale，2024，16（37）：17248-17275. doi:10.1039/d4nr01473a
24	LI Bingfan， QIAN Xiaowen， RAN Longfei，et al. Applications and challenges of superwetted oil-water separation membranes in air under liquids and in specific environments［J］. Progress in Organic Coatings，2024，195：108673. doi:10.1016/j.porgcoat.2024.108673
25	KIM B S， HARRIOTT P. Critical entry pressure for liquids in hydrophobic membranes［J］. Journal of Colloid and Interface Science，1987，115（1）：1-8. doi:10.1016/0021-9797(87)90002-6
26	MOSADEGH-SEDGHI S， RODRIGUE D， BRISSON J，et al. Wetting phenomenon in membrane contactors：Causes and prevention［J］. Journal of Membrane Science，2014，452：332-353. doi:10.1016/j.memsci.2013.09.055
27	和玉光，郝思嘉，杨程. 石墨烯及其复合材料吸油性能研究进展［J］. 化学研究，2022，33（1）：9-25.
	HE Yuguang， HAO Sijia， YANG Cheng. Research progress of graphene and its composites for oil absorption［J］. Chemical Research，2022，33（1）：9-25.
28	JUNAIDI N F D， OTHMAN N H， SHAHRUDDIN M Z，et al. Fabrication and characterization of graphene oxide-polyethersulfone（GO-PES） composite flat sheet and hollow fiber membranes for oil-water separation［J］. Journal of Chemical Technology & Biotechnology，2020，95（5）：1308-1320. doi:10.1002/jctb.6366
29	YANG Shaolin， LI Jinze， YANG Na，et al. Underwater superoleophobic graphene oxide-connected cotton fibers membrane for antifouling oil/water separation［J］. Journal of Water Process Engineering，2021，44：102334. doi:10.1016/j.jwpe.2021.102334
30	YANG Shaolin， LI Jinze， ZHEN Cheng，et al. Graphene-based melamine sponges with reverse wettability for oil/water separation through absorption and filtration［J］. Journal of Environmental Chemical Engineering，2022，10（3）：107543. doi:10.1016/j.jece.2022.107543
31	ZHONG Qi， SHI Guogui， SUN Qing，et al. Robust PVA-GO-TiO₂ composite membrane for efficient separation oil-in-water emulsions with stable high flux［J］. Journal of Membrane Science，2021，640：119836. doi:10.1016/j.memsci.2021.119836
32	XIE Wei， CHEN Mao， WEI Shuxia，et al. Lignin nanoparticles-intercalated reduced graphene oxide/glass fiber composite membranes for highly efficient oil-in-water emulsions separation in harsh environment［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2022，648：129190. doi:10.1016/j.colsurfa.2022.129190
33	FENG Xiaofang， YU Zongxue， LONG Runxuan，et al. Polydopamine intimate contacted two-dimensional/two-dimensional ultrathin nylon basement membrane supported RGO/PDA/MXene composite material for oil-water separation and dye removal［J］. Separation and Purification Technology，2020，247：116945. doi:10.1016/j.seppur.2020.116945
34	MUSTAFA S A， AMOOEY A A， AL-JANABI O Y T. Demulsification of water-in-crude oil emulsion via novel Fe₃O₄@ethylene oxide-propylene oxide copolymer decorated graphene oxide or multiwall carbon nanotubes magnetic nanodemulsifiers［J］. Chemical Papers，2024，78（7）：4165-4174. doi:10.1007/s11696-024-03377-7
35	米远祝. 破乳剂、碳纳米管/超支化聚合物及其制备方法和应用［Z］. 2024-05-10.
36	LIU Juan， LI Xiaocheng， LIU Jun，et al. Molecular level separation of crude oil/water emulsion on carbon nanotube surface induced by weak interaction：A molecular dynamic simulation study［J］. Journal of Dispersion Science and Technology，2020，41（13）：1991-2001. doi:10.1080/01932691.2019.1645026
37	JURAIJ K， CHINGAKHAM C， MANAF O，et al. Polyurethane/multi-walled carbon nanotube electrospun composite membrane for oil/water separation［J］. Journal of Applied Polymer Science，2022，139（19）：52117. doi:10.1002/app.52117
38	WANG Huaiyuan， WANG Enqun， LIU Zhanjian，et al. A novel carbon nanotubes reinforced superhydrophobic and superoleophilic polyurethane sponge for selective oil-water separation through a chemical fabrication［J］. Journal of Materials Chemistry A，2015，3（1）：266-273. doi:10.1039/c4ta03945a
39	YE Shihang， WANG Bo， SHI Yutao，et al. Superhydrophobic and superelastic thermoplastic polyurethane/multiwalled carbon nanotubes porous monolith for durable oil/water separation［J］. Composites Communications，2020，21：100378. doi:10.1016/j.coco.2020.100378
40	ZHANG Tao， GU Bin， QIU Fengxian，et al. Preparation of carbon nanotubes/polyurethane hybrids as a synergistic absorbent for efficient oil/water separation［J］. Fibers and Polymers，2018，19（10）：2195-2202. doi:10.1007/s12221-018-8399-1
41	JING Zefeng， DING Jichao， ZHANG Tao，et al. Flexible，versatility and superhydrophobic biomass carbon aerogels derived from corn bracts for efficient oil/water separation［J］. Food and Bioproducts Processing，2019，115：134-142. doi:10.1016/j.fbp.2019.03.010
42	LIU Yu， PENG Yinxian， ZHANG Tao，et al. Superhydrophobic，ultralight and flexible biomass carbon aerogels derived from sisal fibers for highly efficient oil-water separation［J］. Cellulose，2018，25（5）：3067-3078. doi:10.1007/s10570-018-1774-7
43	YUAN Dengsen， ZHANG Tao， GUO Qing，et al. Superhydrophobic hierarchical biomass carbon aerogel assembled with TiO₂ nanorods for selective immiscible oil/water mixture and emulsion separation［J］. Industrial & Engineering Chemistry Research，2018，57（43）：14758-14766. doi:10.1021/acs.iecr.8b03661
44	LIU Yu， SHI Tianhui， ZHANG Tao，et al. Cellulose-derived multifunctional nano-CuO/carbon aerogel composites as a highly efficient oil absorbent［J］. Cellulose，2019，26（9）：5381-5394. doi:10.1007/s10570-019-02484-z
45	DAI Yuting， JING Zefeng， QIU Zhiwei，et al. Multifunctional biomass carbon fiber aerogel based on resource utilization of agricultural waste—peanut shells for fast and efficient oil-water/emulsion separation［J］. Materials Science and Engineering：B，2022，283：115819.
46	冯子豪. 木质素基超细碳纤维气凝胶的制备及其性能研究［D］. 青岛：青岛大学，2024.
	FENG Zihao. Preparation and properties of lignin-based ultrafine carbon fiber aerogels［D］. Qingdao：Qingdao University，2024.
47	陈鸿，刘其霞，季涛，等. 碳材料在纳米纤维油水分离膜中的应用进展［J］. 棉纺织技术，2022，50（7）：79-84.
	CHEN Hong， LIU Qixia， JI Tao，et al. Application progress of carbon material in nanofiber oil-water separation membrane［J］. Cotton Textile Technology，2022，50（7）：79-84.
48	SUN Yan， YE Wenjie， XI Jianfeng，et al. Ultralight and shape recovery bio-based aerogel for oil-water separation［J］. Journal of Environmental Chemical Engineering，2022，10（6）：108822. doi:10.1016/j.jece.2022.108822
49	HAN Peixing， NIE Wenjie， ZHAO Guanjia，et al. Theoretical investigation on the structure and physicochemical properties of choline chloride-based deep eutectic solvents［J］. Journal of Molecular Liquids，2022，366：120243.
50	LIU Xingyu， Hong OU， GREGERSEN H，et al. Deep eutectic solvent-based ultrasound-assisted extraction of polyphenols from Cosmos sulphureus ［J］. Journal of Applied Research on Medicinal and Aromatic Plants，2023，32：100444. doi:10.1016/j.jarmap.2022.100444
51	LONG Sishi， FENG Yunchao， LIU Yizheng，et al. Renewable and robust biomass carbon aerogel derived from deep eutectic solvents modified cellulose nanofiber under a low carbonization temperature for oil-water separation［J］. Separation and Purification Technology，2021，254：117577.
52	MA Xiang， ZHOU Shuang， LI Junting，et al. Natural microfibrils/regenerated cellulose-based carbon aerogel for highly efficient oil/water separation［J］. Journal of Hazardous Materials，2023，454：131397. doi:10.1016/j.jhazmat.2023.131397
53	LIN Jun， DU Yile， MA Xiaoxiao，et al. Choline chloride/urea etched carbon fiber to improve the elasticity of biomass-based carbon aerogel for efficient oil-water separation［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2023，669：131506. doi:10.1016/j.colsurfa.2023.131506
54	MEDRONHO B， LINDMAN B. Competing forces during cellulose dissolution：From solvents to mechanisms［J］. Current Opinion in Colloid & Interface Science，2014，19（1）：32-40. doi:10.1016/j.cocis.2013.12.001
55	MA Zihao， HAN Ying， XING Xinyue，et al. Preparation of micro-convex rough interface carbon aerogels with cellulose-lithium bromide（LiBr） molten salt hydrate gelled system and application of oil-water separation［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2022，650：129624. doi:10.1016/j.colsurfa.2022.129624
56	MEDRONHO B， LINDMAN B. Brief overview on cellulose dissolution/regeneration interactions and mechanisms［J］. Advances in Colloid and Interface Science，2015，222：502-508. doi:10.1016/j.cis.2014.05.004
57	MOFOKENG M， NTHUNYA L N， GUTIERREZ L，et al. Perflurooctyltriethoxy silane and carbon nanotubes-modified PVDF superoleophilic nanofibre membrane for oil-in-water adsorption and recovery［J］. Journal of Environmental Chemical Engineering，2020，8（6）：104497. doi:10.1016/j.jece.2020.104497
58	LI Bojun， TANG Wenjing， ZHOU Yue，et al. Bioinspired copper-graphene oxide hybrid membrane prepared via electrochemical-driven strategy：Design，mechanism，and oil-water separation［J］. Separation and Purification Technology，2023，319：124037. doi:10.1016/j.seppur.2023.124037
59	CAI Huidong， DUAN Chongxiong， FU Mingli，et al. Scalable fabrication of superhydrophobic coating with rough coral reef-like structures for efficient self-cleaning and oil-water separation：An experimental and molecular dynamics simulation study［J］. Small，2023，19（32）：2207118. doi:10.1002/smll.202207118
60	吕欣妍. 金属氧化物纳米材料的表面修饰及其在分离与富集中的应用［J］. 长春：吉林大学，2022．
	Xinyan LÜ. Surface modification of metal oxide nanomaterials and its application in separation and enrichment［D］. Changchun：Jilin University，2022．
61	FAN Songlin， LI Zhenzhou， FAN Chao，et al. Fast-thermoresponsive carboxylated carbon nanotube/chitosan aerogels with switchable wettability for oil/water separation［J］. Journal of Hazardous Materials，2023，433：128808. doi:10.1016/j.jhazmat.2022.128808

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