FLUORIDE REMOVAL WITH CALCIUM OXIDE-ALUMINA SPHERES

Yıl 2025, Cilt: 13 Sayı: 4, 1208 - 1226, 30.12.2025

Şebnem Muratoğlu , Fatma Burcu Alp , Mehmet Gönen

https://doi.org/10.21923/jesd.1794296

Öz

In this study, calcium oxide (CaO) and alumina (Al2O3) composite spheres were synthesized and their performance in fluoride removal was investigated. The CaO-Al2O3 spheres were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), Brunauer-Emmett-Teller (BET) surface area, Fourier Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD). The data obtained from batch adsorption experiments were evaluated by Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D-R) isotherm models. The maximum adsorption capacity (qm) was found to be 1.488 mg.g-1. The adsorption energy calculated from the D-R isotherm model (E>8 kJ.mol-1) indicated chemical adsorption. Adsorption kinetics were investigated by pseudo-first-order (PFO), pseudo-second-order (PSO) and intraparticle diffusion kinetic models. It was found to be compatible with the PSO model. Thermodynamic analyses showed that the process was spontaneous (ΔG<0), endothermic (ΔH>0), and chemical adsorption (ΔH>40 kJ.mol-1). A positive ΔS value indicated that the degrees of freedom at the solid-liquid interface increased, and that the adsorption efficiency increased with increasing temperature.

Anahtar Kelimeler

Fluoride Removal , Adsorption , Calcium Oxide-Alumina Sphere , Water Treatment

Proje Numarası

FYL-2025-9847

KALSİYUM OKSİT-ALUMİNA KÜRELERİ İLE FLORÜR GİDERİMİ

Öz

Bu çalışmada, kalsiyum oksit (CaO) ve alümina (Al2O3) kompozit küreleri sentezlenerek florür giderimindeki performansları araştırılmıştır. CaO-Al2O3 küreleri taramalı elektron mikroskobu (SEM), enerji dağılımlı X-ışını spektroskopisi (EDX), Brunauer-Emmett-Teller (BET) yüzey alanı, Fourier Dönüşümlü Kızılötesi Spektroskopisi (FTIR) ve X-ışını kırınımı (XRD) ile karakterize edilmiştir. Kesikli adsorpsiyon deneyleri sonucunda elde edilen veriler Langmuir, Freundlich, Temkin ve Dubinin–Radushkevich (D-R) izoterm modelleri ile değerlendirilmiştir. Maksimum adsorpsiyon kapasitesi (qm) 1,488 mg.g-1 bulunmuştur. D-R izoterm modelinden hesaplanan adsorpsiyon enerjisi (E>8 kJ.mol-1) kimyasal adsorpsiyona işaret etmiştir. Adsorpsiyon kinetiği yalancı birinci dereceden (PFO), yalancı ikinci dereceden (PSO) ve partikül içi difüzyon kinetik modelleri ile incelenmiştir. PSO model ile uyumlu olduğu görülmüştür. Termodinamik analizler, sürecin kendiliğinden (ΔG<0), endotermik (ΔH>0) ve kimyasal adsorpsiyon (ΔH>40 kJ.mol-1) olduğunu göstermiştir. Pozitif S değeri katı-sıvı ara yüzeyindeki serbestlik derecesinin arttığını göstermiştir ve artan sıcaklıkla birlikte adsorpsiyon veriminin yükseldiğini ortaya koymuştur.

Anahtar Kelimeler

Florür Giderimi , Adsorpsiyon , Kalsiyum Oksit-Alümina Küreleri , Su Arıtımı

Destekleyen Kurum

Süleyman Demirel Üniversitesi Bilimsel Araştırma Projeleri Koordinasyon Birimi

Proje Numarası

FYL-2025-9847

Kaynakça

• Abin-Bazaine, A., Trujillo, A. C., & Olmos-Marquez, M. (2022). Adsorption isotherms: Enlightenment of the phenomenon of adsorption. In Wastewater treatment (Cilt). IntechOpen.
• Ahmad, K., Shah, I. A., Ali, S., Khan, M. T., Qureshi, M. B. A., Shah, S. H. A., Ali, A., Rashid, W., & Gul, H. N. (2022). Synthesis and evaluation of Ca-doped ferrihydrite as a novel adsorbent for the efficient removal of fluoride. Environmental Science and Pollution Research, 29(4), 6375-6388.
• Alhassan, S. I., Huang, L., He, Y., Yan, L., Wu, B., & Wang, H. (2021). Fluoride removal from water using alumina and aluminum-based composites: A comprehensive review of progress. Critical reviews in environmental science and technology, 51(18), 2051-2085.
• Alkurdi, S. S., Al-Juboori, R. A., Bundschuh, J., & Hamawand, I. (2019). Bone char as a green sorbent for removing health threatening fluoride from drinking water. Environment international, 127, 704-719.
• Amor, A. A., Messaitfa, A., Tabchouche, A., ben Abdeslam, S., Zighmi, S., Amor, F. Z. A., & Omar, A. A. (2025). Biosorption of fluoride ions from drinking water at southern Algeria using the eggshell waste beads in an up flow packed bed column: A chemical study and solution modeling. Desalination, 600, 118521.
• Anirudhan, T., & Radhakrishnan, P. (2008). Thermodynamics and kinetics of adsorption of Cu (II) from aqueous solutions onto a new cation exchanger derived from tamarind fruit shell. The Journal of Chemical Thermodynamics, 40(4), 702-709.
• Aragaw, T. A. (2021). Recycling electro-coagulated sludge from textile wastewater treatment plants as an adsorbent for the adsorptions of fluoride in an aqueous solution. Heliyon, 7(6).
• Asgari, G., Roshani, B., & Ghanizadeh, G. (2012). The investigation of kinetic and isotherm of fluoride adsorption onto functionalize pumice stone. Journal of Hazardous Materials, 217, 123-132.
• Basu, H., Singhal, R., Pimple, M., & Reddy, A. (2013). Synthesis and characterization of alumina impregnated alginate beads for fluoride removal from potable water. Water, Air, & Soil Pollution, 224, 1-12.
• Bhatt, D. B., Bhatt, P. R., Hari Prasad, H., Popat, K. M., & Anand, P. S. (2004). Removal of fluoride ion from aqueous bodies by aluminium complexed amino phosphonic acid type resins. Indian journal of chemical technology, 11(3), 299-303.
• Buamah, R., Oduro, C., & Sadik, M. (2016). Fluoride removal from drinking water using regenerated aluminum oxide coated media. Journal of Environmental Chemical Engineering, 4(1), 250-258.
• Chang, G., Li, W., Cao, J., Wang, Z., Tan, X., & Wang, X. (2024). Aluminum alginate foam synthesis, characterization, and application for low concentration fluoride ion removal. Desalination and Water Treatment, 317, 100156.
• Chowdhury, S., Mishra, R., Saha, P., & Kushwaha, P. (2011). Adsorption thermodynamics, kinetics and isosteric heat of adsorption of malachite green onto chemically modified rice husk. Desalination, 265(1-3), 159-168.
• Dai, J., Yan, H., Yang, H., & Cheng, R. (2010). Simple method for preparation of chitosan/poly (acrylic acid) blending hydrogel beads and adsorption of copper (II) from aqueous solutions. Chemical Engineering Journal, 165(1), 240-249.
• Das, K., Sukul, U., Chen, J.-S., Sharma, R. K., Banerjee, P., Dey, G., Taharia, M., Wijaya, C. J., Lee, C.-I., & Wang, S.-L. (2024). Transformative and sustainable insights of agricultural waste-based adsorbents for water defluoridation: Biosorption dynamics, economic viability, and spent adsorbent management. Heliyon, 10(8).
• Das, L., Das, P., & Bhowal, A. (2023). Synthesis and application of alginate-nanocellulose composite beads for defluoridation process in a batch and fluidized bed reactor. Journal of Environmental Management, 344, 118569.
• Dayananda, D., Sarva, V. R., Prasad, S. V., Arunachalam, J., & Ghosh, N. N. (2014). Preparation of CaO loaded mesoporous Al2O3: efficient adsorbent for fluoride removal from water. Chemical Engineering Journal, 248, 430-439.
• Desta, M. B. (2013). Batch sorption experiments: Langmuir and Freundlich isotherm studies for the adsorption of textile metal ions onto teff straw (Eragrostis tef) agricultural waste. Journal of thermodynamics, 2013(1), 375830.
• Farahinia, L., Rezvani, M., & Rezazadeh, M. (2021). Effect of CaF2 substitution by CaO on spectroscopic properties of oxyfluoride glasses. Materials Research Bulletin, 139, 111265.
• Fordyce, Fiona M.. 2011 Fluorine : human health risks. In: Nriagu, J.O., (ed.) Encyclopedia of environmental health Vol. 2. Elsevier, 776-785.
• Guo, S., Zheng, F., Xu, J., Jiang, J., Cui, Z., Wu, C., Lin, Y., Sun, Q., Zheng, Y., & Sa, B. (2025). Enhanced fluoride removal from drinking water by activated carbon supported Ce–Al oxides: performance and mechanism. RSC advances, 15(18), 14363-14374.
• Guo, W., Lin, H., Zhu, H., Lei, M., & Feng, J. (2023). Preparation and application of magnesium oxide nanoparticles for superiorly fluoride removal. Journal of Alloys and Compounds, 960, 170935.
• Han, R., Wang, Y., Zhao, X., Wang, Y., Xie, F., Cheng, J., & Tang, M. (2009). Adsorption of methylene blue by phoenix tree leaf powder in a fixed-bed column: experiments and prediction of breakthrough curves. Desalination, 245(1-3), 284-297.
• Hota, A., Patro, S. G. K., Panda, S. K., Khan, M. A., Hasan, M. A., Islam, S., Alsubih, M., Khan, N. A., & Zahmatkesh, S. (2024). Removing fluoride ions from wastewater by Fe3O4 nanoparticles: Modified Rhodophytes (red algae) as biochar. Journal of Water Process Engineering, 58, 104776.
• Karekar, J. M., Katamble, R. T., & Divekar, S. V. (2020). Adsorption studies of fluoride on weak base anion exchangers and surface modified strong acid cation exchangers in aqueous medium. Desalination and Water Treatment, 204, 356-365.
• Kamau J, Kamau G (2017) Modeling of Experimental Adsorption Isotherm Data for Chlorothalonil by Nairobi River Sediment. Mod Chem Appl 5: 203. doi: 10.4172/2329-6798.1000203
• Khoudro, A., Sater, S., & Suliman, D. (2024). Study of the atomic packing fraction, specific surface area and morphology index of pure titanium dioxide compound and doped with lead tio2: Pb in different ratios. Scientif. Res. Reports, BioRes. Scientia. Pub, 1(1), 1-7.
• Kiprono, P., Kiptoo, J., Nyawade, E., & Ngumba, E. (2023). Iron functionalized silica particles as an ingenious sorbent for removal of fluoride from water. Scientific Reports, 13(1), 8018.
• Krongkitsiri, P., Krongkitsiri, W., Phukird, S., & Tipparach, U. (2021). A comparison of dielectric properties of eggshells from free-range system and control-range system. Materials Today: Proceedings, 47, 3617–3623
• Kumar, E., Bhatnagar, A., Kumar, U., & Sillanpää, M. (2011). Defluoridation from aqueous solutions by nano-alumina: characterization and sorption studies. Journal of Hazardous Materials, 186(2-3), 1042-1049.
• Kumar, P., Kumar, M., Barnawi, A. B., Maurya, P., Singh, S., Shah, D., Yadav, V. K., Kumar, A., Kumar, R., & Yadav, K. K. (2024). A review on fluoride contamination in groundwater and human health implications and its remediation: A sustainable approaches. Environmental Toxicology and Pharmacology, 106, 104356.
• Liu, M., Yang, X., Chen, D., Guo, J., Zhang, L., & Shao, Y. (2025). Fabrication of SiC-Al2O3 foam ceramic and its application in fluoride-containing water. Ceramics International, 51(2), 2268-2277.
• Liu, Y. (2008). New insights into pseudo-second-order kinetic equation for adsorption. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 320(1-3), 275-278.
• Mahdavinia, G. R., & Mosallanezhad, A. (2016). Facile and green rout to prepare magnetic and chitosan-crosslinked κ-carrageenan bionanocomposites for removal of methylene blue. Journal of Water Process Engineering, 10, 143-155.
• Mohammed, A. A., Khodair, Z. T., & Khadom, A. A. (2020). Preparation and investigation of the structural properties of α-Al2O3 nanoparticles using the sol-gel method. Chemical Data Collections, 29, 100531.
• Mondal, N. K., Bhaumik, R., & Datta, J. K. (2015). Removal of fluoride by aluminum impregnated coconut fiber from synthetic fluoride solution and natural water. Alexandria Engineering Journal, 54(4), 1273-1284.
• Muryanto, S., & Hadi, S. D. (2016). Adsorption laboratory experiment for undergraduate chemical engineering: Introducing kinetic, equilibrium and thermodynamic concepts. IOP Conference Series: Materials Science and Engineering,
• Noor, S., Rashid, A., Javed, A., Khattak, J. A., & Farooqi, A. (2022). Hydrogeological properties, sources provenance, and health risk exposure of fluoride in the groundwater of Batkhela, Pakistan. Environmental Technology & Innovation, 25, 102239.
• Perumal, M. V., Mamallan, A. M., & Ragavan, V. (2023). Determination and eco-friendly suppression of fluoride contamination in ground water samples using activated carbon constituents of carica papaya–A natural adsorbent. Materials Today: Proceedings.
• Qasemi, Z., Jafari, D., Jafari, K., & Esmaeili, H. (2022). Heterogeneous aluminum oxide/calcium oxide catalyzed transesterification of Mespilus germanica triglyceride for biodiesel production. Environmental Progress & Sustainable Energy, 41(2), e13738.
• Ragadhita, R., & Nandiyanto, A. B. D. (2022). Curcumin adsorption on zinc imidazole framework-8 particles: Isotherm adsorption using Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models. J. Eng. Sci. Technol, 17(2), 1078-1089.
• Revellame, E. D., Fortela, D. L., Sharp, W., Hernandez, R., & Zappi, M. E. (2020). Adsorption kinetic modeling using pseudo-first order and pseudo-second order rate laws: A review. Cleaner Engineering and Technology, 1, 100032.
• Saha, P. D., Chakraborty, S., & Chowdhury, S. (2012). Batch and continuous (fixed-bed column) biosorption of crystal violet by Artocarpus heterophyllus (jackfruit) leaf powder. Colloids and Surfaces B: Biointerfaces, 92, 262-270.
• Sarwar, A., Wang, J., Khan, M. S., Farooq, U., Riaz, N., Nazir, A., Mahmood, Q., Hashem, A., Al-Arjani, A.-B. F., & Alqarawi, A. A. (2021). Iron oxide (Fe3O4)-supported SiO2 magnetic nanocomposites for efficient adsorption of fluoride from drinking water: synthesis, characterization, and adsorption isotherm analysis. Water, 13(11), 1514.
• Shukla, A., Zhang, Y.-H., Dubey, P., Margrave, J., & Shukla, S. S. (2002). The role of sawdust in the removal of unwanted materials from water. Journal of Hazardous Materials, 95(1-2), 137-152.
• Srivastava, V. C., Swamy, M. M., Mall, I. D., Prasad, B., & Mishra, I. M. (2006). Adsorptive removal of phenol by bagasse fly ash and activated carbon: equilibrium, kinetics and thermodynamics. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 272(1-2), 89-104.
• Tan, T. L., Nakajima, H., & Rashid, S. A. (2020). Adsorptive, kinetics and regeneration studies of fluoride removal from water using zirconium-based metal organic frameworks. RSC advances, 10(32), 18740-18752.
• Temkin, M. J., & Pyzhev, V. (1940). Recent modifications to Langmuir isotherms.
• Wang, J., & Guo, X. (2020). Adsorption kinetic models: Physical meanings, applications, and solving methods. Journal of Hazardous Materials, 390, 122156.
• Wang, M., Yu, X., Yang, C., Yang, X., Lin, M., Guan, L., & Ge, M. (2017). Removal of fluoride from aqueous solution by Mg-Al-Zr triple-metal composite. Chemical Engineering Journal, 322, 246-253.
• Weber Jr, W. J., & Morris, J. C. (1963). Kinetics of adsorption on carbon from solution. Journal of the sanitary engineering division, 89(2), 31-59.
• Wu, F.-C., Tseng, R.-L., & Juang, R.-S. (2009). Initial behavior of intraparticle diffusion model used in the description of adsorption kinetics. Chemical Engineering Journal, 153(1-3), 1-8.
• Yang, R., Chen, J., Zhang, Z., & Wu, D. (2022). Performance and mechanism of lanthanum-modified zeolite as a highly efficient adsorbent for fluoride removal from water. Chemosphere, 307, 136063.
• Zhou, Y., Li, Y., Liu, D., Liu, D., Xu, L., & Liu, C. (2021). Adsorption optimization of uranium (VI) onto polydopamine and sodium titanate co-functionalized MWCNTs using response surface methodology and a modeling approach. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 627, 127145.