Adsorption-Desorption Profile of Methylene Blue Dye on Raw and Acid Activated Kaolinite

Nurul Ain Safiqah Md Sandollah(1), Sheikh Ahmad Izaddin Sheikh Mohd Ghazali(2), Wan Nazihah Wan Ibrahim(3), Ruhaida Rusmin(4*)

(1) Faculty of Applied Sciences, Universiti Teknologi MARA, Negeri Sembilan Branch, Kuala Pilah Campus, 72000 Kuala Pilah, Negeri Sembilan, Malaysia
(2) Faculty of Applied Sciences, Universiti Teknologi MARA, Negeri Sembilan Branch, Kuala Pilah Campus, 72000 Kuala Pilah, Negeri Sembilan, Malaysia
(3) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(4) Faculty of Applied Sciences, Universiti Teknologi MARA, Negeri Sembilan Branch, Kuala Pilah Campus, 72000 Kuala Pilah, Negeri Sembilan, Malaysia
(*) Corresponding Author


The efficiencies of raw (RK) and acid activated (0.5 M AAK) kaolinite clay minerals to remove methylene blue (MB) dyes in aqueous solution were investigated and compared. The 0.5 M AAK was prepared by treatment of RK in dilute 0.5 M HCl aqueous solution under reflux. Kaolinite adsorbents were characterized and their MB removal performances were evaluated via the batch method. MB desorption from spent kaolinites was investigated at pH 4 to 8. The MB removal was increased with increasing initial dye concentration, agitation speed and adsorbent dosage in 60 min reaction time at pH 6. Both kaolinites showed high MB removal (up to 97%). The Freundlich model has the best-fit equilibrium adsorption isotherm model for RK and 0.5 M AAK. The kinetic data for both adsorbents showed strong agreement with the pseudo second order kinetic model
(r2 > 0.98). Nevertheless, the spent RK adsorbent demonstrated a significant higher MB retention than 0.5 M AAK in desorption experiments. Kaolinite clays have great potential as cost-effective materials for dyes removal in wastewater treatment.


kaolinite; activation; removal; dyes; desorption

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[1] Bafana, A., Devi, S.S., and Chakrabarti, T., 2011, Azo dyes: Past, present and the future, Environ. Rev., 19, 350–371.

[2] Kallel, F., Chaari, F., Bouaziz, F., Bettaieb, F., Ghorbel, R., and Chaabouni, S.E., 2016, Sorption and desorption characteristics for the removal of a toxic dye, methylene blue from aqueous solution by a low cost agricultural by-product, J. Mol. Liq., 219, 279–288.

[3] Rafatullah, M., Sulaiman, O., Hashim, R., and Ahmad, A., 2010, Adsorption of methylene blue on low-cost adsorbents: A review, J. Hazard. Mater., 177 (1-3), 70–80.

[4] Rida, K., Bouraoui, S., and Hadnine, S., 2013, Adsorption of methylene blue from aqueous solution by kaolin and zeolite, Appl. Clay Sci., 83-84, 99–105.

[5] Bergaya, F., and Lagaly, G., 2006, “Chapter 1 General introduction: Clays, clay minerals, and clay science” in Handbook of Clay Science, 1st Ed., Eds. Bergaya, F., Theng, B.K.G., and Lagaly, G., Elsevier Science, Netherlands, 1–18.

[6] Zhou, C.H., and Keeling, J., 2013, Fundamental and applied research on clay minerals: From climate and environment to nanotechnology, Appl. Clay Sci., 74, 3–9.

[7] Madejova, J., and Komadel, P., 2001, Baseline studies of the clay minerals society source clays: Infrared methods, Clays Clay Miner., 49 (5), 410–432.

[8] Rusmin, R., Sarkar, B., Biswas, B., Churchman, J., Liu, Y., and Naidu, R., 2016, Structural, electrokinetic and surface properties of activated palygorskite for environmental application, Appl. Clay Sci., 134, 95–102.

[9] Shi, L., 2017, “The mineral industry of Malaysia” in Minerals Yearbook 2014: Metals and Minerals, Vol. I, U.S. Geological Survey, Reston, VA, 16.1–16.7.

[10] Gao, W., Zhao, S., Wu, H., Deligeer, W., and Asuha, S., 2016, Direct acid activation of kaolinite and its effects on the adsorption of methylene blue, Appl. Clay Sci., 126, 98–106.

[11] Komadel, P., 2016, Acid activated clays: Materials in continuous demand, Appl. Clay Sci., 131, 84–99.

[12] Hai, Y., Li, X., Wu, H., Zhao, S., Deligeer, W., and Asuha, S., 2015, Modification of acid-activated kaolinite with TiO2 and its use for the removal of azo dyes, Appl. Clay Sci., 114, 558–567.

[13] Wu, P., and Ming, C., 2006, The relationship between acidic activation and microstructural changes in montmorillonite from Heping, China, Spectrochim. Acta, Part A, 63 (1), 85–90.

[14] Sarma, G.K., Gupta, S.S., and 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, SN Appl. Sci., 1, 211.

[15] El Mouzdahir, Y., Elmchaouri, A., Mahboub, R., Gil, A., and Korili, S.A., 2010, Equilibrium modeling for the adsorption of methylene blue from aqueous solutions on activated clay minerals, Desalination, 250 (1), 335–338.

[16] Vanaamudan, A., Pathan, N., and Pamidimukkala, P., 2014, Adsorption of Reactive Blue 21 from aqueous solutions onto clay, activated clay, and modified clay, Desalin. Water Treat., 52 (7-9), 1589–1599.

[17] Hu, P., and Yang, H., 2013, Insight into the physicochemical aspects of kaolins with different morphologies, Appl. Clay Sci., 74, 58–65.

[18] Frost, R.L., 1997, The structure of the kaolinite minerals FT-Raman study, Clay Miner., 32 (1), 65–77.

[19] Saikia, B.J., and Parthasarathy, G., 2010, Fourier transform infrared spectroscopic characterization of kaolinite from Assam and Meghalaya, Northeastern India, J. Mod. Phys., 1, 206–210.

[20] Panda, A.K., Mishra, B.G., Mishra, D.K., and Singh, R.K., 2010, Effect of sulphuric acid treatment on the physico-chemical characteristics of kaolin clay, Colloids Surf., A, 363, 98–104.

[21] Ullah, Z., Hussain, S., Gul, S., Khan, S., and Bangash, F.K., 2016, Use of HCl-modified bentonite clay for the adsorption of Acid Blue 129 from aqueous solutions, Desalin. Water Treat., 57 (19), 8894–8903.

[22] Bhattacharyya, K.G., and Gupta, S.S., 2011, Removal of Cu(II) by natural and acid-activated clays: An insight of adsorption isotherm, kinetic and thermodynamics, Desalination, 272 (1-3), 66–75.

[23] Chicinaş, R.P., Bedelean, H., Stefan, R., and Măicăneanu, A., 2018, Ability of a montmorillonitic clay to interact with cationic and anionic dyes in aqueous solutions, J. Mol. Struct., 1154, 187–195.

[24] Mills, A., Hazafy, D., Parkinson, J., Tuttle, T., and Hutchings, M.G., 2011, Effect of alkali on methylene blue (C.I. Basic Blue 9) and other thiazine dyes, Dyes Pigm., 88 (2), 149–155.

[25] Tehrani-Bagha, A.R., Nikkar, H., Mahmoodi, N.M., Markazi, M., and Menger, F.M., 2011, The sorption of cationic dyes onto kaolin: Kinetic, isotherm, and thermodynamic studies, Desalination, 266 (1-3), 274–280.

[26] Berrios, M., Martín, M.Á., and Martín, A., 2012, Treatment of pollutants in wastewater: Adsorption of methylene blue onto olive-based activated carbon, J. Ind. Eng. Chem., 18 (2), 780–784.

[27] Vimonses, V., Lei, S., Jin, B., Chow, C.W.K., and Saint, C., 2009, Kinetic study and equilibrium isotherm analysis of Congo Red adsorption by clay materials, Chem. Eng. J., 148 (2-3), 354–364.

[28] Auta, M., and Hameed, B.H., 2013, Acid modified local clay beads as an effective low-cost adsorbent for dynamic adsorption of methylene blue, J. Ind. Eng. Chem., 19 (4), 1153–1161.

[29] Tempkin, M.J., and Pyzhev, V., 1940, Recent modification to Langmuir isotherms, Acta Physicochim. URSS, 12, 217–222.

[30] 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, J. Thermodyn., 2013, 375830.

[31] Gómez, V., Larrechi, M.S., and Callao, M.P., 2007, Kinetic and adsorption study of acid dye removal using activated carbon, Chemosphere, 69 (7), 1151–1158.

[32] Giles, C.H., MacEwan, T.H., Nakhwa, S.N., and Smith, D., 1960, Studies in adsorption. Part XI. A system of classification of solution adsorption isotherms, and its use in the diagnosis of adsorption mechanisms and in the measurement of specific surface areas of solids, J. Chem. Soc., 14, 3973–3993.

[33] Zamri, T.K.A.T.M., Munaim, M.S.A., and Wahid, Z.A., 2017, Regression analysis for the adsorption isotherms of natural dyes onto bamboo yarn, Int. Res. J. Eng. Technol., 4 (6), 1699–1703.

[34] Yuh-Shan, H., 2004, Citation review of Lagergren kinetic rate equation on adsorption reactions, Scientometrics, 59, 171–177.

[35] Ho, Y.S., 2006, Review of second-order models for adsorption systems, J. Hazard. Mater., 136 (3), 681–689.

[36] Daneshvar, E., Vazirzadeh, A., Niazi, A., Kousha, M., Naushad, M., and Bhatnagar, A., 2017, Desorption of Methylene blue dye from brown macroalga: Effects of operating parameters, isotherm study, and kinetic modeling, J. Cleaner Prod., 152, 443–453.


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