Dye removal from water using emulsion liquid membrane: Effect of alkane solvents on efficiency

  • Ghaemi, Negin (Department of Chemical Engineering, Kermanshah University of Technology) ;
  • Darabi, Farzaneh (Department of Chemical Engineering, Kermanshah University of Technology) ;
  • Falsafi, Monireh (Department of Inorganic Chemistry, Faculty of Chemistry, Razi University)
  • Received : 2019.03.04
  • Accepted : 2019.04.24
  • Published : 2019.09.25


Effect of different alkane based solvents on the stability of emulsion liquid membrane was investigated using normal alkanes (n-hexane, n-heptane, n-octane and n-decane) under various operating parameters of surfactant concentration, emulsification time, internal phase concentration, volume ratio of internal phase to organic phase, volume ratio of emulsion phase to external phase and stirring speed. Results of stability revealed that emulsion liquid membrane containing n-octane as solvent and span-80 (5 % (w/w)) as emulsifying agent presented the highest amount of emulsion stability (the lowest breakage) compared with other solvents; however, operating parameters (surfactant concentration (5% (w/w)), emulsification time (6 min), internal phase concentration (0.05 M), volume ratio of internal phase to organic phase (1/1), volume ratio of emulsion phase to external phase (1/5) and stirring speed (300 rpm)) were also influential on improving the stability (about 0.2% breakage) and on achieving the most stable emulsion. The membrane with the highest stability was employed to extract acridine orange with various concentrations (10, 20 and 40 ppm) from water. The emulsion liquid membrane prepared with n-octane as the best solvent almost removed 99.5% of acridine orange from water. Also, the prepared liquid membrane eliminated completely (100%) other cationic dyes (methylene blue, methyl violet and crystal violet) from water demonstrating the efficacy of prepared emulsion liquid membrane in treatment of dye polluted waters.


  1. Abraham Reife, H.S.F. (1996), Environmental Chemistry of Dyes and Pigments, Wiley, New Jersey, USA.
  2. Agarwal, A.K., Das, C. and De, S. (2010), "Modeling of extraction of dyes and their mixtures from aqueous solution using emulsion liquid membrane", J. Membr. Sci., 360(1), 190-201.
  3. Ahmad, A., Buddin, M.S., Ooi, B. and Kusumastuti, A. (2017), "Utilization of environmentally benign emulsion liquid membrane (ELM) for cadmium extraction from aqueous solution", J. Water Process Eng., 15, 26-30.
  4. Ahmad, A., Kusumastuti, A., Derek, C. and Ooi, B. (2012), "Emulsion liquid membrane for cadmium removal: Studies on emulsion diameter and stability", Desalination., 287, 30-34.
  5. Ahmad, A.L., Kusumastuti, A., Derek, C.J.C. and Ooi, B.S. (2012), "Emulsion liquid membranes for cadmium removal: Studies of extraction efficiency", Membr. Water Treat., 4(1), 11-25.
  6. Ahmad, A.L., Kusumastuti, A., Shah Buddin, M.M.H., Derek, C.J.C. and Ooi, B.S. (2014), "Emulsion liquid membrane based on a new flow pattern in a counter rotating Taylor-Couette column for cadmium extraction", Separation Purification., Technology 127(Supplement C), 46-52.
  7. Bahloul, L., Bendebane, F., Djenouhat, M., Meradi., H. and Ismail, F. (2016), "Effects and optimization of operating parameters of anionic dye extraction from an aqueous solution using an emulsified liquid membrane: Application of designs of experiments", J. Taiwan Institute Chem. Eng., 59(Supplement C), 26-32.
  8. Bahloul, L., Ismail, F. and Samar, M.E.H. (2013), "Extraction and desextraction of a cationic dye using an emulsified liquid membrane in an aqueous solution", Energy Procedia, 36(Supplement C), 1232-1240.
  9. Balasubramanian, A. and Venkatesan, S. (2012), "Removal of phenolic compounds from aqueous solutions by emulsion liquid membrane containing Ionic Liquid [BMIM]+[PF6]- in Tributyl phosphate", Desalination., 289(Supplement C), 27-34.
  10. Cahn, R.P., Li, N.N. and Minday, R.M. (1978), "Removal of ammonium sulfide from wastewater by liquid membrane process", Environ. Sci. Technol., 12(9).
  11. Chakravarti, A., S. Chowdhury, S. Chakrabarty, T. Chakrabarty and D. Mukherjee (1995), "Liquid membrane multiple emulsion process of chromium (VI) separation from waste waters", Colloids Surfaces A Physicochem Eng. Aspects, 103(1), 59-71.
  12. Chaouchi, S. and O. Hamdaoui (2015), "Extraction of endocrine disrupting compound propylparaben from water by emulsion liquid membrane using trioctylphosphine oxide as carrier", J. Industrial Eng. Chem., 22(Supplement C), 296-305.
  13. Chiha, M., O. Hamdaoui, F. Ahmedchekkat and C. Petrier (2010), "Study on ultrasonically assisted emulsification and recovery of copper(II) from wastewater using an emulsion liquid membrane process", Ultrasonics Sonochemistry, 17(2), 318-325.
  14. Chiha, M., Samar, M.H. and Hamdaoui, O. (2006), "Extraction of chromium (VI) from sulphuric acid aqueous solutions by a liquid surfactant membrane (LSM)", Desalination., 194(1), 69-80.
  15. Daas, A. and O. Hamdaoui (2010), "Extraction of anionic dye from aqueous solutions by emulsion liquid membrane", J. Harzardous Mater., 178(1), 973-981.
  16. Das, C., M. Rungta, G. Arya, S. DasGupta and S. De (2008), "Removal of dyes and their mixtures from aqueous solution using liquid emulsion membrane", J. Harzardous Mater. 159(2), 365-371.
  17. Demirel, Y. (2007), Nonequilibrium Thermodynamics: Transport and Rate Processes in Physical and Biological Systems, Elsevier, The Netherlands.
  18. Djenouhat, M., Hamdaoui, O., Chiha, M. and Samar, M.H. (2008), "Ultrasonication-assisted preparation of water-in-oil emulsions and application to the removal of cationic dyes from water by emulsion liquid membrane: Part 1: Membrane stability", Sep. Purification Tech., 62(3), 636-641.
  19. Djenouhat, M., O. Hamdaoui, M. Chiha and M. H. Samar (2008), "Ultrasonication-assisted preparation of water-in-oil emulsions and application to the removal of cationic dyes from water by emulsion liquid membrane: Part 2. Permeation and stripping", Sep. Purification Tech., 63(1), 231-238.
  20. Erkey, C., Rodden, J. and Akgerman, A. (1990), "A correlation for predicting diffusion coefficients in alkanes", The Canadian J. Chem. Eng., 68(4), 661-665.
  21. Fouad, E.A. (2008), "Zinc and Copper Separation through an Emulsion Liquid Membrane Containing Di-(2-Ethylhexyl) Phosphoric Acid as a Carrier", Chem. Eng. Technol., 31(3), 370-376.
  22. Ganesh Prasadh, K., S. Venkatesan, K. Meera Sheriffa Begum and N. Anantharaman (2007), "Emulsion liquid membrane pertraction of zinc and copper: Analysis of emulsion formation using computational fluid dynamics", Chem. Eng. Technol., 30(9), 1212-1220.
  23. Ghaemi, N., S. S. Madaeni, P. Daraei, H. Rajabi, T. Shojaeimehr, F. Rahimpour and B. Shirvani (2015), "PES mixed matrix nanofiltration membrane embedded with polymer wrapped MWCNT: Fabrication and performance optimization in dye removal by RSM", J. Harzardous Mater., 298(Supplement C), 111-121.
  24. Ghodbane, H., Y. Nikiforov Anton, O. Hamdaoui, P. Surmont, F. Lynen, G. Willems and C. Leys (2014), "Non-thermal Plasma Degradation of Anthraquinonic Dye in Water: Oxidation Pathways and Effect of Natural Matrices", J. Adv. Oxidation Technol., 17, 372.
  25. Hu, S.Y.B., Li, J. and Wiencek, J.M. (2003), "Feasibility of surfactant-free supported emulsion liquid membrane extraction", J. Colloid Interface Sci., 266(2), 430-437.
  26. Jegatheesan, V., Pramanik, J.B.K., Chen, D., Navaratna, C.Y. Chang and L. Shu (2016), "Treatment of textile wastewater with membrane bioreactor: A critical review", Bioresource Technology, 204(Supplement C), 202-212.
  27. Kadirvelu, K., M. Kavipriya, C. Karthika, M. Radhika, N. Vennilamani and Pattabhi, S. (2003), "Utilization of various agricultural wastes for activated carbon preparation and application for the removal of dyes and metal ions from aqueous solutions", Bioresource Technology, 87(1), 129-132.
  28. Kageyama, T., Matsumiya, H. and Hiraide, M. (2004), "Separation of traces of heavy metals from an iron matrix by use of an emulsion liquid membrane", Anal Bioanal Chem, 379(7-8), 1083-1087.
  29. Kalmar, J., Lente, G. and Fabian, I. (2016), "Kinetics and mechanism of the adsorption of methylene blue from aqueous solution on the surface of a quartz cuvette by on-line UV-Vis spectrophotometry", Dyes and Pigments, 127(Supplement C), 170-178.
  30. Khan, M.A., Khan, M.I. and Zafar, S. (2017), "Removal of different anionic dyes from aqueous solution by anion exchange membrane", Membr. Water Treat., 8(3), 259-277.
  31. Khayet, M., Zahrim, A.Y. and Hilal, N. (2011), "Modelling and optimization of coagulation of highly concentrated industrial grade leather dye by response surface methodology", Chem. Eng. J., 167(1), 77-83.
  32. Khenifi, A., Bouberka, Z., Sekrane, F., Kameche, M. and Derriche, Z. (2007), "Adsorption study of an industrial dye by an organic clay", Adsorption, 13(2), 149-158.
  33. Kislik, V. (2009), Liquid Membranes, Elsevier Science, The Netherlands.
  34. Kobya, M., Topcu, N. and Demircioglu, N. (1997), "Kinetic analysis of coupled transport of thiocyanate ions through liquid membranes at different temperatures", J. Membr. Sci., 130(1), 7-15.
  35. Kumbasar, R.A. (2008), "Selective separation of chromium (VI) from acidic solutions containing various metal ions through emulsion liquid membrane using trioctylamine as extractant", Sep. Purification Tech., 64(1), 56-62.
  36. Leahy-Dios, A. and Firoozabadi, A. (2007), "Molecular and Thermal Diffusion Coefficients of Alkane- Alkane and Alkane-Aromatic Binary Mixtures: Effect of Shape and Size of Molecules", J. Phys. Chem. B, 111(1), 191-198.
  37. Lee, J.W., Choi, S.P., Thiruvenkatachari, R., Shim, W.G. and Moon, H. (2006), "Evaluation of the performance of adsorption and coagulation processes for the maximum removal of reactive dyes", Dyes Pigments, 69(3), 196-203.
  38. Lende, A.B. and Kulkarni, P.S. (2015), "Selective recovery of tungsten from printed circuit board recycling unit wastewater by using emulsion liquid membrane process", J. Water Process Eng., 8(Supplement C), 75-81.
  39. Lin, C.C. and Long, R.L. (1997), "Removal of nitric acid by emulsion liquid membrane: Experimental results and model prediction", J. Membr. Sci.,134(1), 33-45.
  40. Lu, G., Lu, Q. and Li, P. (1997), "Break-down of liquid membrane emulsion under high electric field", J. Membr. Sci., 128(1), 1-6.
  41. Masu, S., Botau, D. and Manea, F. (2005), "Application of emulsion liquid membrane technique for MB R 12 Red reactive dye-containing simulated wastewater treatment", Chemical Bulletin "POLITEHNICA" University (Timisoara), 50(64), 1-2.
  42. Mokhtari, B. and Pourabdollah, K. (2012), "Inclusion desalination of alkali metal cations by emulsion liquid membranes and nanobaskets of p-tert-calix[4]arene bearing di-[N-(X)sulfonyl carboxamide] and di-(1-propoxy) in para-cone conformation", Desalination., 292(Supplement C), 1-8.
  43. Mokhtari, B. and Pourabdollah, K. (2012), "Inclusion Extraction of Alkali Metals by Emulsion Liquid Membranes and Nanobaskets of p-tert-Calix[4]arene Bearing Di-[N-(X)sulfonyl Carboxamide] and Di-(1-propoxy) in ortho-cone Conformation", Bullet. Kor. Chem. Soc., 33(5), 1509-1516.
  44. Ngulube, T., Gumbo, J.R., Masindi, V. and Maity, A. (2017), "An update on synthetic dyes adsorption onto clay based minerals: A state-of-art review", J. Environ. Manage., 191, 35-57.
  45. Othman, N., Noah, L.N.F.M., Shu, Y., Ooi, Z.Y., Jusoh, N., Idroas, M. and Goto, M. (2017), "Easy removing of phenol from wastewater using vegetable oil-based organic solvent in emulsion liquid membrane process", Chinese J. Chem. Eng. 25(1), 45-52.
  46. Othman, N., Yi, O.Z., Zailani, S.N., Zulkifli, E.Z. and Subramaniam, S. (2013), "Extraction of Rhodamine 6G dye from liquid waste solution: Study on emulsion liquid membrane stability performance and recovery", Sep. Sci. Technol., 48(8), 1177-1183.
  47. Othman, N., Zailani, S.N. and Mili, N. (2011), "Recovery of synthetic dye from simulated wastewater using emulsion liquid membrane process containing tri-dodecyl amine as a mobile carrier", J. Harzardous Mater., 198(Supplement C), 103-112.
  48. Othmana, N., Zing-Yia, O., Harruddina, N., Norimiea, R., Jusoha, N. and Zailania, S.N. (2018) "Carrier Assisted Emulsion Liquid Membrane Process for Recovery of Basic Dye from Wastewater using Continuous Extractor", J. Teknologi., 67(2),
  49. Patnaik, P.R. (1995), "Liquid emulsion membranes: Principles, problems and applications in fermentation processes", Biotechnol. Adv., 13(2), 175-208.
  50. Salazar, E., Ortiz, M.I., Urtiaga, A.M. and Irabien, J.A. (1992), "Kinetics of the separation-concentration of chromium(VI) with emulsion liquid membranes", Industrial Eng. Chem. Res., 31(6), 1523-1529.
  51. Schotte, W. (1992), "Prediction of the molar volume at the normal boiling point", Chem. Eng. J., 48(3), 167-172.
  52. Seader, J.D., Henley, E.J. and Roper, D.K. (1998), Separation Process Principles, Wiley, New Jersey, USA.
  53. Soloman, P.A., Basha, C.A., Velan, M., Ramamurthi, V., Koteeswaran, K. and Balasubramanian, N. (2009), "Electrochemical degradation of remazol black B dye effluent", CLEAN - Soil, Air, Water, 37(11), 889-900.
  54. Sulaiman, R.N.R., Othman, N. and Amin, N.A.S. (2014), "Emulsion liquid membrane stability in the extraction of ionized nanosilver from wash water", J. Industrial Eng. Chem., 20(5), 3243-3250.
  55. Tan, K.B., Vakili, M., Horri, B.A., Poh, P.E., Abdullah, A. Z. and Salamatinia, B. (2015), "Adsorption of dyes by nanomaterials: Recent developments and adsorption mechanisms", Sep. Purification Tech., 150(Supplement C), 229-242.
  56. Tang, B., Yu, G., Fang, J. and Shi, T. (2010), "Recovery of highpurity silver directly from dilute effluents by an emulsion liquid membrane-crystallization process", J. Harzardous Mater., 177(1), 377-383.
  57. Terry, R.E., Li, N.N. and Ho, W.S. (1982), "Extraction of phenolic compounds and organic acids by liquid membranes", J. Membr. Sci., 10(2), 305-323.
  58. Thompson, L. and Doraiswamy, L. (1999), "Sonochemistry: Science and engineering", Indus. Eng. Chem. Res., 38(4), 1215-1249.
  59. Tiaiba, M., Merzouk, B., Mazour, M., Leclerc, J.P. and Lapicque, F. (2018), "Study of chemical coagulation conditions for a disperse red dye removal from aqueous solutions", Membr. Water Treat., 9(1), 9-15.
  60. Vasconcelos, J.M. and Carvalho, J.M. (1993), "Extraction of zinc by alkyl thiophosphoric acids with emulsion liquid membranes", Chem. Eng. Technol., 16(3), 213-217.
  61. Venkatesan, S. and Begum, K.M.S. (2009), "Emulsion liquid membrane pertraction of benzimidazole using a room temperature ionic liquid (RTIL) carrier", Chem. Eng. J., 148(2), 254-262.
  62. Wan, Y.H., Wang, X.D. and Zhang, X.J. (1997), "Treatment of high concentration phenolic waste water by liquid membrane with N503 as mobile carrier", J. Membr. Sci., 135(2), 263-270.
  63. Yagub, M.T., Sen, T.K., Afroze, S. and Ang, H.M. (2014), "Dye and its removal from aqueous solution by adsorption: A review", Adv. Colloid Interface Sci., 209(Supplement C), 172-184.
  64. Zeng, G., Ye, Z., He, Y., Yang, X., Ma, J., Shi, H. and Feng, Z. (2017), "Application of dopamine-modified halloysite nanotubes/PVDF blend membranes for direct dyes removal from wastewater", Chem. Eng. J., 323(Supplement C), 572-583.