Immobilization of Layered Double Hydroxide into Polyvinyl Alcohol/Alginate Hydrogel Beads for Phosphate Removal

Han, Yong-Un;Lee, Chang-Gu;Park, Jeong-Ann;Kang, Jin-Kyu;Lee, In;Kim, Song-Bae

  • Received : 2011.12.03
  • Accepted : 2012.08.02
  • Published : 2012.09.30


Polyvinyl alcohol/alginate hydrogel beads containing Mg-Al layered double hydroxide (LDH-PVA/alginate beads) were synthesized for phosphate removal. Results showed that blending PVA with the LDH-alginate beads significantly improved their stability in a phosphate solution. The kinetic reaction in LDH-PVA/alginate beads reached equilibrium at 12 hr-post reaction with 99.2% removal. The amount of phosphate removed at equilibrium ($q_e$) was determined to be 0.389 mgP/g. The equilibrium data were described well by the Freundlich isotherm with the distribution coefficient ($K_F$, 0.638) and the constant (n, 0.396). Phosphate removal in LDH-PVA/alginate beads was not sensitive to solution pH. Also, the removal capacity of LDH-PVA/alginate beads ($q_e$, 1.543 mgP/g) was two orders of magnitude greater than that of PVA/alginate beads ($q_e$, 0.016 mgP/g) in column experiments. This study demonstrates that LDH-PVA/alginate beads with a higher chemical stability against phosphate compared to LDH-alginate beads have the potential for phosphate removal as adsorptive media.


Column experiment;Layered double hydroxide;Phosphate removal;Polyvinyl alcohol;PVA/alginate beads


  1. Goh KH, Lim TT, Dong Z. Application of layered double hydroxides for removal of oxyanions: a review. Water Res. 2008;42:1343-1368.
  2. Ookubo A, Ooi K, Hayashi H. Preparation and phosphate ion-exchange properties of a hydrotalcite-like compound. Langmuir 1993;9:1418-1422.
  3. Shin HS, Kim MJ, Nam SY, Moon HC. Phosphorus removal by hydrotalcite-like compounds (HTLcs). Water Sci. Technol. 1996;34:161-168.
  4. Badreddine M, Legrouri A, Barroug A, de Roy A, Besse JP. Ion exchange of different phosphate ions into the zincaluminium-chloride layered double hydroxide. Mater. Lett. 1999;38:391-395.
  5. Cheng X, Huang X, Wang X, Zhao B, Chen A, Sun D. Phosphate adsorption from sewage sludge filtrate using zincaluminum layered double hydroxides. J. Hazard. Mater. 2009;169:958-964.
  6. Koilraj P, Kannan S. Phosphate uptake behavior of ZnAlZr ternary layered double hydroxides through surface precipitation. J. Colloid Interface Sci. 2010;341:289-297.
  7. Chitrakar R, Tezuka S, Sonoda A, Sakane K, Ooi K, Hirotsu T. Adsorption of phosphate from seawater on calcined MgMn-layered double hydroxides. J. Colloid Interface Sci. 2005;290:45-51.
  8. Seida Y, Nakano Y. Removal of phosphate by layered double hydroxides containing iron. Water Res. 2002;36:1306-1312.
  9. You Y, Vance GF, Sparks DL, Zhuang J, Jin Y. Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions. J. Environ. Qual. 2003;32:2046-2053.
  10. Gillman GP. A simple technology for arsenic removal from drinking water using hydrotalcite. Sci. Total Environ. 2006;366:926-931.
  11. Othman MR, Rasid NM, Fernando WJ. Mg-Al hydrotalcite coating on zeolites for improved carbon dioxide adsorption. Chem. Eng. Sci. 2006;61:1555-1560.
  12. Kuzawa K, Jung YJ, Kiso Y, Yamada T, Nagai M, Lee TG. Phosphate removal and recovery with a synthetic hydrotalcite as an adsorbent. Chemosphere 2006;62:45-52.
  13. Lazaridis NK, Charalambous Ch. Sorptive removal of trivalent and hexavalent chromium from binary aqueous solutions by composite alginate-goethite beads. Water Res. 2005;39:4385-4396.
  14. Lin YB, Fugetsu B, Terui N, Tanaka S. Removal of organic compounds by alginate gel beads with entrapped activated carbon. J. Hazard. Mater. 2005;120:237-241.
  15. Van Beinum W, Meeussen JC, van Riemsdijk WH. Competitive sorption and diffusion of chromate and sulphate in a flow system with goethite in gel beads. J. Contam. Hydrol. 2006;86:262-278.
  16. Escudero C, Fiol N, Villaescusa I, Bollinger JC. Arsenic removal by a waste metal (hydr)oxide entrapped into calcium alginate beads. J. Hazard. Mater. 2009;164:533-541.
  17. Bezbaruah AN, Krajangpan S, Chisholm BJ, Khan E, Bermudez JJ. Entrapment of iron nanoparticles in calcium alginate beads for groundwater remediation applications. J. Hazard. Mater. 2009;166:1339-1343.
  18. Kobaslija M, McQuade DT. Removable colored coatings based on calcium alginate hydrogels. Biomacromolecules 2006;7:2357-2361.
  19. Das J, Patra BS, Baliarsingh N, Parida KM. Adsorption of phosphate by layered double hydroxides in aqueous solutions. Appl. Clay Sci. 2006;32:252-260.
  20. Yoon CJ, Kim KW. Anatomical descriptions of silicified woods from Madagascar and Indonesia by scanning electron microscopy. Micron 2008;39:825-831.
  21. Greenberg AE, Clesceri LS, Eaton AD. Standard methods for the examination of water and wastewater. 19th ed. Washington: American Public Health Association; 1995.
  22. Dave R, Madamwar D. Esterification in organic solvents by lipase immobilized in polymer of PVA-alginate-boric acid. Process Biochem. 2006;41:951-955.
  23. Idris A, Mohd Zain NA, Suhaimi MS. Immobilization of Baker's yeast invertase in PVA-alginate matrix using innovative immobilization technique. Process Biochem. 2008;43:331- 338.
  24. Idris A, Misran E, Hassan N, Jalil AA, Seng CE. Modified PVAalginate encapsulated photocatalyst ferro photo gels for Cr(VI) reduction. J. Hazard. Mater. 2012;227-228:309-316.
  25. Mathialagan T, Viraraghavan T. Adsorption of cadmium from aqueous solutions by vermiculite. Sep. Sci. Technol. 2003;38:57-76.
  26. Kim HC, Park SJ, Lee CG, Han YU, Park JA, Kim SB. Humic acid removal from water by iron-coated sand: a column experiment. Environ. Eng. Res. 2009;14:41-47.
  27. Han YU, Lee WS, Lee CG, Park SJ, Kim KW, Kim SB. Entrapment of Mg-Al layered double hydroxide in calcium alginate beads for phosphate removal from aqueous solution. Desalination Water Treat. 2011;36:178-186.

Cited by

  1. Environmental Engineering Research in September 2012 vol.17, pp.3, 2012,
  2. Novel nanocomposites of poly(vinyl alcohol) and Mg–Al layered double hydroxide intercalated with diacid N-tetrabromophthaloyl-aspartic vol.120, pp.2, 2015,
  3. Adsorption studies of cadmium ions on alginate–calcium carbonate composite beads vol.7, pp.2, 2017,
  4. Piezoelectrically-driven production of sub 10 micrometer smart microgels vol.10, pp.1, 2016,
  5. Immobilization of Calcined Layered Double Hydroxide into Alginate Hydrogel Beads for PNP and PAP Removal: Kinetics, Isotherms, Thermodynamics, and Mechanism vol.229, pp.10, 2018,
  6. Immobilization of a Laccase/2,2’-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic Acid System to Layered Double Hydroxide/Alginate Biohybrid Beads for Biodegradation of Malachite Green Dye vol.2018, pp.2314-6141, 2018,


Supported by : National Research Foundation of Korea