用于混合一价盐分离的纳滤膜的制备及性能研究

doi:10.11949/0438-1157.20200955

摘要/Abstract

摘要：

针对有机颜料废水中单价相似离子（例如CH₃COO^-和Cl^-）分离难的问题，以表面活化能与脱水现象协同作用的分离机制为指导，在界面聚合中加入3，5-二氨基苯甲酸（DMA）来调控孔径、电性等性质，制备对醋酸根和氯离子具有高选择性的复合纳滤膜。XPS结果表明DMA参与界面聚合反应，形成疏松选择层；Zeta电位表明膜表面负电性增强。通过pH、操作压力等条件优化，得出0.6%（质量） DMA-TFC膜性能最佳，水通量较未改性复合膜提高44%，对于醋酸钠与硫酸钠的分离比达到15.0。本工作为相似离子分离纳滤膜的设计与制备提供了理论和实践基础，在颜料废水等水处理、物料分离等领域展现了良好的应用前景。

关键词: 纳滤膜, 废水, 相似离子分离, 活化能, 水合能, 醋酸钠, 氯化钠

Abstract:

This paper aims to develop new nanofiltration membranes that achieve high selectivity of CH₃COO^- and Cl^-, which is difficult to separate in pigment and other wastewater. Guided by the separation mechanism between the apparent activation energy and dehydration, 3,5-diaminobenzoic acid (DMA) was utilized to adjust the pore size, surface charge and other properties of a thin film composite (TFC) nanofiltration membrane. XPS results show that DMA participates in the interfacial polymerization reaction to form a loose selective layer; Zeta potential shows that the surface of the film is negatively charged. By tuning the pH, operating pressure, and other conditions, the optimized membrane [0.6%(mass) DMA-TFC] was obtained with the water flux 44% higher than that of the unmodified composite membrane, and the separation ratio of CH₃COO^-and Cl^- reached 15.0. This work provides a theoretical and practical basis for the design and preparation of nanofiltration membranes for similar ion separation. It shows great application prospects in the fields of water treatment such as pigment wastewater and material separation.

Key words: nanofiltration membrane, wastewater, similar ions separation, activation energy, hydration energy, sodium acetate, sodium chloride

中图分类号:

TQ 028.8

刘宁, 褚昌辉, 王乾, 孙世鹏. 用于混合一价盐分离的纳滤膜的制备及性能研究[J]. 化工学报, 2021, 72(1): 578-588.

LIU Ning, CHU Changhui, WANG Qian, SUN Shipeng. Preparation of nanofiltration membrane for separation of mixed monovalent salts[J]. CIESC Journal, 2021, 72(1): 578-588.

图/表 16

表1 铸膜液组成及超滤膜相关参数

Table 1 The composition of dope and the related parameters of the ultrafiltration membrane

铸膜液成分/g	膜厚/μm	孔隙率/%	孔径分布/nm	平均孔径/nm
NMP∶PEG∶PI=64∶16∶20	80±5	61.79±3.24	19.36~125.62	56.39

表2 PIP、DMA和TMC分子结构、分子量

Table 2 Structure and molecular weight of PIP, DMA, and TMC

Compound	Chemical structure	Molecular weight
PIP		86.14
DMA		152.15
TMC		265.48

图1 不同浓度DMA复合纳滤膜傅里叶红外光谱图

Fig.1 ATR-FTIR spectra of DMA-TFC membranes with different DMA contents

图2 不同浓度DMA-TFC膜的N1s XPS谱图

Fig.2 X-ray photoelectron spectra of TFC membranes with different DMA contents

表3 DMA-TFC膜的X射线光电子能谱原子组成和不同化学态N的相对含量

Table 3 The X-ray photoelectron spectral atomic composition of the DMA-TFC membrane and the relative composition of N in different chemical states

Membrane	N in different chemical states /%		原子组成/%			N/O
Membrane	—NH—	—NCO—	C 1s	N 1s	O 1s	N/O
0 DMA-TFC	16.88	83.12	82.49	9.42	8.09	1.16
0.2% DMA-TFC	21.06	78.94	84.05	8.85	7.10	1.25
0.6% DMA-TFC	26.43	73.57	83.27	10.22	6.51	1.57
1.0% DMA-TFC	28.43	71.57	84.51	9.68	5.81	1.67

图3 不同浓度DMA-TFC膜的表面Zeta电位

Fig.3 The streaming potential for DMA-TFC membranes with different DMA contents

图4 不同浓度DMA-TFC膜的表面(左)和断面(右)SEM图

Fig.4 Surface (left) and cross-section (right) SEM images of TFC membranes with different DMA contents

表4 不同浓度DMA-TFC膜截留分子量及平均孔径

Table 4 MWCO and rp for TFC membranes with different DMA contents

Membranes	MWCO	r_p/nm
0 DMA-TFC	212	0.14
0.2% DMA-TFC	344	0.18
0.6% DMA-TFC	397	0.21
1.0% DMA-TFC	457	0.22

图5 不同浓度DMA-TFC膜孔径分布曲线

Fig.5 Probability density function curves of the TFC membranes with different DMA contents

图6 不同浓度的DMA-TFC膜混合单价盐截留与通量(压力1 MPa，温度25℃)

Fig.6 Nanofiltration performance of DMA-TFC membranes with different DMA contents (under the pressure of 1 MPa and the temperature of 25℃)

图7 pH对于0.6%（质量） DMA-TFC膜分离混合盐性能的影响(压力0.6 MPa，温度25℃)

Fig.7 Effects of pH on performance of 0.6%（mass） DMA-TFC membrane (under the pressure of 0.6 MPa and the temperature of 25℃)

图8 操作压力对于0.6%(质量) DMA-TFC膜性能的影响

Fig.8 Effects of pressure on performance of 0.6%（mass） DMA-TFC membrane

图9 0.6%(质量) DMA-TFC膜对于不同浓度比的混合单价盐的分离(压力0.6 MPa，温度25℃)

Fig.9 Rejection of 0.6%(mass) DMA-TFC membrane for mixed monovalent salts with different concentration ratios (under the pressure of 0.6 MPa and the temperature of 25℃)

图10 在pH=10时，氯离子和醋酸根阴离子通过膜孔所需的活化能(1 kcal=4186 J)

Fig.10 Activation energy required for chloride and acetate anions to pass through the membrane at pH=10

表5 CH3COO-和Cl-的物理特性[42]

Table 5 Physical properties of CH3COO- and Cl- ions[42]

Δ_hydG_calc^*/

(kJ·mol^-1)^④

CH₃COO^-

Cl^-

图11 0.6%(质量) DMA-TFC膜的长周期稳定性实验(pH=10, 1 MPa, 25℃)

Fig.11 Long-term performance of 0.6%（mass） DMA-TFC membrane (pH=10, 1 MPa, 25℃)

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