乙烯基桥联有机硅膜的羧基化改性及反渗透性能研究

doi:10.11949/0438-1157.20190078

摘要/Abstract

摘要：

利用1,2-二(三乙氧基硅基)乙烯(BTESEthy)和硫代苹果酸(MSA)的巯基-烯点击反应对桥联有机硅进行羧基化改性，以管式α-Al₂O₃微滤膜为支撑体制备羧基官能化的桥联有机硅膜。通过傅里叶变换红外光谱(FT-IR)、激光粒度仪(DLS)、智能重量分析仪(IGA)和扫描电镜(SEM)等对膜结构和表面性质进行了表征。量子化学计算表明羧基化改性的有机硅网络拥有更加致密的孔结构和更高的水亲和力。将改性的BTESEthy-MSA膜用于反渗透脱盐，系统考察了BTESEthy-MSA膜反渗透脱盐性能。实验结果表明，与BTESEthy膜相比，羧基化改性的BTESEthy-MSA膜的水渗透率和盐截留率均有所提高。同时，BTESEthy-MSA膜表现出优异的水热稳定性和耐氯性能。在250 h的长期反渗透测试中，BTESEthy-MSA膜的水渗透率高达3.2×10^-13 m³/(m²·s·Pa)，NaCl截留率始终保持在94.7%以上。

关键词: 膜, 有机硅, 羧基化, 反渗透, 脱盐, 渗透率

Abstract:

Carboxyl functionalized bridged-type organosilica membranes were prepared via the thiol-ene click reaction between 1,2-bis(triethoxysilyl)ethylene (BTESEthy) and mercaptosuccinic acid (MSA), using tubular α-Al₂O₃ microfiltration membranes as the supports. The membrane structure and surface properties were characterized by Fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS), intelligent gravimetric analyzer (IGA) and scanning electron microscopy (SEM). Quantum chemistry calculations show that the carboxylated modified silicone network has a denser pore structure and higher water affinity. The prepared BTESEthy-MSA membranes were applied to desalination by reverse osmosis. The reverse osmosis performance of BTESEthy-MSA membranes was systematically investigated. The experimental results showed that compared with the original BTESEthy membranes, both water permeability and salt rejection of the carboxyl functionalized BTESEthy-MSA membranes were improved. Meanwhile, the BTESEthy-MSA membranes exhibit superior hydrothermal stability and chlorine resistance. Moreover, the BTESEthy-MSA membranes exhibited high stability over long term reverse osmosis test of 250 h, and high water permeability of 3.2×10^-13 m³/(m²·s·Pa) and NaCl rejections of >94.7%.

Key words: membrane, organosilica, carboxyl functionalization, reverse osmosis, desalination, permeability

中图分类号:

TQ 028

徐荣, 程旭, 邓松, 戚律, 任秀秀, 张琪, 钟璟. 乙烯基桥联有机硅膜的羧基化改性及反渗透性能研究[J]. 化工学报, 2019, 70(7): 2766-2774.

Rong XU, Xu CHENG, Song DENG, Lyu QI, Xiuxiu REN, Qi ZHANG, Jing ZHONG. Carboxyl functionalization and reverse osmosis performance of ethenylene-bridged organosilica membranes[J]. CIESC Journal, 2019, 70(7): 2766-2774.

图/表 10

图1 BTESEthy原位羧基官能化反应

Fig.1 Carboxyl functionalization of BTESEthy

图2 BTESEthy和BTESEthy-MSA粉末的红外光谱图和核磁共振碳谱图

Fig.2 FT-IR spectrum and 13C CP MAS NMR spectrum of BTESEthy and BTESEthy-MSA powders

图3 BTESEthy和BTESEthy-MSA溶胶的粒径分布

Fig.3 Size distribution of BTESEthy and BTESEthy-MSA sols

图4 BTESEthy和BTESEthy-MSA的水吸附图

Fig.4 Water adsorption of BTESEthy and BTESEthy-MSA

图5 用密度泛函理论(DFT)计算得到的BTESEthy和BTESEthy-MSA的ESPs图和两种模型分子几何变化的比较

Fig.5 ESPs images of BTESEthy and BTESEthy-MSA calculated by density functional theory (DFT), and comparison of geometry changes in two model molecules

图6 BTESEthy-MSA膜断面的SEM图和BTESEthy-MSA膜的AFM图

Fig.6 Cross-sectional SEM image and AFM image of BTESEthy-MSA membranes

图7 温度循环对BTESEthy-MSA膜反渗透性能的影响(1.15 MPa，2000 mg/L NaCl)

Fig.7 Effect of temperature cycles on reverse osmosis performance of BTESEthy-MSA membranes (1.15 MPa， 2000 mg/L NaCl)

图8 操作时间对BTESEthy-MSA膜的反渗透性能影响(1.15 MPa, 25℃，2000 mg/L NaCl)

Fig.8 Influence of operating time on the RO performance of BTESEthy-MSA membranes (1.15 MPa, 25℃, 2000 mg/L NaCl)

图9 BTESEthy-MSA膜、芳香聚酰胺膜SW30HR的耐氯性能[27]对比和耐氯实验前后BTESEthy-MSA膜的红外光谱图

Fig.9 Comparison of chlorine tolerance of BTESEthy-MSA and SW30HR membranes, and FT-IR spectra of virgin and chorine-exposed BTESEthy-MSA membranes

表1 有机硅膜和一些典型的反渗透膜的脱盐性能对比

Table 1 Comparison of desalination performances of organosilica membranes and some typical RO membranes

膜	测试条件	水渗透率/(m³/(m²·s·Pa))	截留率 /%	参考文献
SW30HR (FilmTec)	21℃, 2.76 MPa, 2000 mg/L-NaCl	(2.2 ± 0.5) × 10^-12	98.5 ± 0.7	[28]
ES10 (Nitto Denko)	24℃, 1 MPa, 104 mg/L-NaCl	(1.2 ± 0.16) × 10^-12	99.2	[29]
ZSM-5, Si/Al=5	25℃, 2.76 MPa, 5848 mg/L-NaCl	1.4 × 10^-13	92.9	[30]
silicalite	25℃, 2.76 MPa, 5848 mg/L -NaCl	1.4 × 10^-13	90.6	[30]
BTESEthy	25℃, 1.15 MPa, 2000 mg/L-NaCl	2.1 ± 0.2 × 10^-13	97 ± 0.8	this work
BTESEthy-MSA	25℃, 1.15 MPa, 2000 mg/L-NaCl	3.5 ± 0.5 × 10^-13	98 ± 0.5	this work

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