1. JCCT
  2. All Volumes and Issues
  3. Volume 18, Number 1, 2024
  4. Parametric and Kinetic Study of Nitrate Removal from Water by Modified Chitosan Composite Beads

Parametric and Kinetic Study of Nitrate Removal from Water by Modified Chitosan Composite Beads

JCCT.
2024;
Volume 18, Number 1
: pp. 83 - 93
https://doi.org/10.23939/chcht18.01.083
Authors:
  1. Zainab N. Jamka
  2. Wadood T. Mohammed
1
hemical Engineering Department, University of Baghdad
2
Chemical Engineering Department, University of Baghdad

The contamination of water bodies with harmful pollutants considers an aggravating global problem. The current research focuses on a developing efficient adsorbed for removing nitrate ions from aqueous solutions. The study proposed modified chitosan-zeolite composite beads to enhance the performance of the adsorption process. The zeolite was used to increase the surface area, and Zirconium was loaded on the beads to promote the selectivity for nitrate anions. The adsorption mechanism was assessed by characterizing the beads and sorbate adsorbed beads utilizing X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), Field Emission Scanning Electron Microscopy (FESEM), and analysis with an energy dispersive X-ray analyzer (EDX). The experiments were conducted in a batch system, and the effect of key parameters like contact time, initial nitrate anion concentration, and adsorbent dosage on the adsorption performance was investigated. The results demonstrated that the highest removal of nitrate ions was determined to be 95.42% at 0.2 g of $Cs-Ze-Zr$ adsorbent with an initial concentration of 50 mg/L and a contact time of 120 minutes. The maximum adsorption capacity of the nitrate ions on the manufactured bead was 80.15 mg/g. In addition, among the Freundlich, Langmuir, and Temkin isotherms, the isotherm equilibrium data were consistent with a Freundlich isotherm model. The kinetic data for adsorption were satisfactorily fitted by a pseudo-first order. Subsequently, the results distinctly indicated that the proposed adsorbed $(Cs-Ze-Zr)$ could be employed fruitfully in removing nitrate ions, demonstrated through the remarkable removal efficiency and adsorption capacity obtained in the study.

modified chitosan
batch adsorption
nitrate
zeolite
zirconium
  1. Yang, K.; Yan, L.G.; Yang, Y.M.; Yu, S.J.; Shan, R.R.; Yu, H.Q.; Zhu, B.C.; Du, B. Adsorptive Removal of Phosphate by Mg- Al and Zn-Al Layered Double Hydroxides: Kinetics, Isotherms and Mechanisms. Sep. Purif. Technol. 2014, 124, 36–42. https://doi.org/10.1016/j.seppur.2013.12.042
  2. Banu, H.T.; Karthikeyan, P.; Meenakshi, S. Zr4+ Ions Embedded Chitosan-Soya Bean Husk Activated Bio-Char Composite Beads for the Recovery of Nitrate and Phosphate Ions from Aqueous Solution. Int. J. Biol. Macromol. 2019, 130, 573– 583. https://doi.org/10.1016/j.ijbiomac.2019.02.100
  3. Kamaraj, R.; Pandiarajan, A.; Jayakiruba, S.; Naushad, M.; Vasudevan, S. Kinetics, Thermodynamics and Isotherm Modeling for Removal of Nitrate from Liquids by Facile One-Pot Electrosynthesized Nano Zinc Hydroxide. J. Mol. Liq. 2016, 215, 204–211. https://doi.org/10.1016/j.molliq.2015.12.032
  4. Van Voorthuizen, E.M.; Zwijnenburg, A.; Wessling, M. Nutrient Removal by NF and RO Membranes in a Decentralized Sanitation System. Water Res. 2005, 39, 3657–3667. https://doi.org/10.1016/j.watres.2005.06.005
  5. Kuokkanen, V.; Kuokkanen, T.; Rämö, J.; Lassi, U.; Roininen, J. Removal of Phosphate from Wastewaters for Further Utilization Using Electrocoagulation with Hybrid Electrodes - Techno-Economic Studies. J. Water Process Eng. 2015, 8, e50–e57. https://doi.org/10.1016/j.jwpe.2014.11.008
  6. Raval, H.D.; Rana, P.S.; Maiti, S. A Novel High-Flux, Thin- Film Composite Reverse Osmosis Membrane Modified by Chitosan for Advanced Water Treatment. RSC Adv. 2015, 5, 6687–6694. https://doi.org/10.1039/c4ra12610f
  7. Quan, X.; Ye, C.; Xiong, Y.; Xiang, J.; Wang, F. Simultaneous Removal of Ammonia, P and COD from Anaerobically Digested Piggery Wastewater Using an Integrated Process of Chemical Precipitation and Air Stripping. J. Hazard. Mater. 2010, 178, 326–332. https://doi.org/10.1016/j.jhazmat.2010.01.083
  8. Liou, Y.H.; Lo, S.L.; Lin, C.J.; Kuan, W.H.; Weng, S.C. Chemical Reduction of an Unbuffered Nitrate Solution Using Catalyzed and Uncatalyzed Nanoscale Iron Particles. J. Hazard. Mater. 2005, 127, 102–110. https://doi.org/10.1016/j.jhazmat.2005.06.029
  9. Rashed, M.N. Adsorption Technique for the Removal of Organic Pollutants from Water and Wastewater, Ch. 7; IntechOpen: Rijeka, 2013. https://doi.org/10.5772/54048
  10. Gumnitsky, J.; Sabadash, V.; Matsuska, O.; Lyuta, O.; Hyvlud, A.; Venger, L. Dynamics of Adsorption of Copper Ions in Fixed-Bed Column and Mathematical Interpretation of the First Stage of the Process. Chem. Chem. Technol. 2022, 16, 267–273. https://doi.org/10.23939/chcht16.02.267
  11. Hammadi, A.; Shakir, I. Adsorption Behavior of Light Naphtha Components on Zeolite (5A) and Activated Carbon. Iraqi J. Chem. Pet. Eng. 2019, 20, 27–33. https://doi.org/10.31699/IJCPE.2019.4.5
  12. Waleed Khalid, M.; D. Salman, S. Adsorption of Chromium Ions on Activated Carbon Produced from Cow Bones. Iraqi J. Chem. Pet. Eng. 2019, 20, 23–32. https://doi.org/10.31699/ijcpe.2019.2.4
  13. Choudhary, V.R.; Vaidya, S.H. Adsorption of Copper Nitrate from Solution on Silica Gel. J. Chem. Technol. Biotechnol. 1982, 32, 888–892. https://doi.org/10.1002/jctb.5030320726
  14. Hummadi, K.K. Optimal Operating Conditions for Adsorption of Heavy Metals from an Aqueous Solution by an Agriculture Waste. Iraqi J. Chem. Pet. Eng. 2021, 22, 27–35. https://doi.org/10.31699/ijcpe.2021.2.4
  15. Karthikeyan, P.; Banu, H.A.T.; Meenakshi, S. Synthesis and Characterization of Metal Loaded Chitosan-Alginate Biopolymeric Hybrid Beads for the Efficient Removal of Phosphate and Nitrate Ions from Aqueous Solution. Int. J. Biol. Macromol. 2019, 130, 407–418. https://doi.org/10.1016/j.ijbiomac.2019.02.059
  16. Hasmath Farzana, M.; Meenakshi, S. Photocatalytic Aptitude of Titanium Dioxide Impregnated Chitosan Beads for the Reduction of Cr(VI). Int. J. Biol. Macromol. 2015, 72, 1265–1271. https://doi.org/10.1016/J.IJBIOMAC.2014.09.029
  17. Keshvardoostchokami, M.; Majidi, M.; Zamani, A.; Liu, B. A Review on the Use of Chitosan and Chitosan Derivatives as the Bio- Adsorbents for the Water Treatment: Removal of Nitrogen- Containing Pollutants. Carbohydr. Polym. 2021, 273, 118625. https://doi.org/10.1016/j.carbpol.2021.118625
  18. Saheed, I.O.; Oh, W.-D.; Suah, F.B.M. Chitosan Modifications for Adsorption of Pollutants – A Review. J. Hazard. Mater. 2021, 408, 124889.https://doi.org/10.1016/j.jhazmat.2020.124889
  19. Nitsae, M.; Madjid, A.; Hakim, L.; Sabarudin, A. Preparation of Chitosan Beads Using Tripolyphosphate and Ethylene Glycol Diglycidyl Ether as Crosslinker for Cr(VI) Adsorption. Chem. Chem. Technol. 2016, 10, 105–114. https://doi.org/10.23939/chcht10.01.105
  20. Rajeswari, A.; Amalraj, A.; Pius, A. Removal of Phosphate Using Chitosan-Polymer Composites. J. Environ. Chem. Eng. 2015, 3, 2331–2341. https://doi.org/10.1016/j.jece.2015.08.022
  21. Karthikeyan, P.; Banu, H. A. T.; Meenakshi, S. Removal of Phosphate and Nitrate Ions from Aqueous Solution Using La3+ Incorporated Chitosan Biopolymeric Matrix Membrane. Int. J. Biol. Macromol. 2019, 124, 492–504. https://doi.org/10.1016/j.ijbiomac.2018.11.127
  22. Azlan, K.; Wan Saime, W.N.; Lai Ken, L. Chitosan and Chemically Modified Chitosan Beads for Acid Dyes Sorption. J. Environ. Sci. 2009, 21, 296–302. https://doi.org/10.1016/S1001-0742(08)62267-6
  23. Kumar, I.A.; Viswanathan, N. Fabrication of Metal Ions Cross-Linked Alginate Assisted Biocomposite Beads for Selective Phosphate Removal. J. Environ. Chem. Eng. 2017, 5, 1438–1446. https://doi.org/10.1016/j.jece.2017.02.005
  24. Kljajević, L.J.; Matović, B.; Radosavljević-Mihajlović, A.; Rosić, M.; Bosković, S.; Devečerski, A. Preparation of ZrO2 and ZrO2/SiC Powders by Carbothermal Reduction of ZrSiO4. J. Alloys Compd. 2011, 509, 2203–2215.https://doi.org/10.1016/j.jallcom.2010.11.002
  25. Wafiroh, S.; Abdulloh, A.; Widati, A.A. Phosphorylated Zeolite-A/Chitosan Composites as Proton Exchange Membrane Fuel Cell. Chem. Chem. Technol. 2018, 12, 229–235. https://doi.org/10.23939/chcht12.02.229
  26. Kulprathipanja, S. Zeolites in Industrial Separation and Catalysis; 2010. https://doi.org/10.1002/9783527629565
  27. Sowmya, A.; Meenakshi, S. Zr(IV) Loaded Cross-Linked Chitosan Beads with Enhanced Surface Area for the Removal of Nitrate and Phosphate. Int. J. Biol. Macromol. 2014, 69, 336–343. https://doi.org/10.1016/j.ijbiomac.2014.05.043
  28. Alver, E.; Metin, A.; Çiftçi, H. Synthesis and Characterization of Chitosan/Polyvinylpyrrolidone/Zeolite Composite by Solution Blending Method. J. Inorg. Organomet. Polym. Mater. 2014, 24, 1048–1054. https://doi.org/10.1007/s10904-014-0087-z
  29. Nathan, A. J.; Scobell, A. APHA AWWA 23rd EDITION; 2017; Vol. 91.
  30. Thamilarasan, V.; Sethuraman, V.; Gopinath, K.; Balalakshmi, C.; Govindarajan, M.; Mothana, R.A.; Siddiqui, N.A.; Khaled, J.M.; Benelli, G. Single Step Fabrication of Chitosan Nanocrystals Using Penaeus Semisulcatus: Potential as New Insecticides, Antimicrobials and Plant Growth Promoters. J. Clust. Sci. 2018, 29, 375–384. https://doi.org/10.1007/s10876-018-1342-1
  31. Zheng, H.; Han, L.; Ma, H.; Zheng, Y.; Zhang, H.; Liu, D.; Liang, S. Adsorption Characteristics of Ammonium Ion by Zeolite 13X. J. Hazard. Mater. 2008, 158, 577–584.https://doi.org/https://doi.org/10.1016/j.jhazmat.2008.01.115
  32. Alshahidy, B.A.; Abbas, A.S. Preparation and Modification of 13X Zeolite as a Heterogeneous Catalyst for Esterification of Oleic Acid. AIP Conf. Proc. 2020, 2213, 020167.https://doi.org/10.1063/5.0000171
  33. Thakkar, H.; Eastman, S.; Hajari, A.; Rownaghi, A. A.; Knox, J. C.; Rezaei, F. 3D-Printed Zeolite Monoliths for CO2 Removal from Enclosed Environments. ACS Appl. Mater. Interfaces 2016, 8, 27753–27761. https://doi.org/10.1021/acsami.6b09647
  34. Gorodylova, N.; Šulcová, P.; Bosacka, M.; Filipek, E. DTA- TG and XRD Study on the Reaction between ZrOCl2·8H2O and (NH4)2HPO4 for Synthesis of ZrP2O7. J. Therm. Anal. Calorim.2014, 118, 1095–1100. https://doi.org/10.1007/s10973-014-3890-4
  35. Elanchezhiyan, S.S.; Sivasurian, N.; Meenakshi, S. Enhancement of Oil Recovery Using Zirconium-Chitosan Hybrid Composite by Adsorptive Method. Carbohydr. Polym. 2016, 145, 103–113. https://doi.org/10.1016/j.carbpol.2016.02.038
  36. Yang, Z.; Peng, H.; Wang, W.; Liu, T. Crystallization Behavior of Poly(ε-Caprolactone)/Layered Double Hydroxide Nanocomposites. J. Appl. Polym. Sci. 2010, 116, 2658–2667. https://doi.org/10.1002/app.31787
  37. De Lucas, A.; Uguina, A. M.; Covián, I.; Rodríguez, L. Synthesis of 13X Zeolite from Calcined Kaolins and Sodium Silicate for Use in Detergents. Ind. Eng. Chem. Res. 1992, 31, 2134–2140. https://doi.org/10.1021/ie00009a010
  38. Lechert, H.; Kacirek, H. The Kinetics of Nucleation of X Zeolites. Zeolites 1993, 13, 192–200. https://doi.org/10.1016/S0144-2449(05)80277-5
  39. Zhou, C.; Alshameri, A.; Yan, C.; Qiu, X.; Wang, H.; Ma, Y. Characteristics and Evaluation of Synthetic 13X Zeolite from Yunnan’s Natural Halloysite. J. Porous Mater. 2013, 20, 587–594. https://doi.org/10.1007/s10934-012-9631-9
  40. Jiang, H.; Chen, P.; Luo, S.; Tu, X.; Cao, Q.; Shu, M. Synthesis of Novel Nanocomposite Fe3O4/ZrO2/Chitosan and Its Application for Removal of Nitrate and Phosphate. Appl. Surf. Sci. 2013, 284, 942–949. https://doi.org/10.1016/j.apsusc.2013.04.013
  41. Nur, T.; Shim, W.G.; Loganathan, P.; Vigneswaran, S.; Kandasamy, J. Nitrate Removal Using Purolite A520E Ion Exchange Resin: Batch and Fixed-Bed Column Adsorption Modelling. Int. J. Environ. Sci. Technol. 2015, 12, 1311–1320. https://doi.org/10.1007/s13762-014-0510-6
  42. Liu, Q.; Hu, P.; Wang, J.; Zhang, L.; Huang, R. Phosphate Adsorption from Aqueous Solutions by Zirconium (IV) Loaded Cross-Linked Chitosan Particles. J. Taiwan Inst. Chem. Eng. 2016, 59, 311–319. https://doi.org/10.1016/j.jtice.2015.08.012
  43. Ali, M.E.A. Synthesis and Adsorption Properties of Chitosan- CDTA-GO Nanocomposite for Removal of Hexavalent Chromium from Aqueous Solutions. Arab. J. Chem. 2018, 11, 1107–1116. https://doi.org/10.1016/j.arabjc.2016.09.010
  44. Purbasari, A.; Ariyanti, D.; Sumardiono, S.; Khairunnisa, K.; Sidharta, T. Adsorption Kinetics and Isotherms of Cu(II) and Fe(II) Ions from Aqueous Solutions by Fly Ash-Based Geopolymer.Chem. Chem. Technol. 2022, 16, 169–176. https://doi.org/10.23939/chcht16.02.169
  45. Nuryanti, S.; Suherman; Rahmawati, S.; Amalia, M.; Santoso, T.; Muhtar, H. Langmuir and Freundlich Isotherm Equation Test on the Adsorption Process of Cu (II) Metal Ions by Cassava Peel Waste (Manihot esculenta crantz). J. Phys. Conf. Ser. 2021, 2126, 012022. https://doi.org/10.1088/1742-6596/2126/1/012022
  46. Radhi, B.D.; Mohammed, W.T. TiO2 Loading on Activated Carbon: Preparation, Characterization, Desulfurization Performance and Isotherm of the Adsorption of Dibenzothiophene from Model Fuel. Egypt. J. Chem. 2022. https://doi.org/10.21608/EJCHEM.2022.109702.5003
  47. Li, M.; Lu, B.; Ke, Q.-F.; Guo, Y.-J.; Guo, Y.-P. Synergetic Effect between Adsorption and Photodegradation on Nanostructured TiO2/Activated Carbon Fiber Felt Porous Composites for Toluene Removal. J. Hazard. Mater. 2017, 333, 88–98. https://doi.org/https://doi.org/10.1016/j.jhazmat.2017.03.019
  48. Jawad, R.J.; Ismail, M.H.S.; Siajam, S.I. Adsorption of Heavy Metals and Residual Oil from Palm Oil Mill Effluent Using a Novel Adsorbent of Alginate and Mangrove Composite Beads Coated with Chitosan in a Packed Bed Column. IIUM Eng. J. 2018, 19, 1–14. https://doi.org/10.31436/iiumej.v19i1.734
  49. Malekbala, M.R.; Soltani, S.M.; Yazdi, S.K.; Hosseini, S. Equilibrium and Kinetic Studies of Safranine Adsorption on Alkali- Treated Mango Seed Integuments. Int. J. Chem. Eng. Appl. 2012, 3, 160–166. https://doi.org/10.7763/ijcea.2012.v3.179