IJE TRANSACTIONS A: Basics Vol. 31, No. 1 (January 2018) 1-11   

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R. Heydari and M. Khavarpour
( Received: September 29, 2017 – Accepted in Revised Form: November 30, 2017 )

Abstract    The object of present study was to examine the adsorption potential of nanozeolite clinoptilolite (CP) for the removal of malachite green (MG) from aqueous phase in a batch equilibrium system. SEM, EDX, XRF, XRD and FT-IR techniques of characterization of zeolite were applied. The effects of initial pH solution, adsorbent dose, temperature, contact time and initial MG concentration on adsorption were evaluated. Adsorption experiments were conducted at initial concentrations in the range of 10–50 mg/L and temperatures at 25, 30 and 35°C. MG adsorption uptake was found to increase with an increase in contact time, initial MG concentration and solution temperature. The adsorption equilibrium data revealed the best fit with Koble-Corrigan model. The kinetics of MG on adsorbent followed the pseudo-second-order model. In addition, the assessment of kinetic data depicted that the adsorption rate was controlled by intraparticle diffusion mechanism. The negative values of standard Gibbs free energy represented the spontaneous adsorption at the stated temperature. The positive values of enthalpy and entropy changes also confirmed the increased randomness and endothermic nature of MG adsorption on nanozeolite CP adsorbent. Furthermore, the obtained activation energy showed the physical adsorption process.


Keywords    Adsorption Kinetics; Thermodynamics; Malachite Green; Nanozeolite Clinoptilolite; Isotherm Models


چکیده    هدف از مطالعه حاضر، بررسی پتانسيل جذب نانو زئولیت کلینوپتیلولیت (CP) برای حذف مالاچیت گرین (MG) از فاز آبی در یک سیستم تعادلی ناپیوسته است. تکنیکهای SEM، EDX، XRF، XRD و FT-IR برای مشخص کردن خصوصیات زئولیت استفاده شد. اثرات pH اولیه محلول، دوز جاذب، دما، زمان تماس و غلظت اولیه MG در جذب مورد بررسی قرار گرفت. آزمایش های جذب در محدوده غلظت های اولیه 10-50 میلی گرم در لیتر در دمای 25، 30 و 35 درجه سانتیگراد انجام شد. میزان جذب MG با افزايش زمان تماس، غلظت اوليه MG و دماي محلول افزايش يافت. داده های تعادلی جذب مناسب ترین تطابق را با مدل کوبل-کوریگان نشان دادند. سینتیک MG روی جاذب از مدل شبه درجه دوم پیروی کرد. علاوه بر این، ارزیابی داده های سینتیکی نشان داد که میزان جذب توسط مکانیسم نفوذ درون ذره ای کنترل می شود. مقادیر منفی انرژی آزاد گیبس استاندارد، جذب خود به خودی را در دماهای مورد مطالعه نشان داد. مقادیر مثبت تغییرات آنتالپی و آنتروپی نیز تصادفی بودن و طبیعت گرماگیر بودن جذب MG را بر روی جاذب نانوزئولیت CP تأیید می کنند. علاوه بر این، انرژی فعال به دست آمده، روند جذب فیزیکی را نشان می دهد.


1. Dezhampanah, H., Mohammad-khah, A. and Aghajani, N., “Equilibrium and thermodynamic studies of thionine adsorption from aqueous solution onto rice husk”, European Chemical Bulletin, Vol. 2, (2014), 709-714.

2. Ajemba, R. O., “Adsorption of Malachite Green from Aqueous Solution using Activated Ntezi Clay: Optimization, Isotherm and Kinetic Studies”, International Journal of Engineering, Vol. 27, No. 6, (2014), 839-854.

3. Bharathi, K. and Ramesh, S., “Removal of dyes using agricultural waste as low-cost adsorbents: a review”, Applied Water Science, Vol. 3, (2013), 773-790.

4. Baldez, E.E., Robaina, N.F. and Cassella, R.J., “Employment of polyurethane foam for the adsorption of Methylene Blue in aqueous medium”, Journal of Hazardous Material, Vol. 159, (2008), 580-586.

5. Mishra, G. and Tripathy, M., “A critical review of the treatment for decolorization of dye wastewater”, Colourage, Vol. 40, (1993), 35-38.

6. Wang, X.S., Zhou, Y., Jiang, Y. and Sun, C., “The removal of basic dyes from aqueous solutions using agricultural by-products”, Journal of Hazardous Material, Vol. 157, (2008), 374-385.

7. Dezhampanah, H., Mousazadeh, A. and Mousazadeh, I., “Sugarcane Bagasse and Modified Rice Husk for the Removal of Malachite Green from Aqueous Wastes”, European Chemical Bulletin, Vol. 3, (2013), 400-406.

8. Ngah, W., Saime, W., Ariff, N.F.M., Hashim, A. and Hanafiah, M.A.K.M., “Malachite green adsorption onto chitosan coated bentonite beads: isotherms, kinetics and mechanism”, Clean-Soil, Air, Water, Vol. 38, (2010), 394-400.

9. Agarwala, S., Nekoueib, F. Kargarzadehc, H., Nekoueib, S., Tyagid, I. and Gupta, V.K., “Preparation of Nickel hydroxide nanoplatesmodified activated carbon for Malachite Greenremoval from solutions: Kinetic, thermodynamic,isotherm and antibacterial studies”, Process Safety and Environmental Protection, Vol. 102, (2016), 85-97.

10. Humelnicu, I., Baiceanu, A., Ignat, M.E. and Dulman, V., “The Removal of Basic Blue 41 Textile Dye from Aqueous Solution by Adsorption onto Natural Zeolitic Tuff: Kinetics and Thermodynamics”, Process Safety and Environmental Protection, Vol. 105, (2017), 274–287.

11. Han, R., Ding, D., Xu, Y., Zou, W., Wang, Y., Li, Y. and Zou, L., “Use of rice husk for the adsorption of congo red from aqueous solution in column mode”, Bioresource Technology, Vol. 99, (2008), 2938-2946.

12. Mall, I.D., Srivastava, V.C., Agarwal, N.K. and Mishra, I.M., “Adsorptive removal of malachite green dye from aqueous solution by bagasse fly ash and activated carbon-kinetic study and equilibrium isotherm analyses”, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 264, (2005), 17-28.

13. El Qada, E.N., Allen, S.J. and Walker, G.M., “Adsorption of basic dyes from aqueous solution onto activated carbons”, Chemical Engineering Journal, Vol. 135, (2008), 174-184.

14. Walker, G. and Weatherley, L., “Textile wastewater treatment using granular activated carbon adsorption in fixed beds”, Separation Science and Technology, Vol. 35, (2000), 1329-1341.

15. Samiey, B. and Toosi, A.R., “Adsorption of malachite green on silica gel: Effects of NaCl, pH and 2-propanol”, Journal of Hazardous Materials, Vol. 184, (2010), 739-745.

16. Zanin, E., Scapinello, J., de Oliveira, M., Rambo, C.L., Franscescon, F., Freitas, L., de Mello, J.M.M., Fiori, M.A., de Oliveira, J.V. and Dal Magro, J. “Adsorption of heavy metals from wastewater graphicindustry using clinoptilolite zeolite as adsorbent”, Process Safety and Environmental Protection,Vol. 105, (2017), 194–200.

17. Kallo, D., Papp, J. and Valyon, J., “Adsorption and catalytic properties of sedimentary clinoptilolite and mordenite from the Tokaj Hills, Hungary”, Zeolites, Vol. 2, (1982), 13-16.

18. Baghbanian, S.M., Rezaei, N. and Tashakkorian, H.,. “Nanozeolite clinoptilolite as a highly efficient heterogeneous catalyst for the synthesis of various 2-amino-4 H-chromene derivatives in aqueous media”, Green Chemistry, Vol. 15, (2013), 3446-3458.

19. Jeon, C. and Park, K.H., “Adsorption and desorption characteristics of mercury (II) ions using aminated chitosan bead”,  Water Research, Vol. 39, (2005), 3938-3944.

20. Ahmad, M.A. and Alrozi, R., “Removal of malachite green dye from aqueous solution using rambutan peel-based activated carbon: Equilibrium, kinetic and thermodynamic studies”, Chemical Engineering Journal, Vol. 171, (2011), 510-516.

21. Langmuir, I., “Constitution and fundamental properties of solids and liquids. I: solids”, Journal of Hazardous Materials, Vol. 139, (2007), 57-66.

22. Weber, T.W. and Chakravorti, R.K., “Pore and solid diffusion models for fixed-bed adsorbers”, AIChE Journal, Vol. 20, (1974), 228-238.

23. Das, D. and Pal, A., “Adsolubilization phenomenon perceived in chitosan beads leading to a fast and enhanced malachite green removal”, Chemical Engineering Journal, Vol. 290, (2016), 371-380.

24. Freundlich, H., “Over the adsorption in solution”, The Journal of Physical Chemistry A, Vol. 57, (1906), 1100-1107.

25. Temkin, M. and Pyzhev, V., “Recent modifications to Langmuir isotherms”,ActaPhysiochimica U. S. S. R., Vol. 12, (1940), 217-222.

26. Polyzopoulos, N., Keramidas, V. and KiossE, H., “Phosphate sorption by some alfisols of Greece as described by commonly used isotherms”, Soil Science Society of America Journal, Vol. 49, (1985), 81-84.

27. Koble, R.A. and Corrigan, T.E., “Adsorption isotherms for pure hydrocarbons”, Ind. Eng. Chem. Vol. 44, (1952), 383-387.

28. Ho, Y.S. and McKay, G., “Pseudo-second order model for sorption processes”, Process Biochemistry, Vol. 34, (1999), 451-465.

29. Weber, W.J. and Morris, J.C., “Kinetics of adsorption on carbon from solution”, Journal of Sanitary Engineering Division, Vol. 89, (1963), 31-60.

30. Wu, X., Wang, Y., Liu, J., Ma, J. and Han, R., “Study of malachite green adsorption onto natural zeolite in a fixed-bed column”, Desalination and Water Treatment, Vol.20, (2010), 228–233.

31. Wang, S., Ariyanto, E., “Competitive adsorption of malachite green and Pb ions on natural zeolite”, Journal of Colloid and Interface Science, Vol. 314, (2007), 25–31.

32. Mohammadi, A., Daemi, H., Barikani,M., “Fast removal of malachite green dye using novel superparamagnetic sodium alginate-coated Fe3O4 nanoparticles”, International Journal of Biological Macromolecules, Vol. 69, (2014), 447-55.

33. Patil, M.R. and Shrivastava, V.S., “Adsorption of malachite green by polyaniline–nickel ferrite magnetic nanocomposite: an isotherm and kinetic study”, Applied Nanoscience, Vol. 5, (2015), 809–816.

34. Mohammadifar, E., Shemirani, F., Majidi, B., Ezoddin, M., “Application of modified nano-γ-alumina as an efficient adsorbent for removing malachite green (MG) from aqueous solution”, Desalination and Water Treatment, Vol. 54, (2014), 758-768.

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