Low-cost magnetic char derived from oily sludge for Methylene Blue dye removal: optimization, isotherm, and kinetic approach

Document Type : Research Paper


1 Department of Environmental Sciences, Faculty of Fisheries and Environmental Sciences, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran

2 Department of Environmental Science, Faculty of Natural Resources, Tarbiat Modares University, Noor, Iran


The excessive increase of dye-contaminated wastewater has become an environmental challenge worldwide, menacing human beings, the environment, and the ecosystem. In light of this subject, the current study for the first time evaluated the potential of oily sludge with its intrinsic magnetic characteristics for Methylene Blue adsorption. A single-step pyrolysis approach was employed to convert oily sludge to magnetic char (Fe3O4/Char). The effects of operational parameters such as pH, contact time, Methylene Blue concentration, and adsorbent dose were examined. The maximum adsorption was 84% with a capacity of 88.71 mg/g at a pH of 3, 100 mg/L Methylene Blue concentration, 100 mg Fe3O4/Char concentration, and 120 min contact time. The Redlich-Peterson isotherm model (R2= 0.9854) best described the adsorption experiment, which revealed that the adsorption process followed a mixed adsorption mechanism, namely physical and chemical adsorption. Moreover, the Elovich kinetic model was more suitable to represent the Methylene Blue adsorption onto Fe3O4/Char, confirming a chemisorption process. The significant function of the sludge-based char with high iron content in the adsorption of Methylene Blue provides insight into the inherent potential of oily sludge as a promising approach for removing hazardous dyes. 

Graphical Abstract

Low-cost magnetic char derived from oily sludge for Methylene Blue dye removal: optimization, isotherm, and kinetic approach


Main Subjects

[1] Xue, H., Wang, X., Xu, Q., Dhaouadi, F., Sellaoui, L., Seliem, M.K., Lamine, A.B., Belmabrouk, H., Bajahzar, A., Bonilla-Petriciolet, A. (2022). Adsorption of methylene blue from aqueous solution on activated carbons and composite prepared from an agricultural waste biomass: A comparative study by experimental and advanced modeling analysis. Chemical engineering journal, 430, 132801.
[2] Zahoor, M., Wahab, M., Salman, S.M., Sohail, A., Ali, E.A., Ullah, R. (2022). Removal of doxycycline from water using Dalbergia sissoo waste biomass based activated carbon and magnetic oxide/activated bioinorganic nanocomposite in batch adsorption and adsorption/membrane hybrid processes. Bioinorganic chemistry and applications, 2694487.
[3] Singh, V., Srivastava, V.C. (2022). Hazardous maize processing industrial sludge: Thermo-kinetic assessment and sulfur recovery by evaporation-condensation technique. Journal of hazardous materials, 424, 127477.
[4] Freeman, H.S., Dos Santos, T.C., Chen, Y., Vendemiatti, J.A., de Oliveira, A.C., Vacchi, F.I., Vinueza, N.R., Umbuzeiro, G.A. (2022). Molecular characterization and ecotoxicological evaluation of the natural dye madder and its chlorinated products. Environmental science and pollution research, 29(16), 24261-24268.
[5] Zhai, S., Li, M., Wang, D., Zhang, L., Yang, Y., Fu, S. (2019). In situ loading metal oxide particles on bio-chars: Reusable materials for efficient removal of methylene blue from wastewater. Journal of cleaner production, 220, 460-474.
[6] Moyo, S., Makhanya, B.P., Zwane, P.E. (2022). Use of bacterial isolates in the treatment of textile dye wastewater: A review. Heliyon, e09632.
[7] Hevira, L., Ighalo, J.O., Aziz, H., Zein, R. (2021). Terminalia catappa shell as low-cost biosorbent for the removal of methylene blue from aqueous solutions. Journal of industrial and engineering chemistry, 97, 188-199.
[8] Jabar, J.M., Odusote, Y.A. (2020). Removal of cibacron blue 3G-A (CB) dye from aqueous solution using chemo-physically activated biochar from oil palm empty fruit bunch fiber. Arabian journal of chemistry, 13(5), 5417-5429.
[9] Dao, T.M., Le Luu, T. (2020). Synthesis of activated carbon from macadamia nutshells activated by H2SO4 and K2CO3 for methylene blue removal in water. Bioresource technology reports, 12, 100583.
[10] Jia, P., Tan, H., Liu, K., Gao, W. (2018). Removal of methylene blue from aqueous solution by bone char. Applied sciences, 8(10), 1903.
[11] Pinheiro, L.R.S., Gradíssimo, D.G., Xavier, L.P., Santos, A.V. (2022). Degradation of Azo Dyes: bacterial potential for bioremediation. Sustainability, 14(3), 1510.
[12] Viswanthan, S.P., Neelamury, S.P., Parakkuzhiyil, S., Njazhakunnathu, G.V., Sebastian, A., Padmakumar, B., Ambatt, T.P. (2020). Removal efficiency of methylene blue from aqueous medium using biochar derived from Phragmites karka, a highly invasive wetland weed. Biomass conversion and biorefinery, 1-17.
[13] Kaya, N., Yıldız, Z., Ceylan, S. (2018). Preparation and characterisation of biochar from hazelnut shell and its adsorption properties for methylene blue dye. Politeknik dergisi, 21(4), 765-776.
[14] Suhaimi, N., Kooh, M.R.R., Lim, C.M., Chou Chao, C.-T., Chou Chau, Y.-F., Mahadi, A.H., Chiang, H.-P., Haji Hassan, N.H., Thotagamuge, R. (2022). The Use of Gigantochloa Bamboo-Derived Biochar for the Removal of Methylene Blue from Aqueous Solution. Adsorption science and technology, 8245797.
[15] Chegini, G., Briens, C., Pjontek, D. (2022). Production and characterization of adsorbents from a hydrothermal char by pyrolysis, carbon dioxide and steam activation. Biomass conversion and biorefinery, 1-17.
[16] Wang, L., Jiang, J., Ma, J., Pang, S., Zhang, T. (2022). A review on advanced oxidation processes homogeneously initiated by copper (II). Chemical engineering journal, 427, 131721.
[17] Karaghool, H.A., Hashim, K., Kot, P., Muradov, M. (2022). Preliminary studies of methylene blue remotion from aqueous solutions by ocimum basilicum. Environments, 9(2), 17.
[18] Ulfa, M., Setiarini, I. (2022). Study The Effect of Zinc Oxide Supported on Gelatin Mesoporous Silica (GSBA-15) on Structural Character and Their Methylene Blue Photodegradation Performance. Bulletin of chemical reaction engineering and catalysis, 17(2), 363-374.
[19] Su, H., Guo, X., Zhang, X., Zhang, Q., Huang, D., Lin, L., Qiang, X. (2022). Ultrafine biosorbent from waste oyster shell: A comparative study of Congo red and Methylene blue adsorption. Bioresource technology reports, 19, 101124.
[20] Dunnett, A.J., Gowland, D., Isborn, C.M., Chin, A.W., Zuehlsdorff, T.J. (2021). Influence of non-adiabatic effects on linear absorption spectra in the condensed phase: Methylene blue. The journal of chemical physics, 155(14), 144112.
[21] Han, F., Zhang, M., Liu, Z., Han, Y., Li, Q., Zhou, W. (2022). Enhancing robustness of halophilic aerobic granule sludge by granular activated carbon at decreasing temperature. Chemosphere, 292, 133507.
[22] Priya, A.K., Gokulan, R., Vijayakumar, A., Praveen, S. 2020. Biodecolorization of remazol dyes using biochar derived from Ulva reticulata: isotherm, kinetics,
desorption, and thermodynamic studies. Desalination and water treatment, 200, 286–295.
[23] Pandey, D., Daverey, A., Dutta, K., Yata, V.K., Arunachalam, K. (2022). Valorization of waste pine needle biomass into biosorbents for the removal of methylene blue dye from water: Kinetics, equilibrium and thermodynamics study. Environmental technology and innovation, 25, 102200.
[24] Hu, M., Deng, W., Hu, M., Chen, G., Zhou, P., Zhou, Y., Su, Y. (2021). Preparation of binder-less activated char briquettes from pyrolysis of sewage sludge for liquid-phase adsorption of methylene blue. Journal of environmental management, 299, 113601.
[25] Ghosh, I., Kar, S., Chatterjee, T., Bar, N., Das, S.K. (2021). Removal of methylene blue from aqueous solution using Lathyrus sativus husk: adsorption study, MPR and ANN modelling. Process safety and environmental protection, 149, 345-361.
[26] Ighalo, J.O., Arowoyele, L.T., Ogunniyi, S., Adeyanju, C.A., Oladipo-Emmanuel, F.M., Belgore, O.R., Omisore, M.O., Adeniyi, A.G. (2021). Utilisation of biomass and hybrid biochar from elephant grass and low density polyethylene for the competitive adsorption of Pb (II), Cu (II), Fe (II) and Zn (II) from aqueous media. Recent innovations in chemical engineering (Formerly recent patents on chemical engineering), 14(2), 148-159.
[27] Sachdev, D., Shrivastava, H., Sharma, S., Srivastava, S., Tadepalli, S., Bhullar, N.K., Sahu, O.P. (2022). Potential for hydrothermally separated groundnut shell fibers for removal of methylene blue dye. Materials today: proceedings, 48, 1559-1568.
[28] KÜÇÜK, İ., Yunus, Ö., BAŞAR, C. (2021). The activated carbon from walnut shell using CO2 and methylene blue removal. Dicle Üniversitesi Mühendislik Fakültesi Mühendislik Dergisi, 12(2), 297-308.
[29] Shelke, H.D., Machale, A.R., Survase, A.A., Pathan, H.M., Lokhande, C.D., Lokhande, A.C., Shaikh, S.F., Palaniswami, M. (2022). Multifunctional Cu2SnS3 Nanoparticles with Enhanced Photocatalytic Dye Degradation and Antibacterial Activity. Materials, 15(9), 3126.
[30] Sarojini, G., Babu, S.V., Rajamohan, N., Rajasimman, M., Pugazhendhi, A. (2022). Application of a polymer-magnetic-algae based nano-composite for the removal of methylene blue–characterization, parametric and kinetic studies. Environmental pollution, 292, 118376.
[31] Shahnaz, T., Bedadeep, D., Narayanasamy, S. (2022). Investigation of the adsorptive removal of methylene blue using modified nanocellulose. International journal of biological macromolecules, 200, 162-171.
[32] Feizi, F., Sarmah, A.K., Rangsivek, R., Gobindlal, K. (2022). Adsorptive removal of propranolol under fixed-bed column using magnetic tyre char: Effects of wastewater effluent organic matter and ball milling. Environmental pollution, 305, 119283.
[33] Li, J., Han, L., Zhang, T., Qu, C., Yu, T., Yang, B. (2022). Removal of Methylene Blue by Metal Oxides Supported by Oily Sludge Pyrolysis Residues. Applied sciences, 12(9), 4725.
[34] Jabar, J.M., Odusote, Y.A., Ayinde, Y.T., Yılmaz, M. (2022). African almond (Terminalia catappa L) leaves biochar prepared through pyrolysis using H3PO4 as chemical activator for sequestration of methylene blue dye. Results in engineering, 14, 100385.
[35] Liu, Y., Jiang, Z., Fu, J., Ao, W., Siyal, A.A., Zhou, C., Liu, C., Dai, J., Yu, M., Zhang, Y. (2022). Iron-biochar production from oily sludge pyrolysis and its application for organic dyes removal. Chemosphere, 301, 134803.
[36] Zhang, J., Cai, D., Zhang, G., Cai, C., Zhang, C., Qiu, G., Zheng, K., Wu, Z. (2013). Adsorption of methylene blue from aqueous solution onto multiporous palygorskite modified by ion beam bombardment: Effect of contact time, temperature, pH and ionic strength. Applied clay science, 83, 137-143.
[37] Huang, W., Pan, S., Yu, Q., Liu, X., Liu, Y., Liu, R. (2019). Adsorption performance of methyl blue onto magnetic Ni (1− x− y) CuyZnxFe2O4 nanoparticles prepared by a novel alcohol-assisted combustion method. Journal of Inorganic and organometallic polymers and materials, 29(5), 1755-1766.
[38] Peer, F.E., Bahramifar, N., Younesi, H. (2018). Removal of Cd (II), Pb (II) and Cu (II) ions from aqueous solution by polyamidoamine dendrimer grafted magnetic graphene oxide nanosheets. Journal of the Taiwan Institute of Chemical Engineers, 87, 225-240.
[39] Saffari, M., Moazallahi, M. (2022). Evaluation of slow-pyrolysis process effect on adsorption characteristics of cow bone for Ni ion removal from Ni-contaminated aqueous solutions. Pollution, 8(3), 1076-1087.
[40] Das, S., Goud, V.V. (2020). Characterization of a low-cost adsorbent derived from agro-waste for ranitidine removal. Materials science for energy technologies, 3, 879-888.
[41] Padmapriya, M., Ramesh, S., Biju, V. (2022). Synthesis of seawater based geopolymer: characterization and adsorption capacity of methylene blue from wastewater. Materials Today: Proceedings, 51, 1770-1776.
[42] Villabona-Ortíz, Á., Figueroa-Lopez, K.J., Ortega-Toro, R. (2022). Kinetics and Adsorption Equilibrium in the Removal of Azo-Anionic Dyes by Modified Cellulose. Sustainability, 14(6), 3640.
[43] Kooh, M.R.R., Thotagamuge, R., Chau, Y.-F.C., Mahadi, A.H., Lim, C.M. (2022). Machine learning approaches to predict adsorption capacity of Azolla pinnata in the removal of methylene blue. Journal of the Taiwan Institute of Chemical Engineers, 132, 104134.
[44] Jia, S., Han, H., Hou, B., Zhuang, H., Fang, F., Zhao, Q. (2014). Treatment of coal gasification wastewater by membrane bioreactor hybrid powdered activated carbon (MBR–PAC) system. Chemosphere, 117, 753-759.
[45] Gao, Y., Hao, B., Xue, N., Wang, Y., Xiao, H., Huang, X., Shi, B. (2022). Steam activation tuned porous structure and surface wetting behaviors of mesoporous biochars for corrosive oily wastewater treatments. Journal of Chemical Technology & Biotechnology, 2179-2185.
[46] Elmorsi, R.R., Abou-El-Sherbini, K.S., Shehab El-Dein, W.A., Lotfy, H.R. (2022). Activated eco-waste of Posidonia oceanica rhizome as a potential adsorbent of methylene blue from saline water. Biomass Conversion and Biorefinery, 1-14.
[47] 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. Journal of hazardous materials, 402, 123579.
[48] Bounaas, M., Bouguettoucha, A., Chebli, D., Gatica, J.M., Vidal, H. (2021). Role of the wild carob as biosorbent and as precursor of a new high-surface-area activated carbon for the adsorption of methylene blue. Arabian journal for science and engineering, 46(1), 325-341.
[49] To, M.-H., Hadi, P., Hui, C.-W., Lin, C.S.K., Tareq, A.-A., Saleem, J., Parthasarathy, P., McKay, G. (2019). Waste biomass gasification char derived activated carbon for pharmaceutical carbamazepine removal from water. Resources environment and information engineering, 1(1), 36-44.
[50] Tang, S.H., Zaini, M.A.A. (2019). Isotherm studies of malachite green removal by yarn processing sludge-based activated carbon. Chemistry-didactics-ecology-metrology, 24.
[51] Shikuku, V.O., Mishra, T. (2021). Adsorption isotherm modeling for methylene blue removal onto magnetic kaolinite clay: a comparison of two-parameter isotherms. Applied water science, 11(6), 1-9.
[52] Ettish, M.N., El-Sayyad, G.S., Elsayed, M.A., Abuzalat, O. (2021). Preparation and characterization of new adsorbent from Cinnamon waste by physical activation for removal of Chlorpyrifos. Environmental challenges, 5, 100208.
[53] Dermawan, D., Febrianti, A.N., Setyawati, E.E.P., Pham, M.-T., Jiang, J.-J., You, S.-J., Wang, Y.-F. (2022). The potential of transforming rice straw (Oryza sativa) and golden shower (Cassia fistula) seed waste into high-efficiency biochar by atmospheric pressure microwave plasma. Industrial Crops and Products, 185, 115122.
[54] Xiao, Y., Tian, L., Liu, X. (2022). Kinetic mechanism on elemental mercury adsorption by brominated petroleum coke in simulated flue gas. RSC Advances, 12(26), 16386-16395.
[55] Chandarana, H., Kumar, P.S., Seenuvasan, M., Kumar, M.A. (2021). Kinetics, equilibrium and thermodynamic investigations of methylene blue dye removal using Casuarina equisetifolia pines. Chemosphere, 285, 131480.
[56] Fakhar, N., Khan, S.A., Khan, T.A., Siddiqi, W.A. (2022). Efficiency of iron modified Pyrus pyrifolia peels biochar as a novel adsorbent for methylene blue dye abatement from aqueous phase: equilibrium and kinetic studies. International Journal of Phytoremediation, 1-11.
[57] Amin, M.T., Alazba, A.A., Shafiq, M. (2021). Successful application of eucalyptus camdulensis biochar in the batch adsorption of crystal violet and methylene blue dyes from aqueous solution. Sustainability, 13(7), 3600.
[58] Kasemodel, M.C., Romão, E.L., Papa, T.B.R. (2022). Adsorption of methylene blue on babassu coconut (Orbignya speciosa) Mesocarp commercial biochar, Research square, 1-21.