Skip to main content
Log in

Preparation of microscale zero-valent iron-fly ash-bentonite composite and evaluation of its adsorption performance of crystal violet and methylene blue dyes

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

New microscale zero-valent iron adsorbent on fly ash and bentonite matrix for removal of crystal violet (CV) and methylene blue (MB) was synthesized through direct reduction of iron oxide using coke and palm kernel shell. The adsorbent was prepared as cylindrical shaped pellets to remove the CV and MB from the aqueous solution. Nitrogen adsorption-desorption isotherm and scanning electron microscopy (SEM) studies showed that the adsorbent is highly porous, and the iron particles are finely dispersed on the supporting material surfaces. FTIR and UV studies indicated that the C=C bonds in CV and C=N+(CH3)2 bonds in MB were affected in the adsorption process. MB switched to the reduced MBH2 species while CV was reduced to two small-size molecular compounds, explaining the higher CV adsorption in comparison to that of MB. The reduction of these compounds was coupled to the oxidation of Fe0 to Fe2O3 as revealed by XRD characterization of the adsorbent after adsorption. CV and MB adsorption isotherms fitted well with the Langmuir adsorption model. Different adsorption and reduction kinetic models were examined for the MB and CV removal processes. A better fit of the experimental data with the pseudo-second-order model was observed. CV and MB adsorption increased with temperature in the 30–50 °C range. At 50 °C, adsorption capacities of CV and MB reached to 89.9 and 42.8 mg/g, respectively. This new adsorbent showed a superior adsorption capacity for CV and MB when compared to other adsorbents.

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

Access this article

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  • Ahmad R (2009) Studies on adsorption of crystal violet dye from aqueous solution onto coniferous pinus bark powder (CPBP). J Hazard Mater 171(1):767–773

    Article  CAS  Google Scholar 

  • de Aragão UG, Freeman HS, Warren SH, de Oliveira DP, Terao Y, Watanabe T, Claxton LD (2005) The contribution of azo dyes to the mutagenic activity of the Cristais River. Chemosphere 60(1):55–64

    Article  Google Scholar 

  • Bhatti HN, Nausheen S (2015) Equilibrium and kinetic modeling for the removal of turquoise blue PG dye from aqueous solution by a low-cost agro waste. Desalin Water Treat 55(7):1934–1944

    Article  CAS  Google Scholar 

  • Chang J, Ma J, Ma Q, Zhang D, Qiao N, Hu M, Ma H (2016) Adsorption of methylene blue onto Fe3O4/activated montmorillonite nanocomposite. Appl Clay Sci 119:132–140

    Article  CAS  Google Scholar 

  • Chen ZX, Jin XY, Chen ZL, Megharaj M, Naidu R (2011) Removal of methyl orange from aqueous solution using bentonite-supported nanoscale zero-valent iron. J Colloid Interf Sci 363(2):601–607

    Article  CAS  Google Scholar 

  • Chen Z, Wang T, Jin X, Chen Z, Megharaj M, Naidu R (2013) Multifunctional kaolinite-supported nanoscale zero-valent iron used for the adsorption and degradation of crystal violet in aqueous solution. J Colloid Interf Sci 398:59–66

    Article  CAS  Google Scholar 

  • Cottet L, Almeida CAP, Naidek N, Viante MF, Lopes MC, Debacher NA (2014) Adsorption characteristics of montmorillonite clay modified with iron oxide with respect to methylene blue in aqueous media. Appl Clay Sci 95:25–31

    Article  CAS  Google Scholar 

  • Dil EA, Ghaedi M, Ghaedi A, Asfaram A, Jamshidi M, Purkait MK (2016) Application of artificial neural network and response surface methodology for the removal of crystal violet by zinc oxide nanorods loaded on activate carbon: kinetics and equilibrium study. J Taiwan Inst Chem E 59:210–220

    Article  CAS  Google Scholar 

  • El-Sayed GO (2011) Removal of methylene blue and crystal violet from aqueous solutions by palm kernel fiber. Desalination 272(1):225–232

    Article  CAS  Google Scholar 

  • Fan Y, Liu HJ, Zhang Y, Chen Y (2015) Adsorption of anionic MO or cationic MB from MO/MB mixture using polyacrylonitrile fiber hydrothermally treated with hyperbranched polyethylenimine. J Hazard Mater 283:321–328

    Article  CAS  Google Scholar 

  • Fan S, Wang Y, Wang Z, Tang J, Tang J, Li X (2017) Removal of methylene blue from aqueous solution by sewage sludge-derived biochar: adsorption kinetics, equilibrium, thermodynamics and mechanism. J Environ Chem Eng 5(1):601–611

    Article  CAS  Google Scholar 

  • Fernandes AN, Almeida CAP, Debacher NA, Sierra MMDS (2010) Isotherm and thermodynamic data of adsorption of methylene blue from aqueous solution onto peat. J Mol Struct 982(1):62–65

    Article  CAS  Google Scholar 

  • Frost RL, Xi Y, He H (2010) Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption. J Colloid Interf Sci 341(1):153–161

    Article  CAS  Google Scholar 

  • Gholami M, Vardini MT, Mahdavinia GR (2016) Investigation of the effect of magnetic particles on the crystal violet adsorption onto a novel nanocomposite based on κ-carrageenan-g-poly (methacrylic acid). Carbohyd Polym 136:772–781

    Article  CAS  Google Scholar 

  • Guo D, Zhu L, Guo S, Cui B, Luo S, Laghari M, Chen Z, Ma C, Zhou Y, Chen J, Xiao B, Hu M, Luo S (2016) Direct reduction of oxidized iron ore pellets using biomass syngas as the reducer. Fuel Process Technol 148:276–281

    Article  CAS  Google Scholar 

  • Gürses A, Karaca S, Doğar Ç, Bayrak R, Açıkyıldız M, Yalçın M (2004) Determination of adsorptive properties of clay/water system: methylene blue sorption. J Colloid Interface Sci 269(2):310–314

    Article  Google Scholar 

  • Hall KR, Eagleton LC, Acrivos A, Vermeulen T (1966) Pore-and solid-diffusion kinetics in fixed-bed adsorption under constant-pattern conditions. Ind Eng Chem Fund 5:212–223

    Article  CAS  Google Scholar 

  • Huang L, Zhou S, Jin F, Huang J, Bao N (2014) Characterization and mechanism analysis of activated carbon fiber felt-stabilized nanoscale zero-valent iron for the removal of Cr(VI) from aqueous solution. Colloid Surface A 447:59–66

    Article  CAS  Google Scholar 

  • Inbaraj BS, Chen BH (2011) Dye adsorption characteristics of magnetite nanoparticles coated with a biopolymer poly (γ-glutamic acid). Bioresour Technol 102(19):8868–8876

    Article  Google Scholar 

  • Inbaraj BS, Chiu CP, Ho GH, Yang J, Chen BH (2008) Effects of temperature and pH on adsorption of basic brown 1 by the bacterial biopolymer poly(gamma-glutamic acid). Bioresour Technol 99(5):1026–1035

    Article  CAS  Google Scholar 

  • Jamal R, Zhang L, Wang M, Zhao Q, Abdiryim T (2016) Synthesis of poly(3,4-propylenedioxythiophene)/MnO2 composites and their applications in the adsorptive removal of methylene blue. Prog Nat Sci Mater 26(1):32–40

    Article  CAS  Google Scholar 

  • Kerkez DV, Tomašević DD, Kozma G, Bečelić-Tomin MR, Prica MD, Rončević SD, Kukovecz Á, Dalmacija BD, Kónya Z (2014) Three different clay-supported nanoscale zero-valent iron materials for industrial azo dye degradation: a comparative study. J Taiwan Inst Chem E 45(5):2451–2461

    Article  CAS  Google Scholar 

  • Kumar KV, Ramamurthi V, Sivanesan S (2005) Modeling the mechanism involved during the sorption of methylene blue onto fly ash. J Colloid Interface Sci 284(1):14–21

    Article  CAS  Google Scholar 

  • Li C, Sun H, Bai J, Li L (2010) Innovative methodology for comprehensive utilization of iron ore tailings. Part 1. The recovery of iron from iron ore tailings using magnetic separation after magnetizing roasting. J Hazard Mater 174:71–77

    Article  CAS  Google Scholar 

  • Li L, Liu F, Duan H, Wang X, Li J, Wang Y, Luo C (2016a) The preparation of novel adsorbent materials with efficient adsorption performance for both chromium and methylene blue. Colloid Surface B 141:253–259

    Article  CAS  Google Scholar 

  • Li D, Li J, Gu Q, Song S, Peng C (2016b) Co-influence of the pore size of adsorbents and the structure of adsorbates on adsorption of dyes. Desalin Water Treat 57(31):14686–14695

    Article  CAS  Google Scholar 

  • Liu Y, Phenrat T, Lowry GV (2007) Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution. Environ Sci Technol 41(22):7881–7887

    Article  CAS  Google Scholar 

  • Liu S, Lim M, Amal R (2014) TiO2-coated natural zeolite: rapid humic acid adsorption and effective photocatalytic regeneration. Chem Eng Sci 105:46–52

    Article  CAS  Google Scholar 

  • Liu X, Li Y, Wang C, Ji M (2015) Comparison study on Cr(VI) removal by anion exchange resins of Amberlite IRA96, D301R, and DEX-Cr: isotherm, kinetics, thermodynamics, and regeneration studies. Desalin Water Treat 55(7):1840–1850

    Article  CAS  Google Scholar 

  • Lonappan L, Rouissi T, Das RK, Brar SK, Ramirez AA, Verma M, Surampalli RY, Valero JR (2016) Adsorption of methylene blue on biochar microparticles derived from different waste materials. Waste Manag 49:537–544

    Article  CAS  Google Scholar 

  • Mahdavian AR, Mirrahimi MAS (2010) Efficient separation of heavy metal cations by anchoring polyacrylic acid on superparamagnetic magnetite nanoparticles through surface modification. Chem Eng J 159(1):264–271

    Article  CAS  Google Scholar 

  • Man Y, Feng JX, Li FJ, Ge Q, Chen YM, Zhou JZ (2014) Influence of temperature and time on reduction behavior in iron ore-coal composite pellets. Powder Technol 256(2):361–366

    Article  CAS  Google Scholar 

  • Marrakchi F, Ahmed MJ, Khanday WA, Asif M, Hameed BH (2017) Mesoporous-activated carbon prepared from chitosan flakes via single-step sodium hydroxide activation for the adsorption of methylene blue. Int J Biol Macromol 98:233–239

    Article  CAS  Google Scholar 

  • Mbacké MK, Kane C, Diouf I, Diop CM (2015) Removal of crystal violet by electrocoagulation: optimization and reaction mechanisms involved. J Soc Ouest-Afr Chim 39:64–76

    Google Scholar 

  • Ogundiran MB, Kumar S (2016) Synthesis of fly ash-calcined clay geopolymers: reactivity, mechanical strength, structural and microstructural characteristics. Constr Build Mater 125:450–457

    Article  CAS  Google Scholar 

  • Osinubi KJ, Yohanna P, Eberemu AO (2015) Cement modification of tropical black clay using iron ore tailings as admixture. Transportation Geotechnics 5:35–49

    Article  Google Scholar 

  • Ovchinnikov OV, Evtukhova AV, Kondratenko TS, Smirnov MS, Khokhlov VY, Erina OV (2016) Manifestation of intermolecular interactions in FTIR spectra of methylene blue molecules. Vib Spectrosc 86:181–189

    Article  CAS  Google Scholar 

  • Özcan AS, Erdem B, Özcan A (2005) Adsorption of acid blue 193 from aqueous solutions onto BTMA-bentonite. Colloids Surf A: Physicochem Eng Aspects 266:73–81

    Article  Google Scholar 

  • Pal U, Sandoval A, Madrid SI, Corro G, Sharma V, Mohanty P (2016) Mixed titanium, silicon, and aluminum oxide nanostructures as novel adsorbent for removal of rhodamine 6G and methylene blue as cationic dyes from aqueous solution. Chemosphere 163:142–152

    Article  CAS  Google Scholar 

  • Pei Y, Wang M, Tian D, Xu X, Yuan L (2015) Synthesis of core-shell SiO2@MgO with flower like morphology for removal of crystal violet in water. J Colloid Interf Sci 453:194–201

    Article  CAS  Google Scholar 

  • Ponder SM, Darab JG, Mallouk TE (2000) Remediation of Cr(VI) and Pb(II) aqueous solutions using supported, nanoscale zero-valent iron. Environ Sci Technol 34(12):2564–2569

    Article  CAS  Google Scholar 

  • Rai P, Gautam RK, Banerjee S, Rawat V, Chattopadhyaya MC (2015) Synthesis and characterization of a novel SnFe2O4@activated carbon magnetic nanocomposite and its effectiveness in the removal of crystal violet from aqueous solution. J Environ Chem Eng 3(4):2281–2291

    Article  CAS  Google Scholar 

  • Rasalingam S, Peng R, Koodali RT (2015) An insight into the adsorption and photocatalytic degradation of rhodamine B in periodic mesoporous materials. Appl Catal B Environ 174:49–59

    Article  Google Scholar 

  • Rauf MA, Ashraf SS (2012) Survey of recent trends in biochemically assisted degradation of dyes. Chem Eng J 209:520–530

    Article  CAS  Google Scholar 

  • Sabna V, Thampi SG, Chandrakaran S (2015) Adsorption of crystal violet onto functionalised multi-walled carbon nanotubes: equilibrium and kinetic studies. Ecotox Environ Safe. doi:10.1016/j.ecoenv.2015.09.018

  • Senthilkumaar S, Kalaamani P, Subburaam CV (2006) Liquid phase adsorption of crystal violet onto activated carbons derived from male flowers of coconut tree. J Hazard Mater 136(3):800–808

    Article  CAS  Google Scholar 

  • Shi L, Zhang X, Chen Z (2011) Removal of chromium(VI) from wastewater using bentonite-supported nanoscale zero-valent iron. Water Res 45(2):886–892

    Article  CAS  Google Scholar 

  • Soon AN, Hameed BH (2013) Degradation of acid blue 29 in visible light radiation using iron modified mesoporous silica as heterogeneous photo-Fenton catalyst. Appl Catal A Gen 450:96–105

    Article  CAS  Google Scholar 

  • Wang JQ, Liu YH, Chen MW, Xie GQ, Louzguine-Luzgin DV, Inoue A, Perepezko JH (2012) Rapid degradation of azo dye by Fe-based metallic glass powder. Adv Funct Mater 22(12):2567–2570

    Article  CAS  Google Scholar 

  • Wang Y, Tian W, Wu C, Bai J, Zhao Y (2016) Synthesis of coal cinder balls and its application for CODCr and ammonia nitrogen removal from aqueous solution. Desalin Water Treat 57(46):21781–21793

    Article  CAS  Google Scholar 

  • Wang Y, López-Valdivieso A, Zhang T, Mwamulima T, Zhang X, Song S, Peng C (2017) Synthesis of fly ash and bentonite-supported zero-valent iron and its application for removal of toxic cationic dyes from aqueous solutions. Environ Eng Sci. doi:10.1089/ees.2016.0418

  • Xing M, Xu L, Wang J (2016) Mechanism of Co(II) adsorption by zero valent iron/graphene nanocomposite. J Hazard Mater 301:286–296

    Article  CAS  Google Scholar 

  • Zhang X, Lin S, Lu XQ, Chen ZL (2010) Removal of Pb(II) from water using synthesized kaolin supported nanoscale zero-valent iron. Chem Eng J 163(3):243–248

    Article  CAS  Google Scholar 

  • Zhu N, Yan T, Qiao J, Cao H (2016) Adsorption of arsenic, phosphorus and chromium by bismuth impregnated biochar: adsorption mechanism and depleted adsorbent utilization. Chemosphere 164:32–40

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the State Key Laboratory of Environmental Criteria and Risk Assessment (No. SKLECRA2013FP12) and the Public Science and Technology Research Funds Projects of Ocean, China (201105020). The authors would like to thank the anonymous reviewers for their recommendations and comments. Also, Y. Wang would like to thank the State Scholarship Fund organized by the China Scholarship Council for offering her the scholarship during her joint Ph.D. studying in Mexico. And the authors are thankful to Aurora Robledo Cabrera for her technical support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Changsheng Peng.

Additional information

Responsible editor: Guilherme L. Dotto

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Y., López-Valdivieso, A., Zhang, T. et al. Preparation of microscale zero-valent iron-fly ash-bentonite composite and evaluation of its adsorption performance of crystal violet and methylene blue dyes. Environ Sci Pollut Res 24, 20050–20062 (2017). https://doi.org/10.1007/s11356-017-9426-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-017-9426-2

Keywords

Navigation