反渗透膜微结构的调控及海水脱硼性能的提升

doi:10.7503/cjcu20190104

摘要/Abstract

摘要：

通过引入聚乙烯亚胺(PEI)链与对叠氮苯甲酸(ABA)分子对薄层芳香聚酰胺复合反渗透膜(TFC)进行接枝改性, 采用傅里叶衰减全反射红外光谱(ATR-FTIR)和X射线光电子能谱(XPS)分析了反渗透膜活性分离层的化学组成和结构, 用静态水接触角仪与Zeta电位仪测试了反渗透膜表面的亲疏水性和电荷性质, 并利用扫描电子显微镜(SEM)及原子力显微镜(AFM)观察其表面形貌, 测试了反渗透膜在苦咸水与海水条件下的分离性能. 实验结果表明, 使用PEI与ABA对反渗透膜改性后, 提升了其分离层的致密度, 使硼渗透通过反渗透膜时的传质阻力变大, 从而将改性反渗透膜(TFC-PEI-ABA)对硼的截留率提升至90.45%, 达到了世界卫生组织对水质的要求.

关键词: 反渗透复合膜, 聚乙烯亚胺, 对叠氮苯甲酸, 海水脱硼

Abstract:

Thin aromatic polyamide composite reverse osmosis membranes(TFC) were modified by grafting polyethyleneimine(PEI) chains and 4-azidobenzoic acid(ABA) molecules. Attenuated total reflectance Fourier transform infrared spectroscopy(ATR-FTIR) and X-ray photoelectron spectroscopy(XPS) were used to analyze the chemical composition and structure of the active separation layer. Then the hydrophobicity and charge of the reverse osmosis membrane were measured by static water contact angle instrument and Zeta potentiometer, the surface morphology was observed by scanning electron microscopy(SEM) and atomic force microscopy(AFM). Finally, the separation performance of the reverse osmosis membranes was tested in brackish water and seawater condition, respectively. The experimental results show that the separation layers of the reverse osmosis membrane become denser after modifying with PEI and/or ABA, and correspondingly the mass transfer resistance of boron permeation through reverse osmosis membranes is increased. The boron retention rate of the TFC-PEI-ABA membrane modified by both PEI and ABA reach 90.45%, which meets the requirements of World Health Organization(WHO) for water quality.

Key words: Reverse osmosis membrane, Polyethyleneimine, 4-Azidobenzoic acid, Removal of boron from seawater

中图分类号:

O631
P747+.5

TrendMD:

谢欣, 张潇, 李蕊含, 宋潇潇, 刘立芬, 高从堦. 反渗透膜微结构的调控及海水脱硼性能的提升. 高等学校化学学报, 2019, 40(9): 2033.

XIE Xin, ZHANG Xiao, LI Ruihan, SONG Xiaoxiao, LIU Lifen, GAO Congjie. Microstructure Regulation of the Reverse Osmosis Membrane to Improve the Boron Removal Performance ^†. Chem. J. Chinese Universities, 2019, 40(9): 2033.

图/表 13

Scheme 1 Schematic illustration of TFC membrane fabrication process

Scheme 2 Modification process of TFC membranes

Scheme 3 Structure of reverse osmosis membrane performance testing machine

Fig.1 ATR-FTIR spectra of fabricated RO membranes a. TFC; b. TFC-ABA; c. TFC-ABA-UV; d. TFC-PEI-ABA; e. TFC-PEI-ABA-UV.

Table 1 XPS determined compositions of the polyamide separation layer

Membrane	Elemental composition(%)
Membrane	C	O	N
TFC	73.18	16.06	10.77
TFC-ABA	73.14	16.45	10.41
TFC-PEI	69.82	16.58	13.65
TFC-PEI-ABA	70.43	16.36	13.21

Fig.2 XPS spectra of TFC-PEI(A) and TFC-PEI-ABA(B)

Fig.3 Contact angles(A) and Zeta potentials(B) of fabricated RO membranes (B) a. TFC; b. TFC-ABA; c. TFC-PEI; d. TFC-PEI-ABA.

Fig.4 FE-SEM images of TFC(A), TFC-ABA(B), TFC-PEI(C) and TFC-PEI-ABA(D)

Fig.5 AFM images of TFC(A), TFC-ABA(B), TFC-PEI(C) and TFC-PEI-ABA(D) (A) Rq=58.6, Ra=46.2; (B) Rq=39.7, Ra=28.8; (C) Rq=60.9, Ra=46.8; (D) Rq=51.9, Ra=39.2.

Fig.6 Separation performances of fabricated membranes under low pressure(A) and simulated seawater conditions(B) (A) 2 g/L NaCl, 15.5 MPa, pH=7.0; (B) 32 g/L NaCl, 0.005 g/L H3BO3, 55 MPa, pH=8. Flux; rejertion.

Fig.7 Permeation selectivity for boron of fabricated membranes(A) and permeability coefficients of boron through the membranes(B)

Table 2 Properties of different RO membranes

RO membrane	Water flux/(L·m^-2·h^-1)	NaCl retention rate(%)	Boron retention rate(%)	Ref.
C12-RO	42.1	98.1	87.8	[31]
SRN-RO	80.3	98.4	62.0	[32]
CAI-RO	7.7	90.0	90.6	[33]
TFC-PEI-ABA	34.2	99.2	90.3	This work

Fig.8 Schematic diagram of modification process

参考文献 33

[1]	Uemura T., Kotera K., Henmi M., Tomioka H., ,. Desalin. Water. Treat 2012, 33, 283— 288
[2]	Wu L. X., Cai Z. B., Chen X. L., Liu L. F., Gao C. J., ,Chem. J. Chinese Universities, 2015,36( 4), 765— 771
	(吴丽项, 蔡志彬, 陈晓林, 刘立芬, 高从堦. 高等学校化学学报, 2015, 36(4), 765— 771)
[3]	Liu L. F., Xu D. Z., Zhang L., Gao C. J., ,Chem. J. Chinese Universities, 2012,33( 7), 1605— 1612 doi: 10.3969/j.issn.0251-0790.2012.07.043
	(刘立芬, 徐德志, 张林, 高从堦. 高等学校化学学报, 2012, 33(7), 1605— 1612) doi: 10.3969/j.issn.0251-0790.2012.07.043
[4]	Liyanaarachchi S., Shu L., Muthukumaran S., Jegatheesan V., Baskaran K., ,. Environ. Sci. 2014, 13, 203— 214
[5]	Argust P., ,. Biol. Trace Elem. Res., 1998, 66, 131— 143
[6]	Nable R. O., Banuelos G. S., Paull J. G., ,. Plant Soil 1997, 193, 181— 198
[7]	Meng J. Q., Yuan J., Kang Y. L., Zhang Y. F., Du Q. Y., ,. J. Colloid. Interf. Sci. 2012, 368, 197— 207
[8]	Shi Q., Men J. Q., Xu R. S., Du X. L., Zhang Y. F., ,. J. Membr. Sci. 2013, 444, 50— 59
[9]	Lee K. P., Arnot T. C., Mattia D., ,. J. Membr. Sci. 2011, 370, 1— 22
[10]	Shultz S. R., Bass M., Semiat R., Freger V., ,. J. Membr. Sci. 2018, 546, 165— 172
[11]	Bernstein R., Belfer S., Freger V., ,. Environ. Sci. Technol. 2011, 45, 3613— 3620
[12]	Tang Y. P., Luo L., Thong Z. W., Chung T. S., ,. J. Membr. Sci. 2017, 541, 434— 446
[13]	Tu K. L., Nghiem L. D., Chivas A. R., ,. Sep. Purif. Technol. 2010, 75, 87— 101
[14]	Busch M., Mickols W. E., Jons S., Redondo J., Witte J. D., ,. Water Reuse Q 2004, 13, 25— 41
[15]	Shultz S., Bass M., Semiat R., Freger V., ,. J. Membr. Sci. 2018, 546, 165— 172
[16]	Kim S. H., Kwak S. Y., Suzuki T., ,. Environ. Sci. Technol. 2005, 39, 1764— 1770
[17]	Coronell O., Mariñas B. J., Zhang X., Cahill D. G., ,Environ. Sci. Technol., 2008, 42, 5260— 5266
[18]	Cahill D. G., Freger V. S., Kwak Y., ,. MRS Bull. 2008, 33, 27— 32
[19]	Shultz S., Freger V ., Desalination 2018, 431, 66— 72
[20]	Hu J. H., Pu Y. L., Ueda M., Zhang X., Wang L. J., ,. J. Membr. Sci. 2016, 520, 1— 7
[21]	Vincenzoa M. D., Barboiua M., Tiraferrib A., Legrand Y. M., ,. J. Membr. Sci. 2017, 540, 71— 77
[22]	Wang S. H., Zhou Y., Gao C. J., ,. J. Membr. Sci. 2018, 554, 244— 252
[23]	Zhu X. Q., Fan X. W., Ju G. N., Cheng M. J., An Q., Nie J., Shi F., ,. Chem. Commun. 2013, 49, 8093— 8095
[24]	Luan X. L., Huang T., Zhou Y., An Q., Wang Y., Wu Y. L., Li X. M., Li H. T., Shi F., Zhang Y. H., ,. ACS Appl. Mater. Interfaces 2016, 8, 34080— 34088
[25]	Amoozgar Z., Rickett T., Park J., Tuchek C., Shi R., Yeo Y., ,. Acta Biomaterialia 2012, 8, 1849— 1858
[26]	Yu H. P., Zeng Z. Q., Liu H. C., Luo Y. Y., ,. Advanced Materials Research 2012, 824, 824— 829
[27]	Bhat V. T., James N. R., Jayakrishnan A., ,. Polym Int. 2008, 57, 124— 132
[28]	Liu L. F., Cai Z. B., Shen J. N., Wu L. X., Hoek E. M. V., Gao C. J., ,. J. Membr. Sci. 2014, 469, 397— 409
[29]	Ma D. C., Peh S. B., Han G., Chen S. B., ,. ACS Appl. Mater. Interfaces 2017, 9, 7523— 7534
[30]	Xu J., Wang Z. J., Wang X., Wang S. C ., Desalination 2015, 365, 398— 406
[31]	Shultz S., Bass M., Semiat R., Freger V., ,. J. Membr. Sci. 2018, 546, 165— 172
[32]	Vincenzo M. Di., Barboiu M., Tiraferri A., Legrand Y. M., ,. J. Membr. Sci. 2017, 540, 71— 77
[33]	Hu J. H., Pu Y. L., Ueda M., Zhang X., Wang L. J., ,. J. Membr. Sci. 2016, 520, 1— 7