Journal of Molecular Liquids 240 (2017) 313–321

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Journal of Molecular Liquids

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

Air agitated tapered bubble column adsorber for hazardous dye

(crystal violet) removal onto activated (ZnCl2) carbon prepared
from bamboo leaves
Sandip K. Ghosh a,b, Asim K. Hajra a, Amitava Bandyopadhyay a,⁎
a
Department of Chemical Engineering, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009. India
b
Indian Institute of Chemical Engineers, Jadavpur, Kolkata 700 032, India

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

Article history: Adsorption of crystal violet, a hazardous dye, from aqueous solution on activated carbon prepared from carbon-
Received 31 March 2017 ized bamboo leaves powder with ZnCl2 activation is reported in this article using a novel air agitated tapered bub-
Received in revised form 13 May 2017 ble column adsorber. The adsorbent prepared was characterized by determining the pHPZC, multipoint BET
Accepted 15 May 2017
surface area and pore analyses, SEM analysis and FTIR analysis. The pHPZC of the prepared adsorbent was 6.6.
Available online 18 May 2017
The multipoint BET area measured was 291.3 m2/g. Batch experiments were conducted as functions of initial con-
Keywords:
centration (50 to 150 mg/L), contact time (1 to 40 min), adsorbent dose (0.2 to 0.9 g/L) and air flow rate (8.75
Activated carbon from bamboo leaves × 10−5 to 70.00 × 10−5 m3/s). The maximum percentage removal observed was 99.99% at equilibrium time of
Air agitated adsorber 20 min under optimum conditions. The maximum adsorption capacity observed was 393.16 mg/g. Results
Biosorption followed Freundlich isotherm (amongst seven isotherms examined) and pseudo-second order kinetics with
Crystal violet intra-particle diffusion. The observed pressure drop was ranging from 2719 to 2837 N/m2 and the energy dissi-
Tapered bubble column pation per unit volume of colored liquid was ranging from 82.75 to 634.51 W/m3 in the system studied. Very high
removal and adsorption capacity of the prepared adsorbent observed in the novel tapered air agitated bubble col-
umn adsorber is the novelty achieved in the present investigation.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
Organic dyes are produced and used in different processes such as
dye manufacture, textile, tannery, dyeing and bleaching. The waste
water containing color is generated from these processes that require
proper treatment before discharge. Different treatment methods for col-
ored effluent, such as chemical oxidation, coagulation, photochemical
oxidation, biological treatment, membrane separation and adsorption
are reported [1]. In water and waste water treatment, the adsorption
seems an important step in treating colored effluent like all other pollut-
ants. Several investigations were carried out on the removal of crystal
violet using activated carbon prepared from biological origins and
others under conventional batch operating mode using Erlenmeyer
flasks such as jute fiber carbon [2], coniferous pinus bark powder [3],
phosphoric acid activation carbon [4], sulphuric acid activated carbon
[4], magnetically modified activated carbon [5], MCM-41 [6], saw dust
[7], magnetic nanocomposite [8], activated carbon prepared from
waste apricot [9], nanoporous carbon prepared from tomato paste
waste [10] so on and forth.
⁎ Corresponding author.
E-mail address: amitava.bandy@gmail.com (A. Bandyopadhyay).
Besides the conventional batch method, investigations using air agi-
tated adsorber (i.e., three phase single/multi-stage bubble columns) for
the removal of pollutants from synthetic waste water stream have
beginning to gain attention of the researchers. For instance, adsorptive
removal of atrazine on powder activated carbon in a bubble column
[11,12] and Zn(II) from acid rock drainage on clinoptilolite in a three
phase slurry bubble column [13] have so far been reported in the liter-
ature. Critical appraisal of these literatures indicates that the adsorptive
removal of organic (except dye) and inorganics (heavy metals) mainly
using bubble columns with uniform circular cross-section as air agitated
adsorber has so far been reported. However, adsorptive removal of dyes
has not yet been reported in an air agitated tapered bubble column ad-
sorber. The proposed system uses air for the purpose of agitation of the
liquid as an alternative to the conventional batch system. Tapered bub-
ble column has gained attention of the researchers mainly for use as a
three phase slurry reactor in biochemical reaction [14] and for the
abatement of particulate and/or SO2 emission control as well as for the
investigation on hydrodynamics and mass transfer for gas-liquid sys-
tems [15]. In the present investigation, an inverted cone i.e., a tapered
column is designed and developed for use as an adsorber. In this tapered
column, the air is introduced into the deep pool of slurry (containing the
dye solution and the solid adsorbent particles) to agitate the slurry. The
air disintegrated into swarm of bubbles, would generate large surface

http://dx.doi.org/10.1016/j.molliq.2017.05.064
0167-7322/© 2017 Elsevier B.V. All rights reserved.
314 S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321

air axially upward. As a result, the superficial gas velocity at the bottom
Nomenclature
is relatively higher than that at the top that ensures the suspension of
larger particles, while smaller particles are prevented from being
aR Redlich–Peterson isotherm constant (L/mg)
entrained at the top (having lower terminal particle settling velocity)
bT Temkin constant related to the heat of sorption indicat-
[16]. The increase in the flow area in the upward direction of the column
ing 1/bT as the adsorption potential of the adsorbent,
was reported to yield lower pressure drop at increased gas flow rate
J/mol
than in a conventional column with uniform cross section [15]. An at-
Ce Equilibrium concentration of CV, mg/L
tempt has therefore, been made to investigate in to the adsorption of
Cf Final concentration, mg/L
CV, onto activated carbon prepared from carbonized bamboo leaves
C0 Initial concentration of CV, mg/L
powder with ZnCl2 activation as an adsorbent under batch operating
Ct Concentration of CV at any time t, mg/L
mode in the proposed air agitated tapered bubble column adsorber.
Df Liquid film diffusion constant, min−1
The performances of the system are characterized as functions of vari-
E Sorption energy, kJ/mol
ous operating variables followed by data validation on well-known iso-
F(t) Fractional attainment of adsorption equilibrium ½¼ qqt ,
e therms and kinetics models. Finally, the calculated pressure drop and
dimensionless the calculated energy dissipation per unit volume of colored liquid (syn-
G Redlich–Peterson isotherm exponent thetic waste water) in the tapered system are also discussed.
I Intercept in Weber-Morris intra-particle diffusion
model, mg/g
k1 Pseudo-first order adsorption kinetic rate constant, 2. Materials and methods
min−1
k2 Pseudo-second order adsorption kinetic rate constant, 2.1. Adsorbent and adsorbate
g/mg.L.min
kf Adsorption capacity [Freundlich isotherm], dimension- The bamboo leaves collected locally were washed to remove any ex-
less traneous materials and dried in an air oven at 105 °C. The dried leaves
kid Rate constant [intra-particle diffusion], mg/g·(min)0.5 were grinded a mixer-grinder into fine powder, screened through 120
KH Halsey constant, dimensionless mesh (British Standard), soaked in saturated solution of ZnCl2 for 24 h
kL Langmuir constant, L/mg and shaken in a mechanical shaker for 12 h. The solids were filtered,
kR Redlich–Peterson isotherm constant (L/g) washed to free from residual chlorides, carbonized at 450 °C for 6 h
kS Sips isotherm model constant (L/g) and cooled to room temperature overnight. Finally, the powder after
KT Temkin isotherm constant, L/gm cooling was packed in a container before being used as adsorbent as
m Mass of the adsorbent per unit volume, W/V, g/mL ZnCl2 activated carbon prepared from carbonized bamboo leaves
n Number of data points powder. The adsorbate used was powdered CV, a cationic or basic dye
nF Freundlich constant, dimensionless [Molecular Formula: C25H30ClN3; Molecular Weight: 407.98 g/mol;
nH Halsey constant, dimensionless CAS No: 548-62-9] (RFCL Limited, New Delhi, India). The stock solution
ns Sips isotherm model exponent (1000 mg/L) was first prepared by dissolving 1000 mg CV in 1.0 L dis-
p Number of parameters tilled water and desired concentrations were obtained by diluting it
Qa Air flow rate, L/min and m3/s with distilled water for use in the actual experiments.
qDR Theoretical monolayer sorption capacity, mg/g
qe Amount of CV adsorbed measured at equilibrium, mg/g 2.2. Characterization of the prepared adsorbent
or qe,meas
qe,cal Amount of CV adsorbed calculated at equilibrium, mg/g The point of zero charge (pHPZC) of the adsorbent prepared was de-
qm Maximum amount of CV adsorbed, mg/g termined using the solid addition method into 0.1 M KNO3 solution. The
qt Amount of CV adsorbed at time t, mg/g
r Correlation coefficient, dimensionless
r2 Coefficient of determination, dimensionless
R Universal gas constant, 8.314 J/mol K
t Contact time, min
T Absolute temperature, K
W Amount of adsorbent per L of dye solution, g/L

Greek letters
β Mean energy of sorption per molecule of sorbate related
to the average energy of sorption as the dye molecule is
transferred from the bulk of the system to the surface of
the solid adsorbent, mol2/J2
χ2 Chi-square, dimensionless
ε Dubinin–Radushkevich isotherm constant

area in the air-solid interface resulting into efficient adsorbate transfer

Fig. 1. Schematic showing the batch experimental set up for the removal of crystal violet
into the solid surface ensuring the possibility of enhanced adsorption on activated carbon prepared from bamboo leaves powder with ZnCl2 activation in an
of the pollutant. The main feature of the air agitated tapered adsorber air agitated tapered bubble column adsorber [COM: Air from compressor, M:
is it's increased cross-sectional area all along the direction of flow of Manometer, R: Rotameter, V1–V2: Gate valves].
 S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321 315

Fig. 2. SEM analysis of activated carbon prepared from bamboo leaves powder with ZnCl2 activation (a) before adsorption and (b) after adsorption.

surface morphologies of the adsorbent prepared before and after ad- 3. Results and discussion
sorption were characterized using SEM (Model Evo–18, Special Edition,
Carl Zeiss, West Germany). The surface area and the mean pore size 3.1. Characterization of the ZnCl2 activated carbon prepared from bamboo
were measured in a BET analyzer (Model: Autosorb iQ Station 1, leaves
Quantachrome ASi Qwin, Quantachrome Instruments, USA). The FTIR
analysis was carried out with the help of a spectrophotometer (Perkin The ZnCl2 activated carbon prepared from bamboo leaves offered a
Elmer Spectrum Version 1.03.00, USA). The FTIR spectra were devel- pHPZC of 6.6 indicating its suitability as adsorbent for solution pH N 6.6
oped by scanning in the range of 400 and 4000 cm−1 using KBr pellet for adsorbing cationic species (like CV) easily. Fig. 2(a) and (b) show
containing the sample. the surface morphologies without and with adsorption respectively of
the ZnCl2 activated carbon prepared. On comparison, the adsorption of
CV onto the surfaces of adsorbent could be seen in Fig. 2(b). The
2.3. Batch adsorption experimental set up and procedure multipoint BET surface area and average pore diameter, pore volume
(density functional theory) measured were 291.3 m2/g, 29.98 Ǻ and
Batch adsorption experiments were carried out in a tapered bubble 0.2072 cm3/g respectively. The other details of BET analyses are
column adsorber as shown in Fig. 1. The experimental column was furnished in the Supplementary Information. The frequencies of major
made up of Perspex with top and bottom diameters of 0.27 m and peaks observed in the adsorbent from FTIR analysis are detailed in the
0.08 m respectively and a vertical height of 1.0 m. The divergence Supplementary Information. The shift of frequencies observed indicates
angle is 10.84O (i.e. a tapered angle of 5.42°). The full height of the ad-
sorber column was not used filling with the slurry to avoid splashing.
Perspex made perforated sparger disc of 80 mm diameter was used
for uniform distribution of air into the column having 93 holes of
0.7 mm diameter. A rotameter was used to measure the flow rate of
air. Manometer was provided as shown in the figure to measure the
pressure drop across the column during operation. All experiments
were carried out at atmospheric pressure and at room temperature uti-
lizing desired batch liquid volume. Initially, the column was filled in
with 3.0 L of the colored liquid prepared in the distilled water with
the introduction of threshold air supplied from a compressor to avoid
the back flow. Under this condition, a desired quantity of adsorbent
was added into the column followed by the supply of air from the com-
pressor at a desired flow rate to agitate the slurry. The time required to
reach the equilibrium was estimated by analyzing few mL of samples
withdrawing from the column at specified intervals in a digital visible
spectrophotometer (Perkin Elmer, UV–Vis Spectrophotometer, Lambda
25, USA) at a λmax of 590 nm. All experimental readings were recorded
under steady operating conditions. After each run, the bed was washed
thoroughly before commencement of the next run. The detailed batch
experimental conditions were as follows: Temperature, T: 305 K; Adsor-
bate concentration, Co: 50, 100, 150 mg/L; Adsorbent dose, W: 0.2, 0.5,
0.7, 0.9 g/L; Contact time, t: 1, 5, 10, 15, 20, 30 and 40 min; pH: 7.36
(natural); Air flow rate, Qa: 8.75 × 10−5, 17.50 × 10−5, 26.23 × 10−5,
35.00 × 10−5, 43.73 × 10−5, 52.00 × 10− 5 and 70.00 × 10− 5 m3/s; Fig. 3. Effect of contact time on adsorption capacity and percentage removal of dye [W =
Batch liquid volume: 3.0 L (3 × 10−3 m3). 0.5 g/L; Qa = 35.00 × 10−5 m3/s].
316 S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321

participation of the relevant groups in the adsorption of CV onto the ac- Table 1
tivated carbon prepared. Estimated values of different isotherm parameters (adsorbent dose: 0.5 g/L).

Type of Isotherms Isotherm parameters determined

3.2. Batch adsorption experiments Langmuir qm = 200; kL = 5.555
Freundlich kf = 127.447; nF = 6.497
The batch experimental studies of adsorption of CV in aqueous Temkin bT = 111.372;kT = 358.468
solution onto the adsorbent were performed at different operating con- Halsey nH = 6.535; KH = 1.72E-14
Dubinin-Radushkevich qDR = 201.542; E = 4.082
ditions as described earlier. The uptakes of CV at any time and at equilib-
Sips qmax = 230; Ks = 2.467; n = 1.059
rium were calculated using the following expressions R-P KR = 1100; aR = 5.601; G = 0.983

ðCo −Ct Þ ðCo −Ce Þ

qt ¼ and qe ¼ :
W W increased sites. The maximum removal was achieved for W = 0.7 g/L,
beyond which the enhancement of % R was insignificant and it could
The percentage removal was estimated from the following be considered as the optimum dose. The solid to liquid ratio under
expression this optimum condition is 0.7:1 (w/v; kg/m3) (0.7 g or 0.7 × 10−3 kg ad-
sorbent was used in 3 L or 3 × 10−3 m3 liquid). The range of solid to liq-
Initial concentration−Final concentration uid ratio studied in this work was ranging between 0.2:1 and 0.9:1. The
Percentage removal; %R ¼
Initial concentration removal efficiency was ranging from 78.63% (W = 0.1 g/L) to 99.99%
Co −C f (W = 0.9 g/L). It can be seen from the figure that increased dose re-
 100 ¼  100
Co duced the adsorption capacity (discussed later) at a fixed CO which
was more than compensated resulting in enhanced % R. The enhance-
ment of % R with W could be explained by the following relationship.
3.2.1. Influence of various parameters (CO, t, Qa and W) on the adsorption

Fig. 3 depicts the influence of batch agitation or contact time (t) on Co −C f Co −C f W
%R ¼  100 ¼  100
both adsorption capacity (qt) and percentage removal (%R) at various
Co  W Co
initial concentrations (CO) and for a constant dose of adsorbent (W) of W
¼ qt  100 ⇒%R∞ðqt  WÞ for fixed Co
0.5 g/L. It can be seen from the figure that qt and %R were enhanced Co
with the batch agitation time perhaps due to the enhancement of ad-
sorption or uptake of CV for longer contact time. Further, the variation The adsorption capacity, qt, was however, decreased with the in-
of the rate of uptake of CV after 20 min was insignificant for all values crease in the adsorbent dose and it was varied between 111.10 mg/g
of CO and hence this time of 20 min was considered as the equilibrium (W = 0.9 g/L) and 393.16 mg/g (W = 0.2 g/L). For a fixed CO, though
time in this study. The percentage removal of CV also behaved similarly increased dose had enhanced % R as explained earlier, the adsorption ca-
with the contact time and here again there was no significant impact of pacity was reduced as a predominating effect. This can be explained by
the contact time N 20 min. Fig. 3 also depicts that the lower initial con- the following relationship.
centration of dye showed lower uptake. The maximum qt observed
  
was 229.35 mg/g for CO of 150 mg/L while the maximum removal ob- Co −C f Co %R
qt ¼ ¼ %R ⇒qt ∞ for fixed Co
served was 99.63% for CO of 50 mg/L for W of 0.5 g/L within the domain W W  100 W
of the experimentation pertaining to Fig. 3. The batch results reported
here for W = 0.5 g/L are used for analyzing the isotherms and kinetics The influence of the air flow rate (Qa) on % R as well as on qt is pre-
reported later. sented in Fig. 4(b) for other fixed operating conditions. It is observed
The effect of adsorbent dose on %R is furnished in Fig. 4(a) for other from the figure that % R was increased with Qa gradually which was
fixed operating conditions. It is observed from Fig. 4(a) that the removal however, tended to level off for Qa of 52.50 × 10−5 m3/s. In this case,
of dye was enhanced with the adsorbent dose mainly due to the the removal was raging from 74.75% (Qa = 8.75 × 10− 5 m3/s) to

Fig. 4. Effects of (a) dose of the prepared activated carbon on the percentage removal of dye [CO = 100 mg/L, Qa = 35.00 × 10−5 m3/s, equilibrium time = 20 min]; (b) air flow rate on the
percentage removal of dye [CO = 100 mg/L, W = 0.5 g/L, equilibrium time = 20 min].
 S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321 317

Table 2 The values of the different parameters as per the linearized isotherm
Different expressions for estimating errors. models obtained by data fitting are furnished in Table 1. Expressions for
Expressions for estimating Abbreviations Expressions estimating errors in addition to the correlation coefficient (r) and coef-
errors ficient of determination (r2) used for statistical validity of the results are
Non-linear chi-square test χ2 n ðqe;calc −qe;meas Þ2 shown in Table 2 while the results of the statistical analyses are detailed
∑i¼1 ½ qe;meas 
n
i in Table 3 for ease of understanding.
Sum of the squares of the errors SSE ∑i¼1 ðqe;calc −qe;meas Þ2i The adsorptive behavior of CV onto activated (ZnCl2) carbon has also
n
Sum of the absolute errors SAE ∑i¼1 jqe;calc −qe;meas ji been analyzed for the seven adsorption isotherms examined and are
Average relative error ARE n ðq −q Þ
100
n ∑i¼1 j e;calcq e;meas j shown in Table 3. It is observed from the table that the R-P model
e;meas i
Hybrid fractional error function HYBRID n ðqe;calc −qe;meas Þ2 gave values of r as 0.998 and r2 as 0.997. The Freundlich and Halsey
ðn−pÞ ∑i¼1 j j
100
qe;meas
Marquardt's percent standard MPSD
i
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi models gave values of r as 0.994 and r2 as 0.988. Though values of r
n ðqe;calc −qe;meas Þ 2
deviation 100 ðn−pÞ ∑i¼1
1
f qe;meas g
i
and r2 for R-P model were marginally better than those of Freundlich
and Halsey models, the overall errors of R-P model were higher than
those of Freundlich and Halsey models. The other errors were however,
99.99% (Qa = 70.00 × 10−5 m3/s). It is further observed from the figure lower for Freundlich isotherm than Halsey isotherm. The statistical
that the adsorption capacity was increased sharply initially and then values and errors for the Langmuir and Temkin models were lower
leveled off for Qa of 52.50 × 10−5 m3/s. The adsorption capacity than the Freundlich and Halsey isotherm models. Sips isotherm showed
was varied between 149.51 mg/g (Qa = 8.75 × 10− 5 m3/s) and lowest r and r2 values and gave poorest values of errors. The D-R iso-
199.98 mg/g (Qa = 70.00 × 10−5 m3/s). therm gave second lowest values of r and r2 and gave poorer values of
Therefore, the maximum removal and maximum adsorption capac- errors. However, the activation energy estimated from this isotherm
ity observed were 99.99% and 393.16 mg/g within the framework of the as 4.082 kJ/mol (b8 kJ/mol) indicated physisorption. The experimental-
batch experimentation carried out. ly observed maximum adsorption capacity of 229.346 mg/g for W =
0.5 g/L was closest to those calculated through Freundlich isotherm as
3.2.2. Adsorption isotherms of CV onto the prepared carbon activated with 220.588 (Table 3). In the light of these findings, it is understandable
ZnCl2 that the adsorption of CV onto the prepared ZnCl2 activated carbon
The adsorptive behaviors of CV onto the activated carbon prepared followed Freundlich isotherm which is physisorption and multi-layer.
were studied using the batch experimental results obtained as a func- Air agitated adsorption of CV onto the activated carbon prepared from
tion of contact time by examining seven well known isotherms for in- carbonized bamboo leaves powder with ZnCl2 activation showed
stance, Langmuir [17], Freundlich [18], Temkin [19], Halsey [20], multi-layered surface coverage followed from the Freundlich isotherm
Dubinin–Radushkevich (D-R) [21], Sips [22] and Redlich-Peterson within the framework of current investigation.
(R-P) [23]. In fact, the linear equations of these isotherms were used
which are given as follows
3.2.3. Monolayer surface coverage calculated from the dye uptake for
1 1 1 1 analyzing adsorption behavior
¼ þ ð1Þ
qe kL qm Ce qm The monolayer surface coverage by CV+, calculated using its ionic
surface area of 1.20 nm2 [24], molecular weight and uptake as a function
1 of contact time is shown in Fig. 5 for different initial CV concentrations.
ln qe ¼ lnk f þ ln Ce ð2Þ
nF The horizontal line indicating the constant BET surface area is shown at
ordinate of 291.3 m2/g for comparison. It can be seen from the figure
RT RT
qe ¼ ln ðKT Þ þ ln ðCe Þ ð3Þ that the calculated monolayer surface coverage was slowly increased
bT bT and was leveled of almost after 20 min. It was also increased with the
increase in the initial CV concentration owing to possibility of increased
1 1
log qe ¼ log KH − log Ce ð4Þ dye uptake. It is interesting to note that the surface coverage calculated
nH nH
overshoots the BET surface area for CO ≥ 100 mg/L. For CO = 50 mg/L, the
calculated surface coverage was well within the BET surface area. It
ln ðqe Þ ¼ ln ðqDR Þ−βε2 ð5Þ
could be attributable due to the fact, for CO = 50 mg/L, the availability
of adsorbate (CV dye) was not sufficient to occupy the all sites. Howev-
where ε ¼ RT ln ½1 þ C1e ; E ¼ pffiffiffiffiffiffiffi
1 ffi
−2β er, for CO ≥ 100 mg/L, the sites available were covered as the monolayer
  surface coverage calculated was higher than the BET surface area. It
qe 1 could only be explained by the multi-layer coverage.
ln ¼ ln Ce þ ln KS ð6Þ
qm −qe ns The calculated surface coverage presented as a function of adsorbent
  dose is shown in Fig. 6(a). The BET surface area overshoot the calculated
Ce surface coverage for 0.1 and 0.5 g/L while for the other two doses such
ln KR −1 ¼ G ln Ce þ ln aR ð7Þ
qe as 0.7 and 0.9 g/L, the adsorbate might have been equilibrated on the

Table 3
Comparison of correlation coefficient (r), coefficient of determination (r2) and other estimated errors for different isotherms [adsorbent dose: 0.5 g/L].

Isotherm models R r2 χ2 ARE ERRSQ EASB HYBRID MPSD Exp. qmax Cal. qmax

Langmuir 0.978 0.956 6.331 8.696 1328.92 51.950 633.122 17.519 229.346 200
Freundlich 0.994 0.988 0.813 3.445 159.837 19.181 81.338 6.523 220.588
Temkin 0.977 0.955 1.989 5.624 376.249 30.079 198.972 10.443 217.458
Halsey 0.994 0.988 0.828 3.373 163.436 19.123 82.189 6.505 220.221
D-R 0.952 0.907 6.812 9.420 1378.03 54.574 681.276 18.542 201.511
Slips 0.817 0.669 16.472 16.436 2051.91 69.900 1647.192 34.134 230
R-P 0.998 0.997 5.539 8.297 1086.94 47.909 553.992 16.951 207.537
318
Fig. 5. Effect of contact time on the calculated monolayer surface coverage [W = 0.5 g/L;
Qa = 35.00 × 10−5 m3/s] as against the BET surface area.
surface. Further, the increased dose increased the available surface con-
siderably and that was augmented with the fact that the adsorbate mol-
ecules were limited in the slurry. Here again, multilayer adsorption
could be observed. Fig. 6(b) depicts the influence of the air flow rate
on the calculated surface coverage. In this batch adsorptive study, the
change in the speed of agitation was achieved by changing the air
flow rate for improved adsorption, as was generally performed in the
case of conventional batch adsorption by changing the shaker speed.
The calculated surface coverage observed was increased with the air
flow rate in most of the cases. It was already explained that the uptake
was increased with the air flow rate (Fig. 4(b)). Increased uptake
700
(a)
Calculated monolayer surface coverage, m /g
2
600
500
400
300
200
0.2
Fig. 6. (a) Effect of adsorbent dose on the calculated monolayer surface coverage [CO = 100 mg/L, Qa = 35.00 × 10−5 m3/s, equilibrium time = 20 min]; (b) Effect of air flow rate on the
calculated monolayer surface coverage [CO = 100 mg/L, W = 0.5 g/L, equilibrium time = 20 min].
S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321
would lead to a situation of increased monolayer surface coverage.
The BET surface area was overshoot in most of the air flow rates studied
indicating occurrence of multilayer adsorption.
It is noteworthy that in many cases the calculated monolayer surface
coverage overshoots the BET surface area. The monolayer surface cover-
age is fundamentally, a single function of the uptake of adsorbate for any
solid-liquid adsorption system. Thus, attaining a surface coverage based
on monolayer calculation more than the BET surface area can only be
possible by the occurrence of the multi-layer adsorption. Furthermore,
the batch experimental results were shown in Section 3.2.2 to follow
the multi-layer Freundlich isotherm. Thus the behavior of the adsorp-
tion observed based on the calculated surface coverage is in excellent
agreement with the multi-layer Freundlich isotherm discussed earlier.
3.2.4. The observed adsorption capacity is compared with those available in
the literature
It has already been mentioned earlier that the adsorptive removal of
CV has not yet been investigated on carbon prepared from carbonized
bamboo leaves powder with ZnCl2 activation as an adsorbent in an air
agitated tapered bubble column slurry adsorber system. However, the
maximum adsorption capacities of similar type of adsorbents for re-
moving CV were reported in the literature by conducting experiments
in conventional batch systems. Since actual comparison of the observed
adsorption capacity was not possible with those obtainable in a similar
system not reported before, the adsorption capacities reported on con-
ventional batch systems are used here for comparison so as to develop
an understanding of the system performance. The comparison is
furnished in Table 4 [2–10]. It can be seen from the table that the
present system offered relatively higher adsorption capacity than
others.
The final solution pH was around 7.54 in the present study and was
well within the permissible limit of 5.5 to 9.0 for effluent discharge from
relevant industries [25] indicating no additional chemical and energy
consumption prior to discharge. Furthermore, the equilibrium time ob-
served was 20 min in the current investigation. Thus, the current aerat-
ed tapered bubble column adsorber with the application of the activated
carbon prepared could be operated several times under batch modes of
operation for handling a large volume of waste water successfully.
Symbol System 350 (b)
Dose vs Surface coverage
Calculated monolayer surface coverage, m /g
BET Surface Area
300
250
200
150 Symbol System
Air rate vs Surface coverage
BET Surface Area
100
50
0
0.4 0.6 0.8 1.0 0 15 30 45 60 75
5 3
Adsorbent dose, g/L Air flow rate, QaX10 , m /s
 S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321 319

Table 4 The IPD was taking place significantly since the values of r2 were higher
Comparison of the maximum observed adsorption capacity with others. (≥0.994 except in one incident). The values of the first and second kid
Adsorbents studied Adsorption References were varying from 5.473 to 11.301 and 1.969 to 5.092 mg/g min0.5 re-
capacity, mg/g spectively (Table 5). The third segment was horizontal and hence no
Jute fiber carbon 27.99 [2] such value was obtained. The appearance of initial two segments
Coniferous pinus bark powder 32.78 [3] might be due to the involvement of micro- and meso-pores in the adsor-
Phosphoric acid activation carbon 60.42 [4] bent prepared (Fig. 7b). It could be further explained that the initial ad-
Sulphuric acid activated carbon 85.84 [4]
sorption took place within 9 min in the micro pores later in the meso
Magnetically modified activated carbon 67.1 [5]
MCM-41 236.64 [6] pores in the next 10 min. The macro pores were insignificant resulting
Saw dust 341 [7] into third segment horizontal to equilibrate. The values of Df were var-
Magnetic nanocomposite 158.73 [8] ied from 0.339 to 0.375 s−1. From the foregoing analyses, it is evident
Activated carbon prepared waste apricot 91.74 [9] that the air agitated tapered bubble column adsorber offered initial ex-
Nanoporous carbon from tomato paste waste 68.97 [10]
Activated carbon prepared from ZnCl2 activation 393.16 Present
ternal mass transfer without any perceptible film diffusion but with IPD.
of carbonized bamboo leaves powder study Air agitation might have removed the resistance existing in the liquid-
side and as a result the film diffusion could not be perceptible.
The maximum value of qt calculated using the pseudo-second order
kinetic equation was 232.558 mg/g in comparison to 229.347 mg/g
3.2.5. Adsorption kinetics as well as diffusion of CV on the prepared carbon observed experimentally and the value was closest. However, similar
activated with ZnCl2 observation does not hold good for the pseudo-first order kinetic equa-
The adsorption kinetics of CV in the current study was examined by tion. Therefore, the experimental data generated in the tapered bubble
pseudo-first-order [26], pseudo-second-order [27] as well as film or column adsorber under batch operating mode followed best with the
boundary layer diffusion [28] or intra-particle diffusion [29], or both pseudo-second order kinetic model with IPD.
[30]. The respective linearized equations are given as follows Similar results were also discussed in the literature for conventional
adsorption studies [31]. The anomalous variation of k1 with CO in con-
k1 trast to decrease in k2 with CO as observed in the current investigation
logðqe −qt Þ ¼ logqe − t ð8Þ
2:303 has also been discussed therein [31] explaining k2 as a time-scaling fac-
tor. The behavior of the tapered bubble column adsorber observed with-
t 1 1 in the frame work of the present investigation has been analogous with
¼ þ t ð9Þ
qt k 2 qe 2 qe those studied in conventional batch systems using Erlenmeyer flasks.
However, the geometry or the shapes of the two systems were just op-
qt ¼ kid t0:5 þ I ð10Þ posite to each other and the modes of shaking were different. This is an

 interesting observation in the present study.
Df
ln ½1− FðtÞ ¼ − t ð11Þ
2:303
4. Influence of air flow rate on the pressure drop and energy
The constants characteristics to kinetics and diffusion, r and r2 are dissipation
presented in Table 5. It is observed from Table 5 that r and r2 were
highest for the pseudo-second order model amongst different models The effects of air flow rate on the pressure drop across the column
examined. The values of k1 and k2 calculated (figure not shown) were and energy dissipation are shown in Fig. 8. It can be seen from the figure
varied from 0.185 to 0.222 min−1 and 0.015 to 0.034 g/mg·min respec- that the pressure drop was slowly decreased with the increase in the air
tively. The multi-linearity with distinct three linear segments could be flow rate owing to the increase in the cross-sectional area along the flow
observed in intra-particle diffusion (IPD) model (Fig. 7a). None of of air vertically upward. The observed pressure drop was ranging be-
them is passing through the origin indicating that initial external mass tween 2719 and 2837 N/m2. The energy dissipation calculated from
transfer or chemical reaction was occurring and that the IPD was not the air flow rate and the pressure drop are generally used to character-
the rate controlling step in the adsorbate-adsorbent system studied. ize the performance of bubble columns. The energy dissipation per unit

Table 5
Calculated values of the rate constants of adsorption kinetics, diffusion parameters and statistical parameters [adsorbent dose: 0.5 g/L].

Pseudo first order kinetics Pseudo second order kinetics

−1 2 2
Co, mg/L K1, min Exp. qmax Cal. qmax r r χ K2, gm/mg·min Exp. qmax Cal. qmax r r2 χ2

50 0.185 99.632 17.230 0.999 0.999 2005 0.034 99.632 100 1.0 1.0 0.063
100 0.222 176.817 31.224 0.999 0.998 0.024 176.817 178.571 1.0 1.0
150 0.186 229.347 38.895 0.997 0.996 0.015 229.347 232.558 1.0 1.0

C0; mg/L Intra-particle diffusion model Film diffusion model

Line segment Kid, mg/g·min0.5 Intercept r r2 Df, min−1 r r2

50 1st 5.473 79.985 0.998 0.996 0.339 0.939 0.883

2nd 1.969 90.849 0.999 0.998
3rd 0 99.632 1.0 1.0
100 1st 9.577 143.63 0.996 0.992 0.375 0.951 0.905
2nd 2.546 165.57 0.980 0.960
3rd 0 176.82 1.0 1.0
150 1st 11.301 187.58 0.994 0.989 0.343 0.939 0.883
2nd 5.092 206.87 0.990 0.980
3rd 0 229.34 1.0 1.0
320 S.K. Ghosh et al. / Journal of Molecular Liquids 240 (2017) 313–321
Fig. 7. (a) Batch experimental data fitted onto Weber and Morris intra-particle diffusion model [W = 0.5 g/L; Qa = 35 × 10−5 m3/s]; (b) Pore size distribution of the activated prepared
carbon from bamboo leaves powder with ZnCl2 activation.
volume of the colored liquid (synthetic waste water) is calculated by
multiplying pressure drop and air flow rate and is presented in Fig. 8.
It can be seen from the figure that the energy dissipation was linearly in-
creased with the air flow rate and was ranging between 82.75 and
634.51 W/m3.
5. Conclusions
In this article, the adsorption of crystal violet from aqueous solution
using activated carbon prepared from carbonized bamboo leaves pow-
der with ZnCl2 activation was reported. A novel air agitated tapered
bubble column adsorber that utilizes air for the purpose of agitation
was used. The adsorbent prepared was first characterized by determin-
ing the pHPZC, multipoint BET surface area and pore volume analyses,
SEM analysis and FTIR analysis. The pHPZC of the prepared adsorbent
Fig. 8. Effects of air flow rate on pressure drop and energy dissipation per unit volume of
colored liquid [CO = 100 mg/L, W = 0.5 g/L, equilibrium time = 20 min].
was 6.6. The multipoint BET area measured was 291.3 m2/g. Batch ex-
periments were conducted as functions of initial concentration (50 to
150 mg/L), contact time (1 to 40 min), adsorbent dose (0.2 to 0.9 g/L)
and air flow rate (8.75 × 10−5 to 70.00 × 10−5 m3/s). The maximum
percentage removal observed was 99.99% at equilibrium time of
20 min under optimum conditions. The maximum adsorption capacity
observed was 393.16 mg/g which was higher than those reported. Re-
sults followed Freundlich isotherm (amongst seven isotherms exam-
ined) and pseudo-second order kinetics with intra-particle diffusion.
Air agitation might have removed the resistance existing in the liquid-
side and as a result the film diffusion could not be perceptible. The ob-
served pressure drop was ranging from 2719 to 2837 N/m2 and the en-
ergy dissipation per unit volume of colored liquid was ranging from
82.75 to 634.51 W/m3 in the system studied. Very high percentage re-
moval and adsorption capacity of the prepared adsorbent observed in
the novel tapered air agitated bubble column adsorber is the novelty
achieved in the current study.
Acknowledgements
Authors acknowledge the Centre for Research in Nanoscience &
Nanotechnology University of Calcutta, for carrying out the SEM analy-
ses and the Post Graduate Department of Chemistry, Rashbehari Siksha
Prangan, University of Calcutta for carrying out the BET surface area, mi-
cro-pore and FTIR Analyses.
The authors have declared no conflict of interest.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.molliq.2017.05.064.
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