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Article history: The phosphorous adsorption on a synthesized magnetic iron oxide (MIO) was conducted using a batch
Received 18 August 2015 type experiment. A dry-form MIO was used in adsorption experiment to obtain useful information for
Received in revised form 14 October 2015 practical application. The Elovich model reasonably simulated the two-step adsorption process in the
Accepted 12 November 2015
kinetic experiments. Freundlich isotherm model was better than the Langmuir model for describing the
Available online 23 November 2015
phosphate isotherm on MIO. The maximum adsorption capacity of MIO was 15.2 mg P/g MIO which was
achieved at the pH less than 5. The adsorbed phosphorous was effectively detached from MIO within
Keywords:
30 min using 20 wt% NaOH solution.
Adsorption
ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Desorption
Equilibrium isotherm reserved.
Magnetic iron oxide
Phosphorus recovery
Introduction On the other hand, despite its extensive use in various fields,
phosphorus is a non-renewable and non-interchangeable finite
Phosphorus is an essential nutrient for the growth of resource. Therefore, the recovery and removal of phosphate should
organisms in ecosystems and is the most important resource in be considered. The material used for removing phosphorus must
many fields, such as the manufacture of fertilizers, detergents, and satisfy the following preconditions as an adsorbent: (1) high
polishers. However, the increased discharge of phosphate into the adsorption rate, (2) easy to recycle, and (3) high potential for
water system contributes to eutrophication, leading to environ- practical application [15,16]. Magnetic iron oxide (MIO) was
mental problems in reservoirs and coastal areas [1,2]. Various selected here as an effective alternative for the removal and
techniques have been successfully applied for phosphate removal, recovery of phosphorus in solution because solid MIO can easily be
such as chemical precipitation, adsorption, and biological separated from a solution using magnets.
processes. However, biological processes are unreliable because Many researches have been carried out to adsorb phosphorous
the quality of water has a significant impact on phosphate in solution using magnetic iron oxide [17]. The magnetic particles
removal. Chemical precipitation often consumes a large amount used in the previous researches were mostly nano-sized particles
of coagulant but requires sludge treatment and material disposal and were kept and used as suspended solid in the adsorption
[3]. Adsorption is an alternative and promising phosphate experiment. However, there was a little study using micro-size or
removal method, especially for wastewater with a low phosphate dry-form magnetic solid. The relatively bigger size and dry-form
concentration [4,5], due to the production of less sludge, easy magnetic solids is more appropriate to the practical application
operation, and high efficiency [6]. Therefore, the removal of than the nano-sized suspended form because of cheap
phosphate using various adsorbents, such as aluminum oxides manufacturing price and easy handling.
[7,8], iron oxides [9], mesoporous silicates [10], red mud [11], In this study, we investigated the basic characteristic of dry-
alum sludge [12], apatite [13], and clinoptilolite [14], has received based MIO (20–100 mm) on adsorbing phosphorous from solution.
increased attention. Kinetic and isotherm experiments were conducted to evaluate the
reaction kinetic behavior and the adsorption capacity of MIO. In
addition, the effect of operational factors (pH and temperature)
was examined to obtain the optimum condition of phosphorous
* Corresponding author. Tel.: +82 2 2220 0325; fax: +82 2 2220 1945. removal by MIO. Finally, the desorption experiment was con-
E-mail address: jk120@hanyang.ac.kr (J.-O. Kim). ducted to verify the reusability of MIO in practical application.
http://dx.doi.org/10.1016/j.jiec.2015.11.008
1226-086X/ß 2015 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
J. Choi et al. / Journal of Industrial and Engineering Chemistry 34 (2016) 198–203 199
Preparation of MIO A desorption experiment was carried out by 2 steps. In the first
step, MIO was reacted with phosphorous at pH 4 and room
The Fe3O4 nanoparticles were synthesized using the co- temperature. The phosphorous concentration on MIO was
precipitation method [17], mixing 2 L of 1 M Fe SO47H2O and 2 L 4.9 mg P/g MIO. In the second step, 1 g of MIO was added to a
of 2 M FeCl36H2O. The solution was then purged with nitrogen 50 mL conical tube containing 20 mL of NaOH solution (3, 5, 10,
in order to prevent Fe2+ ion oxidation. After 30 min of purging, and 20 wt%). The MIO and alkaline solution was mixed using a
1 L of 6 M NaOH was added drop-wise into the solutions noted multi-rotator at room temperature. Sampling was performed for 1,
above, and purging was continued for an additional 10 min. 5, 10, 15, 30, and 60 min.
During the process, the solution was gradually changed to black
and was washed 15 times with deionized water until the pH Results and discussion
value of the solution became neutral. The resulting black
solution was dried at 70 8C for 24 h in an electric furnace Physicochemical characteristics of MIO
(SF-03, SciLab Co., Korea) and then cooled at room temperature.
The dried magnetic iron oxide was crushed using a mortar and The properties of the synthesized MIO were evaluated using
pestle. X-ray diffraction (XRD), scanning electron microscopy (SEM), and
particle size distribution. The XRD result in Fig. 1a showed that
Characterization of MIO the d-space values obtained for the synthesized magnetite were
2.53, 1.48, and 1.61, which were analogous to the reference
The crustal structure of MIO was characterized using X-ray power diffraction file (JCPDS No. 86-1354). There was no
diffractometry (XRD, D8-Advance, Bruker-AXS Co., Germany) noticeable peak for any of the other ferric or ferrous oxide-
after excitement with Cu Ka radiation at 45 kV and 100 mA. The hydroxides except MIO. The d-space value of the MIO-adsorbing
Fourier-transform infrared spectra (FTIR) were recorded on a phosphate was almost the same as that of the synthesized MIO,
Nicolet-380 Fourier-transform infrared spectrometer using which indicated that no structural disruption of MIO or
the KBr method. The MIO particles were classified by size
using the sieving method. The dried MIO was transferred to the
nest of sieves arranged from top to bottom with decreasing
size in the following order: 100-, 75-, 53-, 32-, 20-mm, and pan.
The sieves were then shaken on a sieve shaker for approximately
three min. Each MIO particle fraction was weighed, and the
average of five samples was calculated for use in further
analysis.
Table 1
Adsorption characteristics of MIO with different particle sizes.
formation of precipitates containing phosphorous occurred equilibrium (mg/g), k1 is the rate constant for the pseudo first-
during the adsorption reaction. In addition, the XRD results order (min1), k2 is the rate constant for the pseudo-second-order
indicated that the synthesized MIO was not easily oxidized to (g/mg min), a is the initial phosphate adsorption rate for the
ferric oxide-hydroxide under oxygen exposure. Elovich model (mg/g min), and b is the desorption constant during
Fig. 1b shows the results of FI-IR analysis of MIO before and any one of the experiments using the Elovich model (g/mg).
after phosphorous adsorption. The major peaks appeared at 1,632, Non-linear regression was performed using the least squares
1,070, 619, and 469 cm1, which corresponded to the bending method for each of the kinetic models, and the results are
vibration of H2O molecules, the stretching vibration of Fe–OH
groups, and Fe–OH vibration, respectively. A peak at 1119 cm1
was observed in the sample of MIO with phosphorous, which did
not appear in the sample before the reaction. This result was
evidence that the phosphorous was chemically bound to the
surface of MIO.
The size of MIO was one of the most important factors that
affected the adsorption capacity. The effect of size was initially
evaluated because the size of MIO synthesized in this study varied
from nanometers to micrometers. Four types of samples were
prepared, as shown in Table 1, and then the batch test was
conducted. The adsorption capacity was observed to be 5.5–
5.3 mg P/g MIO, and no measurable difference was not noted
between the samples. Commercial samples from Daejung Chemi-
cal Co. in Korea were also tested in order for a comparison of the
adsorption capability of the synthesized MIO. The particle size of
the commercial magnetite was 1.7 mm and the capacity was
2.2 mg P/g MIO.
k2 q2e t
qt ¼ (2)
1 þ k2 qe t
1 1
qt ¼ lnðabÞ þ lnt (3)
b b
where qt is the amount of phosphate adsorbed onto MIO at time t Fig. 2. Kinetic model analyses: (a) pseudo-first-order model, (b) pseudo-second-
order model, and (c) Elovich model (experimental condition: pH 4.0, initial P
(mg/g), qe is the adsorption capacity of the phosphate at
concentration 165 mg-P/L, MIO concentration 33.3 g/L).
J. Choi et al. / Journal of Industrial and Engineering Chemistry 34 (2016) 198–203 201
Table 2
Kinetic model parameters obtained from model fitting to the experimental data.
Initial P conc. (mg P/L) Pseudo-first-order model Pseudo-second-order model Elovich model
2 2
qt (mg/g) k1 (h 1
) r qt (mg/g) k2 (g/mg min) r a (mg/g min) b (g/mg) r2
165 3.17 1.52 0.97 3.27 0.84 0.98 489.4 3.30 0.98
490 9.52 1.21 0.96 9.93 0.18 0.98 1153 1.08 0.99
815 12.9 1.15 0.97 13.5 0.13 0.99 1555 0.80 0.99
1140 13.4 1.36 0.95 13.9 0.15 0.97 1730 0.77 0.99
presented in Fig. 2 and Table 2. Fig. 2a and b clearly illustrate that which models were appropriate to describe the experimental data
the pseudo-first-order and the pseudo-second-order kinetic and to calculate the isotherm constants of phosphorus adsorption
models were not appropriate for the description of phosphate by MIO.
adsorption in the late period of the reaction. The simulated The results showed that the Freundlich isotherm model was
phosphate concentration was smaller than the measured concen- more appropriate for describing phosphorus adsorption on MIO
tration, especially in the late reaction period. However, the Elovich than was the Langmuir model. The determination coefficient (R2)
model effectively described the experimental kinetic data, and the value of the Freundlich model was 0.98, which was comparatively
calculated coefficient of determination for the Elovich model was higher than that of the Langmuir isotherm model at 0.759. The
greater than 0.99 in all of the cases, indicating that the mechanism estimated maximum adsorption capacity of the MIO using the
of phosphate adsorption on magnetite might be chemisorption Langmuir model (qmax) was 15.2 mg P/g MIO, and the adsorption
(see Fig. 2c) [22]. density of the Freundlich model (KF) was 4.27 L/mg P.
It has been clearly observed in other studies that the pseudo- The obtained maximum adsorption capacity in this study was
second-order model was better than the pseudo-first-order model analogous to that of other studies using iron-bearing oxides or slag
for phosphate adsorption on iron-bearing minerals. In addition, the for phosphate removal. It has been reported that the maximum
pseudo-second-order model provided a better description than the capacity of magnetite or magnetic iron oxide was in the range of
Elovich model when kinetic experiments were conducted at a low 2.6 to 27.15 mg/g MIO [17,23]. Iron-bearing binary oxide has been
level of phosphate adsorption (less than 10 mg of phosphate was shown to have a phosphate capacity of 10–40 mg/g solid
adsorbed per 1 g of adsorbent) [17,20]. However, other studies [19,20,22].
have reported that the pseudo-second-order kinetic model was not
a proper model when the adsorption capacity of the phosphate at Effects of temperature and pH on phosphate adsorption by MIO
equilibrium (qe) exceeded dozens of mg phosphorous per g
adsorbent [20,22]. Fig. 4 shows the effects of temperature on phosphate adsorption
The initial phosphate adsorption rate (a) obtained from non- onto MIO. The batch kinetic experiments were carried out at
linear regressions using the Elovich model was non-linearly temperatures ranging from 283 K to 323 K. The rapid adsorption of
increased with respect to initial phosphate concentration or phosphate onto MIO was observed within five min, and then the
phosphorous to magnetite ratio. The increase in adsorption rate amount of phosphate adsorbed slowly increased during the last
became smaller with an increase in phosphate concentration. In 55 min. The simulations using the pseudo-second-order kinetics
addition, the adsorption capacity of the pseudo-second-order model were carried out, and the results are presented in Fig. 5. The
kinetic model at equilibrium showed an analogous pattern to the adsorption capacity of phosphate onto MIO at equilibrium (qe)
initial phosphate adsorption rate of the Elovich model. This result increased from 5.20 to 6.15 mg P/g MIO with an increase in
indicates that the proper ratio of phosphorous to magnetite is an temperature. The endothermic nature of the adsorption process
important factor in the performance of an effective phosphorous was comparable to that in other studies focusing on phosphate
removal process. adsorption on iron oxide. In addition, this result indicates that the
phosphate was not physically but chemically adsorbed onto the
Adsorption isotherm of MIO MIO, because physisorption is generally known to be an
exothermic process [17,19,22,23].
The batch experiment for the adsorption isotherm study was
conducted to describe the adsorption of phosphate on MIO under
conditions of pH 7 and 23 8C, and the results are presented in
Fig. 3. In addition, the isotherm models, including the Langmuir
and Freundlich models, were used to simulate the experimental
data of phosphorus adsorption. The isotherm models are presented
in Eqs. (4) and (5)
kL C e
Langmuir equation : qe ¼ qmax (4)
1 þ kL C e
1=n
Freundlich equation : qe ¼ K F Ce (5)
where qe is the amount of adsorbate per gram of adsorbent at
equilibrium (mg/g), qmax is the maximum adsorption capacity (mg/
g), KL is the Langmuir isotherm constant (L/mg), Ce is the adsorbate
concentration in solution at equilibrium, KF is the Freundlich
isotherm constant describing the adsorption density (mg/g), and n
is the adsorption intensity. The non-linear regression was Fig. 3. Equilibrium isotherm model analyses with the Freundlich and Langmuir
conducted using the least squares method in order to justify models (experimental condition: pH 4.0, initial P concentration 165–1630 mg-P/L,
MIO concentration 33.3 g/L).
202 J. Choi et al. / Journal of Industrial and Engineering Chemistry 34 (2016) 198–203
Conclusions
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