Skip to main content
SpringerLink
Log in

Cellulose nanocrystal–alginate hydrogel beads as novel adsorbents for organic dyes in aqueous solutions

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

A new generation of recyclable adsorbents comprising of cellulose nanocrystals and alginate (CNC–ALG) with superior adsorption capacity was developed. Sustainable nanomaterials like cellulose nanocrystals derived from pulp fibres and cellulosic biomass are ideal systems to remove contaminants in our water systems. Their use will reduce our dependence on adsorbents, such as activated carbon that contribute to greenhouse gases production. Adsorption characteristics of CNC–ALG hydrogel beads were evaluated using batch adsorption studies of methylene blue (MB) in aqueous solution. The influence of various parameters, such as contact time, adsorbent dosage, initial dye concentration, pH, temperature, ionic strength, crosslinking time and bead size on the MB adsorption were investigated. Thermodynamic analyses confirmed that the adsorption process is spontaneous and exothermic. The kinetics and mechanism of adsorption were best described by a pseudo-second order kinetic model and intra-particle diffusion model. Equilibrium adsorption data fitted well to the Langmuir adsorption isotherm yielding a maximum adsorption capacity of 256.41 mg/g, which is comparable to activated carbon. We demonstrated that after five adsorption–desorption cycles, the removal efficiency of MB remained at ~97 %, and the CNC–ALG hydrogel beads are effective adsorbents for the removal of organic dyes from wastewaters.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • Abitbol T, Johnstone T, Quinn TM, Gray DG (2011) Reinforcement with cellulose nanocrystals of poly(vinyl alcohol) hydrogels prepared by cyclic freezing and thawing. Soft Matter 7:2373. doi:10.1039/c0sm01172j

    Article  CAS  Google Scholar 

  • Abramian L, El-Rassy H (2009) Adsorption kinetics and thermodynamics of azo-dye Orange II onto highly porous titania aerogel. Chem Eng J 150:403–410. doi:10.1016/j.cej.2009.01.019

    Article  CAS  Google Scholar 

  • Ahuja S (ed) (2009) Handbook of water purity and quality. Elsevier, New York

    Google Scholar 

  • Allen SJ, McKay G, Khader KY (1989) Intraparticle diffusion of a basic dye during adsorption onto sphagnum peat. Environ Pollut 56:39–50

    Article  CAS  Google Scholar 

  • 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. doi:10.1016/j.colsurfa.2006.11.045

    Article  CAS  Google Scholar 

  • Auta M, Hameed BH (2013) Acid modified local clay beads as effective low-cost adsorbent for dynamic adsorption of methylene blue. J Ind Eng Chem 19:1153–1161

    Article  CAS  Google Scholar 

  • Batmaz R, Mohammed N, Zaman M et al (2014) Cellulose nanocrystals as promising adsorbents for the removal of cationic dyes. Cellulose 21:1655–1665. doi:10.1007/s10570-014-0168-8

    Article  CAS  Google Scholar 

  • Chatterjee S, Chatterjee S, Chatterjee BP, Guha AK (2007) Adsorptive removal of congo red, a carcinogenic textile dye by chitosan hydrobeads: binding mechanism, equilibrium and kinetics. Colloids Surf A Physicochem Eng Asp 299:146–152

    Article  CAS  Google Scholar 

  • Chavan R (2001) Indian textile industry-environmental issues. Indian J Fibre Text Res 26:11–21

    CAS  Google Scholar 

  • Crini G (2006) Non-conventional low-cost adsorbents for dye removal: a review. Bioresour Technol 97:1061–1085. doi:10.1016/j.biortech.2005.05.001

    Article  CAS  Google Scholar 

  • Deng H, Yang L, Tao G, Dai J (2009) Preparation and characterization of activated carbon from cotton stalk by microwave assisted chemical activation–application in methylene blue adsorption from aqueous solution. J Hazard Mater 166:1514–1521. doi:10.1016/j.jhazmat.2008.12.080

    Article  CAS  Google Scholar 

  • Doğan M, Abak H, Alkan M (2008) Biosorption of methylene blue from aqueous solutions by hazelnut shells: equilibrium, parameters and isotherms. Water Air Soil Pollut 192:141–153. doi:10.1007/s11270-008-9641-z

    Article  Google Scholar 

  • Fan J, Shi Z, Min L et al (2013) Mechanically strong graphene oxide/sodium alginate/polyacrylamide nanocomposite hydrogel with improved dye adsorption capacity. J Mater Chem A 1:7433–7443

    Article  CAS  Google Scholar 

  • Freundlich H (1932) Of the adsorption of gases. Section II. Kinetics and energetics of gas adsorption. Trans Faraday Soc 28:195–201

    Article  CAS  Google Scholar 

  • Gomes PC, Fontes MPF, da Silva AG et al (2001) Selectivity sequence and competitive adsorption of heavy metals by Brazilian soils. Soil Sci Soc Am J 65:1115–1121

    Article  CAS  Google Scholar 

  • Gupta VK, Mohan D, Sharma S, Sharma M (2000) Removal of basic dyes (rhodamine b and methylene blue) from aqueous solutions using bagasse fly ash. Sep Sci Technol 35:2097–2113. doi:10.1081/SS-100102091

    Article  CAS  Google Scholar 

  • Hameed BH, Din ATM, Ahmad AL (2007) Adsorption of methylene blue onto bamboo-based activated carbon: kinetics and equilibrium studies. J Hazard Mater 141:819–825. doi:10.1016/j.jhazmat.2006.07.049

    Article  CAS  Google Scholar 

  • Haynes WM (ed) (2011) CRC handbook of chemistry and physics, 92nd edn, 92, Illust. CRC Press, Taylor & Francis, Boca Raton

    Google Scholar 

  • He X, Male KB, Nesterenko PN et al (2013) Adsorption and desorption of methylene blue on porous carbon monoliths and nanocrystalline cellulose. ACS Appl Mater Interfaces 5:8796–8804. doi:10.1021/am403222u

    Article  CAS  Google Scholar 

  • Ho Y, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465. doi:10.1016/S0032-9592(98)00112-5

    Article  CAS  Google Scholar 

  • Ho Y, McKay G (2003) Sorption of dyes and copper ions onto biosorbents. Process Biochem 38:1047–1061. doi:10.1016/S0032-9592(02)00239-X

    Article  CAS  Google Scholar 

  • Jain A, Gupta V, Bhatnagar A (2003) Utilization of industrial waste products as adsorbents for the removal of dyes. J Hazard Mater 101:31–42. doi:10.1016/S0304-3894(03)00146-8

    Article  CAS  Google Scholar 

  • Jeon YS, Lei J, Kim J-H (2008) Dye adsorption characteristics of alginate/polyaspartate hydrogels. J Ind Eng Chem 14:726–731. doi:10.1016/j.jiec.2008.07.007

    Article  CAS  Google Scholar 

  • Klemm D, Kramer F, Moritz S et al (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed Engl 50:5438–5466. doi:10.1002/anie.201001273

    Article  CAS  Google Scholar 

  • Kurecic M, Smole MS (2012) Polymer nanocomposite hydrogels for water purification. InTech, Croatia

  • Lagergren S (1898) Zur theorie der sogenannten adsorption gelˆster stoffe, Kungliga Svenska Vetenskapsakademiens. Handlingar 24:1–39

    Google Scholar 

  • Lagoa R, Rodrigues JR (2009) Kinetic analysis of metal uptake by dry and gel alginate particles. Biochem Eng J 46:320–326. doi:10.1016/j.bej.2009.06.007

    Article  CAS  Google Scholar 

  • Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40:1361–1403

    Article  CAS  Google Scholar 

  • Lee KY, Mooney DJ (2012) Alginate: properties and biomedical applications. Prog Polym Sci 37:106–126. doi:10.1016/j.progpolymsci.2011.06.003

    Article  CAS  Google Scholar 

  • Lezehari M, Basly J-P, Baudu M, Bouras O (2010) Alginate encapsulated pillared clays: removal of a neutral/anionic biocide (pentachlorophenol) and a cationic dye (safranine) from aqueous solutions. Colloids Surf A Physicochem Eng Asp 366:88–94. doi:10.1016/j.colsurfa.2010.05.021

    Article  CAS  Google Scholar 

  • Lim S-F, Zheng Y-M, Zou S-W, Chen JP (2009) Removal of copper by calcium alginate encapsulated magnetic sorbent. Chem Eng J 152:509–513. doi:10.1016/j.cej.2009.05.029

    Article  CAS  Google Scholar 

  • 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. doi:10.1016/j.cej.2012.01.136

    Article  CAS  Google Scholar 

  • Mall ID, Srivastava VC, Agarwal NK, Mishra IM (2005) Adsorptive removal of malachite green dye from aqueous solution by bagasse fly ash and activated carbon-kinetic study and equilibrium isotherm analyses. Colloids Surf A Physicochem Eng sAsp 264:17–28. doi:10.1016/j.colsurfa.2005.03.027

    Article  CAS  Google Scholar 

  • Maurya NS, Mittal AK, Cornel P, Rother E (2006) Biosorption of dyes using dead macro fungi: effect of dye structure, ionic strength and pH. Bioresour Technol 97:512–521. doi:10.1016/j.biortech.2005.02.045

    Article  CAS  Google Scholar 

  • Métivier-Pignon H, Faur-Brasquet C, Le Cloirec P (2003) Adsorption of dyes onto activated carbon cloths: approach of adsorption mechanisms and coupling of ACC with ultrafiltration to treat coloured wastewaters. Sep Purif Technol 31:3–11

    Article  Google Scholar 

  • Ozacar M, Sengil IA (2005) Adsorption of metal complex dyes from aqueous solutions by pine sawdust. Bioresour Technol 96:791–795. doi:10.1016/j.biortech.2004.07.011

    Article  Google Scholar 

  • Parekh P, Parmar A, Chavda S, Bahadur P (2011) Modified calcium alginate beads with sodium dodecyl sulfate and clay as adsorbent for removal of methylene blue. J Dispers Sci Technol 32:1377–1387. doi:10.1080/01932691.2010.505113

    Article  CAS  Google Scholar 

  • Peng BL, Dhar N, Liu HL, Tam KC (2011) Chemistry and applications of nanocrystalline cellulose and its derivatives: a nanotechnology perspective. Can J Chem Eng 89:1191–1206. doi:10.1002/cjce.20554

    Article  CAS  Google Scholar 

  • Rafatullah M, Sulaiman O, Hashim R, Ahmad A (2010) Adsorption of methylene blue on low-cost adsorbents: a review. J Hazard Mater 177:70–80. doi:10.1016/j.jhazmat.2009.12.047

    Article  CAS  Google Scholar 

  • Reddy MR, Dunn SJ (1986) Distribution coefficients for nickel and zinc in soils. Environ Pollut Ser B Chem Phys 1:303–313

    Article  Google Scholar 

  • Rocher V, Bee A, Siaugue J-M, Cabuil V (2010) Dye removal from aqueous solution by magnetic alginate beads crosslinked with epichlorohydrin. J Hazard Mater 178:434–439. doi:10.1016/j.jhazmat.2010.01.100

    Article  CAS  Google Scholar 

  • Saha P, Chowdhury S, Gupta S et al (2010) Assessment on the removal of malachite green using tamarind fruit shell as biosorbent. Clean Soil Air Water 38:437–445. doi:10.1002/clen.200900234

    Article  CAS  Google Scholar 

  • Sharma P, Kaur H, Sharma M, Sahore V (2011) A review on applicability of naturally available adsorbents for the removal of hazardous dyes from aqueous waste. Environ Monit Assess 183:151–195. doi:10.1007/s10661-011-1914-0

    Article  CAS  Google Scholar 

  • Sun L, Fugetsu B (2013) Effect of encapsulated graphene oxide on alginate-based bead adsorption to remove acridine orange from aqueous solutions. arXiv:1307.0223 [cond-mat.mtrl-sci], Cornell University Library

  • Unuabonah EI, Adebowale KO, Dawodu FA (2008) Equilibrium, kinetic and sorber design studies on the adsorption of Aniline blue dye by sodium tetraborate-modified Kaolinite clay adsorbent. J Hazard Mater 157:397–409. doi:10.1016/j.jhazmat.2008.01.047

    Article  CAS  Google Scholar 

  • Vimonses V, Lei S, Jin B et al (2009) Kinetic study and equilibrium isotherm analysis of Congo Red adsorption by clay materials. Chem Eng J 148:354–364. doi:10.1016/j.cej.2008.09.009

    Article  CAS  Google Scholar 

  • Wang W, Zong L, Wang A (2013) A nanoporous hydrogel based on vinyl-functionalized alginate for efficient absorption and removal of Pb2+ ions. Int J Biol Macromol 62:225–231. doi:10.1016/j.ijbiomac.2013.08.038

    Article  CAS  Google Scholar 

  • Weber WJ, Morris JC (1963) Kinetics of adsorption on carbon from solution. J Sanit Eng Div Am Soc Civ Eng Sanit Eng Div 89:31–60

    Google Scholar 

  • Yan H, Yang L, Yang Z et al (2012) Preparation of chitosan/poly(acrylic acid) magnetic composite microspheres and applications in the removal of copper(II) ions from aqueous solutions. J Hazard Mater 229–230:371–380. doi:10.1016/j.jhazmat.2012.06.014

    Article  Google Scholar 

  • Yang X, Bakaic E, Hoare T, Cranston ED (2013) Injectable polysaccharide hydrogels reinforced with cellulose nanocrystals: morphology, rheology, degradation, and cytotoxicity. Biomacromolecules 14:4447–4455. doi:10.1021/bm401364z

    Article  CAS  Google Scholar 

  • You S, Cheng S, Yan H (2009) The impact of textile industry on China’s environment. Int J Fash Des Technol Educ 2:33–43. doi:10.1080/17543260903055141

    Article  Google Scholar 

  • Youssef ME, Soliman EA, Abu-Saied MA et al (2010) Laboratory studies and numerical modeling of using natural micro beads for environmental applications. Int J Electrochem Sci 5:1887–1897

    Google Scholar 

  • Yu Y, Zhuang Y-Y, Wang Z-H (2001) Adsorption of water-soluble dye onto functionalized resin. J Colloid Interface Sci 242:288–293. doi:10.1006/jcis.2001.7780

    Article  CAS  Google Scholar 

  • 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. doi:10.1016/j.jhazmat.2006.12.045

    Article  CAS  Google Scholar 

  • Zhou C, Wu Q, Yue Y, Zhang Q (2011) Application of rod-shaped cellulose nanocrystals in polyacrylamide hydrogels. J Colloid Interface Sci 353:116–123. doi:10.1016/j.jcis.2010.09.035

    Article  CAS  Google Scholar 

  • Zhou C, Wu Q, Lei T, Negulescu II (2014) Adsorption kinetic and equilibrium studies for methylene blue dye by partially hydrolyzed polyacrylamide/cellulose nanocrystal nanocomposite hydrogels. Chem Eng J 251:17–24. doi:10.1016/j.cej.2014.04.034

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemical Engineering, Waterloo Institute for Nanotechnology, University of Waterloo, 200 University Avenue West, Waterloo, ON, N2L 3G1, Canada

    Nishil Mohammed, Nathan Grishkewich & Kam Chiu Tam

  2. CelluForce Inc, 625, Président-Kennedy Avenue, Montreal, QC, H3A 1K2, Canada

    Richard M. Berry

Authors
  1. Nishil Mohammed
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Nathan Grishkewich
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Richard M. Berry
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kam Chiu Tam
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kam Chiu Tam.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 2741 kb)

Supplementary material 2 (MP4 15316 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mohammed, N., Grishkewich, N., Berry, R.M. et al. Cellulose nanocrystal–alginate hydrogel beads as novel adsorbents for organic dyes in aqueous solutions. Cellulose 22, 3725–3738 (2015). https://doi.org/10.1007/s10570-015-0747-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-015-0747-3

Keywords

Search

Navigation