Fabrication of graphene oxide composite membranes and their application for pervaporation dehydration of butanol

doi:10.1016/j.cjche.2015.04.018

Abstract

Abstract: As a newkind of 2D nanomaterials, graphene oxide (GO)with 2-4 layerswas fabricated viaamodified Hummers method and used for the preparation of pervaporation (PV) membranes. Such GO membranes were prepared via a facile vacuum-assisted method on anodic aluminiumoxide disks and applied for the dehydration of butanol. To obtain GO membranes with high performance, effects of pre-treatments, including high-speed centrifugal treatment of GO dispersion and thermal treatment of GO membranes, were investigated. In addition, effects of operation conditions on the performance of GO membranes in the PV process and the stability of GO membranes were also studied. It is of benefit to improve the selectivity of GO membrane by pre-treatment that centrifuges the GO dispersion with 10000 r·min^-1 for 40 min, which could purify the GO dispersion by removing the large size GO sheets. As prepared GO membrane showed high separation performance for the butanol/water system. The separation factor was 230, and the permeability was as high as 3.1 kg·m^-2·h^-1 when the PV temperature was 50 ℃ and the water content in feed was 10% (by mass). Meanwhile, the membrane still showed good stability for the dehydration of butanol after running for 1800 min in the PV process. GO membranes are suitable candidates for butanol dehydration via PV process.

Key words: Graphene oxide, Membrane, Pervaporation, Dehydration, Butanol

摘要： As a newkind of 2D nanomaterials, graphene oxide (GO)with 2-4 layerswas fabricated viaamodified Hummers method and used for the preparation of pervaporation (PV) membranes. Such GO membranes were prepared via a facile vacuum-assisted method on anodic aluminiumoxide disks and applied for the dehydration of butanol. To obtain GO membranes with high performance, effects of pre-treatments, including high-speed centrifugal treatment of GO dispersion and thermal treatment of GO membranes, were investigated. In addition, effects of operation conditions on the performance of GO membranes in the PV process and the stability of GO membranes were also studied. It is of benefit to improve the selectivity of GO membrane by pre-treatment that centrifuges the GO dispersion with 10000 r·min^-1 for 40 min, which could purify the GO dispersion by removing the large size GO sheets. As prepared GO membrane showed high separation performance for the butanol/water system. The separation factor was 230, and the permeability was as high as 3.1 kg·m^-2·h^-1 when the PV temperature was 50 ℃ and the water content in feed was 10% (by mass). Meanwhile, the membrane still showed good stability for the dehydration of butanol after running for 1800 min in the PV process. GO membranes are suitable candidates for butanol dehydration via PV process.

关键词: Graphene oxide, Membrane, Pervaporation, Dehydration, Butanol

Xianfu Chen, Gongping Liu, Hanyu Zhang, Yiqun Fan. Fabrication of graphene oxide composite membranes and their application for pervaporation dehydration of butanol[J]. Chin.J.Chem.Eng., 2015, 23(7): 1102-1109.

References

[1] J. Kim, L.J. Cote, J.X. Huang, Two dimensional soft material: New faces of graphene oxide, Acc. Chem. Res. 45 (8) (2012) 1356-1364.

[2] B.X. Mi, Graphene oxide membranes for ionic and molecular sieving, Science 343 (6172) (2014) 740-742.

[3] H. Zarrin, D. Higgins, Y. Jun, Z.W. Chen, M. Fowler, Functionalized graphene oxide nanocomposite membrane for low humidity and high temperature proton exchange membrane fuel cells, J. Phys. Chem. C 115 (42) (2011) 20774-20781.

[4] H.Y. Liu, P.X. Xi, G.Q. Xie, Y.J. Shi, F.P. Hou, L. Huang, F.J. Chen, Z.Z. Zeng, C.W. Shao, J. Wang, Simultaneous reduction and surface functionalization of graphene oxide for hydroxyapatite mineralization, J. Phys. Chem. C 116 (5) (2012) 3334-3341.

[5] M. Hu, B.X. Mi, Enabling graphene oxide nanosheets as water separation membranes, Environ. Sci. Technol. 47 (8) (2013) 3715-3723.

[6] W. Choi, J. Choi, J. Bang, J.H. Lee, Layer-by-layer assembly of graphene oxide nanosheets on polyamide membranes for durable reverse-osmosis applications, ACS Appl. Mater. Interfaces 5 (23) (2013) 12510-12519.

[7] V. Singh, D. Joung, L. Zhai, S. Das, S.I. Khondaker, S. Seal, Graphene based materials: past, present and future, Prog. Mater. Sci. 56 (8) (2011) 1178-1271.

[8] N.X.Wang, S.L. Ji, G.J. Zhang, J. Li, L.Wang, Self-assembly of graphene oxide and polyelectrolyte complex nanohybrid membranes for nanofiltration and pervaporation, Chem. Eng. J. 213 (2012) 318-329.

[9] K. Hu, M.K. Gupta, D.D. Kulkarni, V.V. Tsukruk, Ultra-robust graphene oxide-silk fibroin nanocomposite membranes, Adv. Mater. 25 (16) (2013) 2301-2307.

[10] B.M. Ganesh, A.M. Isloor, A.F. Ismail, Enhanced hydrophilicity and salt rejection study of graphene oxide-polysulfone mixed matrix membrane, Desalination 313 (2013) 199-207.

[11] B.G. Choi, Y.S. Huh, Y.C. Park, D.H. Jung, W.H. Hong, H. Park, Enhanced transport properties in polymer electrolyte composite membranes with graphene oxide sheets, Carbon 50 (15) (2012) 5395-5402.

[12] H.Y. Zhao, L.G.Wu, Z.J. Zhou, L. Zhang, H.L. Chen, Improving the antifouling property of polysulfone ultrafiltration membrane by incorporation of isocyanate-treated graphene oxide, PCCP 15 (23) (2013) 9084-9092.

[13] H.W. Kim, H.W. Yoon, S.M. Yoon, B.M. Yoo, B.K. Ahn, Y.H. Cho, H.J. Shin, H. Yang, U. Paik, S. Kwon, J.Y. Choi, H.B. Park, Selective gas transport through few-layered graphene and graphene oxide membranes, Science 342 (6154) (2013) 91-95.

[14] D.W. Boukhvalov, M.I. Katsnelson, Y.W. Son, Origin of anomalous water permeation through graphene oxide membrane, Nano Lett. 13 (8) (2013) 3930-3935.

[15] H. Huang, Z. Song, N. Wei, L. Shi, Y. Mao, Y. Ying, L. Sun, Z. Xu, X. Peng, Ultrafast viscous water flow through nanostrand-channelled graphene oxide membranes, Nat. Commun. 4 (2013) 2979-2987.

[16] R.R. Nair, H.A. Wu, P.N. Jayaram, I.V. Grigorieva, A.K. Geim, Unimpeded permeation of water through helium-leak-tight graphene-based membranes, Science 335 (6067) (2012) 442-444.

[17] J. Lee, H.R. Chae, Y.J.Won, K. Lee, C.H. Lee, H.H. Lee, I.C. Kim, J.M. Lee, Graphene oxide nanoplatelets composite membrane with hydrophilic and antifouling properties for wastewater treatment, J. Membr. Sci. 448 (2013) 223-230.

[18] H. Li, Z. Song, X. Zhang, Y. Huang, S. Li, Y. Mao, H.J. Ploehn, Y. Bao, M. Yu, Ultrathin, molecular-sieving graphene oxide membranes for selective hydrogen separation, Science 342 (6154) (2013) 95-98.

[19] C.Z. Sun, M.S.H. Boutilier, H. Au, P. Poesio, B. Bai, R. Karnik, N.G. Hadjiconstantinou, Mechanisms of molecular permeation through nanoporous graphene membranes, Langmuir 30 (2) (2013) 675-682.

[20] M.X. Shan, Q.Z. Xue, N.N. Jing, C.C. Ling, T. Zhang, Z.F. Yan, J.T. Zheng, Influence of chemical functionalization on the CO₂/N₂ separation performance of porous graphene membranes, Nanoscale 4 (17) (2012) 5477-5482.

[21] W.S. Hung, Q.F. An, M. De Guzman, H.Y. Lin, S.H. Huang, W.R. Liu, C.C. Hu, K.R. Lee, J.Y. Lai, Pressure-assisted self-assembly technique for fabricating composite membranes consisting of highly ordered selective laminate layers of amphiphilic graphene oxide, Carbon 68 (2014) 670-677.

[22] T.M. Yeh, Z. Wang, D. Mahajan, B.S. Hsiao, B. Chu, High flux ethanol dehydration using nanofibrous membranes containing graphene oxide barrier layers, J. Mater. Chem. A 1 (41) (2013) 12998-13003.

[23] K. Huang, G.P. Liu, Y.Y. Lou, Z.Y. Dong, J. Shen,W.Q. Jin, A graphene oxide membrane with highly selective molecular separation of aqueous organic solution, Angew. Chem. Int. Ed. 53 (27) (2014) 6929-6932.

[24] Y.P. Tang, D.R. Paul, T.S. Chung, Free-standing graphene oxide thin films assembled by a pressurized ultrafiltrationmethod for dehydration of ethanol, J. Membr. Sci. 458 (2014) 199-208.

[25] Y.Y. Lou, G.P. Liu, S.N. Liu, J. Shen, W.Q. Jin, A facile way to prepare ceramicsupported graphene oxide composite membrane via silane-graft modification, Appl. Surf. Sci. 307 (2014) 631-637.

[26] M. Hu, B.X. Mi, Layer-by-layer assembly of graphene oxide membranes via electrostatic interaction, J. Membr. Sci. 469 (2014) 80-87.

[27] H.B. Huang, Y.Y. Mao, Y.L. Ying, Y. Liu, L.W. Sun, X.S. Peng, Salt concentration, pH and pressure controlled separation of small molecules through lamellar graphene oxide membranes, Chem. Commun. 49 (53) (2013) 5963-5965.

[28] X. Huang, Z.Y. Yin, S.X. Wu, X.Y. Qi, Q.Y. He, Q.C. Zhang, Q.Y. Yan, F. Boey, H. Zhang, Graphene-based materials: Synthesis, characterization, properties, and applications, Small 7 (14) (2011) 1876-1902.

[29] G.P. Liu, W. Wei, W.Q. Jin, Pervaporation membranes for biobutanol production, ACS Sustainable Chem. Eng. 2 (4) (2014) 546-560.

[30] T.A. Peters, C.H.S. Poeth, N.E. Benes, H. Buijs, F.F. Vercauteren, J.T.F. Keurentjes, Ceramic-supported thin PVA pervaporation membranes combining high flux and high selectivity; Contradicting the flux-selectivity paradigm, J. Membr. Sci. 276 (1-2) (2006) 42-50.

[31] Y.X. Zhu, S.S. Xia, G.P. Liu, W.Q. Jin, Preparation of ceramic-supported poly(vinyl alcohol)-chitosan composite membranes and their applications in pervaporation dehydration of organic/water mixtures, J. Membr. Sci. 349 (1-2) (2010) 341-348.

[32] T. Gallego-Lizon, E. Edwards, G. Lobiundo, L.F. dos Santos, Dehydration of water/tbutanol mixtures by pervaporation: Comparative study of commercially available polymeric, microporous silica and zeolite membranes, J. Membr. Sci. 197 (1-2) (2002) 309-319.

[33] H.M. van Veen, Y.C. van Delft, C.W.R. Engelen, P. Pex, Dewatering of organics by pervaporation with silica membranes, Sep. Purif. Technol. 22-3 (1-3) (2001) 361-366.

[34] H.L. Castricum, A. Sah, R. Kreiter, D.H.A. Blank, J.F. Vente, J.E. ten Elshof, Hybrid ceramic nanosieves: Stabilizing nanopores with organic links, Chem. Commun. 9 (2008) 1103-1105.

[35] Y. Han, Z. Xu, C. Gao, Ultrathin graphene nanofiltration membrane for water purification, Adv. Funct. Mater. 23 (29) (2013) 3693-3700.

[36] D. Li, M.B. Muller, S. Gilje, R.B. Kaner, G.G. Wallace, Processable aqueous dispersions of graphene nanosheets, Nat. Nanotechnol. 3 (2) (2008) 101-105.

[37] X.J. Shu, X.R. Wang, Q.Q. Kong, X.H. Gu, N.P. Xu, High-flux MFI zeolite membrane supported on YSZ hollow fiber for separation of ethanol/water, Ind. Eng. Chem. Res. 51 (37) (2012) 12073-12080.

[38] D.P. Suhas, A.V. Raghu, H.M. Jeong, T.M. Aminabhavi, Graphene-loaded sodium alginate nanocomposite membranes with enhanced isopropanol dehydration performance via a pervaporation technique, RSC Adv. 3 (38) (2013) 17120-17130.

[39] D.R. Dreyer, S.Murali, Y. Zhu, R.S. Ruoff, C.W. Bielawski, Reduction of graphite oxide using alcohols, J. Mater. Chem. 21 (10) (2011) 3443.

[40] A. Buchsteiner, A. Lerf, J. Pieper,Water dynamics in graphite oxide investigated with neutron scattering, J. Phys. Chem. B 110 (45) (2006) 22328-22338.

[41] J. Zhu, C.M. Andres, J. Xu, A. Ramamoorthy, T. Tsotsis, N.A. Kotov, Pseudonegative thermal expansion and the state of water in graphene oxide layered assemblies, ACS Nano 6 (9) (2012) 8357-8365.

[42] K.S. Andrikopoulos, G. Bounos, D. Tasis, L. Sygellou, V. Drakopoulos, G.A. Voyiatzis, The effect of thermal reduction on the water vapor permeation in graphene oxide membranes, Adv. Mater. Interfaces 1 (8) (2014) 1-8.

[43] J.F. Shen, Y.Z. Hu, M. Shi, X. Lu, C. Qin, C. Li, M.X. Ye, Fast and facile preparation of graphene oxide and reduced graphene oxide nanoplatelets, Chem. Mater. 21 (2009) 3514-3520.

[44] R.L. Liu, G. Arabale, J. Kim, K. Sun, Y.W. Lee, C.K. Ryu, C.G. Lee, Graphene oxidemembrane for liquid phase organic molecular separation, Carbon 77 (2014) 933-938.

[45] W.F. Guo, T.S. Chung, Study and characterization of the hysteresis behavior of polyimide membranes in the thermal cycle process of pervaporation separation, J. Membr. Sci. 253 (1-2) (2005) 13-22.

[46] Y. Wang, S.H. Goh, T.S. Chung, P. Na, Polyamide-imide/polyetherimide dual-layer hollow fiber membranes for pervaporation dehydration of C1-C4 alcohols, J. Membr. Sci. 326 (1) (2009) 222-233.

[47] G. Zhang, X. Song, S. Ji, N.Wang, Z. Liu, Self-assembly of inner skin hollow fiber polyelectrolyte multilayer membranes by a dynamic negative pressure layer-by-layer technique, J. Membr. Sci. 325 (1) (2008) 109-116.

[48] G.M. Shi, T. Yang, T.S. Chung, Polybenzimidazole (PBI)/zeolitic imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation dehydration of alcohols, J. Membr. Sci. 415 (2012) 577-586.

[49] Y.K. Ong, H. Wang, T.S. Chung, A prospective study on the application of thermally rearranged acetate-containing polyimide membranes in dehydration of biofuels via pervaporation, Chem. Eng. Sci. 79 (2012) 41-53.

[50] S. Biduru, S. Sridhar, G.S. Murthy, S. Mayor, Pervaporation of tertiary butanol/water mixtures through chitosan membranes cross-linked with toluylene diisocyanate, J. Chem. Technol. Biotechnol. 80 (12) (2005) 1416-1424.

[51] T. Gallego-Lizon, E. Edwards, G. Lobiundo, L. Freitas dos Santos, Dehydration of water/t-butanol mixtures by pervaporation: comparative study of commercially available polymeric, microporous silica and zeolite membranes, J. Membr. Sci. 197 (1-2) (2002) 309-319.