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Multi-walled carbon nanotubes (MWCNTs) are used for the adsorption and removal of Sb(III) from model solutions
and real environmental samples. The effects of different factors that affect the adsorption process; the results showed
that most of the Sb(III) ions were removed from the solution within 30 min, at pH 7.0, using 200 mg MWCNTs. Further,
it was observed that the adsorption process was greatly enhanced by lowering the solution temperature, which
indicated the exothermic nature of the adsorption. The adsorption study was analyzed kinetically, using different
kinetic models, and the results showed that the adsorption of Sb(III) by MWCNTs from the model solution followed
pseudo-second-order kinetics with good correlation coefcients. In addition, it was found that the adsorption of
Sb(III) occurred in more than one step, including the liquid lm diffusion of the Sb(III) ions from the aqueous phase
through the liquid lm around the MWCNTs and further intra-particle diffusion through the nanotubes bundles and
aggregates.
2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction form (Gurnani et al., 1994; Gebel, 1997; Oorts et al., 2008;
Smichowski et al., 1998a, 1998b). Due to antimonys toxicity,
One of the worlds major environmental problems is the the European Union (EU) and the US Environmental Protec-
disposal of large volumes of wastewater containing heavy tion Agency (USEPA) consider antimony and its compounds
metals. Most heavy metals are known to be toxic, and they as pollutants that should be removed and regulated (Filella
represent a severe threat to living organisms in general et al., 2002). Traditionally, antimony-containing wastewater
and humans in particular. Consequently, their presence in is treated with different methods, such as reverse osmosis
wastewater requires treatment and control before the waste- (Kang et al., 2000), solvent extraction (Mok and Wai, 1990),
water can be disposed. Among other toxic metals, antimony membrane ltration (Saito et al., 2004), reduction and pre-
(Sb) is one of the least studied. Antimony is present in cipitation (Gannon and Wilson, 1986), biosorption (Tomko
the environment as a result of natural processes and vari- et al., 2006; Perez-Corona et al., 1997), sorption in a xed-
ous industries (Filella et al., 2002), such as semiconductors, bed column (Bakir et al., 2009), ion exchange (Guin et al.,
infrared detectors, diodes, bearing metal, pipe, rubber com- 1998), and other processes. Generally, adsorption technology
pounds, ceramic enamels, reproof textiles, cable sheathing, has proved to be one of the most effective techniques for
lead alloys, battery grids, plumbers solder, pewter, ammu- the separation and removal of heavy metals from polluted
nition, sheet, paints, lacquers, and certain types of matches water (Bhattacharyya and Sen Gupta, 2008; Chang et al., 2007;
(Khalid et al., 2000). Antimony is a potentially toxic element Demirbas et al., 2009; Sheng et al., 2009; Srivastava et al.,
with an unknown biological function. The toxicological effects 2007). Adsorption has many advantages over other treatment
of antimony mainly depend on its oxidation state; the Sb(III) methods, such as simplicity, fastness, and a lack of harmful
form, for example, is ten times more toxic than the Sb(V) byproducts; moreover, both the adsorbent and the pollutants
can be regenerated. Discussions of applying the adsorption
technique for the removal of antimony from water are scarce
Corresponding author. Tel.: +966 541886660; fax: +966 2 6952292.
E-mail address: masalam16@hotmail.com (M.A. Salam).
Received 28 September 2012; Received in revised form 20 January 2013; Accepted 11 February 2013
0263-8762/$ see front matter 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2013.02.007
chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360 1353
in the literature (Deorkar and Tavlarides, 1997; Kathrinleuz dispersing of a certain amount of the CNTs in different aque-
et al., 2006; Hasany and Chaudhary, 1996; Imai et al., 1980; ous solutions of NaOH, NaHCO3 or Na2 CO3 , left for a period
Xi et al., 2011; Wu et al., 2012; Leng et al., 2012; Wang et al., of time, centrifuge, lter and certain amount of HCl solution
2012; Xu et al., 2011). One of the challenges faced by adsorp- was added to the supernatant to neutralize the unreacted
tion technologies is the discovery of a new class of adsorbents base, and the solutions were back-titrated with NaOH using
that could remove toxic heavy metals, such as antimony, from a potentiometer to determine the endpoint. Infrared spec-
aqueous solutions. Carbon nanotubes (CNTs) are a relatively tra measurement of the pristine MWCNTs was performed on
new adsorbent that have been shown to possess great poten- PerkinElmer-Universal ATR sampling accuracy Spectrum 100
tial for removing many types of pollutants. CNTs have been FT-IR Spectrometer. Zeta potential of the MWCNTs was mea-
successfully and efciently used for the removal of several sured by a Malvern zetameter (Zetasizer 2000). The pH values
types of pollutants, including organic compounds (Li, 2012; of MWCNTs solution were adjusted from 2.0 to 10.0 by adding
Abdel Salam et al., 2010; Abdel Salam and Burk, 2008a, 2009; 0.1 M hydrochloric acid or sodium hydroxide solution to the
Abdel Salam and Burk, 2008b) and inorganic pollutants (Liang glass beaker at 25 C.
et al., 2005, 2004; Staej and Pyrzynska, 2007; Rao et al., 2007;
Tuzen et al., 2008; Kosa, 2012), from various aqueous envi- 2.3. Adsorption experiment
ronments. The remediation ability of CNTs, relative to other
adsorbents, is due to its strong interactions with the pollut- Adsorption experiments were performed to determine the
ants. These interactions result from the delocalized electrons effect of time and temperature on the adsorption process and
in the hexagonal arrays of carbon atoms on the surfaces of the to identify the adsorption rate. The experimental procedures
CNTs. were performed as follows: (1) a series of solutions of vari-
Although there are many research studies focused on ous Sb(III) concentrations were prepared; (2) the initial pH was
the adsorption and removal of Sb(III) from aqueous solu- measured, and a dened amount of the MWCNTs was then
tions by different adsorbents (Deorkar and Tavlarides, 1997; added to the solutions; (3) these solutions were agitated on
Kathrinleuz et al., 2006; Hasany and Chaudhary, 1996; Imai a magnetic stirrer for a certain period of time, at room tem-
et al., 1980; Xi et al., 2011; Wu et al., 2012; Leng et al., 2012; perature; (4) at dened points in time, a certain volume of
Wang et al., 2012; Xu et al., 2011), up to the best of authors the solution was removed and immediately ltered to collect
knowledge, there is no such study applied carbon nanotubes the supernatant; and (5) the residual Sb(III) concentration in
as a promising and potential adsorbent. This manuscript rep- the supernatant was determined using inductively coupled
resents the rst attempt to study the adsorption of Sb(III) from plasma-optical emission spectrometry (ICP-OES Optima 4100
a model solution and from real environmental samples by DV), Perkin Elmer, USA. The amount of Sb(III) adsorbed was
MWCNTs. The effects of various operating conditions such as determined by measuring the difference in the concentra-
adsorption time, the mass of the carbon nanotubes, solution tions of the samples that were obtained at two consecutive
pH, and temperature have been studied and optimized. In time intervals over the course of the adsorption experiment.
addition, the adsorption of Sb(III) from an aqueous solution by The adsorption capacity of the MWCNTs qt (mol g1 ), which
MWCNTs at different temperatures have been studied kinet- represents the amount of Sb(III) adsorbed per amount of
ically to understand the factors and transport mechanisms MWCNTs was calculated using a massbalance relation-
that affect Sb(III) interactions with MWCNTs. ship:
ln qt = ln a + b ln t, (2)
Temperature A b ab R2
Ea
ln k2 = ln A (8)
RT
Fig. 8 Intra-particle diffusion plots of Sb(III) on MWCNTs
at different temperatures (experimental conditions: 20 ml
solution, pH 7.0, 120 min, 200 mg MWCNTs, and Sb(III) where Ea is the Arrhenius activation energy of adsorption, rep-
concentration 4 mg L1 ). resenting the minimum energy that reactants require for the
reaction to proceed, A is the Arrhenius factor, R is the gas
diffusion model (Weber and Morris, 1963) could be expressed constant and is equal to 8.314 J mol1 K1 , and T is the solu-
by the following equation: tion temperature. A linear plot was obtained between ln k2
versus 1/T for MWCNTs adsorption of the Sb(III) ions and the
qt = kid t1/2 + C, (6) adsorption activation energy was calculated from the slope.
The adsorption activation energy obtained was 15.6 kJ mol1
where qt is the adsorption capacity at any time (t), kid is for Sb(III) adsorbed by the MWCNTs from an aqueous solution,
the intra-particle diffusion rate constant (mg/g min1/2 ), and indicating that the adsorption is physical in nature, since the
C (mg/g) is a constant proportion to the thickness of the physical adsorption was characterized by activation energy in
boundary layer. When the intra-particle diffusion model was a range between 5 and 40 kJ mol1 .
applied to the Sb(III) adsorption data at different tempera-
tures, no straight lines passed through the origin, as presented
in Fig. 8. This may indicate that the intra-particle diffusion 3.3. Environmental applications
model is not the rate-determining step. Only the last part of
the adsorption process converged well with the intra-particle It is very important to use real water samples in order to
diffusion model, providing satisfactory correlation coefcient investigate the applicability of a certain type of adsorbents
values (>0.95), which indicated that the last step of the Sb(III) to remove specic pollutants from polluted water. Three real
adsorption by MWCNTs from an aqueous solution was the water samples were collected; Red Sea water (RSW), wastewa-
inter-particle diffusion step but was not the slowest step (i.e., ter collected from the King Abdulaziz University Wastewater
the rate-determining step). (KAUWW) Treatment Plant, and tap water (TW). The concen-
Liquid lm diffusion, another kinetic model, assumes that tration of Sb(III) was measured for the three samples, and
the ow of the adsorbate molecules through a liquid lm the Sb(III) concentrations were found to be lower than the
surrounding the solid adsorbent is the slowest step in the detection limit of the ICP-OES. The three samples were then
adsorption process (i.e., the one that determines the kinetics spiked with 4.0 mg L1 , and 200 mg MWCNTs were added to
of the rate processes). The liquid lm diffusion model is (Boyd the solution after adjusting the pH to 7.0 and keeping the
et al., 1947) given by the following equation: solution temperature at 298 K; the samples were then shaken
for 120 min. The percentages of Sb(III) removed from the real
ln (1 F) = kfd t, (7) samples were found to be 81.2% (model solution), 76.3% (TW),
20.8% (RSW), and 48.3% (KAUWW) when the samples were
where F is the fractional attainment of equilibrium (F = qt /qe ), spiked with 4.0 mg L1 Sb(III), as noted in Fig. 9. The low per-
and kfd (min1 ) is the lm diffusion rate coefcient. A linear centage of Sb(III) removed from the RSW sample could be
plot of ln(1 F) versus t, with a zero intercept, suggests that attributed to the presence of very high concentrations of Na+ ,
the kinetics of the adsorption process are controlled by dif- K+ , Mg2+ , and Ca2+ , which outcompeted with Sb(III) for the
fusion through the liquid lm around the MWCNTs. As it is adsorption on MWCNTs and caused a screening effect (Kosa,
clear from Table 1, the applications of the liquid lm diffusion 2012). The reduction in the percentage of Sb(III) adsorbed from
model to the adsorption of Sb(III) by MWCNTs from an aque- the KAUWW sample might have been due to the presence
ous solution at different temperatures did not converge and of various pollutants that competed with Sb(III) for the same
did not provide straight lines that passed through the origin binding sites available on the MWCNTs surfaces and conse-
with very low correlation coefcients; this indicated that the quently affected the adsorption process. The percentage of
diffusion of the Sb(III) ions through the liquid lm around the Sb(III) removed from the TW sample was similar to the per-
MWCNTs was not the rate-determining step. centage removed from the model solution, since tap water
The adsorption mechanism of Sb(III) ions on MWCNTs generally contains very low concentrations of inorganic ions
could be attributed mainly to the electrostatic attraction and organic pollutants.
chemical engineering research and design 9 1 ( 2 0 1 3 ) 13521360 1359
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