Kinetic, Isotherm, and Thermodynamic Modeling of Methylene Blue Adsorption by Hibiscus Plant Waste Derived Biosorbents
محورهای موضوعی :Khaled Muftah Elsherif 1 , Abdulfattahaz Mohamed Alkherraz 2 , Aisha Hussein Madri 3 , Abdelmeneim Eldali 4 , Maysson Mohammed Yaghi 5
1 - Libyan Authority for Scientific Research, Tripoli, Libya
2 - Chemistry Department, Faculty of Science, Misurata University, Misurata, Libya
3 - Chemistry Department, Faculty of Science, Misurata University, Misurata, Libya
4 - Libyan Authority for Scientific Research, Tripoli, Libya
5 - Department of Chemistry, Faculty of Science Al-Abyar, University of Benghazi, Benghazi, Libya
کلید واژه: Methylene blue, Biosorption, Isotherms, Kinetics, Thermodynamics,
چکیده مقاله :
Dye pollution is a severe environmental issue for which there are no short-term fixes. Adsorption has become the most popular method for removing dyes because of its remarkable effectiveness, ease of use, affordability, and environmental friendliness. This study intends to assess how well two biosorbents; dried powder (DHM) and charcoal (CHM), made from hibiscus plant debris remove methylene blue (MB) from aqueous solutions. Adsorption kinetics, isotherms, and thermodynamics were examined in order to better understand the adsorption mechanisms. The adsorption capacity and efficiency of methylene blue on both adsorbent materials were assessed using the batch adsorption experiment. Several parameters, including pH, initial dye concentration, contact time, adsorbent dosage, and temperature, were examined in relation to the biosorption process. For both biosorbents, the biosorption equilibrium was reached in 20 min, and at pH 10.5, the maximum adsorption capacities were 11.60 and 11.80 mg g-1 for DHM and CHM, respectively. Despite not going through the extra activation step, CHM was assessed in its non-activated condition and, surprisingly, showed equal or even slightly superior MB adsorption ability than DHM. The experimental data was well-fitted by the Freundlich and pseudo-second-order models, indicating a physical adsorption mechanism. The thermodynamic study's conclusions demonstrated that MB's adsorption on CHM was non-spontaneous and endothermic, with positive values for ΔHo (15.900 kJ mol-1), ΔGo (0.404 kJ mol-1), and ΔSo (0.052 kJ mol-1 K-1). The MB adsorption on DHM, on the other hand, was exothermic and spontaneous, with negative values for ΔGo (-5.41 kJ mol-1), ΔHo (-42.36 kJ mol-1), and ΔSo (-0.124 kJ mol-1 K-1). The study's findings demonstrate that hibiscus plant waste can be utilised as an inexpensive, environmentally beneficial biosorbent to remove MB from wastewater.
Dye pollution is a severe environmental issue for which there are no short-term fixes. Adsorption has become the most popular method for removing dyes because of its remarkable effectiveness, ease of use, affordability, and environmental friendliness. This study intends to assess how well two biosorbents; dried powder (DHM) and charcoal (CHM), made from hibiscus plant debris remove methylene blue (MB) from aqueous solutions. Adsorption kinetics, isotherms, and thermodynamics were examined in order to better understand the adsorption mechanisms. The adsorption capacity and efficiency of methylene blue on both adsorbent materials were assessed using the batch adsorption experiment. Several parameters, including pH, initial dye concentration, contact time, adsorbent dosage, and temperature, were examined in relation to the biosorption process. For both biosorbents, the biosorption equilibrium was reached in 20 min, and at pH 10.5, the maximum adsorption capacities were 11.60 and 11.80 mg g-1 for DHM and CHM, respectively. Despite not going through the extra activation step, CHM was assessed in its non-activated condition and, surprisingly, showed equal or even slightly superior MB adsorption ability than DHM. The experimental data was well-fitted by the Freundlich and pseudo-second-order models, indicating a physical adsorption mechanism. The thermodynamic study's conclusions demonstrated that MB's adsorption on CHM was non-spontaneous and endothermic, with positive values for ΔHo (15.900 kJ mol-1), ΔGo (0.404 kJ mol-1), and ΔSo (0.052 kJ mol-1 K-1). The MB adsorption on DHM, on the other hand, was exothermic and spontaneous, with negative values for ΔGo (-5.41 kJ mol-1), ΔHo (-42.36 kJ mol-1), and ΔSo (-0.124 kJ mol-1 K-1). The study's findings demonstrate that hibiscus plant waste can be utilised as an inexpensive, environmentally beneficial biosorbent to remove MB from wastewater.
1. Nizam N.U.M., Hanafiah M.M., Mahmoudi E., Halim A.A., Mohammad A.W., 2021. The Removal of Anionic and Cationic Dyes from an Aqueous Solution Using Biomass-Based Activated Carbon. Sci Rep. 11(1), 8623. https://doi.org/10.1038/s41598-021-88084-z.
2. El Hashani A., Ben Khayal N., Elsherif K.M., 2018. Selective Transport of Aromatic Compounds across Parchment Supported Prussian blue Membrane. Chem. Methodol. 2(3), 194–203. https://doi.org/10.22034/chemm.2018.60860.
3. Elsherif K.M., El-Hashani A., El-Dali A., 2013. Potentiometric Determination of Fixed Charge Density and Permselectivity for Thallium Chromate Membrane. Ann Chem Forsch. 1(3), 15–25.
4. Alkherraz A.M., Elsherif K.M., El-Dali A., Blayblo N.A., Sasi M., 2022. Thermodynamic, Equilibrium, and Kinetic Studies of Safranin Adsorption onto Carpobrotus Edulis. Asian J Nanosci Mater. 5(2), 118–131. https://doi.org/10.26655/ajnanomat.2022.2.4.
5. Elsherif K.M., El-Hashani A., El-Dali A., El-kailany R., 2014. Bi-Ionic Potential Studies for Thallium Chromate Parchment-Supported Membrane. Int J Res Pharm Chem. 4(2), 267–273.
6. Sahu S., Pahi S., Tripathy S., Singha S.K., Behera A., Sahu U.K., Patel R.K., 2020. Adsorption of Methylene Blue on Chemically Modified Lychee Seed Biochar: Dynamic, Equilibrium, and Thermodynamic Study. J Mol Liq. 315, 113743. https://doi.org/10.1016/j.molliq.2020.113743.
7. Elsherif K.M., El-Dali A., Alkarewi A.A., Ewlad-Ahmed A.M., Treban A. 2021. Adsorption of Crystal Violet Dye onto Olive Leaves Powder: Equilibrium and Kinetic Studies. Chem Int. 7(2), 79–89. https://doi.org/10.5281/zenodo.4441851.
8. Tang X., Ran G., Li J., Zhang Z., Xiang C., 2021. Extremely Efficient and Rapidly Adsorb Methylene Blue Using Porous Adsorbent Prepared from Waste Paper: Kinetics and Equilibrium Studies. J Hazard Mater. 402, 123579. https://doi.org/ 10.1016/j. jhazmat.2020.123579.
9. Elsherif K.M., El-Hashani A., El-Dali A., Saad M., 2014. Ion-Permeation Rate of (1:1) Electrolytes across Parchment-Supported Silver Chloride Membrane. Int J Chem Pharm Sci. 2 (6), 890–897.
10. Alkherraz A.M., Elsherif K.M., Blayblo N.A., 2023. Safranin Adsorption onto Acasia Plant Derived Activated Carbon: Isotherms, Thermodynamics and Kinetic Studies. Chem Int. 9(4), 134–145. https://doi.org/10.5281/zenodo.8127687.
11. Djama C., Bouguettoucha A., Chebli D., Amrane A., Tahraoui H., Zhang J., Mouni L., 2023. Experimental and Theoretical Study of Methylene Blue Adsorption on a New Raw Material, Cynara Scolymus—A Statistical Physics Assessment. Sustainability. 15(13), 10364. https://doi.org/ 10.3390/su151310364.
12. Bouguettoucha A., Chebli D., Mekhalef T., Noui A., Amrane A., 2015. The Use of a Forest Waste Biomass, Cone of Pinus Brutia for the Removal of an Anionic Azo Dye Congo Red from Aqueous Medium. Desalin. Water Treat. 55(7), 1956–1965. https://doi.org/10.1080/19443994.2014.928235.
13. Elsherif K.M., El-Hashani A., El-Dali A., Musa M., 2014. Ion Selectivity across Parchment-Supported Silver Chloride Membrane in Contact with Multi-Valent Electrolytes. Int J Anal Bioanal Chem. 4(2), 58–62.
14. Kuang Y., Zhang X., Zhou S., 2020. Adsorption of Methylene Blue in Water onto Activated Carbon by Surfactant Modification. Water. 12(2), 587. https://doi.org/10.3390/w12020587.
15. Tan I.A.W., Ahmad A.L., Hameed B.H., 2008. Adsorption of Basic Dye on High-Surface Area Activated Carbon Prepared from Coconut Husk: Equilibrium, Kinetic and Thermodynamic Studies. J Hazard Mater. 154, 337–346. https://doi.org/10.1016/j.jhazmat.2007.10.031.
16. Zaidi Z., Manchanda A., Sharma A., Shehnaz, Choudhry A., Sajid M., Khan S.A., Khan A., Chaudhry S.A., 2023. Adsorptive Removal of Methylene Blue Using Fruit Waste Activated Carbon and Its Binary Metal Oxide Nanocomposite. Chem Eng J Adv. 16, 100571. https://doi.org/ 10.1016/j.ceja.2023.100571.
17. Elsherif K.M., El-Hashani A., El-Dali A., El-kailany R., 2014. Bi-Ionic Potential Studies for Silver Thiosulphate Parchment-Supported Membrane. Int. J. Adv. Sci. Tech. Res. 1 (4), 638–646.
18. Sharma A., Mangla D., Choudhry A., Sajid M., Chaudhry S.A., 2022. Facile Synthesis, Physico-Chemical Studies of Ocimum Sanctum Magnetic Nanocomposite and Its Adsorptive Application against Methylene Blue. J Mol Liq. 362, 119752. https://doi.org/10.1016/j.molliq.2022.119752.
19. Alkherraz A.M., Ali A.K., Elsherif K.M., 2020. Removal of Pb(II), Zn(II), Cu(II) and Cd(II) from Aqueous Solutions by Adsorption onto Olive Branches Activated Carbon: Equilibrium and Thermodynamic Studies. Chem Int. 6(1), 11–20. https://doi.org/10.5281/zenodo.2579465.
20. Han Q., Wang J., Goodman B.A., Xie J., Liu Z., 2020. High Adsorption of Methylene Blue by Activated Carbon Prepared from Phosphoric Acid Treated Eucalyptus Residue. Powder Technol. 366, 239–248. https://doi.org/10.1016/j.powtec.2020.02.013.
21. Alkherraz A.M., Ali A.K., Elsherif K.M., 2020. Equilibrium and Thermodynamic Studies of Pb(II), Zn(II), Cu(II) and Cd(II) Adsorption onto Mesembryanthemum Activated Carbon. J Med Chem Sci. 3 (1), 1–10. https://doi.org/ 10.33945/SAMI/JMCS.2020.1.1.
22. Sivakumar R., Lee N.Y., 2022. Adsorptive Removal of Organic Pollutant Methylene Blue Using Polysaccharide-Based Composite Hydrogels. Chemosphere. 286, 131890. https://doi.org/10.1016/j.chemosphere.2021.131890.
23. Elsherif K.M., El-Hashani A., Haider I., 2018. Biosorption of Fe (III) onto Coffee and Tea Powder: Equilibrium and Kinetic Study. Asian J Green Chem. 2(4), 380–394. https://doi .org/10.22034/ ajgc.2018.65163.
24. Elsherif K.M., Ewlad-Ahmed A.M., Treban A., 2017. Removal of Fe (III), Cu (II), and Co (II) from Aqueous Solutions by Orange Peels Powder: Equilibrium Study. World J Biochem Mol Biol. 2(6), 46–51.
25. Meili L., Lins P.V.S., Costa M.T., Almeida R.L., Abud A.K.S., Soletti J.I., Dotto G.L., Tanabe E.H., Sellaoui L., Carvalho S.H.V., Erto A., 2019. Adsorption of Methylene Blue on Agroindustrial Wastes: Experimental Investigation and Phenomenological Modelling. Prog Biophys Mol Biol. 141, 60–71. https://doi.org/10.1016/j.pbiomolbio.2018.07.011.
26. Li H., Budarin V.L., Clark J.H., North M., Wu X., 2022. Rapid and Efficient Adsorption of Methylene Blue Dye from Aqueous Solution by Hierarchically Porous, Activated Starbons®: Mechanism and Porosity Dependence. J Hazard Mater. 436, 129174. https://doi.org/ 10.1016/j.jhazmat.2022.129174.
27. Elsherif K.M., El-Hashani A., El-Dali A., 2013. Potentiometric Determination of Fixed Charge Density and Permselectivity for Silver Thiosulphate Membrane. J Appl Chem. 2(6), 1543–1551.
28. Miyah Y., Lahrichi A., Idrissi M., Khalil A., Zerrouq F., 2018. Adsorption of Methylene Blue Dye from Aqueous Solutions onto Walnut Shells Powder: Equilibrium and Kinetic Studies. Surf Interfaces. 11, 74–81. https://doi.org/10.1016/j.surfin.2018.03.006.
29. Üner O., Geçgel Ü., Bayrak Y., 2016. Adsorption of Methylene Blue by an Efficient Activated Carbon Prepared from Citrullus Lanatus Rind: Kinetic, Isotherm, Thermodynamic, and Mechanism Analysis. Water Air Soil Pollut. 227(7), 247. https://doi.org/10.1007/s11270-016-2949-1.
30. Adesina A.O., Elvis O.A., Mohallem N.D.S., Olusegun S.J., 2021. Adsorption of Methylene Blue and Congo Red from Aqueous Solution Using Synthesized Alumina–Zirconia Composite. Environ Technol. 42(7), 1061-1070. https://doi.org/10. 1080/09593330.2019.1652696.
31. Lelifajri, Rahmi, Supriatno, Susilawati, Indarum A.S.M., 2020. Study on Methylene Blue Dye Adsorption in Aqueous Solution by Heat-Treated Gnetum Gnemon Shell Waste Particles as Low-Cost Adsorbent. AIP Conf. Proc. 2243, 020012. https://doi.org/10.1063/5.0001358.
32. Vargas A.M.M., Cazetta A.L., Kunita M.H., Silva T.L., Almeida V.C., 2011. Adsorption of Methylene Blue on Activated Carbon Produced from Flamboyant Pods (Delonix Regia): Study of Adsorption Isotherms and Kinetic Models. Chem Eng J. 168, 722–730. https://doi.org/ 10.1016/j.cej.2011.01.067.
33. Thang N.H., Khang D.S., Hai T.D., Ngac D.T., Tuan P.D., 2021. Methylene Blue Adsorption Mechanism of Activated Carbon Synthesized from Cashew Nut Shells. RSC Adv. 11, 26563. https://doi.org/10.1039/d1ra04672a.
34. He X., Male K.B., Nesterenko P.N., Brabazon D., Paull B., Luong J.H.T., 2013 Adsorption and Desorption of Methylene Blue on Porous Carbon Monoliths and Nanocrystalline Cellulose. ACS Appl Mater Interfaces. 5, 8796–8804. https://doi.org/10.1021/am403222u.
35. Derakhshan Z., Baghapour M.A., Ranjbar M., Faramarzian M., 2013. Adsorption of Methylene Blue Dye from Aqueous Solutions by Modified Pumice Stone: Kinetics and Equilibrium Studies. Health Scope. 2(3), 136–144. https://doi.org/10.17795/jhealthscope-12492.
36. Gao J.J., Qin Y.B., Zhou T., Cao D.D., Xu P., Hochstetter D., Wang Y.F., 2013 Adsorption of Methylene Blue onto Activated Carbon Produced from Tea (Camellia Sinensis L.) Seed Shells: Kinetics, Equilibrium, and Thermodynamics Studies. J Zhejiang Univ Sci. B14(7), 650–658. https://doi.org/10.1631/jzus.B12a0225.
37. Liu Q.X., Zhou Y.R., Wang M., Zhang Q., Ji T., 2019. Adsorption of Methylene Blue from Aqueous Solution onto Viscose-Based Activated Carbon Fiber Felts: Kinetics and Equilibrium Studies. Adsorpt Sci Technol. 37(3-4), 312–332. https://doi.org/10.1177/0263617419827437.
38. El-Shafie A.S., Karamshahi F., El-Azazy M., 2023. Turning Waste Avocado Stones and Montmorillonite into Magnetite-Supported Nanocomposites for the Depollution of Methylene Blue: Adsorbent Reusability and Performance Optimization. Environ Sci Pollut Res. No Pagination Specified. 30, 118764–118781. https://doi.org/10.1007/s11356-023-30538-0.
39. Elashery S.E.A., El-Bouraie M.M., Abdelgawad E.A., Attia N.F., Mohamed G.G., 2023. Adsorptive Performance of Bentonite-Chitosan Nanocomposite as a Dual Antibacterial and Reusable Adsorbent for Reactive Red 195 and Crystal Violet Removal: Kinetic and Thermodynamic Studies. Biomass Convers Biorefin. https://doi.org/10.1007/s13399-023-05059-y.
40. Amode J.O., Santos J.H., Alam Z.M., Mirza A.H., Mei C.C., 2016. Adsorption of Methylene Blue from Aqueous Solution Using Untreated and Treated (Metroxylon Spp.) Waste Adsorbent: Equilibrium and Kinetics Studies. Int J Ind Chem. 7, 333–345. https://doi.org/10.1007/s40090-016-0085-9.
41. Elsherif K.M., Saad R.A.A., Ewlad-Ahmed A.M., Treban A.A., Iqneebir A.M., 2024. Adsorption of Cd(II) onto Olive Stones Powder Biosorbent: Isotherms and Kinetic Studies. Adv. J Chem Sect. A7(1), 59–74. https://doi.org/ 10.48309/ ajca.2024.415865.1415.
42. Alkherraz A.M., Ali A.K. El-Dali A., Elsherif K.M., 2019. Biosorption Study of Zn(II), Cu(II), Pb(II) And Cd(II) Ions by Palm Leaves Activated Carbon. To Chem. 4(2019), 8–17.
43. Elsherif K.M., El-Dali A., Ewlad-Ahmed A.M., Treban A.A., Alqadhi H., Alkarewi S., 2022. Kinetics and Isotherms Studies of Safranin Adsorption onto Two Surfaces Prepared from Orange Peels. Mor J Chem. 10(4), 639–651. https://doi.org/10.48317/IMIST.PRSM/morjchem-v11i1.32137.
44. El-Bery H.M., Saleh M., El-Gendy R.A., Saleh M.R., Thabet S.M., 2022. High Adsorption Capacity of Phenol and Methylene Blue Using Activated Carbon Derived from Lignocellulosic Agriculture Wastes. Sci Rep. 12(1), 5499. https://doi.org/10.1038/s41598-022-09475-4.
45. Elsherif K.M., Haider I., El-Hashani A., 2019. Adsorption of Co (II) Ions from Aqueous Solution onto Tea and Coffee Powder: Equilibrium and Kinetic Studies. J Fundam Appl Sci. 11(1), 65–81. https://doi.org/10.4314/jfas.v11i1.5.
46. Elsherif K.M., El-Hashani A., Haider I., 2018. Equilibrium and Kinetic Studies of Cu (II) Biosorption Onto Waste Tea and Coffee Powder (WTCP). Iran J Anal Chem. 5(2), 31–38. https://doi.org/20.1001.1.23832207.2018.5.2.5.4.
47. El-Hashani A., Elsherif K.M., Edbey K., Alfaqih F., Alomammy M., Alomammy S., 2018. Biosorption of Eriochrome Black T (EBT) onto Waste Tea Powder: Equilibrium and Kinetic Studies. To Chem. 1(3), 263–275.
48. Elsherif K.M., El-Dali A., Ewlad-Ahmed A.M., Treban A., Alttayib I., 2021. Removal of Safranin Dye from Aqueous Solution by Adsorption onto Olive Leaves Powder. J Mater Environ Sci. 12(3), 418–430.
49. Mohamed F., Shaban M., Zaki S.K., Abd-Elsamie M.S., Sayed R., Zayed M., Khalid N., Saad S., Omar S., Ahmed A.M., Gerges A., Abd El-Mageed H.R., Soliman N.K., 2022. Activated Carbon Derived from Sugarcane and Modified with Natural Zeolite for Efficient Adsorption of Methylene Blue Dye: Experimentally and Theoretically Approaches. Sci Rep. 12(18031). https://doi.org/10.1038/s41598-022-22421-8.
50. Fito J., Abewaa M., Mengistu A., Angassa K., Ambaye A.D., Moyo W., Nkambule T., 2023. Adsorption of Methylene Blue from Textile Industrial Wastewater Using Activated Carbon Developed from Rumex Abyssinicus Plant. Sci Rep. 13, 5427. https://doi.org/10.1038/s41598-023-32341-w.
51. Alardhi S.M., Salih H.G., Ali N.S., Khalbas A.H., Salih I.K., Cata Saady N.M., Zendehboudi S., Albayati T.M., Harharah H.N., 2023. Olive Stone as an Eco-Friendly Bio-Adsorbent for Elimination of Methylene Blue Dye from Industrial Wastewater. Sci Rep. 13, 21063. https://doi.org/10.1038/s41598-023-47319-x.
52. Modi S., Yadav V.K., Ali D., Choudhary N., Alarifi S., Sahoo D.K., Patel A., Fulekar M.H., 2023. Photocatalytic Degradation of Methylene Blue from Aqueous Solutions by Using Nano-ZnO/Kaolin-Clay-Based Nanocomposite. Water. 15(22), 3915. https://doi.org/10.3390/w15223915.
53. Turp S.M., Turp G.A., Ekinci N., Özdemir S., 2020. Enhanced Adsorption of Methylene Blue from Textile Wastewater by Using Natural and Artificial Zeolite. Water Sci. Technol. 82(3), 513–523. https://doi.org/10.2166/wst.2020.358.
54. Wang G., Wang S., Sun Z., Zheng S., Xi Y., 2017. Structures of Nonionic Surfactant Modified Montmorillonites and Their Enhanced Adsorption Capacities towards a Cationic Organic Dye. Appl Clay Sci. 148, 1–10. https://doi.org/10.1016/j.clay.2017.08.001.
55. Santoso E., Ediati R., Kusumawati Y., Bahruji H., Sulistiono D.O., Prasetyoko D., 2020. Review on Recent Advances of Carbon Based Adsorbent for Methylene Blue Removal from Waste Water. Mater Today Chem. 16, 100233. https://doi.org /10.1016/j.mtchem.2019.100233.
56. Zhang J., Zhou Q., Ou L., 2012. Kinetic, Isotherm, and Thermodynamic Studies of the Adsorption of Methyl Orange from Aqueous Solution by Chitosan/Alumina Composite. J Chem Eng Data. 57(2), 412–419. https://doi.org/10.1021/je2009945.
57. Vairavel P., Rampal N., Jeppu G., 2023. Adsorption of Toxic Congo Red Dye from Aqueous Solution Using Untreated Coffee Husks: Kinetics, Equilibrium, Thermodynamics and Desorption Study. Int J Environ Anal Chem. 103(12), 2789-2808. https://doi.org/ 10.1080/ 03067319. 2021.1897982.
58. Lafi R., Montasser I., Hafiane A., 2019. Adsorption of Congo Red Dye from Aqueous Solutions by Prepared Activated Carbon with Oxygen-Containing Functional Groups and Its Regeneration. Adsorpt Sci Technol. 37(1–2), 160–181. https://doi.org/10.1177/0263617418819227.
59. Djilani C., Zaghdoudi R., Djazi F., Bouchekima B., Lallam A., Modarressi A., Rogalski M., 2015. Adsorption of Dyes on Activated Carbon Prepared from Apricot Stones and Commercial Activated Carbon. J Taiwan Inst Chem Eng. 53, 112–121. https://doi.org/10.1016/j.jtice.2015.02.025.