石墨烯掺杂聚砜基正渗透膜的结构和性能

doi:10.16085/j.issn.1000-6613.2017-0475

摘要/Abstract

摘要： 采用相转化法分别制备了掺杂有石墨、石墨烯和氧化石墨烯的聚砜正渗透（FO）膜支撑层，通过间苯二胺和均苯三甲酰氯间的界面聚合在支撑层表面制备了聚酰胺活性层。采用扫描电子显微镜（SEM）表征膜表面和断面的结构形貌，测定膜孔隙率和亲水性，考察不同掺杂物时FO膜的性能。结果表明，掺杂石墨烯和氧化石墨烯，支撑层断面结构更加疏松，孔隙率和纯水透过常数（PWP）明显增加，制备的相应FO膜性能得到改善，水通量增大。掺杂石墨则导致支撑层上表面变粗糙，断面结构密实，其孔隙率减小，PWP值降低，膜性能变差。其中，掺杂了氧化石墨烯的FO膜表现出最好的性能，水通量在活性层朝向驱动液侧（AL-DS）模式下可达37.10L/（m²·h），相比无掺杂FO膜增加了38.7%。

关键词: 氧化石墨烯, 掺杂, 正渗透, 膜, 结构, 性能

Abstract: Polysulfone supporting layers incorporated with graphite(GI),graphene(GE),and graphene oxide(GO)were respectively prepared by phase inversion method. Then the polyamide active layers were prepared via interfacial polymerization of m-phenylenediamine and trimesoyl chloride on the supporting layers. The morphologies of top surface and cross section of the membranes were characterized by SEM. The porosity,hydrophilicity and performance of FO membranes with different incorporated additives were investigated. The results showed that the structures of the cross section of the supporting layers incorporated with GE or GO were looser,resulting in increased porosity and pure water permeability(PWP)constant. Thus the properties of corresponding FO membranes were improved. However,the incorporating of GI resulted in the prepared membrane with rough surface,dense cross section,lower PWP constant,and worse performance. The FO membrane prepared on the supporting layer incorporated with GO exhibited the best performance. The water flux reached 37.10L/(m²·h) under the AL-DS membrane orientation,increased by 38.7% compared with FO membrane prepared on pure polysulfone substrate.

Key words: graphene oxide, incorporation, forward osmosis, membrane, structure, performance

中图分类号:

TQ028.8

胡念, 左浩然, 付佳蓓, 吕慧, 童奕皓, 刘慧清, 曹贵平. 石墨烯掺杂聚砜基正渗透膜的结构和性能[J]. 化工进展, 2017, 36(12): 4524-4532.

HU Nian, ZUO Haoran, FU Jiabei, LÜ Hui, TONG Yihao, LIU Huiqing, CAO Guiping. Structure and performance of forward osmosis membranes based on polysulfone substrates incorporated with graphene[J]. Chemical Industry and Engineering Progress, 2017, 36(12): 4524-4532.

参考文献

[1] ZHAO J J,SU Y L,HE X,et al. Dopamine composite nanofiltration membranes prepared by self-polymerization and interfacial polymerization[J]. J. Membr. Sci.,2014,465:41-48.
[2] LI D,YAN Y S,WANG H T. Recent advances in polymer and polymer composite membrane for reverse and forward osmosis processes[J]. Prog. Polym. Sci.,2016,61:104-155.
[3] 朱姝,赵颂,王志,等. 用于反渗透复合膜的海绵状结构支撑膜制备研究[J]. 化工学报,2015,66(10):3991-3999. ZHU S,ZHAO S,WANG Z,et al. Investigation of sponge-like substrates for preparation of reverse osmosis composite membranes[J]. CIESC Journal,2015,66(10):3991-3999.
[4] 施人莉,杨庆峰. 正渗透膜分离的研究进展[J]. 化工进展,2011,30(1):66-73. SHI R L,YANG Q F. Research advances in forward osmosis membrane separation[J]. Chem. Ind. Eng. Prog.,2011,30(1):66-73.
[5] 王亚琴,徐铜文,王焕庭. 正渗透原理及分离传质过程浅析[J]. 化工学报,2013,64(1):252-260. WANG Y Q,XU T W,WANG H T. Forward osmosis membrane process and its mass transport mechanisms[J]. CIESC Journal,2013,64(1):252-260.
[6] AKTHER N,SODIQ A,DAER S,et al. Recent advancements in forward osmosis desalination:A review[J]. Chem. Eng. J.,2015,281:502-522.
[7] ALEJOA T,ARRUEBOAB M,CARCELENC V,et al. Advances in draw solutes for forward osmosis:hybrid organic-inorganic nanoparticles and conventional solutes[J]. Chem. Eng. J.,2017,309:738-752.
[8] HUANG L W,NHUNGOC B,MARK M,et al. Novel hydrophilic nylon 6,6 microfiltration membrane supported thin film composite membranes for engineered osmosis[J]. J. Membr. Sci.,2013,437:141-149.
[9] NGUYEN T P N,YUN E T,KIM I C,et al. Preparation of cellulose triacetate/cellulose acetate(CTA/CA)-based membrane for forward osmosis[J]. J. Membr. Sci.,2013,433:49-59.
[10] YU Y B,SEO S K,KIM I C,et al. Nanoporous polyethersulfone(PES) membrane with enhances flux applied in forward osmosis process[J]. J. Membr. Sci.,2011,375:63-68.
[11] HUANG Y B,JIN H Y,LI H,et al. Synthesis and characterization of a polyamide thin film composite membrane based on a polydopamine coated support layer for forward osmosis[J]. RSC Adv.,2015,5:106113-106121.
[12] EMADZADEH D,LAU W J,MATSUURA T,et al. A novel thin film composite forward osmosis membrane prepared from PSF-TiO₂ nanocomposite substrate for water desalination[J]. Chem. Eng. J.,2014,237:70-80.
[13] LIU X,NG H Y. Fabrication of layered silica-polysulfone mixed matrix substrate membrane for enhancing performance of thin-film composite forward osmosis membrane[J]. J. Membr. Sci.,2015,481:148-163.
[14] MA N,WEI J,LIAO R,et al. Zeolite-polyamide thin film nanocomposite membranes:toward enhanced performance for forward osmosis[J]. J. Membr. Sci.,2012,405:149-157.
[15] WANG Y Q,QU R W,GE Q Q,et al. Preparation of polyethersulfone/carbon nanotube substrate for high-performance forward osmosis membrane[J]. Desalination,2013,330:70-78.
[16] HUANG H B,SONG Z G,WEI N,et al. Ultrafast viscous water flow through nanostand-channelled graphene oxide membranes[J]. Nat. Commun.,2013,4:2979-2987.
[17] KARAN S,SAMITSU S,PENG X,et al. Ultrafast viscous permeation of organic solvents through diamond-like carbon nanosheets[J]. Science,2012,335:444-447.
[18] CHI C L,WANG X R,PENG Y W,et al. Facile preparation of graphene oxide membranes for gas separation[J]. Chem. Mater.,2016,28:2921-2927.
[19] GHANBARIA M,EMADZADEHABC D,LAUA W J,et al. Minimizing structural parameter of thin film composite forward osmosis membranes using polysulfone/halloysite nanotubes as membrane substrates[J]. Desalination,2016,377:152-162.
[20] KUO A,PU Z. Polymer data handbook[M]. Oxford:Oxford Press,1999.
[21] TANG C Y,SHE Q H,LAY W C L,et al. Coupled effects of internal concentration polarization and fouling on flux behavior of forward osmosis membranes during humic acid filtration[J]. J. Membr. Sci.,2010,354:123-133.
[22] ACHILLI A,CATH T Y,CHILDRESS A E. Selection of inorganic-based draw solutions for forward osmosis applications[J]. J. Membr. Sci.,2010,364:233-241.
[23] GHANBARIA M,EMADZADEHABC D,LAUA W J,et al. Super hydrophilic TiO₂/HNT nanocomposite as a new approach for fabrication of high performance thin film nanocomposite membranes for FO application[J]. Desalination,2015,371:104-114.
[24] HEMANDEZ Y,NICOLOSI V,LOTYA M,et al. High-yield production of graphene by liquid phase exfoliation of graphite[J]. Nature Nanotech.,2008,3:563-568.
[25] DANG D K,KIM E J. Solvothermal-assisted liquid-phase exfoliation of graphite in a mixed solvent of toluene and oleylamine[J]. Anoscale Res. Lett.,2015,10:727-734
[26] CHEN C,LI Y R,et al. High-yield preparation of graphene oxide from small graphite flakes via an improved Hummers method with a simple purification process[J]. Carbon,2015,81:826-834.
[27] 王咚,黄颖为. 还原氧化石墨烯-纤维素复合薄膜的制备及性能[J]. 化工进展,2017,36(5):1838-1842. WANG D,HUANG Y W. Preparation and properties of reduced graphene oxide/cellulose films[J]. Chemical Industry and Engineering progress,2017,36(5):1838-1842.
[28] HAMRA A A B,LIM H N,CHEE W K,et al. Electro-exfoliating graphene from graphite for direct fabrication of supercapacitor[J]. Appl. Surf. Sci.,2016,360:213-223.
[29] HAN G,CHUNG T S,TORⅡDA M,et al. Thin-film composite forward osmosis membrane with novel hydrophilic supports for desalination[J]. J. Membr. Sci.,2012,423:543-555.
[30] WU H Q,TANG B B,WU P Y,et al. Development of novel SiO₂-GO nanohybrid polysulfone membrane with enhanced performance[J]. J. Membr. Sci.,2014,451:94-102.
[31] LI J G,LIU Q,LI X,et al. Template-assisted fabrication of thin-film composite forward osmosis membrane with controllable internal concentration polarization[J]. Ind. Eng. Chem. Res.,2016,55:5327-5334.
[32] ZIREHOUUR A,RAHIMPOUR A,ULBRICHT M. Nano-sized metal organic framework to improve the structual properities and desalination performance of thin film composite forward osmosis membrane[J]. J. Membr. Sci.,2017,531:59-67.
[33] MORALES-TORRES S,ESTEVES C M P,FIGUEIREDO J,et al. Thin-film composite forward osmosis membranes based on polysulfone supports blended with nanostructured carbon materials[J]. J. Membr. Sci.,2016,520:326-336.
[34] SINGH P S,JOSHI S V,TRIVEDI J J,et al. Probing the structural variations of thin film composite RO membranes obtained by coating polyamide over polysulfone membranes of different pore dimensions[J]. J. Membr. Sci.,2006,278:19-25.
[35] GHOSH A K,HOEK E M V. Inpacts of support membrane structure and chemistry on polyamide-polysulfone interfacial composite membrane[J]. J. Membr. Sci.,2009,336:140-148.
[36] CHEN G,LIU R,SHON H K,et al. Open porous hydrophilic supported thin-film composite forward osmosis membrane via co-casting for treatment of high-salinity wastewater[J]. Desalination,2017,405:76-84.
[37] SONG X,WANG L,TANG C Y,et al. Fabrication of carbon nanotubes incorporated double-skinned thin film nanocomposite membranes for enhanced separation performance and antifouling capability in forward osmosis process[J]. Desalination,2015,369:1-9.
[38] WU K,LIU Z N,et al. Invesigation of internal concentration polarization reduction in forward Osmosis membrane using nano-CaCO₃ particles as sacrificial component[J]. J. Membr. Sci.,2016,497:485-493.
[39] EMADZADEH D,LAU W J,MATSUURA T,et al. Synthesis and characterization of thin film nanocomposite forward osmosis membrane with hydrophilic nanocomposite support to reduce internal concentration polarzation[J]. J. Membr. Sci.,2014,449:74-85.