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Carbohydrate Polymers 140 (2016) 299307

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Chemical ltration of Cr (VI) with electrospun chitosan


nanober membranes
Lei Li a,b,c , Yanxiang Li a,b , Chuanfang Yang a,b,
a
b
c

National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
University of Chinese Academy of Sciences, Beijing 100049, China

a r t i c l e

i n f o

Article history:
Received 22 September 2015
Received in revised form
27 November 2015
Accepted 24 December 2015
Available online 29 December 2015
Keywords:
Electrospun chitosan nanober membrane
Chemical ltration
Chromium (VI) adsorption
Breakthrough curves
Model tting

a b s t r a c t
Chitosan nanobers (average diameter of 75 nm) were electrospun on polyester (PET) scrim to form
composite nanober membranes with controlled pore size. The membranes were then stacked as a membrane bed for chemical ltration of Cr (VI) of 15 mg/L. The performance of the bed with respect to loading
capacity at breakthrough, bed saturation and utilization efciency were carefully investigated. The results
showed that while these three parameters were dependent on pH, ow rate, ow distribution and packed
pattern of the membrane, the latter two were less affected by feed Cr (VI) concentration and bed length.
The maximum bed loading capacity for 1 mg/L Cr (VI) ltration at breakthrough was found to be 16.5 mgchromium/g-chitosan, higher than the static adsorption capacity of 11.0 mg-chromium/g-chitosan using
nanober mats, indicating the membranes better potential for dynamic adsorption. The minimum bed
length required to avoid breakthrough was determined to be three layers of stacked membranes with
nanober deposition density of 1 g/m2 by applying bed depth service time (BDST) model.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Electrospinning is a simple and versatile method for preparing
nanobers in the form of either a loose web, or a dense membrane, depending on the bers deposition density (Ahmed, Lalia,
& Hashaikeh, 2015; Bhardwaj & Kundu, 2010; Doshi & Reneker,
1995; Reneker & Yarin, 2008; Rutledge & Fridrikh, 2007; Teo &
Ramakrishna, 2006). Electrospun nanobrous membranes exhibit
extraordinary properties, such as small ber diameter, large surface area and high porosity, as well as easy pore size tailorability.
These properties make such membranes more attractive than common nonwovens or even casted membranes for a wide variety of
mechanical ltration and chemical ltrationa ltration process
involving interface reaction between the porous material surface
and the target solute (Aliabadi, Irani, Ismaeili, Piri, & Parnian, 2013;
Deng et al., 2011; Li, Li, Cao, & Yang, 2015; Ma, Hsiao, & Chu,
2013; Niu et al., 2013). Adsorptive ltration is one of the examples. Adsorptive electrospun nanober membranes have drawn

Corresponding author at: National Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190,
China.
E-mail addresses: lileilyq@outlook.com (L. Li), yxli@ipe.ac.cn (Y. Li),
cfyang@ipe.ac.cn (C. Yang).
http://dx.doi.org/10.1016/j.carbpol.2015.12.067
0144-8617/ 2015 Elsevier Ltd. All rights reserved.

considerable interest in adsorption applications (Aliabadi et al.,


2013; Hardick, Dods, Stevens, & Bracewell, 2013; Li, Li, et al., 2015;
Yoon, Hsiao, & Chu, 2008) because they offer high ow rate and
fast mass transfer advantages of microporous membranes for ltration. Another advantage of using the randomly deposited ber
membrane is the creation of impeded ow that results in reduced
channeling (Suen & Etzel, 1992).
However, in many of the studies, electrospun nanobrous membranes were simply used for static adsorption. In these cases,
electrospinning processes were allowed to last for relatively long
time till the randomly deposited bers formed a mat. Such multilayered nanobers normally overlap tightly and form very small
internal pores, which unavoidably sacrices some intended surface
area and causes slow liquid inltration that work against effective adsorption, leading to disappointing adsorption capacity. This
problem, as also observed in our past work using electrospuntailored chitosan nanobers (Li, Li, et al., 2015), could be addressed
in three ways. The rst one is to use a faster yield spinning technique such as the recently reported force spinning (Sarkar et al.,
2010; Yang, 2012), which allows for large quantities of nanober
production in short times to form a uffy and porous spun cotton candy structure. However, this kind of structure is believed
to provide only the benets of more effective static adsorption
because of easier accessibility of most of the small bers by the
solute to be captured. In addition, the structure also depends on

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L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

the nature of the polymers to be spun. For chitosan, a hydrophilic


polymer with abundant functional groups that tend to enforce a
dense 2D nanobrous structure by itself, force spinning may not
generate the open 3D structure highly desired. The second way is
to produce thinner and loosely packed chitosan nanober mats by
electrospinning, which will adversely lead to high cost and low
productivity of nanober production. The third way is to fabricate a dense, non-self-supportive nanober membrane on a strong
substrate with tunable pore size and porosity, and use the membrane by allowing water to ow through it for chemical ltration
of the heavy metals targeted. In its essence, the membrane now
acts as an afnity membrane, and by pressure-driven ow, most
of the adsorption sites can be accessed by the solute to enhance
adsorption.
Afnity membranes have rapid mass transfer rate because of
the small pore size and the non-existence of internal pores such
as adsorption resins typically used for a xed bed column. There
are only a few studies illustrating the use of electrospun nanobrous membranes in dynamic ltration processes to remove heavy
metals. Horzum prepared electrospun chitosan nanober mats
and lled them into a micro-column to test the ltration performance for Fe (III), Cu (II), Ag (I) and Cd (II) ions (Horzum, Boyaci,
Eroglu, Shahwan, & Demir, 2010). The result showed that the
afnity of the nanobers toward Fe (III) and Ag (I) was different from that observed in static sorption, while similar behavior
was found for Cu (II) and Cd (II). Desai fabricated electrospun
chitosan/PEO nanobers on spunbond polypropylene for Cr (VI)
adsorption (Desai et al., 2009). He found that the dynamic metal
binding capacity for ten consecutive ow passes using as little as
0.5 gsm (gram per square meter) of un-cross-linked nanobers was
up to 35 mg-chromium/g-chitosan. However, the capacity achieved
was mainly due to recirculation of the solution through the medium
that made the mass transfer approximated to that in static adsorption.
Single-pass ow dynamic adsorption of heavy metals is
preferred because it offers sustainable process control, high
throughput and exibility for both small and large-scale applications. Cr (VI) is a toxic metal that must be removed from water as per
regulation, and the effectiveness of electrospun chitosan nanobers
for its removal has been conrmed earlier (Li, Li, et al., 2015). The
objective of this work is to study the chemical ltration behavior
of chitosan nanober membranes with respect to their interaction
with Cr (VI), similar goal was discussed in Mahadevaiahs work for a
xed bed column (Mahadevaiah, Venkataramani, & Prakash, 2008).
To this end, rst, chitosan nanober membranes with different
nanober deposition density on spunbond PET scrim were fabricated by electrospinning. The as-prepared membranes were then
cross-linked with glutaraldehyde to minimize their solubility and
swelling in acidic water. Second, a single-pass ow was applied to
challenge the membranes stacked in layers as a membrane bed for
dynamic adsorption of Cr (VI) in small concentrations. The effect of
feed concentration, membrane thickness, pH, ow rate, and membrane packing pattern on the adsorption was investigated in detail.
The performance criteria of the nanober membranes including
loading capacity, bed saturation and bed capacity utilization efciency were also determined.

of 25.5 g/m2 was obtained from Fiberweb, Inc. All other chemicals
were analytical grade and used without purication.
2.2. Electrospinning and cross-linking process
An electrospinning solution containing 5 wt% chitosan was prepared by dissolving chitosan in 90 wt% acetic acid solution (Li, Li,
et al., 2015). The apparatus used for electrospinning was purchased
from Ucalery Co., China. The solution was ejected from the syringes
using a feed rate of 0.1 mm/min, an applied voltage of 23 kV, and
a tip-to-collector distance of 6.8 cm. The bers 75 nm in diameter were collected on the spunbond PET substrate continuously.
Composite membranes with different nanober basis weight were
obtained by controlling the electrospinning time. After electrospinning, the composite membranes were placed in a vacuum oven
at 60 C for 24 h to remove the remaining solvent. They were then
transferred to a desiccator containing 20 mL glutaraldehyde liquid
for cross-linking by glutaraldehyde vapor at room temperature for
12 h. The cross-linked nanober membranes were dried in a vacuum oven at 60 C for 12 h to remove the remaining cross-linker.
2.3. Dynamic adsorption experiments
The set-up for ltration experiments is shown in Fig. S1 in Supplementary Material le. It is composed of a peristaltic pump, a
pressure gauge and a cylindrical membrane holder. The effective
diameter of the holder is 34.7 mm. Membrane discs 47 mm in diameter were layered together to form a stacked membrane bed as
shown in Fig. 1. The bed was then placed in the holder and sealed.
Water containing Cr (VI) was pumped through the membrane just
once for continuous adsorption. The feed concentration of Cr (VI)
was controlled at 15 mg/L. pH of the solutions was adjusted using
diluted H2 SO4 and NaOH. Flow rate was 13 ml/min. Efuent samples were collected at different times for Cr (VI) concentration
measurement.
The amount of Cr (VI) adsorbed on the membrane was
determined by comparing the difference of feed and efuent concentrations of Cr (VI). The ratio of the efuent concentration and
feed concentration was plotted against time to obtain the breakthrough curves. The adsorption capacity of the membrane was
determined using the following equation:

t
q=

2.1. Materials and chemicals


Chitosan powders (Mw = 300 kDa, degree of de-acetylation
(DDA) 90%, 80 meshes) were purchased from Golden-Shell Pharmaceutical Co., Ltd., China. Acetic acid was purchased from Beijing
Chemical Works, China. The spunbond PET scrim with basis weight

(C0 Ct )Qdt

(1)

where q is the amount of adsorbed Cr (VI) onto unit mass of the


nanobers (mg/g); C0 and Ct (mg/L) are the feed concentration and
the efuent concentration at time t, respectively; Q is the ow rate
(ml/min) and m the amount of adsorbent (g) used.
In this work, breakthrough and saturation points of the membrane bed are dened as the time elapsed for the efuent
concentration to reach 10% and 80% of the feed concentration. The
bed utilization efciency , which represents the percentage of saturation bed capacity used, is dened by the following equation:
=

2. Experimental

qtb
=
qts

 tb
0ts
0

(C0 Ct )Qdt
(C0 Ct )Qdt

100%

(2)

where qtb and qts are the amounts of adsorbed Cr (VI) onto unit mass
of the membrane at breakthrough time and saturation time (mg/g).
For an ideal membrane bed, the bed utilization efciency should be
close to 100%, and the breakthrough curve is typically a step function. The non-ideal situation always gives a breakthrough curve
with a prole of changing slope, which is commonly encountered
in practice. Nonetheless, higher bed efciency is always desired

L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

to fully take advantage of the membranes saturation capacity for


dynamic adsorption (Li, Wang, Cao, Zhang, & Yang, 2015).
Two mathematical models developed to describe the dynamic
adsorption behavior of a column bed were chosen to predict similar behavior of the nanober membrane bed. They are
AdamsBohart (Bohart & Adams, 1920) and doseresponse models (Senthilkumar, Vijayaraghavan, Thilakavathi, Iyer, & Velan,
2006; Yan, Viraraghavan, & Chen, 2001), as expressed in Eqs. (3)
and (4):
AdamsBohart model :

C
= exp[kAB C0 t (kAB N0 Z/v)]
C0

(3)

Doseresponse model :

C
=1
C0

(4)

1+

C0 V
q0 m

a

where C is the efuent solute concentration (mg/L), C0 the


inuent solute concentration (mg/L), kAB the AdamsBohart constant (L/mg min), N0 the maximum volumetric adsorption capacity
of bed (mg/L), Z the bed length, v the linear ow rate (cm/min),
q0 the maximum adsorption capacity (mg/g), V the efuent volume, m the weight of the adsorbent (g), and a the doseresponse
constant.
2.4. General characterization
The surface and cross-section morphology of the composite
membranes was characterized by eld emission scanning electron
microscope (JSM-6700F) at an accelerating voltage of 10 kV. The
cross-sectioned samples were prepared by cutting the membranes
frozen in liquid nitrogen for 5 min. The ber diameter was measured by image processing software Image-Pro Plus from the SEM
images of the nanobers produced.
The pore size and its distribution of the membranes were
characterized with a porometer through-pore size analyzer
(Porometer3Gzh, Quantachrome Instruments, USA), where a wetting uid PorolTM with surface tension of 16 dynes/cm was used.
Cr (VI) concentration was measured by UVvisible spectrophotometric method (APHA, AWWA & WEF, 2005). Cr (VI) reacted
with diphenylcarbazide and the solution appeared in purple color.
The maximum absorbance for the Cr (VI) complex occurred at
wavelength of 540 nm.

301

3. Results and discussion


3.1. Preparation of chitosan nanober membranes
By controlling the electrospinning time, chitosan membranes
with different ber deposition density were prepared. The reason
that chitosan was chosen for electrospinning and adsorption of Cr
(VI) had been discussed in our earlier work, where the reaction
between chitosan and Cr (VI) was detailed in terms of adsorption kinetics, isotherms and mechanisms (Li, Li, et al., 2015). Fig. 2
shows the morphology of the composite membranes with different
nanober basis weight. The diameter of the PET bers and chitosan
nanobers is 20 4 m and 75 5 nm, respectively. When more
time was allowed for electrospinning, more chitosan nanobers
were deposited on the substrate, which resulted in smaller pore
size of the composite membranes. As the basis weight of chitosan
nanober was increased from 0 to 2 g/m2 , the average pore size of
the composite decreased from 114 m to 0.56 m. In addition, as
the pore size was reduced, the pore size distribution tted much
better with Gauss distribution, indicating more uniform nanober
membranes.
The cross-section image of a single layer composite membrane with 1.0 g/m2 of chitosan nanobers is shown in Fig. 1
previously. Some nanobers settle into the void space of the substrate having trilobal ber cross-section. Such mechanical interlock
helps to prevent nanober delamination from the substrate. Overall, the bonding between the chitosan nanobers and the PET
scrim is strong enough for applying the composite in ltration
experiments.
3.2. Metal adsorption
For dynamic adsorption using membranes, a low pressure drop
is expected. In our experiments, the pressure drop was lower than
5 kPa. It is also worth noting that PET has no afnity for Cr (VI)
(Fig. S2). pH typically affects the adsorption process. In our case, pH
greatly affects the ionic species of Cr (VI); it also affects the protonation of amino groups of chitosan bers (Chitosan has a pKa near 6.5,
therefore, some of the amino groups on chitosan become protonated in even slightly acidic solutions). The synergistic effect of the
two aspects resulted in increased adsorption based on electrostatic
interaction, and hence longer breakthrough times in accordance
with decreasing pH (as shown in Fig. S3).

Fig. 1. Illustration of the stacked membranes and the individual part structure of the composite membrane.

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L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

Fig. 2. SEM images and corresponding pore size of the composite membranes with different basis weight of chitosan nanobers (a, substrate; b, 0.18 g/m2 ; c, 0.5 g/m2 ; d,
1.0 g/m2 ; e, 1.5 g/m2 ; f, 2.0 g/m2 ).

In the following, experimental data obtained at different feed


Cr (VI) concentration, ow rate and bed length were tted to the
two models aforementioned. The tting results are discussed in
different sections separately. However, all the tting parameters
and the values of correlation coefcient R2 according to nonlinear
regressive analysis are summarized in Table S1 for quick review.
It is also noteworthy to mention that the AdamsBohart model,
which assumes that the sorption rate is proportional to the residual
capacity of the solid and concentration of the adsorbed substance,
is only used to describe the initial part of the breakthrough curve
(C/C0 < 0.15), and both models assume fast mass transfer.

3.2.1. Effect of feed Cr (VI) concentration


Generally, the change in feed or initial concentration affects
the shape and position of breakthrough curves (Sridhar, 1996). As
shown in Fig. 3a (solid lines are prediction using doseresponse
model, the initial part of the curves are better predicted by
AdamsBohart model shown in the inset), with decreasing
feed concentration, breakthrough point is more slowly reached,
resulting in a broadened mass transfer zonethe region where
concentration is changing and thus mass transfer is occurring
(Sridhar, 1996). At the same ow rate of 2 ml/min, more Cr (VI)
passed through the beds at the same time length when feed Cr (VI)
concentration was higher. However, when re-plotting the breakthrough curves by using the absolute amount of Cr (VI) fed to
the bed as the abscissa, the three curves nearly coincided with
each other (Fig. 3b). This indicates the composite membranes
dynamic adsorption capacity is largely independent on Cr (VI)
feed concentration, higher feed concentration simply shortens the
breakthrough time. The loading capacity of the membrane bed at
10% breakthrough in terms of Cr (VI) adsorbed per bed volume
was calculated to be about 0.80.9 mg/ml for feed concentrations of
15 mg/L. Since the substrate of the composite membrane does not
absorb, and it is also important to know how the dynamic adsorption capacity compares with that of static adsorption, calculation

of the loading capacity of chitosan nanobers only in the bed is


therefore necessary. Fig. 3c shows the results. The loading at 10%
breakthrough ranges from 10.4 to 12.3 mg/g for feed concentrations
from 1 to 5 mg/L; that at 80% breakthrough or saturation ranges
from 39.5 to 47.5 mg/g. The loading at higher breakthrough does
increase more obviously as the feed concentration increases, but
it is noted that the bed utilization efciency is feed concentration
independent (Fig. 3d). Within the experimental conditions, the efciency is around 26%, far away from the high two digits efciency
desired. It is believed this is both adsorption chemistry, and probably more bed defects related because of the thick substrate used,
which could be improved with engineering optimization.
After applying the models to t our experimental data, we found
both AdamsBohart model (inset of Fig. 3a) and doseresponse
model (solid lines of Fig. 3a) gave reasonable results. The values
of R2 from the two models are higher than 0.97 (Table S1). For
AdamsBohart model, when feed Cr (VI) concentration is increased,
kAB decreases while N0 increases. These results agree with other
studies using different adsorption systems (Ahmad & Hameed,
2010; Calero, Hernainz, Blazquez, Tenorio, & Martin-Lara, 2009; Li,
Li, Cao, & Yang, 2016). The maximum adsorption capacity q0 calculated with doseresponse model increases with increasing feed Cr
(VI) concentration.

3.2.2. Comparison with static adsorption


Static adsorption was carried out using cross-linked chitosan
nanober mats with basis weight of 48 g/m2 . These mats were
made by electrospinning the same way but without PET substrate,
as reported previously (Li, Li, et al., 2015). These mats have been
proven to be better adsorbents than chitosan powders, but are still
short in the supposed large adsorption capacity because of the tight
2D structure.
The nanober mats dosage for static adsorption is different for
the three initial Cr (VI) concentrations in order to better compare
the static adsorption capacity with dynamic adsorption capacity

L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

303

Fig. 3. Effect of feed concentration on dynamic adsorption [(a) breakthrough as a function of time at different feed concentration, solid lines are prediction using doseresponse
model, inset shows the experimental data and prediction lines using AdamsBohart model for initial breakthrough where C/C0 < 0.15, (b) breakthrough as a function of mass
of Cr (VI) fed to the bed, (c) adsorption capacity as a function of Cr (VI) feed concentration and (d) bed utilization as a function of feed concentration. Experiment conditions:
pH = 6, 15 layers of 1 g/m2 chitosan nanober membrane, ow rate = 2 ml/min].

Fig. 4. Static adsorption kinetics using cross-linked chitosan nanober mats [experimental conditions: pH = 6, nanober dosage is 11, 21 and 44 mg/L for 1, 2 and 5 mg/L
Cr (VI) respectively].

at each concentration. The dosage was determined using the ratio


of the total amount of chitosan nanobers in the 15 layer membrane bed (14.2 mg) and the efuent volume at 80% breakthrough,
which is 1290, 690 and 320 mL respectively. Fig. 4 and Table S2
show the results, where the method of curve tting and kinetic
parameter determination can be found elsewhere (Ho & McKay,
2000). Static adsorption of Cr (VI) using these nanober mats tted
Pseudo-second order kinetics and Freundlich adsorption isotherm
as reported earlier (Li, Li, et al., 2015). The saturation adsorption capacity obtained for 1, 2, and 5 mg/L Cr (VI) is 12.3, 18.1
and 35.7 mg-chromium/g-chitosan, respectively. In contrast, the
dynamic adsorption capacity at 80% bed saturation shown in Fig. 3c

is 39.5, 42.5 and 47.5 mg-chromium/g-chitosan corresponding to


each concentration; that at 10% bed breakthrough is 10.4, 11.6
and 12.3 mg-chromium/g-chitosan. This indicates that dynamic
adsorption is more advantageous than static adsorption for small
Cr (VI) concentration, which is exactly the reason for applying
adsorptive membranes. Liquid ow through the membranes allows
the solute to be in close contact with the sorption sites for more
and quicker adsorption. To guarantee a fair comparison with the
dynamic adsorption capacity, static adsorption experiments using
the same amount of chitosan nanober mats as used in the membrane bed (14.2 mg) were put into contact with 1, 2, and 5 mg/L Cr
(VI) solutions and the sorbent dosage was maintained the same as
11, 21 and 44 mg/L. The saturation adsorption capacity was found
to be 11.0, 18.0 and 32.3 mg-chromium/g-chitosan respectively,
not much different from what is shown in the second column of
Table S2.
Another comparison may provide more insight when the total
amount of Cr (VI) available for both static and dynamic adsorption is xed for each concentration studied. Take 1 mg/L Cr (VI),
for example, in static adsorption, the total amount of Cr (VI) in
the solution was 0.2 mg. After 8 h of adsorption as shown in Fig. 4,
0.17 mg Cr (VI) was captured, the removal efciency was 85%. From
Fig. 3b we can see that when 0.2 mg (200 g) Cr (VI) was fed to
the bed, C/C0 = 0.33, corresponding to an elapsed time of 100 min
of operation at 2 ml/min ow. The total amount of Cr (VI) captured by the bed at this point was 0.19 mg. The dynamic removal
efciency of Cr (VI) now was 95%, and the bed capacity was 13.2 mgchromium/g-chitosan compared to 12.3 mg-chromium/g-chitosan
in the static adsorption. Table S3 summarizes all the data for more
straightforward comparison. The general trend is that, as the initial
Cr (VI) is increased, both dynamic and static adsorption efciencies decrease since the adsorption sites are over numbered by the

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L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

Fig. 5. Effect of ow rate on dynamic adsorption and the predicted breakthrough curves using doseresponse model [experiment conditions: pH = 6, C0 = 1 mg/L, 10 layers
of 1 g/m2 chitosan nanober membrane].

metal ions. However, dynamic adsorption efciency and capacity


are always higher than those of static adsorption when treating the
same amount of Cr (VI).
3.2.3. Effect of ow rate
Flow rate is closely bound up with the contact time between
adsorbent and adsorbate. Breakthrough is faster at higher ow rate.
Low ow rate increases the residence time of solute in the bed,
allowing more time for adsorption and permitting near-local equilibrium conditions (Sridhar, 1996). Fig. 5a shows the effect of ow
rate on the dynamic adsorption behavior of Cr (VI). The abscissa
is expressed as the number of bed volumes, which is efuent volume divided by bed volume. Lower ow rate (1 ml/min) greatly
increased the adsorption capacity and bed utilization efciency.
As the ow rate was increased from 1 to 2 ml/min, breakthrough
occurred sooner and the slope of the breakthrough curves became
sharper. However, the breakthrough curves at ow rate of 2 ml/min
and 3 ml/min nearly overlap, indicating the loading of Cr (VI) in
this ow range is independent on ow rate. The bed utilization
decreases from 30% to 22% as the ow rate increases from 1 to
3 ml/min (Fig. 5b), suggesting higher throughput at a cost of lower
bed capacity utilization.
The results of modeling for different ow rate are similar
to those obtained for different feed concentration, where both
AdamsBohart model and doseresponse model tted the experimental data well. In the initial part of the curves, the prediction
by AdamsBohart model best tted to the experimental plot with
R2 > 0.96. Increased ow rate leads to decreased kAB but increased
N0 (Table S1), indicating favorable adsorption at lower ow rate.
Inset of Fig. 5a shows the predicted breakthrough curves using
doseresponse model, which align well with the experimental data.
According to this model prediction as shown in Table S1, q0 is
declined as the ow rate is increased.
3.2.4. Effect of bed length
Fig. 6 demonstrates the effect of bed length/thickness in terms
of number of stacked membrane layers on breakthrough proles.
Greater length implies more adsorbent and larger amount of Cr
(VI) ions to be adsorbed, resulting in longer breakthrough time and
broadened mass transfer zone. Breakthrough of the membrane with
5 layers occurred quickly with low adsorption capacity because of
relatively less binding sites provided, less even ow distribution
across the membrane bed, and smaller residence time (Fig. 6a, the
solid lines are the doseresponse model prediction curves). The
membrane beds with 1020 layers have an obvious extension of
the breakthrough times in the order of 20-layers > 15-layers > 10layers, indicating more adsorption of Cr (VI). In fact, multiple-layer

conguration can minimize the non-uniformity of ow channels


of the bed that in turn prevents early breakthrough. It is noticed
that an increase in bed length does not always boost bed adsorption capacity and bed utilization. The adsorption capacity depends
on not only the volume of solution passing through the bed before
breakthrough, but also the bed volume used. It is a ratio of the loading at breakthrough and the bed volume or mass in use. Fig. 6b
shows such a behavior, where except for the 5-layers membrane,
the membranes dynamic adsorption loading capacity of Cr (VI)
at breakthrough is independent on bed length. Fig. 6c is a bar
chart, more directly showing the bed adsorption capacity in mgchromium/g-chitosan at 10% and 80% breakthrough respectively vs.
membrane length. The bed utilization efciency follows the same
trend. From Fig. 6c we can conclude that after the bed reaches a certain length, the bed loading capacity and utilization efciency do
not change any more. This phenomenon was also observed in literature for biomolecules separation using adsorptive membranes
(Roper & Lightfoot, 1995), where the authors claimed that heightening the diffusional path length allowed volumetric throughputs
to be decreased substantially, while the membrane capacity was
maintained.
Bed depth service time (BDST) model is widely used to estimate the required bed depth for a given service time for a column
bed (Elwakeel, Atia, & Guibal, 2014; Li et al., 2016; Vijayaraghavan,
Jegan, Palanivelu, & Velan, 2005). The model is expressed as:
t=

N0 Z
1

ln
C0 v
kB C0

C

Cb

(5)

where t is the bed service time until breakthrough (min), N0 the


sorption capacity of bed (mg/L), Z the bed length (cm), v the linear velocity (cm/min), kB the rate constant (L/mg min) and Cb the
breakthrough metal ion concentration (mg/L). The values of N0 can
be calculated from the slope of the plot and kB from the intercept.
The critical bed length (Z0 ) can be calculated by setting time to
zero. Then Eq. (5) can be rearranged as:
Z0 =

v
kB N0

ln

C

Cb

(6)

Z0 is the minimum theoretical bed length that is sufcient such that


the efuent concentration at t = 0 will not exceed the breakthrough
concentration. The column service time was selected as the time
at 10% breakthrough. Fig. 6d indicates the present system interestingly follows the BDST model. The correlation coefcient for the
linear plot of t versus Z is 0.9853. N0 and kB were calculated to be
54.77 mg/L (10.42 mg/g) and 0.126 L/mg min, respectively. From
Fig. 6c, the adsorption capacity at 10% breakthrough for different
bed length are 9.93, 10.36 and 9.88 mg/g for 10, 15 and 20 layers
nanober membranes, respectively. These values are very close to

L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

305

Fig. 6. Effect of bed length on dynamic adsorption (ac) and BDST model plot (d) [experiment conditions: pH = 6, C0 = 1 mg/L, ow rate = 2 ml/min].

the value of N0 , which indicates that the bed length has a minor
effect on column adsorption capacity. kB and Z0 indicate the capability of the bed to resist breakthroughlarge kB and small Z0 imply
better bed performance. By calculation, the value of the critical bed
length was determined to be 0.057 cm, equivalent to a bed length
of a 3-layer membrane. The relatively large value of kB and small
value of Z0 of the present system are strong indication that a short
bed length will be sufcient to avoid breakthrough (Elwakeel et al.,
2014; Li et al., 2016; Vijayaraghavan et al., 2005). This further indicates that nanober membrane bed is highly efcient for removing
Cr (VI) ions.
The AdamsBohart and doseresponse models again present
a good interpretation of Cr (VI) sorption results. The trend of the
values of kAB , N0 and q0 is similar to those studied at other experimental conditions as shown in Table S1.

3.2.5. Effect of nanober deposition density


Membranes with 0.5 g/m2 , 1 g/m2 , 1.5 g/m2 and 2 g/m2 chitosan
nanobers were chosen to examine the effect of nanober deposition density, which is directly related to membrane pore size, on the
breakthrough behavior. The total amount of chitosan nanobers
in mass was the same in each bed. Higher ber deposition density
implies thicker chitosan nanober layer and smaller nanober
membrane pore size as discussed in Section 3.1 (Fig. 2). Due to the
thick substrate (184 m) used, the total thickness of the bed with
0.5 g/m2 nanober membrane (40 layers) is almost four times the
bed of the 2 g/m2 nanober membrane (10 layers). Fig. 7a shows
that the stacked 2 g/m2 nanober membrane bed exhibits better
dynamic adsorption behavior than the other three nanober membrane beds. If they perform the same, the number of bed volumes
at breakthrough for the former should be 4, 2 and 1.3 times of the
0.5 g/m2 , 1 g/m2 , and 1.5 g/m2 nanober membrane beds. Thanks
to the smaller pore size of the 2 g/m2 nanober membranes, the
interaction between nanobers and Cr (VI) ions becomes easier

than the other three beds, which leads to a net increase of 237%,
100% and 28% bed volumes at 10% breakthrough compared with
the other three beds respectively. It translates to a loading capacity
of 16.5 mg-chromium/g-chitosan. At 80% saturation, the loading is
44.9 mg-chromium/g-chitosan. The bed utilization is also increased
from 23% to 37%. The trend is better shown in Fig. 7b, where the
nanober deposition density is expressed as the corresponding
pore size, against which the bed adsorption capacity and bed
utilization efciency are plotted. Smaller pore size gives rise to
high capacity and higher bed utilization. This result has practical
implications for more efcient brous membrane design using
electrospinning technology, simply because it offers the exibility
of depositing controllable amounts of functional nanobers to
maximize their utilization as adsorptive membranes.

3.2.6. Effect of ow distribution and membrane packing pattern


Flow distribution is very important for dynamic adsorption.
In this work, two strategies were applied to distribute the ow.
The rst one is inserting one piece of stainless steel wire mesh
(SSWM) every 5 layers of chitosan membranes (1 g/m2 nanober
density) counting from the top. The steel mesh has a thickness of
400 m and a mesh size of 691 m. From Fig. 8a, it can be seen that
the breakthrough curves with or without SSWM for the 10-layer
membrane stack are not different. However, when 2 SSWM were
used for the 15-layer membrane bed, the loading was improved by
about 40%. The initial thought was that the mesh size was so large
compared with the pore size of the substrate (114 m) and the
nanober membrane (1.3 m) that the dynamic adsorption ought
not to be affected. Obviously, redistribution of the ow through the
stacked nanober membranes can be more inuential that it must
be addressed in membrane bed design. In reality, using SSWM as a
ow distributor inside the membrane bed is not expected; thinner
materials with much small mesh/hole size can serve the purpose
better.

306

L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

Fig. 7. Effect of ber deposition density (a) and corresponding pore size (b) on dynamic adsorption of Cr (VI) [experiment conditions: pH = 6, C0 = 1 mg/L, ow rate = 2 ml/min].

Fig. 8. Effect of ow distribution on breakthrough curves [experiment conditions: pH = 6, C0 = 1 mg/L, ow rate = 2 ml/min].

The other strategy used was to pack the composite nanobrous


membranes in two different ways as illustrated in the inset of
Fig. 8b. One way was to align the composite membrane layers in
series with nanobers facing the same direction but away from
each other, spaced by the substrate. This is the common membrane
packing pattern throughout our experiments. The other way was to
put two composite membranes together by aligning the nanober
layers in the middle to form a sandwich, and then stacked these
sandwiches so a double thickness nanober layer and substrate
were constructed. The nanober deposition density of the composite membrane used under this strategy was 2 g/m2 . The total
amount of chitosan nanobers and the pore size of each individual
membrane were all the same in the two beds packed differently
with 10-layer membranes. Apparently the packing structure signicantly affected the dynamic adsorption behavior of Cr (VI) in
terms of loading and saturation capacity, as illustrated by the breakthrough proles in Fig. 8b. The difference of the breakthrough
curves is believed to be related to ow re-distribution on top of
each individual nanober layer. More uniform ow allows the bed
to be more effective for adsorption. Because of the large pore size
of the PET scrim, doubling its thickness does not ne tune the ow
distribution of the solution before it enters the nanober layer for
adsorption. This means for the sandwiched structure, ow was only
redistributed 5 times before the solution eluted from the bed. For
the bed with individual membrane orientated the same way, ow
was redistributed 10 times, resulting in a much better adsorption
performance. This again concurred with the ndings with SSWM
as the added ow distributor for improving the bed performance.
Finally, a comparison of dynamic Cr (VI) adsorption between
the electrospun chitosan nanober membrane and the traditional
membranes is provided in Table S4. Keep in mind that the experimental conditions are all different, a quantitative comparison of the
membrane performance should be treated with caution. As can be

seen from the table, even though the number of the entire bed volumes at breakthrough for chitosan nanober/PET membrane is less
than that of Thiol-eggshell and PGMAFe membranes because of the
presence of thick PET substrate that does not adsorb, the number of
adsorptive chitosan nanober volumes is much larger. In addition,
the electrospun chitosan nanober membrane has an advantage
over the other membranes in effective area and bed length, which
is of signicance for practical applications.
4. Conclusions
Chitosan nanober membranes with different ber deposition
density on polyester scrim were fabricated by electrospinning.
Nanober membranes used as a packed bed exhibited fairly good
dynamic adsorption capacity for Cr (VI) ions. While the performance of the nanober membranes including adsorption capacity
and bed utilization efciency was pH, ow rate and membrane
packing pattern dependent, it was less sensitive to feed concentration and bed length change. However, bed adsorption capacity
and utilization can be greatly improved by increasing nanober
deposition density of the composite membrane. The best loading and bed utilization could be established by using 10 layers
of 2 g/m2 nanober membranes to treat 1 mg/L Cr (VI) at a ow
rate of 2 ml/min. The maximum adsorption capacity obtained for
1 mg/L Cr (VI) using the nanober membranes at 10% breakthrough
is 16.5 mg-chromium/g-chitosan, exceeding the saturation capacity of static adsorption of 11.0 mg-chromium/g-chitosan using
chitosan nanober mats. The result indicated that the nanober
membranes designed in this work were effective for chemical ltration of Cr (VI) in a single-pass ow as adsorptive membranes,
a promising outcome for applying such membranes for water
decontamination. The bed breakthrough data obtained at different feed Cr (VI) concentration, ow rate and bed length were well

L. Li et al. / Carbohydrate Polymers 140 (2016) 299307

tted by AdamsBohart model for initial stage of sorption and


doseresponse model for large time sorption in general. By applying BDST model, it was found that a short bed length (less than 3
layers) was sufcient to avoid breakthrough, indicating the high
efciency of the chitosan nanober bed for chemical ltration of Cr
(VI) ions.
Acknowledgments
This work is supported by the Chinese Academy of Sciences
under the talented program and the National Nature Science Foundation of China (Grant No. 51302267, 21476237 and 21401210).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carbpol.2015.12.067.
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