Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557

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Process Safety and Environmental Protection

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

Performance evaluation of activated neem bark for

the removal of Zn(II) and Cu(II) along with other
metal ions from aqueous solution and synthetic
pulp & paper industry effluent using fixed-bed
reactor

Utkarsh Maheshwari a , Suresh Gupta b,∗

a Department of Chemical Engineering Birla Institute of Technology and Science (BITS), Pilani 333031, Rajasthan,
India
b Department of Chemical Engineering Birla Institute of Technology and Science (BITS), Pilani 333031, Rajasthan,

India

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

Article history: The fixed-bed adsorption experiments are performed for the removal of copper [Cu(II)] and
Received 11 December 2015 zinc [Zn(II)] by utilizing activated neem bark as an adsorbent. The present study demon-
Received in revised form 21 April strated the effect of various parameters such as inlet concentration, adsorbent mass and
2016 inlet flowrate for the removal of Cu(II) and Zn(II) from aqueous solutions. Various kinetic
Accepted 10 May 2016 parameters such as EBRT, stoichiometric capacity, breakthrough time, etc. are evaluated
Available online 20 May 2016 using the experimental data. Yoon–Nelson and Yan model available in the literature are
also validated with the experimental data. The developed adsorbent is also tested for the
Keywords: simultaneous removal of multiple metal ions [Cr(VI), Cu(II), Zn(II), Pb(II), Ni(II) and Cd(II)]
Zinc from the synthetically prepared pulp & paper industrial effluent.
Copper © 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Yoon model
Column studies
Pulp & paper industry
Multiple metal ions

1. Introduction The effluent from most of the metal processing industries

contain a divalent form of Copper [Cu(II)] and Zinc [Zn(II)].
Water pollution is leading to a new row with an increase in The effluent from pulp & paper industries contains several
industrialization and utilization of heavy metals in diverse heavy metals such as Cr, Cu, Zn, Pb, Ni, Cd, etc. (Thippeswamy
operations. The industries such as textile, pulp & paper, tan- et al., 2012). Although, copper and zinc are among the essen-
ning, electroplating, fertilizer production, washing of brass tial nutrients required for the human being for the proper
units, etc. are using different heavy metals in their processes. metabolism activity, excessive dosage can lead to the lethal
The effluent from these industries are rich in heavy metal ions consequences. Cu(II) is having carcinogenic and mutagenic
and are considered as the primary source of water pollution properties, which can lead to a vital condition for lung cancer.
(Gupta and Maheshwari, 2014; Maheshwari, 2013; Maheshwari This type of problems is very frequent among the personnel
and Gupta, 2011, 2016b) working in a vicinity exposed to the Cu(II) containing spray

∗
Corresponding author. Tel.: +91 1596 515224; fax: +91 1596 244183.
E-mail addresses: [email protected], [email protected] (U. Maheshwari),
[email protected] (S. Gupta).
http://dx.doi.org/10.1016/j.psep.2016.05.009
0957-5820/© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
548 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557

A low-cost adsorbent, capable for the removal of multi-

Abbreviation ple metal ions may be an added advantage to the process.
A number of researchers are working for the development of
AAS Atomic Absorption Spectrophotometer (AA- the adsorbents using different low-cost resources such as rice
7000, Shimadzu) husk (Mohan and Sreelakshmi, 2008), tamarind seeds (Gupta
Ac area underneath the curve (Cad vs t) and Babu, 2009b), wheat bran (Kaya et al., 2014), fly ash (Gupta
ai Yan model parameters and Babu, 2010b), sawdust (Larous and Meniai, 2012), tree
Cad adsorbed concentration, mg L−1 bark (Salem and Awwad, 2014), tea factory waste (Wasewar,
C0 initial inlet concentration, mg L−1 2010), cashew nut shell (SenthilKumar et al., 2011), tomato
Ce exit concentration, mg L−1 waste (Yargıç et al., 2015), etc. as a potential alternative to
EBRT empty bed residence time, s the commercially available adsorbents. Many of the reported
KYN,i rate constant of ith component for Yoon–Nelson studies are limited to batch mode for the pollutant removal
model, h−1 from wastewater streams. Most of the adsorbents are tested
mt total amount of metal fed to the column, g for the treatment of the single metal ion rich effluent streams.
nANB nano-porous activated neem bark However, in the real situation, the industrial wastewater con-
Q flowrate, ml min−1 tains multiple metal ions. Hence, there is a need to develop an
q0,i Yan model parameters adsorbent from a low-cost material which can be efficiently
qt total amount of metal adsorbed in time t, mg employed for the removal of multiple metal ions from indus-
g−1 trial effluent. The low-cost adsorbent being nanoporous may
Ra adsorbent exhaustion rate provide the high surface area which results in the increase in
S total percentage removal of metal active sites for the adsorption process to occur.
t sampling time, h The present work deals with the exploitation of the devel-
tb breakpoint time, h oped adsorbent (activated neem bark) for the remediation
tf final time, h of Cu(II) and Zn(II) from aqueous solutions in a fixed-bed
tt equivalent time corresponding to the stoichio- column. Continuous experiments are conducted to study
metric capacity of the fixed-bed column, h the effect of inlet concentration, adsorbent dosage (column
W amount of adsorbent utilized height) and the inlet flowrate on the removal of Cu(II) and
y fraction of unused bed length Zn(II). The Yoon–Nelson and Yan model are utilized to deter-
mine different kinetic parameters using the experimental
Greek symbol data. Furthermore, the developed adsorbent is utilized for the
i time corresponding to the 50% of ith adsorbate treatment of synthetically prepared pulp & paper industry
breakthrough, h effluent containing Cr(VI), Cu(II), Zn(II), Pb(II), Ni(II) and Cd(II)
as per the composition reported in the literature.

(Liang et al., 2010). The high intake of Zn(II) can lead to nausea, 2. Materials and methods
loss of appetite and irritability (Naiya et al., 2009). The speci-
fied allowable limit provided by United States Environmental The neem bark is gathered from the Birla Institute of Tech-
Protection Agency (US-EPA) for the presence of Cu(II) and Zn(II) nology and Science (BITS), Pilani region. The bark is washed,
in safe potable water is 1.0 and 5 mg L−1 respectively (USEPA, crushed and screened out to obtain the required particle
2009). Similarly, the permissible limit for Cr, Cd, Ni and Pb in size (dp ≈ 1.2 mm) particles. The specified particles are treated
potable water is 0.1, 0.005, 0.1 and 0.015 mg L−1 respectively chemically with H2 SO4 (98%) (1:1 weight%) and later kept for
(USEPA, 2009). drying at 70 ◦ C for 24 h. Further, the dried neem bark is washed
The negative impact of these metals present in the effluent with purified water for the removal of any free acid on the sur-
streams led to a need for proper treatment technique before face. The activated neem bark has already been characterized
it get discharged to the external water bodies such as lakes, and reported in one of the earlier studies and is termed as
ponds, rivers, etc. The effluents from industries must contain nANB (Maheshwari and Gupta, 2015).
pollutants in their permissible limit, failing to which can lead Stock solutions of 1000 mg L−1 for various metals are pre-
to severe environmental regulations breach. pared using stoichiometric amount of different salts (Table 1).
There are various techniques available for the removal of The stock solutions are further diluted to the desirable concen-
heavy metals from industrial wastewaters. These range from trations using distilled water. A fixed-bed glass column, 1 inch
electrolysis (Khattab et al., 2013), ion exchange (Shek et al., in diameter is utilized for the continuous studies. The column
2009), polymer inclusion membrane (Kaya et al., 2016), sol- is properly packed with the nANB. A pictographic depiction of
vent extraction (Zhang and Zhu, 2012), chemical precipitation the column is given in Fig. 1.
(Kim et al., 2008), membrane separation (Salahi et al., 2013), The effect of inlet concentration (50 and 100 mg L−1 ) on the
adsorption (Gangadhar et al., 2012; Maheshwari and Gupta, Cu(II) and Zn(II) removal is evaluated by performing contin-
2016a; Olgun and Atar, 2011), etc. Out of all the available meth- uous experiments, keeping the adsorbent dosage and inlet
ods, adsorption is proven to be a more reliable method (Atar flowrate constant at 75 gm and 10 ml min−1 respectively. The
et al., 2012; Bhargavi et al., 2015; Maheshwari and Gupta, 2015). effect of adsorbent dosage on the removal of Cu(II) and Zn(II) is
The basic advantage of adsorption on other techniques is its studied by varying the adsorbent dosage as 25, 50, 75, 100, 125,
cost effectiveness and ability to handle large volume & multi- 150 and 175 gm while maintaining the flowrate at 10 ml min−1
ple metal ion solutions. Adsorption is much more effective for and inlet concentration constant at 50 mg L−1 respectively. The
the simultaneous removal of multiple pollutants (Maheshwari effect of flowrate is assessed by keeping the inlet concentra-
and Gupta, 2016b). tion and adsorbent dosage at 50 mg L−1 and 75 g while varying
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557 549

Table 1 – Stoichiometric amounts of different metals used for the stock solution and composition of synthetically
developed pulp & paper industrial effluent.
Metal Complex salt Formulae Mol. wt. Amount used for Conc. in pulp & paper
(g) 1000 mg L−1 in 1 L (g) industrial effluent (mg L−1 )

Cd(II) Cadmium Nitrate tetra-hydrate Cd(NO3 )2 ·4H2 0 236.42 2.7442 1.44

Cr(VI) Potassium Dichromate K2 Cr2 O7 294.18 2.8287 59.02
Cu(II) Copper Sulphate Penta-hydrate CuSO4 ·5H2 O 249.69 3.9293 7.72
Ni(II) Nickel nitrate hexa-hydrate (NiNO3 )2 ·6H2 O 290.79 4.9545 3.49
Pb(II) Lead Nitrate Pb(NO3 )2 331.2 1.608 1.54
Zn(II) Zinc Sulphate Hepta-hydrate ZnSO4 ·7H2 O 287.55 4.397 2.9

the flowrate in the range of 5–15 ml min−1 . The optimum pH The various parameters are calculated using different
(≈2) obtained from the batch experiments are considered dur- equations and are stated below as Eqs. (1)–(7) (Maheshwari
ing the overall study (Arun et al., 2013). The pulp & paper and Gupta, 2016b).
industrial effluent is synthetically developed as per the com-
 t=ttotal
position given in Table 1. Continuous experiment is performed QAc Q
qt = = Cad dt (1)
for the simultaneous multiple metal ions removal from the 1000 1000 t=0
synthetically developed pulp & paper industrial effluent. The
metal concentration in the inlet (before adsorption) and out-
C0 Qtt
let (after adsorption) are analyzed using Atomic Absorption mt = (2)
1000
Spectrophotometer (AA-7000, Shimadzu).
qt tf
tt = (3)
3. Modeling of fixed-bed adsorption mt
process
qt
S= × 100 (4)
mt
The performance of the fixed-bed adsorption column can be
estimated in different ways. The most significant ones are the
Bed volume
utilization of bed up to the breakthrough time and the shape EBRT = (5)
Volumetric flow rate of liquid
of the breakthrough curve. The breakthrough time represents
the time required by column to achieve the breakthrough,
mass of adsorbent in column
beyond which the column is not allowed to operate to main- Ra = (6)
volume treated at breakthrough
tain the permissible limits of pollutants in outlet streams.
The breakthrough curves are represented in terms of the ratio
tb
of exit to inlet concentration (C/C0 ) with respect to time of y=1− (7)
tt
adsorption (Gupta and Babu, 2009a; Gupta and Babu, 2010a;
Maheshwari and Gupta, 2016b)
There are various models available in the literature, out of
which Yan and Yoon–Nelson model are utilized here to explain
the fixed-bed column behavior.

1 Metal solution feed tank 3.1. The Yoon–Nelson model

1 2 Outlet control valve 1
3 Liquid Rotameter
4 Fixed-bed column The Yoon–Nelson model (Maheshwari and Gupta, 2016b; Yoon
5 Outlet control valve 2 and Nelson, 1984) is one of the simplest model which is
6 Outlet collection tank
2 3 7 Base employed to address the adsorption and the breakthrough
trend of the gaseous pollutant on the adsorbents. In that
respect is an assumption stating that the decay rate in the
possibility of adsorption for all adsorbate particles is in accor-
dance to the chance of sorbate sorption and the prospects of
4 a sorbate breakthrough on the adsorbent (Calero et al., 2009).
The Yoon–Nelson model for a solo element arrangement is
given by Eq. (8) (Keshtkar et al., 2012).

Ci 1
= (8)
C0,i 1 + exp(KYN,i × t − KYN,i × i )
5

3.2. The Yan model

6
7 Yan used the experimental results to statistically analyze
them by incorporating some physical aspects of the process.
Fig. 1 – Fixed-bed adsorption setup for the removal of This model turns out to be more trustworthy as more accurate
metals from wastewater. in explaining the entire breakthrough curve. Mathematical
550 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557

1.0 1.0

0.8 0.8

0.6 0.6

C/C0
C/C 0

0.4 0.4

0.2 0.2

50 mg L 50 mg L
100 mg L 100 mg L
0.0 0.0
0 50 100 150 200 0 20 40 60 80 100 120 140
Time (h) Time (h)

(a) (b)
Fig. 2 – The effect of inlet concentration on the removal of (a) Cu(II), (b) Zn(II) using nANB.

form of Yan model is represented by Eq. (9) (Keshtkar et al., adsorption respectively with an increase in inlet concentra-
2012; Maheshwari and Gupta, 2016b; Yan et al., 2001) tion. The overall percentage removal of Zn(II) obtained as
62.48% at 50 mg L−1 while 55.85% at 100 mg L−1 . The total time
Ci 1 essential for the process is corresponding to the stoichio-
=1− a (9)
C0,i 1 + (((0.001 × Co,i × Q)/(qo,i × M)) × t) i metric capacity of the fixed-bed and is observed to decrease
from 99.1 to 75.9 and 75.0 to 72.6 h for Cu(II) and Zn(II)
adsorption respectively when the inlet concentration varies
4. Results and discussion
from 50 to 100 mg L−1 . This is due to the availability of addi-
tional molecules of metal ions in the solution for the same
The detailed development procedure and characterization of
amount of adsorbent to get saturated (Gupta and Babu, 2009a;
nANB is already discussed in a previous study (Maheshwari
Maheshwari and Gupta, 2016b; Riazi et al., 2014).
and Gupta, 2015). The developed nANB is successfully utilized
for the removal of Cr(VI) from aqueous solutions in batch and
continuous mode (Maheshwari and Gupta, 2015, 2016b). The 4.2. Effect of inlet flowrate
present work deals with the utilization of the developed nANB
for the remediation of Cu(II) and Zn(II) in continuous mode. The effect of inlet flowrate on the breakthrough curve for Cu(II)
The developed nANB is also tested for the removal of multiple and Zn(II) adsorption is evaluated at different flowrate ranges
metal ions from synthetically prepared pulp & paper industrial from 5 to 15 ml min−1 while maintaining the constant adsor-
effluent. bent dosage and initial metal ion concentration as 75 g and
50 mg L−1 respectively (Fig. 3(a) and (b)).
4.1. Effect of inlet concentration The breakthrough time for Cu(II) and Zn(II) adsorption is
obtained as 31.93 and 32.07 h at 5 ml min−1 while 13.46 and
The effect of the initial concentration (50 and 100 mg L−1 ) 25.06 h at 15 ml min−1 respectively (Table 2). This decrease in
on the shape of the breakthrough curve for Cu(II) and Zn(II) breakthrough time may be due to the availability of large quan-
adsorption from aqueous solution is given in Fig. 2(a) and (b) tity of metal ions for the same number of active sites in the
respectively. The parameters for Cu(II) and Zn(II) adsorption same duration. The total adsorbed amount of Cu(II) and Zn(II)
are evaluated for all the experimental sets (Table 2). increases from 1086 to 1656 and 841 to 1810 mg respectively,
It is noted that, with an increase in the initial metal as the flowrate changes from 5 to 15 ml min−1 . The steepness
concentration from 50 to 100 mg L−1 , there is a decline in of the breakthrough curve also increases with an increase in
breakthrough time from 27.5 to 20.37 and 19.81 to 8.88 h for the flowrate. This increase in the amount adsorbed and the
the Cu(II) and Zn(II) adsorption respectively. This may be due to steepness may be due to the better mixing at high flowrate,
the additional amount of metal ions passing through the fixed- which reduces the film thickness over the adsorbent. This sub-
bed in per unit time. This contributes to the faster saturation sequently reduces the film mass transfer resistance for metal
of the bed and further reduction in breakthrough time. The transfer from bulk to adsorbent surface (Gupta, 2008) and leads
adsorption exhaustion rate for the removal of Cu(II) and Zn(II) to higher rate of mass transfer. With a rise in the flowrate
are 6.31 and 4.55 g L−1 at 50 mg L−1 while 14.08 and 6.14 g L−1 from 5 to 15 ml min−1 , the residence time reduces from 30.41
at 100 mg L−1 respectively. The increase in the concentration to 10.14 sec. The decrease in the contact time affects the
in bulk liquid phase increases the driving force (concentration proper utilization of the adsorbent. The part of the unused
difference) for mass transfer which further increases the rate bed length raises from 56.27 to 64.17% with a rise in the inlet
of diffusion. This also results in the increase of diffusion and flowrate from 5 to 15 ml min−1 for Cu(II) adsorption. The per-
mass transfer coefficients for metal transport from liquid to centage removal of Cu(II) and Zn(II) decreases from 57.10 to
solid phase. This leads to the relatively higher rate of transfer 54.93 and 61.10 to 57.90% respectively, with an increase in the
of the molecules from the aqueous phase to solid surface of flowrate from 5 to 15 ml min−1 . The total time required cor-
nANB (Aksu and Gönen, 2004; Gupta and Babu, 2009a). responding to the stoichiometric capability of the adsorbent
The fraction of the unused bed length increases from bed decreases from 126.8 to 67.0 and 91.7 to 69.5 h for Cu(II)
60.01 to 76.97 and 42.58 to 50.51% for Cu(II) and Zn(II) and Zn(II) adsorption respectively with the change in flowrate
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557
Table 2 – Different parameters for the removal of Cu(II) and Zn(II) from aqueous solution in a fixed-bed adsorption column.
Metal S.No. Co Q W tt tf tb qs qt mt S EBRT Ra y
Units mg L−1 ml min−1 gm h h h mg metal per gm mg mg % s gm L−1 %
of Adsorbent

1 50 10 75 99.1 198 19.8148 19.82 1488.6 2973.60 50.06 15.21 6.31 0.6001
2 100 10 75 75.9 150 8.875 30.83 2305.02 4554.69 50.61 15.21 14.08 0.7697
3 50 5 75 126.8 222 31.9266 14.60 1085.7 1901.42 57.10 30.41 7.83 0.5627
4 50 15 75 67.0 122 13.4595 22.54 1656.45 3015.61 54.93 10.14 6.19 0.6417
5 50 10 25 70.9 183 6.0357 33.35 823.5 2126.27 38.73 5.07 6.90 0.7828
For Cu(II)
6 50 10 50 85.1 185 11.3097 23.62 1173.6 2552.15 45.98 10.14 7.37 0.7128
7 50 10 100 134.5 246 23.608 22.18 2205.12 4034.08 54.66 20.28 7.06 0.6807
8 50 10 125 163.6 270 46.075 24.15 2973.33 4907.54 60.59 25.35 4.52 0.5421
9 50 10 150 189.7 298 53.9158 24.23 3621.15 5689.73 63.64 30.41 4.64 0.5549
10 50 10 175 209.4 320 69.317 23.52 4112.55 6283.35 65.45 35.48 4.21 0.4948

1 50 10 75 75.0 120 27.5 19.16 1405.5 2249.40 62.48 15.21 4.55 0.4258
2 100 10 75 72.6 130 20.37 32.93 2432.85 4356.17 55.85 15.21 6.14 0.5051
3 50 5 75 91.7 150 32.069 11.54 840.075 1374.83 61.10 30.41 7.80 0.4444
4 50 15 75 69.5 120 25.0575 24.80 1810.35 3126.64 57.90 10.14 3.33 0.3938
5 50 10 25 44.0 90 8.748 26.45 645.3 1319.97 48.89 5.07 4.76 0.6031
For Zn(II)
6 50 10 50 47.4 100 13.889 18.47 675 1423.02 47.43 10.14 6.00 0.5488
7 50 10 100 109.1 190 36.273 19.09 1879.5 3273.09 57.42 20.28 4.59 0.4301
8 50 10 125 145.3 270 49.94 19.30 2346.3 4359.48 53.82 25.35 4.17 0.3790
9 50 10 150 171.1 280 70.136 21.30 3135.6 5132.16 61.10 30.41 3.56 0.3416
10 50 10 175 188.9 300 79.032 20.80 3569.85 5668.21 62.98 35.48 3.69 0.3486

551
552 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557

1.0 1.0

0.8 0.8

0.6 0.6
C/C

C/C
0.4 0.4

0.2 0.2
5 ml min
5 ml min
10 ml min 10 ml min
15 ml min 15 ml min
0.0 0.0
0 50 100 150 200 250 0 20 40 60 80 100 120 140 160
Time (h) Time (h)

(a) (b)
Fig. 3 – The effect of inlet flowrate on the removal of (a) Cu(II), (b) Zn(II) using nANB.

from 5 to 15 ml min−1 . The average saturation loading (qs ) for and breakthrough time may be due to the availability of more
Cu(II) and Zn(II) adsorption are found as 18.99 and 18.5 mg g−1 number of active sites offered for the adsorption of the metal
respectively. The saturation loading values estimated from ions (Deng et al., 2014). This also increases the overall per-
continuous studies for Cu(II) removal are less than the values centage adsorption of Cu(II) and Zn(II) from 38.73 to 65.45 and
obtained from batch studies (21.23 mg g−1 ) (Maheshwari et al., 48.89 to 62.98% respectively, with increase in the adsorbent
2013). However, the saturation loading value for Zn(II) removal mass from 25 to 175 g. The residence time also increases from
estimated from continuous studies is significantly higher than 5.07 to 35.48 sec with an increase in the adsorbent mass. Aver-
the values obtained from the batch studies (11.904 mg g−1 ) age stoichiometric capacity for the adsorption of Cu(II) and
(Arun et al., 2013). Zn(II) are evaluated as 24.41 and 20.65 mg g−1 , respectively. The
attained stoichiometric capacity values from the fixed-bed
4.3. Effect of mass of adsorbent adsorption experiments are better than the values obtained
from the batch experiments (Arun et al., 2013; Maheshwari
The effect of mass of adsorbent on the shape of the break- et al., 2013). The total time for adsorption which is analogous
through curve on Cu(II) and Zn(II) adsorption is studied. to the stoichiometric capacity of the fixed-bed increases from
The breakthrough curves for different mass of adsorbent i.e. 70.9 to 209.4 and 44 to 188.9 h for Cu(II) and Zn(II) adsorption,
25–175 g are shown in Fig. 4(a) and (b) for Cu(II) and Zn(II) respectively when the adsorbent mass increases from 25 to
adsorption respectively. Adsorption parameters for fixed-bed 175 g. This may be due to the availability of more amount
adsorption experiments are calculated and reported in Table 2. of adsorbent for the adsorption. The fraction of unused bed
With an increase in the adsorbent mass from 25 to 175 g, length decreases from 78.28 to 49.48 and 60.31 to 34.86% for
the breakthrough time increases from 6.03 to 69.32 and 8.75 Cu(II) and Zn(II) adsorption, respectively, with a rise in the
to 79.03 h for Cu(II) and Zn(II) adsorption respectively [Fig. 4(a) adsorbent mass from 25 to 175 g (Table 2). The unused bed
and (b)]. The increase in the breakthrough time may be due length is constant for a given particle size of the adsorbent
to the longer bed length (Rout et al., 2014). It is observed that and fluid velocity. With the change in the bed height, the
with an increase in the adsorbent mass, the total amount of length of unused bed remains constant. Hence, the fraction of
Cu(II) and Zn(II) adsorbed is increased from 824 to 4113 and 645 the unused bed length decreases with an increase in the bed
to 3570 mg respectively. The increase in the adsorbed amount height (McCabe et al., 2007). With the rise in the adsorbent

1.0 1.0

0.8 0.8

0.6 0.6
C/C0

C/C0

0.4 25 gm 0.4 25 gm
50 gm 50 gm
75 gm 75 gm
100 gm 100 gm
0.2 0.2
125 gm 125 gm
150 gm 150 gm
175 gm 175 gm
0.0 0.0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Time (h) Time (h)

(a) (b)
Fig. 4 – The effect of adsorbent dosage on the removal of (a) Cu(II), (b) Zn(II) using nANB.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557 553

Table 3 – Different parameters for the Yoon–Nelson and Yan models for Cu(II) and Zn(II) removal.
Metal Inlet conc. Co Flowrate Mass of Yoon–Nelson model Yan model
(mg L−1 ) (ml min−1 ) adsorbent (g) −1 2 2
KYN,i (h )  i (h) R Chi q0,i ai R2 Chi2

50 10 75 0.1292 46.824 0.998 0.00039 0.00031 5.780 0.999 0.00009

100 10 75 0.1460 36.165 0.998 0.00046 0.00047 4.936 0.999 0.00005
50 5 75 0.0816 69.540 0.997 0.00054 0.00023 5.400 0.999 0.00006
50 15 75 0.1741 35.431 0.997 0.00058 0.0035 5.848 0.998 0.00033
50 10 25 0.1504 25.940 0.997 0.00066 0.00049 3.284 0.999 0.00027
For Cu(II)
50 10 50 0.1305 36.058 0.998 0.00041 0.00035 4.191 0.999 0.00005
50 10 100 0.0849 69.310 0.998 0.00041 0.00034 5.578 0.999 0.0002
50 10 125 0.0676 96.323 0.998 0.00032 0.00038 6.159 0.999 0.00008
50 10 150 0.0586 114.772 0.995 0.00082 0.00038 6.379 0.998 0.00039
50 10 175 0.0518 129.451 0.993 0.00116 0.00037 6.376 0.997 0.00052

50 10 75 0.1163 44.584 0.996 0.00076 0.00029 4.862 0.999 0.00014

100 10 75 0.1648 38.765 0.998 0.00032 0.00051 6.103 0.999 0.00022
50 5 75 0.0881 53.738 0.996 0.00072 0.00017 4.426 0.999 0.00006
50 15 75 0.1563 38.413 0.998 0.00038 0.00038 5.695 0.999 0.00013
50 10 25 0.1838 20.797 0.997 0.00079 0.00039 3.218 0.998 0.00047
For Zn(II)
50 10 50 0.1575 28.795 0.999 0.00022 0.00028 4.196 0.999 0.00028
50 10 100 0.0897 59.757 0.998 0.00038 0.00029 5.103 0.999 0.00008
50 10 125 0.0705 74.868 0.997 0.00058 0.00029 5.034 0.999 0.00007
50 10 150 0.0649 100.958 0.998 0.00043 0.00033 6.371 0.999 0.00012
50 10 175 0.0569 113.716 0.996 0.00078 0.00032 6.231 0.998 0.00032

mass from 25 to 175 g, there is a decrease in the adsorbent mass transfer resistance. The decrease in  i with the increase
exhaustion rate from 6.90 to 4.21 and 4.76 to 3.69 g L−1 for in the inlet concentration is a result of rapid saturation of
Cu(II) and Zn(II) adsorption, respectively. This decrease with nANB adsorbent in the fixed-bed column (Aksu and Gönen,
the increase in adsorbent mass is due to the increase in the 2006; Sugashini and Begum, 2013).
time required for the saturation of the bed (Gupta, 2008). With the increase in the adsorbent mass to 175 from 25 g,
The average saturation loading capacity from Table 2 of the value of  i increases to 129.451 from 25.94 h and to 113.716
the overall process for Cu(II) adsorption is obtained to be from 20.797 h for Cu(II) and Zn(II) adsorption, respectively. This
around 23.38 mg g−1 . This saturation loading capacity is in increase in the  i may be due to the presence of larger num-
agreement to the maximum adsorption capacity (21.6 mg g−1 ) ber of active sites for the same driving force, which leads to
obtained from the batch experiments (Maheshwari et al., 2013; the delay in saturation of the nANB surface (Aksu and Gönen,
Maheshwari et al., 2015). While, from Table 2, the average sat- 2006).
uration loading capacity for Zn(II) adsorption is obtained as
21.38 mg g−1 which is higher in comparison to the maximum 4.4.2. The Yan Model
adsorption capacity (11.906 mg g−1 ) obtained from the batch The Yan model parameter, ai , increases with an increase in
experiments (Arun et al., 2013; Maheshwari et al., 2015). the inlet flowrate and adsorbent mass for the Cu(II) and Zn(II)
adsorption. The ai increases from 3.287 to 6.376 and 3.218 to
4.4. Estimation of the various kinetic parameters 6.231 with the increase in adsorbent mass from 25 to 175 g for
using column data modeling Cu(II) and Zn(II) adsorption respectively.

The experimental-data obtained from the continuous exper- 4.4.3. Concluding Remarks
iments are validated with the Yoon–Nelson and Yan models The coefficient of determination (R2 ) value is higher for the Yan
utilizing the non-linear regression technique. The Origin 6.0 model, however trend is no specific trend obtained for model
software is used for the purpose. The evaluated parametric parametric values with the change of operating parameters,
values for Yoon–Nelson and Yan models for Cu(II) and Zn(II) which is not the case of Yoon–Nelson model. Furthermore,
adsorption are provided in Table 3. the R2 for Yoon–Nelson model is very close to that obtained
for Yan model. Therefore, for the scaling up the existing pro-
4.4.1. The Yoon–Nelson Model cess, the applicability of Yoon–Nelson model is more suitable.
It is observed that when the inlet concentration is increased For these models, the constants are estimated using the labo-
from 50 to 100 mg L−1 , the value of, a Yoon–Nelson rate con- ratory scale experimental data of breakthrough curve. Further,
stant (KYN,i ) increases from 0.129 to 0.146 h−1 and from 0.116 these model equations could be utilized to get the break-
to 0.165 h−1 for Cu(II) and Zn(II) adsorption, respectively. The through curve at different operating conditions (pilot scale and
value of KYNi also increases from 0.082 to 0.174 and 0.088 to commercial scale) which could be helpful in designing of the
0.156 h−1 with the rise in flowrate from 5 to 15 ml min−1 for scaled-up fixed-bed adsorption column.
Cu(II) and Zn(II) adsorption, respectively (Table 3),. The value
of  i is decreased from 46.824 to 36.165 and 44.584 to 38.765 h 5. Utilization on synthetic pulp & paper
with the increase in inlet concentration to 100 from 50 mg L−1 industrial effluent
for Cu(II) and Zn(II) adsorption, respectively. The higher value
of KYN,i at higher inlet concentration and flow rate may be due The applicability of the developed nANB for the simulta-
to the increase in driving force for adsorption and decrease in neous elimination of multiple metal ions present in the
554 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557

Table 4 – Parameters for the removal of various metal ions from aqueous solution in a fixed bed adsorption column.
Metal C0 Q W tt tf tb qs qt mt S EBRT Ra y
mg L−1 ml min−1 g h h h mg g−1 mg mg % s g L−1

Cr(VI) 59.2 10 75 99.52 198 9.425 24.73 1776.84 3535.03 50.26 15.21 13.26 0.8195
Cu(II) 7.72 10 75 104.55 198 34.96 16.52 255.72 484.28 52.80 15.21 3.58 0.8693
Zn(II) 2.9 10 75 75.52 198 34.342 0.99 50.118 131.40 38.14 15.21 3.64 0.1986
Cd(II) 1.44 10 75 64.90 198 4.393 0.25 18.378 56.07 32.78 15.21 28.45 0.7995
Pb(II) 1.54 10 75 155.47 198 22.136 0.71 112.8 143.66 78.52 15.21 5.65 0.6182
Ni(II) 3.49 10 75 60.61 198 6.397 0.50 38.856 126.93 30.61 15.21 19.54 0.6427

At overall breakpoint
Cr(VI) 59.2 10 75 99.52 198 4.393 24.73 1776.84 3535.03 50.26 15.21 28.45 0.9159
Cu(II) 7.72 10 75 104.55 198 4.393 3.42 255.72 484.28 52.80 15.21 28.45 0.9206
Zn(II) 2.9 10 75 75.52 198 4.393 0.68 50.118 131.40 38.14 15.21 28.45 0.8506
Cd(II) 1.44 10 75 64.90 198 4.393 0.25 18.378 56.07 32.78 15.21 28.45 0.7995
Pb(II) 1.54 10 75 155.47 198 4.393 0.72 112.8 143.66 78.52 15.21 28.45 0.9251
Ni(II) 3.49 10 75 60.61 198 4.393 0.50 38.856 126.93 30.61 15.21 28.45 0.7539

Table 5 – Comparison of adsorption capacity for the removal of different metals using various materials.
Adsorbent Metal ion Type of Adsorption Reference
study capacity, mg g−1

Multi-carboxyl-functionalized silica gel Cu (II) Batch 47.07 Li et al. (2014)

nANB Cr(VI), Cu(II), Zn(II), Pb(II), Column 43.71 Present study
Ni(II), and Cd(II)
Passion fruit shell Cd(II) Column 42.6 Chao et al. (2014)
Multi-carboxyl-functionalized silica gel Cd (II) Batch 41.48 Li et al. (2014)
Passion fruit shell Cu(II) Column 40.8 (Chao et al., 2014)
Multi-carboxyl-functionalized silica gel Zn (II) Batch 39.96 Li et al. (2014)
Mansonia wood sawdust Pb(II) Batch 39.5 Ofomaja et al. (2010)
Multi-carboxyl-functionalized silica gel Ni (II) Batch 30.80 Li et al. (2014)
Sugarcane Bagasse Pb(II) Column 28.1 Chao et al. (2014)
nANB Cr(VI) Batch 26.95 Maheshwari and Gupta (2015)
Iron coated Zeolites Cd, Cr, Cu, Pb, and Zn Batch 26.66 Nguyen et al. (2015)
Sugarcane Bagasse Cd(II) Column 26.3 Chao et al. (2014)
Passion fruit shell Ni(II) Column 25.8 Chao et al. (2014)
Chemically activated carbon residue Cu(II) Batch 23 Runtti et al. (2014)
Sugarcane Bagasse Cu(II) Column 23 Chao et al. (2014)
Zeolites Cd, Cr, Cu, Pb, and Zn Batch 22.81 Nguyen et al. (2015)
Lemon peel Co(II) Batch 22 Bhatnagar et al. (2010)
nANB Cu(II) Batch 21.6 Maheshwari et al. (2015)
Fly ash Cr(VI) Batch 21 Gupta and Babu (2010b)
Sugarcane Bagasse Ni(II) Column 16.1 Chao et al. (2014)
Activated carbon prepared from Van Zn(II) Batch 12.91 Depci et al. (2012)
apple pulp
Modified corn stalk Cd(II) Batch 12.73 Zheng et al. (2010)
nANB Zn(II) Batch 11.904 Maheshwari et al. (2015)
Impregnated granular activated carbon Cu, Fe, Mn, Zn Batch 7.4235 Satyro et al. (2016)
Iron coated Zeolites Cd, Cr, Cu, Pb, and Zn Column 4.44 Nguyen et al. (2015)
Zeolites Cd, Cr, Cu, Pb, and Zn Column 2.43 Nguyen et al. (2015)

synthetically developed pulp & paper industrial effluent is 1.0

evaluated. A continuous experiment is performed by main-

taining the inlet concentration of different metal ions in 0.8
adsorbate as provided in Table 1. The breakthrough curves
for the concurrent adsorption of all the metal ions are shown
0.6
in Fig. 5. The fixed bed adsorption parameters for different
Ce/C0

metal ions are evaluated by considering their individual per-

missible limits and are reported in Table 4. It is noted that 0.4
Cr(VI)
the breakthrough time for the individual metal ions (consider- Cu(II)
ing individual breakpoint concentration) are obtained as 34.96, 0.2 Zn(II)
Cd(II)
34.34, 22.14, 9.43, 6.40 and 4.39 h for Cu(II), Zn(II), Pb(II), Cr(VI),
Pb(II)
Ni(II) and Cd(II), respectively. The percentage removal is esti- Ni(II)
0.0
mated as 78.52, 52.80, 50.26, 38.14, 32.78 and 30.61% for Pb(II), 0 20 40 60 80 100 120 140
Cu(II), Cr(VI), Zn(II), Cd(II) and Ni(II) respectively when the fixed Contact time, t (h)
bed column is allowed to reach the saturation till 198 h. The
saturated loading capacity for Cr(VI), Cu(II), Zn(II), Pb(II), Ni(II), Fig. 5 – Breakthrough curve for the simultaneous removal
and Cd(II) are obtained as 24.73, 16.52, 0.99, 0.71, 0.50 and of multiple metal ions.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557 555

Fig. 6 – SEM of (a) fresh nANB (Maheshwari and Gupta, 2015), (b) used nANB & (c) EDS analysis of the used nANB.

0.25 mg g−1 respectively. The presence of all metal ions on the On comparing with the adsorption capacity of nANB for each
surface of the adsorbent is confirmed by SEM and EDS analy- metal ions, the adsorption capacity found to be increased for
sis given in Fig. 6(b) and (c) respectively. The overall saturation the simultaneous multiple metal ions adsorption. This sup-
loading capacity is evaluated as 43.71 mg metals per g of adsor- ports the utilization of the developed nANB for the adsorption
bent. This saturation loading capacity is higher as compared of multiple metal pollutants from industrial effluents.
to many of the other materials used for the single or multiple The saturated nANB utilized on the synthetically devel-
metal ion removals. The comparison of total saturation capac- oped pulp & paper industry effluent is also characterized using
ity of developed adsorbent with the other adsorbents reported Scanning Electron Microscope (SEM) and Energy Dispersive
in the literature is given in Table 5. Spectroscopy (EDS) (ZEISS EVO Series SEM Model EVO 50 at
The effluent containing multiple metal ions are allowed to Indian Institute of Technology (IIT), Delhi). The SEM image of
be released into the environment, when the each of the pol- the fresh nANB and used nANB are provided in Fig. 6(a) and
lutants present in the effluent must be in their permissible (b) respectively, while the EDS image of the used adsorbent
limit. The fixed bed adsorption is required to be stopped, if is given in Fig. 6(c). It is observed that the nano pores avail-
the concentration of any metal ion in the effluent exceeds able on the surface of fresh nANB [Fig. 6(a)] are not visible on
their permissible limit. Due to this reason, the parameters the surface of saturated nANB [Fig. 6(b)]. This confirms that
are re-estimated by considering the lower value of break- the active sites available on the surface are utilized during
through time i.e. 4.393 h among all metal ions and are reported adsorption. The EDS analysis [Fig. 6(c)] confirms the pres-
in Table 4. The overall unused bed length of the column is ence of multiple metal ions on the surface of the developed
obtained as 16.56%, which is very less in comparison to any nANB. This EDS analysis also supports the higher adsorp-
of the column studies considering individual metal ions. The tion of Pb and Cr in comparison to other metal ions. The
saturation loading capacity also reduces to 24.73, 3.42, 0.72, presence of other impurities such as Sulphur, Magnesium,
0.68, 0.50, and 0.28 mg g−1 for Cr(VI), Cu(II), Pb(II), Zn(II), Ni(II) Cobolt, Chlorine, Silicon, etc. is due to the salts utilized for the
and Cd(II) respectively. The overall saturation loading capac- preparation of stock solution and the EDS coating & analysis
ity of nANB is obtained as 30.30 mg metals per g of adsorbent. procedure.
556 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 547–557

6. Conclusion sugarcane bagasse in a fixed-bed column. J. Ind. Eng. Chem.

20, 3408–3414.
Deng, L., Shi, Z., Li, B., Yang, L., Luo, L., Yang, X., 2014. Adsorption
The developed nANB has been successfully utilized for the
of Cr(VI) and phosphate on Mg–Al hydrotalcite supported
removal of single [Cu(II) and Zn(II)] and multiple metal ions
kaolin clay prepared by ultrasound-assisted coprecipitation
[Cr(VI), Cu(II), Pb(II), Zn(II), Ni(II) and Cd(II)] from aqueous solu- method using batch and fixed-bed systems. Ind. Eng. Chem.
tion in a fixed-bed adsorption column. The variance in the Res. 53, 7746–7757.
breakthrough curves confirms the significant dominance of Depci, T., Kul, A.R., Önal, Y., 2012. Competitive adsorption of lead
three parameters on Cu(II) and Zn(II) adsorption. The break- and zinc from aqueous solution on activated carbon prepared
through time is found increasing as the flowrate decreases, from Van apple pulp: study in single- and multi-solute
systems. Chem. Eng. J. 200–202, 224–236.
adsorbent mass increases and initial metal concentration
Gangadhar, G., Maheshwari, U., Gupta, S., 2012. Application of
decreases. It is concluded that the sharpness of the curve nanomaterials for the removal of pollutants from effluent
is unchanged by the change in mass of adsorbent while it streams. Nanosci. Nanotechnol. – Asia 2, 140–150.
is considerably affected by the change in flowrate and inlet Gupta, S., 2008. Theoretical & Experimental Investigations for
metal concentration. The column behavior is well understood Removal of Pollutants using Adsorption. Department of
by the values of the parametric various of adsorption col- Chemical Engineering, Birla Institute of Technology &
Science(BITS) – Pilani, Pilani Campus, Pilani, pp. 223.
umn such as breakthrough time, adsorption exhaustion rate,
Gupta, S., Babu, B.V., 2009a. Modeling, simulation, and
total stoichiometric capacity, fraction of unused bed length,
experimental validation for continuous Cr(VI) removal from
etc. The average saturation loading capacity for Cu(II) and aqueous solutions using sawdust as an adsorbent. Bioresour.
Zn(II) adsorption are obtained as 23.38 mg g−1 and 21.38 mg g−1 Technol. 100, 5633–5640.
respectively, which are in agreement to the adsorption capac- Gupta, S., Babu, B.V., 2009b. Utilization of waste product
ity obtained from the batch experiments. The Yoon–Nelson (tamarind seeds) for the removal of Cr(VI) from aqueous
model is found suitable for the scaling up fixed-bed adsorption solutions: equilibrium, kinetics, and regeneration studies. J.
Environ. Manage. 90, 3013–3022.
process for Cu(II) and Zn(II) adsorption from aqueous solu-
Gupta, S., Babu, B.V., 2010a. Experimental investigations and
tions. The developed adsorbent is successfully investigated
theoretical modeling aspects in column studies for removal of
for the multiple metal ions removal from a synthetically devel- Cr(VI) from aqueous solutions using activated tamarind
oped pulp & paper industrial effluent and it is concluded that it seeds. J. Water Resour. Prot. 2, 706–716.
is more suitable for multiple metal ions removal in comparison Gupta, S., Babu, B.V., 2010b. Experimental, kinetic, equilibrium
to single metal ions removal. and regeneration studies for adsorption of Cr(VI) from
aqueous solutions using low cost adsorbent (activated flyash).
Desal. Water Treat. 20, 168–178.
Acknowledgment Gupta, S., Maheshwari, U., 2014. Copper (II) removal using
activated neem bark from waste water as a low cost
adsorbent: column studies. In: 2014 AIChE Annual Meeting,
The authors would like to thank the Department of Science & Atlanta, GA, USA.
Technology (DST), New Delhi and the University Grants Com- Kaya, A., Onac, C., Alpoguz, H.K., Yilmaz, A., Atar, N., 2016.
mission (UGC), New Delhi for their monetary help. Removal of Cr(VI) through calixarene based polymer inclusion
membrane from chrome plating bath water. Chem. Eng. J. 283,
141–149.
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