Journal of Environmental Chemical Engineering 6 (2018) 834–841

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Kinetic analysis of the adsorption of dyes from high strength wastewater on T

cement kiln dust
⁎
Y.H. Magdya, H. Altaherb,
a
Department of Chemical Engineering, Faculty of Engineering, El-Minia University, P.O. Box 61511, Egypt
b
College of Health Sciences, Jumeira University, P.O. Box 555532, Dubai, United Arab Emirates

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, the adsorption of Basic Blue 69 (BB69) and Acid Red 114 (AR114) dyes on cement kiln dust using
Adsorption batch technique was studied. The effects of contact time, mass of adsorbent and initial concentration of dyes
Cement were analyzed. Five kinetic models namely, pseudo first order, pseudo second order, Elovich, intraparticle
Dye diffusion, and Boyd were applied to analyze the experimental data. The data best fitted to pseudo second order
Kinetic
and Elovich models indicating the chemical nature of the adsorption process. The maximum adsorption capa-
Waste
cities of BB69 and AR114 were 2119 mg/g and 2125 mg/g, respectively. The equilibrium time was 240 min
when using a dose of 8 g/L compared to 300 min when using a dose of 40 g/L. The adsorption rate was fast in the
initial stage. Initial equilibrium was attained after 30 min when using a dose of 40 g/L and initial dye con-
centration of 500 mg/L. That value increased to 90 min when using the same adsorbent dose with initial dye
concentration of 300 mg/L. Generally, the equilibrium was attained within 90–300 min depending on the dye,
adsorbent dose, and initial dye concentration. The rate of adsorption was found to be affected by both film
diffusion and intraparticle diffusion.

1. Introduction
Wastewater containing dyes represents a threat to aquatic life [1].
In addition to being toxic, dyes hinder the penetration of the sun light
which is different forms of life required. Furthermore, the presence of
dyes in water bodies inhibits the growth of aquatic biota and decreases
the oxygen solubility [2]. The adverse effects of dyes on human being
include allergy, dermatitis, skin irritation, and cancer. Mutagenic and
teratogenic effects on aquatic life as well as humans are also con-
siderable [3].
More than 100,000 dyes are produced every year with a total
amount of 7 × 105 metric tons. From this amount, approximately 100
tons/year are disposed as a wastewater [4]. One reason for the huge
amount of the discharged dyes is the high residual dyes that remains in
the water bath during the dying process [5]. Another important reason
is their utilization in a wide variety of industries including textile in-
dustry [6,7], rubber and plastics [8], cosmetics [9], paper industry
[10], leather industry [11], tannery [12], food processing [13], and
pharmaceutical industry [14].
Various treatment methods such as adsorption, ozonation, photo-
catalysis, flocculation–coagulation, oxidation, advanced oxidation,
electro-flocculation, membrane separation, electrochemical
degradation and biodegradation [15–22] are being applied for treat-
ment of wastewater containing dyes. Many of the conventionally used
techniques are not efficient in the treatment process especially at high
concentration of dyes in the wastewater. Consequently, alternative
treatment processes are necessary to achieve the required removal ef-
ficiency [5].
The adsorption of dyes on activated carbon is considered to be very
effective [23]. However, many factors must be taken into consideration
such as the cost of the manufacturing of activated carbon, the cost for
regeneration after exhausting and the loss of adsorption efficiency after
regeneration [24]. The feasibility of the adsorption process is largely
dependent on the availability of cheap and widely available adsorbents
[25,26].
Many conventional and non-conventional materials have been in-
vestigated for their ability to adsorb dyes. However, all of these ad-
sorbents have various drawbacks such as low availability and high cost
of preparation [27]. Some of the tested materials are clay, bentonite,
Lignocellullosic materials, chitosan and its derivatives, industrial solid
wastes, biomass, bagasse pith, impregnated rice husk ash, zeolites,
agricultural by-products, peat, silica, date palm, cashew nut shell,
mixtures of carbon and fly ash, activated bio-char, saw dust, natural
and synthetic polymers, waste materials, and various nanotubes

⁎
Corresponding author.
E-mail address: haltaher@hotmail.com (H. Altaher).

https://doi.org/10.1016/j.jece.2018.01.009
Received 2 October 2017; Received in revised form 2 January 2018; Accepted 3 January 2018
Available online 04 January 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
Y.H. Magdy, H. Altaher
[24,27–42].
Cement kiln dust (CKD) which is a solid waste of cement industry
has many advantages which makes it superior to other adsorbents. The
first advantage is its low cost of use since it is a waste material that does
not require any pretreatment. The only cost associated with this ma-
terial is the cost of transportation which is common with any other
adsorbent. Another advantage is its continuous supply taking into
consideration that approximately 30 million tons/year of CKD are
generated globally [43]. Another important advantage of CKD is its safe
use. Most of the carbon-based adsorbents will leach different organic
compounds to the treated water during the adsorption process [44].
These organic compounds may react with chlorine during the disin-
fection to produce carcinogenic disinfection byproducts. This is not the
case when using CKD.
The aim of this paper is to assess the potential use of CKD as a low
cost adsorbent for removal of BB69 and AR114 from aqueous solutions.
Furthermore, another objective is to study the effect of mass of ad-
sorbent, concentration of adsorbates, and mixing time on the kinetic
parameters.
2. Methods and procedure
2.1. Adsorbates
Basic blue 69 was supplied by Bayer. This dye does not have a
specific known structure. However, it belongs to the methine group.
The general structure of methine group is illustrated by Fig. 1.
Acid red (AR 114) was supplied by Ciba-Geigy. The structure of the
dye is indicated in Fig. 2.
The dyes were used as received (without any treatment). They were
dissolved in distilled water to prepare the stock solution. The working
solutions (300, 500, 700 mg/L) were obtained by dilution using dis-
tilled water. The initial and final concentrations of the dyes were de-
termined at their maximum wavelengths (380, 520 nm for BB69 and
AR114, respectively) using UV-1800 UV–vis Spectrophotometer,
Shimadzu, Japan. Each experiment was duplicated under the same
conditions.
2.2. Adsorbent
In this work CKD was used as an adsorbent. The cement kiln dust
was obtained from El-Minia White Portland Cement Factory, El-Minia
Governorate, Egypt. It was received as a very fine powder. A sieve
analysis was performed to characterize the cement dust. However, the
dust was used without ant treatment. The chemical composition of CKD
was determined using X-ray fluorescence (ARL, made in Switzerland).
2.3. Batch equilibrium study
Batch adsorption was performed in the tank illustrated by Fig. 3. All
experiments were conducted at room temperature (25 °C). The agitation
speed was kept at constant value for all tests (400 rpm). All samples
were filtered before analysis to separate the adsorbent from the solu-
tion.
Fig. 1. General structure of the methine group.
835
Journal of Environmental Chemical Engineering 6 (2018) 834–841
To study the effect of time, three tanks were loaded with 1700 cm3
of the tested dye at different initial concentration (300, 500, 700 mg/L).
To every tank, 0.2 g of CKD was added. The tanks were agitated at
400 rpm. Samples were taken from the tanks at different time intervals,
filtered and analyzed to determine the final dye concentration.
Another set of experiments was conducted to study the effect of
adsorbent mass. Three different vessels were loaded with 1700 cm3 of
300 mg/L of the dye. To every vessel, a different mass of CKD (0.2, 0.4,
and 1.0 g) was added. The mixtures were agitated until equilibrium is
attained. Samples were analyzed to calculate the final dye concentra-
tion. The experiment was repeated with different sets with initial con-
centrations of 500 and 700 mg/L. A similar technique was applied to
study the effect of initial dye concentration on the adsorption process.
2.4. Kinetic models
The kinetics analysis of any adsorption process represents an im-
portant stage in the design of the adsorption system. Determining the
time required for the adsorption process to reach equilibrium is very
important. This equilibrium time is one result of the kinetic analysis of
the adsorption system. The kinetic analysis determines the mechanism
of adsorption and the rate determining step. The experimental data was
analyzed using pseudo first order model, pseudo second order model,
Intraparticle diffusion model, Boyd model, and Elovich model. The
linear forms of these models are introduced in Table 1.
2.4.1. Pseudo first second order models
These two models estimate the rate of adsorption of adsorbate on
adsorbent. The values of k1 and k2 introduced in Table 1 represent the
rate constants for pseudo first and pseudo second order models, re-
spectively. These values are obtained by fitting the experimental data to
the equations in Table 1. The pseudo first order model is usually used to
describe the initial state of adsorption, while the pseudo second order
model predicts the behavior over the entire range of the adsorption
process.
2.4.2. Intraparticle diffusion model
This model considers the intraparticle diffusion as the rate con-
trolling step for adsorption. If the plot of qt against t0.5 passes through
the origin, the intraparticle diffusion is the rate determining step. The
constant C in the equation indicates the layer surrounding the ad-
sorbent.
2.4.3. Boyd model
This model is applied to distinguish between the pore and film
diffusion and help determine the rate determining step. According to
this model if the plot of Bt versus t produces a straight line that passes
through the origin, pore diffusion is the rate limiting step. Otherwise,
the adsorption process is film diffusion controlled.
2.4.4. Elovich model
While Elovich equation does not provide a definite mechanism of
adsorption, it gives information about the nature of the adsorption
process. If the experimental data fits this equation, then the adsorption
process has a chemical nature. An important feature of this model is the
constant B (g/mg) which is the adsorption constant related to the extent
of the surface coverage and activation energy for chemisorption.
3. Results and discussion
3.1. Characterization of the cement
Table 2 illustrates the sieve analysis of the CKD. It is clear from the
analysis that the size of cement dust particles is widely distributed in
the range between 0.3 mm to less than 0.075 mm. However, 85% of
them are less than 0.18 mm diameter.
Y.H. Magdy, H. Altaher Journal of Environmental Chemical Engineering 6 (2018) 834–841

Fig. 2. Molecular structure of Acid red 114.

3.2. Effect of mixing time

The kinetic of adsorption describes the relation between the mixing

Fig. 3. Schematic representation of the adsorption vessel, Z = height of liquid in vessel,
D = diameter of vessel, d = diameter of impeller blade, b height of impeller blade (0.01
D).
The chemical composition of CKD as determined using X-ray
fluorescence, is presented in Table 3. The chemical analysis indicates a
wide concentration range of the different constituents. However, the
bulk constituents are calcium oxide (45%) and silicate (22.2%). The
high concentration of CaO gives the cement kiln dust its alkaline
character. Typically 6–10% of this CaO represent free lime [46]. The
considerable percentage of sulfate (4%) may also contribute to the
adsorption property of the cement kiln dust [47].
time and the adsorbate uptake by the adsorbent. In doing so, the time
required for attaining equilibrium between the adsorbate and adsorbent
is determined. The kinetic of adsorption is also important for selecting
optimum operating conditions for the full-scale batch adsorption pro-
cess. It also helps determine the mechanism and adsorption rate [48].
Fig. 4 illustrates the effect of mixing time on BB69 uptake on CKD.
The plots in the figure show that the adsorption increases with time
until the equilibrium is attained. It is clear that there are two adsorption
stages. The adsorption was fast at the initial stage and became slow
near equilibrium. This phenomenon can be attributed to the presence of
large number of vacant adsorption sites during the initial stage. The
high concentration of the adsorbate at that initial stage might also
provide a high driving force for adsorption. With time, the number of
available sites decreased and the adsorbate molecules started com-
peting for the remaining sites. It must also be noted that the adsorbed
molecules might create repulsive forces during further adsorption. As
shown in Fig. 5, similar trend was observed for adsorption of AR114.
However, equilibrium was attained faster in case of AR114 adsorption.
Hameed [49] observed the same stages for the adsorption of 2,4,6-tri-
chlorophenol onto activated clay. He illustrated the difference in ad-
sorption rate to the adsorption on the exterior surface of adsorbent at
the initial stage which is a fast process. At the later stages, and after
occupying most of the exterior sites, the adsorbate molecules would
start penetrating the pores to reach the interior adsorption sites. This
process is always a slow process.
3.3. Effect of initial concentration
As can be observed from Fig. 6, and for adsorbent mass of 0.2 g, the
adsorption uptake increased from 714 mg/g to 2100 mg/g with the
increase of initial concentration of BB69 from 300 mg/L to 700 mg/L.
The same trend can be observed for adsorbent masses 0.4 g and 1.0 g.
However, the maximum uptake decreased from 2500 mg/g to 625 mg/g
with the increase of adsorbent mass from 0.2 g to 1.0 g. That means the
adsorption process is highly dependent on the initial concentration.
That close relationship between adsorption and concentration may be

Table 1
Equations and parameter of different kinetic models [7,37].

Model Parameters

Pseudo first order
1n(qe − qt) = 1n qe − k1t
Pseudo second order
t / qt = 1/ k2 qe2 + t / qe
Elovich
qt=1/B1n(αB) + 1/B1nt
Intraparticle diffusion
qt=kidt0.5 + C
Boyd model
Bt = −0.4977 − 1n(1 − qt/qe)
qe, qt (mg/g) are the amounts of dye adsorbed at equilibrium and at any time t (min), respectively; and k1 (min−1) is the rate constant of the
pseudo first order equation
k2 (g/mg.min) is the rate constant of the pseudo second order equation, qe (mg/g) is the maximum adsorption capacity, qt (mg/g) is the amount
adsorbed at time t (min)
α (mg/g min) is the initial adsorption rate and B (g/mg) is the adsorption constant related to the extent of the surface coverage and activation
energy for chemisorption
qt (mg/g) is the amount adsorbed at time t (min) and kid (mg/g min0.5) is the rate constant for the intraparticle diffusion model
qe, qt (mg/g) are the amounts of dye adsorbed at equilibrium and at any time t (min), Bt is the mathematical function of fractional attainment of
equilibrium

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Y.H. Magdy, H. Altaher Journal of Environmental Chemical Engineering 6 (2018) 834–841

Table 2
Screen analysis of white cement kiln dust.

Mesh No. 50 60 70 80 100 120 140 170 200 Less

Diameter, mm 0.3 0.25 0.21 0.18 0.15 0.125 0.1 0.09 0.075 Less
Remaining mass, gm 2.68 8.9 40.8 59.85 74.55 48.9 42.39 40.5 21.62 9.31
% occurrence 0.76 2.54 11.6 17.1 21.3 13.97 12.11 11.57 6.17 2.61

Table 3
Chemical analysis of cement dust.

Compound SiO2 Fe2O3 Al2O3 CaO MgO SO3 Cl2

Weight per cent 22.2 0.11 2.78 45.0 0.21 4.0 1.80

Fig. 7. Effect of initial concentration of AR114 on its adsorption on CKD (mass of ad-
sorbent = 0.2 g).

Fig. 4. Effect of mixing time on uptake of BB69.
attributed to the high mass transfer driving force that is excreted by the
high dye concentration at the initial stages of the adsorption process.
The increase in initial concentration had a considerable effect on the
final equilibrium time. The equilibrium was achieved after 110, 250,
and 300 min for initial concentrations 300, 500, and 700 mg/L, re-
spectively (Fig. 6). Moreover, the initial uptake rate changed from one
initial concentration to another. In case of low concentration, the
number of vacant adsorption sites was enough to accommodate the
number of dye molecules in solution thus no competition occurred
between the adsorbent molecules. Increase of surface coverage with
time lead to a decrease in the rate of adsorption until plateau was at-
tained [50]. A similar trend can be observed for the adsorption of
AR114 on CKD (Fig. 7). However, the equilibrium was attained earlier
for all tested concentrations.

3.4. Effect of adsorbent mass

The effect of mass on the adsorption parameters for both dyes is

given in Tables 4 and 5. The results indicate that, for all tested initial
Fig. 5. Effect of mixing time on uptake of AR114. concentrations, the increase of the adsorbent mass results in a decrease
of the uptake of the dye. Fig. 8 illustrates the effect of mass of CKD on
the adsorption of BB69 uptake. It is clear that the increase of the ad-
sorbent dose of CKD from 0.2 g to 1.0 g (at 300 mg/L of initial dye
concentration) lead to decrease of adsorption uptake from 691.4 mg/g
to 295.9 mg/g.
At the same initial concentration for AR114, the increase of ad-
sorbent dose from 0.2 g to 1.0 g resulted in a decrease of the uptake
from 1872.4 mg/g to 163.3 mg/g (Table 5). The decrease of dye uptake
with increase of adsorbent dose may be due to two reasons. First, high
doses of adsorbent may lead to the agglomeration of adsorbent particles
which results in the decrease of both the specific surface area and the
number of active sites. This will also result in an increase in the dif-
fusional path length. Second, increase of adsorbent mass will lead to
increase of available adsorption sites for the adsorbate molecules which
results in less saturation and less adsorption capacity [51].
Fig. 6. Effect of initial concentration of BB69 on its adsorption on CKD (mass of ad-
sorbent = 0.2 g).
3.5. Kinetic analysis

Tables 4 and 5 show a poor fit of the experimental data to the

pseudo first order equation. Moreover, the calculated qe values from

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Y.H. Magdy, H. Altaher Journal of Environmental Chemical Engineering 6 (2018) 834–841

Table 4
Kinetic parameters for adsorption of BB69 on CKD.

Model Parameter 0.2 g 0.4 g 1.0 g

300 mg/L 500 mg/L 700 mg/L 300 mg/L 500 mg/L 700 mg/L 300 mg/L 500 mg/L 700 mg/L

Pseudo-First-Order
qe,calc (mg/g) 1058.28 703.66 2329.01 487.69 761.74 865.58 96.96 175.11 1653.75
qe,exp (mg/g) 691.42 1158.7 2119 458.7 681.7 1382 296 203.5 533.83
K1 (min−1) −0.0298 −0.0115 −0.0117 −0.0154 −0.0137 −0.0106 −0.0205 −0.0139 −0.0257
R2 0.8566 0.9282 0.9673 0.9376 0.8602 0.7613 0.9203 0.9434 0.873

Pseudo-Second-Order
qe (mg/g) 714.2857143 1250 2500 526.32 769.23 1428.57 303.030303 227.27 625
qe,exp (mg/g) 691.42 1158.7 2119 458.7 681.7 1382 296 203.5 533.83
K2 (g mg−1min−1) 0.00007 0.00003 0.000005 0.00004 0.00002 0.00001 0.0002 0.0001 0.00002
h2 (g−1 mg min−1) 34.60 48.31 28.74 11.29 13.51 38.02 15.89 5.77 6.24
R2 0.9991 0.9985 0.9899 0.9945 0.9886 0.9889 0.9997 0.9955 0.9899

Elovich
α (g−1 mg min−1) 18.46 30.72 157.57 25.49 64.05 1337.09 30.28 0.9916 78.04
β (g mg−1) 0.0566 0.0341 0.0096 0.0109 0.0069 0.0051 0.0389 0.0273 0.0074
R2 0.9455 0.9847 0.976 0.9671 0.9644 0.9337 0.8394 0.9781 0.9714

Intraparticle Diffusion
kid 17.663 29.351 104.39 16.389 26.338 35.509 4.2299 6.5577 24.083
C 397.98 645.64 253.53 170.95 205.21 613.81 227.79 87.574 116.15
R2 0.866 0.9562 0.9822 0.9676 0.9843 0.9569 0.7066 0.9716 0.9548

Film Diffusion
B −0.0176 −0.0095 −0.0119 −0.0156 −0.0137 0.0107 −0.0205 −0.0139 −0.0257
R2 0.9662 0.9897 0.9605 0.9362 0.8602 0.7609 0.9203 0.9434 0.8729

Fig. 8. Effect of adsorbent mass on adsorption of BB69.
this model (for the two dyes) do not match the experimental values.
Accordingly, pseudo first order model is not suitable for explaining the
rate of adsorption of the two dyes on CKD. On the other hand, the
experimental data for both dyes indicates excellent compliance with
both second order equation and Elovich model for all tested initial dye
concentrations and for all tested adsorbent doses. The regression coef-
ficients (R2) for the linear plots of the two dyes according to pseudo
second order equation were higher than 0.99 for all the systems as
indicated in Tables 3 and 4. In case of Elovich model, the regression
coefficients values were higher than 0.95 for most of the systems. The
good fitting of the experimental data to pseudo second order equation
and Elovich model indicates the chemical nature of the adsorption
process [45,52]. The values of the rate constant k2, illustrated in Tables
4 and 5 for BD69 and AR114, respectively, show a linear relationship
with the initial concentration of dye.
The fitting of the experimental data to both pseudo second order
and Elovich models provided valuable information about the dye up-
take, the rate of adsorption, and the nature of the adsorption process
(chemisorption). However, it does not provide any information about
the mechanism of adsorption. The adsorption of the adsorbate follows
four consecutive stages. First, the molecules of the adsorbate migrate
from the bulk of the solution to the thin layer of adsorbate surrounding
the surface of the adsorbent. In the second stage the adsorbate mole-
cules diffuse through the thin aqueous layer surrounding the adsorbent.
The third stage is due to the penetration of the adsorbate molecules
through the pores on the surface of the adsorbent. In the final stage the
adsorbate molecules are adsorbed on the surface of adsorbent. The
second and third stages are taken as the rate determining steps of the
adsorption process since the other two stages are usually fast [2]. These
two stages act in series and the slower of the two will be the rate de-
termining step. The two stages were investigated using film diffusion
model (Boyd model) and intraparticle diffusion model. According to
Tsibranska and Hristova [53] the diffusion of adsorbate molecules
through the adsorbent pores determines the adsorption rate in most of
liquid systems. The intraparticle diffusion model is applied by drawing
qt against t0.5. If the adsorption process follows this model the line
obtained must be a straight one with an intercept C that gives an in-
dication about the thickness of the boundary layer. The larger the value
of C, the thicker the boundary layer is. If the straight line passes by the
origin, the intraparticle diffusion is the sole rate determining step.
Otherwise, other mechanism may be involved. Fitting of the data to
Intraparticle diffusion model is depicted by Figs. 9 and 10.
Since the lines obtained from fitting the data to the intraparticle
diffusion do not pass through the origin, it may be assumed that in-
traparticle diffusion is not the sole mechanism that controls the ad-
sorption. It may be assumed that the external mass transfer is sig-
nificant only at the initial adsorption stages, and the final stages are
controlled by the intraparticle diffusion [54]. The considerable high R2
values for both intraparticle diffusion and Film diffusion suggest a
combination mechanism. As indicated by Figs. 4–8, the uptake of the
dyes on the adsorbent goes through different stages. At the beginning of
the adsorption process, the uptake rate is very fast. This uptake rate
decreases with time until reaching the equilibrium state. During the
early stages of the adsorption process, boundary layer resistance may be
involved. To understand the relation between the time and uptake of
dye, every stage can be analyzed separately in a process known as
piecewise analysis. Applying the piecewise linear regression especially
at the initial stage of adsorption will indicate the different stages of
mass transport [53]. Some researchers [55,56] indicated that the

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Y.H. Magdy, H. Altaher Journal of Environmental Chemical Engineering 6 (2018) 834–841

Table 5
Kinetic parameters for adsorption of AR114 on CKD.

Model Parameter 0.2 g 0.4 g 1.0 g

300 mg/L 500 mg/L 700 mg/L 300 mg/L 500 mg/L 700 mg/L 300 mg/L 500 mg/L 700 mg/L

Pseudo-First-Order
qe (mg/g) 818.358 781.722 1174.97 239.13 107.986 872.096 102.760 66.72 373.1942
qe,exp (mg/g) 1782.42 2125.75 1202.17 390.58 1174.46 664.67 163.32 475.33 323.72
K1 (min−1) −0.202 −0.021 −0.0113 −0.014 −0.0063 −0.018 −0.016 −0.0078 −0.021
R2 0.9451 0.8048 0.9053 0.9623 0.9476 0.935 0.9854 0.98 0.8928

Pseudo-Second-Order
qe (mg/g) 2000 2000 1428.571 416.67 1250 769.231 172.414 476.190 357.143
qe,exp (mg/g) 1782.42 2125.75 1202.17 390.5833 1174.458 664.6667 163.32 475.33 323.72
K2 (g mg−1min−1) 0.00006 0.0001 0.00001 0.0001 0.0001 0.00003 0.0003 0.0003 0.00009
h2 (g−1 mg min−1) 238.095 434.783 19.569 17.762 212.766 15.244 8.347 64.103 11.325
R2 0.9996 1.000 0.9801 0.9988 0.9997 0.9927 0.9996 0.9997 0.998

Elovich
α (g−1 mg min−1) 96.779 117.532 161.33 92.165 36.970 366.065 44.129 23.684 0.0002
β (g mg−1) 0.0111 0.0091 0.0003 0.019 0.028 0.007 0.044 0.045 0.017
R2 0.9018 0.8686 0.943 0.9874 0.9019 0.9577 0.969 0.9743 0.9575

Intraparticle Diffusion
kid (mg g−1 min−0.5) 16.302 18.086 52.69 9.212 6.232 25.166 3.931 3.999 10.109
C (mg g−1) 1500.2 1829.9 260.14 229.52 1050.9 226.5 96.765 403.36 152.94
R2 0.9141 0.7357 0.9747 0.9646 0.9656 0.9591 0.8961 0.9791 0.9049

Film Diffusion
B −0.202 −0.0138 −0.0112 −0.014 −0.006 −0.0163 −0.016 −0.0078 −0.0205
R2 0.9451 0.8796 0.8703 0.9623 0.9476 0.8771 0.9854 0.98 0.8928

intraparticle diffusion plots might be classified into more than one re-
gion. The first sharp region at the initial stage is attributed to the in-
stantaneous adsorption, probably due to the interaction between the
functional groups at the external surface of adsorbent and the adsorbate
molecules (external surface adsorption). The second region is char-
acterized by gradual adsorption where the intraparticle diffusion is the
rate limiting step. The last region (if present) is due to the low adsorbate
concentration in the solution. In this stage, the intraparticle diffusion
slows down. The results of this present work are in agreement with the
above mentioned mechanisms. It is clear that the rate limiting step is a
combination of the two mechanisms.

3.6. Comparison of CKD adsorption capacity and feasibility study

Table 6 illustrates the maximum adsorption capacity of CKD to-

Fig. 9. Fitting the kinetic data of adsorption of BB69 on CKD to intraparticle diffusion wards BB69 and AR114 compared with other adsorbents. It is clear that
model. CKD has the highest adsorption uptake. The uptake values of CKD are
higher than that of activated carbon. To the best of our knowledge, and
according to the extensive literature review, CKD can be considered the
best adsorbent for both BB69 and AR114.

Table 6
Comparison for the adsorption capacities of different adsorbents to DD69 and AR114.

Dye Adsorbent qe, mg/g Reference

BB69
Egyptian bagasse pith 168 [57]
AC from Pinewwod 1119 [58]
palm-fruit bunch 92 [59]
Wood sawdust 74.4 [60]
Peat 226 [61]
Cement Kiln Dust 2119 This work

AR114
Egyptian bagasse pith 23 [36]
Impregnated Rice Husk ash 111 [37]
Fig. 10. Fitting the kinetic data of adsorption of AR114 on CKD to intraparticle diffusion AC from Kattamanakku tree leaves 450.02 [62]
model. AC from Ceiba Pentandra wood bark 69.45 [63]
Gingelly seed shell 102.24 [64]
Cotton seed shell 15.85 [65]
Cement Kiln Dust 2125 This work

839
Y.H. Magdy, H. Altaher
Most of the researches who used the adsorption as a technique for
wastewater treatment did not answer an important question; “what is
the final destination of adsorbent that is loaded with the adsorbate?”
Some researches, however, discussed the regeneration of the adsorbent,
especially if this adsorbent is AC. But, what happens after complete
exhaustion of the adsorbent? Will this adsorbent be incinerated or sent
to landfill? This is an added advantage of CKD over other adsorbents.
Many practices are already applied to get rid of this industrial waste.
Some of these practices are: recycling into the cement kiln, landfilling
of highway, soil stabilization, stabilization/solidification processes, soil
amendment, and as liming agent [46,65–67]. So, in this case, the ad-
sorption of pollutants from wastewater onto CKD can be a pre-stage
before the final disposal of CKD.
The cost incurred when using different adsorbents include: (1) cost
of adsorbent collection, (2) cost of transportation from site of collection
to the site of water treatment, (3) cost of pretreatment of adsorbent
(washing, drying, size reduction.), (4) cost of adsorbent treatment if for
example AC will be manufactured from precursor or if physical or
chemical treatment are required to enhance the performance of ad-
sorbent, (5) cost of purchasing the adsorbent if it is commercially
available, (6) cost of regeneration, and (7) cost of final disposal of
adsorbent after exhaustion.
It is obvious that items number (2), and (7) are common among all
adsorbents. These are the only costs that are required for use of CKD as
adsorbent. That gives economic advantage of CKD over other ad-
sorbents. Other advantages include the nature of the adsorption process
(chemisorption), which is an irreversible process and prevents the ad-
sorbate from being leached to the environment. Continuous supply of
the adsorbent throughout the year with the required quantity is another
important advantage of CKD. High adsorption capacity, low size to
mass ratio (implying reducing the transportation cost), and the well-
established methods of disposal must also be mentioned.
4. Conclusion
In this study, CKD was evaluated as an adsorbent for removal of two
dyes belonging to two different categories; Basic Blue 69 and Acid red
114. The results indicate the close relation between initial dye con-
centration, adsorbent dose and time of contact between the dye and
adsorbent on the adsorption process. The dye uptake increased with the
increase of initial dye concentration and contact time. On the other
hand increasing the adsorbent dose decreased the dye uptake. The
adsorption of the two dyes followed both the pseudo second order ki-
netic and Elovich models. Both the intraparticle diffusion and film
diffusion were involved as mechanism for adsorption. The high uptake
of the two dyes suggests that CKD has the potential to be used as a
value-added product useful in solving both the problem of industrial
waste disposal and industrial wastewater treatment.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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