Membrane Separation

付长欣

2013.4.13

JOURNAL CLUB

New crosslinking method of polyamide–imide membranes for potential application in harsh

polar aprotic solvents

S.M. Dutczak, F.P. Cuperus, M. Wessling, D.F. Stamatialis

Separation and Purification Technology 102 (2013) 142–146

通讯作者单位： Membrane Science and Technology Group, Institute for Nanotechnology MESA+, University of Twente, Faculty of Science and Technology, Membrane Technology Group, P.O. Box 217,NL-7500 AE Enschede, The Netherlands

最近发表文章

1 Balster, J. et al. Tailoring the interface layer of the bipolar membrane. Journal of Membrane Science 365, 389-398, doi:10.1016/j.memsci.2010.09.034 (2010).

2 Dutczak, S. M., Cuperus, F. P., Wessling, M. & Stamatialis, D. F. New crosslinking method of polyamide-imide membranes for potential application in harsh polar aprotic solvents. Separation and Purification Technology 102, 142-146, doi:10.1016/j.seppur.2012.10.018 (2013).

3 Kopec, K. K., Dutczak, S. M., Bolhuis-Versteeg, L., Wessling, M. & Stamatialis, D. F. Solvent-resistant P84-based mixed matrix membrane adsorbers. Separation and Purification Technology 80, 306-314, doi:10.1016/j.seppur.2011.05.012 (2011).

4 Stamatialis, D. F. et al. INTEGRATION OF HOLLOW FIBER MEMBRANES IMPROVES NUTRIENT SUPPLY IN 3D TISSUE CONSTRUCTS. International Journal of Artificial Organs 34, 645-645 (2011).

5 Unadkat, H. V. et al. A modular versatile chip carrier for high-throughput screening of cell-biomaterial interactions. Journal of the Royal Society Interface 10, doi:10.1098/rsif.2012.0753 (2013).

PI and PAI polymers are typically soluble in harsh polar aprotic solvents (e.g. NMP, DMSO, DMF or DMAc).

PI membranes are crosslinked by thermal imidization or diamines in an imide-ring opening reaction either during phase separation or in post casting process. However, long exposure to the diamine crosslinking solution may cause deterioration of the polymer and on long term cause membrane dissolution .

基于上述： In this work the authors report a new method of crosslinking of

PAI membranes using di-isocyanates(二异氰酸盐 ). The resulting membranes are mainly evaluated concerning stability to NMP mixtures.

研究思路

Experimental

PAI

浸 入 交 联 溶 液 （ 70 % THF ， 14% hexamethylene diisocyanate (HMDI) ， 7% triethylene diamine (TEA), 5% NMP, and 4% tin 2-ethylhexanoate）

置于密闭容器反应 用 THF,甲醇，丙酮清洗 室温干燥

During crosslinking, one amide group is consumed and a new one is created. Therefore, we did not find a difference between the FTIR spectra of non-crosslinked and crosslinked membrane.

Direct evidence of the membrane crosslinking is the fact that it does not dissolve in NMP,DMF or DMAc which are solvents for the non-crosslinked membrane.

FTIR

The PS retention by the crosslinked membrane is much higher

(up to 95%) and the membrane MWCO is 260 Da.

截留分子质量

A Feasible Post-Treatment of Drying and Rewetting for Preparation of High-Flux Pluronic F127/Polyethersulfone

Nanofiltration Membranes

Yan Zhang, Yanlei Su, Wenjuan Chen, Jinming Peng, Yanan Dong,and Zhongyi Jiang

Environmental Science & Technology, 2011. 45(9): p. 4003-4009.

最近发表文章1 Lv, C. et al. Enhanced permeation performance of cellulose acetate ultrafiltration membrane by

incorporation of Pluronic F127. Journal of Membrane Science 294, 68-74, doi:10.1016/j.memsci.2007.02.011 (2007).

2 Shi, Q. et al. Probing molecular-level surface structures of polyethersulfone/Pluronic F127 blends using sum-frequency generation vibrational spectroscopy. Langmuir 24, 7939-7946, doi:10.1021/la800570a (2008).

3 Wang, Y. et al. Improved permeation performance of Pluronic F127-polyethersulfone blend ultrafiltration membranes. Journal of Membrane Science 282, 44-51, doi:10.1016/j.memsci.2006.05.005 (2006).

4 Zhao, W. et al. Fabrication of antifouling polyethersulfone ultrafiltration membranes using Pluronic F127 as both surface modifier and pore-forming agent. Journal of Membrane Science 318, 405-412, doi:10.1016/j.memsci.2008.03.013 (2008).

5 Zhang, Y. et al. Composite nanofiltration membranes prepared by interfacial polymerization with natural material tannic acid and trimesoyl chloride. Journal of Membrane Science 429, 235-242, doi:10.1016/j.memsci.2012.11.059 (2013).

作者单位：Key Laboratory for Green Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University,Tianjin 300072, ChinaNational Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

研究思路

The most important manufacturing approach for nanofiltration membrane is interfacial polymerization. However, the interfacial polymerization technique is quite complex ， requiring sophisticated preparation conditions.

For this reason, there is growing interest in the development of nanofiltration membranes in a relatively simple way, such as immersion precipitation and dip-coating methods.

由此：The initial wet membranes prepared via the phase inversion

method were post-treated by drying at roomtemperature and then immersion into water for rewetting to obtain Pluronic F127/PES nanofiltration membranes.

表面积和厚度由游标卡尺和千分尺测得 The introduction of Pluronic F127 in PES membranes can remarkably decrease the membrane shrinkage.

溶胀度

通量和截留率测试

耐氯性测试

Since avoiding the generation of waste(organic solvent) and no energy consumption, the post-treatment of drying and rewetting is really a green process.

Study on the modification of positively charged

composite nanofiltration membrane by TiO2

nanoparticlesXue Bai, Yatao Zhang, Hui Wang, Haoqin Zhang , Jindun Liu

Desalination 313 (2013) 57–65

刘金盾：研究领域：“化学工程与技术”、“环境科学与环境工程”领域的科学研究，主要从事“工业气体净化”、“膜分离科学与技术”、精细化工产品的研究与开发等工作等方向的研究工作。

最近发表文章1. Chen, Y.F., et al., Preparation and antibacterial property of polyethersulfone ultrafiltration

hybrid membrane containing halloysite nanotubes loaded with copper ions. Chemical Engineering Journal, 2012. 210: p. 298-308.

2. Dang, J.C., et al., Antibacterial properties of PES/CuCl2 three-bore hollow fiber UF membrane. Water Science and Technology, 2012. 66(4): p. 799-803.

3. Duan, J.M., et al., Halloysite nanotube-Fe3O4 composite for removal of methyl violet from aqueous solutions. Desalination, 2012. 293: p. 46-52.

4. Liu, L.E., et al., EQUILIBRIUM, KINETIC, AND THERMODYNAMIC STUDIES OF LEAD (II) BIOSORPTION ON SESAME LEAF. Bioresources, 2012. 7(3): p. 3555-3572.

5. Liu, L.E., et al., Removal of Auramine O from Aqueous Solution Using Sesame Leaf: Adsorption Isotherm and Kinetic Studies. Asian Journal of Chemistry, 2013. 25(4): p. 1991-1998.

6. Zhai, R., et al., Chitosan-halloysite hybrid-nanotubes: Horseradish peroxidase immobilization and applications in phenol removal. Chemical Engineering Journal, 2013. 214: p. 304-309.

7. Zhang, J.Y., et al., Preparation and Characterization of Novel Polyethersulfone Hybrid Ultrafiltration Membranes Bending with Modified Halloysite Nanotubes Loaded with Silver Nanoparticles. Industrial & Engineering Chemistry Research, 2012. 51(7): p. 3081-3090.

研究思路

Nanoparticles have small size effect, surface effect, quantum size effect, and macroscopic quantum tunneling effect, which could improve the pore structure of the membranes and increase the hydrophilicity, anti-fouling ability and the flux of the separation membrane.

With the addition of the dispersant agent of 2-hydroxypropyl trimethyl ammoniumchloride chitosan (HACC), TiO2 could keep longer the stable dispersion in the aqueous solution, and the NF membrane showed better separation performance.

1. 将 PEI, HACC, TiO2, and Na2CO3 (0.1%, as acid acceptor) and SDS(0.1%, as surfactant)溶于去离子水，超声至 TiO2分散均匀

2. 将 1得到的溶液相涂于支撑膜上， 30 min，干燥

3. TMC 溶于正己烷形成有机相，并将其涂于 2中得到的干燥膜上

4. 将 3得到的膜，移至烘箱内干燥

Experimental

正交试验

TiO2含量影响

Preparation of PMDA/ODA polyimide membrane for

use as substrate in a thermally stable composite reverse

osmosis membrane

Chaoyi Ba, James Economy

Journal of Membrane Science 363 (2010) 140–148.

通讯作者单位： Center of Advanced Materials for the Purification of Water with Systems, Department of Materials Science and Engineering,

University of Illinois at Urbana-Champaign, 1304W. Green St., Urbana, IL 61801, USA

最近发表文章1 Ba, C. Y. & Economy, J. ENVR 118-Preparation of nanofiltration membranes by chemical modification of P84 polyimide

membranes using polyethylenimine. Abstracts of Papers of the American Chemical Society 235 (2008).2 Ba, C. Y. & Economy, J. POLY 65-Preparation of PMDA-ODA polyimide membrane for use as substrate in a thermally stable

composite membrane. Abstracts of Papers of the American Chemical Society 238 (2009).3 Ba, C. Y. & Economy, J. Preparation of PMDA/ODA polyimide membrane for use as substrate in a thermally stable composite

reverse osmosis membrane. Journal of Membrane Science 363, 140-148, doi:10.1016/j.memsci.2010.07.019 (2010).4 Ba, C. Y. & Economy, J. Preparation and characterization of a neutrally charged antifouling nanofiltration membrane by coating

a layer of sulfonated poly(ether ether ketone) on a positively charged nanofiltration membrane. Journal of Membrane Science 362, 192-201, doi:10.1016/j.memsci.2010.06.032 (2010).

5 Ba, C. Y., Ladner, D., Clark, M. M. & Economy, J. POLY 13-Using protective polyelectrolyte films to improve fouling resistance of a positively charged NF membrane. Abstracts of Papers of the American Chemical Society 238 (2009).

6 Ba, C. Y., Ladner, D., Yao, Y. X. & Economy, J. Design of antifouling nanofiltration membranes using polyelectrolyte coatings. Abstracts of Papers of the American Chemical Society 239 (2010).

7 Ba, C. Y., Ladner, D. A. & Economy, J. Using polyelectrolyte coatings to improve fouling resistance of a positively charged nanofiltration membrane. Journal of Membrane Science 347, 250-259, doi:10.1016/j.memsci.2009.10.031 (2010).

8 Ba, C. Y., Langer, J. & Economy, J. Chemical modification of P84 copolyimide membranes by polyethylenimine for nanofiltration. Journal of Membrane Science 327, 49-58, doi:10.1016/j.memsci.2008.10.051 (2009).

9 Ba, C. Y. et al. Ethanol/water separation characteristics of thermally rearranged polymers. Abstracts of Papers of the American Chemical Society 242 (2011).

TFC membranes （ thin layer of aromatic polyamide onto a polysulfone substrate ） are well accepted for water desalination because of their high rejection rate and high water permeability. However, it is still a challenge to develop chemically and thermally stable polymeric membranes (pH extremes, chlorine, organic solvents, and very low or high temperatures).PI (PMDA/ODA) has a very high glass transition temperature of approximately 400 ◦C and excellent resistance to most nonoxidizing acids at room temperature and almost all organic solvents.Because of the carboxylic groups of PAA strong coordination with the transition metal ions can be neutralized by cations, such as Zn2+,Ni2+and Cu2+, to form ionomers. These divalent cations may act as cross-linkers so that these ionomers behave as thermoplastic elastomers.

研究思路

Experimental

15% PAA/NMP

不同浓度的 ZnCl2 ，搅拌，真空静置脱气 ，刮膜（ 100μm），水凝胶浴，用异丙醇、正己烷分别处理 30min，得PAA膜

亚胺化PI膜

Ac2O 和 TEA （ 4:1）

PI膜MPDA TMC（正己

烷） 溶剂挥发

IR 和 XPS

IR ： The typical polyamic acid absorption bands at 1660 cm−1 (C=O stretching, amide I) and 1550 cm−1 (C–N stretching, amide II).XPS ： The only role of ZnCl2 was to regulate membrane morphology and permeability and it can be completely removed during membrane preparation process.

The thermal stability of this membrane may be attributed to the high mechanical strength of the polyimide substrate, which can resist pore expansion as temperature increases.

Thank you !