- Research Article
- Open Access
Effect of Brønsted acidity of HY zeolites in adsorption of methylene blue and comparative study with bentonite
© Springer Nature Switzerland AG 2018
- Received: 16 April 2018
- Accepted: 12 August 2018
- Published: 18 August 2018
In the present study, HY zeolite with various Si/Al ratios have been used as adsorbents for the removal of a cationic dye; methylene blue, from aqueous solution using a batch process, and a comparative study with bentonite was conducted. Characterizations of the adsorbents were carried out by nitrogen adsorption–desorption, pyridine chemisorption followed by infrared spectroscopy and X-ray fluorescence. The effects of various parameters such as contact time, initial MB concentration, adsorbent concentration and solution pH were investigated. The adsorption of methylene blue on the zeolites is directly related to the Brønsted acidity where each molecule of MB corresponds to one Brønsted acid site. This means that the adsorption mechanism occurs via a cation exchange. So, adsorption of MB can be used to determine the Brønsted acidity of HY zeolites. The highest removal efficiency (181 mg g−1) corresponding to 86% of the abatement rate has been obtained with the bentonite. At lower dye concentrations (≤ 50 mg L−1), HY (16.6) and bentonite have a close adsorption capacities, 93 mg g−1 (97%) and 96 mg g−1 (99%) respectively. For both material types, the pseudo-second-order kinetic model fits very well with the experimental data. Equilibrium data fitted well the Langmuir isotherm model in the studied concentrations range of MB.
- Brønsted acidity
- Methylene blue
The industry has always been considered as a major source of pollution. Among the various pollutants released into the environment, dyes are found in large quantities because of the textile industry that consumes a large amount of water and thus releases a considerable fraction of these dyes in its aqueous effluents . Dyes are not only visually detected and aesthetically displeasing, they affect aquatic life and photosynthesis reactions by preventing sunlight from penetrating water, their degradation is so dangerous to the aquatic environment and human life even at low concentrations. Different types of dyes exist and methylene blue is widely used in medicine, dyeing cotton, wood and silk. Its overuse can cause serious problems for human life, thus, it must be eliminated from our environment [2, 3]. Several techniques are used for the removal of organic and inorganic pollutants, such as: chemical oxidation processes , photocatalysis , decolorization , enzymatic elimination [7, 8] and adsorption [9, 10]. The simplest technique and most effective is adsorption, and the most widely used adsorbent is activated carbon because of its large surface area leading to a large adsorption capacity, but in recent decades much research has been conducted with the aim of replacing activated carbon because of its low selectivity and the difficulty of its regeneration [11, 12]. For this reason, other effective synthetic and natural adsorbents have been tested as silico-aluminates . Bentonite is one of the most extensively used adsorbents of dyes removal and it has already been shown to have a high adsorption capacity . The bentonite is not the only silico-aluminate used for the adsorption of organic molecules; other materials such as zeolites are very attractive because they offer several possibilities in terms of specific surface, pore size, Si/Al ratio, acidity and high thermal stability. However, a number of research studies have been conducted on dye removal using natural zeolite , and other investigations have been conducted on methylene blue removal using synthetic zeolite where the effect of experimental parameters has been examined such as pH, time, adsorbent concentration and initial dye concentration . The effectiveness of the zeolites is related to their specific surfaces and the diameter of their pores . So, in order to avoid the problems of diffusion, HY zeolite is suitable for removing organic molecules [18, 19]. HY zeolite has a tri-dimensional porous structure (porous volume accounts for 50% of total volume) in which pores form large interconnected cavities accessible by large openings (7.4 Å). Thus, HY zeolite structure provides a good accessibility for organic molecules to the internal adsorption sites.
In our study, in addition to these structural properties (specific surfaces and pores diameter), we want to examine the effects of the functional property of the HY zeolites on the adsorption of methylene blue. This study was not done before. For this purpose, we used zeolite in their protonic form (HY) at different Si/Al ratios to determine the effects of their acidity on their adsorption capacities to remove methylene blue (MB) from an aqueous solution. The effect of the experimental conditions such as pH, time, adsorbent concentration and initial dye concentration has been examined as well as the adsorption equilibrium and kinetics. A comparative study with bentonite was conducted.
Adsorbate and adsorbent
The three commercial zeolites HY (Si/Al = 2.9, Si/Al = 16.6, Si/Al = 30.0) were purchased from Zeolyst International, the acid-activated bentonite (Si/Al = 3.3) was donated to us by the Algerian industry Cevital; these samples were directly used as adsorbents without further post-treatment. Faujasite samples were denoted as HY (2.9), HY (16.6) and HY (30.0), where the numbers 2.9, 16.6 and 30.0 indicate the global Si/Al ratios determined by X-ray fluorescence. The adsorbate Methylene blue (3,7 bis (Dimethylamino)- phenazathionium chloride), (chemical formula, C16H18N3SCl; M, 319.85 g mol−1) was purchased from MERCK Eurolab S.A.
The Si/Al ratio of the materials was determined by X-ray fluorescence. The textural characteristics of the adsorbents were determined by nitrogen adsorption at 77 K using Micromeritics ASAP-2000. The specific surface area (SBET) was calculated by the BET equation. The total pore volume (Vtotal) was estimated from nitrogen adsorption at a relative pressure of 0.97, the microporous volume (Vmicro) was determined by the t-plot method and the mesoporous volume (Vmeso) was the difference between Vtotal and Vmicro. The acidity of the different zeolites and the bentonite was determined by pyridine chemisorption followed by infrared spectroscopy using FT-IR NEXUS Thermo–Nicollet under secondary vacuum. The adsorbents were pretreated from room temperature to 450 °C (heating rate of 2 °C/min for 12 h) under secondary vacuum. After collecting the reference spectra, pyridine adsorption takes place at 150 °C. The amount of pyridine adsorbed on the Brønsted and Lewis sites is determined by integrating the band areas at respectively 1545 cm−1 and 1454 cm−1 and using the following extinction coefficients: ε1545 = 1.13 and ε1454 = 1.28 cm mol−1 .
The MB absorbance measurements were done at 666 nm with a UV–vis spectrometer (UV-SCAN, Shimadzu spectroscan 50).
Batch adsorption procedure and statistics
All the adsorption experiments, whatever the studied parameter, were carried out in batch conditions at 25 °C and under atmospheric pressure. Each adsorption experiment consisted in preparing 20 mL of dye solution by diluting the stock solution with distilled water to a given concentration and transferring them into an Erlenmeyer flask on a mechanic agitator. A weighted amount of adsorbent was then added to the solution and agitated mechanically for a given period. Thereafter the samples were centrifuged to separate the adsorbent from the liquid phase, and the dye concentration was determined by UV-visible spectrophotometry.
Each experiment was repeated three times and the mean results with the error bar (± standard deviation) were presented using MS Excel 2010. All the figures were drawn using MS Excel 2010.
Physico-chemical characteristics of adsorbents used
atom per cell
To avoid the collapse of the zeolites structures, no exchange of the alkaline cations was made. The zeolites are used with the acidity values determined by pyridine chemisorption followed by infrared spectroscopy and mentioned in the Table 1. The effect of Brønsted acidity of zeolites on the adsorption of MB has been demonstrated.
MB batch adsorption experiments
Effect of adsorbent concentration
Effect of pH
Effect of contact time and initial dye concentration
The contact time necessary to reach equilibrium depends on the initial dye concentration and on the nature of the materials. For the bentonite, the equilibrium is reached more quickly compared to zeolites. For an initial dye concentration of 5 mg L−1 and 10 mg L−1, equilibrium is reached after only 1 h for bentonite while it takes 2 h for HY. For initial dye concentration of 50 mg L−1 and 100 mg L−1 equilibrium is reached after 5 h for bentonite and 10 h for the zeolites. In the case of bentonite, the interlayer cations neutralize the randomly distributed negative charges on the octahedral sheet. And in this case the cations do not act as locks between two neighbouring sheets. Consequently, the crystal sheets are weakly bonded together and, thus, more water molecules can penetrate into the interlayer space which becomes larger and facilitates the diffusion of methylene blue molecules .
Adsorption kinetics modeling and mechanism
The values of the adsorption rate constant, k1, equilibrium adsorption capacity, qe(theo), and the correlation coefficient, R2, were determined from the plot of ln (qe– qt) against t at different initial concentrations.
MB adsorption kinetics constants
aC0 (mg L−1)
bqe (exp) (mg g−1)
cqe (theo) (mg g−1)
cK2 (g mg−1 h−1)
cH (mg g−1 h−1)
dKt (mg g−1 h-0.5)
dDip 10−6 (cm2 s−1)
dDf 10−6 (cm2 s−1)
For the intra-particle diffusion, the adsorption process occurs in two phases for all the different adsorbents except for bentonite at low initial concentrations. The two phases suggest that the adsorption process proceeds by surface adsorption followed by the intra-particle diffusion . The first straight section is characterized by a fast uptake. This behavior can be explained by the availability of free sites on the external surface of the solid and strong adsorbate-adsorbent interactions. At the second phase, adsorption becomes very slow because of the low diffusion of adsorbed molecules MB from the film surface through the micropores which are hardly accessible. For the bentonite at low concentration (5 and 10 mg L−1), adsorption occurs in one step, and at high concentrations (50 and 100 mg L−1), the adsorption is controlled by two steps, the first is attributed to the surface adsorption and the second is expressed as the intra-particle diffusion.
Isotherms of adsorption
The isotherm parameters of the Langmuir model for the adsorption of MB have been obtained using the non-linear regression method.
Parameter values of adsorption models
qmax (μmol g−1)
KL (L mg−1)
Comparison of MB adsorption capacities of various adsorbents
Adsorption capacity (mg g−1)
activated carbon from tobacco stalks
gold nanoparticles loaded on activated carbon
Fly Ash-based Geopolymer
Cold plasma treated bentonite
The adsorption of MB does not depend on solution pH from 5 to 11 while it depends on contact time, initial dye concentration and adsorbent amount. The equilibrium data fit perfectly the Langmuir model of adsorption, showing homogeneous distribution of active sites on all adsorbents surface. Zeolites can be used as adsorbent for the removal of MB from wastewater. The results show that adsorption of MB was highly dependent on the acid properties of zeolites. One molecule of MB is adsorbed by one Brønsted acid site. So, to determine the Brønsted acidity of HY zeolites we can use adsorption of methylene blue which is much cheaper than adsorption of pyridine. The maximum adsorption uptake is obtained with bentonite. At lower dye concentrations (≤ 50 mg L−1), HY (16.6) and bentonite have the same adsorption efficiency (98%). The pseudo-second-order kinetic model agrees very well with the experimental results. The kinetics of MB adsorption in all adsorbents follows the intraparticle diffusion model, and the data related by two straight lines indicate that the intraparticle diffusion is not the only rate controlling step.
The authors would like to acknowledge the support provided by both the Algerian and French governments for funding this work through project Tassili No. 12-MDU/859. We are grateful to Faculty of Technology, Abderrahmane Mira University of Bejaia for its support. We also want to thank Mr. Brahim KASMI of the INALCO (Institut Nationale des Langues et Civilisations Orientales), France, for the valuable corrections of the English language.
Compliance with ethical standards
Conflicts of interest
The authors declare no conflict of interest.
- Ganjali MR, Khoobi M, Nazmara S, Mahvi AH. Modeling of reactive blue 19 azo dye removal from colored textile wastewater using L-arginine-functionalized Fe3O4 nanoparticles: optimization, reusability, kinetic and equilibrium studies. J Magn Magn Mater. 2015;404:179–89. https://doi.org/10.1016/j.jmmm.2015.12.040.Google Scholar
- Vadivelan V, Kumar KV. Equilibrium, kinetics, mechanism, and process design for the sorption of methylene blue onto rice husk. J Colloid Interface Sci. 2005;286:90–100.View ArticleGoogle Scholar
- Augustine EO. Sorptive removal of methylene blue from aqueous solution using palm kernel fibre: effect of fibre dose. J Biochem Eng. 2008;40:8–18.View ArticleGoogle Scholar
- Ana RR, Olga CN, Manuel FRP, Adrián MTS. An overview on the advanced oxidation processes applied for the treatment of water pollutants defined in the recently launched directive 2013/39/EU. Environ Int. 2015;75:33–51.View ArticleGoogle Scholar
- Reddy PV, Kim KH. A review of photochemical approaches for the treatment of a wide range of pesticides. J Hazard Mater. 2015;285:325–35.View ArticleGoogle Scholar
- Mirzadeh SS, Khezri SM, Rezaei S, Forootanfar H, Mahvi AH, Faramarzi MA. Decolorization of two synthetic dyes using the purified laccase of Paraconiothyrium variabile immobilized on porous silica beads. J Environ Health Sci Eng. 2014;12:6.View ArticleGoogle Scholar
- Kamani H, Safari GH, Asgari G, Ashrafi SD. Data on modeling of enzymatic elimination of direct red 81 using response surface methodology. Data Brief. 2018;18:80–6.View ArticleGoogle Scholar
- Ashrafi SD, Rezaei S, Forootanfar H, Mahvi AH, Faramazi MA. The enzymatic decolorization and detoxification of synthetic dyes by the laccase from a soil-isolated ascomycete, Paraconiothyrium variabile. Int Biodeterior Biodegrad. 2013;85:173–81.View ArticleGoogle Scholar
- Shirmardi M, Mesdaghinia A, Mahvi AH, Nasseri S, Nabizadeh R. Kinetics and equilibrium studies on adsorption of acid red 18 (azo-dye) using multiwall carbon nanotubes (MWCNTs) from aqueous solution. E-J Chem. 2012;9:2371–83.View ArticleGoogle Scholar
- Ashrafi SD, Kamani H, Mahvi AH. The optimization study of direct red 81 and methylene blue adsorption on NaOH-modified rice husk. Desalin Water Treat. 2014;57(2):738–46.View ArticleGoogle Scholar
- Shirmardi M, Mahvi AH, Mesdaghinia A, Nasseri S, Nabizadeh R. Adsorption of acid red18 dye from aqueous solution using single-wall carbon nanotubes: kinetic and equilibrium. Desalin Water Treat. 2013;51:6507–16.View ArticleGoogle Scholar
- Shirmardi M, Mahvi AH, Hashemzadeh B, Naeimabadi A, Hassani G, Vosoughi NM. The adsorption of malachite green (MG) as a cationic dye onto functionalized multi walled carbon nanotubes. Korean J Chem Eng. 2013;30:1603–8.View ArticleGoogle Scholar
- Andrejkovičová S, Sudagar A, Rocha J, Patinha C, Hajjaji W, Ferreira da Silva E, et al. The effect of natural zeolite on microstructure, mechanical and heavy metals adsorption properties of metakaolin based geopolymers. Appl Clay Sci. 2016;126:141–52.View ArticleGoogle Scholar
- Kurniawan A, Sutiono H, Ju YH, Soetaredjo FE, Ayucitra A, Yudha A, et al. Utilization of rarasaponin natural surfactant for organo-bentonite preparation: application for methylene blue removal from aqueous effluent. Microporous Mesoporous Mater. 2011;142:184–93.View ArticleGoogle Scholar
- Han R, Zhang J, Han P, Wang Y, Zhao Z, Tang M. Study of equilibrium, kinetic and thermodynamic parameters about methylene blue adsorption onto natural zeolite Y. J Chem Eng. 2009;145:496–504.View ArticleGoogle Scholar
- Sapawe N, Jalil AA, Triwahyono S, Shah MIA, Jusoh R, Salleh NFM, et al. Cost-effective microwave rapid synthesis of zeolite NaA for removal of methylene blue. J Chem Eng. 2013;229:388–98.View ArticleGoogle Scholar
- Jamil TS, Abdel-Ghafar HH, Ibrahim HS, Abd-El-Maksoud IH. Removal of methylene blue by two zeolites prepared from naturally occurring Egyptian kaolin as cost effective technique. Solid State Sci. 2011;13:1844–51.View ArticleGoogle Scholar
- Martucci A, Pasti L, Marchetti N, Cavazzini A, Dondi F, Alberti A. Adsorption of pharmaceuticals from aqueous solutions on synthetic zeolites. Microporous Mesoporous Mater. 2012;148:174–83.View ArticleGoogle Scholar
- Sannino F, Ruocco S, Marocco A, Esposito S, Pansini M. Cyclic process of simazine removal from waters by adsorption on zeolite H-Y and its regeneration by thermal treatment. J Hazard Mater. 2012;229-230:354–60.View ArticleGoogle Scholar
- Chaouati N, Soualah A, Hussein I, Comparot JD, Pinard L. Formation of weak and strong Brønsted acid sites during alkaline treatment on MOR zeolite. Appl Catal A Gen. 2016;526:95–104.View ArticleGoogle Scholar
- Paixao V, Carvalho AP, Rocha J, Fernandes A, Martins A. Modification of MOR by desilication treatments: structural, textural and acidic characterization. Microporous Mesoporous Mater. 2010;131:350–7.View ArticleGoogle Scholar
- Guisnet M, Ribeiro FR. Les zéolithes: un nanomonde au service de la catalyse. EDP Sciences: chimie, matériaux, avenue du Hoggar, France; 2006.Google Scholar
- Ashrafi SD, Kamani H, Soheil Arezomand H, Yousefi N, Mahvi AH. Optimization and modeling of process variables for adsorption of basic blue 41 on NaOH-modified rice husk using response surface methodology. Desalin Water Treat. 2015;57(30):14051–9.View ArticleGoogle Scholar
- Takdastan A, Mahvi AH, Lima EC, Shirmardi M, Babaei AA, Goudarzi G, et al. Preparation, characterization, and application of activated carbon from low-cost material for the adsorption of tetracycline antibiotic from aqueous solutions. Water Sci Technol. 2016;74:2349–63.View ArticleGoogle Scholar
- Almeida CAP, Debacher NA, Downs AJ, Cottet L, Mello CAD. Removal of methylene blue from colored effluents by adsorption on montmorillonite clay. J Colloid Interface Sci. 2009;332:46–53.View ArticleGoogle Scholar
- Alver E, Metin AU. Anionic dye removal from aqueous solutions using modified zeolite: adsorption kinetics and isotherm studies. J Chem Eng. 2012;200–202:59–67.View ArticleGoogle Scholar
- Ashrafi SD, Kamani H, Jaafari J, Mahvi AH. Experimental design and response surface modeling for optimization of fluoroquinolone removal from aqueous solution by NaOH-modified rice husk. Desalin Water Treat. 2015;57(35):16456–65.View ArticleGoogle Scholar
- Rida K, Bouraoui S, Hadnine S. Adsorption of methylene blue from aqueous solution by kaolin and zeolite. Appl Clay Sci. 2013;83–84:99–105.View ArticleGoogle Scholar
- Sohrabnezhad S, Pourahmad A. Comparison absorption of new methylene blue dye in zeolite and nanocrystal zeolite. Desalination. 2010;256:84–9.View ArticleGoogle Scholar
- Li C, Zhong H, Wang S, Xue J, Zhang Z. Removal of basic dye (methylene blue) from aqueous solution using zeolite synthesized from electrolytic manganese residue. J Ind Eng Chem. 2015;23:344–52.View ArticleGoogle Scholar
- Daou I, Zegaoui O, Chfaira R, Ahlafi H, Moussout H. Physico-chemical characterization and kinetic study of methylene blue adsorption onto a Moroccan bentonite. Int J Sci Res Publ. 2015;5:1–9.Google Scholar
- Wang L, Zhang J, Wang A. Fast removal of methylene blue from aqueous solution by adsorption onto chitosan-g-poly (acrylic acid)/attapulgite composite. Desalination. 2011;266:33–9.View ArticleGoogle Scholar
- Ofomaja AE. Kinetic study and sorption mechanism of methylene blue and methyl violet onto mansonia (Mansonia altissima) wood sawdust. J Chem Eng. 2008;143:85–95.View ArticleGoogle Scholar
- Chabania M, Amrane A, Bensmaili A. Kinetic modelling of the adsorption of nitrates by ion exchange resin. J Chem Eng. 2006;125:111–7.View ArticleGoogle Scholar
- Gupta VK, Rastogi A. Biosorption of hexavalent chromium by raw and acid-treated green alga Oedogonium hatei from aqueous solutions. J Hazrd Mater. 2009;163:396–402.View ArticleGoogle Scholar
- Giles CH, Smith D, Huitson A. A general treatment and classification of the solute adsorption isotherm. J Colloid Interface Sci. 1974;47:755–65.View ArticleGoogle Scholar
- Mudyawabikwa B, Mungondori HH, Tichagwa L, Katwire DM. Methylene blue removal using a low-cost activated carbon adsorbent from tobacco stems: kinetic and equilibrium studies. Water Sci Technol. 2017;75(10):2390–402.View ArticleGoogle Scholar
- Roosta M, Ghaedi M, Daneshfar A, Sahraei R, Asghari A. Optimization of the ultrasonic assisted removal of methylene blue by gold nanoparticles loaded on activated carbon using experimental design methodology. Ultrason Sonochem. 2014;21(1):242–52.View ArticleGoogle Scholar
- EL Alouani M, Alehyen S, EL Achouri M, Taibi M. Removal of cationic dye – methylene blue- from aqueous solution by adsorption on fly ash-based Geopolymer. J Mater Environ Sci. 2018;9(1):32–46.Google Scholar
- Sen TK, Afroze S, Ang H. Equilibrium, kinetics and mechanism of removal of methylene blue from aqueous solution by adsorption onto pine cone biomass of Pinus radiata. Water Air Soil Pollut. 2011;218:499–515.View ArticleGoogle Scholar
- Şahin Ö, Kaya M, Saka C. Plasma-surface modification on bentonite clay to improve the performance of adsorption of methylene blue. Appl Clay Sci. 2015;116–117:46–53.Google Scholar
- Sarma GK, SenGupta S, Bhattacharyya KG. Methylene blue adsorption on natural and modified clays. Sep Sci Technol. 2011;46:1602–14.View ArticleGoogle Scholar