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  • Iranica Journal of Energy and Environment 7(2): 129-136, 2016

    Please cite this article as: R. Alrozi, N. S. Anuar, F. Senusi, M. A. Kamaruddin, 2016. Enhancement of Remazol Brilliant Blue R Adsorption Capacity by using Modified Clinoptilolite, Iranica Journal of Energy and Environment 7 (2): 129-136.

    Iranica Journal of Energy & Environment

    Journal Homepage: IJEE an official peer review journal of Babol Noshirvani University of Technology, ISSN:2079-2115

    Enhancement of Remazol Brilliant Blue R Adsorption Capacity by using Modified

    Clinoptilolite R. Alrozi1*, N. S. Anuar1, F. Senusi1, M. A. Kamaruddin2 1Faculty of Chemical Engineering, UniversitiTeknologi MARA Pulau Pinang, 13500 PermatangPauh, Penang 2School of Civil Engineering, UniversitiSains Malaysia, 14300 NibongTebal, Penang

    P A P E R I N F O

    Paper history: Received 22July 2015 Accepted in revised form 15December 2015

    Keywords: Adsorption Clinoptilolite RBBR Kinetic Isotherm models

    A B S T R A C T

    In this study, the adsorption behavior of Remazol Brilliant Blue R (RBBR) from aqueous solution by

    using raw and modified clinoptilolites were investigated. In the experimental work, raw clinoptilolite (R-CL) was treated with Zn(NO3)2 in ethanol and produced zinc-grafted clinoptilolite (Zn-CL).The

    adsorption experiments were carried out under different conditions of initial concentration (25-250 mg/L), adsorption time (0-2h), solution pH (2-12), and temperature (300-353 K) to determine

    optimum conditions for the highest RBBR removal. The influence of these parameters on the

    adsorption capacity was studied using the batch process. The results indicated that the solution pH was observed to be a key factor of the RBBR adsorption process. The maximum dye adsorption was

    achieved with Zn-CL adsorbent at pH~6 and the corresponding adsorption capacity was found to be

    42.2 mg/g, which was higher than R-CL (12.5 mg/g). Lower adsorption capacity of RBBR was found by Zn-CL between pH 8 and 12 opposite to R-CL which showed a marginal increase in

    adsorption capacity within the same pH range. The results proved that Zn-CL which is a modified

    clinoptilolite is an effective adsorbent for the removal of RBBR from aqueous solution.

    doi: 10.5829/idosi.ijee.2016.07.02.07

    INTRODUCTION1 Reactive dyes have been extensively used intextile

    dyeing by which, significant amount of these types of

    dyes are released into the receiving water without

    appropriate and efficient treatment [1]. As a result,

    reoxygenation of water will be retarded due to limited

    sunlight penetration into the water surface.

    Nevertheless, reactive dyes are the most common dye

    employed in textile related industry due to their

    beneficial characteristics including bright color, water

    fastness, simple application techniques and low energy

    consumption. As a matter of fact, most of the dyes used

    in the industry nowadays carries significant amount of

    coloring materials that are toxic and harmful to

    organisms and human well being [2]. Up to 40% of the

    color is discharged in the effluent from reactive dyeing

    *Corresponding author: O. A. Oyelaran

    E-mail: [email protected];

    Tel:+04-3822445; Fax: +04-3822812

    operation resulting in a highly colored effluent. They are

    not easily biodegradable, thus, even after extensive

    treatment, color may still remain in the effluent [3].

    Therefore, there is a need to effectively remove

    these dyes from wastewater and some of the available

    methods to remove the dyes including chemical

    precipitation, adsorption, ion exchange, flotation,

    membrane filtration, electrochemical treatment and

    coagulation-flocculation. Until now, adsorption has

    been the most favourable process than others and this

    process has become more efficient if low-cost

    adsorbents are used [4].

    Natural zeolites are crystalline hydrated alumina

    silicates with a framework structure adsorbent. Zeolite

    normally exhibit pores occupied with, alkali and

    alkaline earth cations. They are abundant in nature,

    which can be obtained at low cost. The advantages of

    high cation-exchange and having the characteristics of

    molecular sieve properties, natural zeolites have been

    widely used as adsorbents in separation and purification

    for many years [5]. Akgl [1] found that the properties

  • Iranica Journal of Energy and Environment 7(2): 129-136, 2016


    of zeolites external surface can be tailored for specific

    applications through surface functionalization. These

    modifications can alter physical and chemical properties

    of the zeolites and the resulting modified zeolite can be

    used for a variety of applications such as ion-exchange,

    adsorption, catalysis, etc. [1, 6-7].

    In this study, raw clinoptilolite was modified via

    Zn2+-grafting to prepare a functionalized zeolite material

    that enhanced adsorptive properties for remazol brilliant

    blue R (RBBR) in aqueous solution. The dye adsorption

    capacity of the resulting modified zeolite was evaluated

    to determine the adsorption characteristics for RBBR.

    MATERIALS AND METHODS Adsorbate Remazol Brilliant Blue R (RBBR) supplied by Sigma-

    Aldrich (M) Sdn. Bhd, Malaysia was used as a model

    organic dye for evaluating the adsorption behavior of

    the sorbent. The negatively charged dye, RBBR has a

    chemical formula of C22H16N2Na2O11S3 with molecular

    weight of 626.54 g/mol. The chemical structure of

    RBBR is shown in Figure 1. Deionized water supplied

    by USF ELGA water treatment system was used to

    prepare all the reagents and solutions.

    Figure 1. The chemical structure of RBBR

    Adsorbent preparation and modifications Natural zeolite, clinoptilolite, sample was obtained from

    Malaysia Agricultural Research and Development

    Institute (MARDI) which mainly supplied to farmers as

    fertilizer to increase crops yield. Preparation of raw

    clinoptilolite (R-CL) was done by washing the

    clinoptilolite using deionized water to remove all dust or

    other impurities and to maintain the natural pH of the

    clinoptilolite. Next, the clinoptilolite was dried in an

    oven for 24 hour at 373.15 K to remove moisture. In

    order to obtain modified form, the R-CL was treated

    with Zn(NO3)2 in ethanol at 333 K. The treatment was

    carried out by adding 1.0 g R-CL into a Zn(NO3)2 (0.3

    g) solution in ethanol (15 mL). The concentration of

    Zn(NO3)2 was 0.1 mol/L with 99.9% purity. The

    mixture was treated in an oil bath at 333 K for 6 h.

    Then, the zeolite sample was separated by filtration,

    washed with ethanol to remove excess salt and dried at

    353 K for 24 h. The resulting Zn2+-grafted sample is

    designated as Zn-CL.

    Characterization Fourier transform infrared (FTIR) analysis was applied

    to determine the surface functional groups, using FTIR

    spectroscope (FTIR-2000, Perkin Elmer), where the

    spectra were recorded from 4000 to 450 cm1. The BET

    surface area, total pore volume and average pore size of

    the R-CL and Zn-CL were measured using ASAP 2020

    Micrometrics instrument by BrunauerEmmettTeller

    (BET) method.

    Adsorption studies Batch equilibrium studies were carried out by adding a

    0.5g of R-CL and Zn-CL each into 250 mL Erlenmeyer

    flasks containing 200 mL of different initial

    concentrations (25-250 mg/L) of dye solution. The

    flasks were agitated in an isothermal water-bath shaker

    at 120 rpm and different solution temperature (300-350

    K) for 24 h until equilibrium was reached. The pH was

    adjusted by adding a few drops of diluted 0.1M NaOH

    or 0.1M HCl and was measured using a pH meter

    (Model Delta 320, Mettler Toledo, Switzerland). The

    dye concentrations before and after treatment were

    measured using UV-Visible spectrophotometer (Model

    Shimadzu UV-1800, Japan) at 590 nm. The amount of

    equilibrium adsorption, qe (mg/g), was calculated by:

    qe = Co Ce

    W (1)

    where Co and Ce (mg/L) are the liquid-phase

    concentrations of RBBR at initial and at equilibrium,

    respectively. V is the volume of the solution (L) and W

    is the mass of dry adsorbent used (g).

    Batch kinetic studies The procedure of kinetic adsorption tests was identical

    to that of batch equilibrium tests, however the aqueous

    samples were taken at present time intervals. The

    concentrations of RBBR were similarly measures. The

    RBBR uptake at any time, qt (mg/g), was calculated by:

    Combustion rate: Burning time is obtained by

    observing the mass changes recorded on mechanical

    balance and also by using stop watch. It is the time for

    the biomass combustion to be completed. With known

    amount of total burnt briquette and burning time,

    average combustion rate can be calculated using the

    following formula [12].

    = ( )


    where Ct (mg/L) is the liquid-phase concentration of

    RBBR at any time, t (h).

  • Iranica Journal of Energy and Environment 7(2): 129-136, 2016


    RESULTS AND DISCUSSION Characterization FTIR spectra of R-CL and Zn-CL are shown in Figure

    2. The characteristic infrared signals for SiOAl