Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-021-17216-9

RECENT INNOVATIONS IN CLEAN AND GREEN CONVERSION TECHNOLOGIES

DEALING WITH AIR, WATER, BIOMASS, AND SOIL

Adsorptive removal of ­Cd2+ ions using dolochar at an industrial‑scale

process optimization by response surface methodology
Utkarsh Upadhyay1 · Sarthak Gupta1 · Ankita Agarwal1 · Inkollu Sreedhar1 · Kayamkulathethu Latitha Anitha2

Received: 18 August 2021 / Accepted: 21 October 2021

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
In this work, performance of laboratory-synthesized dolochar has been investigated for adsorption of ­Cd2+ ions in a large-
scale process with the application of Aspen Adsorption. Moreover, the optimum values of the operating parameters (namely,
flow rate, bed height, and inlet metal ion concentration) that would result into maximum amount of cadmium ion adsorption
(high exhaustion capacity) in minimum time (less exhaustion time) for a fixed mass of dolochar have been calculated via the
application of response surface methodology. It was found that, at optimum values of bed height (3.48 m), flow rate (76.31
­m3/day), and inlet concentration (10 ppm), the optimized value of exhaustion capacity and exhaustion time for cadmium ion
adsorption in dolochar packed bed is equal to 1.85 mg/g and 11.39 h, respectively. The validity of these simulation experi-
ments can be proven by the fact that the obtained exhaustion capacity of dolochar packed bed always remained in close prox-
imity of the experimentally obtained value of adsorption capacity of the dolochar in batch process mode (equal to 2.1 mg/g).

Keywords  Dolochar · Large-scale biosorption · Response surface methodology · Aspen Adsorption · Simulation

Introduction effects and permissible discharge levels of toxic metal ions

(Agarwal et al. 2020; Foroutan et al. 2021e; Peighambar-
Heavy metal ions are one of the major pollutants that pos- doust et al. 2021). As evident from Table 1, heavy metal
sess serious threat to the environment. Release of effluents ions, if present in high concentration inside the human body,
contaminated with high concentrations of metal ions via can lead to very serious health conditions which might even-
the industries can have very toxic effect on nature as these tually result in death. Given the high concentrations in which
released metal ions can enter the food chain with the help of these heavy metal ions are present in the industrial efflu-
plants and fish. Metals ions dissolved in water get accumu- ents, humans will be more prone to the hazardous effects of
lated at the roots of plants and later get translocated to the toxic metal ions, if these industries discharge their effluents
edible parts of the plant (like fruits) and hence eventually into the environment without prior treatment. For example,
enter the food chain (Ahmad et al. 2020). These heavy metal concentrations of cadmium ions found in the few effluent
ions can be classified into three categories: toxic metals (Hg, samples from electroplating (Bankole et al. 2019), mining
Cr, Sn, Co, As, Cd, Ni, Cu, Zn, Pb), radioactive metals (Am, (Fu et al. 2020), smelting (Xu et al. 2018), and automobile
Ra, Th, U), and valuable and worthy metals (Pd, Ru, Au, industries (Akpomie and Dawodu 2016) have been reported
Ag, Pt) (Shafiee et al. 2019). Table 1 summarizes the toxic to be equal to 3.02 ppm, 21.3 ppm, 60 ppm, and 6.09 ppm,
respectively, which is significantly higher than the WHO
Responsible Editor: Tito Roberto Cadaval Jr permissible limits, and hence, it is extremely important to
treat the effluent before discharging it to the environment.
* Inkollu Sreedhar To achieve the separation of metal ions from the indus-
[email protected] trial effluents, several techniques like ion exchange, precipi-
1
Department of Chemical Engineering, BITS Pilani
tation, solvent extraction, and reverse osmosis are available.
Hyderabad Campus, Hyderabad 500078, India However, most of these techniques are tedious, expensive,
2
R&D, H B L Power Systems Ltd,
and known to cause secondary pollution. On the other hand,
Shameerpet, Hyderabad 500078, India adsorption has been one of the most popular techniques

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 Environmental Science and Pollution Research

Table 1  Toxic metal ions, their health effects, and permissible limits

S. no Metal ion Health effects Maximum contaminant
level set by WHO (mg/L)

1 Cd Lung cancer, kidney damage, diarrhea, bone problem, vomiting 0.003

2 Pb Headache, effect on central nervous system, kidney problem, gastrointestinal diseases, memory 0.05
loss
3 Hg Kidney and lung damage, degradation of immune system, Skin disease 0.001
4 As Hematological disorder, skin problems, cardiovascular diseases, bladder cancer 0.01
5 Cr Diarrhea, ulcer, kidney dysfunction, skin and eye irritation, irritation in respiratory track 0.05
6 Co Heart and liver problems, carcinogenic, asthma-like allergy 0.1
7 Cu Liver toxicity, cellular damage, headache, lung cancer 2.5
8 Ni Chest pain, vomiting, dermatitis, lung cancer, gastrointestinal diseases 2.0
9 Zn Depression, neurological diseases, lethargy 5.0
10 Fe Tinnitus, depression, gastrointestinal complains, headache, constipation 0.3

for removal of metal ions due to its low cost, effective- we design a dynamic large-scale adsorption process whose
ness, and simplicity (Liao and Huang 2019; Foroutan et al. parameters (namely flow rate, bed height, and inlet metal ion
2021c). Easy regeneration of the adsorbent and recovery concentration) have been optimized with the application of
of the adsorbate further make adsorption one of the most response surface methodology (RSM) in order to get maxi-
attractive options. Most of the industries, today, use either mum value of bed exhaustion capacity in minimum time
activated carbon, zeolites, or polymeric adsorbents in their (and hence ensuring the maximum removal of metal ions
adsorption process setup. In spite of achieving high metal in minimum time). This work can help in predicting and
removal efficiencies with these adsorbents, the industries are optimizing the expected behavior of any adsorbent, which
aiming to shift towards another class of adsorbents called is synthesized in lab, for a real industrial setup.
biosorbents (Wang and Chen 2014). Biosorbents are those
low-cost adsorbents which are usually produced from com-
mercially worthless products, i.e., from industrial waste Materials and methods
(such as dolochar, slag, and fly ash) or forestry/agricultural
waste (such as neem bark, banana peels, and coconut husk) The system of cadmium ion–contaminated stream flowing
(Ogata et al. 2020). Many different types of biosorbents have through the dolochar packed fixed bed adsorption column
shown high efficiency on a lab scale, and dolochar is one of was simulated on the software Aspen Adsorption V11.0.
them. Dolochar, a commercially worthless product, can be Physical properties that are crucial for execution of these
obtained from the waste of sponge iron industries and has simulation-based experiments were taken from the literature.
been tested multiple times for adsorption of heavy metal Bulk density, particle density, and particle size of dolochar,
ions in a laboratory setup where it has yielded satisfactory as reported in literature, are equal to 1203 kg/m3, 2250 kg/
results (Panda et al. 2011, 2017). Dolochar is a carbona- m3, and 63 µ, respectively (Panda et al. 2011, 2014). For
ceous material with extremely porous structure as desired the application of response surface methodology, software
for an ideal adsorbent. In addition, dolochar also possess Design Expert V11.0 was used.
several electron-donating groups like hydroxyl and amine
groups which substantially contribute towards the adsorp- Aspen Adsorption
tion of heavy metal ions. Hence, it is expected that, with
dolochar, it is possible to achieve high removal percentages Under Aspen Adsorption, liquid adsorption model was used
for cadmium, which is one of the toxic heavy metal ions. to conduct the experiments. The general assumptions made
Therefore, this work focuses on industrialization of dolochar in this model were (Zhang et al. 2019):
as an adsorbent by predicting its behavior, if it is applied for
cadmium removal on a large industrial scale. • The behavior of fluid across the column was assumed
While potential of many biosorbents have been explored to be plug flow with axial dispersion. The value of axial
in laboratory setup, very few studies have tried to scale up dispersion was estimated with Slater correlation (Slater
the biosorption process and predict the performance of these 1991) as represented in Eq. (1), where Ez denotes axial
biosorbents in a large-scale industrial setup. Since ultimate dispersion coefficient, vl denotes velocity of the liquid
goal is commercialization of these biosorbents, in this work, flowing through the bed, εi is the bed porosity, rp is the

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Environmental Science and Pollution Research

radius of dolochar particles, and Re is the Reynold’s UDS 1 was chosen in this work because of its uncondi-
number. The liquid phase pressure and superficial veloc- tionally non-oscillatory, unconditionally stable nature, mini-
ity are assumed to have a constant value throughout the mum simulation time, and good accuracy. The accuracy can
bed. These assumptions are valid since the quantity of be further increased with increase in number of nodes. In
metal being adsorbed is negligible in comparison to vol- this work, number of nodes was selected to be equal to 30.
ume of liquid flowing through the bed, and hence, metal
ion adsorption will have negligible effect on mass bal- Mass balance
ance equation.
( )0.48 Equation (4) presents the partial differential mass balance
vl rp 0.2 0.011 Re equation which was used to express the metal ion concen-
= + (1)
𝜀i Ez 𝜀i 𝜀i 𝜀i tration in a small control volume inside the adsorbent bed,
where εi is the bed porosity, Ez is the axial dispersion coeffi-
• Molar concentrations are calculated from molar volumes.
cient ­(m2/s), z is the distance along the bed (m), q is the con-
Ideal mixing is assumed to occur in the liquid phase, so centration of adsorbed cadmium ions onto dolochar (mg/g),
molar volume is a linear function of composition. C is the concentration of cadmium ions in the liquid phase,
• Isothermal conditions are applicable.
ρa is the bulk density, and vi is the interstitial velocity of the
fluid through the adsorbent bed (Ahmed et al. 2020).
Figure 1 shows the adsorption process as designed in
Aspen Adsorption. 𝜕 2 ci 𝜕( ) 𝜕c 𝜕w
The discretization method used in all the simulations was −𝜀i Ei + v c + 𝜀i i + 𝜌 s i = 0 (4)
𝜕z 2 𝜕z i i 𝜕t 𝜕t
upwind differencing scheme 1 (UDS 1) which is based upon
the first-order Taylor series expansion. Equations (2) and The first term of Eq.  (4) indicate dispersion forces,
(3) show the general differencing scheme made under the whereas the second term denote the convective forces that
UDS 1 method. are responsible for the biosorption process. The third term
is to account for accumulation of the cadmium ions onto
𝜕Γi Γ − Γi−1 dolochar, and finally, the fourth term is the mass transfer
= i (2)
𝜕z Δz term to account for the transfer of cadmium ions from liquid
to a solid phase.
𝜕 2 Γi Γi+1 − 2Γi + Γi−1 The bed porosity, in Eq. (4), was calculated from Eq. (5),
= (3) where ρb is the bulk density and ρp is the particle density.
𝜕z2 Δz2
(5)
( )
ρb = ρp 1 − 𝜀i

Fig. 1  Adsorption process as
designed in Aspen Adsorption

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Kinetic model which makes three basic assumptions—(i) adsorption on

one site is independent of its other neighboring sites, (ii)
In this work, linear lumped resistance kinetic model was adsorption sites are homogenous, (iii) monolayer adsorp-
assumed. This model assumes that driving force for mass tion takes place (Upadhyay et al. 2020). Based upon the
transfer of the components is a linear function of the compo- convention of Aspen Adsorption, Eq. (11) and Eq. (12) can
nent concentration in liquid phase or solid phase and can be be used to calculate the isotherm parameters, where qmax is
mathematically represented by Eq. (6) (Ahmed et al. 2020). the adsorbate concentration on the adsorbent surface (mg/g)
and kL is the Langmuir constant (L/mg), and ­IP1 and ­IP2
𝜕wk
= MTCsk w∗k − wk (6) are input parameters to Aspen Adsorption. Values of Lang-
( )
𝜕t muir isotherm parameters, namely, qmax and kL, are taken
where wk is the instantaneous equilibrium loading of adsorb- to be equal to 2.02 mg/g and 0.33 L/mg, respectively. Also,
ate onto adsorbent (mg/g) and MTC is the overall mass another important parameter, equilibrium factor (RL), was
transfer coefficient (m/s). MTC accounts for mass transfer found equal to 0.13, which indicates the favorability of the
resistance between the liquid and external adsorbent sur- adsorption process as the values lie between 0 and 1 (Panda
face, and the mass transfer resistance due to pore structure et al. 2011).
of adsorbent surface. The value of MTC can be calculated qmax
from Katoka correlation (Eq. (7)) (Zulfadhly et al. 2001). IP1 = (11)
1000M
)1∕3 k Sc2∕3
1−𝜀
( �
L
= 1.85Re −2∕3 (7) IP2 = 1000kL M (12)
𝜀 uf ∕𝜀

where kl represents MTC, Sc represents Schdmidt num- Evaluation of bed

ber; ­Re′ = Reynolds number; U = superficial velocity (m/s);
ε = bed porosity. One of the most widely used parameters for the evaluation
Along with linear lumped resistance model, solid film of an adsorbent bed is its exhaustion capacity (Kavand et al.
assumption was considered in this work since it expresses 2018). In order to calculate exhaustion capacity, Eq. (13) can
the mass transfer driving force in terms of the solid-phase be used, where, qtote is the exhaustion capacity of the bed
concentrations of the components (here, cadmium ions). (mg/g), m is the total mass of adsorbent packed in the bed,
Ct is the metal ion concentration in the exiting stream, C0 is
Isotherm the inlet metal ion concentration, and Q is the flow rate of
effluent through the bed.
There are several isotherm models available for modeling
adsorption of heavy metal ions onto a solid adsorbent. t

m1000 ∫
Q
Amongst these models, Langmuir (Foroutan et al. 2020a), qetot (13)
( )
= C0 − Ct dt
Freundlich (Bonyadi et al. 2019), and Dubinin-Radushk- 0
evitch (Esvandi et al. 2020) isotherm models are the most
frequently used models and can be represented by Eq. (8), The evaluation of integral term in Eq. (13) has been done
Eq. (9), and Eq. (10), respectively. with the help of Origin Pro software in this work. The data
points obtained from simulation experiments were plotted
Ce 1 C on Origin Pro followed by required area calculation in the
= + e (8)
qe kL qmax qmax graph using the Integrator gadget of the Origin Pro software.

1 Response surface methodology

lnqe = lnCe + lnkf (9)
n
One of the aims of this work is to find the optimum set of
exhaustion capacity (maximum) and exhaustion time (mini-
lnqe = lnqs − 𝛽𝜀 2
(10)
mum) from a set of varying values of inlet metal ion con-
The adsorption of cadmium ions onto dolochar process centration, bed height, and flow rate. The working range of
can be best described by Langmuir isotherm as it gives a these parameters were taken to be between 1 to 5 m for bed
much higher R2 value (equal to 0.99) in comparison to Fre- height, 10 to 100 ppm for cadmium ion inlet concentration,
undlich and Dubinin-Radushkevitch isotherm models (Panda and 50 to 100 ­m3/day for flow rate through the bed.
et al. 2011). Therefore, this work assumes that adsorption To achieve the desired task, response surface method-
process is being governed by Langmuir isotherm (Eq. (8)) ology has been applied which is a method based on the

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Environmental Science and Pollution Research

fitting of mathematical models (linear, square polynomial metal ions (via complexation with electron-donating groups)
functions, and others) to the experimental results generated and negatively charged species like nitrate and phosphate
from the designed experiment and the verification of the (via complexation with iron, calcium, aluminum, and mag-
obtained model by means of statistical techniques. The fol- nesium compounds). To summarize, based upon the metal-
lowing steps were followed in order to reach at the set of binding capability, extremely low cost, and ability to adsorb
optimum parameters (Witek-Krowiak et al. 2014): both positively charged and negatively charged ions simul-
taneously, it can be said that dolochar has great potential
1. Deciding upon the independent variables, working range as an adsorbent and hence can be considered for usage in
of the independent variables, and responses to be con- treatment of real industrial effluents.
sidered in the study. All the simulation experiments, conducted on Aspen
2. Designing of experiments. Adsorption, were conducted for a fixed mass of 1200 kg of
3. Carrying out the experiments designed in step (2) in dolochar (and hence 3.94 m ­ 3 volume of the packed bed reac-
order to get results, i.e., getting responses. tor). In one of the conducted experiments, bed height, flow
4. Fitting a model to the obtained set of variable-response rate, and inlet cadmium ion concentration were set to be
data. equal to 3 m, 75 ­m3/day, and 55 ppm, respectively. Since the
5. Validation of the model with analysis of variance mass of adsorbent is fixed to 1200 kg and the bulk density
(ANOVA). of the adsorbent is taken to be 1203 kg/m3, the diameter
6. Determination of the optimum parameters set. of the bed was calculated to be 0.65 m. The overall mass
transfer coefficient, as calculated from Eq. (7), was equal to
For designing of experiments, various experimental strat- 0.000137 for this case.
egies are available such as factorial design (Cestari et al. Post running the simulation for this system, it was found
2008), central composite design (Oden and Sari-Erkan that the bed reached its breakthrough point (C/C0 = 0.05) at
2018), Box-Behnken approach (Jaafari and Yaghmaeian 11.11 h and eventually exhausted after 19 h (C/C0 = 0.95).
2019), and Plackett–Burman design. In this work, the experi- The concentration profile (C/C0) was plotted against time,
mental route has been mapped with help of central compos- and the resulting graph obtained has been shown in Fig. 2.
ite design (CCD) strategy due to its ability to analyze the From the application of Eq. (13), the exhaustion capacity of
complex interaction between the parameters with low num- the bed was calculated to be 1.71 mg/g.
ber of experimental run requirements (Lingamdinne et al.
2018; Oden and Sari-Erkan 2018). Design Expert software Response surface methodology
has been used for applying RSM in this work.
For an industrial setup, it is preferable that maximum
amount of effluent is treated (hence, high exhaustion
Results and discussion

Adsorbent dolochar and simulation experiments

Dolochar, along with being porous, is also rich in electron-

donating groups like –OH, -NH, -SiO, and -C≡N. These
electron-donating groups interact with cadmium ions via
complexation mechanism which results in high performance
of dolochar as shown by Panda et al. (2011). Besides being
rich in metal-binding groups, dolochar is extremely cheap
as well. Its cost is around only Rs.1000 per ton, and hence,
it can significantly lower the cost of the effluent treatment
plants that use expensive conventional adsorbents. Another
added benefit of using dolochar for industrial effluents lies in
its way of interaction with other negatively charged species
like nitrate and phosphate. Dolochar contains iron, calcium,
aluminum, and magnesium compounds which interact only
with these negatively charged species (and not metal ions)
via complexation and precipitation mechanisms and remove
Fig. 2  Concentration profile of the stream exiting from the dolochar
them from the effluent (Rout et  al. 2015). Hence, with packed bed when inlet metal ion concentration, flow rate, and bed
dolochar, it is possible to achieve simultaneous removal of height were set equal to 75 ­m3/day, 55 ppm, and 3 m, respectively

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capacity is required) in minimum time (hence, low exhaus- Simulation experiments were conducted for all the designed
tion time is preferred). This ensures that the industry will 17 experiments in Aspen Adsorption, and the response
have to bear the minimum cost for the metal ion separation variables, namely exhaustion time and exhaustion capacity,
process since the run time of the equipment and adsorbent were obtained. Table 3 shows the CCD matrix and results
quantity requirement are being minimized. Therefore, RSM obtained.
is being applied here to optimize the values of exhaustion
capacity and exhaustion time as the independent variables Analysis of variance and examination of the relationship
flow rate, bed height, and inlet metal ion concentration vary between factors and responses
(Zinatizadeh et al. 2006).
The regression analysis of experimental data obtained in
Central composite design Table 3 led to the conclusion that exhaustion time of the bed
for this system can be expressed as a function of bed height,
The experiments were designed with the use of CCD strat- flow rate, and inlet metal ion concentration via Eq. (14). The
egy (Jiryaei Sharahi and Shahbazi 2017; Foroutan et al. same, for the case of exhaustion capacity of the bed, can be
2020b). The independent variables and their input range are modeled by Eq. (15). Both the models obtained were ana-
presented in Table 2. lyzed and were found to be significant with the P-value less
CCD approach designed a total of 17 experiments than 0.0001 in both cases. Moreover, for both the models,
out of which, at central point, 3 were replicates so as to the lack of fit is not significant (relative to the pure error)
measure the accuracy level of results (Zhang et al. 2016). which further proves the suitability of these models (P-value
equal to 0.19 for exhaustion time model and equal to 0.57 for
exhaustion capacity model) (Foroutan et al. 2021a). The R2,
Table 2  Levels for CCD predicted R2, and adjusted R2 values were found to be very
Symbol Factor Low level Mid level High level close to 1 in case of both the models which indicates that the
suggested models can be good predictors of the experiment
A Height (m) 1 3 5 results (refer to Table 4 and Fig. 3). Moreover, the signal-
B Flow rate (­ m3/day) 50 75 100 to-noise ratio (adeq. ratio) was also much greater than the
C Inlet metal ion con- 10 55 100 minimum required value (i.e., 4) for both the models which
centration (ppm)

Table 3  CCD matrix and Factors Responses

responses
Run A: Height B: Flow rate C: Initial conc Exhaustion time Exhaus-
Meters m3/day PPM Hours tion
capacity
mg/g

1 3 100 55 14.9 1.71

2 3 75 55 18.5 1.73
3 5 50 100 15.21 1.76
4 1 50 10 97.79 1.39
5 5 50 10 93.54 1.40
6 5 75 55 16.7 1.71
7 5 100 100 8.7 1.73
8 1 100 100 11.03 1.80
9 1 100 10 51.7 1.39
10 3 50 55 24.81 1.74
11 3 75 55 17.58 1.73
12 3 75 100 11.71 1.90
13 3 75 55 17.89 1.73
14 1 50 100 18.04 1.73
15 5 100 10 18.12 1.75
16 1 75 55 19.37 1.67
17 3 75 10 65.2 1.41

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Table 4  Fit statistics parameters for exhaustion time and exhaustion where R1 is exhaustion time (hours), R2 is exhaustion capac-
capacity models ity (mg/g), A is bed height (m), B is flow rate ­(m3/day), and
Parameter Value (exhaustion Value (exhaus- C is inlet concentration of cadmium ions (kmol/m3).
time) tion capacity) Table  5 and Table  6 show the analysis of variance
(Foroutan et al. 2021d) for exhaustion time and exhaustion
R2 0.98 0.99
capacity models. While it was observed that, for exhaus-
Adjusted R2 0.97 0.99
tion time, all three factors, i.e., height, flow rate, and inlet
Predicted R2 0.89 0.94
concentration, were significant factors (with P-value equal
Adeq. precision 35.11 110.75
to 0.0004, < 0.0001, and < 0.0001, respectively), for exhaus-
tion capacity, only inlet concentration (P-value < 0.0001)
and flow rate (P-value = 0.002) were significant factors and
further indicates the suitability of developed models (Kavi- bed height was less significant (P-value = 0.1). The reason
tha et al. 2019; Foroutan et al. 2020c). behind this less significant behavior of height factor could
be the fact that the same mass of dolochar biosorbent is
1
= 0.0534 + 0.0079 ∗ A + 0.0165 ∗ B + 0.0301 ∗ C being used in all experiments (1200 kg). Therefore, with
R1 (14) increase in bed height, diameter decreases and vice versa
+ 0.0062 ∗ AB − 0.0002 ∗ AC + 0.0039 ∗ BC
which leads to minimal change in exhaustion capacity
of the bed in response to the change in bed height. With
√
R2 = 1.31 + 0.0031 ∗ A − 0.0057 ∗ B + 0.0955 ∗ C

+ 0.0127 ∗ AB − 0.0204 ∗ AC − 0.0156 ∗ BC − 0.0104A2 respect to flow rate, it was found that increasing the flow rate
− 0.0016B2 − 0.0321C2 − 0.022ABC + 0.025A2 B − 0.04A2 + 0.0136AB2
results in the decrease in both exhaustion time and exhaus-
(15) tion capacity. The decrease in exhaustion capacity with the
increase in flow rate is the result of decrease in residence
time of the cadmium ions inside the bed which ceases the

Fig. 3  Predicted vs actual plot

for a exhaustion capacity and b (a) (b)
exhaustion time

Table 5  ANOVA table for Source Sum of squares df Mean square F-value p-value
response variable exhaustion
time Model 0.0129 6 0.0021 91.41  < 0.0001 Significant
A—height 0.0006 1 0.0006 26.74 0.0004
B—flow rate 0.0027 1 0.0027 115.98  < 0.0001
C—initial conc 0.0091 1 0.0091 387.69  < 0.0001
AB 0.0003 1 0.0003 12.99 0.0048
AC 3.678E-07 1 3.678E-07 0.0157 0.9028
BC 0.0001 1 0.0001 5.06 0.0481
Residual 0.0002 10 0.0000
Lack of fit 0.0002 8 0.0000 4.61 0.1904 Not significant
Pure error 0.0000 2 6.024E-06
Cor total 0.0131 16

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Table 6  ANOVA table for Source Sum of squares df Mean square F-value p-value
response variable exhaustion
time Model 0.0641 13 0.0049 1258.24  < 0.0001 Significant
A—height 0.0000 1 0.0000 4.80 0.1161
B—flow rate 0.0001 1 0.0001 16.65 0.0266
C—initial conc 0.0182 1 0.0182 4656.10  < 0.0001
AB 0.0013 1 0.0013 331.80 0.0004
AC 0.0033 1 0.0033 849.24  < 0.0001
BC 0.0019 1 0.0019 496.07 0.0002
A2 0.0003 1 0.0003 74.02 0.0033
B2 7.079E-06 1 7.079E-06 1.81 0.2714
C2 0.0028 1 0.0028 704.31 0.0001
ABC 0.0039 1 0.0039 1004.03  < 0.0001
A 2B 0.0010 1 0.0010 256.19 0.0005
A 2C 0.0027 1 0.0027 691.21 0.0001
AB2 0.0003 1 0.0003 75.30 0.0032
Residual 0.0000 3 3.916E-06
Lack of fit 2.087E-06 1 2.087E-06 0.4320 Not significant
Pure error 9.662E-06 2 4.831E-06
Cor total 0.0641 16

opportunity for the cadmium ions to reach the micro- and Optimization of variables
mesopores of the dolochar particles (Simate and Ndlovu
2015). However, the decrease in exhaustion time is a Based upon the models, the optimum values that would
favorable factor which results from the increase in the maximize the exhaustion capacity of bed and minimize
volume of contaminated stream being treated per unit the exhaustion time (hence achieve maximum cadmium
time (Hernández-Hernández et al. 2017). With respect to ion adsorption in minimum time) were calculated with
inlet metal ion concentration, it was found that increas- the help of a multiple response method called desirabil-
ing the inlet metal ion concentration results in increase ity function (Zaferani et al. 2019). The optimum values
in exhaustion capacity and decrease in exhaustion time. of bed height, flow rate, and inlet metal ion concentra-
Since the lumped linear resistance kinetic model has tion were found to be equal to 3.48 m, 76.31 ­m3/day, and
been assumed in this work (which assumes that rate of 10 ppm, respectively. For these set of values, the pre-
metal uptake is directly proportional to its concentration dicted exhaustion time and exhaustion capacity from the
gradient), it was expected to observe that increase in model were equal to 11.55 h and 1.87 mg/g, respectively,
metal ion concentration in the incoming stream would and the desirability level was 0.835. When experiments
result in increase in exhaustion capacity. Therefore, were conducted with the same optimum values as input,
decrease in mass transfer resistance and increase in the values of exhaustion time and exhaustion capacity
concentration gradient with increase in inlet metal ion were found to be equal to 11.39 h and 1.85 mg/g, respec-
concentration can be attributed for the observed increase tively, which is in a very close approximation with the
in exhaustion capacity (Sarin et al. 2006). Moreover, predicted values from the model and hence further justi-
with the increase in the metal ion concentration, the fies the preciseness of the models.
exhaustion time decreases. This is the result of adsorp-
tion sites being exhausted early since more number of Validation of simulation with the experimental
ions are entering into the system per unit time in addi- results
tion to more number of ions being adsorbed due to lower
mass transfer resistance (Popovic et al. 2020). Figure 4 As can be inferred from the Table  3, the exhaustion
and Fig. 5 help to visually represent the effect of varying capacity of the dolochar packed bed lies in the range
factors onto the response variables via help of 2D and of 1.3 to 1.9 mg/g. In this work, the values of dolochar
3D contours (Foroutan et al. 2021b). bulk density, particle density, particle size, and isotherm

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Fig. 4  Three-dimensional contour plots to examine the relationship between the factors and responses

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◂Fig. 5  Two-dimensional contour plots to examine the relationship performance of a biosorbent in a real industrial pro-
between the factors and responses cess can be predicted. With the observed proximity
between the exhaustion capacity of dolochar obtained
parameters were taken from the work of Panda et  al. from Aspen Adsorption and the maximum adsorption
(2011). The same work tested the performance of capacity obtained from laboratory experiments, it was
dolochar for adsorption of cadmium in the laboratory confirmed that Aspen Adsorption can be used as a good
setup and reported the maximum adsorption capacity predictor of an adsorbent performance. Furthermore,
of the dolochar biosorbent for cadmium ions is equal through the application of response surface methodol-
to 2.1 mg/g. Therefore, the visible proximity between ogy, the effect of variation in column bed height, flow
the values obtained from Aspen Adsorption and the lab- rate, and inlet metal concentration onto the exhaustion
based experiments shows the validity of the conducted time and exhaustion capacity of the dolochar packed
simulation-based experiments. bed was examined. Moreover, it was shown that how
the optimum working parameters can be calculated for
Other adsorbents for consideration of future works the dynamic adsorption process that would maximize
the performance of the corresponding biosorbent in
Like dolochar, there are several other adsorbents as well the industrial process being considered. Finally, it was
which have been already reported in the literature for found out that, for a fixed mass of dolochar biosorb-
adsorption of cadmium ions (refer to Table  7). These ent and at optimum values of bed height (3.48  m),
adsorbents, relative to dolochar, are expensive and fol- f low rate (76.31 m ­ 3 /day), and inlet concentration
low difficult synthesis procedures. However, their adsorp- (10  ppm), the optimized value of exhaustion capac-
tion capacity values are significantly higher than those ity and exhaustion time for cadmium ion adsorption
obtained with dolochar (equal to 2.02 mg/g) and hence in a dolochar packed bed is equal to 1.85  mg/g and
can act as attractive options for many industries. Future 11.39 h, respectively. It is high time to truly utilize the
works can be aimed at exploring the possibility of indus- potential of biosorbents in the treatment of industrial
trialization of these adsorbents via carrying out similar eff luents, and hence, it is recommended that future
simulation experiments. works focus more on industrialization of biosorbents.
Studies focused upon scaling up the synthesis process
of successful biosorbents, designing of optimized con-
Conclusions tinuous adsorption processes including regeneration
cycles (and the management of waste stream gener-
This work was aimed at providing motivation for the ated from regeneration of adsorbents), and designing
industrialization of biosorbents for the application of metal recovery systems for the spent adsorbents are
of heavy metal ion adsorption. Through the applica- highly desirable, and researchers are encouraged to
tion of Aspen Adsorption, this work showed how the work in this direction.

Table 7  Other high-performance adsorbents for cadmium adsorption

Adsorbent Adsorption capacity value (for cadmium Reference
ions)

Nano-silica particles generated from white sandstone 55.13 mg/g (Foroutan et al. 2020b)
Chitosan zero-valent iron nanoparticle-supported 142.8 mg/g (Ahmadi et al. 2017)
Citrus limon wood carbon/Fe3O4 39.6 mg/g (Peighambardoust et al. 2021)
Hydroxyapatite powder 22.94 mg/g (Foroutan et al. 2021e)
Callinectes sapidus biomass 29.23 mg/g (Foroutan et al. 2019)
Penaeuse semisulcatuse chitin 19.15 mg/g (Esvandi et al. 2019)
Padina sanctae-crucis biomass 93.45 mg/g (Foroutan et al. 2018)

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Acknowledgements  The authors would like to thank BITS Pilani real wastewater. Korean J Chem Eng. https://​doi.​org/​10.​1007/​
Hyderabad Campus and HBL Power Systems for facilitating this s11814-​019-​0373-0
project. To be presented in the International Chemical Engineering Cestari AR, Vieira EFS, Mota JA (2008) The removal of an anionic
Conference on “100 Glorious Years of Chemical Engineering & Tech- red dye from aqueous solutions using chitosan beads-the role of
nology” from September 17 to 19, 2021, organized by Department of experimental factors on adsorption using a full factorial design.
Chemical Engineering at Dr. B R Ambedkar NIT Jalandhar, Punjab, J Hazard Mater. https://​doi.​org/​10.​1016/j.​jhazm​at.​2008.​03.​004
India (organizing chairman: Dr. Raj Kumar Arya and organizing sec- Esvandi Z, Foroutan R, Mirjalili M, Sorial GA, Ramavandi B (2019)
retary: Dr. Anurag Kumar Tiwari). Physicochemical behavior of Penaeuse semisulcatuse chitin for
Pb and Cd removal from aqueous environment. J Polym Environ.
Author contribution  UU: simulation studies and drafting. https://​doi.​org/​10.​1007/​s10924-​018-​1345-x
SG: experimental validation. Esvandi Z, Foroutan R, Peighambardoust SJ, Akbari A, Ramavandi B
AA: adsorbent synthesis. (2020) Uptake of anionic and cationic dyes from water using natu-
IS: project mentoring and monitoring. ral clay and clay/starch/MnFe2O4 magnetic nanocomposite. Sur-
KLA: characterization of effluent. faces and Interfaces. https://​doi.​org/​10.​1016/j.​surfin.​2020.​100754
Foroutan R, Esmaeili H, Sanati AM, Ahmadi M, Ramavandi B (2018)
Adsorptive removal of Pb(II), Ni(II), and Cd(II) from aqueous
Funding This study received funding from CSIR under the
media and leather wastewater using Padina sanctae-crucis bio-
scheme 22(0783)/19/EMR-II (recipient: I. Sreedhar).
mass. Desalin Water Treat. https://​doi.​org/​10.​5004/​dwt.​2018.​
23179
Availability of data and materials  Not applicable. Foroutan R, Mohammadi R, Farjadfard S, Esmaeili H, Saberi M,
Sahebi S, Dobaradaran S, Ramavandi B (2019) Characteristics
Declarations  and performance of Cd, Ni, and Pb bio-adsorption using Cal-
linectes sapidus biomass: real wastewater treatment. Environ Sci
Pollut Res. https://​doi.​org/​10.​1007/​s11356-​018-​04108-8
Ethics approval  Not applicable.
Foroutan R, Mohammadi R, MousaKhanloo F, Sahebi S, Ramavandi
B, Kumar PS, Vardhan KH (2020a) Performance of montmoril-
Consent to participate  Not applicable.
lonite/graphene oxide/CoFe2O4 as a magnetic and recyclable
nanocomposite for cleaning methyl violet dye-laden wastewater.
Consent for publication  Not applicable.
Adv Powder Technol. https://​doi.​org/​10.​1016/j.​apt.​2020.​08.​001
Foroutan R, Mohammadi R, Peighambardoust SJ, Jalali S, Ramavandi
Conflict of interest  The authors declare no competing interests. B (2020b) Application of nano-silica particles generated from
offshore white sandstone for cadmium ions elimination from aque-
ous media. Environ Technol Innov. https://​doi.​org/​10.​1016/j.​eti.​
2020.​101031
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