, Volume 17, Issue 6, pp 1159–1169 | Cite as

Microfiltration performance of regenerated cellulose membrane prepared at low temperature for wastewater treatment

  • Shilin Liu
  • Jian Zeng
  • Dandan Tao
  • Lina Zhang


A series of regenerated cellulose membranes with pore diameters ranging from 21 to 52 nm have been prepared by dissolving cellulose in 5 wt% LiOH/12 wt% urea aqueous solution re-cooled to −12 °C. The influences of cellulose concentration on the structure, pore size, and the mechanical properties of the membrane were studied by using Wide angle X-ray diffraction, scanning electron micrography and tensile testing. Their pore size, water permeability, equilibrium-swelling ratio and fouling behaviors of the cellulose membranes were characterized. The water-soluble synthetic and natural polymers as organic matter were used to evaluate the microfiltration performance of the regenerated cellulose membrane for wastewater treatment in aqueous system. The results revealed that the organic matter with molecular weight more than 20 kDa effected significantly on the membrane pore density, and reducing factor a 2, whereas that having molecular weight less than 20 kDa exhibited a little influence on the membrane pore size reducing factor a 1. Furthermore, a simple model to illustrate of microfiltration process of the RC membrane for wastewater treatment was proposed.


Cellulose membrane Water permeability Microfiltration Pore size Wastewater treatment 

List of symbols


Membrane pore size change coefficient (m−1)


Pore density change coefficient (m−1)


Thickness of wet membrane (cm)


Permeability of the pure water (m3/m2 s)


Flux of polluted water per unit membrane area (m3/m2 s)


Total number of pores per unit area (-)


Pressure (Pa)


Porosity of the wet membrane (%)


Equilibrium-swelling ratio (-)


The accumulated permeate volume (m3)


Pore diameter (cm)


The radius of the wet membrane (cm)


The mean pore diameter (cm)


Regenerated cellulose


The area of all diffraction peaks of crystalline


The area of all diffraction peaks of amorphous


Ultrafilter rate of membrane for pure water (mL h−1 m−2 mm Hg−1)


Weight of the membrane at dry state (g)


Density of bulk cellulose (g cm−3)


Density of the wet membrane containing pore (g cm−3)


Tensile strength (MPa)


Breaking elongation (%)


The solvent viscosity (N s/m2)


The length of the pores (μm)



This work was supported by National Basic Research Program of China (973 Program, 2010CB732203), and National Natural Science Foundation of China (20374025). Dr. S. Liu thanks the goal-oriented project (SKLF-MB-200805) from State Key Laboratory of Jiangnan University.


  1. Belfort G, Davis R, Zydney A (1994) The behavior of suspensions and macromolecular solutions in crossflow microfiltration. J Membr Sci 96:1–58CrossRefGoogle Scholar
  2. Bell C, Peppas N (1996) Water, solute and protein diffusion in physiologically responsive hydrogels of poly(methacrylic acid-g-rthylene glycol). Biomaterials 17:1203–1218CrossRefGoogle Scholar
  3. Burns D, Zydney A (1999) Effects of solution PH on protein transport through semipermeable ultrafiltration membranes. Biotechnol Bioeng 64:27–37CrossRefGoogle Scholar
  4. Burns D, Zydney A (2000) Buffer effects on the zeta potential of ultrafiltration membranes. J Membr Sci 172:39–48CrossRefGoogle Scholar
  5. Cai J, Zhang L, Chang C, Cheng G, Chen X, Chu B (2007a) Hydrogen-bond-induced inclusion complex in aqueous cellulose/LiOH/urea solution at low temperature. ChemPhysChem 8:1572–1579CrossRefGoogle Scholar
  6. Cai J, Wang L, Zhang L (2007b) Influence of coagulation temperature on pore size and properties of cellulose membranes prepared from NaOH–urea aqueous solution. Cellulose 14:205–215CrossRefGoogle Scholar
  7. Cai J, Zhang L, Liu S, Liu Y, Xu X, Chen X, Chu B, Guo X, Xu J, Cheng H, Han H, Kuga S (2008) Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules 41:9345–9351CrossRefGoogle Scholar
  8. Capar G, Yilmaz L, Yetis U (2006) Reclamation of acid dye bath wastewater: effect of pH on nanofiltration performance. J Membr Sci 281:560–569CrossRefGoogle Scholar
  9. Chan R, Chen V (2004) Characterization of protein fouling on membranes: opportunities and challenges. J Membr Sci 242:169–188CrossRefGoogle Scholar
  10. Clech P, Chen V, Fane T (2006) Fouling in membrane bioreactors used in wastewater treatment. J Membr Sci 284:17–53CrossRefGoogle Scholar
  11. Cuissinat C, Navard P (2006) Swelling and dissolution of cellulose Part II: free floating cotton and wood fibres in NaOH-water-additives systems. Macromol Symp 244:19–30CrossRefGoogle Scholar
  12. Duclos-Orsello C, Li W, Ho C (2006) A three mechanism model to describe fouling of microfiltration membranes. J Membr Sci 280:856–866CrossRefGoogle Scholar
  13. Egal M, Budtova T, Navard P (2008) The dissolution of microcrystalline cellulose in sodium hydroxide-urea aqueous solutions. Cellulose 15:361–370CrossRefGoogle Scholar
  14. Fane A, Fell C (1987) A review of fouling and fouling control in ultrafiltration. Desalination 62:117–136CrossRefGoogle Scholar
  15. Gavillon R, Budtova T (2007) Kinetics of cellulose regeneration from cellulose-NaOH-water gels and comparison with cellulose-N-methylmorpholine-N-oxide-water solutions. Biomacromolecules 8:424–432CrossRefGoogle Scholar
  16. Hong S, Elimelech M (1997) Chemical and physical aspects of nom fouling of nanofiltration membranes. J Membr Sci 132:159–181CrossRefGoogle Scholar
  17. Isogai A, Usuda M, Koto T, Ulyu T, Atalla R (1989) Solid-state CP/MASS 13C NMR study of cellulose polymorphs. Macromolecules 22:3168–3172CrossRefGoogle Scholar
  18. Kamide K, Iijima H, Matsuda S (1993) Thermodynamics of formation of porous polymeric membrane by phase separation method I: nucleation and growth of nuclei. Polym J 25:1113–1131CrossRefGoogle Scholar
  19. Khayet M, Khulbe K, Matsuura T (2004) Characterization of membranes for membrane distillation by atomic force microscopy and estimation of their water vapor transfer coefficients in vacuum membrane distillation process. J Membr Sci 238:199–211CrossRefGoogle Scholar
  20. Kim J, Yun S (2006) Discovery of cellulose as a smart material. Macromolecues 39:4202–4206CrossRefGoogle Scholar
  21. Liu S, Zhang L (2009) Effects of polymer concentration and coagulation temperature on the properties of regenerated cellulose films prepared from LiOH/urea solution. Cellulose 16:189–198CrossRefGoogle Scholar
  22. Loeb S, Sourirajan S (1963) Sea water demineralization by means of an osmotic membrane. Adv Chem Ser 38:117–132CrossRefGoogle Scholar
  23. Lue A, Zhang L, Ruan D (2007) Inclusion complex formation of cellulose in NaOH–thiourea aqueous system at low temperature. Macromol Chem Phys 208:2359–2366CrossRefGoogle Scholar
  24. Mao Y, Zhou J, Cai J, Zhang L (2006) Effects of coagulants on porous structure of membranes prepared from cellulose in NaOH/urea aqueous solution. J Membr Sci 279:246–255CrossRefGoogle Scholar
  25. Marshall A, Munro P, Tragardh G (1993) The effect of protein fouling in microfiltration and ultrafiltration on permeate flux, protein retention and selectivity: a literature review. Desalination 91:65–108CrossRefGoogle Scholar
  26. Mehta A, Zydney A (2006) Effects of membrane charge on flow and protein transport during ultrafiltration. Biotechnol Prog 22:484–492CrossRefGoogle Scholar
  27. Mosqueda-Jimenez D, Narbaitz R, Matsuura T (2004) Membrane fouling test: apparatus evaluation. J Environ Eng ASCE 130:90–98CrossRefGoogle Scholar
  28. Parameshwaran K, Fane A, Cho B, Kim K (2001) Analysis of microfiltration performance with constant flux processing of secondary effluent. Water Res 35:4349–4358CrossRefGoogle Scholar
  29. Pujar N, Zydney A (1994) Electrostatic and electrokinetic interactions during protein transport through narrow pore membranes. Ind Eng Chem Res 33:2473–2482CrossRefGoogle Scholar
  30. Qi H, Cai J, Zhang L, Nishiyama Y, Rattaz A (2008) Influence of finishing oil on structure and properties of multi-filament fibers from cellulose dope in NaOH/urea aqueous solution. Cellulose 15:81–89CrossRefGoogle Scholar
  31. Rabek J (1980) Experimental methods in polymer chemistry: applications of wide-angle X-ray diffraction (WAXD) to the study of the structure of polymers. Wiley Interscience, ChichesterGoogle Scholar
  32. Ruan D, Zhang L, Mao Y, Zeng M, Li X (2004a) Microporous films prepared from cellulose in NaOH/thiourea aqueous solution. J Membr Sci 241:265–274CrossRefGoogle Scholar
  33. Ruan D, Zhang L, Zhang Z, Xia X (2004b) Structure and properties of regenerated cellulose/tourmaline nanocrystal composite films. J Polym Sci Polym Phys 42:367–373CrossRefGoogle Scholar
  34. Samir M, Alloin F, Paillet M, Dufresne A (2004) Tangling effect in fibrillated cellulose reinforced nanocomposites. Macromolecules 37:4313–4316CrossRefGoogle Scholar
  35. Sang Y, Dong I, Younsook S, Hwan C, Hak Y, Yong S, Won H, Ji H (2005) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy. Carbohydr Res 340:2376–2391CrossRefGoogle Scholar
  36. Sescousse R, Budtova T (2009) Influence of processing parameters on regeneration kinetics and morphology of porous cellulose from cellulose–NaOH–water solutions. Cellulose 16:417–426CrossRefGoogle Scholar
  37. Singh S, Khulbe K, Matsuura T, Ramamurthy P (1998) Membrane characterization by solute transport and atomic force microscopy. J Membr Sci 142:111–127CrossRefGoogle Scholar
  38. Tao Y, Zhang L, Yan F, Wu X (2007) Chain conformation of water-insoluble hyperbranched polysaccharide from fungus. Biomacromolecules 8:2321–2328CrossRefGoogle Scholar
  39. Teixeira M, Rosa M, Nystrom M (2005) The role of membrane charge on nanofiltration performance. J Membr Sci 265:160–166CrossRefGoogle Scholar
  40. Wang L, Wang X (2006) Study of membrane morphology by microscopic image analysis and membrane structure parameter model. J Membr Sci 283:109–115CrossRefGoogle Scholar
  41. Weng L, Zhang L, Ruan D, Shi L, Xu J (2004) Thermal gelation of cellulose in a NaOH/thiourea aqueous solution. Langmiur 20:2086–2093CrossRefGoogle Scholar
  42. Yang G, Zhang L (1996) Regenerated cellulose microporous membranes by mixing cellulose cuoxan with a water soluble polymer. J Membr Sci 114:149–155CrossRefGoogle Scholar
  43. Yuan W, Zydney A (1999) Effects of solution environment on humic acid fouling during microfiltration. Desalination 122:63–76CrossRefGoogle Scholar
  44. Zhao C, Zhou X, Yue Y (2000) Determination of pore size and pore size distribution on the surface of hollow-fiber filtration membrane: a review of methods. Desalination 129:107–123CrossRefGoogle Scholar
  45. Zhou J, Zhang L, Cai J, Shu H (2002) Cellulose microporous films prepared from NaOH/urea aqueous solution. J Membr Sci 210:77–90CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2010

Authors and Affiliations

  • Shilin Liu
    • 1
    • 2
  • Jian Zeng
    • 1
  • Dandan Tao
    • 2
  • Lina Zhang
    • 1
  1. 1.Department of ChemistryWuhan UniversityWuhanChina
  2. 2.College of Chemical and Material EngineeringJiangnan UniversityWuxi, JiangsuChina

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