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Removal of Hexavalent Chromium by Cross-Linking Chitosan and N,N’-Methylene Bis-Acrylamide

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Abstract

The present work aims to make a novel chemical modification of chitosan to improve its ability in removing hexavalent chromium from its aqueous solution. Therefore, the use of N,N/−methylene bis-acrylamide as a cross linker for chitosan has been studied using simple method via nucleophilic addition, in the presence of FeCl3.6H2O as a Lewis acid catalyst. The obtained product (CMBA) was tested as an adsorbent for removal of Cr6+ ions from its aqueous solution. The CMBA was characterized using instrumental techniques such as FTIR, SEM, EDX, and TGA analyses. The FTIR analysis showed the presence of a peak at 3297–3355 cm−1 due to the stretching vibration mode of –OH and –NH2 groups, and a peak at 1745 cm−1 due to the C=O stretching in carboxylic group. The equilibrium data were studied using Langmuir, Freundlich and Tempkin isotherm models. The maximum monolayer adsorption capacity (Qm) calculated from Langmuir isotherm was 149 mg/g, which showed a 3-fold greater uptake for CMBA over non-modified chitosan. The pseudo-second-order kinetic model was the best model representing the adsorption data with correlation coefficient close to one, indicating that chemisorption is dominating the adsorption process. The intraparticle diffusion study proved that the adsorption process was performed under the control of more than one mechanisms. The present study proved that the novel cross-linked chitosan CMBA is a helpful material for the adsorption of Cr6+ ions from its water solution.

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References

  • Abdelwahab O, El Sikaily A, Khaled A, El Nemr A (2007) Mass transfer processes of chromium (VI) adsorption onto guava seeds. Chem Ecol 23(1):73–85

    Google Scholar 

  • Barbosa RFS, Souza AG, Maltez HF, Rosa DS (2020) Chromium removal from contaminated wastewaters using biodegradable membranes containing cellulose nanostructures. Chem Eng J 395:125055. https://doi.org/10.1016/j.cej.2020.125055

    Article  Google Scholar 

  • Bidgoli H, Zamani A, Taherzadeh MJ (2010) Effect of carboxymethylation conditions on the water-binding capacity of chitosan-based superabsorbents. Carbohydr Res 345:2683–2689. https://doi.org/10.1016/j.carres.2010.09.024

    Article  Google Scholar 

  • Biyan J, Fei S, Hu G, Zheng S, Zhang Q, Xu Z (2009) Adsorption of methyl tert-butyl ether (MTBE) from aqueous solution by porous polymeric adsorbent. J Hazard Material 161(1):81–87

    Google Scholar 

  • Boamah PO, Huang Y, Hua M, Zhang Q, Wu J, Onumah J, Sam-Amoah LK, Boamah PO (2015) Sorption of heavy metal ions onto carboxylate chitosan derivatives-a mini-review. Ecotoxicology and Environmental Safety 116:113–120

    Google Scholar 

  • Cetin D, Dönmez S, Dönmez G (2008) The treatment of textile wastewater including chromium (VI) and reactive dye by sulfate-reducing bacterial enrichment. J Environ Manag 88:76–82

    Google Scholar 

  • Crini G, Peindy HN, Gimbert F, Robert C (2007) Removal of C.I. basic green 4 (malachite green) from aqueous solutions by adsorption using cyclodextrin-based adsorbent: kinetic and equilibrium studies. Sep Purif Technol 53:97–110

    Google Scholar 

  • El Nemr A (2007) Pomegranate husk as an adsorbent in the removal of toxic chromium from wastewater. Chem Ecol 23(5):409–425

    Google Scholar 

  • El Nemr A (2009) Potential of pomegranate husk carbon for Cr(VI) removal from wastewater: kinetic and isotherm studies. J Hazard Mater 161:132–141

    Google Scholar 

  • El Nemr A (Editor) (2011) Impact, Monitoring and Management of Environmental Pollution, Nova Science Publishers, Inc. Hauppauge New York, USA. [ISBN-10: 1608764877, ISBN-13: 9781608764877]. 638 pages

  • El Nemr A, El Sikaily A, Khaled A, Abdelwahab O (2007) Removal of toxic chromium (VI) from aqueous solution by activated carbon using Casuarina equisetifolia. Chem Ecol 23:119–129

    Google Scholar 

  • El Nemr A, El-Sikaily A, Khaled A (2010) Modeling of adsorption isotherms of methylene blue onto rice husk activated carbon. Egy J Aquat Res 36(3):403–425

    Google Scholar 

  • El Nemr A, Ismail MNM, El Ashry ESH, Abdel Hamid H (2020) Novel simple modification of chitosan as adsorptive agent for removal of Cr6+ from aqueous solution. Egypt J Chem. Article 133, 63(4): 21-22. DOI: https://doi.org/10.21608/ejchem.2019.11157.1716

  • El Nemr A, Khaled A, Abdelwahab O, El-Sikaily A (2008) Treatment of wastewater containing toxic chromium using new activated carbon developed from date palm seed. J Hazard Mater 152(1):263–275

    Google Scholar 

  • El Nemr A, Ragab S, El Sikaily A, Khaled A (2015) Synthesis of cellulose triacetate from cotton cellulose by using NIS as a catalyst under mild reaction conditions. Carbohydr Polym 130:41–48

    Google Scholar 

  • El Sikaily A, El Nemr A, Khaled A (2011) Copper sorption onto dried red alga Pterocladia capillacea and its activated carbon. Chem Eng J 168:707–714

    Google Scholar 

  • El Sikaily A, El Nemr A, Khaled A, Abdelwahab O (2007) Removal of toxic chromium from wastewater using green alga Ulva lactuca and its activated carbon. J Hazard Mater 148:216–228

    Google Scholar 

  • Eldeeb TM, El Nemr A, Khedr MH, El-Dek SI, Imam NG (2020) Novel, three-dimensional, chitosan-carbon nanotube–PVA nanocomposite hydrogel for removal of Cr6+ from water. Desalin Water Treat 184:163–177

  • Eleryan A, El Nemr A, Mashaly M, Khaled A (2019) 6-Triethylenetetramine 6-deoxycellulose grafted with crotonaldehyde as adsorbent for Cr6+ removal from wastewater. Inter J Sci Eng Res 10(7):1199–1211

    Google Scholar 

  • Freundlich HMF (1906) Über die Adsorption in Lösungen. Z Phys Chem (Leipzig) 57A:385–470

  • Gavilan KC, Pesto AV, Garcia HM, Yatluk Y, Roussy J, Guibal E (2009) Mercury sorption on a thiocarbamoyl derivative of chitosan. J Hazard Mater 165:415–426

    Google Scholar 

  • Gierszewska M, Jakubowska E, Olewnik-Kruszkowska E (2019) Effect of chemical crosslinking on properties of chitosan-montmorillonite composites. Polym Test 77:105872. https://doi.org/10.1016/j.polymertesting.2019.04.019

    Article  Google Scholar 

  • Gilcreas FW, Tarars MJ, Ingols RS (1965) Standard methods for the examination of water and wastewater, 12th, American public health association (APHA), New York, USA

  • Giri AK, Patel R, Mandal S (2012) Removal of Cr(VI) from aqueous solution by Eichhornia crassipes root biomass-derived activated carbon. Chem Eng J 185-186:71–81

    Google Scholar 

  • Golbaz S, Jafari AJ, Rafiee M, Kalantary RR (2014) Separate and simultaneous removal of phenol, chromium, and cyanide from aqueous solution by coagulation/precipitation: mechanisms and theory. Chem Eng J 253:251–257

    Google Scholar 

  • Gopalakannana V, Periyasamyb S, Viswanathan N (2016) One pot eco-friendly synthesis of highly dispersed alumina supports dalginate biocomposite for efficient chromium (VI) removal. J Water Process Eng 10:113–119

    Google Scholar 

  • Hassaan MA, El Nemr A, Madkour FF (2016) Environmental assessment of heavy metal pollution and human health risk. Amer J water Sci Eng 2(3):14-19. Doi: https://doi.org/10.11648/j.ajwse.20160203.11

  • Ho YS, McKay G, Wase DAJ, Foster CF (2000) Study of the sorption of divalent metal ions on to peat. Adsorp Sci Technol 18:639–650

    Google Scholar 

  • Jabasingh SA, Lalith D, Garre P (2015) Sorption of chromium (VI) from electroplating effluent onto chitin immobilized mucor racemosus sorbent (CIMRS) impregnated in rotating disk contactor blades. J Ind Eng Chem 23:79–92

    Google Scholar 

  • Jashni E, Hosseini SM (2020) Promoting the electrochemical and separation properties of heterogeneous cation exchange membrane by embedding 8-hydroxyquinoline ligand: chromium ions removal. Sep Purif Technol 234:116118. https://doi.org/10.1016/j.seppur.2019.116118

    Article  Google Scholar 

  • Kang Sofla MS, Mortazavi S, Seyfi J (2020) Preparation and characterization of polyvinyl alcohol/chitosan blends plasticized and compatibilized by glycerol/polyethylene glycol. Carbohydr Poly 232:115784. https://doi.org/10.1016/j.carbpol.2019.115784

  • Kavitha D, Namasivayam C (2007) Experimental and kinetic studies on methylene blue adsorption by coir pith carbon. Bioresour Technol 98:4–21

    Google Scholar 

  • Lagergren S (1898) Zur Theorie der sogenannten Adsorption gelöster Stoffe. Kungliga Svenska Vetenskapsakademiens Handlingar 24:1–39

  • Langmuir I (1916) The constitution and fundamental properties of solids and liquids. J Am Chem Soc 38:2221–2295

    Google Scholar 

  • Li Z, Li T, An L, Liu H, Gu L, Zhang Z (2016) Preparation of chitosan/polycaprolactam nanofibrous filter paper and its greatly enhanced chromium (VI) adsorption. Colloids Surf A Physicochem Eng Asp 494:65–73

    Google Scholar 

  • Liu L, Xu Y, Wang K, Li K, Xu L, Wange J, Wang J (2019) Fabrication of a novel conductive ultrafiltration membrane and its application for electrochemical removal of hexavalent chromium. J Membrane Sci 584:191–201. https://doi.org/10.1016/j.memsci.2019.05.018

    Article  Google Scholar 

  • Liu Q, Yang B, Zhang L, Huang R (2015) Adsorptive removal of Cr(VI) from aqueous solutions by cross-linked chitosan/bentonite composite. Korean J Chem Eng 32:314–1322

    Google Scholar 

  • Lu X, Li M, Deng H, Lin P, Matsumoto MR, Liu X (2016) Application of electrochemical depassivation in PRB systems to recover Fe reactivity. Front Environ Sci Eng 10(4):04

    Google Scholar 

  • McKay G (1983) The adsorption of dyestuff from aqueous solution using activated carbon: analytical solution for batch adsorption based on external mass transfer and pore diffusion. Chem Eng J 27:187–196

    Google Scholar 

  • Meriç S, De Nicola E, Iaccarino M, Gallo M, Di Gennaro A, Morrone G (2005) Toxicity of leather tanning wastewater effluents in sea urchin early development and in marine microalgae. Chemosphere 61:208–217

    Google Scholar 

  • Milewski A, Lezzaik K, Rotz R (2020) Sensitivity analysis of the groundwater risk index in the Middle East and North Africa region. Environ Process 7:53–71. https://doi.org/10.1007/s40710-019-00421-7

    Article  Google Scholar 

  • Mobarak M, Mohamed EA, Selim AQ, Sellaoui L, Lamine AB, Erto A, Bonilla-Petriciolet A, Seliem MK (2019) Surfactant –modified serpentine for fluoride and Cr(VI) adsorption in single and binary systems: experimental studies and theoretical modeling. Chem Eng J 369:333–343

    Google Scholar 

  • Mohtashami R, Shang JQ (2019) Electroflotation for treatment of industrial wastewaters: a focused review. Environ Process 6:325–353. https://doi.org/10.1007/s40710-019-00348-z

    Article  Google Scholar 

  • Ogata F, Nagai N, Itami R, Nakamura T, Kawasaki N (2020) Potential of virgin and calcined wheat bran biomass for the removal of chromium (VI) ion from a synthetic aqueous solution. J Environ Chem Eng 8(2):103710. https://doi.org/10.1016/j.jece.2020.103710

    Article  Google Scholar 

  • Ozturk S, Kaya T, Aslim B, Tan S (2012) Removal and reduction of chromium by Pseudomonas spp. and their correlation to rhamnolipid production. J Hazard Mater 231-232:64–69

    Google Scholar 

  • Pakzadeh B, Batista JR (2011) Chromium removal from ion-exchange waste brines with calcium polysulfide. Water Res 45:3055–3064

    Google Scholar 

  • Pan C, Qian J, Zhao C, Yang H, Zhao X, Guo H (2020) Study on the relationship between crosslinking degree and properties of TPP crosslinked chitosan nanoparticles. Carbohydr Polym 241:116349. https://doi.org/10.1016/j.carbpol.2020.116349

    Article  Google Scholar 

  • Panda H, Tiadi N, Mohanty M, Mohanty CR (2017) Studies on adsorption behavior of an industrial waste for removal of chromium from aqueous solution. South Afr J Chem Eng 23:132–138

    Google Scholar 

  • Rajeev KK, Kim E, Nam J, Lee S, Mun J, Kim T-H (2020) Chitosan-grafted polyaniline copolymer as an electrically conductive and mechanically stable binder for high performance Si anodes in Li-ion batteries. Electrochim Acta 333:135532. https://doi.org/10.1016/j.electacta.2019.135532

    Article  Google Scholar 

  • Sakti SCW, Narita Y, Sasaki T, Tanaka NS (2015) A novel pyridinium functionalized magnetic chitosan with pH-independent and rapid adsorption kinetics for magnetic separation of Cr(VI). J Environ Eng 3:1953–1961

    Google Scholar 

  • Sharma G, Kumar A, Naushad M, Pathania D, Sillanpa M (2016) Polyacrylamide Zr(IV) vanadophosphate nanocomposite: ion exchange properties, antibacterial activity, and photocatalytic behavior. J Ind Eng Chem 33:201–208

    Google Scholar 

  • Son EB, Poo KM, Mohamed HO, Choi YJ, Cho WC, Chae KJ (2018) A novel approach to developing a reusable marine macro-algae adsorbent with chitosan and ferric oxide for simultaneous efficient heavy metal removal and easy magnetic separation. Bioresour Technol 259:381–387

    Google Scholar 

  • Srinivasan K, Balasubramanian N, Ramakrishan TV (1988) Studies on chromium removal by rice husk carbon. Ind J Environ Heal 30:376

    Google Scholar 

  • Tahira I, Aslam Z, Abbas A, Monim-ul-Mehboob M, Ali S, Asghar A (2019) Adsorptive removal of acidic dye onto grafted chitosan: a plausible grafting and adsorption mechanism. Inter J Biological Macromol 136:1209–1218. https://doi.org/10.1016/j.ijbiomac.2019.06.173

    Article  Google Scholar 

  • Tempkin MJ, Pyzhev V (1940) Acta Physiochim URSS 12:217–222

    Google Scholar 

  • Travlou NA, Kyzas GZ, Lazaridis NK, Deliyanni EA (2013) Functionalization of graphite oxide with magnetic chitosan for the preparation of a nanocomposite dye adsorbent. Langmuir 29:1657–1668

    Google Scholar 

  • Vaiopoulou E, Gikas P (2020) Regulations for chromium emissions to the aquatic environment in Europe and elsewhere. Chemosphere 254:126876. https://doi.org/10.1016/j.chemosphere.2020.126876

    Article  Google Scholar 

  • Vakili M, Deng S, Li T, Wang W, Wang W, Yu G (2018) Novel cross linked chitosan for enhanced adsorption of hexavalent chromium in acidic solution. Chem Eng J 347:782–790

    Google Scholar 

  • Vasudevan S, Lakshmi J, Vanathi R (2010) Electrochemical coagulation for chromium removal: process optimization, kinetics, isotherms and sludge characterization. Clean 38:9–16

    Google Scholar 

  • Wang J, Liu M, Duan C, Sun J, Xu Y (2019) Preparation and characterization of cellulose-based adsorbent and its application in heavy metal ions removal. Carbohydr Polym 206:837–843

    Google Scholar 

  • Wang Q, Zhou C, Kuang Y-j, Z-h J, Yang M (2020) Removal of hexavalent chromium in aquatic solutions by pomelo peel. Water Sci Eng 13(1):65–73. https://doi.org/10.1016/j.wse.2019.12.011

    Article  Google Scholar 

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

    Google Scholar 

  • Wu Y, Fan Y, Zhang M, Ming Z, Yang S, Arkin A, Fang P (2016) Functionalized agricultural biomass as a low-cost adsorbent: utilization of rice straw incorporated with amine groups for the adsorption of Cr(VI) and Ni(II) from single and binary systems. Biochem Eng J 105:27–35

    Google Scholar 

  • Yang D, Li L, Chen B, Shi S, Nie J, Ma G (2019) Functionalized chitosan electrospun nanofiber membranes for heavy-metal removal. Polym 163:74–85

    Google Scholar 

  • Zargham Z, Akbari A, Latifi AM, Amani MA (2016) Design of a new integrated chitosan-PAMAM dendrimer biosorbent for heavy metals removing and study of its adsorption kinetics and thermodynamics. Bioresour Technol 205:230–238

    Google Scholar 

  • Zhang Y, Xu L, Zhao L, Peng J, Li C, Li J, Zhai M (2012) Radiation synthesis and Cr(VI) removal of cellulose microsphere adsorbent. Carbohydr Polym 88:931–938

    Google Scholar 

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Authors and Affiliations

  1. Marine Pollution Department, Environmental Division, National Institute of Oceanography and Fisheries, Kayet Bey, El-Anfoushy, Alexandria, Egypt

    Mohamed N. M. Ismael & Ahmed El Nemr

  2. Department of Chemistry, Faculty of Science, Alexandria University, Alexandria, Egypt

    El Sayed H. El Ashry & Hamida Abdel Hamid

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  1. Mohamed N. M. Ismael
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  2. Ahmed El Nemr
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  4. Hamida Abdel Hamid
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Ismael, M.N.M., El Nemr, A., El Ashry, E.S.H. et al. Removal of Hexavalent Chromium by Cross-Linking Chitosan and N,N’-Methylene Bis-Acrylamide. Environ. Process. 7, 911–930 (2020). https://doi.org/10.1007/s40710-020-00447-2

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