Abstract
Cross-linking agents play a crucial role on the adsorptive performance of ionically crosslinked hydrogel beads. In this study, the impact of a cross-linking agent viz., calcium chloride (CaCl2) on the adsorption of methylene blue (MB) onto cellulose nanocrystal–alginate (CNC–ALG) hydrogel beads were investigated using both batch and fixed bed column adsorption experiments. The effect of calcium ions on the swelling and shrinkage of hydrogel beads and the corresponding bed height in a fixed bed column were also examined. Batch adsorption studies suggested that the adsorption capacity of CNC–ALG hydrogel beads for MB was reduced due to the charge screening by calcium ions. The results from the fixed bed column experiments showed that high concentrations of Ca2+ was directly responsible for the overshoot in MB concentration observed at the beginning of the effluent concentration profile, and washing pretreatment of the adsorbent removed this overshoot in the concentration profile. Also, the presence of Ca2+ in the hydrogel beads influenced the size change of the beads during the column adsorption experiments, as an initial water rinse resulted in the shrinkage of the beads due to the loss of Ca2+ ions reducing the net repulsion between the sodium alginate chains. The expansion of the bed was further attributed to the adsorption of MB that led to adsorbent shrinkage due to the loss of water, resulting in a 40% reduction in the packed bed volume. Thus, this study provided new insights on the impact of cross-linking agents on the adsorption behavior of CNC–ALG hydrogel beads that could be used for the removal of various contaminants in wastewater.
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References
An B, Son H, Chung J et al (2013) Calcium and hydrogen effects during sorption of copper onto an alginate-based ion exchanger: batch and fixed-bed column studies. Chem Eng J 232:51–58. https://doi.org/10.1016/j.cej.2013.07.079
Aravindhan R, Fathima NN, Rao JR, Nair BU (2007) Equilibrium and thermodynamic studies on the removal of basic black dye using calcium alginate beads. Colloids Surf A Physicochem Eng Asp 299:232–238. https://doi.org/10.1016/j.colsurfa.2006.11.045
Augst AD, Kong HJ, Mooney DJ (2006) Alginate hydrogels as biomaterials. Macromol Biosci 6:623–633. https://doi.org/10.1002/mabi.200600069
Batmaz R, Mohammed N, Zaman M et al (2014) Cellulose nanocrystals as promising adsorbents for the removal of cationic dyes. Cellulose 21:1655–1665. https://doi.org/10.1007/s10570-014-0168-8
Bruchet M, Melman A (2015) Fabrication of patterned calcium cross-linked alginate hydrogel films and coatings through reductive cation exchange. Carbohydr Polym 131:57–64. https://doi.org/10.1016/j.carbpol.2015.05.021
Chuang JJ, Huang YY, Lo SH et al (2017) Effects of pH on the shape of alginate particles and its release behavior. Int J Polym Sci. https://doi.org/10.1155/2017/3902704
Davidovich-Pinhas M, Bianco-Peled H (2010) A quantitative analysis of alginate swelling. Carbohydr Polym 79:1020–1027. https://doi.org/10.1016/j.carbpol.2009.10.036
Drury JL, Dennis RG, Mooney DJ (2004) The tensile properties of alginate hydrogels. Biomaterials 25:3187–3199. https://doi.org/10.1016/j.biomaterials.2003.10.002
Gong JP (2010) Why are double network hydrogels so tough? Soft Matter 6:2583. https://doi.org/10.1039/b924290b
Grant GT, Morris ER, Rees DA et al (1973) Biological interactions between polysaccharides and divalent cations: the egg-box model. FEBS Lett 32:195–198. https://doi.org/10.1016/0014-5793(73)80770-7
Gurikov P, Smirnova I (2018) Non-conventional methods for gelation of alginate. Gels. https://doi.org/10.3390/gels4010014
Lee KY, Mooney DJ (2012) Alginate: properties and biomedical applications. Prog Polym Sci 37:106–126. https://doi.org/10.1016/j.progpolymsci.2011.06.003
Liu L, Wan Y, Xie Y et al (2012) The removal of dye from aqueous solution using alginate-halloysite nanotube beads. Chem Eng J 187:210–216. https://doi.org/10.1016/j.cej.2012.01.136
Mohammed N, Grishkewich N, Berry RM, Tam KC (2015) Cellulose nanocrystal–alginate hydrogel beads as novel adsorbents for organic dyes in aqueous solutions. Cellulose 22:3725–3738. https://doi.org/10.1007/s10570-015-0747-3
Mohammed N, Grishkewich N, Waeijen HA et al (2016) Continuous flow adsorption of methylene blue by cellulose nanocrystal-alginate hydrogel beads in fixed bed columns. Carbohydr Polym 136:1194–1202. https://doi.org/10.1016/j.carbpol.2015.09.099
Newcombe G, Drikas M (1997) Adsorption of NOM onto activated carbon: electrostatic and non-electrostatic effects. Carbon N Y 35:1239–1250. https://doi.org/10.1016/S0008-6223(97)00078-X
Papageorgiou SK, Katsaros FK, Kouvelos EP et al (2006) Heavy metal sorption by calcium alginate beads from Laminaria digitata. J Hazard Mater 137:1765–1772. https://doi.org/10.1016/j.jhazmat.2006.05.017
Schuldt U, Hunkeler D (2007) Alginate-cellulose sulphate-oligocation microcapsules: optimization of mass transport and mechanical properties. J Microencapsul 24:1–10. https://doi.org/10.1080/02652040601058350
Sulaeva I, Hettegger H, Bergen A et al (2020) Fabrication of bacterial cellulose-based wound dressings with improved performance by impregnation with alginate. Mater Sci Eng C 110:110619. https://doi.org/10.1016/j.msec.2019.110619
Worch E (2012) Chapter 6: adsorption dynamics in fixed-bed adsorbers. Walter de Gruyter, Berlin
Zhao F, Yu B, Yue Z et al (2007) Preparation of porous chitosan gel beads for copper(II) ion adsorption. J Hazard Mater 147:67–73. https://doi.org/10.1016/j.jhazmat.2006.12.045
Acknowledgments
The authors would like to acknowledge Celluforce Inc. for providing the cellulose nanocrystals critical for this work. K. C. Tam wishes to acknowledge funding from CFI and NSERC. Nathan Grishkewich gratefully acknowledges support of the NSERC Canada Graduate Doctoral Scholarship.
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Natural Science and Engineering Council of Canada: Grant: RGPIN-2017-04236.
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NG: experimental planning, data acquisition and analysis, writing manuscript draft. NM: writing manuscript draft. KCT: Securing funding, supervision of project, editing of manuscript.
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Grishkewich, N., Mohammed, N. & Tam, K.C. Impact of cross-linking agents on the adsorptive performance of cellulose nanocrystal–alginate hydrogel beads. Cellulose 30, 6933–6943 (2023). https://doi.org/10.1007/s10570-023-05300-x
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DOI: https://doi.org/10.1007/s10570-023-05300-x