Journal of Hazardous Materials 291 (2015) 7482

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Journal of Hazardous Materials

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Treatment of a simulated textile wastewater in a sequencing batch

reactor (SBR) with addition of a low-cost adsorbent
Slvia C.R. Santos , Rui A.R. Boaventura
LSRE Laboratory of Separation and Reaction Engineering, Associate Laboratory, LSRE/LCM, Faculdade de Engenharia da Universidade do Porto,
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

h i g h l i g h t s

Treating textile dyeing efuents by SBR coupled with waste sludge adsorption.
Metal hydroxide sludge: a good adsorbent for a direct textile dye.
Good adsorption capacities were found with the low-cost adsorbent.
Adsorbent performance considerably reduced by auxiliary products.
Color removal complies with discharge limits.

a r t i c l e

i n f o

Article history:
Received 4 November 2014
Received in revised form 2 February 2015
Accepted 27 February 2015
Available online 28 February 2015
Keywords:
Adsorption
Sequencing batch reactor
Textile dyes
Direct Blue 85
Low-cost adsorbents

a b s t r a c t
Color removal from textile wastewaters, at a low-cost and consistent technology, is even today a challenge. Simultaneous biological treatment and adsorption is a known alternative to the treatment of
wastewaters containing biodegradable and non-biodegradable contaminants. The present work aims
at evaluating the treatability of a simulated textile wastewater by simultaneously combining biological
treatment and adsorption in a SBR (sequencing batch reactor), but using a low-cost adsorbent, instead
of a commercial one. The selected adsorbent was a metal hydroxide sludge (WS) from an electroplating
industry. Direct Blue 85 dye (DB) was used in the preparation of the synthetic wastewater. Firstly, adsorption kinetics and equilibrium were studied, in respect to many factors (temperature, pH, WS dosage and
presence of salts and dyeing auxiliary chemicals in the aqueous media). At 25 C and pH 4, 7 and 10, maximum DB adsorption capacities in aqueous solution were 600, 339 and 98.7 mg/g, respectively. These
values are quite considerable, compared to other reported in literature, but proved to be signicantly
reduced by the presence of dyeing auxiliary chemicals in the wastewater. The simulated textile wastewater treatment in SBR led to BOD5 removals of 5379%, but color removal was rather limited (1018%).
The performance was signicantly enhanced by the addition of WS, with BOD5 removals above 91% and
average color removals of 6069%.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Textile dyeing industry is an intensive water consumer, and
thus, generates high volumes of wastewaters. Dyehouse efuents
contain the unxed dyes on bres, auxiliary dyeing chemicals,
salts, acids, bases, chlorinated compounds and occasionally heavy
metals [1,2]. These wastewaters are highly variable in composition due to the existence of different cloths, the huge variety of
dyes available commercially and fashion trends of each season.

Corresponding author. Tel.: +351 220414976; fax: +351 225081674.

E-mail address: scrs@fe.up.pt (S.C.R. Santos).
http://dx.doi.org/10.1016/j.jhazmat.2015.02.074
0304-3894/ 2015 Elsevier B.V. All rights reserved.

In general, these efuents are characterized by high organic content, low biodegradability, variable pH values, low suspended solids
content and presence of color. Typical parameters obtained in
chemical analysis of textile wastewaters can be found in literature [35]. If not adequately treated, these efuents can originate
strong negative impacts on water resources. The input of dyes
in aqueous streams changes the natural color, limits water uses
(abstraction of drinking water, recreation), affects sunlight penetration and photosynthesis, and can present a toxic effect to aquatic
life. The color removal is, however, challenging in the textile efuents treatment, owing to the recalcitrant nature of some dyes.
Conventional biological treatment techniques remove a signicant
part of the organic content but are generally ineffective on color

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

removal. Coagulation/occulation is, in some cases, effective, but

fails completely in other situations [5], besides generating high
sludge amounts. Electrocoagulation [3], advanced oxidation processes [6,7] and membrane separation [8] are generally effective,
but limited by the high operating costs. Adsorption has shown good
decolorization results. Activated carbon is a widely used adsorbent
in commercial systems but the considerable costs related to its
replacement and regeneration has encouraged the search for lowcost adsorbents, such as various natural materials and industrial
wastes [4,913].
Generally, satisfactory results are obtained using a biological
treatment followed by a tertiary rening step of decolorization by
adsorption onto granular activated carbon (GAC) in a xed-bed column [14]. Another combination between biological methods and
adsorption is the PACT (Powdered Activated Carbon Treatment),
which is a patented technology developed in the 70 s by DuPont and
Zimpro, consisting in the addition of powdered activated carbon
(PAC) to the biological reactor. The PACT system combines simultaneously biological treatment and carbon adsorption into a single,
synergistic treatment stage and has proved to be efcient in the
removal of both biodegradable and non-biodegradable compounds.
Sequencing batch reactors (SBR) are a variant of the conventional activated sludge process. An SBR operates in successive
cycles, each one consisting of a sequence of ve discrete stages:
lling, reaction, settling, extraction (or draw) and idle (a facultative stage to purge the excess biomass). SBR is easy to monitor
and control, presents a exible operation and a compact layout.
Recently, the application of SBR in textile wastewater treatment,
especially on the removal of azo dyes, has received attention from
scientists. Various types of SBR under different operating conditions
have been investigated, such as aerobic SBR [1517], anaerobic
SBR [17] and anaerobicaerobic SBR [1821]. In the integration of
anaerobic and aerobic environments, the removal of azo dyes is
achieved by bonds cleavage, yielding colorless and hazardous aromatic amines (anaerobic reaction) followed by biodegradation of
these metabolites (aerobic reaction).
Many other approaches using SBR have been tested to overcome the low success of aerobic biological removal of dyes, such as
coupling photo-Fenton with SBR [22], combining SBR with nanoltration membranes [23], use of novel bacterial consortia [15], use
of GAC as a support for biolm attachment [24,25] and combined
biological SBR-PAC adsorption systems [26].
In the present study, an alternative to the PACT process is
explored. A combination between aerobic biological treatment (in
SBR) with adsorption by a low-cost adsorbent (instead of activated
carbon) was studied. According to the authors knowledge, this kind
of alternative to treat textile wastewater was not previously studied or reported in literature. The waste sludge selected as adsorbent
is an industrial waste, previous studied for the adsorption of a reactive dye [27]. A simulated dyeing efuent containing an azo direct
dye was prepared and used in the experiments. First, the adsorption of the direct dye was studied onto the waste sludge, regarding
equilibrium and adsorption kinetics. Then, the performance of SBR,
operating only with the simulated efuent, and after the addition
of waste sludge, was evaluated.

2. Materials and methods

2.1. Aqueous solutions of dye and simulated textile wastewater
Sirius Blue K-CFN (Direct Blue 85), designated hereafter as DB,
was selected for this study. It is a commercial dye, kindly supplied
by DyStar (Portugal), anionic type and from the azo chemical class.
Chemical structure of DB dye is shown in Fig. 1. Direct dyes are
mainly applied in the dyeing of cellulosic bres, as cotton, viscose

75

Fig. 1. Chemical structure of DB dye.

and modal and are still commonly used, instead of reactive dyes,
due to their lower cost and easy application Fig. 1.
In this work, two kinds of solutions were prepared: aqueous dye
solutions (only composed by distilled water and DB) and simulated
textile wastewater (a synthetic wastewater, reconstituted with DB
dye, NaCl and three dyeing auxiliary chemicals, commonly used in
industry).
Aqueous DB dye solutions were simply prepared by dissolving
the proper mass of dye in water. These solutions were only used in
batch adsorption experiments.
Simulated textile wastewater, containing DB dye (approx.
85 mg/L), was prepared as follows: (1) heating of approx. 250 mL of
distilled water; (2) addition of 0.25 g of each one of the three dyeing
auxiliary chemicals (wetting, lubricant and sequestrant agents);
(3) addition of 85 mg of DB dye; (4) heating up to 100 C and, after
15 min, addition of 2.5 g NaCl; (5) keeping constant temperature
for 45 min more, and (6) cooling and dilution, making up 1 L. This
procedure was based on the typical scheme for dyeing cellulosic
bres with direct dyes and on details provided by the dye supplier.
The dilution factor of 4 (applied in the nal dilution: 250 mL of
dyeing bath, made up to 1 L) simulated the washing baths after the
dyeing process. Distilled water was used instead of tap water since
the direct dyes are sensible to hardness. The nal dye concentration (85 mg/L) was established considering about 1.1% of dye in the
dyeing bath, 30% of unxed dye onto the bre, and a dilution factor
of 4. The nal characteristics of this simulated textile wastewater
are presented in Table 1.
2.2. Adsorbent: waste sludge
The waste sludge (WS) selected for this study is a typical waste
generated in electroplating industry by alkaline precipitation of
Table 1
Physico-chemical analysis of the simulated textile wastewater.
Parameter

Value

pH
TOC (mg/L)
COD (mg O2 /L)
BOD5 (mg O2 /L)
Color (1:40)a
Total N (mg N/L)
Total P (mg P/L)
Alkalinity (mg CaCO3 /L)

67
117
329
73
Visible
13.6
14.9
15.8

a
Color after 1:40 dilution is a Portuguese legislated parameter for wastewater
discharge from textile industries.

76

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

metal ions in wastewater. This kind of waste is mainly composed

by metal hydroxides and oxo(hydroxides). The WS was rstly dried
at room temperature, disaggregated, sieved in different ranges of
particle sizes and dried at 105 C. The fraction 0.1500.300 mm was
used in the experiments. WS is mainly composed by iron (26%), zinc
(21%), chromium (2.5%), sodium (4.5%), silicon (1.2%), aluminum
(0.4%), potassium (0.3%), calcium (0.3%) and Mn (0.2%), and presented 29% (w/w) of loss on ignition. pHZPC (zero point of charge)
was 6.8. Details on these determinations and other textural and
chemical properties of WS can be found in a previous published
paper [27].
2.3. Analytical methods
After batch adsorption experiments or SBR treatment, the
concentrations of DB dye were determined by UVvis spectrophotometry (Helius Alpha Unicam Spectrophotometer). Solid and liquid
phases were previously separated by centrifugation (Mini Spin
Eppendorf; 13,400 rpm; 6 min).
Other physicochemical parameters were measured using standard methods [28]: alkalinity (potentiometric titration, 2320-B),
BOD5 (biochemical oxygen demand, 5 days incubation, 5210B), COD (chemical oxygen demand, 5220-B), SVI (Sludge Volume
Index, 30 min settling, 2710-D), OD (dissolved oxygen, membrane
electrode method, 4500-O), ORP (oxidation-reduction potential;
potentiometry), pH (potentiometry), T (temperature), TOC (total
dissolved organic carbon; catalytical oxidation at 700 C, 5310),
total N (total dissolved nitrogen, persulfate method, 4500-N, and
colorimetric determination [29]), total P (total dissolved phosphorous, 4500-P), TSS and VSS (total suspended solids and volatile
suspended solids, 2540).
2.4. Adsorption studies
2.4.1. Adsorption kinetics
In order to evaluate the effect of contact time on the adsorption,
experiments were conducted in batch reactors, and the decrease
in the liquid dye concentration evaluated. A volume of 500 mL of
aqueous DB solution was continuously stirred with WS, at 400 rpm,
25 C and constant pH 7 (0.3). Diluted HCl or NaOH solutions were
used for the initial pH adjustment and for readjustments during
adsorption runs. Samples (2 mL) were withdrawn at predened
time instants and analyzed for the DB concentration. The experiments were carried out at different initial DB concentrations (50
and 85 mg/L) and adsorbent dosages (0.251.0 g/L). Additionally,
adsorption experiments were conducted using the simulated textile wastewater and two different WS dosages (0.50 and 1.0 g/L).
2.4.2. Adsorption equilibrium isotherms
Adsorption equilibrium isotherms were determined at 25 C, pH
values of 4, 7 and 10, and at 35 C, at pH 7. DB dye aqueous solutions (initial concentrations in the range 85250 mg/L) were stirred
with WS (dosages ranging from 0.25 to 4.0 g/L) in Erlenmeyer
asks. pH was initially adjusted and readjusted when necessary
to a constant value (0.3). After several days of contact time (10
days for the 0.25 g/L dosage and 7 days for the others, based on
adsorption kinetics results), DB concentration in the liquid phase
was analyzed and the amount of dye adsorbed per gram of WS
calculated from a mass balance equation. Equilibrium adsorption
data were also determined using the simulated textile wastewater. In order to evaluate the effect of the NaCl and the auxiliary
dyeing chemicals, two simulated wastewaters were prepared: (i)
simulated wastewater containing salt and auxiliary chemicals (as
described in Section 2.1), and (ii) simulated wastewater prepared
without NaCl addition. Adsorption isotherms for these simulated

Fig. 2. Schematic representation of SBR experimental set-up.

wastewaters were determined at pH 7, 25 C and varying WS dosage

(0.253.0 g/L).
2.5. SBR and WSSBR studies
The treatment of the simulated textile wastewater was studied
in a SBR by two different ways: (i) conventional SBR biological treatment; (ii) biological treatment combined with adsorption onto WS,
hereafter designated as WSSBR.
2.5.1. Experimental set-up
SBR experimental setup, illustrated in Fig. 2, consisted in: a
cylindrical acrylic reactor (20 cm diameter; 45 cm total height),
with a conical bottom and a valve; a mechanical stirrer; two peristaltic pumps (feed and extraction); a compressed air line with an
on/off regulating valve, linked to a control system, and ne bubble
diffusers placed in the bottom of the reactor; an OD probe and meter
(YSI models 5739, 58); pH and ORP electrodes (Hanna Instruments)
and a thermocouple. For simplicity, Fig. 2 does not show individually each measuring device. A computer and a software developed
in LabView 5.0 were used to automatically control the SBR operation (time periods of each stage, stirring, valves and pumps), in
accordance with the user dened information. The pH, temperature, OD and ORP were continuously monitored, in the mixed liquor
inside the reactor. In the reaction stage, OD was also controlled
through automatic opening/closing of the regulating valve, in order
to maintain OD levels in the reactor in a predened concentration
range.
2.5.2. SBR startup and operation
The inuent for SBR and WSSBR was the simulated textile
wastewater (Section 2.1, Table 1). The COD/BOD5 ratio, calculated
as 4.5, indicates a moderate/low biodegradability and conrms
the important contribution of the recalcitrant dye to the total
organic matter, thus justifying the use of a combined biological and
adsorption process. The need of nutrients or alkalinity adjustment
was evaluated using the empirical relation BOD5 :N:P:alkalinity of
100:5:1:50 [30]. According to the chemical analysis (Table 1), it was
only found necessary to correct alkalinity, and then only sodium
bicarbonate was added to the textile simulated wastewater.

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

77

Table 2
Experimental conditions used in SBR and WSSBR studies.
Runs

Cycle time (h)

Time period (min)

F

WS (g/L) addition

Biomass/WS purge

IA
IB
IC
ID
IE

12
16
8
20
24

60
60
60
60
60

450
690
240
900
1140

150
150
120
180
180

48
48
48
48
48

12
12
12
12
12

(b)
(b)
(b)
(b)
(b)

WSSBR IIA
IIB
IIC

24
24
24

60
60
60

1140
1140
1140

180
180
180

48
48
48

12
12
12

1,0 g/L (a)

1,0 g/L (a)
1,0 g/L (a)

No purge
(c)
(d)

SBR

(a) Addition of WS (5 g) in the start of reaction stage, in all cycles; (b) extraction of biomass only when an excess is detected by VSS analysis (in fact, no excess was observed
and no purge was done); (c) purge of mixed biomass-WS every cycle; (d) purge of mixed biomass/WS in a cycle out of three cycles.

The biomass used for the SBR startup was obtained from a
Portuguese wastewater treatment plant (Rabada, Santo Tirso),
mostly treating textile industrial wastewaters. The biomass in the
biological reactor is then somewhat acclimated to this kind of
wastewaters. The fresh biomass (2 L) was introduced in the reactor and 3 L of the simulated wastewater was added. The operation
of SBR started immediately according to the conditions dened in
Table 2. In the ten rst cycles, some acclimation of the biomass still
occurs, and so they were not considered in the evaluation of SBR
performance.
SBR was operated with typical cycles and stages: lling (F), reaction (aeration) (R), settling (S), extraction (E) and idle (I). Different
experimental trials were performed. Experimental runs designated
as I consisted only in the biological treatment (SBR), and runs IAIE
were conducted to evaluate the effect of the reaction time period.
Experimental runs II correspond to the biological treatment plus
WS addition (WSSBR), and IIAIIC were conducted in order to
evaluate different means to extract sludge. Table 2 presents the
conditions used in each experimental run and respective cycles. For
each set of conditions, the reactor was operated for some cycles till
a pseudo-stationary state was obtained.
The duration of SBR cycles was varied between 8 and 24 h, and
reaction times between 4 and 19 h, as these times are typically used
in industrial wastewater treatment and referred in scientic literature [17,3134]. The length of the settling phase was also varied
accordingly, since it typically takes about one-fth of the total cycle
time [35].
In the lling stage, 3.25 L of inuent (simulated textile wastewater) was fed into the reactor at constant ow (54.2 mL/min). When
the reaction stage started, the mixed liquor in the reactor made up
a total volume of 5 L (3.25 L of fresh inuent and 1.75 L of biomass
ocs, from the previous cycle).
The reaction occurred under stirring (400 rpm), with controlled
aeration to ensure OD levels between 1.5 and 2.5 mg/L. In WSSBR
operation (experimental runs II), 5 g WS was added to the mixed
liquor at the beginning of the reaction stage. In SBR and WSSBR
operation, the concentration of biomass and solids was monitored
at the middle of the reaction time, by measuring the TSS and VSS
contents in the mixed-liquor. In certain cycles, the behavior of
biomass sedimentation was evaluated by SVI determination. In
order to evaluate living biomass and inhibitory effects, in cycles
no. 13, 34 and 46, 5 mL-samples (in duplicate) were withdrawn
from mixed-liquor and used for respirometric tests (YSI Incorporated 5300 Biological). Dissolved oxygen (saturation percentage)
was monitored for 1020 min. The specic oxygen uptake rate was
calculated, by normalizing the oxygen consumption by VSS and
organic matter (TOC).
In the next stage, biomass and WS were allowed to settle under
static conditions and with no aeration. The claried liquid was
then extracted (3.25 L) and 1.75 L of settled biomass was left in

the reactor (extraction phase). The claried liquid of each cycle

was analyzed for dye concentration and TOC. Composite samples
(equal volumes of claried efuents from successive cycles in each
experimental run, stationary state) were analyzed for TSS, COD and
BOD5 .
When necessary, the excess of biomass and adsorbent was
extracted (using the valve or manually) in the idle stage.
3. Results
3.1. Adsorption studies
3.1.1. Adsorption kinetics
Fig. 3 presents adsorption kinetic data obtained in different
experimental conditions. A fast concentration decay in the liquid
phase was observed in the rst hours of contact time. A gradual
decrease in the adsorption rate was then observed up to equilibrium was reached. Using a WS dosage of 0.25 g/L, the time required
to achieve equilibrium for initial DB concentrations (Cin ) of 50 and
85 mg/L, was 5 and 9 days, respectively (Fig. 3a). However, in both
cases, 90% of the maximum removal was found after a 3-day contact
time. With the increase in the WS dosage (from 0.25 to 1.0 g/L), the
time required to attain equilibrium decreased from 9 days to 1 day
(Fig. 3b), which means a strong effect of the adsorbent dosage on
the adsorption dynamics. In a practical situation, the use of a higher
dosage is then favorable, considering the shorter time needed for
adsorption and the lower residual concentration achieved.
The adsorption kinetics of DB proved to be slower than other
reported in literature for the same adsorbent and a reactive dye
[27], which is explained by the higher dimensions of direct dye
molecules. Very different equilibrium times have been reported
in literature for the adsorption of direct dyes. Values in the range
of the obtained in the present work (36 h) were reported on the
adsorption of Direct Blue 71 by wheat shells [36], using much higher
adsorbents dosages (10 g/L). Other studies referred contact times of
only 3 h for Direct Navy Blue 106 adsorption, onto activated carbon
from orange peel [12].
Using the simulated textile wastewater (Fig. 3c), equilibrium
was attained faster (about 12 h), compared with the pure aqueous dye solutions. In this case, a signicant decrease in the amount
adsorbed was observed and a faster saturation occurred. In aqueous
DB solutions, maximum adsorbed amounts (experimental values
obtained when equilibrium was achieved) were 169 and 78 mg/g
(WS dosages of 0.50 and 1.0 g/L, respectively), and in the simulated
textile wastewater, 16 and 20 mg/g were found. The other compounds in the aqueous media may be also adsorbed and due to their
lower molecular weight (compared with DB dye), a faster saturation
was observed. Khaled et al. [12] also compared the use of an articial textile wastewater (containing NaCl and Na2 SO4 salts) with
a pure dye solution. The results obtained showed no effect on the

78

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

1.0

1.0
Aqueous DB solutions

(a)

WS=0.25 g/L pH 7 T=25 C

0.8

Aqueous DB solutions (b)

Cin=85 mg/L pH 7 T=25 C

0.8

WS=0.25 g/L

0.6

Cin=85 mg/L

C/Cin

C/Cin

Cin=50 mg/L
0.6

WS=1.0 g/L

0.4

0.4

0.2

0.2

0.0

WS=0.50 g/L

0.0
0

6
time (d)

10

12

6
time (d)

10

12

1.0
(c)
Cin=85 mg/L
pH 7 T=25 C

0.8

Simulated
wastewater:
WS=0.50 g/L

C/Cin

0.6
0.4

WS=1.0 g/L

0.2

Aqueous DB dye
solution:
WS=0.50 g/L
WS=1.0 g/L

0.0
0

12
16
time (h)

20

24

Fig. 3. Adsorption kinetics of DB dye onto WS (a) at different initial dye concentrations, (b) at different adsorbent dosages, and (c) at different adsorbent dosages, comparing
the use of simple aqueous dye solutions and the simulated textile wastewater: experimental data, pseudo-rst () and pseudo-second order () modelling.

time required to reach equilibrium and a slight increase in the dye

adsorbed amount when the simulated real wastewater was used. In
the present study, a different behavior was observed. The difference
observed is probably related to the dyeing auxiliary chemicals used
in present work (and not used in the above referred study). This
question was elucidated through the equilibrium results (Section
3.1.2).
Lagergrens pseudo-rst-order [37] and pseudo-second order
[38,39] equations (Eqs. (1) and (2), respectively) were tted to the
experimental data by nonlinear regression, using Fig. P software
from Biosoft. The regression was based on the minimization of the
sum of squared residuals, between experimental and estimated q
values. Pseudo-rst and pseudo-second order parameters and the
respective uncertainty were calculated. The determination coefcient (R2 ) was also obtained, in order to evaluate the quality of the
ttings.
q = qe [1 exp (k1 t)]
q = qe

k2 qe t
1 + k2 qe t

(1)

(2)

In these equations, q and qe denote the DB adsorbed amounts per

unit mass of adsorbent, at a time t and at equilibrium, respectively;
k1 and k2 are the kinetic constants of pseudo-rst and pseudosecond order models.
Results obtained in mathematical ttings are presented in
Table 3 and Fig. 3. Both models described reasonably well the
adsorption kinetics, but pseudo-second order model yielded better ts: higher R2 -values and predicted qe values closer to the
experimental ones. The kinetic constant k2 increased with the
increase in initial adsorbate concentration, from 50 to 85 mg/g,
due to the increase in the driving force for adsorption, and
increased signicantly with the increase in the WS dosage from
0.5 to 1.0 g/L.

3.1.2. Adsorption equilibrium

Adsorption isotherms for DB dye removal by WS are presented
in Fig. 4. Experimental data obtained using the pure DB dye aqueous solutions showed appreciable amounts of DB dye adsorbed,
especially for neutral and acidic conditions (Fig. 4a). A strong
afnity of the WS to the dye results from the high slope of the
equilibrium curves, at very low dye concentrations.

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

79

Table 3
Adsorption kinetic modelling: parameters (standard error) and determination coefcient (R2 ).
Pseudo-rst order
Cin (mg/L)
50 a
85 a
85 a
85 a
85 b
85 b
a
b

Pseudo-second order

WS dosage(g/L)

k1 104 (min1 )

qe (mg/g)

R2

k2 105 (g mg1 min1 )

qe (mg/g)

R2

0.25
0.25
0.50
1.0
0.50
1.0

9.47 2.4
27.5 5.6
10.3 1.5
82.5 8.7
141 22
255 49

187 12
228 8
159 6
73.5 2.5
14.5 0.6
17.8 0.7

0.91
0.91
0.96
0.97
0.96
0.90

0.811 0.250
1.61 0.30
0.815 0.104
13.4 1.17
118 17
185 28

203 12
243 6
178 4
81.9 1.6
16.2 0.5
19.2 0.5

0.94
0.97
1.0
0.99
0.99
0.97

Aqueous DB dye solutions.

Simulated textile wastewater.

400

DB dye
aqueous solutions:

400

T=25 C pH 7
T=25 C pH 4

200

DB aqueous dye
solution

300
qe (mg/g)

qe (mg/g)

(b)

(a)

600

nada
Simulated wastewater:

200

auxiliary
chemicals

100

T=25 C pH 10
T=35 C pH 7

0
0

50

100
Ce (mg/L)

150

auxiliary
chemicals + NaCl

0
0

200

25

50
75
Ce (mg/L)

100

Fig. 4. Equilibrium isotherms for the adsorption of DB dye by WS, (a) at different pH and temperature, and (b) comparing aqueous dye solution with simulated textile
wastewaters: experimental data, () Langmuir and (- - -) Freundlich modelling.

Table 4
Equilibrium modelling: parameters (standard error) and determination coefcient (R2 ).
Langmuir

T( C)
25
25
25
35

pH
4
7
10
7

Freundlich

kL 10 (L/mg)

Qm (mg/g)

KF (mg11/n g1 L1/n )

R2

73.5 28.5
20.1 5.1
15.9 6.1
52.7 12.3

600 24
339 14
98.7 5.5
334 7

0.96
0.98
0.96
0.99

14.8 8.8
7.80 2.48
4.32 0.22
14.5 4.4

428 72
179 28
32.4 1.7
238 21

0.92
0.94
1.0
0.98

Adsorption isotherms are usually described by mathematical

equations relating the equilibrium concentration (Ce ) with the
adsorbed amount, per unit mass of adsorbent (qe ). The well-known
Langmuir [40] (Eq. (3)) and Freundlich [41] (Eq. (4)) models were
tted to the equilibrium experimental data (Fig. 4a, Table 4). Fig. P
(Biosoft) software was used for the nonlinear regressions.
qe =

Qm KL Ce
1 + KL Ce

qe = KF Ce 1/n

(3)
(4)

The Langmuir model parameters are Qm , the maximum adsorption capacity (monolayer coverage), and KL , a constant related to
the energy of adsorption. Freundlich model parameters are KF and
n (n > 1), constants related to the adsorption capacity and intensity, respectively. Table 4 presents the Langmuir and Freundlich
parameters obtained.
Fairly good ttings were achieved by applying both models,
but slightly better for the Langmuir model. The isotherms (Fig. 4a)
showed well-dened plateaus, depicting monolayer coverages in
accordance to Langmuir model theory. Temperature, in the range
2535 C (believed to be usually found in dyehouse efuents), did
not signicantly affect the amount of dye adsorbed. On the contrary, pH showed a strong effect on the adsorption extent, with
maximum removal at the lowest pH tested (pH 4). At pH 4 and 7,
maximum adsorption capacities were very high, 600 and 339 mg/g,
respectively, decreasing to 98.7 mg/g, at pH 10. This kind of metal
hydroxide waste has shown to act as a buffer [42,43]. In this work,

WS also showed buffering capacity. Based on the adsorption runs

performed for the equilibrium study and also in preliminary experiments (not shown), if the initial pH range of the dye solution was
410, and no further adjustment in pH was done, the nal pH would
be around 7; when initial pH was 11, a nal pH near 10 was attained.
This means that if the pH is not controlled to a constant value, and
if initial pH values in the range 410 are used, no major variations in the adsorbed amount are predicted. In the adsorption of
DB anionic dye onto the WS two mechanisms are involved: electrostatic attraction, between the charged adsorbate and adsorbent
surface, and ligand exchange mechanism, where metal hydroxide
waste (in this case, rich in hydrous oxides of Fe), being of amphoteric nature, presents anion exchange capacities with the dye. The
pHZPC of WS is around 7, which means that in acidic conditions,
surface charge of WS is positive and thus suited to DB dye attraction. At higher pH, especially at the alkaline pH of 10 (above pHZPC ),
the negatively charged adsorbent hinders the anionic dye adsorption via electrostatic attraction, and then total adsorbed amount
decreased.
Adsorption capacities obtained in the present work were compared to others reported in literature for direct azo dyes. A waste
sludge generated in removal of heavy metal by electrocoagulation presented an adsorption capacity of 293 mg/g [43], which is
in the order of the values obtained in the present work. Agricultural wastes, as garlic peel [44] and rice husk [45] presented
lower adsorption capacities: 37.96 mg/g and 26 mg/g, respectively.
WS used in the present work still presented better adsorption
capacities than the reported values for commercial activated

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

carbons, 7.69 mg/g [46] and 18.7 mg/g [47], and better than activated carbons prepared from agricultural wastes, 4358 mg/g [48]
and 31108 mg/g [12].
Fig. 4b shows the effect of auxiliary dyeing chemicals and NaCl
(present in the simulated textile wastewaters), on DB dye adsorption. Experimental values obtained in the presence and absence
of NaCl were relatively close, and then, this salt exerted little
effect on the adsorption of DB dye. Auxiliary chemicals, on the
contrary, showed a signicant and negative effect on the dye
removal. Experimental data obtained with this simulated wastewater congured an atypical isotherm form, which is explained by
competitive adsorption. With the exception of the lubricant agent,
both sequestering and wet agents are anionic and then can compete with DB dye to the active sites. Within the range of conditions
tested and using the simulated wastewater containing NaCl and the
dyeing auxiliaries, maximum adsorption removal by the WS was
47 mg/g (using 1.5 g/L of WS dosage). Total dye removal (100%) was
found using a minimum WS dosage of 2.0 g/L. It is important to refer
that in this simulated wastewater, the maximum concentrations of
auxiliary dyeing chemicals (inside the typical practice range) were
used, and further, it was considered as hypothesis that 100% of these
chemicals were lost to the efuent. A somewhat extreme situation
was then evaluated here.
3.2. SBR and WSSBR studies
The results obtained in the daily SBR and WSSBR operation are
presented in Fig. 5 and Table 5.
3.2.1. SBR
IAIE experiments were conducted to evaluate the SBR treatment performance, under different aeration/reaction times. Run IA
(cycle time 12 h; aeration 7.5 h) initiated with the startup of the
reactor (VSS = 1.8 g/L). The high TOC and color removal observed
in the rst cycles were due to the dilution effect of the water
contained in the inoculated biomass as well as to the adsorption of dye onto the fresh biological ocs. In the rst 10 cycles,
there was biomass acclimation, and the pseudo-stationary state
was attained in cycle no. 11. During the operation of SBR (IAIE),
the concentration of biomass was in the range 1.31.8 g/L (1.5 g/L
on average). Since only small variations were found (sometimes
growing, sometimes decreasing) no purge of biomass was carried
out. Other authors also reported no excess biomass in the treatment of real textile dyes in SBR [24]. The pH in the mixed liquor
and in the treated efuent were in the range 6.57.2, which is
similar to the optimum bacteria growth pH range, 6.57.5 [30],
and complies with the legislated discharge limits. The specic
oxygen uptake rate, obtained by respirometry, was 2.0 0.2 and
4.2 0.2 mgO2 L min1 mgVSS 1 mgTOC 1 , respectively, for cycles
no. 13 (IA) and no. 34 (ID). The duplication on the uptake rate
depicts an increasingly adapted biomass. Average TSS values in
the treated efuent varied between 8 and 22 mg/L, below the Portuguese discharge limits (60 mg/L). Comparing the TSS obtained in
each run with the respective time of the settling stage, no relation
seems to exist between both variables. Settling characteristics of
the biomass also varied along the operation. SVI was evaluated in
cycles no. 13 (IA) and no. 37 (IE) and 219 mL/g and 167 mL/g were
respectively found. These values indicated relatively poor settling
properties, especially in IA runs, but an improvement along the
operation of the SBR.
Under the conditions tested, 1018% of dye, 3449% of organic
carbon, 2558% of COD and 5379% of BOD5 removals were
achieved biologically (Table 5). Fig. 6 shows the performance of
the SBR as a function of the reaction time. In general, the treatment
efciency increased slightly with the reaction time. The use of 16 h
cycles (11.5 h of reaction) is, however, a good option, since the loss

in efciency is minimal compared to 24 h cycles (19 h of reaction).

Nevertheless, in practical situations, the use of 1 day-cycle time is
more adequate for routine monitoring. In the treatment of industrial wastewaters in SBR, reaction times are usually in the range
424 h [34]. In scientic literature, cycle times of 24 h and aerobic reaction times in the range 1923 h have been reported for the
treatment of synthetic and real textile wastewaters [17,32,49].
According to Portuguese legislation for textile wastewater discharge, color should be invisible after 1:40 dilution. With biological
SBR treatment, dye removal was rather limited and not enough to
meet this goal. Color removal was in the range 1018%, which is
similar to the 15% found by Ong et al. [21] for an azo orange dye.
According to the characteristics provided by the supplier, BOD5 and
COD of DB dye are 25 and 500 mg O2 per gram of dye, respectively.
These values indicated a very low potential to mineralization (complete biodegradation), and therefore, adsorption onto the biological
ocs or degradation by rupture of specic bonds (without corresponding decrease in BOD or COD) will be important contributions
for the overall color removal.
3.2.2. WSSBR
Experimental runs II consisted in biological treatment combined with WS daily addition, working at a 24 h-cycle time, which
includes a reaction time of 19 h. In cycles IIA, no purge was done,
because it was aimed to provide a sufcient time to bacteria adaption to the WS and avoid a signicant loss of biomass in rst purges.
After 3 cycles, the amount of WS in the reactor was already considerable and the purge would not represent a signicant biomass
loss. Then, in cycles IIB daily purge was done, aiming at the extraction of approx. 5 g (equivalent to the added adsorbent), in order
to maintain an almost constant TSS content in the reactor. This
was reasonably achieved, with TSS in the range 4.75.1 g/L (average 4.8 g/L) and VSS in the range 1.61.7 g/L (Fig. 5). TOC and
COD removals in IIA were about 77%, showing a quite better performance than that obtained in cycles IAIE. Color removal also
presented a much better efciency, but decreased from 67 to 49%
during cycles IIB. The observed successive decrease in IIB was
attributed to the fact that the purge does not favor the extraction
of the oldest adsorbent. According to kinetic data, the reaction
time of 19 h is more than enough to equilibrium attainment. However, it is important to note that the saturated adsorbent which
remained in the reactor from one cycle to another, will contacted
with a higher concentration of dye in the next lling, and then an
additional amount of adsorption occurred, until the new equilibrium. Considering this aspect, and in order to allow a better avail
of the adsorbent capacity, it was decided to start IIC runs, purging
the solids once in each three cycles. In these operation cycles, it
was intended to purge 15 g of solids each time, but due to practical

100

TOC
COD

80
% Removal

80

Color
Dye
BOD
5
BDO5

60
40
20
0
0

10
15
Reaction time (h)

20

Fig. 6. SBR treatment performance for different reaction time.

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

100

IA

IB

IC

ID

12 h

16 h

8h

20 h

IE IIA IIB

IIC

24 h 24 h

24 h

24 h

81

15.0
12.0
9.0

50
6.0
25

SS (g/L)

% Removal

75

3.0

0.0
0

10

15

20

Color
Dye Removal

25
30
Cycle

35

TOC Removal

40

45

TSS

50

55

VSS

Fig. 5. Experimental results obtained in the SBR and WSSBR operation (experimental conditions in Table 2).
Table 5
Chemical analysis of treated water and performance of SBR and WSSBR operation.
Run

IA
IB
IC
ID
IE
IIA
IIB
IIC

Cyclesa

114(1114)
1522 (1822)
2329 (2329)
3035 (3035)
3638 (3638)
3942b
4346 (4346)
4755 (4755)

TOC(mg/L)

78.6
64.2
71.4
60.3
57.1
28.241.2
26.6
26.0

COD(mgO2 /L)

247
154
172
139
158

76.8
66.9

BOD5 (mgO2 /L)

34
21
25
20
15

6.9
4.5

TSS(mg/L)

22
12
8
16
14

58
48

% Removal
Color

TOC

COD

BOD5

16
15
10
16
18
4567
60
69

34
46
38
48
49
6378
77
79

25
53
48
58
52

77
80

53
71
66
73
79

91
94

a
Operation cycles; cycles inside brackets are the cycles where pseudo-stationary state was achieved and treated water from these cycles was used to prepare the composite
sample for analysis.
b
The aim was not to establish pseudo-stationary state, but only to provide adaptation of biomass to the WS; only TOC and color were monitored in the treated efuent.

problems in the bottom valve and in manual extraction, lower

amounts were withdrawn and a certain accumulation of solids
occurred (Fig. 5). Even so, slightly better removals were obtained
for TOC, COD and BOD5 (6980%); dye removal increased from 45%
(cycle no. 47) to 79% (cycle no. 55), seeming to stabilize around 77%.
Color, after proper 40-factor dilution, as required by legislation, was
not visible in the treated efuents from IIB and IIC cycles.
With the addition of WS, faster settling also occurred. SVI was
measured and values of 30 mL/g (IIB) and 27 mL/g (IIC) were found.
Clearly these values should not be directly compared with the SVI
for IA and IE cycles, due to the contribution of WS. TSS in the treated
efuent, although respecting limits for discharge, were higher than
in IAIE. In either case, in practical situations, and if necessary, a
nal ltration can be employed to remove the ne particles.
The operation of WSSBR was found to be feasible. The specic oxygen uptake rate, obtained by respirometry in cycle no. 46
(IIB), was 2.8 0.1 mgO2 L min1 mgVSS 1 mgTOC 1 , which indicates
some degree of inhibition (comparing with cycle 34).
The WSSBR system was used in the present study to conduct
a screening test of treatability of a simulated textile wastewater.
In fact, a considerable enhancement of the treatment performance
occurred in terms of color and organic matter removal. However,
some practical limitations during the execution of tests II have to
be remarked: the short number of cycles conducted for each one of
the experimental conditions, and the difculty of nding an adequate strategy to purge the solids. It is also important to refer that,
if the biomass growth in each cycle was null (as it was observed
during biological operation IAIE), the WSSBR cannot operate for a
long time, since the solids purge will gradually remove the biomass.
In a practical situation, the operation of WSSBR will require the
addition of an external carbon source to promote biomass growth
and overcome this operation problem. The addition of glucose and
acid acetic is commonly reported in literature for textile wastewater treatment [49,50], but in the scope of WSSBR operation

requires further studies. The performance of WSSBR should also

be evaluated in comparison with a biological treatment followed
by adsorption, in two separated reactors connected in series. In
the WSSBR conguration, advantages are essentially related to
the synergetic effect, compact conguration, exibility and easy pH
control to favorable biological conditions and accepted discharge
limits, as WS has buffering capacity to pH values around 7. On
the other hand, the use of separated reactors for biological treatment and adsorption can be favorable, since optimum conditions
(residence time and pH, for example) can be used independently.
4. Conclusions
WS showed to be a promising adsorbent for direct dyes. Maximum adsorption capacities (calculated from Langmuir ttings)
were in the range 98.7600 mg/g. At 25 C, and pH 7 the adsorption capacity was 339 mg/g. The performance of the WS adsorbent
was, however, found to be considerably reduced by the presence
of dyeing auxiliary chemicals present in real textile wastewaters.
NaCl showed little effect on the adsorption extent.
The aerobic biological treatment of simulated textile wastewater in the SBR conrmed a limited decolorization efciency
(1018%), although a signicant organic carbon removal (2552%
COD) was achieved. Performing SBR biological treatment in simultaneous with WS addition, a signicant enhance in the performance
of the reactor was obtained, as concerns TOC, COD, BOD5 and color
removals. Regarding dye removal, with the WS addition, average
efciencies of 6069% were achieved. This work is somewhat innovative though further experiments are necessary to explore the
performance of this kind of combination.
Acknowledgements
The
authors
are
grateful
to
Portuguese
Foundation for Science and Technology (FCT) for S. Santos

82

S.C.R. Santos, R.A.R. Boaventura / Journal of Hazardous Materials 291 (2015) 7482

scholarship (SFRH/BD/18477/2004). This work was co-nanced

by FCT/MEC and FEDER under Programme PT2020 (Project
UID/EQU/50020/2013).

[25]

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