壳聚糖复合渗透汽化膜分离有机溶剂的研究进展

冯颖; 王卓; 王子鑫; 张建伟; 董鑫

壳聚糖复合渗透汽化膜分离有机溶剂的研究进展

沈阳化工大学　机械与动力工程学院沈阳110142

基金项目: 国家自然科学基金委(21406142);辽宁省教育厅2023年度基本科研项目面上项目(JYTMS20231492);沈阳化工大学优青托举计划项目(2022YQ005);

详细信息

通讯作者:
董鑫,博士,副教授,硕士生导师,研究方向为环境流体多相流传递理论与技术装备。　E-mail:dongxin1106@syuct.edu.cn

中图分类号: TB332;TQ028.4
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- 被引次数: 0
出版历程
- 收稿日期: 2024-05-09
- 修回日期: 2024-06-26
- 录用日期: 2024-07-13
- 网络出版日期: 2024-07-30

Study on the progress of chitosan composite pervaporation membrane for the separation of organic solvents

College of mechanical and power engineering, Shenyang University of chemical technology, Shenyang 110142, China

Funds: National Natural Science Foundation of China(No. 21406142); Liaoning Provincial Department of Education 2023 Basic Research Project Top Level Project (No. JYTMS20231492); Shenyang University of Chemical Technology UYC Support Programme Project (No. 2022YQ005)

摘要

摘要: 有机溶剂的高效分离与纯化是化学合成、生物技术、药物研发等领域中不可或缺的重要环节，含有机溶剂的废水若直接排放会对环境和人类健康造成极大危害，并造成资源浪费。渗透汽化(PV)是一种新型膜分离技术，利用膜对不同组分的选择性和渗透速率差异实现对有机溶剂的分离。本文介绍了渗透汽化分离有机溶剂的原理以及常用渗透汽化膜材料，详细阐述了壳聚糖渗透汽化膜应用于有机溶剂分离的研究进展，从乙醇、异丙醇、丙酮等有机溶剂与水的分离和有机溶剂混合物分离两个方面进行了总结。归纳了壳聚糖复合渗透汽化膜用于提高有机溶剂分离与提纯效率的方法与分离机制。最后，对利用天然生物质壳聚糖基复合渗透汽化膜分离有机溶剂的发展方向进行了展望。
- 壳聚糖 /
- 渗透汽化膜 /
- 有机溶剂 /
- 分离 /
- 废水处理 /
- 膜材料
Abstract: The efficient separation and purification of organic solvents is an important and indispensable link in the fields of chemical synthesis, biotechnology, and drug discovery, etc. Direct discharge of wastewater containing organic solvents can cause great harm to the environment and human health, and result in resource waste. Pervaporation (PV) is a novel membrane separation technology that utilizes membrane selectivity for different components and permeation rate differences to achieve separation of organic solvents. This paper introduces the principles of pervaporation for organic solvent separation and details commonly used pervaporation membrane materials. It reviews the research progress on chitosan pervaporation membranes for organic solvent separation, focusing on separating solvents like ethanol, isopropanol, and acetone from water, as well as the separation of organic solvents mixtures. Furthermore, summarized the methods and separation mechanisms of chitosan composite pervaporation membranes for improving the efficiency of organic solvent separation and purification. Finally, the development direction of using natural biomass chitosan-based composite pervaporation membranes for the separation of organic solvents is discussed.
- chitosan /
- pervaporation membrane /
- organic solvent /
- separation /
- Wastewater treatment /
- Membrane material

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图 1 渗透汽化膜分离原理

Figure 1. Pervaporation membrane separation principle

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图 2 壳聚糖分子结构式

Figure 2. Chitosan molecular structure formula

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图 3 水和乙醇通过NU-906/CS MMMs运输机理示意图^[40]

Figure 3. Schematic representation of the mechanism for water and ethanol transfer through NU-906/CS MMMs^[40]

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图 4 制备膜的分离因子(α) ^[48]

Figure 4. Separation factor (α) of the prepared membranes^[48]

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图 5 水和丙酮在CS-SCMS杂交膜内运输的示意图^[57]

Figure 5. Schematic representation of water and ace- tone transport within CS-SCMS hybrid membrane^[57]

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表 1 常见有机渗透汽化膜材料

Table 1. Common organic permeable vapour membrane materials

Membrane materials	Characteristic	Examples of applications for separating organic solvents	Reference
Polyvinyl alcohol (PVA)	The affinity for water is higher than that of organic solvents, but it is easy to contaminate and more costly.	Silicotungstic acid (STA) and phosphomolybdic acid (PMA) are loaded into polyvinyl alcohol (PVA) matrix to produce hybrid membranes. The flux and selectivity values of the hybrid PVA membranes loaded with 5 wt% STA and 5 wt% PMA were 0.499 kg/m²·h,12848; 0.471 kg/m²·h, 74991,respectively.	[19]
Polyimide (PI)	High temperature stability, excellent mechanical properties but expensive, difficult to process and not easy to degrade.	PI/ZIF-8 hybrid membrane consisting of 2% (ZIF-8) mass fraction. At 40℃, the fluxes and separation factors are 242.2 g/(m²·h), 17.8 and 126.2 g/(m²·h), 55.2 for the DMF/H₂O and DMAc/H₂O systems, respectively.	[20]
Sodium alginate (SA)	Excellent stability, wear resistance. However, short service life, easy to contamination and scaling.	SA/phosphotungstic acid (PTA) hybrid membranes for methanol/water separation. 6 wt% PTA, 30℃, 95 wt% methanol solution, the membrane flux and separation factor were 318.2 g/(m²·h) and 656.9, respectively, which were 3.7 and 26.3 times higher than those of pure sodium alginate membrane.	[21]
Polysulfone (PES)	Chemical resistant and stable, but more expensive and susceptible to contaminateon.	Fluoropolymer-containing composite membranes (PFHI /PES) are prepared, and the separation factor as well as the total permeate flux are 194.19 and g/(m²·h) at 20℃, 98 wt% acetic acid/water solution, respectively.	[22]
Chitosan (CS)	Excellent antimicrobial, de-gradability and regeneration properties. However, pure chitosan membranes may have low mechanical strength and permeability may be easily affected by temperature, etc., and need to be modified to show good performance.	PVA-CS-O-MWNTs/PAN hollow fibre membranes are prepared for methanol (MeOH)/dimethyl carbonate (DMC) separation by impregnation coating. 0.1 wt% O-MWNTs, thermal treatment temperature of 80℃, feed temperature of 40℃, 70 wt% MeOH, permeate flux of 210 g/(m²·h) , and methanol selectivity of 7.82.	[23]

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表 2 CS复合渗透汽化膜分离乙醇/水

Table 2. Chitosan composite pervaporation membrane for ethanol/water separation

Pervaporation membrane	Ethnol/wt%	Particle/mixture loading/wt%	Temperature/℃	Fluxes/(g·m^-2·h^-1)	Separation factor α	Reference
CS/ Ti₃C₂T_x	99.7	3%MXene(Ti₃C₂T_x)	50	1400	1421	[39]
CS/NU-906	90	5% NU-906	76	1086	2651	[40]
SiO /CS	99.5	0.05% siloxane	25	468	2182	[41]
CS	90	0	60	400	500	[42]
CS/PSS	90	0.75% PSS	70	495	904	[43]
(CS-P)/ALG	96	10% CS-P	25	1900	136.2	[44]
Al-MOF/CS	90	0.15%Al-MOF	25	378	3429	[45]
Notes：Ti₃C₂T_x (MXene) multilayer Nanoflake (Ti₃C₂T_x); siloxane(SiO); poly(4-styrenesulfonic acid) (PSS); Phosphorylated chitosan (CS-P) ; alginate(ALG); Aluminum-Metal organic Framework (Al-MOF)

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表 3 CS复合渗透汽化膜分离异丙醇/水

Table 3. Chitosan composite pervaporation membrane for isopropanol/water separation

Pervaporation membrane	Isopropanol/wt%	Particle/mixture loading/wt%	Temperature/℃	Fluxes/(g·m^-2·h^-1)	Separation Factor α	Reference
CS/PVA	90	75% CS	60	644	Water permeability>99.9%	[47]
CS/PVA/NH₂-MWCNT	70	10%NH₂-MWCNT	60	795	99.5	[48]
CS-PAN	90	-----	70	330	1410	[49]
GTMAC/CS	90	40% GTMAC	30	691	2133	[50]
CS/NAY	95	40% NAY	30	115	2620	[51]
CS/Gel	90	15%Gel	30	42.01	6330	[52]
TiO₂/CS	95	40% TiO₂	30	121.7	94984	[53]
Notes：polyvinyl alcohol (PVA); polyacrylonitrile (PAN); Glycidyltrimethylammonium chloride (GTMAC); Multi walled carbon nanotubes (MWCNT); NaY zeolite (NAY); Gelatin (Gel); Titanium Dioxide (TiO₂)

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表 4 CS复合渗透汽化膜分离丙酮/水

Table 4. Chitosan composite pervaporation membrane for acetone/water separation

Pervaporation membrane	Actone/wt%	Particle/mixture loading/wt%	Temperature/℃	Fluxes/(g·m^-2·h^-1)	Separation Factor α	Reference
CS/PVA-MWCNT/PVDF	95	0.06%PVA-MWCNT	30-50	89	1450.5	[55]
K⁺MMT-CS/PAN	95	10% K⁺MMT	50	1560	2200	[56]
SCMS-CS/PAN	90	2% SCMS	30	1810	832	[57]
NaMMT/MA/PVA-CS	99	39.3%CS;3%M；3% NaMMT	30-45	176-733	277-168	[58]
Notes：Polyvinylidene fluoride (PVDF); kalium Montmorillonite (K⁺MMT); Sulfonated Carbon Molecular Sieves (SCMS); Natrium Montmorillonite (NaMMT); Maleic acid (MA)

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表 5 CS复合渗透汽化膜分离其他有机溶剂/水

Table 5. Chitosan composite pervaporation membrane for other organic solvents/water separation

Pervaporation membrane	organic solvent	Particle/mixture loading/wt%	Temperature/℃	Fluxes/(g·m^-2·h^-1)	Separation Factor α	Reference
PVA/CS/Zeolite-A	Tert-butyl alcohol	0.9 %Zeolite-A	30	136700	1324	[60]
PSSAMA/CS	Tert-butyl alcohol	9% PSSAMA	30	41.45	5352	[61]
SiO₂ dry gel-CS	Butanol	0.25% SiO₂	50	736	1498	[63]
PVA-CS/PVDF	Butyl acetate	25% CS	40	402	27000	[65]
Notes：Polystyrene sulfonic acid maleic acid (PSSAMA); Silicon dioxide (SiO₂)

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表 6 CS复合渗透汽化膜分离有机溶剂/有机溶剂

Table 6. Chitosan composite pervaporation membrane for organic solvents/organic solvents separation

Pervaporation membrane	Organic solvent	Particle/mixture loading/wt%	Temperature/℃	Fluxes/(g·m^-2·h^-1)	Separation Factor α	Reference
PVA/CS	Bz/Chx	50% CS	50	51.41	49.9	[68]
CG-PVA/CS	Bz/Chx	6%CG;60%PVA; 40% CS	50	124.2	59.8	[69]
MWNT-Ag⁺/CS	Bz/Chx	MWNT-Ag⁺/CS=1.5%	20	357.96	7.89	[70]
GA-STA-CS/PEK-C	DMC/MeOH	0.3% GA	30	910.2	120.3	[72]
UiO-66(ZrCl₄)/CS	DMC/MeOH	10%UiO-66 (ZrCl₄)	50	355	337	[73]
CS/PTFE/ TEOS	MeOH/TOL	TEOS/CS=0.08	---	130	58.4	[76]
Notes：carbon-graphite (CG); glutaraldehyde (GA); Silicotungstic acid hydrate (STA); poly(ether-ketone) (PEK-C); University of Oslo (UiO-66); Tetraethyl orthosilicate (TEOS); Polytetrafluoroethylene (PTFE)

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