Chemical Papers

, Volume 72, Issue 4, pp 955–970 | Cite as

Mathematical modeling for facilitated transport of Ge(IV) through supported liquid membrane containing Alamine 336

  • Hossein Kamran Haghighi
  • Mehdi Irannajad
  • Agustin Fortuny
  • Ana Maria Sastre
Original Paper


A mathematical model was developed for the germanium-facilitated transport from a medium containing tartaric acid using Alamine 336 as a carrier. Modeling was carried out based on the extraction constant (K ext) obtained from the liquid–liquid extraction (LLX) modeling. The LLX data were achieved from experiments with conditions being Alamine 336 concentrations of 0.1–10% v/v from a solution containing about 1.378 mmol/L Ge (100 mg/L) and tartaric acid as an anionic complexant. The LLX model was attained using the equilibrium-based procedure and fitted to extraction experimental data for various carrier concentrations. This model presented an accurate extraction constant (K ext = 0.02) used in the facilitated transport modeling. The flat sheet supported liquid membrane (FSSLM) experiments were conducted in the condition of 1.378 mmol/L Ge (100 mg/L), tartaric acid concentration of 2.760 mmol/L, 1 M HCl as a stripping phase and various Alamine 336 concentrations in the range of 0–35% v/v. The FSSLM model was developed according to the Fick’s law, the diffusional transport, and equilibrium equations. According to the model, mass transfer and diffusion coefficients for various concentrations of the carrier were found. In addition, the calculated and experimental values had a good correlation with together showing the validity of the model. This model can be used in the further process simulation such as hollow fiber SLMs.


Germanium Supported liquid membrane Diffusion Mathematical modeling Transport 



This research has been conducted in the laboratory of Department of Chemical Engineering, Universitat Politècnica de Catalunya, Vilanova i la Geltrú Campus, Spain. The authors wish to thank all staffs for their help and suggestions.


  1. Aguilar JC, Sánchez-Castellanos M, de San Miguel ER, de Gyves J (2001) Cd(II) and Pb(II) extraction and transport modeling in SLM and PIM systems using Kelex 100 as carrier. J Membr Sci 190:107–118. CrossRefGoogle Scholar
  2. Alguacil FJ, Alonso M (2005) Description of transport mechanism during the elimination of copper(II) from wastewaters using supported liquid membranes and Acorga M5640 as carrier. Environ Sci Technol 39:2389–2393CrossRefGoogle Scholar
  3. Alguacil FJ, Alonso M, Sastre AM (2001a) Modelling of mass transfer in facilitated supported liquid membrane transport of copper(II) using MOC-55 TD in Iberfluid. J Membr Sci 184:117–122. CrossRefGoogle Scholar
  4. Alguacil FJ, Coedo A, Dorado M, Padilla I (2001b) Phosphine oxide mediate transport: modelling of mass transfer in supported liquid membrane transport of gold(III) using Cyanex 923. Chem Eng Sci 56:3115–3122CrossRefGoogle Scholar
  5. Alguacil FJ, Alonso M, Sastre A (2005) Facilitated supported liquid membrane transport of gold(I) and gold(III) using Cyanex® 921. J Membr Sci 252:237–244CrossRefGoogle Scholar
  6. Alonso AI, Urtiaga AM, Irabien A, Ortiz MI (1994) Extraction of Cr(VI) with Aliquat 336 in hollow fiber contactors: mass transfer analysis and modeling. Chem Eng Sci 49:901–909CrossRefGoogle Scholar
  7. Alonso M, López-Delgado A, Sastre AM, Alguacil FJ (2006) Kinetic modelling of the facilitated transport of cadmium(II) using Cyanex 923 as ionophore. Chem Eng J 118:213–219. CrossRefGoogle Scholar
  8. Ammari Allahyari S, Minuchehr A, Ahmadi SJ, Charkhi A (2016) Th(IV) transport from nitrate media through hollow fiber renewal liquid membrane. J Membr Sci 520:374–384. CrossRefGoogle Scholar
  9. Ata ON (2007) Mathematical modelling of unsteady-state transport of metal ions through supported liquid membrane. Hydrometallurgy 87:148–156CrossRefGoogle Scholar
  10. Bachmann RT, Wiemken D, Tengkiat AB, Wilichowski M (2010) Feasibility study on the recovery of hexavalent chromium from a simulated electroplating effluent using Alamine 336 and refined palm oil. Sep Purif Technol 75:303–309. CrossRefGoogle Scholar
  11. Baes CF, Mesmer RS (1977) The Hydrolysis of Cations Berichte der Bunsengesellschaft für physikalische. Chemie 81:245–246. Google Scholar
  12. Benzal G, Kumar A, Delshams A, Sastre AM (2004) Mathematical modelling and simulation of cotransport phenomena through flat sheet-supported liquid membranes. Hydrometallurgy 74:117–130. CrossRefGoogle Scholar
  13. Bhatluri KK, Manna MS, Ghoshal AK, Saha P (2015) Supported liquid membrane based removal of lead (II) and cadmium (II) from mixed feed: conversion to solid waste by precipitation. J Hazard Mater 299:504–512CrossRefGoogle Scholar
  14. Boateng DAD, Neudorf DA, Saleh VN (1990) Recovery of germanium from aqueous solutions by solvent extraction. US Patent 4,915,919, 10 Apr 1990Google Scholar
  15. Bringas E, San Román MF, Ortiz I (2006) Separation and recovery of anionic pollutants by the emulsion pertraction technology. Remediation of polluted groundwaters with Cr(VI). Ind Eng Chem Res 45:4295–4303. CrossRefGoogle Scholar
  16. Buachuang D, Ramakul P, Leepipatpiboon N, Pancharoen U (2011) Mass transfer modeling on the separation of tantalum and niobium from dilute hydrofluoric media through a hollow fiber supported liquid membrane. J Alloy Compd 509:9549–9557CrossRefGoogle Scholar
  17. Campderros ME, Marchese J (1994) Membrane transport of cobalt, copper and nickel with trioctyl amine. Indian J Chem Technol 1:35–39Google Scholar
  18. Campderrós ME, Marchese J (2001) Transport of niobium(V) through a TBP–Alamine 336 supported liquid membrane from chloride solutions. Hydrometallurgy 61:89–95. CrossRefGoogle Scholar
  19. Castillo E, Granados M, Cortina JL (2002) Liquid-supported membranes in chromium(VI) optical sensing: transport modelling. Anal Chim Acta 464:197–208. CrossRefGoogle Scholar
  20. Chaturabul S, Srirachat W, Wannachod T, Ramakul P, Pancharoen U, Kheawhom S (2015) Separation of mercury(II) from petroleum produced water via hollow fiber supported liquid membrane and mass transfer modeling. Chem Eng J 265:34–46. CrossRefGoogle Scholar
  21. Clark ER (1959) Interaction between organic hydroxy acids and germanic acid in aqueous solution. Nature 183:536–537CrossRefGoogle Scholar
  22. Clark ER, Waddams JA (1957) Interaction between organic hydroxy acids and silicic and germanic acids in aqueous solutions. Nature 180:904–905CrossRefGoogle Scholar
  23. Danesi PR (1984) A simplified model for the coupled transport of metal ions through hollow-fiber supported liquid membranes. J Membr Sci 20:231–248CrossRefGoogle Scholar
  24. Duan H, Wang S, Yang X, Yuan X, Zhang Q, Huang Z, Guo H (2017a) Simultaneous separation of copper from nickel in ammoniacal solutions using supported liquid membrane containing synergistic mixture of M5640 and TRPO. Chem Eng Res Des 117:460–471. CrossRefGoogle Scholar
  25. Duan H, Yuan X, Zhang Q, Wang Z, Huang Z, Guo H, Yang X (2017b) Separation of Ni2+ from ammonia solution through a supported liquid membrane impregnated with Acorga M5640. Chem Pap 71:597–606. CrossRefGoogle Scholar
  26. El Aamrani F, Kumar A, Beyer L, Cortina J, Sastre A (1998) Uphill permeation model of gold(III) and its separation from base metals using thiourea derivatives as ionophores across a liquid membrane. Hydrometallurgy 50:315–330CrossRefGoogle Scholar
  27. El Aamrani F, Kumar A, Sastre A (1999) Kinetic modelling of the active transport of copper(II) across liquid membranes using thiourea derivatives immobilized on microporous hydrophobic supports. New J Chem 23:517–523. CrossRefGoogle Scholar
  28. Everest DA, Harrison JC (1960) 747. The chemistry of quadrivalent germanium. Part VIII. Complexes of germanium with tartaric, lactic, and mucic acid. J Chem Soc (Resumed):3752-3758. doi:
  29. Fortuny A, Coll MT, Kedari CS, Sastre AM (2014) Effect of phase modifiers on boron removal by solvent extraction using 1,3 diolic compounds. J Chem Technol Biotechnol 89:858–865. CrossRefGoogle Scholar
  30. Gherrou A, Kerdjoudj H, Molinari R, Drioli E (2001) Modelization of the transport of silver and copper in acidic thiourea medium through a supported liquid membrane. Desalination 139:317–325. CrossRefGoogle Scholar
  31. Hiss TG, Cussler EL (1973) Diffusion in high viscosity liquids. AIChE J 19:698–703. CrossRefGoogle Scholar
  32. Hosseini SS, Bringas E, Tan NR, Ortiz I, Ghahramani M, Shahmirzadi MAA (2016) Recent progress in development of high performance polymeric membranes and materials for metal plating wastewater treatment. J Water Process Eng 9:78–110CrossRefGoogle Scholar
  33. Jahanmahin O, Montazer Rahmati MM, Mohammadi T, Babaee J, Khosravi A (2016) Cr(VI) ion removal from artificial waste water using supported liquid membrane. Chem Pap 70:913–925. CrossRefGoogle Scholar
  34. Janjam SVSB, Peddeti S, Roy D, Babu SV (2008) Tartaric acid as a complexing agent for selective removal of tantalum and copper in CMP. Electrochem Solid State Lett 11:H327–H330. CrossRefGoogle Scholar
  35. Kalachev AA, Kardivarenko LM, Platé NA, Bagreev VV (1992) Facilitated diffusion in immobilized liquid membranes: experimental verification of the “jumping” mechanism and percolation threshold in membrane transport. J Membr Sci 75:1–5. CrossRefGoogle Scholar
  36. Kaya A, Alpoguz HK, Yilmaz A (2013) Application of Cr(VI) transport through the Polymer inclusion membrane with a new synthesized Calix[4]arene derivative. Ind Eng Chem Res 52:5428–5436. CrossRefGoogle Scholar
  37. Kaya A, Onac C, Alpoguz HK (2016) A novel electro-driven membrane for removal of chromium ions using polymer inclusion membrane under constant DC electric current. J Hazard Mater 317:1–7. CrossRefGoogle Scholar
  38. Kolev SD, St John AM, Cattrall RW (2013) Mathematical modeling of the extraction of uranium(VI) into a polymer inclusion membrane composed of PVC and di-(2-ethylhexyl) phosphoric acid. J Membr Sci 425–426:169–175. CrossRefGoogle Scholar
  39. Kumar A, Sastre A (2000) Hollow fiber supported liquid membrane for the separation/concentration of gold(I) from aqueous cyanide media: modeling and mass transfer evaluation. Ind Eng Chem Res 39:146–154CrossRefGoogle Scholar
  40. Lantto J (2015) Analytical model of mass transfer through supported liquid membranes. KTH University, StockholmGoogle Scholar
  41. Liang J, Fan L, Xu K, Huang Y (2012) Study on extracting of Germanium with trioctylamine. Energy Procedia 17:1965–1973. CrossRefGoogle Scholar
  42. Liu F, Yang Y, Lu Y, Shang K, Lu W, Zhao X (2010) Extraction of Germanium by the AOT Microemulsion with N235 System. Ind Eng Chem Res 49:10005–10008. CrossRefGoogle Scholar
  43. Marchese J, Campderrós M, Acosta A (1995) Transport and separation of cobalt, nickel and copper ions with alamine liquid membranes. J Chem Technol Biotechnol 64:293–297CrossRefGoogle Scholar
  44. Marchese J, Valenzuela F, Basualto C, Acosta A (2004) Transport of molybdenum with Alamine 336 using supported liquid membrane. Hydrometallurgy 72:309–317CrossRefGoogle Scholar
  45. Marinova M, Albet J, Molinier J, Kyuchoukov G (2005) Specific influence of the modifier (1-decanol) on the extraction of tartaric acid by different extractants. Ind Eng Chem Res 44:6534–6538CrossRefGoogle Scholar
  46. Martsinko EE, Seifullina II, Minacheva LK, Pesaroglo AG, Sergienko VS (2008) Synthesis, properties, and molecular and crystal structure of diantipyrylmethanium Bis(μ-tartrato)dihydroxydigermanate(IV) tetrahydrate (HDAm)2[Ge2(μ-L)2(OH)2]·4H2O. Russ J Inorg Chem 53:1694–1702. CrossRefGoogle Scholar
  47. Mattock G (1954) The complex-forming behaviour of tin, germanium, and titanium with some dibasic carboxylic acids. J Chem Soc (Resumed):989–997. doi:
  48. Mokhtarani B, Khormaei H, Amini MH, Mortaheb HR (2015) Experimental Study on performance of modified hybrid liquid membrane process for removal of cadmium from wastewater. J Chem Petroleum Eng 48:109–118Google Scholar
  49. Nakamura S, Akiba K (1989) Transport of Europium through supported liquid membrane containing dihexyl-N, N-diethylcarbamoylmethylphosphonate. Sep Sci Technol 24:1317–1328. CrossRefGoogle Scholar
  50. Peydayesh M, Esfandyari GR, Mohammadi T, Alamdari EK (2013) Pertraction of cadmium and zinc ions using a supported liquid membrane impregnated with different carriers. Chem Pap 67:389–397. CrossRefGoogle Scholar
  51. Pflugmacher A, Rohrmann I (1957) Über Komplexverbindungen des Germaniums mit organischen Hydroxysäuren. Angew Chem 69:778–7781. CrossRefGoogle Scholar
  52. Pokrovski GS, Schott J (1998) Experimental study of the complexation of silicon and germanium with aqueous organic species: implications for germanium and silicon transport and Ge/Si ratio in natural waters. Geochim Cosmochim Acta 62:3413–3428. CrossRefGoogle Scholar
  53. Pokrovski GS, Martin F, Hazemann J-L, Schott J (2000) An X-ray absorption fine structure spectroscopy study of germanium-organic ligand complexes in aqueous solution. Chem Geol 163:151–165. CrossRefGoogle Scholar
  54. Prakorn R, Weerawat P, Ura P (2006) Mass transfer modeling of membrane carrier system for extraction of Ce(IV) from sulfate media using hollow fiber supported liquid membrane. Korean J Chem Eng 23:85–92CrossRefGoogle Scholar
  55. Prapasawat T, Ramakul P, Satayaprasert C, Pancharoen U, Lothongkum AW (2008) Separation of As (III) and As (V) by hollow fiber supported liquid membrane based on the mass transfer theory. Korean J Chem Eng 25:158–163CrossRefGoogle Scholar
  56. Prasad R, Sirkar K (1988) Dispersion-free solvent extraction with microporous hollow-fiber modules. AIChE J 34:177–188CrossRefGoogle Scholar
  57. Rathore NS, Leopold A, Pabby AK, Fortuny A, Coll MT, Sastre AM (2009) Extraction and permeation studies of Cd(II) in acidic and neutral chloride media using Cyanex 923 on supported liquid membrane. Hydrometallurgy 96:81–87. CrossRefGoogle Scholar
  58. Sastre AM, Madi A, Alguacil FJ (2000) Facilitated supported liquid-membrane transport of gold(I) using LIX 79 in cumene. J Membr Sci 166:213–219CrossRefGoogle Scholar
  59. Sergienko VS, Minacheva LK, Churakov AV (2010) Specific features of the structure of germanium(IV) complexes with polybasic acids. Russ J Inorg Chem 55:2001–2030. CrossRefGoogle Scholar
  60. Swain B, Jeong J, J-c Lee, Lee G-H (2007) Extraction of Co(II) by supported liquid membrane and solvent extraction using Cyanex 272 as an extractant: a comparison study. J Membr Sci 288:139–148. CrossRefGoogle Scholar
  61. Ura P, Prakorn R, Weerawat P, Milan H (2006) Feasibility study on the separation of uranium and thorium by a hollow fiber supported liquid membrane and mass transfer modeling. Ind Eng Chem Res 12:673Google Scholar
  62. Valdés H, Romero J, Sanchez J, Bocquet S, Rios GM, Valenzuela F (2009) Characterization of chemical kinetics in membrane-based liquid–liquid extraction of molybdenum(VI) from aqueous solutions. Chem Eng J 151:333–341. CrossRefGoogle Scholar
  63. Valenzuela F, Vega M, Yanez M, Basualto C (2002) Application of a mathematical model for copper permeation from a Chilean mine water through a hollow fiber-type supported liquid membrane. J Membr Sci 204:385–400CrossRefGoogle Scholar
  64. Vartapetian O (1957) Contribution a` l’e´tude des complexes du germanium et de quelques acides a-alcools. Ann Chem 2:917–965Google Scholar
  65. Wang D, Chen Q, Hu J, Fu M, Luo Y (2015) High flux recovery of copper (II) from ammoniacal solution with stable sandwich supported liquid membrane. Ind Eng Chem Res 54:4823–4831CrossRefGoogle Scholar
  66. Wannachod T, Leepipatpiboon N, Pancharoen U, Nootong K (2014) Separation and mass transport of Nd(III) from mixed rare earths via hollow fiber supported liquid membrane: experiment and modeling. Chem Eng J 248:158–167. CrossRefGoogle Scholar
  67. Yang Q, Kocherginsky N (2007) Copper removal from ammoniacal wastewater through a hollow fiber supported liquid membrane system: modeling and experimental verification. J Membr Sci 297:121–129CrossRefGoogle Scholar
  68. Zoecklein BW, Fugelsang KC, Gump BH, Nury FS, Gump BH, Nury FS (1990) Tartaric acid and its salts. In: Zoecklein BW, Fugelsang KC (eds) Production wine analysis. Springer, Boston, pp 289–315. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2017

Authors and Affiliations

  • Hossein Kamran Haghighi
    • 1
  • Mehdi Irannajad
    • 1
  • Agustin Fortuny
    • 2
  • Ana Maria Sastre
    • 3
  1. 1.Department of Mining and Metallurgical EngineeringAmirkabir University of TechnologyTehranIran
  2. 2.Department of Chemical EngineeringUniversitat Politècnica de Catalunya, EPSEVGVilanova I La GeltrúSpain
  3. 3.Department of Chemical EngineeringUniversitat Politècnica de Catalunya, ESTEIBBarcelonaSpain

Personalised recommendations