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PII: S0167-7322(18)30929-2
DOI: doi:10.1016/j.molliq.2018.05.100
Reference: MOLLIQ 9155
To appear in: Journal of Molecular Liquids
Received date: 22 February 2018
Revised date: 29 April 2018
Accepted date: 22 May 2018
Please cite this article as: Zoha Heidarinejad, Omid Rahmanian, Mehdi Fazlzadeh,
Mohsen Heidari , Enhancement of methylene blue adsorption onto activated carbon
prepared from Date Press Cake by low frequency ultrasound. The address for the
corresponding author was captured as affiliation for all authors. Please check if
appropriate. Molliq(2017), doi:10.1016/j.molliq.2018.05.100
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* Corresponding author: Mohsen Heidari, Email: moheidari84@gmail.com
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Abstract
This study was aimed to evaluate the adsorption of methylene blue onto activated
carbon prepared from Date Press Cake (AC-DPC) in the absence (stirring) and
presence of low frequency ultrasound (no stirring). Date Press Cake (DPC) was
converted into activated carbon (BET surface area of 2632.5 m 2 g-1) using solid KOH.
Batch adsorption experiments illustrated that the adsorption of MB onto AC-DPC was
more favored at alkaline conditions. Kinetics analysis showed that the adsorption of MB
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onto AC-DPC was controlled by film diffusion in both agitation methods. The values of
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adsorption rate constants in kinetic models were increased by applying low frequency
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ultrasound to the adsorption system. Such acceleration effect was reflected in
equilibrium contact times, which were 180 and 20 min in the absence and presence of
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ultrasound, respectively. The experimental equilibrium data for both agitation methods
were best fitted with Redlich-Peterson isotherm model, indicating chemisorption nature
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of MB adsorption onto AC-DPC. The maximum monolayer adsorption capacity of MB on
AC-DPC was found to be increased from 546.8 mg g -1 (stirring) to 613.8 mg g-1 in the
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carbon prepared from Date Press Cake efficiently adsorbed MB from aqueous
solutions. Moreover, the equilibrium and kinetics of MB adsorption onto AC-DPC could
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Keywords: Low frequency ultrasound; Adsorption; Activated Carbon; Date Press Cake;
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Methylene Blue
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1. Introduction
Dyestuffs are broadly used in paper, leather, textile and cosmetic industries. The waste
of such industries is abundant and poses detrimental impacts on public health and
environment [1-3]. Increasing concerns about the release of pollutants, including
dyestuffs, in water resources have led to the search for new treatment methods, and the
development of new materials [1,4]. Among the various techniques for the treatment of
aqueous environments, adsorption has gained importance due to system easy
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application, simple design, flexibility and low energy consumption [5,6]. Adsorption
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system is extensively applied for the removal of various pollutants and recovery of
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precious metal from aqueous solutions [7,8].
Carbon-based materials, especially activated carbon, are among the most common
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industrial adsorbents due to well-developed internal pore structure, high surface area
and high content of functional groups [9]. Nevertheless, large-scale usage of activated
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carbon is hampered when it produced from expensive and non-renewable precursors
[10]. Thus, preparing high quality activated carbon from abundant, cheap, renewable
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and sustainable precursors has been attracted great attention. In this regard, more
focus has been directed toward the search on the development of activated carbon from
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press [13]. Thus, the caked material remained on the filter press, here named Date
Press Cake (DPC), seems to be an inevitable by-product of such industries. According
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to the Food and Agriculture Organization of the United Nations (FAO), around 1157000
tons of date palm fruit was produced in Iran in 2014 [14]. In Hormozgan province (one of
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the country’s largest date producers), a massive amount of DPC is currently produced
and mainly dumped into open lands and drains [15]. The dumped DPC, which may pose
environmental problems, can be considered as a cheap, renewable and abundant
precursor for the production of activated carbon.
Ultrasonic waves are wildly used in metallurgy, modification and chemical industries due
to the advantage of mechanical action and acoustic cavitation [16]. The role of
ultrasound in adsorption of various pollutants from aqueous solutions has been recently
studies and controversial results have been reported. Li et al. (2002) reported that the
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capacity of activated carbon for the adsorption of phenol was reduced in the presence
of ultrasound [17]. However, several studies reported the positive effect of ultrasound on
adsorption process through enhancing the mass transfer rate in the solid-liquid systems
[1,18,19].
To our knowledge, KOH-activated carbon derived from DPC has not yet been prepared
and used for the removal of dyestuffs from aqueous solutions. Moreover, no specific
study has been done on the adsorption of methylene blue (MB), as a representative of
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cationic dyes, onto DPC-derived activated carbon (AC-DPC) in the presence of low
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frequency ultrasound. Therefore, the influence of low frequency ultrasound on the
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equilibrium and kinetics of MB/AC-DPC adsorption system is unknown. In this regard,
the main aim of this research was to evaluate the properties of MB adsorption on KOH-
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activated carbon prepared from DPC in the absence (stirring) and presence of low
frequency ultrasound (no stirring). The main textural and surface properties of the
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prepared activated carbon were also evaluated.
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stock solution of MB was prepared in deionized water and the required working dye
solutions were obtained from the stock solution. Raw Date Press Cake was gathered
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from a local date processing industry, dried at 105 °C, and ground to particle size < 1
mm.
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under nitrogen flow (100 mL min-1) at a rate of 20 °C min-1. After cooling, the mixture
was washed on a filter with deionized water and 0.1 HCl, repeatedly, unti l the pH of
filtrate became neutral. The obtained material (AC-DPC) was dried at 105 °C and
preserved in a sealed bottle. The yield values based on the original weight of raw DPC
were calculated as follow:
𝑊𝐶
𝑌𝑖𝑒𝑙𝑑 (%) = × 100
𝑊𝑅
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where WC and WR are dry weights of products (CM or AC-DPC) and raw DPC (g),
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respectively.
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2.3. Adsorption experiments
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The experiments for the adsorption of MB onto AC-DPC were performed in batch mode
by taking 25 ml of MB solution into 50 ml Erlenmeyer flasks. The experiments for the
evaluation of initial pH (3-10), contact time (2.5-240 min), initial MB concentration (10-
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1000 mg L-1), and ionic strength (0-1 Mol NaCl) effects on adsorption process were
tested using two agitation methods; conventional stirring (at a fixed stirring rate of 250
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Before adding the adsorbent to the dye solutions, the initial pH of the solutions was
adjusted by dilute acid (HCl) or base (NaOH) reagents using a calibrated pH meter
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(WTW, Germany). In each experiment, after a given contact time, the adsorbent was
separated from suspension using 0.45 μm membrane filter. The concentration of MB in
filtrate was measured by a double beam spectrophotometer (SP-1900 UV-vis) at 665
nm wavelength. Pretests showed that the loss of MB in samples without activated
carbon was <2%, indicating the negligible wall losses and degradation of the dye during
stirring and ultrasonication.
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The removal efficiency, RE (%), adsorption capacity at equilibrium, qe (mg g-1) and at
time t, qt (mg g-1) were calculated as follows:
(𝐶𝑖 − 𝐶𝑡 ) (1)
𝑅𝐸 = × 100
𝐶𝑖
(𝐶𝑖 − 𝐶𝑒 )𝑉 (2)
𝑞𝑒 =
𝑊
(𝐶𝑖 − 𝐶𝑡 )𝑉
𝑞𝑡 = (3)
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𝑊
where C i, C e and C t are the initial, equilibrium and at time t of MB concentrations (mg L -
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), respectively, V is the volume of suspension (L), and W is the dry weight of AC -DPC
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in suspension (g).
Desorption of MB from AC-DPC was tested with deionized water, 0.1 M NaOH and 0.1
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M H3PO4. Before desorption, the adsorbent was loaded with MB at the following
conditions: initial MB concentration 800 mg L -1, pH 7, adsorbent dose 1 g L -1,
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equilibrium contact time, stirring rate 250 rpm and temperature 298±0.5 K, respectively.
Afterward, the suspension was filtered and the MB loaded adsorbent was placed in the
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MB-free desorbing eluents. After a given contact time of stirring and/or ultrasonication,
the adsorbent was separated and the concentration of MB in desorbing eluents was
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amount of MB adsorbed
All the batch adsorption and desorption experiments were duplicated and the mean
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FT-IR spectra of the materials were recorded at 4 cm -1 of resolution in the wavenumber
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range of 4000-400 cm-1.
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Additionally, the surface chemical characteristics of CM and AC-DPC were analyzed by
Boehm titration according to the method described by Goertzen et al. (2010) [23]. The
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pH at the point of zero charge or pHPZC of the materials was determined according to pH
drift procedure [24].
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2.5. Data analysis
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second order, Elovich, Intraparticle diffusion and Boyd kinetic models. Moreover, four
commonly used isotherm models, namely Freundlich, Langmuir, Redlich-Peterson and
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Temkin, were used to analyze the equilibrium experimental data (Table 1). Non-linear
forms of other models were fitted to the experimental adsorption data by OriginLab Pro
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(2018) software. The experimental adsorption data were also analyzed by linear forms
of Intraparticle diffusion and Boyd models.
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based carbon matrix after heating at 500 °C for 2 hr [25]. After activation, YO was
decreased to 25.2%, which is good compared to those reported for some metallic
hydroxide-activated carbons derived from agro-industrial wastes [25,26]. The decrease
in the yield after activation with KOH could be attributed to the intercalation of K into the
CM structure and subsequent burn-off of carbonaceous compounds [25].
The N2 adsorption/desorption isotherms of AC-DPC correspond to type I of IUPAC
classification, characteristic of microporous solids [27]. AC-DPC showed an average
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pore diameter of 1.9044 nm and micropore volume of 0.952 cm3 g-1 corresponding to
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76.84% of total pore volume (1.239 cm3 g-1), indicating its microporous texture. The
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mesopore volume was equal to 0.286 cm3 g-1 corresponds to 23.08% of total pore
volume.
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Surface area is a crucial parameter in adsorption process, especially when it comes of
activated carbon. The analysis of N2 isotherms for AC-DPC provided BET surface area
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(SBET) as high as 2632.5 m2 g-1, indicating the suitability of KOH-activation conditions for
the preparation of activated carbon from Date Press Cake.
It is worth to note that CM showed S BET and total pore volume of 3.47 m2 g-1 and 0.0048
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cm3 g-1 (with 7% micropores), respectively. Therefore, the action of KOH on CM led to
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the development of porosity. The main reactions that may be occurred during KOH
activation process are as follow [28];
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The penetration of KOH into the carbon layers, burn-off of some carbon molecules, and
the release of gaseous products may led to the development of porosity.
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lactone and carboxyl groups. The band observed at 1091 cm -1 can be assigned to
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stretching vibration of ester (C-O) and the -OH bending modes of phenol structures [30].
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The band at 873 cm-1 is characteristic of out-of-plane deformation vibrations of aromatic
C-H and the band at 471 cm-1 is attributed to the vibrational mode of C-N-C group
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[30,31]. After activation process, the position and intensity of most of bands were
changed, evidencing a change in the functionality of the CM surface. In AC-DPC
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spectrum, the position of peaks related to –OH, C=O, C-O (-OH bending) and C-N-C
were changed to 3436, 1635, 1082 and 475 cm-1. Moreover, the intensity of most of the
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peaks, especially those related to the carbon-hydrogen bonds, was reduced, indicating
the dehydrating action of KOH during activation process. Similar phenomenon has been
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reported for the activation of carbonized material with metallic hydroxides [22,32].
Surface oxygen functional groups contribute significantly to adsorption process because
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they act as binding sites capable of capturing adsorbate molecules [32]. The Boehm
titration method assumes that various surface oxygen groups with different acidities
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exist on the surface of material, hence they can be neutralized by bases of different
strengths [33]. It was found that the total amount of functional groups in AC-DPC (2.067
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mmol g-1) was higher than that of CM (0.642 mmol g-1). AC-DPC contained 1.078 mmol
g-1 and 0.990 mmol g-1 of acid and base groups, respectively. The acid groups were due
to phenolic (0.490 mmol g -1)>carboxylic (0.424 mmol g -1)>lactonic (0.164 mmol g-1)
groups. The approximately similar amounts of acid and base groups in AC-DPC is in
agreement with its near neutral pHPZC (7.7) (Fig. S1).
The solution chemistry of contaminants and the ionic state of functional groups of the
adsorbent depends on the solution pH [34]. The experiments for the effect of initial pH
on the adsorption of MB were done at initial MB concentration of 800 mg L -1, adsorbent
dose of 1 g L-1, and contact time of 90 min. As shown in Fig. 3, the amount of adsorbed
MB increased slightly with increasing pH in a range from 3 to 10 for both agitation
methods. At acidic pH, H+ ions compete with cationic dye molecules for the adsorption
onto the adsorbent surface. Therefore, the inhibitory effect of H+ ions on the adsorption
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of MB would be decreased with the increase in solution pH [35]. Moreover, adsorbent
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surface acquires positive charge at pH<pHPZC and negative charge at pH>pHPZC [36].
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Therefore, at pH values over pHPZC (7.7), the attractive interaction between cationic dye
molecules and negatively charged sites probably increased the adsorption amount.
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Nevertheless, the percentage removal of MB was still high at acidic and neutral
conditions. Such behavior implies that besides electrostatic interaction, other
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phenomena such as Van der Waals attraction, π-interaction of the aromatic dye
molecules with adsorbent surface, and chemical interaction may also play important
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9 converged rapidly (<5 min) to pHPZC. At initial pH<pHPZC, H+ ions may be exhausted
by reducing functional groups on sorbent surface, while at higher pH values, the
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released H+ of hydroxyl and/or carboxyl groups may neutralize alkali solution (i.e.,
𝐶𝑋 𝑂𝐻 + 𝐻 + ↔ 𝐶𝑋 𝑂𝐻2+ 𝑎𝑡 𝑎𝑐𝑖𝑑𝑖𝑐 𝑝𝐻, 𝑎𝑛𝑑 𝐶𝑋 𝑂𝐻 ↔ 𝐶𝑋 𝑂− + 𝐻 + 𝑎𝑡 𝑏𝑎𝑠𝑖𝑐 𝑝𝐻) [37]. With
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respect to the trends of final pH and MB adsorption rate at various initial pH values, the
subsequent experiments were done at neutral pH.
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driving force) and more vacant active sites on the adsorbent surface during this period.
After a given time, the reduced amounts of MB molecules and vacant surface active
sites probably lead to negligible increase in MB uptake with time. As depicted in Fig. 4,
the initial increase in the RE of MB in the presence of low frequency ultrasound was far
higher than that of stirring. Such enhancement in initial RE of MB decreased the
equilibrium time for MB adsorption onto AC-DPC in ultrasound-assisted system. As is
explicit in Fig. 4, under abovementioned conditions, the MB/AC-DPC adsorption system
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reached equilibrium after around 180 and 20 min in the absence (stirring) and presence
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of low frequency ultrasound (no stirring), respectively. Such trend imply that the rate of
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MB mass transfer in the adsorption system was improved in the presence of low
frequency ultrasound [38].
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Adsorption kinetics were analyzed to understand the adsorption dynamics in view of the
order of the rate constants in the absence and presence of ultrasound. The results for
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the non-linear adjustments of the Pseudo-first order, Pseudo-second order and Elovich
kinetic models with the experimental data are presented in Table 2. With respect to the
magnitude of R2 values, Elovich and Pseudo-second order kinetic models well
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described the adsorption of MB onto AC-DPC for both agitation methods (Fig. 4). This
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surface is energetically heterogeneous and that the adsorption interactions does not
influence the kinetics of adsorption [32]. The values of β parameter, which is related to
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the desorption coefficient, were as low as 0.0121 and 0.0187 for stirred and ultrasound-
assisted systems, respectively. These values are an indication of effective interaction
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between MB and AC-DPC and then limited desorption rates. Pseudo-second order
model assumes that the chemical reaction between adsorbent and adsorbate controls
the rate of adsorption process [39]. As shown in Table 2, the values of h0 (Pseudo-
second order) and α (Elovich), which are related to initial adsorption rate, were
increased from 108.29 and 647.2 mg g -1 min-1 (ultrasound) to 599.97 and 269511.2 mg
g-1 min-1 in the presence of low frequency ultrasound. Therefore, the rate of MB
adsorption onto AC-DPC was accelerated by ultrasound, probably through generating
acoustic cavitation (formation, growth and collapse of the cavity). Micro-jets and
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acoustic streaming resulted from the collapse of the cavity could increase the diffusion
of adsorbate in the solid-liquid system [19,38].
The Weber-Morris Intraparticle diffusion model was applied to understand how the
diffusion of MB molecules onto AC-DPC takes place. This model assumes that i) the
direction of diffusion is radial, ii) the external resistance to mass transfer of adsorbate
molecules is not significant or only significant within a short time at the beginning of
diffusion and iii) the intraparticle (pore) diffusivity changes neither with time nor with
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position [40]. Based on these assumptions, the diffusion process may be occurred in
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three stages, i.e. mass transportation from the bulk solution to the external surface of
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sorbent by diffusion through the liquid film layer, mass transportation to the pores of
sorbent, and adsorption of adsorbate molecules onto internal surface of the pores [41].
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The values of K id and C i parameters in the linear equation of Weber-Morris Intraparticle
diffusion model (qt = Kid (t)0.5 + C i) were determined through plotting q t versus t0.5 (Fig.
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5a). As can be seen from the Figure, there exist three stages of linearity for each
adsorption process. The first stage, starting from the origin, is related to the transfer of
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adsorbate molecules from bulk liquid to the external surface of adsorbent. The second
stage indicates intraparticle diffusion, i.e. the entrance of the adsorbate molecules into
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the porous structure of AC-DPC. The third linear part with a small slope indicates the
equilibrium phase [40]. The intercept value of the plots, C i, characterizes the thickness
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of boundary layer. With respect to the equations presented in Fig. 5(a), the Ci values
were in order of C 1 < C 2 < C 3, indicating the higher external diffusion resistance at the
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last stage of adsorption. At initial stage, the vacant adsorption sites may result in easy
mobility of adsorbate molecules and minimize external diffusion resistance. In the other
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hand, at later stage, most of adsorption sites are occupied with adsorbate molecules,
which hinders the mobility of the free adsorbate molecules and increases external
diffusion resistance. The intercept of the second stage plots, C 2, give an insight into the
tendency of the adsorbate to adsorb on the adsorbent or remain in solution [19]. The
value of C 2 was greater in the presence of ultrasound (440.4 mg g -1) than in its absence
(338.7 mg g-1), depicting the positive effect of low frequency ultrasound on the tendency
of AC-DPC surface to the MB molecules.
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The slope of the plots, Kid, characterizes the adsorption rate. As shown in Fig. 5(a), the
value of Kid for the first linear stage of adsorption in ultrasound method (255.13 mg g -1
min-0.5) was higher than that of stirring (111.26 mg g -1 min-0.5). Therefore, in accordance
to the h0 and α values in Pseudo-second order and Elovich models, respectively, the
initial rate of MB adsorption onto AC-DPC was significantly increased in the presence of
ultrasound. Such enhancement in the rate of MB adsorption onto AC-DPC by low
frequency ultrasound may be related to the extreme conditions generated by cavitation
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bubbles. The violent collapse of cavitation bubbles produces high velocity micro-jets
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and acoustic streaming (movement of liquid induced by ultrasound waves). They could
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improve the adsorption rate through enhancing mass transfer across interfacial film
surrounding sorbent as well as into the adsorbent pores [41-43].
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Among three consecutive stages of adsorption process, the last one, adsorption, is very
rapid in comparison to the first two stages [41]. In this regard, Boyd kinetic model was
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employed to identify if the rate-limiting step of adsorption is film diffusion or intraparticle
diffusion. If the Boyd’s plot (B t versus time) is linear and passes through the origin,
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intraparticle diffusion is the sole rate-limiting step in adsorption process; otherwise film
diffusion governs the process [22]. As shown in Fig. 5b, although the Boyd’s plots
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present some linearity, they do not pass through the origin. Therefore, the film diffusion
or chemical reaction controlled the adsorption rate of MB onto AC-DPC for both
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agitation methods. Kostić et al. (2016) also reported that the adsorption of Cu (II) by
xanthated Lagenaria vulgaris shell was controlled by film diffusion as well as that the
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separation factor (RL), a dimensionless equilibrium parameter, indicates if the
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adsorption process is irreversible (RL = 0), favorable (0 < RL > 1), linear (RL = 1) or
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unfavorable (RL > 1) [22]. For the value range of concentrations studied (10-1000 mg
L−1), the RL values were 0.0001-0.0136 and 0.0001-0.0142 for stirred and ultrasound-
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assisted systems, confirming the favorability of MB adsorption onto AC-DPC.
The Temkin isotherm model assumes the linear decrease in adsorption heat with the
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increase in the coverage of adsorbent. The Temkin constant, b T, is related to the heat of
adsorption, which indicates if the adsorption reaction is endothermic (bT < 1 J mol-1) or
exothermic (bT > 1 J mol-1) [46]. The bT values were 49.64 and 61.41 J mol-1 for stirring
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of Langmuir and Freundlich models. This model becomes Henry law if g=0. On the
other hand, it converges to Freundlich model if g<1 and the a RP and bRP>>1.
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equilibrium data were best fitted with Redlich–Peterson isotherm model in both agitation
methods. The non-linear adjustment of this model to the experimental equilibrium data
are presented in Fig. 6. It is well known that this model approaches to Langmuir and
Freundlich isotherm models at high and low adsorbate concentrations, respectively [47].
Because of such dual features, this model can be successfully applied over a wide
range of adsorbate concentrations in various systems [48]. Since the values of g
parameter in both adsorption modes were near to 1, it seems that the adsorption of MB
molecules onto AC-DPC occurred according to the mechanism proposed by Langmuir.
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Such suitability is confirmed by the values of 1/nF parameter in Freundlich model. The
1/nF>1 is an indicator of cooperative adsorption, while 1/nF below one indicates a
normal Langmuir isotherm. As shown in Table 3, the values of 1/nF for both agitation
methods were lower than 1. In the other hand, the values of a RP and bRP constants were
also far greater than 1, indicating that the Redlich-Peterson isotherm model also
followed the Freundlich isotherm. The abovementioned results imply that the adsorption
of MB onto AC-DPC, in both agitation methods, occurred in a monomolecular layer with
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a homogenous distribution among the adsorption sites at different energies.
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Overall, AC-DPC showed maximum monolayer adsorption capacities of 546.8 and
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613.8 mg g-1 in the absence and presence of low frequency ultrasound, respectively.
These values are considerable compared to several biomass-derived activated carbons
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applied for the adsorption of MB (Table 4). The isotherm results imply that the amount
of adsorbed MB onto AC-DPC was increased by low frequency ultrasound. Therefore,
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low frequency ultrasound not only accelerated mass transfer, but also improved the
equilibrium adsorption in MB/AC-DPC adsorption system. The positive effect of
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The desorption of MB from AC-DPC was evaluated with neutral deionized water and 0.1
M solutions of NaOH and H3PO4 at 180 (stirring) and 20 min (ultrasound) contact times.
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It was found that the rates of MB desorption by various eluents were in the order of
H3PO4>deionized water>NaOH. As discussed previously, MB adsorption was favored
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under basic condition and thus its higher desorption with acidic reagents was
expectable. Nevertheless, the desorption rate was below 15% with both agitation
modes, which suggests a strong irreversible chemical binding of the dye molecules with
AC-DPC surface. Kavitha and Namasivayam (2007) also reported MB desorption rates
below 10% from coir pith carbon [55].
Theoretically, when the electrostatic interaction between adsorption sites and sorbate
species controls an adsorption system, the ionic strength of solution would negatively
effect on the adsorption capacity [56]. Contrarily, the results showed a significant
increase in the adsorption rate of MB in both agitation methods by increasing ionic
strength from 0 to 1 Mol NaCl (Fig. S2). Therefore, as noted previously, the adsorption
of MB onto AC-DPC was not completely controlled by electrostatic interaction.
The positive effect of ionic strength on MB adsorption may be due to two mechanisms;
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i) the intermolecular forces between dye molecules such as ion-dipole, dipole-dipole
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and Van der Waals dispersion forces probably increased with the addition of NaCl.
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These forces decrease the repulsive interaction between dye molecules and promote
the dimerization of dyes in solution. The dimerization causes the dye molecule volume
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both smaller and more hydrophobic, which is beneficial for the adsorption process [57],
ii) the increased ionic strength in solution compresses the diffuse double layer on the
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adsorbent surface, which is favorable for the electrostatic attraction of the dye
molecules to the surface of sorbent [58].
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The applicability of AC-DPC for the adsorption of MB from real treated wastewater
(EC=6330 μS m-1) and real seawater (EC=72750 μS m-1) was tested at initial MB
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removal from treated wastewater, seawater and deionized water were 98.5%, 99.4%
and 73.9%, respectively, in stirred adsorption system. The corresponding values for the
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desorption from loaded AC-DPC confirmed the chemisorption nature of the adsorption
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process. Therefore, electrostatic interaction along with chemical binding between
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adsorbate and adsorbent mainly controlled the MB/AC-DPC adsorption process.
The positive effect of low frequency ultrasound on the MB adsorption rate may be
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attributed to the actions of micro-jets and acoustic streaming produced by the
ultrasound waves. These phenomena increased MB adsorption rate probably through
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accelerating mass transfer across liquid film as well as into the AC-DPC pores.
Moreover, the equilibrium MB adsorption was improved in ultrasound-assisted system
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4. Conclusion
In this study, a microporous activated carbon prepared from Date Press Cake was
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applied for the adsorption of MB from aqueous solutions in the absence and presence
of low frequency ultrasound. The results of batch experiments showed that the required
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time to reach equilibrium MB adsorption was reduced from 180 min (stirring) to 20 min
in ultrasound-assisted system at a given condition. Moreover, the kinetic constants of
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MB/AC-DPC adsorption system confirmed that the rate of MB adsorption onto AC-DPC
was enhanced in the presence of low frequency ultrasound. Moreover, the maximum
monolayer adsorption capacity was increased from 546.8 mg g -1 (stirring) to 613.8 mg g-
1
in the presence of low frequency ultrasound. Such enhancements in the rate and
amount of MB adsorption onto AC-DPC could be attributed to the actions of micro-jets
and acoustic streaming produced by ultrasound waves. This study showed that the
KOH-activated carbon derived from DPC has a good potential for the adsorption of MB
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5. Acknowledgement
The authors acknowledge the funding provided by the vice Chancellor for Research in
Hormozgan University of Medical Sciences (HUMS) (Grant No. 950179).
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Figure captions
Fig. 1. FESEM image CM (left) and AC-DPC (right)
Fig. 2. FT-IR spectra of CM and AC-DPC
Fig. 3. Effect of initial pH on the removal of MB in the absence (stirring) and presence of
low frequency ultrasound (C0= 800 mg L-1, adsorbent dose= 1 g L-1, contact time= 90
min)
Fig. 4. Best kinetic models fitted to the MB adsorption onto AC-DPC in the absence
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(stirring) and presence of low frequency ultrasound (C 0=800 mg L-1, pH=7, adsorbent
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dose= 1 g L-1)
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Fig. 5. Intraparticle diffusion and Boyd’s plots for the adsorption of MB onto AC-DPC
Fig. 6. Best isotherm model fitted to the MB adsorption onto AC-DPC in the absence
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(stirring) and presence of low frequency ultrasound (C0=10-1000 mg L-1, pH=7,
adsorbent dose= 1 g L-1)
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Table 1. General forms of the kinetic and isotherm models used in this study
Kinetic models
Pseudo-first order 𝑞𝑡 = 𝑞𝑒 (1 − 𝑒 −𝑘1 𝑡 ); ℎ0 = 𝑘1 𝑞𝑒
Pseudo-second order 𝑘2 𝑞𝑒2 𝑡
𝑞𝑡 = ; ℎ = 𝑘2 𝑞𝑒2
1 + 𝑘2 𝑞 𝑒 𝑡 0
Elovich 1
𝑞𝑡 = ln(1 + 𝛼𝛽𝑡)
𝛽
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Intraparticle Diffusion 𝑞𝑡 = 𝐾𝑖𝑑 (𝑡)0.5 +𝐶𝑖
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Boyd 𝑞
𝐵𝑡 = − ln (1 − 𝑡 ) − 0.4977
𝑞𝑒
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Isotherm models
Freundlich 𝑞𝑒 = 𝑘𝐹 𝐶𝑒1 ⁄𝑛𝑓
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Langmuir 𝑞𝑚 𝑘𝐿 𝐶𝑒 1
𝑞𝑒 = ; 𝑅𝐿 =
1 + 𝑘𝐿 𝐶𝑒 1 + 𝑘𝐿 𝐶𝑒
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Redlich-Peterson 𝑎𝑅𝑃 𝐶𝑒
𝑞𝑒 =
1 + 𝑏𝑅𝑃 𝐶𝑒𝑔
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Temkin 𝑅𝑇 𝑅𝑇
𝑞𝑒 = 𝑙𝑛𝛼 + 𝑙𝑛𝐶𝑒
𝑏 𝑏
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k1 and k2= rate constants of the Pseudo-first order and Pseudo-second order models,
respectively; h0=initial adsorption rate; α and β = Elovich constants; Kid and C i =
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Table 2. Parameters of kinetic models for the adsorption of MB onto AC-DPC in the
absence (stirring) and presence of low frequency ultrasound
Stirring Ultrasound
Pseudo-first order
qe (mg g-1) 537.2 647.5
k1 (min-1) 0.1308 0.4656
h0 (mg g-1 min-1) 70.26 301.44
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0.918 0.983
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Pseudo-second order
qe (mg g-1) 581.6 676.7
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-1 -1
k2 (g mg min ) 0.0003 0.0013
h0 (mg g-1 min-1) 108.29 599.97
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R2 0.976 0.998
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Elovich
α (mg g-1 min-1) 647.2 269511.2
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Table 3. Parameters of isotherm models for the adsorption of MB onto AC-DPC in the
absence (stirring) and presence of low frequency ultrasound
Stirring Ultrasound
Freundlich
kF (mg g-1) 297.13 334.94
nF 7.50 7.20
1/nF 0.133 0.139
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R2
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0.873 0.820
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Langmuir
qm (mg g-1) 546.8 613.8
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-1
kL (L mg ) 8.699 6.938
R2 0.971 0.975
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Redlich-Peterson
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g 0.951 0.964
R2 0.996 0.988
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Temkin
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R2 0.960 0.931
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Coconut shell NaOH Stirring 916.3 30 min [22]
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Stems of palm tree K2SO4 Stirring 128.9 480 min [49]
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Grape processing industry ZnCl2 Stirring 417.0 60 min [50]
waste
Fox nutshell ZnCl2 Stirring 968.7 60 min [51]
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Karanj fruit hulls KOH Stirring 239.4 24 h [52]
Buriti shells ZnCl2 Stirring 274.6 90 min [53]
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Date Press Cake KOH Stirring 546.8 180 min Present
Ultrasound 613.8 20 min study
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Fig. 1.
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100
90
80 2856
873 2923
Transmittance, % 70
60 1635
475
50 1620
471 1569
40 2856
1082
30 2923
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1091
20
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10 CM AC-DPC 3436
0
3432
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400 1000 1600 2200 2800 3400 4000
Wavenumber, cm -1
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Fig. 2.
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Initial pH
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Fig. 3.
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700
600
500
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qt, mg g-1
400
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300
Experimental data-Stirring
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200 Experimental data-Ultrasound
Pseudo-second order model
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Elovich model
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0 50 100 150 200 250 300
Time, min
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Fig. 4.
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(a)800
700
600
500
qt, mg g-1
400
Stirring Ultrasound
300
1) qt = 111.3(t)0.5 + 25.7 1) qt = 255.1(t)0.5 + 16.2
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200 2) qt = 23.1(t)0.5 + 338.7 2) qt = 47.2(t)0.5 + 440.4
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3) qt = 5.5(t)0.5 + 505.9 3) qt = 1.8(t)0.5 + 648.6
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0 4 8 12 16
t0.5
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(b) 6
5
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0 20 40 60 80 100 120
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Time, min
Fig. 5.
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700
600
500
qe, mg g-1
400
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300
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Experimental data-Stirring
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Experimental data-Ultrasound
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Redlich-peterson model
0
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Ce, mg L-1
Fig. 6.
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Graphical abstract
Fresh Date
Press Other
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Cake Wastes
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KOH-Activation
60
40
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20 Stirring
Ultrasound
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0 100 200 300
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Contact tim e, min
800
Adsorption Capacity, m g g -1
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400
200 Stirring
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Final MB Concentration, mg L -1
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Highlights
- KOH-activated carbon with high surface area (2632.5 m 2 g-1) and microporous texture
was prepared from Date Press Cake
- Adsorption of Methylene Blue onto the activated carbon was tested in the absence and
presence of low frequency ultrasound
- Low frequency ultrasound increased both the rate and amount of Methylene Blue
adsorption onto the activated carbon
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