Preparation of nanofiltration membrane for separation of mixed monovalent salts

doi:10.11949/0438-1157.20200955

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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

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

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℃)

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

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

Δ_hydG_calc^*/

(kJ·mol^-1)^④

CH₃COO^-

Cl^-

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

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