Journal of Environmental Chemical Engineering 3 (2015) 24842491

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Journal of Environmental Chemical Engineering

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

Color removal from anaerobic/aerobic treatment efuent of bakery

yeast wastewater by polyaniline/beidellite composite materials
Erhan Gengec*
a

Department of Environmental Protection, University of Kocaeli, Turkey

A R T I C L E I N F O

A B S T R A C T

Article history:
Available online 16 September 2015

The adsorption technique is widely applied for the removal of pollutants from wastewater, especially for
toxic or non-biodegradable wastewater. In recent years, the production of alternative adsorbents to
replace costly adsorbents has been paid more attention to in literature. Polyaniline/beidellite (PAn + Bei)
composite material as an absorbent, which is efcient and low cost can easily be prepared via H2SO4, KIO3
and aniline. This paper deals with color and total organic carbon (TOC) removal of biologically treated
bakery yeast wastewater (BYW) using the PAn + Bei composite material by adsorption processes. The
effects of experimental variables were chosen as the initial pH (pHi), sorbent dosage (ms), contact time
(tc) and mixing speed (s) by a batch sorption process. It was found that by increasing the adsorbent dosage
(0.0250.400 g/50 ml of composite dosage), contact time (2240 min) and decreasing the pHi (93)
improved the color and TOC removal efciencies. The optimum color and TOC removal efciencies were
obtained as 88.7% and 63.3% at 0.400 g/50 ml of adsorbent dosage, a pHi of 3, 240 rpm, and 240 min. In
addition, a pseudo-second order kinetic model was proposed to correlate the experimental data. To
understand the removal mechanism and characterize the surface of the PAn + Bei composite material,
size exclusion chromatography (SEC), BET surface analysis, fourier transform infrared spectroscopy (FTIR)
analysis, scanning electron microscope (SEM), thermal gravimetric analysis (TGA), and differential
scanning calorimetry (DSC) were employed. As a consequence, the proposed mechanism for the removal
by PAn+Bei composite material seems to be driven by an ion exchange process.
2015 Elsevier Ltd. All rights reserved.

Keywords:
Bakery yeast wastewater
Beidellite
Polyaniline composite
Adsorption

1. Introduction
Bakers yeast production by fermentation uses molasses as a
raw material which is a by-product of the sugar industry. Due to
the molasses, bakers yeast wastewater (BYW) has a high organic
content and dark brown color. Melanoidins are the source of this
dark brown color in BYW which is resistant to biodegradation.
Melanoidins restrict the sunlight and make a reduction in the
natural photochemical process for self-purication of the surface
waters [1,2].
Various treatment methods such as a biological process
(anaerobic, aerobic), physico-chemical treatment (adsorption,
membrane process, reverse osmosis, coagulation/occulation,
electrocoagulation) and oxidation processes (ozone, Fenton) have
been performed for the treatment of BYW [3,4]. Nowadays
biological treatment of BYW is realized by combinations of
anaerobic digestion and aerobic systems that successfully reduce

* Corresponding author: Fax: +90 262 3513629.

E-mail address: erhan.gengec@kocaeli.edu.tr (E. Gengec).
http://dx.doi.org/10.1016/j.jece.2015.09.009
2213-3437/ 2015 Elsevier Ltd. All rights reserved.

BOD and COD to acceptable limits, but do not deal effectively with
the dark color and limits the reuse/recycling of the process water.
Treatment by oxidation technology is generally effective on the
color, but not COD, membrane ltration processes are prone to
fouling [5,6], and reverse osmosis generates a high salinity that
presents disposal difculties [7]. Coagulation removes color and
COD effectively, but possesses a number of drawbacks such as
necessities for high quantity of inorganic coagulants. Decolorization through chemical treatment by ozone, Fentons reagent and
H2O2/UV lead to temporary color reduction because of the
transformation of the chromophores [811].
For these reasons, the BYW requires an alternative treatment
technology which is relatively simple and effective in the removal
of color before its safe disposal into the environment. Adsorption
techniques are widely used to remove pollutants from the water,
especially those that are toxic and not easily biodegradable. The
studies focused on the production of alternative adsorbents to
replace the costly ones reported in literature. Attention has focused
on composite materials which are generally produced with various
natural solids such as beidellite, cheap natural clay, and polymeric
materials like polyaniline (PAn) for the effective removal of

E. Gengec / Journal of Environmental Chemical Engineering 3 (2015) 24842491

pollutants when compared with other polymeric materials. PAn

has a large variety of advantages such as high removal efciencies,
low cost, easy synthesis, both chemically (powder form) and
electrochemically (a lm), and environmental stability. Thus,
studies have focused on the production of PAn coated different
composite materials recently [12,13]. In literature, sawdust
[1417], rice husk and saw dust of Eucalyptus camaldulensis [18],
palygorskite [19], montmorrillonite [20], silica gel [21] were
coated by polyaniline for the removal of pollutants from water/
wastewater.
The novelty of this study is the production of a new composite
material by coating beidellite with aniline to use it for color and
TOC removal of biological treated bakers yeast wastewater for the
rst time. The effects of the variables such as initial pH (pHi),
sorbent dosage (ms), contact time (tc) and mixing speed (s) on the
adsorption were examined by using a batch method. Several
kinetic mechanisms were applied on data and molecular weight
distributions (MWDs) were monitored during treatment by SEC.
SEM, TGA, BET surface analysis, DSC, and FTIR were used to
characterize the PAn + Bei composite materials.
2. Materials and methods
2.1. Preparation of beidellite/polyaniline composite
Beidellite is a dioctahedral smectite named after Beidell, CO,
USA. Large deposits of beidellite minerals were explored in
different locations of Turkey [22]. It was used for daily cleaning
processes in the Black Sea region of Turkey. PAn is a poly aromatic
amine that can be easily synthesized chemically from Brnsted
acidic aqueous solutions. It is one of the most potentially
conducting polymers and has obtained considerable attention in
recent years. Chemical polymerization of aniline in aqueous acidic
media (Brnsted acid) can easily be performed by the use of
chemical oxidizing agents such as (NH)4S2O8, KIO3 and K2Cr2O7 as
shown in Fig. 1 [23]. There are a few studies regarding the
production of polyaniline composites material in which different
coated material, oxidizer, acid types and production processes
were used. Ansari [14] and Ghorbani et al. [24], have produced
different polyaniline composite materials by similar production
processes with this study. Ghorbani et al. [24], produced the
polyaniline and polypyrrole composites material for treatment of a
real wastewater, paper mill wastewater, and the results showed
that polyaniline/polypyrrole composite material have an important potential for using pollutants from real wastewater. In this
study, preliminary studies were realized according to literature,
then the production conditions of Ansari [14] and Ghorbani et al.,
were modied for production of PAn + Bei composite materials. For
preparation of composite materials, 1 g of beidellite was added to
100 ml H2SO4 (1 M) solution and the solution was mixed at a
stirring rate of 500 rpm [25]. Then, 1 g KIO3 was added at room
temperature and 1 ml of aniline monomer was injected slowly. The
polymerization was carried out at room temperature for 2 h. In

NH2

H2SO4
Oxidation

NH

NH

2485

order to remove the unreacted monomers and oxidants, the nal

product was washed thoroughly with 500 ml of deionized water.
Then, the product was dried at 60
C for 24 h. The beidellite was
used as received without any pretreatment.
2.2. Experimental set-up and analytical methods
The anaerobic-aerobic treated wastewater was obtained from
the baker yeast production industry in Turkey and batch
adsorption tests were carried out in a NUVE ST-402 model shaker.
TOC levels were determined through combustion of the samples at
680
C using a non-dispersive IR source (Shimadzu, TOC-L model).
The pH of the sample was adjusted with H2SO4 or NaOH and
measured by a pH meter (WTW Inolab pH 720) and the color of the
wastewater was measured utilizing a UVVis spectrophotometer
at 475 nm (PerkinElmer 550 SE).
JEOL 6.060 type scanning electron microscopy (SEM) was used
to obtain SEM images. The FTIR spectra of the beidellite and
PAn + Bei composite material were recorded on a PerkinElmer
Spectrum 100. The TGA curves were performed on a Mettler Toledo
TGA 1 Star Sytem at a heating rate of 15
C/min from room
temperature to 1000
C. For DSC analysis, a Mettler Toledo
DSC1 instrument was used. The BET surface area was measured
from the N2 adsorption/desorption isotherms with a Micromeritics
ASAP 2010 analyzer (US).
The MWD was determined using HPSEC with a Hewlett
Packard HPLC 1100-series system equipped with a refractive index
(RI) detector, a diode array detector (DAD) and two ultrahydrogel
(Waters, Product Number: WAT011535 and WAT011525) columns.
RID measures change in refractive index and its unit was called
Refractive Index Units (nRIU). DAD is a type of UVvis detector
and its unit was named as absorbance unit (AU) at any wavelength.
Deionized water at a ow rate of 1 ml/min was used as the mobile
phase. The results were calibrated using 1 g/l of polyethylene oxide
with different molecular weights (25.3, 44.0, 78.3, 152.0 and
326.0 kDa). The weight-average molecular weight (Mw) and
number-average molecular weight (Mn) were calculated from
the data using the following equations [26] and these calculations
were processed by ChemStation software.
X
ni M2i
1
Mw Xi
nM
i i i
X
nM
i i i
Mn X
ni

Mi and ni are the molecular weight and the height of each ith
fraction eluted at the ith volume in the chromatogram, respectively. The polydispersity index (PDI) or heterogeneity index, is a
measure of the distribution of molecular mass in a given polymer
sample. PDI is calculated from Mw/Mn.

NH

SO4-2

NH
SO4-2

n
Fig. 1. Overall polymerization reaction of polyaniline [23].

2486

E. Gengec / Journal of Environmental Chemical Engineering 3 (2015) 24842491

2.3. Adsorption kinetics

The percentage removal of TOC and the adsorption capacity
of adsorbents (mg/g) were calculated using the following relationships:


100 C i  C f
3
TOC removal%
Ci


Ci  Cf V
The adsorption capacity of adsorbents; qe
m

2.3.1. The pseudo-rst-order equation

A pseudo-rst-order equation can be expressed in a linear form
as:
k1
t
2:303

where qe and qt are the amount of TOC adsorbed (mg/g) on the

adsorbents at the equilibrium and at time t, respectively, and k1 is
the rate constant of adsorption (min1). Values of k1 were
calculated from the plots of log(qeqt) versus t.
2.3.2. The pseudo-second-order equation
The pseudo-second-order adsorption kinetic rate equation is
expressed as
dqt
k2 qe  qt 2
dt

2.3.3. Intraparticle diffusion

The rate constant for intraparticle diffusion (kid) is calculated
using following equation:
q kid t1=2 C i

where m is the mass of PAn + Bei (g), V(l) is the volume of

wastewater. Ci and Cf are the initial and nal concentrations
(in mg/l) of TOC, respectively.
The study of adsorption kinetics describes the solute uptake
rate and evidently this rate controls the residence time of
adsorbate uptake at the solidsolution interface. The adsorption
rate constants for the TOC removal were calculated by using
pseudo-rst order, second-order and intraparticle diffusion kinetic
models [27] which were used to describe the mechanism of the
adsorption. The accord between the experimental data and the
model-predicted values were expressed by the correlation
coefcients (R2). A relatively high R2 value indicates that the
model successfully describes the kinetics of the adsorption.

logqe  qt logqe 

where qe is the amount of TOC adsorbed at equilibrium (mg/g). The

second-order rate constants were used to calculate the initial
sorption rate, h k2 q2e . Values of k2 and qe were calculated using
the intercept and the slope of the linear plots of t/qt versus t.

where k2 is the rate constant of pseudo-second-order adsorption

(g/mg min). By integrating and applying the initial conditions, we
have a linear form as:
 
t
1
1
t
7

qt
k2 q2e qe

where q is the amount TOC adsorbed (mg/g) at time (t), kid (mg/
g min1/2) is the rate constant for intraparticle diffusion and Ci is the
thickness of the boundary layer. The values of kid were calculated
from the slope of the linear plots of q versus t1/2 [28,29].
3. Results and discussion
3.1. Morphology and characterization
In this study, a scanning electron microscope (SEM) was used to
characterize the surface of the PAn + Bei composite material at a
very high magnication and an accelerating voltage of 15 kV.
Samples were coated with gold using a sputter coater with
conductive materials to improve the quality of the micrograph. The
morphology of beidellite and PAn + Bei composite material was
illustrated in Fig. 2. The coating by conducting polymer by surface
polymerization was very visible.
The BET specic surface area, Langmuir surface area and
adsorption average pore width were calculated as 66.53,
89.48 m2/g, and 4.95 nm for beidellite and 16.12, 22.74 m2/g, and
17.94 nm for PAn + Bei composite material. During polymerization,
some of the pores in the beidellite were stocked by PAn particles, so
PAn + Bei had a smaller surface area than beidellite. Small surface
areas and higher removal efciencies by PAn + Bei showed that the
removal mechanism by PAn+Bei depended on the ions exchange
process. In literature, the main removal mechanism by polyaniline
composite materials was reported as the ions exchange process
[14,3033].
The chemical structure of the composite material was determined by FTIR spectrum (Fig. 3) which was a signicant tool to
distinguish the characteristics of the functional groups. Small
amounts of silica species such as amorphous material or quartz
were indicated by the presence of a minor band around 836 cm1.
The octahedral Al
OH groups in the beidellite structures were
reported around 911 cm1. The infrared spectra of the beidellite
were very similar in the SiO region around 1000 cm1. The
interlayer water in the beidellite samples was characterized by an
H2O bending vibration at 1635 cm1. The shoulder around
3240 cm1 was ascribed to interlayer H2O chemically bound or
coordinated to the interlayer cation. The band at about 3618 cm1

Fig. 2. SEM images of (a) beidellite and (b) PAn + Bei composite material.

E. Gengec / Journal of Environmental Chemical Engineering 3 (2015) 24842491

983 792

0.5

1002

Beidellite
PAn+Bei

0.4

1127

Absorbance

1486

0.3

911

1243

1558
836

0.2

0.1

3618

1635

3240

0.0
4000

3500

3000

2500

2000

1500

1000

-1

Wavenumbers (cm )
Fig. 3. FTIR spectra of (a) beidellite and (b) PAn + Bei composite.

of the beidellite was assigned as stretching vibrations of structural

OH groups. The small sharp band at 1633 cm1 in the beidellite was
due to H
OH bending vibrations from adsorbed water [34]. The
characteristic absorption peak of Al
O
Si for Beidellite was
observed at 983 cm1, which merged into a strong peak at
1127 cm1 of PAn + Bei [35]. The peaks at 792, and 1243 cm1
were reported as CH out of plane, and CN stretching vibrations,

92

4.0 %

88

84

Beidellite
80
100

200

respectively [18]. The peaks at 1558 and 1486 cm1 for PAn+Bei
were usually representative of the CC stretching vibrations of
quinine and benzene rings [24,35]. On the other hand, the peak at
1296 cm1 was correspondent to the C
N stretching vibration
[24]. The FTIR analysis conrmed that PAn was successfully grafted
on the surface of beidellite.
TGA curves for beidellite, and PAn + Bei were presented in Fig. 4.
There were three main mass loss steps observed for beidellite. The
rst mass loss (5.5 wt%) occurring from room temperature to
100
C was related to the loss of adsorbed water. Between 100 and
200
C, a maximum weight loss (9.5 wt%) was realized, attributed
to the removal of interlayer water and the onset of dehydroxylation. The dehydroxylation reached a low level of loss (4.0 wt%)
between 400 and 750
C. Similarly, TGA curves for PAn + Bei
showed the weight loss of 4.9% up to 100
C due to the presence of
moisture. The weight loss (50.1 wt%) between 100 and 1000
C
mainly corresponded to the removal of interlayer water, the
dehydroxylation and the decomposition of polymer coverage on
the beidellite. The presence of excess water in beidellite and
PAn + Bei was also conrmed by the FTIR spectrum.
The differential scanning calorimetry (DSC) curve (Fig. 5)
showed that an endothermic reaction took place between 50 and
250
C corresponding to water loss from the beidellite surface and
interlayered space. On the other hand, there were three different
conditions observed for PAn + Bei; an endothermic reaction
between 50 and 140
C, an exothermic between 140 and 314
C,
and an endothermic reaction between 314 and 400
C. The
endothermic reaction between 50 and 140
C corresponded to
water loss from the surface and the interlayered space of
composite material was observed. The presence of PAn caused
an exothermic reaction between 140 and 314
C and above 314
C a
second endothermic reaction was present corresponding to the
beginning of the collapse of the interlayered structure [36].
3.2. Effect of variables on removal efciencies

9.5 %

Weight (%)

96

5.5 %

100

300

400

500

600

700

800

900

1000

Temperature (0C)

In the adsorption process, pHi, pollutant concentration,

pollutant types, temperature, adsorbent dosage, operating time,
mixing speed, particle size are some of the effective process
parameters. In this study, the effects of pHi, adsorbent dosage,
mixing speed, and operating time were investigated on color and
TOC removal efciencies as discussed below.
pH is one of the important parameters that affect the
interaction between the adsorbent and adsorbate [37]. In
addition, pHi affected the polymerization degree of melanodins

4.9 %

100

50.1 %

80
70
PAn+Bei
60

H e a t F lo w ( m V )

90

Weight (%)

2487

-5

-10
PAn+Bei
Beidellite

-15

50

-20
40
100

200

300

400

500

600

700

800

900

Temperature ( C)
Fig. 4. TGA curves (a) beidellite and (b) PAn + Bei composite.

1000

-25
0

50

100

150

200

250

300

350

400

Temperature ( C)
Fig. 5. Differential scanning calorimetric analysis of beidellite and PAn + Bei.

2488

E. Gengec / Journal of Environmental Chemical Engineering 3 (2015) 24842491

80
70

50
40
30
pH 3
pH 4
pH 5
pH 6
pH 7
pH 9

20
10
0
0

20

40

60

80

100

120

140

Time (min)
25

TOC Removal (%)

20

15

90

10

80

pH 3
pH 4
pH 5
pH 6
pH 7
pH 9

0
0

20

40

60

80

100

120

140

Time (min)

Color Removal (%)

Color Removal (%)

60

from 21.8% to 6.5% for TOC. The arrangement of wastewater for

<pH 3 by H2SO4 was a major cost item in the calculation of the
operating cost as reported in the previous study [40]. Due to its
high cost, the experimental conditions (<pH 3) were not
considered.
Commonly, the increase of adsorbent dosages improved
adsorption efciencies. This could be explained by the increase
in adsorbent dosages and surface area, where the adsorption took
place [41]. It was clear that increasing the adsorbent dosage
(0.0250.400 g/50 ml of composite dosage) improved the removal
efciencies from 62.5% to 88.8% for color and from 9% to 42% for
TOC as seen in Fig. 7.
Due to the solute distribution in the bulk solution and external
boundary lm formation, it was reported that the mixing speed
had an impact on adsorption efciencies [42]. In this study, the
effect of mixing speed on adsorption efciencies was examined in
the range of 40240 rpm during an operating time of 120 min. As
seen in Fig. 8, the mixing speed of 240 rpm was appropriate for the
performed study.
The results for effect of contact time were shown in Figs. 68. As
shown in Figs. 68, PAn+Bei composite material rapidly removed
color and TOC in less than 30 min due to the abundant availability
of active binding sites on the sorbent, and with gradual occupancy

Fig. 6. Effects of pHi on color and TOC removals (conditions: ms; 0.1 g/50 ml, tc;
120 min, and s; 240 rpm).

70
60
0.025 g/50 ml
0.05 g/50 ml
0.1 g/50 ml
0.3 g/50 ml
0.4 g/50 ml

50
40
0
0

20

40

60

80

100

120

Time (min)

40

TOC Removal (%)

which was the source of color in BYW. Decreasing pH caused a

decrease of color intensity [38]. Thus, the treatment of BYW was
examined at different pHi and the results were presented in Fig. 6.
The results showed that the removal of BYW by PAn + Bei
composite material was higher in acidic conditions than those in
neutral and alkaline. In literature, two possible pollutants
removal mechanism were reported via polyaniline composite
materials. If wastewater contains positive ions, the effective
removal was realized under neutral and alkaline conditions
[15,16]. On the other hand, if wastewater contains negative ions,
the effective removal was realized under acidic conditions [18].
Under acidic conditions the nitrogen atom present in the PAn + Bei
composite material was protonated. As a result, the higher
adsorption behavior of the composite was explained by the
electrostatic interaction between this protonated polymer and
pollutants. However, as the pH increased (59) deprotonation of
nitrogen atoms occurred leading to the depletion of active sites in
the polymer skeleton. Therefore, the interaction of composite
with the pollutant molecule was hindered and consequently
results were in the lower adsorption. This result is in agreement
with literature [18,37,39].
As seen in Fig. 3, when pHi was increased from 3 to 9, the
removal efciencies decreased from 82.6% to 24% for color and

30

20

10
0.025 g/50ml
0.05 g/50 ml
0.1 g/50ml
0.3 g/50ml
0.4 g/50ml

20

40

60

80

100

120

Time (min)
Fig. 7. Effects of the adsorbent dosage on color and TOC removals (condition: pHi; 3,
tc; 120 min, and s; 240 rpm).

E. Gengec / Journal of Environmental Chemical Engineering 3 (2015) 24842491

3.3. Kinetic studies and intra-particle diffusion models

80
75

Color Removal (%)

70
65
60
80 rpm
120 rpm
160 rpm
240 rpm

55
50
10
0
0

20

40

60

80

100

120

Time (min)
30
25

TOC Removal (%)

2489

20
15
10
80 rpm
120 rpm
160 rpm
240 rpm

5
0

In this study, pseudo-rst order, pseudo-second order and the

intraparticle diffusion model were tested with the results to obtain
kinetics of the adsorption processes and mass transfer models. The
constants and correlation coefcient (R2) values for pseudo-rst
order, pseudo-second order and intraparticle diffusion model with
respect to pHi, ms (g) and s (rpm) were given in Table 1. The linear
correlation values close to 1 showed that the model was
statistically signicant and indicated the applicability of these
kinetic equations.
All R2 values for pseudo-second order were >96%. However, R2
values for the pseudo-rst order and the intraparticle diffusion
model were varying at a high range. The data tting for TOC
illustrated that the pseudo-second order model tted well and
suggested chemical sorption as the rate-limiting step of the
adsorption mechanism and no involvement of a mass transfer in
solution [43].
In literature, the studies which dealt with the preparation of
polyaniline composite materials generally focused on the removal
of synthetic wastewater. On the other hand, Ghorbani et al. [24],
produced the polyaniline composites material for treatment of real
wastewater, paper mill wastewater, and reported that the
complete removal of COD was not possible by adsorption with
polyaniline composite materials. However, Ghorbani and Eisazadeh [44], reported >97% of COD removal for cotton textile
wastewater by using polyaniline nanocomposites coated on rice
husk ash. These results showed that the composite types and
wastewater content affect the removal efciencies. The best color
and TOC removal efciencies for anaerobic/aerobic treated baker
yeast wastewater were reported as 86% and 43% by electrocoagulation process in our previous study [2], which were the
similar to the results of this study. This similarity showed that
PAn + Bei composite material had an important potential in the
treatment of anaerobic/aerobic treated baker yeast wastewater.

-5
0

20

40

60

80

100

120

3.4. The molecular weight distributions of treated BYW

Time (min)
Fig. 8. Effects of the mixing speed on color and TOC removal (conditions: ms; 0.1 g/
50 ml, pHi; 3, and tc; 120 min).

of these sites. The sorption became less efcient in the later stages.
These results agreed with literature and the removal mechanism
by using PAn + Bei composite material seemed to mostly occur via
an ion exchange process [16].

The HPSEC method was able to successfully used to detect the

MWDs of BYW. In HPSEC, larger molecules move rapidly through
the column with eluent and leave the column faster than the
smaller ones. The molecular weight distributions of colorful
components (Fig. 9) were obtained by the DAD detector and it was
clear that there was a remarkable removal of colorful components
in wastewater.

Table 1
The model parameters of pseudo rst order, pseudo second order and intraparticle diffusion.
Pseudo rst order

pHi

ms(g)

S (rpm/min)

3
4
5
6
7a
9
0.025
0.05
0.1
0.3
0.4
80
120
160
240

Pseudo second order

2

Intraparticle diffusion
2

qe.cal

k1

qe.exp

k2

5.0
3.1
2.9
1.9

1.6
16.4
7.3
4.1
2.4
1.8
3.7
2.7
5.3
7.2

0.029939
0.058727
0.128738
0.034084

0.045139
0.029478
0.017273
0.032242
0.048363
0.058036
0.032472
0.054121
0.034315
0.029939

0.855
0.869
0.988
0.851

0.877
0.968
0.958
0.939
0.889
0.971
0.96
0.838
0.725
0.855

11.5
10.9
10.2
9.2

3.4
19.0
14.3
10.4
7.0
5.6
6.9
6.9
7.9
11.5

3.5
4.7
9.2
10.2
11.1
11.6
22.7
14.3
10.4
6.5
5.6
7.0
7.1
8.1
11.6

0.0891
0.0712
0.0509
0.076
0.052
0.0183
0.0021
0.0085
0.0243
0.0466
0.0653
0.0216
0.0492
0.0249
0.0183

1.11
1.58
4.31
7.92
6.38
2.46
1.07
1.75
2.61
1.98
2.03
1.04
2.45
1.62
2.46

0.999
0.996
0.998
0.999
0.999
0.997
0.998
0.996
0.997
0.986
0.969
0.994
0.999
0.996
0.996

Satisfactory positive log(qeqt) values was not available at pH 7.

k3

R2

0.9877
0.6147
0.8539
0.2998
0.344
0.3122
2.2238
0.7946
0.752
0.5928
0.3362
0.3572
0.4871
0.9583
1.1573

4.443
7.282
6.758
6.913
2.701
1.554
0.071
5.607
4.982
3.298
3.443
3.125
3.777
2.211
3.957

0.825
0.967
0.994
0.87
0.554
0.95
0.965
0.964
0.95
0.959
0.988
0.958
0.919
0.855
0.804

2490

E. Gengec / Journal of Environmental Chemical Engineering 3 (2015) 24842491

10

15

20

25

30

References

35

20
15

0.4 g PAn+Bei

10

-3
Absorbance (AUx10 )

5
0
20
15
10

0.3 g PAn+Bei

5
0
20
15
10

0.05 g PAn+Bei

5
0
20
15
Raw Wastewater

10
5
0

10

15

20

25

30

35

Time (min)
Fig. 9. DAD chromatograms of raw wastewater and treated wastewater (AU475nm).

Table 2
Mn,Mw and PDI results at different adsorbent dosage.

Raw wastewater
0.05 g PAn + Bei
0.3 g PAn + Bei
0.4 g PAn + Bei

Mn

Mw

231.44
176.74
92.61
76.08

4038.4
8129.9
12124.1
13500.1

17.45
45.99
130.91
177.46

In addition, Mw values increased gradually by contrast with Mn,

and BYW has the smallest PDI value for raw wastewater (Table 2).
These results showed that PAn + Bei composite material preferentially removed the lower molecular weight components.

4. Conclusions
In this study, beidellite was coated with polyaniline to obtain
low cost and effective adsorbent. The effects of pHi, contact time,
adsorbent dosage, and mixing speed were studied for the removal
performance of the composite material on color and TOC removal
efciencies. The results showed that polyaniline coated beidellite
had an important potential for use in wastewater treatment. The
optimum color and TOC removal efciencies were obtained as
88.7% and 63.3% at 0.400 g/50 ml of adsorbent dosage, pHi of 3,
240 rpm, and 240 min. SEC results indicated that the composite
material preferentially removed the lower molecular weight
components and TOC removal data tted well to the pseudosecond order. The results of the SEC, SEM, Bet surface area, FTIR
analysis and kinetics models showed that the removal mechanism
by PAn + Bei composite material was the ion exchange process.

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