Synthesis and characterization of supported Phenolic resin/Carbon nanotubes Carbon membranes for gas separation

Document Type : Reasearch Paper


1 Separation Processes Research Group (SPRG), Department of Engineering, University of Kashan, Kashan, Iran.

2 Department of chemical engineering, Science and Research branch, Islamic Azad University, Shiraz, Iran.


In this work, separation performance of supported carbon membranes produced from Novolac Phenolic resin as the main precursor and carbon nanotubes as nanofiller were investigated for separation of CO2 from N2 and CH4. Supports were produced by carbonization of Novolac Phenolic resin-activated carbon mixture, and selective layer was coated by dip coating of prepared supports into solutions with different concentrations of Novolac Phenolic resin/carbon nanotubes. The composite membranes were pre-oxidized and carbonized under vacuum condition up to 160°C and 700°C, respectively. Carbon membranes were characterized using FE-SEM, BET, and gas permeation test. Results revealed that the best proportion of Novolac Phenolic resin/activated carbon was 40/60 wt% to make a defect-free and applicable support, most pores of which had sizes less than 10 nm. Membranes were tested at different pressures, and the results showed that CO2 permeability increased with pressure. The carbon membrane made with 40 wt% Novolak phenolic resin and 1 wt% carbon nanotubes showed the best separation performance with CO2/CH4 and CO2/N2 selectivity of 19.5 and 18.3 in 10 bar, respectively.


Main Subjects

[1] Nejad M. N., Asghari M., Afsari M., (2016), Investigation of Carbon nanotubes in mixed matrix membranes for gas separation: A review. Chem. Bio. Eng. Rev. 3: 276-298.
[2] Article O., (2017), Effect of nano Zinc Oxide on gas permeation through mixed matrix Poly ( Amide-6-b-Ethylene Oxide )-based membranes. Int. J. Nano Dimens. 8: 31-39.
[3] Esmaeili N., Kazemian H., Bastani D., (2011), Synthesis of nano particles of LTA zeolite by means of microemulsion technique. Iranian J. Chem. Chem. Eng. 30: 1–8.
[4] Kazemzadeh A., Bayati B., Kalantari N., (2012), Tubular MFI zeolite membranes made by in-situ crystallization. Iran J. Chem. Chem. Eng. 31: 37-44.
[5] Scholes C. A., Stevens G. W., Kentish S. E., (2012), Membrane gas separation applications in natural gas processing. Fuel. 96: 15-28.
[6] Barbosa-Coutinho E., Salim V. M. M., Borges C. P., (2003), Preparation of carbon hollow fiber membranes by pyrolysis of polyetherimide. Carbon N. Y. 41: 1707-1714.
[7] David L. I. B., Ismail A. F., (2003), Influence of the thermastabilization process and soak time during pyrolysis process on the polyacrylonitrile carbon membranes for O2/N2 separation. J. Memb. Sci. 213: 285–291.
[8] Asadi S. Z., Shekarian E., Tarighaleslami A. H., (2015), Preparation and characterization of nano-porous Polyacrylonitrile (PAN) membranes with hydrophilic surface. Int. J. Nano Dimens. 6: 217–226.
[9] Centeno T. A., Fuertes A. B., (2001), Carbon molecular sieve membranes derived from a phenolicresin supported on porous ceramic tubes. Sep. Purif. Technol.  25: 379–384.
[10] Wei W., Qin G., Hu H., (2007), Preparation of supported carbon molecular sieve membrane from novolac phenol-formaldehyde resin. J. Memb. Sci. 303: 80–85.
[11] Suda H., Haraya K., (1997), Gas permeation through micropores of Carbon molecular sieve membranes derived from Kapton Polyimide. J. Phys. Chem. B. 101: 3988–3994.
[12] Kalantari H., Yaghmaei S., Roostaazad R., (2014), Removal of zirconium from aqueous solution by Aspergillus niger. Sci. Iran Trans. C. Chem. Chem. Eng. 21: 772-776.
[13] Liang C., Sha G., Guo S., (1999), Carbon membrane for gas separation derived from coal tar pitch. Carbon N. Y. 37: 1391–1397.
[14] Steriotis T., Beltsios K., Mitropoulos A. C., (1997), On the structure of an asymmetric carbon membrane with a novolac resin precursor. J. Appl. Polym. Sci. 64: 2323–2345.
[15] Shusen W., Meiyun Z., Zhizhong W., (1996), Asymmetric molecular sieve carbon membranes. J. Memb. Sci. 109: 267–270.
[16] Habibzare S., Asgari M., Djirsarai A., (2014), Nano composite PEBAX ®/PEG membranes: Effect of MWNT filler on CO2/CH4 separation. Int. J. Nano Dimens. 5: 247–254.
[17] Mastali N., Bakhtiari H., (2013), Investigation on the structural, morphological and photochemical properties of spin-coated TiO2 and ZnO thin films prepared by sol-gel method. Int. J. Nano Dimens. 5: 113–121.
[18] Yampolskii Y., Freeman B., (2010), Membrane Gas Separation Gas separation membranes offer a number of benefits over other separation technologies, John Wiley & Sons, Ltd.
[19] Mahmoudi A., Namdari M., Zargar V., (2014), Nano composite PEBAX ® membranes: Effect of zeolite X filler on CO2 permeation. Int. J. Nano Dimens. 5: 83-89.
[20] Thommes M., Kaneko K., Neimark A. V., (2015), Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87: 1051–1069.
[21] Li S., Fan C.Q., (2010), High-Flux SAPO-34 Membrane for CO2/N2 Separation. Ind. Eng. Chem. Res. 49: 4399–4404.
[22] Grainger D., Hägg M. B., (2007), Evaluation of cellulose-derived carbon molecular sieve membranes for hydrogen separation from light hydrocarbons. J. Memb. Sci. 306: 307–317.
[23] Sebastian V., Kumakiri I., Bredesen R., (2007), Zeolite membrane for CO2 removal: Operating at high pressure. J. Memb. Sci. 292: 92–97.
[24] Sircar S., Rao M. B., Thaeron C. M. A., (1999), Selective surface flow membrane for gas separation. Sep. Sci. Technol. 34: 2081–2093.
[25] Huang D. S., Yi Z. Z., Huang Z. L., (2012), Mass transfer mechanism and mathematical model for extraction process of L-Theanine across bulk liquid membrane. Iran. J. Chem. Chem. Eng. 31: 53–58.
[26] Allahbakhsh A., Bahramian A. R., (2016), Novolac-derived carbon aerogels pyrolyzed at high temperatures: Experimental and theoretical studies. RSC Adv. 6: 72777–72790.
[27] Khalaj M., Allahbakhsh A., Bahramian A. R., (2017), Structural, mechanical and thermal behaviors of novolac/graphene oxide nanocomposite aerogels. J. Non. Cryst. Solids. 460: 19-28.
[28] Yuan F.-Y., Zhang H.-B., Li X., (2014), In situ chemical reduction and functionalization of graphene oxide for electrically conductive phenol formaldehyde composites. Carbon N. Y. 68: 653–661.
[29] Noparvar-Qarebagh A., Roghani-Mamaqani H., Salami-Kalajahi M., (2015), Functionalization of carbon nanotubes by furfuryl alcohol moieties for preparation of novolac phenolic resin composites with high carbon yield values. Colloid Polym. Sci. 293: 3623–3631.
[30] Yeh M.-K., Tai N.-H., Liu J.-H., (2006), Mechanical behavior of phenolic-based composites reinforced with multi-walled carbon nanotubes. Carbon N. Y. 44: 1–9.
[31] Noparvar-Qarebagh A., Roghani-Mamaqani H., Salami-Kalajahi M., (2017), Nanohybrids of novolac phenolic resin and carbon nanotube-containing silica network: Two different approaches for improving thermal properties of resin. J. Therm. Anal. Calorim. 128: 1027–1037.
[32] Noparvar-Qarebagh A., Roghani-Mamaqani H., Salami-Kalajahi M., (2016), Novolac phenolic resin and graphene aerogel organic-inorganic nanohybrids: High carbon yields by resin modification and its incorporation into aerogel network. Polym. Degrad. Stab. 124: 1-14.
[33] Ouchi K., (1966), Infra-red study of structural changes during the pyrolysis of a phenol-formaldehyde resin. Carbon N. Y. 4: 59–66.
34] Dante R. C., Santamaria D. A., Gil J. M., (2009), Crosslinking and thermal stability of thermosets based on novolak and melamine. J. Appl. Polym. Sci. 114: 4059–4065.
[35] Llosa Tanco M. A., Pacheco Tanaka D. A., Rodrigues S. C., (2015), Composite-alumina-carbon molecular sieve membranes prepared from novolac resin and boehmite. Part I: Preparation, characterization and gas permeation studies. Int. J. Hydrogen Energy. 40: 5653–5663.
[36] Hussain R., Qadeer R., Ahmad M., (2000), X-ray diffraction study of heat-treated graphitized and ungraphitized carbon. Turkish J. Chem. 24: 177–183.