Dual-Functional PVC/MWCNT Nanocomposite Ion-Exchange Membranes for Water Desalination and Chemical Production

Document Type : Regular Article

Authors

1 Department of Chemical Engineering, University of Kashan, Kashan, Iran

2 Thermodynamic Research Laboratory, University of Kashan, Kashan, Iran

3 Department of Chemical Engineering, University of Qom, Qom, Iran

10.22034/ijche.2026.573395.1585
Abstract
This study investigates the performance of an electrodialysis metathesis (EDM) process using polyvinyl chloride/carbon nanotube (PVC/MWCNTs) nanocomposite ion-exchange membranes (IEMs) for simultaneous water desalination and chemical production. IEMs with MWCNTs loadings of 0% (M1), 4% (M2), 8% (M3), and 10% (M4) by weight were fabricated and characterized for water sorption, areal electrical resistance, hydrophobicity, and mechanical strength. Their ion selectivity, separation performance, desalination efficiency, and production yield were systematically evaluated under varying applied voltage, feed composition, and operation time. Among the fabricated membranes, M3 (8 wt% MWCNTs) exhibited the best performance, providing optimal ionic conductivity, selectivity, and structural stability. Maximum chemical yield was achieved when solute concentrations in the electrode chambers exceeded those in the desalination chamber. In contrast, M4 (10 wt% MWCNTs) showed reduced efficiency, attributed to MWCNTs agglomeration and pore blockage that hindered ion transport. Increasing voltage improved ion transport up to an optimal level, but excessive voltage (15 V) caused water splitting and concentration polarization, lowering both chemical yield and desalination efficiency. These results highlight the importance of MWCNTs loading optimization and controlled operating conditions. Overall, PVC/MWCNTs composite IEMs exhibited significant potential for integrated chemical production and saline wastewater treatment, providing a cost-effective and scalable strategy for resource recovery.

Keywords

Subjects

[1] Liu L, Cheng Q. Mass transfer characteristic research on electrodialysis for desalination and regeneration of solution: A comprehensive review. Renew Sustain Energy Rev 2020;134:110115. https://doi.org/https://doi.org/10.1016/j.rser.2020.110115.
[2] Carstea EM, Bridgeman J, Baker A, Reynolds DM. Fluorescence spectroscopy for wastewater monitoring: a review. Water Res 2016;95:205–19. https://doi.org/https://doi.org/10.1016/j.watres.2016.03.021.
[3] Elgallal M, Fletcher L, Evans B. Assessment of potential risks associated with chemicals in wastewater used for irrigation in arid and semiarid zones: A review. Agric Water Manag 2016;177:419–31. https://doi.org/https://doi.org/10.1016/j.agwat.2016.08.027.
[4] Carolin CF, Kumar PS, Saravanan A, Joshiba GJ, Naushad M. Efficient techniques for the removal of toxic heavy metals from aquatic environment: A review. J Environ Chem Eng 2017;5:2782–99. https://doi.org/https://doi.org/10.1016/j.jece.2017.05.029.
[5] Tanaka Y. A computer simulation of continuous ion exchange membrane electrodialysis for desalination of saline water. Desalination 2009;249:809–21. https://doi.org/10.1016/j.desal.2009.04.011
[6] Tedesco M, Hamelers H, Biesheuvel P. Nernst-Planck transport theory for (reverse) electrodialysis: III. Optimal membrane thickness for enhanced process performance. J Membr Sci 2018;565:480–7. https://doi.org/https://doi.org/10.1016/j.memsci.2018.07.090.
[7] Azad H, Mohsennia M. A novel free-standing polyvinyl butyral-polyacrylonitrile/ZnAl-layered double hydroxide nanocomposite membrane for enhanced heavy metal removal from wastewater. J Membr Sci 2020;615:118487. https://doi.org/https://doi.org/10.1016/j.memsci.2020.11848.
[8] Ghasemi M, Sedighi M, Usefi MMB. A comprehensive review on membranes in microbial desalination cells; processes, utilization, and challenges. Int J Energy Res 2022;46:14716–39. https://doi.org/https://doi.org/10.1002/er.8265.
[9] Mehdizadeh S, Yasukawa M, Kuno M, Kawabata Y, Higa M. Evaluation of energy harvesting from discharged solutions in a salt production plant by reverse electrodialysis (RED). Desalination 2019;467:95–102. https://doi.org/10.1016/j.desal.2019.04.007
[10]      Jang J, Kang Y, Han J-H, Jang K, Kim C-M, Kim IS. Developments and future prospects of reverse electrodialysis for salinity gradient power generation: Influence of ion exchange membranes and electrodes. Desalination 2020;491:114540. https://doi.org/10.1016/j.desal.2020.114540
[11]      Chen T-H, Chen Y-A, Tsai S-W, Wang D-M, Hou C-H. Development of an integrated capacitive-electrodialysis process (CapED) for continuous, low-energy electrochemical deionization. Sep Purif Technol 2021;274:119063. https://doi.org/https://doi.org/10.1016/j.seppur.2021.119063.
[12]      Dammak L, Fouilloux J, Bdiri M, Larchet C, Renard E, Baklouti L, Sarapulova V, Kozmai A, Pismenskaya N. A review on ion-exchange membrane fouling during the electrodialysis process in the food industry, part 1: Types, effects, characterization methods, fouling mechanisms and interactions. Membranes 2021;11:789. https://doi.org/https://doi.org/10.3390/membranes11100789.
[13]      Mohammadi R, Tang W, Sillanpää M. A systematic review and statistical analysis of nutrient recovery from municipal wastewater by electrodialysis. Desalination 2021;498:114626. https://doi.org/10.1016/j.desal.2020.114626.
[14]      Hosseini S, Usefi MB, Habibi M, Parvizian F, Van der Bruggen B, Ahmadi A, Nemati M. Fabrication of mixed matrix anion exchange membrane decorated with polyaniline nanoparticles to chloride and sulfate ions removal from water. Ionics 2019;25:6135–45. https://doi.org/https://doi.org/10.1007/s11581-019-03151-w.
[15]      Azad H, Mohsennia M, Cheng C, Amini A. Cross-linked poly (vinyl butyral)/amine-functionalized polyacrylonitrile adsorptive membrane nano-composited with CeO2 nanoparticles for simultaneous aqueous removal of heavy metals and cefotaxime. Chem Eng J 2022;435:134849. https://doi.org/10.1016/j.cej.2022.134849.
[16]      Chakraborty I, Das S, Dubey B, Ghangrekar M. Novel low cost proton exchange membrane made from sulphonated biochar for application in microbial fuel cells. Mater Chem Phys 2020;239:122025. https://doi.org/https://doi.org/10.1016/j.matchemphys.2019.122025.
[17]      Pendergast MM, Hoek EM. A review of water treatment membrane nanotechnologies. Energy Environ Sci 2011;4:1946–71. https://doi.org/DOI%09https://doi.org/10.1039/C0EE00541J.
[18]      Alabi A, AlHajaj A, Cseri L, Szekely G, Budd P, Zou L. Review of nanomaterials-assisted ion exchange membranes for electromembrane desalination. Npj Clean Water 2018;1:10. https://doi.org/https://doi.org/10.1038/s41545-018-0009-7.
[19]      Mishra JR, Samal SK, Mohanty S, Nayak SK. Polyvinylidene fluoride (PVDF)/Ag@ TiO2 nanocomposite membrane with enhanced fouling resistance and antibacterial performance. Mater Chem Phys 2021;268:124723. https://doi.org/https://doi.org/10.1016/j.matchemphys.2021.124723.
[20]      Nasrollahi N, Aber S, Vatanpour V, Mahmoodi NM. Development of hydrophilic microporous PES ultrafiltration membrane containing CuO nanoparticles with improved antifouling and separation performance. Mater Chem Phys 2019;222:338–50. https://doi.org/https://doi.org/10.1016/j.matchemphys.2018.10.032.
[21]      Sahoo NG, Rana S, Cho JW, Li L, Chan SH. Polymer nanocomposites based on functionalized carbon nanotubes. Prog Polym Sci 2010;35:837–67. https://doi.org/10.1016/j.progpolymsci.2010.03.002.
[22]      Spitalsky Z, Tasis D, Papagelis K, Galiotis C. Carbon nanotube–polymer composites: chemistry, processing, mechanical and electrical properties. Prog Polym Sci 2010;35:357–401. https://doi.org/10.1016/j.progpolymsci.2009.09.003.
[23]      Jhaveri JH, Murthy Z. A comprehensive review on anti-fouling nanocomposite membranes for pressure driven membrane separation processes. Desalination 2016;379:137–54. https://doi.org/10.1016/j.desal.2015.11.009
[24]      Fernandez-Gonzalez C, Zhang B, Dominguez-Ramos A, Ibañez R, Irabien A, Chen Y. Enhancing fouling resistance of polyethylene anion exchange membranes using carbon nanotubes and iron oxide nanoparticles. Desalination 2017;411:19–27. https://doi.org/10.1016/j.desal.2017.02.00.
[25]      Liu Y, Chen J, Chen R, Zhou T, Ke C, Chen X. Effects of multi-walled carbon nanotubes on bipolar membrane properties. Mater Chem Phys 2018;203:259–65. https://doi.org/10.1016/j.matchemphys.2017.09.068.
[26]      Jaroszek H, Dydo P. Potassium nitrate synthesis by electrodialysis-metathesis: The effect of membrane type. J Membr Sci 2018;549:28–37. https://doi.org/https://doi.org/10.1016/j.memsci.2017.11.062.
[27]      Zhang X, Han X, Yan X, Chen X, Jin Z, Hu X. Continuous synthesis of high purity KNO3 through electrodialysis metathesis. Sep Purif Technol 2019;222:85–91. https://doi.org/https://doi.org/10.1016/j.seppur.2019.04.027.
[28]      Wei X, Gao W, Wang Y, Wu K, Xu T. A green and economical method for preparing lithium hydroxide from lithium phosphate. Sep Purif Technol 2022;280:119909. https://doi.org/https://doi.org/10.1021/acs.iecr.1c04556.
[29]      Han X, Yan X, Wang X, Ran J, Wu C, Zhang X. Preparation of chloride-free potash fertilizers by electrodialysis metathesis. Sep Purif Technol 2018;191:144–52. https://doi.org/https://doi.org/10.1016/j.seppur.2017.09.022.
[30]      Hosseini S, Koranian P, Gholami A, Madaeni S, Moghadassi A, Sakinejad P, Khodabakhshi A. Fabrication of mixed matrix heterogeneous ion exchange membrane by multiwalled carbon nanotubes: Electrochemical characterization and transport properties of mono and bivalent cations. Desalination 2013;329:62–7. https://doi.org/10.1016/j.desal.2013.09.007
[31]      Zendehnam A, Mokhtari S, Hosseini S, Rabieyan M. Fabrication of novel heterogeneous cation exchange membrane by use of synthesized carbon nanotubes-co-copper nanolayer composite nanoparticles: Characterization, performance in desalination. Desalination 2014;347:86–93. https://doi.org/10.1016/j.desal.2014.05.041
[32]      Hosseini S, Jeddi F, Nemati M, Madaeni S, Moghadassi A. Electrodialysis heterogeneous anion exchange membrane modified by PANI/MWCNT composite nanoparticles: Preparation, characterization and ionic transport property in desalination. Desalination 2014;341:107–14. https://doi.org/10.1016/j.desal.2014.03.001
[33]      Chan W-F, Chen H, Surapathi A, Taylor MG, Shao X, Marand E, Johnson JK. Zwitterion functionalized carbon nanotube/polyamide nanocomposite membranes for water desalination. Acs Nano 2013;7:5308–19. https://doi.org/https://doi.org/10.1021/nn4011494.
[34]      Hosseini S, Madaeni S, Heidari A, Amirimehr A. Preparation and characterization of ion-selective polyvinyl chloride based heterogeneous cation exchange membrane modified by magnetic iron–nickel oxide nanoparticles. Desalination 2012;284:191–9. https://doi.org/10.1016/j.desal.2011.08.057
[35]      Barros KS, Scarazzato T, Pérez-Herranz V, Espinosa DCR. Treatment of cyanide-free wastewater from brass electrodeposition with edta by electrodialysis: Evaluation of underlimiting and overlimiting operations. Membranes 2020;10:69. https://doi.org/https://doi.org/10.3390/membranes10040069.
[36]      Ferreira AR, Couto N, Guedes P, Pinto J, Mateus EP, Ribeiro AB. Electrodialytic 2-compartment cells for emerging organic contaminants removal from effluent. J Hazard Mater 2018;358:467–74. https://doi.org/https://doi.org/10.1016/j.jhazmat.2018.04.066.
[37]      La Cerva M, Gurreri L, Tedesco M, Cipollina A, Ciofalo M, Tamburini A, Micale G. Determination of limiting current density and current efficiency in electrodialysis units. Desalination 2018;445:138–48. https://doi.org/10.1016/j.desal.2018.02.020
[38]      Yan K-K, Jiao L, Lin S, Ji X, Lu Y, Zhang L. Superhydrophobic electrospun nanofiber membrane coated by carbon nanotubes network for membrane distillation. Desalination 2018;437:26–33. https://doi.org/10.22078/jpst.2017.2577.1441.
[39]      Hosseini SM, Alibakhshi H, Khodabakhshi AR, Nemati M. Enhancing electrochemical performance of heterogeneous cation exchange membranes by using super activated carbon nanoparticles. J Pet Sci Technol 2018;8:14–29. https://doi.org/10.22078/jpst.2017.2577.1441.
[40]      Zhao Y, Duan L. Research on Measuring Pure Membrane Electrical Resistance under the Effects of Salinity Gradients and Diffusion Boundary Layer and Double Layer Resistances. Membranes 2022;12:816. https://doi.org/https://doi.org/10.3390/membranes12080816.
[41]      Sharma PP, Gahlot S, Rajput A, Patidar R, Kulshrestha V. Efficient and cost effective way for the conversion of potassium nitrate from potassium chloride using electrodialysis. ACS Sustain Chem Eng 2016;4:3220–7. https://doi.org/https://doi.org/10.1021/acssuschemeng.6b00248.
[42]      Zahakifar F, Keshtkar A, Souderjani EZ, Moosavian M. Use of response surface methodology for optimization of thorium (IV) removal from aqueous solutions by electrodeionization (EDI). Prog Nucl Energy 2020;124:103335. https://doi.org/https://doi.org/10.1016/j.pnucene.2020.103335.
[43]      Chang J, Duan F, Cao H, Tang K, Su C, Li Y. Superiority of a novel flow-electrode capacitive deionization (FCDI) based on a battery material at high applied voltage. Desalination 2019;468:114080. https://doi.org/10.1016/j.desal.2019.114080.
[44]      Phuoc NM, Tran NAT, Khoi TM, Jung HB, Ahn W, Jung E, Yoo C-Y, Kang HS, Cho Y. ZIF-67 metal-organic frameworks and CNTs-derived nanoporous carbon structures as novel electrodes for flow-electrode capacitive deionization. Sep Purif Technol 2021;277:119466. https://doi.org/https://doi.org/10.1016/j.seppur.2021.119466.
[45]      Al-Amshawee SKA, Yunus MYBM. Electrodialysis membrane with concentration polarization–a review. Chem Eng Res Des 2024;201:645–78. https://doi.org/https://doi.org/10.1016/j.cherd.2023.10.060.
[46]      Geise GM, Curtis AJ, Hatzell MC, Hickner MA, Logan BE. Salt concentration differences alter membrane resistance in reverse electrodialysis stacks. Environ Sci Technol Lett 2014;1:36–9. https://doi.org/https://doi.org/10.1021/ez4000719.
[47]      Jia YW, Chen GQ, Kentish SE. Investigating the effect of temperature and concentration on the performance of reverse electrodialysis systems. Desalination 2024;592:118184. https://doi.org/10.1016/j.desal.2024.118184.
[48]      Avci AH, Messana DA, Santoro S, Tufa RA, Curcio E, Di Profio G, Fontananova E. Energy harvesting from brines by reverse electrodialysis using nafion membranes. Membranes 2020;10:168. https://doi.org/https://doi.org/10.3390/membranes10080168.
[49]      Ebrahimi M, Van der Bruggen B, Askari M, Nemati M. Improving electrochemical properties of cation exchange membranes by using activated carbon-co-chitosan composite nanoparticles in water deionization. Ionics 2019;25:1199–214. https://doi.org/https://doi.org/10.1007/s11581-018-2724-y.
[50]      Fan H, Huang Y, Yip NY. Advancing the conductivity-permselectivity tradeoff of electrodialysis ion-exchange membranes with sulfonated CNT nanocomposites. J Membr Sci 2020;610:118259. https://doi.org/https://doi.org/10.1016/j.memsci.2020.118259.
[51]      Zhou R, Rana D, Matsuura T, Lan CQ. Effects of multi-walled carbon nanotubes (MWCNTs) and integrated MWCNTs/SiO2 nano-additives on PVDF polymeric membranes for vacuum membrane distillation. Sep Purif Technol 2019;217:154–63. https://doi.org/https://doi.org/10.1016/j.seppur.2019.02.013.
[52]      Moghadassi A, Koranian P, Hosseini S, Askari M, Madaeni S. Surface modification of heterogeneous cation exchange membrane through simultaneous using polymerization of PAA and multi walled carbon nano tubes. J Ind Eng Chem 2014;20:2710–8. https://doi.org/10.1016/j.jiec.2013.10.059.
[53]      Bagheripour E, Moghadassi A, Hosseini SM. Preparation of mixed matrix PES-based nanofiltration membrane filled with PANI-co-MWCNT composite nanoparticles. Korean J Chem Eng 2016;33:1462–71. https://doi.org/https://doi.org/10.1007/s11814-015-0257-x.

Articles in Press, Accepted Manuscript
Available Online from 29 May 2026