Chemical Papers

, Volume 70, Issue 2, pp 153–163 | Cite as

Relationship between acidification factors and methylene blue uptake by Ca-bentonite: optimisation and kinetic study

  • Amin SalemEmail author
  • Mohsen Saghapour
Original Paper


This investigation studied the uptake of methylene blue from wastewater by normal and treated bentonites to evaluate the effects of acidification factors on removal efficiency. Hydrochloric, sulphuric and nitric acids were blended in accordance with the response surface methodology to prepare acidic agents. The normal clay was then mixed with the prepared solutions after drying in a laboratory oven. The set-up provided controllable conditions for producing nano-porous powders for which the residence time and temperature were changed. The removal efficiency of the treated powders was assessed by defining an adsorption ratio and determining the optimal composition for acidic agent. Based on the statistical theory and experimental data, nitric acid is a suitable agent for manufacturing porous material to remove methylene blue from wastewater. In addition, the Brunauer-Emmett-Teller method, X-ray diffraction and Fourier transform infrared spectroscopy techniques were applied to identify the structural changes. The experimental data obtained from the batch tests were analysed by a new kinetic model which predicted the data variation with higher regression coefficients and lower relative errors. The proposed procedure can be an important tool in optimising the acidification conditions for manufacturing a nano-porous powder with maximal removal efficiency.


bentonite nano-porous active solid response surface methodology adsorption methylene blue uptake kinetics 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Babaki, H., Salem, A., & Jafarizad, A. (2008). Kinetic model for the isothermal activation of bentonite by sulfuric acid. Materials Chemistry and Physics, 108, 263–268. DOI:  10.1016/j.matchemphys.2007.09.034.CrossRefGoogle Scholar
  2. Bieseki, L., Bertell, F., Treichel, H., Penha, F. G., & Pergher, S. B. C. (2013). Acid treatments of montmorillonite-rich clay for Fe removal using a factorial design method. Materials Research, 16, 1122–1127. DOI:  10.1590/s1516-14392013005000114.CrossRefGoogle Scholar
  3. Brezovska, S., Marina, B., Burevski, D., Angjusheva, B., Bosevska, V., & Stojanovska, L. (2005). Adsorption properties and porous structure of sulfuric acid treated bentonites determined by the adsorption isotherms of benzene vapor. Journal of Serbian Chemical Society, 70, 33–40.CrossRefGoogle Scholar
  4. Chiappone, A., Marello, S., Scavia, C., & Setti, M. (2004). Clay mineral characterization through the methylene blue test: Comparison with other experimental techniques and applications of the method. Canadian Geotechnical Journal, 41, 1168–1178. DOI:  10.1139/t04-060.CrossRefGoogle Scholar
  5. Çkça, E. (2002). Relationship between methylene blue value, initial soil suction and swell percent of expansive soil. Turkish Journal of Engineering and Environmental Sciences, 26, 521–529.Google Scholar
  6. Dellisanti, F., & Valdré, G. (2005). Study of structural properties of ion treated and mechanically deformed commercial bentonite. Applied Clay Science, 28, 233–244. DOI:  10.1016/j.clay.2003.12.036.CrossRefGoogle Scholar
  7. Díaz, F. R. V., & Santos, P. S. (2001). Studies on the acid activations of Brazilian smectitic clays. Química Nova, 24, 345–353. DOI:  10.1590/s0100-40422001000300011.Google Scholar
  8. Gates, W. P., Anderson, J. S., Raven, M. D., & Churchman, G. J. (2002). Mineralogy of a bentonite from Miles, Queensland, Australia and characterisation of its acid activation products. Applied Clay Science, 20, 189–197. DOI:  10.1016/s0169-1317(01)00072-2.CrossRefGoogle Scholar
  9. Gurnham, C. F. (1965). Industrial waste control. New York, NY, USA: Academic Press.Google Scholar
  10. Gürses, A., Yalçin, M., & Doğar, C. (2002). Electrocoagulation of some reactive dyes: a statistical investigation of some electrochemical variables. Waste Management, 22, 491–499. DOI:  10.1016/s0956-053x(02)00015-6.CrossRefGoogle Scholar
  11. Gürses, A., Doğar, C., Yalçin, M., Açıkyıldız, M., Bayrak, R., & Karaca, S. (2006). The adsorption kinetics of the cationic dye, methylene blue, onto clay. Journal of Hazardous Materials, 131, 217–228. DOI:  10.1016/j.jhazmat.2005.09.036.CrossRefGoogle Scholar
  12. Hao, O. J., Kim, H., & Chiang, P. C. (2000). Decolourization of wastewater. Critical Reviews in Environmental Science and Technology, 30, 449–505. DOI:  10.1080/10643380091184237.CrossRefGoogle Scholar
  13. Ijagbemi, C. O., Baek, M. H., & Kim, D. S. (2009). Montmorillonite surface and sorption characteristics for heavy metals removal from aqueous solutions. Journal of Hazardous Materials, 166, 538–546. DOI:  10.1016/j.jhazmat.2008.11.085.CrossRefGoogle Scholar
  14. Jenson, V. G., & Jeffreys, G. V. (1977). Mathematical methods in chemical engineering (2nd ed.). New York, NY, USA: Academic Press.Google Scholar
  15. Kahr, G., & Madsen, F. T. (1995). Determination of the cation exchange capacity and the surface area of bentonite, illite and kaolinite by methylene blue adsorption. Applied Clay Science, 9, 327–336. DOI:  10.1016/0169-1317(94)00028-o.CrossRefGoogle Scholar
  16. Karimi, L., & Salem, A. (2011). Analysis of bentonite specific surface area by kinetic model during activation process in presence of sodium carbonate. Microporous and Mesoporous Materials, 141, 81–87. DOI:  10.1016/j.micromeso.2010.10.031.CrossRefGoogle Scholar
  17. Kirali, E. G., & Laçin, O. (2006). Statistical modeling of acid activation on cotton oil bieaching by Turkish bentonite. Journal of Food Engineering, 75, 137–141. DOI:  10.1016/j.jfoodeng.2005.06.010.CrossRefGoogle Scholar
  18. 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, 61–69. DOI:  10.9767/bcrec.8.1.4530.61-69.CrossRefGoogle Scholar
  19. Ma, Y. L., Xu, Z. R., Guo, T., & You, P. (2004). Adsorption of methylene blue on Cu(II)-exchanged montmorillonite. Journal of Colloid and Interface Science, 280, 283–288. DOI:  10.1016/j.jcis.2004.08.044.CrossRefGoogle Scholar
  20. Margulies, L., Rozen, H., & Nir, S. (1988). Model for competitive adsorption of organic cations on clays. Clays and Clay Minerals, 36, 270–276.CrossRefGoogle Scholar
  21. Markovska, L., Meshko, V., Noveski, V., & Marinovski, M. (2001). Solid diffusion control of basic dyes adsorption on granular activated carbon and natural zeolite in fixed bed column. Journal of Serbian Chemical Society, 66, 463–475.Google Scholar
  22. Murray, H. H. (2000). Traditional and new applications for kaolin, smectite, and palygorskite: a general overview. Applied Clay Science, 17, 207–221. DOI:  10.1016/s0169-1317(00)00016-8.CrossRefGoogle Scholar
  23. Neumann, M. G., Gessner, F., Schmitt, C. C., & Sartori, R. (2002). Influence of the layer charge and clay particle size on the interactions between the cationic dye methylene blue and clays in an aqueous suspension. Journal of Colloid and Interface Science, 255, 254–259. DOI:  10.1006/jcis.2002.8654.CrossRefGoogle Scholar
  24. Önal, M., Sarikaya, Y., & Alemdaroğlu, T. (2001). Investigation of the microporous and mesoporous structures of the Reşadiye (Tokat/Turkey) bentonite and its fractions. Turkish Journal of Chemistry, 25, 241–249.Google Scholar
  25. Önal, M., Sarikaya, Y., & Alemdaroğlu, T. (2002). The effect of acid activation on some physico-chemical properties of a bentonite. Turkish Journal of Chemistry, 26, 409–416.Google Scholar
  26. 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. DOI:  10.1016/j.jcis.2004.03.043.CrossRefGoogle Scholar
  27. Pollard, S. J. T., Fowler, G. D., Sollars, C. J., & Perry, R. (1992). Low-cost adsorbents for waste and wastewater treatment: a review. Science of the Total Environment, 116, 31–52. DOI:  10.1016/0048-9697(92)90363-w.CrossRefGoogle Scholar
  28. Reife, A., & Freeman, H. S. (1996). Environmental chemistry of dyes and pigments. New York, NY, USA: Wiley.Google Scholar
  29. Salem, A., & Akbari Sene, R. (2011). Removal of lead from solution by combination of natural zeolite-kaolin-bentonite as a new low-cost adsorbent. Chemical Engineering Journal, 174, 619–628. DOI:  10.1016/j.cej.2011.09.075.CrossRefGoogle Scholar
  30. Salem, A., & Akbari Sene, R. (2012). Optimization of zeolite-based adsorbent composition for fabricating reliable Raschig ring shaped by extrusion using Weibull statistical theory. Microporous and Mesoporous Materials, 163, 65–75. DOI:  10.1016/j.micromeso.2012.06.026.CrossRefGoogle Scholar
  31. Salem, A., Afshin, H., & Behsaz, H. (2012). Removal of lead by using Raschig rings manufactured with mixture of cement kiln dust, zeolite and bentonite. Journal of Hazardous Materials 223–224, 13–23. DOI:  10.1016/j.jhazmat.2012.01.002.CrossRefGoogle Scholar
  32. Salem, A., & Saghapour, M. (2013). Effect of activation factors on adsorption of methylene blue by modified bentonite. Progress in Color, Colorants and Coatings, 6, 97–180.Google Scholar
  33. Salem, S., Salem, A., & Agha Babaei, A. (2015a). Preparation and characterization of nano porous bentonite for regeneration of semi-treated waste engine oil: Applied aspects for enhanced recovery. Chemical Engineering Journal, 260, 368–376. DOI:  10.1016/j.cej.2014.09.009.CrossRefGoogle Scholar
  34. Salem, S., Salem, A., & Agha Babaei, A. (2015b). Application of Iranian nano-porous Ca-bentonite for recovery of waste lubricant oil by distillation and adsorption techniques. Journal of Industrial and Engineering Chemistry, 23, 154–162. DOI:  10.1016/j.jiec.2014.08.009.CrossRefGoogle Scholar
  35. Santamarina, J. C., Klein, K. A., Wang, Y. H., & Prencke, E. (2002). Specific surface: determination and relevance. Canadian Geotechnical Journal, 39, 233–241. DOI:  10.1139/t01-077.CrossRefGoogle Scholar
  36. Slokar, Y. M., & Le Marechal, A. M. (1998). Methods of decoloration of textile wastewaters. Dyes and Pigments, 37, 335–356. DOI:  10.1016/s0143-7208(97)00075-2.CrossRefGoogle Scholar
  37. St. John, R. C. (1984). Experiments with mixtures, ill-conditioning, and ridge regression. Journal of Quality Technology, 16, 81–96.Google Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2015

Authors and Affiliations

  1. 1.Mineral Processing Research Centre, Chemical Engineering DepartmentSahand University of TechnologyTabrizIran
  2. 2.Centre of Excellence for Colour Science and TechnologyTehranIran

Personalised recommendations