Chemical Engineering Journal 260 (2015) 444–453

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Chemical Engineering Journal

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

Adsorption of Sb(III) from aqueous solution by QFGO particles in batch

and fixed-bed systems
Xiuzhen Yang, Zhou Shi ⇑, Lishan Liu
Department of Water Engineering and Science, College of Civil Engineering, Hunan University, Changsha, Hunan 410082, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A new material of quartz sand/Fe3O4/

GO particles has been prepared.
Fe3O4 GO
 The applicability was demonstrated
150 150
by batch and laboratory columns Effluent Digital heating circulating
sand sand/Fe 3O4 sand/Fe3O4/GO water
experiments. water bath

 Coexistence ion of As(III) and Hg(II)

could be removed simultaneously.
 The regeneration study showed the
new material can be reused.
Peristaltic pump
Peristaltic pump

Sb(III)

a r t i c l e i n f o a b s t r a c t

Article history: A composite of quartz sand coated with Fe3O4 and graphene oxide (QFGO) was prepared. SEM, FTIR, XRD
Received 30 June 2014 and XPS measurements confirmed that smooth surface of the sand was modified with spherical latex
Received in revised form 8 September 2014 beads and some flake-like materials which were attributed as coated Fe3O4 and graphene oxide (GO),
Accepted 9 September 2014
respectively, and function groups of OH, C@O, CAO, SiAO, C@C, and FeAO were also identified. Batch
Available online 17 September 2014
and continuous fixed-bed column studies were undertaken to evaluate the efficiency of the QFGO as
an adsorbent for the removal of Sb(III) from aqueous solutions. The results showed that Sb(III) as well
Keywords:
as its co-absorbates, As(III) and Hg(II), could be effectively adsorptive removed with the QFGO in batch
Antimony
Adsorption
test. The adsorption of Sb(III) on the QFGO followed the pseudo-first-order Kinetic and the Freundlich
Quartz sand adsorption isotherm in batch study and Thomas models in column studies. Further, column tests under
Fe3O4 various parameters of bed depths (10–30 cm), Sb(III) concentrations (20–60 mg/mL), and flow rates
Graphene oxide (8–16 mL/min) showed that the removal of Sb(III) was effective with capacity of 2.88–6.09 mg/g, which
was greater than that of many other current evaluated absorbents of MWCNTs, bentonite, and iron-oxide
coated sand. The adsorptive exhausted column can be restored with EDTA. According to the facts
established in the study, the QFGO based adsorption process could be a promise technology for remedi-
ation of Sb(III) contaminated waters.
Crown Copyright Ó 2014 Published by Elsevier B.V. All rights reserved.

1. Introduction and so on. According to recent surveys, Sb in the surface water in

Antimony (Sb) is often observed in various industry effluents,
such as antimony mining, beneficiation, metallurgy, electroplating,
⇑ Corresponding author.
E-mail address: shizhou53@126.com (Z. Shi).
Xikuangshan antimony mine, the world largest antimony mine in
the central part of China, reached 7 mg/L [1], and Sb in the soil
samples in this area was reported to range from 100.6 to
5045 mg/kg [2]. Such high concentration of Sb in the environment
threatened the residents’ health through food chain of water-soil-
crops-human. It was reported that Sb and Sb-containing multimer-
izings can easily combine with sulfhydryls in the human body, and

http://dx.doi.org/10.1016/j.cej.2014.09.036
1385-8947/Crown Copyright Ó 2014 Published by Elsevier B.V. All rights reserved.
 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453
thus can disturb enzyme activity and destroy ion balance in cells,
causing cellular hypoxia. These adverse effects will finally lead to
the metabolic disorders, and damage to the nervous system and
other organs. Thus, antimony and its compounds are considered
as priority interest pollutants and strict environmental standards
concerning Sb have been established in many countries [3–6],
and in China the Sb concentration should be <5 lg/L in drinking
water [7]. Due to lack of relative research, control of Sb pollution
in the antimony mine area becomes an urgent task.
Antimony generally exists in Sb(III) and Sb(V) oxidation states,
and Sb(III) is reported to be 10 times more toxic than Sb(V) [8,9].
Therefore, removal of Sb(III) is the focus of this study. Methods
available to remove Sb from water include solvent extraction
[10,11], ion exchange [12], coagulation [13], osmosis [14], sedi-
mentation [13], and adsorption [15–17]. Among these methods,
adsorption is the most commonly used one due to its potential of
simple operation, low-cost and high efficiency as compared to
the other equally effective technologies.
Successful application of adsorption process largely depends on
the absorbent. Among the adsorption materials, graphene oxide
(GO) has been the hotspot of the current researches. GO, a two-
dimensional nano-material, is treated as an oxidized form of
graphene. In contrast to graphene, the GO possesses series of oxy-
gen functional groups, e.g. hydroxyl and carboxyl groups. In addi-
tion, GO has a huge specific surface area with the theoretical value
of 2630 m2/g [16]. Possessing such good properties, GO could be an
excellent adsorbent [16–18]. However, its strong hydrophilicity
keeps pure GO adsorbent hard to be separated from applying solu-
tion, and the separation cost is very high. These factors make it dif-
ficult to be widely used in pollutant removal. In order to overcome
these problems, numerous experiments have been done through
using GO composites with metals and metal oxides to remove pol-
lutants from aqueous phase [19–22]. It is proved that hybrids of
magnetic NPs and GO possess fine efficiency in the wastewater
treatment [23–28].
Cost is a critical criterion in application of GO based adsorbent
materials. Developing a cheaper, more efficient and eco-friendly
graphenic adsorbent is desirable for water and wastewater treat-
ment. Recently, researchers have reported that coated coarse sand
coated with GO can serve as an effective and low-cost absorbent
for water purification [29–31]. However, due to its hydrophilic nat-
ure and less strong binding with the support material of sand, it is
difficult to be recovered from the applying solution. Furthermore,
partial of the coated GO would easily fall off from the sand surface
and dissolved in the solution during application, which might
result in the solution being re-polluted.
In 1989, Edwards and Benjamin developed an innovative tech-
nique by which significant quantities Fe oxides could be firmly
attached to quartz sand. After that, several researchers have
improved this method for coating oxides onto the surface of the
quartz sand to adsorb heavy metals [32–35]. Herein, in this work
Fe3O4 was adopted as an intermediate carrier to enhance the bind-
ing of GO on the surface of sand. A new adsorbent of quartz sand/
Fe3O4/GO (QFGO) was composed and has been successfully applied
in batch and column studies to evaluate adsorptive removal of
Sb(III) from aqueous solution. Experimental parameters were
investigated in detail and the optimal experimental conditions
were established.
2. Materials and methods
2.1. Adsorbate
To create the adsorbate, 0.54848 g Sb potassium tartrate
(K(SbO)C4H4O61/2H2O) (analytical pure) was dissolved in
1000 mL double distilled water to prepare stock solution with Sb
445
concentration of 200 mg/L. Solutions with desired Sb concentra-
tions for the experiment were created by diluting this Sb stock
solution with double distilled water. And the initial pH of the
tested solution was adjusted to 7.0 ± 0.1 using NaOH (0.1 M) in
both the batch and the column studies.
2.2. Adsorbent
GO was purchased from Nanjing Pioneer of Nanoscience and
Technology Co., Ltd (China). All chemicals used in the experiments
were analytical grade.
Sieved raw quartz sand with particle diameters ranging from
0.6 to 0.8 mm was soaked in hydrochloric acid (1 M) for 24 h. After
washing with double distilled water, the quartz sand was dried at
110 °C in an oven for 24 h. After cooling down to room tempera-
ture, the sand was storied for further use.
QFGO was composited through the following steps, Solution
with Fe3+: Fe2+ molar ratio of 2:1 were prepared by dissolving
0.02 mol of FeCl36H2O and 0.01 mol of FeCl24H2O in 40 mL of
double distilled water. After 50 g of the pretreated quartz sand
was added to the solution, the mixture was stirred well in a ther-
mostatic water bath at 80 °C under a nitrogen flow (30 mL/min),
then ammonia (28 wt%) solution was added drop by drop at a
dropping rate of 10 d/min until the solution reached a pH of 10,
which was necessary for synthesis of magnetite Fe3O4. After the
reaction completed, the composite was dried at 150 °C in a vacuum
drying oven for 24 h, cooled to room temperature, and then
washed with double distilled water to scour off ferrous oxide par-
ticles that had failed to combine with the quartz sand. The scoured
ferrous oxide particles were collected and ultrasonically stirred
(40 kHz, 200 W) in double distilled water for 30 min. To control
the water temperature of ultrasonic bath below 10 °C, ice blocks
were added into the bath. After the pre-prepared quartz sand/ferric
oxide composite were remixed with the ultrasonically stirred
scoured ferrous oxide particles, the whole mixture were dried in
a vacuum drying oven, and the final quartz sand/ferric oxide com-
posite prepared. 0.20 g of the GO was added in 30 mL double dis-
tilled water and was ultrasonically stirred for 1 h, then mixed
with the prepared quartz sand/ferric oxide composite. This mixture
was thoroughly stirred and then dried at 150 °C in a vacuum drying
oven for 24 h. After cooling, the composite was washed off the non
combined GO with double distilled water. This process was
repeated using another 0.20 g of the GO to increase the coating
thickness on sand and was dried again in a vacuum drying oven.
Thus, the QFGO was obtained and stored in a polyethylene bottle
for use.
2.3. Analytical methods
Quartz sand, quartz sand plus Fe3O4, and QFGO were examined
by the following instrument or methods. Scanning electron micros-
copy (SEM) was obtained using a scanning electron microscope
(JSM-6700F, JEOL Corporation). Infrared spectra of the adsorbents
were recorded using a FT-IR spectrometer (Thermo Nicolet,
Nexus-470, USA) at 500–4000 cm1. XRD patterns were recorded
by an X-ray diffract meter (D8-ADVANCE, Bruker) using Cu Ka
radiation. X-ray photoelectron spectroscopy (XPS) was performed
with a Thermo Fisher Scientific (K-Alpha 1063) probe using mono-
chromatic AlKa radiation (hm = 1486.6 eV). Spectrum analysis was
done by performing a Shirley background subtraction, followed by
decomposition into several Gaussian peaks. The fitting method was
set up so that peak positions and widths were the same for all
spectra, and only the amplitude was fitted independently for each
spectra and each Gaussian sub-peak. Sb(III) was detected by an AA-
7000 atomic absorption spectrophotometer (Shimadzu, Japan). As
(III) and Hg(II) were detected by 7700 series ICP-MS (Agilent Tech-
nologies, Japan).
446 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453
2.4. Experimental methods
2.4.1. Batch adsorption
Batch adsorption experiments were performed at room temper-
ature (25 ± 0.5 °C), where 1 g of sorbent material was placed in a
100 mL plastic bottle containing 50 mL of Sb(III) solution. The bot-
tles were sealed and placed on a shaking table at 140 rpm in the
dark for certain time period required. For adsorption isotherms,
the equilibrium time was set at 24 h with initial Sb(III) concentra-
tions ranging from 30 to 180 mg/L. Following adsorption step, the
solutions were filtered with a polycarbonate membrane (0.45 lm),
and the amount of target ion residue was measured by AAS. Exper-
iments were duplicate under identical conditions.
2.4.2. Column adsorption
Although batch adsorption studies provide useful information
on the application of adsorption for the removal of specific waste
constituents, column studies can provide basic data on the system-
atic process, which is useful for engineering applications in waste-
water treatment [36]. The fixed-bed column experimental
arrangement for Sb(III) removal is shown in Fig. 1.
For the pilot experiments, a polymethyl methacrylate column
with an inner diameter of 2 cm and a length of 50 cm was used.
Certain quantities of the composites were then added into the col-
umn. Sb(III) solution was injected into the column in an upward
flow direction using a peristaltic pump. The filtering velocity was
then adjusted and the empty bed contact time was ensured. Sam-
ples were taken at 1 h intervals and filtered through a 0.45 lm
polycarbonate membrane. The concentration of Sb(III) in the solu-
tion was then measured by AAS in order to determine the break-
through curve of Sb(III) under different conditions. Triplicate
experiments were carried out.
2.4.3. Regeneration
Regeneration ability of the adsorbent material is important for
its practical application. The exhausted column containing 20 cm
packed QFGO was regenerated by running 0.1 mol/L EDTA through
the bed in an upwards flow direction at 10 ml/min for 150 min. and
following by washing with distilled water at 10 ml/min for 60 min.
3. Results and discussion
3.1. Characterization of QFGO
Photographs and SEM measurements were employed to char-
acterize morphological properties of the sand, sand/Fe3O4 and
Fig. 1. Schematic diagram of experimental setup for column studies.
QFGO (Fig. 2). From the inset pictures of Fig. 2(a), (c) and (e), it
can be seen that the color of the adsorbent changed from yellow-
ish white to blackish gray to dark after coating process, which
indicated Fe3O4 and GO were coated on the surface of the quart
sand successfully, and little particle size change was observed
after coating. From the SEM (X60) of Fig. 2(a), (c) and (e), the sur-
face of the material was obviously different from each other. In
contrast to the quartz sand surface which was quite smooth
(Fig. 2(b)), some spherical latex beads appeared on the surface
of quartz sand after coating Fe3O4 (Fig. 2(d)). This spherical latex
beads were possibly contributed to Fe3O4 coated on the sand.
Comparing SEM in Fig. 2(f) with that in Fig. 2(d), some flake-like
materials were identified on the surface of QFGO, this flakes were
likely attributed to GO coated on the surface of quartz sand/
Fe3O4.
FTIR spectra and XRD of QFGO were shown in Fig. 3. FTIR spec-
tra (Fig. 3(a)) reveal the information of functional groups on the
composite. A strong and broad band in the range of 2800–
3600 cm1 may be related to H-bonding stretching vibration of
the OH group, peaks at 1720 cm1, 1060 cm1, and 1100 cm1
may attribute the stretching of C@O, stretching vibration of
CAO, and stretching of SiAO, respectively. Moreover, the signa-
ture of aromatic C@C stretching at 1400 cm1 indicated the
presence of a sp2 hybridized honeycomb lattice. The peaks
between 400 and 700 cm1 were corresponding to the FeAO in
Fe3O4 [37].
XRD was utilized to investigate the crystallinity of the compos-
ite. Fig. 3(b) depicts the XRD patterns of QFGO. The main character-
istic peaks at 10.9°, 30.1°,35.4°, 43.3°, 54.5°, 57.3° and 62.8°, were
indexed as the diffractions of the (0 0 1), (2 2 0), (3 1 1), (4 0 0),
(4 2 2), (5 1 1) and (4 4 0) crystalline planes of GO and Fe3O4 accord-
ing to the standard spectrum of GO and Fe3O4. Other peaks left
were the peaks of SiO2 (the main composition of quartz sand), indi-
cating that the particle was composed of three phases: GO, Fe3O4
and SiO2.
XPS measurements were carried out to determine the composi-
tion of sand, sand/Fe3O4 and QFGO (Fig. 4). From Fig. 4(a), on the
surface of the sand particle, there are three predominant peaks at
100 eV, 285 eV, and 530 eV, accounting for Si2p, C1s, and O1s,
respectively. After Fe3O4 coating on the surface of sand particle,
the peak intensity of Si and O is weakened, and a Fe 2p peak at
710 eV appears, indicating that Fe bearing compound covered on
the sand surface. In the spectra of QFGO, the peak of Si was almost
disappeared, the peak of Fe was weakened and the peak of C was
increased. Which indicated that GO was coated on the surface of
 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453 447

a c e

b d f

Fig. 2. Photographs and SEMs of the quart sand before and after coating. (a) and (b) Quartz sand. (c) and (d) Quartz sand after coating Fe3O4. (e) and (f) Quart sand after
coating Fe3O4 and GO.

a b

C=O
(311)

C=C
(001)

(511)
(440)

Si-O
(422)
(220)

Fe-O
(400)

C-O-C
4000 3500 3000 2500 2000 1500 1000 500 10 20 30 40 50 60 70 80
Wave number (cm-1) 2 Theta(deg.)

Fig. 3. (a) FTIR spectra of QFGC; (b) XRD patterns of QFGC.

quart sand/Fe3O4. Deconvolution of the XPS spectra has been per-
formed using multipack software and it is plotted in Fig. 4(b) and
(c). It was found from Fig. 4(b) that peaks of Fe 2p1/2 and Fe 2p3/2
were at 710.9 eV and 725 eV, respectively, indicating that the iron
bearing compound in the sample is Fe3O4 [37,38]. From Fig. 4(c),
there is a major peak centered at 284.9 eV (carbon sp2), and peaks
at 284.9, 287.0, 288.3 and 289.3 eV could be assigned to carbon
atoms in the binding form of C@C/CAC, CAO, C@O and OAC@O,
respectively, these results established conclusion that GO was
coated on the surface of the tested material, i.e. Sand/Fe3O4 [38].
In summary, according to the results demonstrated with SEM,
FTIR, XRD and XPS measurements, the surface of the quartz sand
was successfully coated with Fe3O4 and GO, therefore the profile
and the surface chemical functional groups of the quartz sand have
been modified too.
3.2. Effect of pH on the adsorption
The pH value of the solution is one of the most important envi-
ronmental factors that characterize the metal ion’s adsorption pro-
cess, because it influences both the metal binding sites on the
adsorbent and the metal ion chemistry in the aqueous solution.
The effect of pH on Sb(III) removal was investigated in the pH
range of 1.5–11 through batch experiments, and the result is
shown in Fig. 5. It was found that Sb(III) adsorption by QFGO
was pH-dependent with the highest adsorption achieving at pH
3–9. This relative broad pH range could benefit its application in
water/wastewater treatment with different pH. According to the
literature [14], the species of Sb(III) are pH dependent: when pH
is below 3, the predominant species of Sb(III) are SbO+ and Sb
(OH)2+; when the pH ranges from 3 to 9, Sb(OH)3 and HSbO2 are
448 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453

250000
a O
200000
150000

100000
Si C

Intensity(a.u)
50000
quartz sand
0
Fe
100000

50000 quartz sand/Fe3O4

0

100000
50000 QFGO
0
100 200 300 400 500 600 700 800
Binding Energy (eV)

3800 b 2p3/2
(710.9 eV)
4000 c C=C
2p(725
1/2
eV)
3500
3600
C1s
3000
3400
Intensity/au

Fe
Intensity/au

2500
3200
2000
3000
1500
C-O
2800
1000 O-C=O
C=O
2600
500

700 710 720 730 740

284 286 288 290
Binding Energy (eV) Binding Energy (eV)

Fig. 4. XPS of quart sand before and after coating; (a) XPS of quart sand, quart sand/Fe3O4 and QFGO; (b) Fe2p; (c) C1s.

3.3. Simultaneous removal of Sb(III), As(III) and Hg(II)

100
Pollutant in industrial wastewater does not often exist as single
Removal sufficiency of Sb(III) (%)

species, so evaluation of effects imposed by the coexisted pollu-

80
tants is of great importance [39]. Since As(III) and Hg(II) are usually
present as the co-pollutants of Sb in polluted waters in mine
60 area[40], they are selected as the co-pollutant ions in this study.
The results of sole removal of Sb(III) and simultaneous removal
of Sb(III), As(III) and Hg(II) were shown in Fig. 6.
40 Compared with the result of sole removal of Sb(III) showed in
Fig. 6(a), it is found that Sb(III), the coexist of As(III) and Hg (II)
in the solution has no significant effect on the adsorption removal
20
of Sb(III) by QFGO. These results proved that QFGO could not only
effectively remove Sb(III), but also is capable of removing both
0 As(III) and Hg (II) simultaneously in short time.
0 2 4 6 8 10 12
Initial solution pH 3.4. Adsorption kinetics

Fig. 5. Effect of pH on the adsorption of Sb(III) (initial concentration of Sb(III), In order to evaluate the adsorption kinetics, two kinetic models,
10 mg/L; QFGO 1 g/50 mL; T = 298 K; contact time 120 min.).
namely, the pseudo-first-order and pseudo-second-order models,
were used as given in the following.
Pseudo-first-order model:
q ¼ qe ð1  ek1 t Þ ð1Þ
2
the main species of Sb(III), and only SbO exists when the pH is Pseudo-second-order model:
above 9. Since the highest adsorption achieved at pH 3–9, and  1
pH value of the aquatic environment is usually around 7, thus, 1 1 1
q¼ þ t ð2Þ
pH 7 is selected for further experiments. qe k2 q2e
 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453 449

a 10 b 10

Residual concentration (mg/L)

Residual concentration (mg/L) 8
8

6
6 Sb(III)
As(III)
Sb(III) Hg(II)
4
4

2
2

0
0 0 10 20 30 40 50 60
0 10 20 30 40 50 60 Time (min)
Time (min)

Fig. 6. (a) Sb(III) sole removal by QFGO (initial concentration of Sb(III) is 10 mg/L, QFGO is 1 g/50 mL, T = 298 K, pH 7.0 ± 0.1, contact time 120 min.). (b) Simultaneous removal
of Sb(III), As(III) and Hg(II) by QFGO (Initial concentration of Sb(III), As(III) and Hg(II) is 10 mg/L, respectively; QFGO is 1 g/50 mL, T = 298 K, pH 7.0 ± 0.1, contact time
120 min.).

where qe and qt (mg/g) are the amount of Sb(III) adsorbed per unit Ce 1 Ce
¼ þ ð3Þ
weight of the adsorbent at equilibrium and time t respectively, k1 is qe Q 0 b Q 0
the pseudo-first-order rate constant, and k2 is the pseudo-second-
order rate constant. The k1 and k2 were determined as 0.353/min where Q0 (mg/g) is a constant related to the maximum amount of
and 0.276 g/(mg min), respectively, according to the regression of adsorbed solute, b (L/mg) is a constant related to the energy of
the model and the experimental data in Fig. 7. adsorption, and Ce is the equilibrium Sb(III) concentration in solu-
Fig. 7 showed the curve plot of the pseudo-first-order and tion (mg/L). The values of constants Q0 and b are determined exper-
pseudo-second-order model for the Sb(III) adsorption. In contrast imentally by plotting 1/qe versus Ce as shown in Table 1.
to the pseudo-second-order model, the high correlation coefficient The Freundlich isotherm is particularly well suited for an
(R2 > 0.99) and the closer value of qe,cal (1.99 mg/g) and qe,exp (2 mg/ empirical isotherm for heterogeneous surfaces and multilayer
g) confirmed that the adsorption of Sb(III) on QFGO fit well with adsorption with interactions between adsorbed molecules. The
the pseudo-first-order model, suggesting that Sb(III) adsorption Freundlich isotherm theory states that the ratio of the amount of
on the QFGO follows the pseudo-first-order kinetics[41]. adsorbate adsorbed in a given amount of adsorbent to the adsor-
bate concentration in the solution is not constant under different
concentrations. The Freundlich isotherm is commonly expressed
3.5. Adsorption isotherms by Eq. (4) [43].

Two commonly used isotherms, Langmuir isotherm and Fre- 1

ln qe ¼ ln K f þ ln C e ð4Þ
undlich isotherm, are used to evaluate adsorption results in the n
study. where Kf (mg/g) and 1/n (L/g), constants describing characteristics
The Langmuir isotherm, which is applied as monolayer adsorp- of the system, indicate the adsorption capacity of the sorbent and
tion, assumes that the uptake of the adsorbate occurs on a specific the intensity of the adsorption, respectively. The Freundlich coeffi-
homogeneous surface containing a finite number of binding sites. cients are determined by plotting ln qe versus ln Ce as shown in
Once a molecule occupies a site, no additional adsorption occurs Table 1.
there. The linear form of the Langmuir equation is written as [42]: Results of Langmuir and Freundlich isotherms fitting data of
adsorption of Sb(III) onto the QFGO composite are shown in
Fig. 8 and Table 1. It can be seen from Table 1 that the isotherm
2.0 data fit the Freundlich (R2 = 0.99) equation better than the Lang-
muir equation (R2 = 0.96). The maximum adsorption capacities of
Sb (III) calculated from the Freundlich isotherm was 2.01 mg/g,
Sb(III) adsorbed (mg/g)

1.5 which was close to those experimentally determined value of

2.00 mg/g. The well fitness of the Freundlich isotherm with the
experimental data implying that the adsorption of Sb (III) on the
1.0
QFGO may be the interactions between heterogeneous surfaces
Sb(III) adsorbed and multilayer adsorption with the absorbents [42,43]. The
pseudo-first model fit obtained values of 1/n from the Freundlich isotherm is 0.074 which
pseudo-second model fit
0.5

Table 1
Adsorption isotherms parameter for Sb(III) removal.
0.0
Values Parameters
0 20 40 60 80 100 120
Time (min) Q0 (mg/g) b (L/mg) R2 Kf (L/g) 1/n
Langmuir 1.93 0.940 0.96
Fig. 7. Adsorption kinetics of Sb(III) by QFGO at 298 K, adsorbent dosage 1 g/50 mL, Freundlich 2.01 0.99 1.37 0.074
pH 7.0 ± 0.1.
450 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453

initial concentration, respectively. The column adsorption break-

2.0 through capacity was calculated by the methodology of Treybal
[45], which was expressed as:

1.5 breakthrough time  flow rate  feed concentration

breakthrough capacity ¼
mass of the adsorbent in bedðgÞ
ð5Þ
qe(mg/g)

1.0
In order to confirm the role of the QFGO on the removal Sb(III)
in the aqueous solution, the raw sand without coating material is
experiment data used as the blank control. Parameters for the blank column adsorp-
0.5 Langmuir isotherm model
tion test are as the follows, the bed depth was 20 cm; the concen-
Freundlich isotherm model
tration of the Sb(III) was 20 mg/L and the flow rate was 8 mL/min.
As is shown in Fig. 9(a), the bed breakthrough time is within
0.0
0 20 40 60 80 100 120 140 20 min, indicating pure sand used as adsorbent has inconspicuous
Ce᧤PJ/ ᧥ effect on the Sb(III) removal.

Fig. 8. Langmuir and Freundlich isotherms for adsorption Sb(III) on QFGO
(T = 298 K, adsorbent dosage 1 g/50 mL, pH 7.0 ± 0.1.).
is much less than 1, indicating a favorable adsorption process
under the experimental conditions [44].
3.6. Column Adsorption
The column breakthrough curves were obtained by plotting the
concentration ratio (Ce/C0) versus volume of effluent as shown in
Fig. 9, the Ce and C0 represent ion concentration at time t and the
3.6.1. Effect of bed depth
The breakthrough curves of Sb(III) adsorption obtained at differ-
ent bed depths with a Sb(III) concentration of 40 mg/L and a flow
rate of 8 mL/min are shown in Fig. 9(b). The bed depth of the col-
umn was packed to approximately 10 cm, 20 cm and 30 cm, corre-
sponding to 40 g, 80 g and 120 g of QFGO adsorbents, respectively.
According to Fig. 9(b), it was found that the time for breakthrough
was extended when the bed depth increased. Since both axial and
longitudinal directions of dispersion predominated the transfer of
Sb(III) in the column, when depth of the column bed increased,
the percentage of the column bed with adsorption of Sb(III)
increased at the breakthrough point comparing with the column

1.0
a 1.0
b
0.8
0.8

0.6
Ce/C

C e/C

sand 0.4 10 cm
0.6
20 cm
30 cm
0.2 Thomas model fit

0.4
0.0
0 10 20 30 40 50 60
0 10 20 30 40 50 60
Time (h)
Time (min)

1.0 1.0
c d
0.8 0.8

0.6 0.6
C e/C
C e /C

0.4 0.4
8 mL/min
12 mL/min
20 mg/L
16 mL/min
0.2 40 mg/L 0.2
Thomas model fit
60 mg/L
Thomas model fit
0.0 0.0
0 10 20 30 40 50 0 5 10 15 20 25 30 35
Time (h) Time (h)

Fig. 9. (a) Break through curve for raw sand (blank control), bed depth, 20 cm; Sb(III), 20 mg/L; flow rate 8 mL/min. (b) Break through curve for QFGO with different bed
depth. Sb(III), 40 mg/L; flow rate 8 mL/min. (c) Breakthrough curve for QFGO with different feed concentration, bed depth, 20 cm; flow rate 8 mL/min. (d) Break through curve
for QFGO with different hydraulic loading rate, bed depth, 20 cm; Sb(III), 40 mg/L.
 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453
with shorter depth of bed, therefore the more mass of the bed
played role in Sb (III) adsorption, the longer breakthrough time
resulted in, which leaded to an increase in the volume of solution
successfully treated [46].
3.6.2. Effect of initial concentration
Effect of the initial influent concentration was investigated using
synthetic solutions containing 20 mg/L, 40 mg/L and 60 mg/L of
Sb(III) respectively (Fig. 9(c)). As can be seen from Fig. 9(c), the
change in the initial metal ion concentration significantly affected
the breakthrough curve under the conditions of column bed depth
of 20 cm and a flow rate of 8 mL/min. The breakthrough time was
found to be 25 h, 40 h and 52 h for the Sb(III) synthetic solutions
at 60 mg/L, 40 mg/L and 20 mg/L, respectively (Fig. 9(c)). For certain
mass of column bed, a high Sb(III) concentration saturated the
absorbent bed more quickly than a lower concentration at the same
feeding rate.
Further, it was found that when the concentration increased
from 20 mg/L to 60 mg/L, the adsorption capacities increased from
3.60 mg/g to 5.04 mg/g. This is because the driving force for
adsorption was the concentration difference between the solute
in the absorbent and the solute in the solution. A high concentra-
tion difference provided a large driving force for the adsorption
process, thus, explaining why higher adsorption capacities were
achieved in the column fed with a higher Sb(III) concentration [47].
3.6.3. Effect of flow rate
Experiments were conducted at a bed height of 20 cm with a
constant feed concentration of 40 mg/L and a hydraulic loading
rate of 8.0 mL/min, 12.0 mL/min and 16.0 mL/min respectively.
Results are plotted in Fig. 9(d), and demonstrate that the break-
through time decreased from 35 h to 16 h as the flow rate
increased from 8.0 mL/min to 16.0 mL/min.
As shown in Fig. 9(d), the increase in the flow rate reduced the
contacting time of the Sb(III) with the bed, therefore, decreased the
bed treating efficiency prior to reaching the breakthrough point.
3.6.4. Mathematical modeling
Thomas model is adopted to describe the dynamic behavior of
column performance at continuous flow conditions in the study
[48]. It is given as:
 
C0 kTh q0 W
ln 1 ¼  kTh C 0 t
Ct Q
where kTh (mL/min/mg) is the Thomas model constant, qo (mg/g) is
Sb(III) adsorbed per g of the adsorbent at equilibrium, Co (mg/L) is
the inlet Sb(III) concentration, Ct (mg/L) is the outlet concentration
at time t, W (g) is the mass of adsorbent, and Q (mL/min) is the flow
rate. The plots of ln [Co/Ct)  1] versus time (t) resulted in a straight
line, where the slope is kTh and intercept is qo (figure not shown).
Parameters of the Thomas model were determined and presented
in Table 2.
Table 2
Thomas model parameters at different conditions.
C0 (mg/L) H (cm) Q (mL/min)
20 20 8 6.955
40 20 8 5.335
60 20 8 4.227
40 10 8 8.718
40 30 8 2.740
40 20 12
40 20 16
451
Data in Table 2 indicated that the adsorption capacity (q0) of the
Sb(III) is much higher for the column process than that for the
batch process (q0 = 2 mg/g). This is due to higher concentration
deferential between the solution phase and the absorbent phase
as the adsorbate passes through the column, while the concentra-
tion gradient decreases during a batch process. Furthermore, the
capacity of the QFGO in column processing in this study is more
than 2.88 mg/g, which is larger than many other adsorbent, such
as MWCNTs (0.33 mg/g) [49], bentonite (0.56 mg/g) [50], iron-
oxide coated sand (2 mg/g) [51].
The Thomas model is suitable for studying adsorption processes
where limitations on external and internal diffusion are absent.
Table 2 shows that the value of kTh decreased with the increase of
the bed depth, indicating that the mass transport resistance had
increased [52]. Also, as the flow rate increased, the values of q0
and kTh increased, suggesting the mass transport resistance
increased in this case. Regressions of the Thomas model with the
experimental data are shown in Fig. 9. Correlation coefficients
(R2) are all greater than 0.90 (Table 2), theoretical and experimental
q0 values are in accordance with each other. Therefore, the adsorp-
tion process could be well described with the Thomas model.
3.6.5. Column regeneration
The column with a bed depth of 20 cm and an initial concentra-
tion of 40 mg/L were selected for this study. The adsorption break-
through curve for this column is shown in Fig. 9(b). It was observed
that breakthrough occurred for this column was approximately
35 h.
Desorption experiments were carried out using a 0.1 mol/L
EDTA solution flowing at a rate of 10 mL/min through the bed in
an upward direction. The concentration of Sb(III) was monitored
at different time intervals as shown in Fig. 10(a). There is a sharp
Sb(III) concentration peak in eluent soon after the bed regeneration
process started. The maximum concentration of Sb(III) eluting
from the column bed was recorded as about 415 mg/L, which is
10 times higher than the influent Sb(III) concentration. When the
eluent volume were 900 mL, desorption of the Sb(III) was negligi-
ble. Thus desorption cycle time was determined as 900 mL/
10 mL/min = 1.5 h. Further, the sharp patent of the Sb(III) concen-
tration in eluting solution could help in handling Sb(III) by recov-
ery the first 1.5 h eluent for recovery of Sb(III).
After eluting with EDTA, the column was washed with double
distilled water in an upward direction. The second adsorption–
ð6Þ desorption cycles of Sb(III) were carried out to test the reusability
in situ, and the parameters were kept the same as in the first cycle.
The second cycle adsorption efficiency was also high, as it took
about 30 h operating until breakthrough. This result indicates that
the adsorbent material could be used in multiple cycles without
significantly affecting the adsorption capacity.
Fig. 10(b) is the SEM of the regenerated adsorbent surface. Com-
pared with Fig. 2(f), it can be seen that the adsorbent surface is
nearly unchanged, which indicated the regeneration process did
not destroy QFGO’s surface structure.
kTh  103 (L/(mg h)) q0,exp (mg/g) q0,cal (mg/g) R2
3.60 3.60 0.96
4.32 4.10 0.95
5.04 5.01 0.95
6.09 6.03 0.98
2.88 2.83 0.90
8.305 4.50 4.43 0.96
8.632 4.75 4.52 0.97
452 X. Yang et al. / Chemical Engineering Journal 260 (2015) 444–453

400 a b
350

300
Sb(ൗPJO
250
200 Desorbing agent : 0.1mol/l EDTA
Bed depth = 20 cm
ID of column = 2 cm
150
Flow rate = 10 ml/min
100
50
0
0 200 400 600 800 1000 1200
Eluent volume, ml
Fig. 10. (a) Column regeneration with 0.1 M EDTA for desorption of Sb(III). (b) The SEM of QFGO after regeneration with EDTA.
4. Conclusions
The composite of QFGO was prepared and applied in batch and
column systems for adsorption removal of Sb(III). It was found that
Sb(III) as well as its co-absorbates, As(III) and Hg(II), can be effec-
tively adsorptive removed with the QFGO, and the adsorption of
Sb(III) on the QFGO followed the pseudo-first-order Kinetic and
the Freundlich adsorption isotherm in batch study and Thomas
models in column studies as well. The Sb(III) adsorption capacity
of QFGO in column processing is much greater than that of many
other absorbents, such as MWCNTs, bentonite, iron-oxide coated
sand. The adsorptive exhausted column can be restored with EDTA.
These facts established in the study might support the conclusion
that the QFGO based adsorption process could be promise for
remediation of Sb(III) as well as other metals contaminated waters.
Acknowledgment
This work was supported by the National Science & Technology
Pillar Program of China the Twelfth Five-year Plan under contract
No. 2012BAJ24B03.
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