The Optimization of Adsorption Potentials of Nigerian Kaolinite Mineral Through Acid Activation
DOI:
https://doi.org/10.53704/fujnas.v12i2.438Keywords:
Bentonite, Kaolinite, Adsorption, Heavy metals, DesorptionAbstract
The adsorption capacities of Nigerian Kaolinite minerals obtained from Share in Kwara State in raw and acid-activated forms towards some heavy metal ions were evaluated. The clay mineral was purified by sedimentation method and modified with 0.1M nitric, sulphuric, phosphoric, acetic, and oxalic acids. The properties of the raw clay and the effects of acid activation were investigated by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier-Transform infrared spectroscopy (FTIR) and BET surface area analyses. Adsorption and desorption studies were subsequently carried out to evaluate the efficiencies of clay samples in removing Pb2+, Cd2+ and Ni2+ ions from aqueous solutions. Effects of operation parameters viz pH, initial concentration, temperature, and time on the adsorption process were determined on the raw samples, and optimum conditions obtained were utilized for evaluation on the acid-activated samples. The acid modification was found to achieve considerable leaching of exchangeable cations on the clay mineral as confirmed by variations of the d-spacings, lowering of peak intensities and changes in absorption bands of the acid-modified samples (A-K (Acetic acid-Kaolinite), N-K (Nitric acid-Kaolinite), O-K (Oxalic acid-Kaolinite), P-K (Phosphoric acid-Kaolinite) and S-K (Sulphuric acid-Kaolinite). The surface areas increased in S-K, O-K and especially N-K (162.227 m2/g) from 114.9457 m2/g [Raw Kaolinite (R-K)] to) but reduced in A-K 112.865 m2/g and P-K (113.872 m2/g). The activated clay samples were found to adsorb higher amounts of all the heavy metal ions studied than the raw form of the clay. Desorption analysis results revealed that the clay mineral can be regenerated and reused. Compared with other methods, modification with dilute acid provides a simple, effective, and environmentally friendly method of improving the surface characteristics of clay minerals to enhance their adsorption capacities as suitable adsorbents for water remediation purposes.
Keywords: Bentonite, Kaolinite, Adsorption, Heavy metals, Desorption
References
Abechi, E., Gimba, C., Uzairu , A., & Kagbu , J. (2011). Kinetics of adsorption of methylene blue onto activated carbon prepared from palm kernel shell. Archives of Applied Science Research, 3(1), 154-164.
Adekola, F. A., Hodonou, D. S. S. & Adegoke, H. I. (2016). Thermodynamic and Kinetic Studies of Biosorption of Iron and Manganese from Aqueous Medium Using Rice Husk Ash, Applied Water Sciences, 6, 319–330
Ahmadi, A., Foroutan, R., Esmaeili, H. & Tamjidi, S. (2020). The role of bentonite clay and bentonite clay@MnFe2O4 composite and their physico-chemical properties on the removal of Cr(III) and Cr(VI) from aqueous media. Environmental Science and Pollution Research, 27 (12), 14044-14057
Akpomie, K. G. & Dawodu, F. (2016). Acid-modified montmorillonite for sorption of heavy metals from automobile effluent. Beni - Suef University Journal of Basic and Applied Sciences, 5, 1–12.
Al-Anber, M. A. (2011). Thermodynamics Approach in the Adsorption of Heavy Metals. In J. M. Piraján (Ed.), Thermodynamics - Interaction Studies - Solids, Liquids and Gases. Shanghai, China: In Tech. pp. 737-764
Alshameri, A., Hea, H., Zhua, H., Xic, Y., Zhua, R., Maa, L. & Tao, Q. (2018). Adsorption of ammonium by different natural clay minerals: Characterization, kinetics and adsorption isotherms. Applied clay Science, 159,83-93
Aziz, K. H. H., Mustafa, F. S., Omer, K. M., Hama, S., Hamaraw, R. F., & Rahman, K. O. (2023). Heavy metal pollution in the aquatic environment: efficient and low-cost removal approaches to eliminate their toxicity: a review, RSC Advances, 13(26): 17595–17610.
Bahl, A., Bahl, B. S. & Tuli, G. D. (2012). Essentials of physical chemistry, S. Chand, New Delhi, pp 303-860.
Balali-Mood M., Naseri K., Tahergorabi Z., Khazdair M. R., & Sadeghi M. (2021) Toxic Mechanisms of Five Heavy Metals: Mercury, Lead, Chromium, Cadmium, and Arsenic. Frontiers in Pharmacology, 12 (643972) 1-18
Bennour, H. A. M. (2017) Effect of Acid Activation on Adsorption of Iron and Manganese Using Libyan Bentonite Clay, Chemical Science Transactions, 6, (2), 209-218
Berihun, D. & Solomon, Y. (2017). Assessment of the Physicochemical and Heavy Metal Concentration from Effluents of Paint Industry in Addis Ababa, Ethiopia. International Journal of Waste Resources, 7(4), 1-5.
Bertagnolli, C. & Carlos da Silva, M. G. (2012). Characterization of Brazillian Bentonite Organoclays as Sorbents of Petroleum-derived Fuels. Materials Research, 15, (2), 253-259
Boparai, H. K., Joseph, M. & O’Carroll, D. (2011). Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles. Journal of HazardousMaterials, 186(1), 458-465
Budash, Y., Plavan, V., Tarasenko, N., Ishchenko, O. & Koliada, M. (2023). Effect of Acid Modification on Porous Structure and Adsorption Properties of Different Type Ukrainian Clays for Water Purification Technologies. Journal of Ecological Engineering, 24, (5), 210–221
Bukalo, N. N., Ekosse, G. E., Odiyo, J. O. & Ogola, J. S. (2017). Fourier Transform Infrared Spectroscopy of Clay Size Fraction of Cretaceous-Tertiary Kaolins in the Douala Sub-Basin, Cameroon. Open Geosciences, 9, 407–418
Chai, J. -B., Au, P. -I., Mubarak, N. M., Khalid, M., Ng, W. P. -Q., Jagadish, P., Walvekar, R., & Abdullah, E. C. (2020). Adsorption of heavy metal from industrial wastewater onto low-cost Malaysian kaolin clay–based adsorbent. Environmental Science and Pollution Research, 27, (12), 13949 – 13962
Chao, H. -P., & Chang, C. -C. (2012) Adsorption of copper (II), cadmium (II), nickel (II) and lead(II) from aqueous solution using biosorbents, Adsorption, 18, 395–401
Chen, M., Yang, T., Han, J., Zhang, Y., Zhao, L., Zhao, J., Li, R., Huang, Y., Gu, Z., & Wu, J. The Application of Mineral Kaolinite for Environment Decontamination: A Review. Catalysts, 2023, 13 (123), 1-17
Dim, P. E., Mustapha, L. S., Termtanun, M., Okafor, J. O. (2021) Adsorption of chromium (VI) and iron (III) ions onto acid-modified kaolinite: Isotherm, kinetics and thermodynamics studies, Arabian Journal of Chemistry,14, (103064), 1-14
Do, D. D. (1998). Adsorption Analysis: Equilibria and Kinetics; Series on Chemical Engineering, Vol. 2, Imperial College Press, London. pp 7-101
Eba, F., Ndong Nlo, J., Ondo, J., Andeme Eyi, P. & Nsi–Emvo, E. (2013) Batch experiments on the removal of U(VI) ions in aqueous solutions by adsorption onto a natural clay surface, Journal of Environment and Earth Science, 3, (1), 11-23
El?Naggar, I. M., Ahmed, S. A., Shehata, N., Sheneshen, E. S., Fathy, M., & Shehata, A. (2019). A novel approach for the removal of lead (II) ion from wastewater using Kaolinite/Smectite natural composite adsorbent. Applied Water Science, 9, (7), 1-13
Elsheikh, M. A., Muchaonyerwa, P., Johan, E., Matsue, N. & Henmi, T. (2018) Mutual Adsorption of Lead and Phosphorus onto Selected Soil Clay Minerals, Advances in Chemical Engineering and Science, 8, 67-81
Emam A.A., Ismail L.E.M., Abdelkhalek M.A., (2016). Adsorption study of some heavy metal ions on modified kaolinite. International journal of Advancement in Engineering Technology, Management and Applied Science. 3(7):152-163.
Es-said, A., Nafai, H., Lamzougui, G., Bouhaouss, A. & Bchitou, R. (2021) Comparative adsorption studies of cadmium ions on phosphogypsum and natural clay, Scientific African, 13, (e00960), 1-10
Ewere, E. E., Omoigberale, M. O., Bamawo, O. E. & Erhunmwunse, N. O. (2014). Physio-Chemical Analysis of Industrial Effluents in parts of Edo States Nigeria. Journal of Applied Sciences and Environmental Management, 18(2), 267-272.
Fernandes, J. V., Rodrigues, A. M., Menezes, R. R., & Neves, G. A. (2020). Adsorption of Anionic Dye on the Acid-Functionalized Bentonite, Materials, 13 (3600), 1-19
Foo, K. Y. and Hameed, B. H. (2010). Insights in to the modeling of adsorption isotherm systems. Chemical Engineering Journal, 156, 2–10
Galindo, L. S. G., Neto, A. F., da Silva, M. G. C. & Vieira, M. G. A. (2013) Removal of Cadmium (II) and Lead(II) Ions from Aqueous Phase on Sodic Bentonite, Materials Research,16, (2), 515-527
Gebretsadik, H., Gebrekidan, A. & Demlie, L. (2020). Removal of heavy metals from aqueous solutions using Eucalyptus Camaldulensis: An alternate lowcost adsorbent, Cogent Chemistry, 6, (1), 1-16
Hai, Y., Li, X., Wua,, H., Zhao, S., Deligeer, W. & Asuha, S. (2015) Modification of acid-activated kaolinite with TiO2 and its use for the removal of azo dyes, Applied Clay Science, 114, 558–567
Hamdaoui, O. & Naffrechoux, E. (2007). Modeling of adsorption isotherms of phenol and. Journal of Hazardous Materials 147, 381–394.
Ho, Y. S. & Mckay, G. (1998). Sorption of dye from aqueous solution by peat. Chemical Engineering Journal, 115-124
Hooshiar, A., Uhlik, P., Ivey, D. G., Liu, Q. & Etsell, T. H. (2012) Clay minerals in nonaqueous extraction of bitumen from Alberta oil sands Part 2. Characterization of clay minerals, Fuel Processing Technology, 96, 183-194
Huang, X., Zhao, H., Zhang, G., Li, J., Yang, Y. & Ji, P. (2020) Potential of removing Cd(II) and Pb(II) from contaminated water using a newly modified fly ash, Chemosphere 242, (125148), 1-10
Ihekweme, G. O., Shondo, J. N., Orisekeh, K. I., Kalu-Uka, G. M., Nwuzor, i. C. & Onwualu, A. P. (2020). Characterization of certain Nigerian clay minerals for water purification and other industrial applications, Heliyon ,6, e03783, 1-11
Kakaei, S., Khameneh, E. S., Hosseini, M. H. & Moharreri, M. M. (2020) A modified ionic liquid clay to remove heavy metals from water: investigating its catalytic activity International Journal of Environmental Science and Technology, 17, 2043–2058
Khalfa, L., Sdiri, A., Bagane, M., & Cervera, M. L. (2020). Multi?element modeling of heavy metals competitive removal from aqueous solution by raw and activated clay from the Aleg formation (Southern Tunisia). International Journal of Environmental Science and Technology, 17, 2123–2140
Khan, M. I., Almesfer, M. K., Danish, M., Ali, I. H., Shoukry, H., Patel, R., Gardy, J., Nizami, A. S. & Rehan, M. (2019). Potential of Saudi natural clay as an effective adsorbent in heavy metals removal from wastewater, Desalination and Water Treatment, 158, 140–151
Krika, F., Azzouz, N. & Ncibi, M. C. (2016). Adsorptive removal of cadmium from aqueous solution by cork biomass: Equilibrium, dynamic and thermodynamic studies. Arabian Journal of Chemistry, 9, (2), 1077-1083
Kumar, A. & Lingfa, P. (2020). Sodium bentonite and kaolin clays: Comparative study on their FT-IR, XRF, and XRD, Materials Today: Proceedings ,22, 737-742
Kumar, S., Panda, A.K. & Singh, R. K. (2013). Preparation and Characterization of Acids and Alkali Treated Kaolin Clay. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1), 61 – 69
Lawal J.A., Odebunmi E.O., & Adekola F.A., (2020). Adsorption of Fe^(2+),Pb^(2+), Zn^(2+) and Cr^(6+) ions from aqueous solutions using natural, ammonium oxalate and sodium hydroxide modified kaolinite clay. Ife Journal of Science 22(3): 001-023.
Levine, I. N. (2009). Physical chemistry, Mc-Graw Hill International Edition, Mc-Graw Hill, New York. pp 161-575
Li, T., Huang, X., Wang, Q. & Yang, G. (2020). Adsorption of metal ions at kaolinite surfaces: Ion-specific effects, and impacts of charge source and hydroxide formation. Applied Clay Science, 194, (105706), 1-10
Likita, M. B., Nura, G. K., Nuhu, C. D. & Isah, S. D. (2016). Physico-Chemical Characterization of Industrial Effluents in Minna Niger State, Nigeria. International Journal of Modern Analytical and Separation Sciences, 5(1), 12-19.
Maged, A., Ismael, I. S., Kharbish, S., Sarkar, B., Peräniemi, S. & Bhatnagar, A. (2020) Enhanced interlayer trapping of Pb (II) ions within kaolinite layers: intercalation, characterization, and sorption studies. Environmental Science and Pollution Research 27, 1870–1887
Malima, N. M., Owonubi, · S. J., Lugwisha, E. H. & Mwakaboko, A. S. (2021) Thermodynamic, isothermal, and kinetic studies of heavy metals adsorption by chemically modified Tanzanian Malangali kaolin clay, International Journal of Environmental Science and Technology, 18, (10), 3153-3168.
Meneguin, J. G., Moisés, M. P., Karchiyappana, T., Fariaa, S. H. B., Gimenes, M. L., de Barros, M. S. D. & Venkatachalam, S. (2017) Preparation and characterization of calcium treated bentonite clay and its application for the removal of lead and cadmium ions: Adsorption and thermodynamic modelling, Process Safety and Environmental Protection, 1 1 1, 244–252
Mnasri-Ghnimi, S. & Srasra, N. (2019) Removal of heavy metals from aqueous solutions by adsorption using single and mixed pillared clays, Applied Clay Science, 179, (105151), 1-17
Mobasherpour, I., Salahi, E., & Pazouki, M. (2012) Comparative of the removal of Pb2+, Cd2+ and Ni2+ by nano crystallite hydroxyapatite from aqueous solutions: Adsorption isotherm study, Arabian Journal of Chemistry, 5, 439-446
Mohamed, H. S., Soliman, N. K., Abdelrheem, D. A., Ramadan, A. A., Elghandour, A. H. & Ahmed, S. A. (2019). Adsorption of Cd2+ and Cr3+ ions from aqueous solutions by using residue of Padina gymnospora waste as promising low-cost adsorbent. Heliyon, 5, e01287, 1-32
Moretti, L. Natali, S., Tiberi, A. & D’Andrea, A. (2020). Proposal for a Methodology Based on XRD and SEM-EDS to Monitor Effects of Lime-Treatment on Clayey Soils, Applied Sciences 10, 2569, 1-17
Mudzielwana, R., Gitari, M. W. & Ndungu, P. (2019) Performance evaluation of surfactant modified kaolin clay in As(III) and As(V) adsorption from groundwater: adsorption kinetics, isotherms and thermodynamics, Heliyon, e02756, 1-13
Nordin, N. A., Abdul Rahman, N. & Abdullah, A. (2020) Effective Removal of Pb(II) Ions by Electrospun PAN/Sago Lignin-Based Activated Carbon Nanofibers, Molecules , 25, (3081), 1-21
Novakovic., T., Rozi?c´, L., Petrovic´, S. & Rosic´, A. (2008). Synthesis characterization of acid-activated Serbian smectite clays obtained by statistically designed experiments, Chemical Engineering Journal, 137, 436–442
Ogbu, I. C., Akpomie, K. G., Osunkunle, A. A., & Eze, S. I. (2019). Sawdust-kaolinite composite as efficient sorbent for heavy metal ions. Bangladesh Journal of Scientific and. Industrial Research, 54, (1), 99-110
Omer, O. S., Hussein, M. A., Hussein, B. H. & Mgaidi, A. (2018). Adsorption thermodynamics of cationic dyes (methylene blue and crystal violet) to a natural clay mineral from aqueous solution between 293.15 and 323.15 K. Arabian Journal of Chemistry, 11, 615–623.
Omidi Khaniabadi, Y., Basiri, H., Nourmoradi, H., Mohammadi, M. J., Yari, A. R., Sadeghi, S., & Amrane, A. (2017). Adsorption of Congo Red Dye from Aqueous Solutions by Montmorillonite as a Low-cost Adsorbent. DE GRUYTER: International Journal of Chemical Reactor Engineering, 20160203, 1-11
Özcan, A. S. & Özcan, A. (2004). Adsorption of acid dyes from aqueous solutions onto acid-activated bentonite. Journal of Colloid and Interface Science, 276, 39–46.
Ozdes, D., Duran, C. & Senturk, H. B. (2011). Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay. Journal of Environmental Management, 92, 3082-3090.
Panda, A. K., Mishra, B. G., Mishra, D. K. & Singh, R. K. (2010). Effect of sulphuric acid treatment on the physico-chemical characteristics of kaolin clay. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 363, 98–104
Pathania, D., Sharma, S. & Singh, P. (2017). Removal of methylene blue by adsorption onto activated carbon developed from Ficus carica bast. Arabian Journal of Chemistry, 10, 1445–1451.
Ramachandran, P., Vairamuthu, R. & Ponnusamy, S. (2011). Adsorption Isotherms, Kinetics, Thermodynamics and Desorption Studies of Reactive Orange 16 ob Activated Carbon Derived fron Ananascomosus (L.). ARPN Journal of Engineering and Applied Sciences, 6(11), 15-26.
Rao, R. A. K. & Khan, U. (2017) Adsorption studies of Cu(II) on Boston fern (Nephrolepis exaltata Schott cv. Bostoniensis) leaves, Applied Water Science, 7, 2051–2061
Sarma, G. K., Sen Gupta, S., & Bhattacharyya, K. G. (2019) Removal of hazardous basic dyes from aqueous solution by adsorption onto kaolinite and acid?treated kaolinite: kinetics, isotherm and mechanistic study, Springer Nature Applied Sciences, 1, (211), 1-15
Saxena, A., Bhardwaj, M., Allen, T., Kumar, S. & Sahney, R. (2017) Adsorption of heavy metals from wastewater using agricultural–industrial wastes as biosorbents, Water Science, 31, (2), 189-197
Sdiri, A., Higashi, T., Hatta, T., Jamoussi, F. & Tase, N. (2011). Evaluating the adsorptive capacity of montmorillonitic and calcareous clays on the removal of several heavy metals in aqueous systems. Chemical Engineering Journal, 172, 37-46
Siyanbola, T., Ajanaku , K. O., James , O. O. & Olugbuyiro, J. A. (2011). Physico-Chemical Characteristics of Industrial Effluents In Lagos State, Nigeria. G. J. P&A Sc and Tech., I, 49-54.
Sukpreabprom, H., Arquero , A., Naksata, W., Sooksa, P. & Janhom, S. (2014). Isotherm, Kinetic and Thermodynamic Studies on the Adsorption of Cd (II) and Zn (II) ions from Aqueous Solutions onto Bottom Ash. International Journal of Environmental Science and Development, 5 (2), 165-170.
Tian, L., Fu1, K., Chen, S., Yao, J. & Bian, L. (2022). Comparison of microscopic adsorption characteristics of Zn(II), Pb(II), and Cu(II) on kaolinite. Scientific Reports, 12, (15936), 1-12
Uddin, M. K. ( 2017). A review on the adsorption of heavy metals by clay minerals, with special focus on the past decade. Chemical Engineering Journal 308, 438–462.
Yin, J., Deng, C., Yu, Z., Wang, X. & Xu, G.(2018) Effective Removal of Lead Ions from Aqueous Solution Using Nano Illite/Smectite Clay: Isotherm, Kinetic, and Thermodynamic Modeling of Adsorption, Water, 10, (210), 1-13
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