Selective removal of phenol by spherical particles of α-, β- and BoldItalic-cyclodextrin polymers: kinetics and isothermal equilibrium

Abstract

Spherical particles of α-, β- and γ-cyclodextrin (CD) polymers to efficiently remove phenol from waste water were prepared by reverse suspension polymerization with epichlorohydrin as crosslinker in liquid paraffin. By controlling the amounts of crosslinker and water, well-defined spherical polymer particles with controllable size were obtained. Due to the selective inclusion associations between CD groups and phenol, these CD spherical polymer particles were demonstrated to be ideal candidates for removal of phenol. Among them β-CD polymer particles showed the best performance. The kinetics and isothermal equilibrium models were used to fit the experimental data of phenol removal from aqueous solution using these CD polymer particles. It was found that the kinetics followed the Ho and Mckay equation, suggesting that the adsorption process of phenol was controlled by diffusion and the host-guest interaction between CD and phenol. Equilibrium isothermal data can be well fitted by the Freundlich equation. The negative free energy change indicated the spontaneous nature of adsorption of phenol by α-, β- and γ-CD spherical polymer particles, while the lowest free energy for β-CD polymer reflected its best adsorption ability, compared to α- and γ-CD polymer particles.

Key words： cyclodextrin polymer particles; phenol; kinetic models; adsorption isotherm equilibrium models

Acknowledgements

We gratefully acknowledge the National Natural Science Foundation of China (Grant No. 21004021), the Fundamental Research Funds for the Central Universities (WA1014007), Chemical Engineering National Key Laboratory Open Subject SKL-ChE-11CO2, the Start Funding of East China University of Science and Technology YA0142119 for support this work.

References

1 Kumar N S, Suguna M, Subbaiah M V, Reddy A S, Kumar N P, Krishnaiah A. Adsorption of phenolic compounds from aqueous solutions onto chitosan-coated perlite beads as biosorbent. Industrial & Engineering Chemistry Research, 2010, 49(19): 9238–9247

2 Zeng F X, Liu W J, Luo S W, Jiang H, Yu H Q, Guo Q X. Design, Preparation, and characterization of a novel hyper-cross-linked polyphosphamide polymer and its adsorption for phenol. Industrial & Engineering Chemistry Research, 2011, 50(20): 11614–11619

3 Guo X H, Abdala A A, May B L, Lincoln S F, Khan S A, Prud’homme R K. Novel associative polymer networks based on cyclodextrin inclusion compounds. Macromolecules, 2005, 38(7): 3037–3040

4 Wang J, Pham D T, Guo X H, Li L, Lincoln S F, Luo Z F, Ke H, Zheng L, Prud’homme R K. Polymeric networks assembled by adamantyl and β-cyclodextrin substituted poly(acrylate)s: host-guest interactions, and the effects of ionic strength and extent of substitution. Industrial & Engineering Chemistry Research, 2010, 49(2): 609–612

5 Guo X H, Wang J, Li L, Chen Q C, Zheng L, Pham D T, Lincoln S F, May B L, Prud’homme R K, Easton C J. Tunable polymeric hydrogels assembled by competitive complexation between cyclodextrin dimers and adamantyl substituted poly(acrylate)s. AIChE Journal, 2010, 56(11): 3021–3024

6 Wang J, Li L, Guo X H, Zheng L, Pham D T, Lincoln S F, Ngo H T, Clements P, May B L, Prud’homme R K, Easton C J. Aggregation of hydrophobic substituents of poly(acrylate)s and their competitive complexation by β- and γ-cyclodextrins and their linked dimers in aqueous solution. Industrial & Engineering Chemistry Research, 2011, 50(12): 7566–7571

7 Baruch-Teblum E, Mastai Y, Landfester K. Miniemulsion polymerization of cyclodextrin nanospheres for water purification from organic pollutants. European Polymer Journal, 2010, 46(8): 1671–1678

8 Badruddoza A Z M, Hazel G S S, Hidajat K, Uddin M S. Synthesis of carboxymethyl-β-cyclodextrin conjugated magnetic nano-adsorbent for removal of methylene blue. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2010, 367(1-3): 85–95

9 Crini G, Janus L, Morcellet M, Torri G, Morin N. Sorption properties toward substituted phenolic derivatives in water using macroporous polyamines containing β-cyclodextrin. Journal of Applied Polymer Science, 1999, 73(14): 2903–2910

10 Pan J M, Zou X H, Wang X, Guan W, Li C X, Yan Y S, Wu X Y. Adsorptive removal of 2,4-didichlorophenol and 2,6-didichlorophenol from aqueous solution by β-cyclodextrin/attapulgite composites: Equilibrium, kinetics and thermodynamics. Chemical Engineering Journal, 2011, 166(1): 40–48

11 Wu J, Xu A W, Zhang W M, Lv L, Pan B C, Nie G Z, Li M H, Du Q. Application of heterogeneous adsorbents in removal of dimethyl phthalate: equilibrium and heat. AIChE Journal, 2010, 56(10): 2699–2705

12 Yuh-Shan H. HO Y S. Citation review of Lagergren kinetic rate equation on adsorption reactions. Scientometrics, 2004, 59(1): 171–177

13 Ho Y S, McKay G. Pseudo-second order model for sorption processes. Process Biochemistry, 1999, 34(5): 451–465

14 Ho Y S, McKay G. A comparison of chemisorption kinetic models applied to pollutant removal on various sorbents. Trans IChemE, 1998, 76(4): 332–340

15 Chern J M, Wu C Y. Desorption of dye from activated carbonbeds: effects of temperature, pH, and alcohol. Water Research, 2001, 35(17): 4159–4165

16 Delval F, Crini G, Vebrel J. Removal of organic pollutants from aqueous solutions by adsorbents prepared from an agroalimentary by-product. Bioresource Technology, 2006, 97(16): 2173–2181

17 Crini G. Kinetic and equilibrium studies on the removal of cationic dyes from aqueous solution by adsorption onto a cyclodextrin polymer. Dyes and Pigments, 2008, 77(2): 415–426

18 Yamasaki H, Makihata Y, Fukunaga K. Makihata1 Y, Fukunaga K. Efficient phenol removal of wastewater from phenolic resin plants using crosslinked cyclodextrin particles. Journal of Chemical Technology and Biotechnology, 2006, 81(7): 1271–1276

19 Ho Y S, McKay G. Kinetic of sorption of basic dyes from aqueous solution by sphagnum moss peat. Canadian Journal of Chemical Engineering, 1998, 76(4): 822–827