517

A publication of

CHEMICAL ENGINEERING TRANSACTIONS

VOL. 92, 2022 The Italian Association
of Chemical Engineering
Online at www.cetjournal.it

Guest Editors: Rubens Maciel Filho, Eliseo Ranzi, Leonardo Tognotti

Copyright © 2022, AIDIC Servizi S.r.l.
DOI: 10.3303/CET2292087
ISBN 978-88-95608-90-7; ISSN 2283-9216

Computer-aided Modeling and Evaluation of a Packed Bed

for Chromium (vi) Removal using Residual Biomass of
Theobroma Cacao L.
Ángel Darío González-Delgadoa, Candelaria Tejada-Tovarb,*, Angel Villabona-
Ortízb
a
Chemical Engineering Department, Nanomaterials and Computer-Aided Process Engineering Research Group (NIPAC),
Universidad de Cartagena, Avenida del Consulado St. 30, Cartagena de Indias 130015, Colombia
b
Chemical Engineering Department, Process Design and Biomass Utilization Research Group (IDAB), Universidad de
Cartagena, Avenida del Consulado St. 30, Cartagena de Indias 130015, Colombia
[email protected]

The use of residual biomass in environmental applications continues gaining attention of the scientific
community, the presence of heavy metals in the environment represents a problem of interest due to their
toxicity, accumulation, and persistence. Bio-adsorption allows the use of agricultural or industrial waste, it is an
efficient and non-destructive method for the removal of heavy metals, making it a viable method due to its low
cost and easy implementation, however, the behaviour at large scale of these biomass-based emerging
technologies is unknown; in this work, the modeling and computer-aided scaling up of an industrial scale column
for the adsorption of Cr (VI) present in aqueous solution on an adsorbent based on Theobroma cacao L. was
performed using Aspen Adsorption V10 software. The parameters for the modeling were obtained from
experiments performed by the authors and scientific literature. Results show parameters as flowrate of
feedstock, bed diameter and bed length showed sensitivity in the performance of the breakthrough column.

1. Introduction
Heavy metals in water bodies could be concentrated in the living tissues of organisms due of bioaccumulation
and magnification; thus, caused by the increase in polluted effluents product of industrial activities such as
battery manufacturing, mining, smelting, refining, tanneries and soldering (Jencarova and Luptakova, 2012).
Usually, Cr (VI) is found in water environments as chromate ions (CrO42-) o dichromate (Cr2O72-), which easily
crosses biological barriers, being carcinogenic, moreover, Cr (VI) is 500 times more toxic than Cr (III). Due to
its toxicity, chromium causes respiratory problems, lung cancer and affects the male reproductive system
(Hedberg et al., 2019). In addition, the concentration of chromium in industrial wastewater usually exceeds the
threshold limit set by governing institutions, thus those effluents need to be treated in order to reduce the
concentration before being discharged. Several processes are being implemented for this issue, such as
membrane filtration, chemical precipitation, ion-exchange, oxidative techniques, filtration and ultrafiltration
(Jencarova and Luptakova, 2012).
Adsorption is an economic process widely used to separate heavy metal at low concentrations from aqueous
solution, considering it is a simple and highly efficient operation without toxic sludge generation. The use of
adsorbents of agricultural and agro-industrial origin are extensively used due to their high availability and high
selectivity for heavy metals (Khalil et al., 2021). Adsorption studies using agricultural and agro-industrial
materials as adsorbents for removing heavy metals in a batch system, have allowed to have comprehensive
isotherm data, in order to understand the interactions mechanisms between the pollutant and the adsorbent (Al-
Ghouti and Da’ana, 2020). Yet, experimental approaches are costly and time-consuming and restricts the
evaluation of operating variables desirable to design a packed bed column. From the isotherm equilibrium data,
a viability study can be explored to prove their scalability onto a bigger proportion (Chatterjee et al., 2018).

Paper Received: 22 December 2021; Revised: 9 March 2022; Accepted: 15 May 2022
Please cite this article as: Gonzalez-Delgado A., Tejada-Tovar C., Villabona-Ortiz A., 2022, Computer-aided Modeling and Evaluation of a
Packed Bed for Chromium (vi) Removal Using Residual Biomass of Theobroma Cacao L., Chemical Engineering Transactions, 92, 517-522
DOI:10.3303/CET2292087
518

Packed bed columns are devices stuffed with adsorbent, in which the polluted solution flows through the bed
containing the contaminant to be removed into the adsorbent surface. Then, continuous packed bed systems
are preferred for industrial wastewater treatment due of their capacity for handling large volumes of polluted
solution (Jafari and Jamali, 2016). It also provides information on breakthrough and exhaustion times, which are
important to evaluate the feasibility of adsorbents, considering the packed beds operate until the saturation of
adsorbents (Elabbas et al., 2016). The breakthrough curves information can be used for design adsorption
columns, because provide information about the change of the concentration as a function of the time (Shahid
et al., 2019). Nevertheless, the experimental work at big scale in continuous systems is expensive and require
large intervals of time. In this sense, few studies have reported the challenge to scale, model and simulate the
system for future transition from laboratory to industrial application (Igberase and Osifo, 2019; Upadhyay et al.,
2021). Hence, in this present work, simulation of packed bed adsorption of Cr (VI) ion onto cocoa husk was
carried out using Aspen Adsorption simulator tool to solve sets of equations of the model. Factors affecting the
dynamic column performance were investigated, including the effect of as flowrate of feedstock, bed diameter,
porosity and, bed length.

2. Methodology
The system of chromium (VI) ion–contaminated stream flowing through the cacao husk packed fixed bed
adsorption column was simulated on the software Aspen Adsorption ® V10.0. Physical properties that are crucial
for execution of these simulation-based experiments were taken from data base of the investigation line, as well
as bulk density, particle density, and particle size of cocoa husk. For the application of response surface
methodology, software Statgraphics V19 was used.
2.1 Data collection
The data required for the simulation of the properties of the adsorbent and the adsorption isotherm were
obtained from research group data collection. The Bulk density and particle size of the cocoa husk, were
determined by experimentation, and are equal to 518 kg/m3 500 µm, respectively. Freundlich parameters are
shown in Table 1:
Table 1. Freundlich isotherm parameters
Model Parameter Value
Freundlich KF [(mg g-1)(mg L-1)-1/n] 8.69
1/n 1.53
R2 0.9974
SS 0.5782

2.2 Aspen adsorption assumptions and mathematical background

Using Aspen Adsorption® V10, liquid adsorption system was used to developed the simulations, taking
intoaccount the below assumptions: The behaviour of fluid across the column was assumed to be without axial
dispersion; ideal mixing in the liquid phase, so molar concentrations are calculated from molar volumes;
Isotherm model used was Freundlich; with an isothermal energy Balance; lumped mass-transfer rate, with a
solid-film linear resistance; the film model wasfluid; there is no pressure drop through the column; constant
superficial velocity; and mass transfer coefficient was assumed constant. Figure 1a shows the adsorption
process as designed in Aspen Adsorption for simulation. The discretization method used in all the simulations
was based on the first-order Taylor series expansion, by assuming a volume of control (Vc), considering that the
column has a cylindrical configuration with an area A and height Δz. Then, the partial differential mass balance
equation which was used to express the chromium ion concentration in a small control volume inside the
adsorbent bed is presented in Eq(1):
𝛿𝐶𝑖 𝛿𝐶𝑖 𝛿𝐶𝑖 𝛿𝑄𝑖
𝜀Δ𝑍 = (𝜇0 𝜀𝐶𝑖 ) − (𝜇0 𝜀𝐶𝑖 ) − (𝜀𝐷𝐿𝑖 ) + (𝜀𝐷𝐿𝑖 ) − 𝜌𝑠 Δ𝑍 (1)
𝛿𝑡 𝑧+Δ𝑧 𝛿𝑧 𝛿𝑧 𝛿𝑡
𝑧 𝑧 𝑧+Δ𝑧

In Eq(1), DLi is the axial dispersion coefficient (m2/s), ρs is the bed column density (kg/m3), µ0 is the interstitial
velocity (m/s),z is the axial position (m), t is the process time (s), Ci is the concentration of pollutant in liquid-
phase (kg/m3), and Qi is the solid-phase concentration of pulutan (g/kg) (Biswas et al., 2020).
For simulation, linear lumped resistance kinetic model was assumed, which indicates that the initial
concentration is a driving force for mass transfer during adsorption process. In addition, the adsorption of
chromium ions onto cocoa husk process is represented by Freundlich model as it gives a much higher R 2 value
(equal to 0.99), as well as the adjustment of experimental points was closer.
 519

2.3 Experimental design

The experiments were designed by using a Response Surface Central composite design: 2 3 + star, made in
Statgraphics V.19. The independent variables and their ranges are presented in Table 2. Simulation
experiments were developed for the 17 experiments in Aspen Adsorption, and the response variables, namely
saturation time and exhaustion C/Co, were obtained.

Table 2. Parameters used for simulation

Parameter -1 0 1
Inlet flowrate, m3/s 7.5×10-7 2.88×10-6 5×10-6
Bed height, m 0.30 0.45 0.60
Bed diameter, m 0.06 0.072 0.084

3. Results and discussion

3.1 Establishment of the base simulation breakthrough
A base simulation for the adsorption of Cr (VII) onto cocoa husk was established as a reference point, prior to
the studies on the affecting parameters. The initial values specifications are presented in Table 3, and these
values will remain the same throughout the study except for the manipulated variable.
Table 3. Parameters used for base case simulation
Parameter Value
Inlet flowrate, m3/s 7.5×10-7
Inlet concentration, mg/L 30 mg/L
Bed height, m 0.3
Bed diameter, m 0.06
Bed porosity, m3 void/m3 bed 0.25
Bulk density, kg/m3 518
Constant mass transfer coefficient, 1/s 3.2×10-10
Freundlich isotherm
KF, (mg g-1 (mg L-1)1/n 8.69
1/n 1.53

The plot of the base-case simulation breakthrough curve is shown in Figure 1b. The plot indicates that the
column achieves breakthrough time at about 118.65 s, under the conditions stated in Table 2. It is observed a
common “S” shape on the simulated breakthrough.
(b)
F EE D
1.0
F EE D (a)
0.8

B ED 1 0.6
Cf/Ci

0.4

0.2

0.0
P R O D U CT
0 200 400 600 800
P RO D Time (s)

Figure 1. (a) Adsorption process flowsheet in Aspen Adsorption ®, (b) Concentration ratio profile of the stream
exiting from the cacao husk for the base simulation case

3.2 Analysis of variance and factors and response interactions

The regression analysis of experimental data obtained in Table 4 led to the conclusion that breakthrough time
of the bed for this system can be expressed as a function of inlet flowrate, bed height and breakthrough time,
via Eq(2). The same, for the case of saturation time of the bed, can be modeled by Eq.(3). In addition, the
description of exhaustion C/Co ratio, can be described by Eq(4). The predicted R2, values were found to be very
close to 1 in case of all models which indicates that the suggested models can be good predictors of the
experiment results.
520

Table 4. Parameters used for simulation and responses

Factors Responses
Run Inlet flowrate, m3/s Bed height, m Bed diameter, m Breakthrough time,Saturation time, s Exhaustion C/Co
s
1 2.88×10-6 0.60 0.075 97.21 372.87 0.9590
2 2.88×10-6 0.45 0.075 76.01 273.92 0.9503
3 5×10-6 0.3 0.084 37.25 149.66 0.9791
4 7.5×10-7 0.3 0.06 118.65 442.64 0.9475
5 5×10-6 0.3 0.06 15.82 68.26 0.9533
6 5×10-6 0.45 0.075 42.96 165.17 0.9648
7 5×10-6 0.60 0.084 79.89 273.92 0.9649
8 7.5×10-7 0.60 0.084 521.66 1703.49 0.9503
9 7.5×10-7 0.60 0.06 252.74 883.15 0.9560
10 2.88×10-6 0.3 0.075 76.02 277.79 0.9533
11 2.88×10-6 0.45 0.075 73.96 279.62 0.9560
12 2.88×10-6 0.45 0.084 92.34 343. 0.9503
13 2.88×10-6 0.45 0.075 76.01 279.62 0.9560
14 7.5×10-7 0.3 0.084 248.79 853.10 0.9503
15 5×10-6 0.60 0.06 35.20 138.03 0.9503
16 7.5×10-7 0.45 0.075 301.19 1023.94 0.9533
17 2.88×10-6 0.45 0.06 48.88 180.67 0.9560
Table 5 show the analysis for the three evaluated responses for the breakthrough time, saturation time,
exhaustion C/Co ratio. While it was observed that, for breakthrough time and saturation time, as well as all three
evaluated factors, i.e., inlet flowrate (A), bed height (B), and bed diameter (C), as well as their interaction such
as AA, AB and AC, with significant factors (with P-value <0.005); for Exhaustion C/Co ration time, there was not
any significant variable. Thus, might be because, the increase of the bed height enhance the adsorption due to
the growth of the amount of active sites that allow the union of the ions with the functional groups, this effect is
evident in the adsorption of Cr(VI) with bed heights as shown in Figure 2.

Table 5. ANOVA for evaluated factors over response

Response Source Sum of square F-Ratio P-Value
Breakthrough time, s A: Inlet flowrate, m3/s 146241.0 123.22 0.0000
B: Bed height, m 23118.1 19.48 0.0031
C: Bed diameter, m 25891.3 21.82 0.0023
AA 21979.5 18.52 0.0036
AB 14890.0 12.55 0.0094
AC 13941.3 11.75 0.0110
BB 78.8 0.07 0.8041
BC 2519.97 2.12 0.1884
CC 11.78 0.01 0.9234
Total error 8307.71
Saturation time, s A: Inlet flowrate 1.63×106 163,99 0,0000
B: Bed height 241180.0 24,21 0,0017
C: Bed diameter 259537.0 26,05 0,0014
AA 227331.0 22,82 0,0020
AB 150546.0 15,11 0,0060
AC 129208.0 12,97 0,0087
BB 1428.5 0,14 0,7162
BC 20679.1 2,08 0,1928
CC 0.11 0,00 0,9975
Total error 69733.5
Exhaustion C/Co A: Inlet flowrate, m3/s 0,000105177 1,87 0,2142
B: Bed height, m 0,0000133722 0,24 0,6411
C: Bed diameter, m 0,000124238 2,20 0,1812
AA 0,0000352913 0,63 0,4548
AB 0,0000365513 0,65 0,4472
AC 0,0000365513 0,65 0,4472
BB 0,00000710613 0,13 0,7330
BC 0,000105851 1,88 0,2129
CC 0,0000594573 1,05 0,3386
Total error 0,000394616
 521

(a) (b)

(c)

Figure 2. Three-dimensional contour plots to examine the relationship between the factors and (a) breakthrough
time, (b) saturation time and (c) exhaustion C/Co

In addition, the diminution in exhaustion C/Co caused by increasing in inlet flowrate and bed height, which leads
to minimal change in exhaustion capacity. With respect to flow rate, it was found that increasing the inletflow
rate results in the decrease in both saturation and breakthrough time, as the result of reduction in residence
time of the chromium ions inside the bed which ceases the opportunity for the exchange between the ions and
active adsorption centers into the micro- and mesopores of the adsorbent particles, as reported by cadmium
and copper adsorption onto water hyacinth (Soriano et al., 2016). Meanwhile, the diminution of the breakthrough
time with the augmentation in flowrate is related with the early exhaustion of adsorption sites, since a greater
number of ions are entering into the system per unit time in addition to higher number of ions being adsorbed
due to lower mass transfer resistance (Upadhyay et al., 2021). 3D contours of Figure 2, visually illustrates the
behavior of response variables while varying factors.

BT = −118.37 + 5.71 106 F − 212.29 H + 2252.48 D + 2.01 1013 F 2 − 1.35  108 F  B

(2)
−1.63  109 F  D + 241.03H 2 + 97.99.01H  D + 15664.4 D 2

ST = −572.41 − 1.11 107 F − 670.47 H + 15250 D + 6.45  1013 H 2 − 4.30 108 F  B

(3)
−4.95  109 F  D + 1026.24 H 2 + 28070.5 H  D − 1506.95 D 2

C / C0 = 0.89 + 5494.02 F − 0.088 H + 1.88 D + 3.92 F 2 − 6705.88 F  H − 83823F  D

(4)
−0.035 H 2 + 2.02 H  D − 15.95 D 2
4. Conclusions
The analysis of breakthrough curves by simulation in Aspen Adsorption® V10, was found that chromium removal
onto cocoa a packed bed of cocoa husk shows higher performance both influent flow rate and bed height.
Through the application of response surface methodology, the effect of variation in column bed height, inlet
flowrate and bed diameter over the breakthrough time, saturation time time and exhaustion C/C 0 ratio of the
cocoa husk packed bed was evaluated, finding great influence by all the evaluated variables and their
interactions over the system.
Nomenclature
A– cross-sectional area of the packed bed, m2 F – inlet flowrate, m3/s
BT – the breakthrough time, s F-ratio–relates the variances of independent
C/C0 – exhaustion C/C0 samples
D – bed diameter, m H – bed height, m
522

T – temperature, °C Qi – cocoa husk adsorption capacity, mg/g

P – pressure, bar ST – the saturation time, s
P-value–probability of obtaining the observed w – fin width, m
results z – bed axial position, m

Acknowledgments
The authors thank to the Universidad de Cartagena for the time of the researchers and the laboratory equipment
for developing this research.

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