sustainability

Article
Experimental Design and Breakthrough Curve Modeling
of Fixed-Bed Columns Utilizing a Novel 3D Coconut-Based
Polyurethane-Activated Carbon Composite Adsorbent for
Lead Sequestration
Rubie Mae D. Fernandez 1,2 , Renz John R. Estrada 1 , Tomas Ralph B. Tomon 1,2 , Roger G. Dingcong, Jr. 1 ,
Ruben F. Amparado, Jr. 2 , Rey Y. Capangpangan 3 , Roberto M. Malaluan 1,4 , Gerard G. Dumancas 5 ,
Alona A. Lubguban 6 , Arnold C. Alguno 1,7 , Hernando P. Bacosa 1,2 and Arnold A. Lubguban 1,4, *

1 Center for Sustainable Polymers, MSU-Iligan Institute of Technology, Iligan City 9200, Philippines;
[email protected] (R.M.D.F.); [email protected] (R.J.R.E.);
[email protected] (T.R.B.T.); [email protected] (R.G.D.J.);
[email protected] (R.M.M.); [email protected] (A.C.A.);
[email protected] (H.P.B.)
2 Environmental Science Graduate Program, Department of Biological Sciences,
College of Science and Mathematics, MSU-Iligan Institute of Technology, Iligan City 9200, Philippines;
[email protected]
3 Department of Physical Sciences and Mathematics, College of Marine and Allied Sciences,
Mindanao State University at Naawan, Naawan 9023, Philippines; [email protected]
4 Department of Chemical Engineering and Technology, MSU-Iligan Institute of Technology,
Iligan City 9200, Philippines
5 Department of Chemistry, The University of Scranton, Scranton, PA 18510, USA;
Citation: Fernandez, R.M.D.;
Estrada, R.J.R.; Tomon, T.R.B.;
[email protected]
6 Department of Mathematics, Statistics, and Computer Studies, Rural High School, University of the
Dingcong, R.G., Jr.; Amparado, R.F.,
Philippines, Paciano Rizal, Bay 4033, Philippines; [email protected]
Jr.; Capangpangan, R.Y.; Malaluan, 7 Department of Physics, College of Science and Mathematics, MSU-Iligan Institute of Technology,
R.M.; Dumancas, G.G.; Lubguban, Iligan City 9200, Philippines
A.A.; Alguno, A.C.; et al. * Correspondence: [email protected]
Experimental Design and
Breakthrough Curve Modeling of Abstract: This study presents a novel polyurethane-activated carbon composite (PACC) as an effective
Fixed-Bed Columns Utilizing and sustainable adsorbent for treating lead-ion-contaminated waters. The PACC was characterized
a Novel 3D Coconut-Based
using Scanning Electron Microscopy with Energy Dispersive X-ray (SEM-EDX), Fourier Transform
Polyurethane-Activated Carbon
Infrared Spectroscopy (FTIR), Brunauer, Emmett, and Teller (BET) surface area analyzer, X-ray Diffrac-
Composite Adsorbent for Lead
tion (XRD), and Thermogravimetric Analyzer (TGA) to evaluate its physicochemical and thermal
Sequestration. Sustainability 2023, 15,
properties. Furthermore, the PACC was employed in an experimental column adsorption setup to
14344. https://doi.org/10.3390/
su151914344 investigate its adsorption performance and to develop a dynamic method suitable for industrial
implementation. Parameters such as bed height (50, 100, 150 mm), flow rate (4, 6, 8 mL min−1 ),
Academic Editor: Agostina Chiavola
pH (2, 4, 6), and initial metal-ion concentrations (10, 50, 100 mg L−1 ) were examined. The exper-
Received: 2 September 2023 imental data exhibited strong agreement with the Thomas and Yoon–Nelson models (R2 ≥ 0.96),
Revised: 25 September 2023 indicating efficient adsorption mechanisms. Remarkably, the used adsorbent has the potential for
Accepted: 27 September 2023 facile regeneration without substantial loss in capacity. The PACC demonstrated excellent adsorption
Published: 28 September 2023 performance for lead ions in aqueous solutions in a fixed-bed column system. Thus, the novel PACC
material holds the potential for scalable application in industrial settings to address water pollution
challenges, especially in regions with uncontrolled effluent discharge.

Copyright: © 2023 by the authors.

Keywords: polyurethane foam; activated carbon; adsorption; lead; heavy metals
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
1. Introduction
creativecommons.org/licenses/by/ Serious concerns have been raised regarding the environmental pollution caused by
4.0/). heavy metals and their detrimental effects on both human well-being and ecological sys-

Sustainability 2023, 15, 14344. https://doi.org/10.3390/su151914344 https://www.mdpi.com/journal/sustainability

Sustainability 2023, 15, 14344 2 of 23

tems. Multiple sources, including industrial waste, soil leaching, and petroleum products,
contribute significantly to the presence of these heavy metals [1]. Lead (Pb) has garnered
considerable interest, especially given its extensive application across multiple industrial
domains [2]. Drinking water is a primary source of Pb2+ that enters the food web, and
as a result, the World Health Organization has established a maximum allowable limit of
48 nmol/L for Pb2+ in drinking water [3]. Exceeding this limit can lead to severe health
complications [4]
Various physical and chemical techniques are at our disposal to eliminate contami-
nants, such as filtration, electrocoagulation, reverse osmosis, precipitation, biosorption,
and adsorption. The costs associated with implementing and operating these techniques
vary significantly, as does their efficacy in removing contaminants. Adsorption-based
methods, in particular, often offer cost advantages in terms of infrastructure and operation,
although the efficiency of eliminating the contaminants relies on the properties inherent
to the utilized sorbent. Despite the numerous industrial adsorbents available for heavy
metal removal in wastewater, there is a growing interest in the advancement of sustain-
able biosorbents. This interest stems from their renewable abundance and potential for
incorporation into composite materials [5].
The utilization of activated carbon (AC) has become popular due to its excellent
adsorption performance. However, the effective reusability of AC poses challenges due to
the complexity of recovery methods [6]. In many instances, modifications are necessary
to enhance the affinity of conventional AC towards specific pollutants. This is because
common AC may exhibit limitations in adsorption capacity due to its small specific surface
area, elevated ash content, inadequate adsorption selectivity, restricted surface functional
groups, and electrochemical properties [7,8]. Additionally, powdered AC tends to disperse
in water, resulting in poor recyclability, potential secondary contamination, and cost-
intensive operational procedures, rendering it unsuitable for treating high-flux effluents [9].
Alternative materials such as fly ash and biomass have a historical precedent as
the foundation for composite adsorbents. Although this method effectively prevents
aggregation and yields favorable adsorption outcomes, it is crucial to acknowledge that
most of these composite materials exist in powdered form. The use of powdered adsorbents
in water treatment encounters practical issues, notably bed cracking and column blockage,
especially in column experiments [10]. These issues result in elevated back pressure and
decreased operational efficiency. Such limitations diminish the applicability of powdered
materials for large-scale water treatment processes [10]. To address these challenges and
enhance the viability of wastewater treatment technology, the development of adsorbent
structures with three-dimensional (3D) geometries has been proposed [11]. Additionally,
the structural deterioration observed within adsorbent bodies after multiple adsorption
cycles poses a substantial barrier to long-term operational success [12].
Recognizing these challenges, extensive research has been performed using polyurethane
(PU) in heavy metal treatment [13]. PU foam is a promising and cost-effective material
that exhibits favorable thermodynamics for sequestering and binding cations, therefore
proving successful in the heavy metals and volatile compounds eradication from wastew-
ater and aqueous systems [14]. The manufacturing and shaping of PU adsorbents are
relatively straightforward, adding to their appeal [15]. The characteristics of the resulting
foam are significantly influenced by the choice of polyol, the key starting material for
PU [16]. Although petroleum-based polyols are commonly employed, their limited avail-
ability and environmental concerns have spurred investigations into alternative bio-based
polyol sources.
In the present study, a novel coconut oil (CO)-based polyurethane foam-activated
carbon composite (PACC) is formulated to address reusability, economic, environmental,
and sustainability concerns. The process starts with the sequential glycerolysis and amida-
tion of CO to produce bio-based polyol [17]. This polyol was then employed along with
AC in a PU formulation to produce a PACC material. Moreover, the produced PACC is
designed to exhibit excellent chemical and thermal stability, enhanced accessibility, and
Sustainability 2023, 15, 14344 3 of 23

cost-effectiveness in production. To assess its performance, the dynamic adsorption behav-

ior of these foams in relation was examined through experiments conducted in a fixed-bed
column setup, particularly for Pb2+ sequestration.
In a controlled laboratory setting, a method involving a fixed-bed column was em-
ployed to systematically investigate the effects of various operational factors. These factors
included bed height, pH levels, influent flow rate, and initial concentration. The aim of
this study was to thoroughly evaluate the effectiveness of using PACC as a medium for the
process of adsorption [18]. The patterns illustrating the breakthrough of Pb2+ adsorption
were additionally evaluated using the Bohart–Adams, Thomas, and Yoon–Nelson models.
This present investigation stands as the initial documented study on the incorporation
of AC, derived from coconut shells, into an innovative CO-based PU matrix that possesses
a remarkable Pb2+ adsorption efficiency. The results of the adsorption experiments demon-
strate that PACC effectively adsorbs Pb2+ ions in water solutions, suggesting its potential
for treating lead-contaminated industrial wastewater. This could be particularly beneficial
in regions or industries where unregulated wastewater discharge is a major issue and
where water quality monitoring plays a vital role in promoting sustainability.

2. Materials and Methods

2.1. Materials
The activated carbon used in this research, sourced from Philippine Japan Active
Carbon, was derived from coconut shells. To ensure uniform particle dimensions, the
AC underwent comminution and passed through a 50-mesh sieve. The lead (II) nitrate
(Pb(NO3 )2 ) of analytical grade, surfactant (INV® 690), and catalyst (Polycat® 8) were
acquired from Sigma-Aldrich Chemicals in Taguig, Philippines. The polyol part was
created by blending a combination of polyol sourced from coconut oil and a portion of
polyol derived from petroleum (namely Voranol® 4701, categorized as a polyether polyol).
To this mixture, a stabilizing agent and a dispersant in the shape of silicon oil were added,
along with methylene diphenyl diisocyanate (MDI, also known as PAPI 135 SH).

2.2. Polyol Synthesis

The polyol derived from coconut oil was synthesized through a sequential two-stage
procedure. Initially, coconut triglycerides were disintegrated into individual acylglycerol
constituents via glycerolysis (220 ◦ C, 2 h) under constant stirring [17]. This was followed by
an amidation step (140 ◦ C, 3 h). Following the synthesis process, the resultant polyol was
given time to cool down to ambient room temperature and then carefully placed and stored
within a glass container that was securely sealed to prevent any external contamination.

2.3. Preparation of the Adsorbate Solution

A standard solution containing Pb2+ at 1000 ppm was formulated by dissolving 1.598 g
of Pb(NO3 )2 in 1000 mL of distilled water. The resulting solution was then transferred
into a glass container to ensure safe storage. The necessary concentrations for this study
were achieved through sequential dilution of the initial stock solution (ranging from 0 to
150 ppm). The adsorption experiments were conducted using the resulting solutions with
varying Pb2+ concentrations.

2.4. Polyurethane Foam-Activated Carbon Composite Formulation

The laboratory procedure for PU foams entailed combining the A-side component
(MDI) with the B-side components (polyol and formulation additives). To achieve this,
the appropriate quantities of polyols, INV 690, silicon oil, Polycat 8 (B-side), as well as
activated carbon and abaca fiber (fillers), were vigorously mixed using a mechanical stirrer
in a paper cup. Following this, MDI (A-side) was added to the B-side with the fillers and
agitated vigorously for 10 s. The obtained mixture was then left uninterrupted to allow
the PU to expand in the open mold and rise vertically. After expansion, the foam was
put in a preheated oven at 60 ◦ C for a duration of two hours. The detailed formulation
Sustainability 2023, 15, 14344 4 of 23

for the preparation of the PU foam samples is provided in Table 1. The quantities of each
additive were determined based on a ratio of 100 parts by weight relative to the total polyol
components. The isocyanate index for the foam is 100.

Table 1. Integration of A-side components, B-side components, and filler in the formulation of
polyurethane-activated carbon composite (PACC) material.

Concentration
Ingredients
(Based on 100 Parts Polyol)
B-side Components
VORANOL® 4701 (petroleum-based polyol) 80.00
Coconut-based polyol 20.00
Polycat® 8 (gelling catalyst) 0.50
INV® 690 (surfactant) 1.75
Silicon oil 5.00
Fillers
Coconut activated carbon 40.00
A-side Component
Isocyanate index of PAPI® 27 100.0

Following the curing procedure, the foam specimens were allowed to stand undis-
turbed overnight before being sectioned into cubes with 0.5 × 0.5 × 0.5 cm dimensions for
subsequent testing.

2.5. Characterization
The analysis of surface morphology for both the untreated polyurethane (PU) and
polyurethane with activated carbon (PACC) samples was conducted by utilizing a scanning
electron microscope (SEM) (JSM-6510LA Analytical Scanning Electron Microscope, Tokyo,
Japan). The determination of the open-cell content (OCC) was carried out utilizing a
nitrogen pycnometer (ULTRAPYC 1200e Automatic Density Analyzer, Boynton Beach, FL,
USA). The surface area and pore size of the composite material were measured with a
surface area analyzer (Microtrac BELSORP MINI X, Osaka, Japan). To discern the functional
groups present in the composite, Fourier Transform Infrared (FTIR) spectroscopy was
employed (Shimadzu FTIR-ATR IR Tracer-100, Tokyo, Japan) across a spectral range of
4000–400 cm−1 . Thermal degradation analysis was executed through Thermogravimetric
Analysis (TGA) in a nitrogen atmosphere, employing a Shimadzu DTG 60H instrument
(Tokyo, Japan), with a constant flow rate of 20 mL min−1 and a temperature increment of
10 ◦ C per minute. The pH values were determined using a digital pH meter (KEM AT-710,
Kyoto, Japan). X-ray Diffraction (XRD) patterns were captured using a Rigaku HR-XRD
instrument (SMART Lab, 9 kW power type) equipped with a Cu K-α radiation source
(40 kV and 30 mA). The measurements encompassed the range of 3–60 degrees 2θ, and the
scanning speed was set at 0.02 degrees 2θ/0.60 s.

2.6. Column Adsorption Experiment

Figure 1 illustrates the actual fixed-bed column setup. The adsorption trial employed
a laboratory-scale continuous experimental arrangement comprising a transparent column
measuring 2 cm by 20 cm. The complete procedure was conducted under conditions
of ambient temperature. A mass of 1 g of the PACC per centimeter of the column was
measured and compacted in alignment with the preferred column height. To guarantee the
even distribution of the inlet solution and avert any potential seepage, a specially designed
3D-printed funnel was utilized to provide support for the column on both terminations, as
illustrated in Figure 1.
 most suitable combination of flow rate, pH, and bed height, the impact of varying Pb2+
concentrations on adsorption efficiency was assessed at levels of 10, 50, and 100 mg L−1.
The fixed-bed experiment was conducted until saturation was attained, signifying
the cessation of further adsorption of Pb2+ ions. Generating breakthrough curves is a cru-
Sustainability 2023, 15, 14344
cial aspect of assessing the efficiency of a fixed-bed column. These graphs are depicted
5 of 23
by
graphing the ratio of Ct/Co against the elapsed time, t [21].

Figure 1. Laboratory-scale fixed-bed column setup using polyurethane-activated carbon composite

(PACC) as a sorbent material.
Figure 1. Laboratory-scale fixed-bed column setup using polyurethane-activated carbon composite
(PACC) as a sorbent
The solution, the intended concentration of Pb2+ , underwent continuous
material.
containing
stirring at a rate of 100 revolutions per minute (rpm) while being transported downward
through the apparatus aided by a peristaltic pump. At various time intervals during this
process, samples were methodically collected. After this protocol, the concentration of
the resultant solution was ascertained using a UV-Vis spectrophotometer (Thermo Fisher
Scientific Genesys 10s, Waltam, MA, USA), operating within the wavelength range spanning
from 190 nm to 300 nm [19,20].
The main objective of this investigation was to evaluate how altering flow rates and
bed heights affect the adsorption of Pb2+ ions. This was accomplished through a sequence of
experimental procedures. The experimental configuration was systematically investigated
using a range of flow rates (4, 6, and 8 mL min−1 ), pH values (2, 4, 6), and bed heights
(50, 100, and 150 mm), with the other factors being held steady. After determining the
most suitable combination of flow rate, pH, and bed height, the impact of varying Pb2+
concentrations on adsorption efficiency was assessed at levels of 10, 50, and 100 mg L−1 .
The fixed-bed experiment was conducted until saturation was attained, signifying the
cessation of further adsorption of Pb2+ ions. Generating breakthrough curves is a crucial
aspect of assessing the efficiency of a fixed-bed column. These graphs are depicted by
graphing the ratio of Ct /Co against the elapsed time, t [21].

2.7. Analysis of Data from the Column

In fixed-bed column setups, a breakthrough curve is typically used to measure its
effectiveness. Breakthrough curves indicate the total mass adsorbed by the adsorbent, qtotal
at specific conditions over time t, as determined by Equation (1):
Z t
QA Q total
qtotal = = Cad dt (1)
1000 1000 0

where Q represents the flow rate (expressed in mL min−1 ), A signifies the area under the
curve, t denotes the total duration of the run (measured in minutes), and Cad represents the
amount of adsorbed concentration of Pb2+ ions in milligrams per liter (mg L−1 ).
Sustainability 2023, 15, 14344 6 of 23

Equation (2) was employed for the calculation of the maximum metal uptake, denoted
as qeq , within the continuous adsorption system. Additionally, Equation (3) was employed
to calculate the total volume of effluent, Veff , expressed as follows:

qtotal
qeq = (2)
m

Ve f f = Qttotal (3)
where m represents the continuous system’s dry weight.

2.8. Breakthrough Curve Modeling

The behavior of the continuous sorption process can be assessed through breakthrough
curves, which illustrate the variation in pollutant concentration in the effluent over time
within a fixed-bed column. Mathematical models that rely on these curves are employed to
depict and forecast experimental data, serving as valuable tools for optimizing fixed-bed
column designs and scaling up the process [22].
The Thomas model is commonly utilized to ascertain the parameters linked with
breakthrough curves, and assessing the efficiency of adsorption often serves as an initial
stage in the design of a removal system for a fixed-bed column [23].
The determination of parameters, particularly the rate constant indicated as kTh
and the maximum adsorption capacity known as qmax , can be accomplished through the
utilization of the linear approximation of the Thomas equation, represented by the following
equation [24]:  
C0 k q m
ln − 1 = Th Th − k Th C0 t (4)
Ct Q
where kTh represents the Thomas rate constant (measured in L mg−1 min−1 ); qTh signifies
the adsorption capacity (measured in mg g−1 ); t represents the total flow time (measured
in minutes); m is the mass of the adsorbent (measured in grams); and Q indicates the flow
rate (measured in mL min−1 ).
According to the Bohart–Adams model, the adsorption efficiency relies on the proper-
ties of both the sorbent and the substance undergoing adsorption [25]. This relationship is
mathematically described by the following equation:
 
Ct Z
ln ( ) = k AB C0 t − k AB N0 (5)
C0 U0

where kAB signifies the Bohart–Adams rate constant (measured in L mg−1 min−1 ); N0
represents the saturation concentration (measured in mg L−1 ); t signifies the flow time
(measured in minutes); Z denotes the bed height (measured in centimeters); and U0
indicates the superficial velocity (measured in cm min−1 ).
Conversely, the Yoon–Nelson model is based on the concept of diminishing adsorp-
tion probability [21]. In prior research, the Yoon–Nelson model has been mathematically
formulated in a linearized manner for the analysis of individual systems [26,27]:

Ct
ln ( ) = kYN t − τkYN (6)
C0 − C t

where kYN for the Yoon–Nelson rate constant (measured in min−1 ); τ represents the time
required for 50% breakthrough of the adsorbate (measured in minutes); and t signifies the
breakthrough time.
 Sustainability 2023, 15, 14344 7 of 23

3. Results and Discussion

3.1. Adsorbent Characterization
3.1.1. SEM-EDX Analysis
This study involved the examination of the surface structure and morphology of the
PACC adsorbent by utilizing scanning electron microscopy (SEM). Figure 2 displays SEM
images revealing the morphological structures of the blank PU foam and the PACC before
and after subjecting to adsorption. It can be observed that the PACC exhibited a more
distinct open-cell structure compared to the blank PU foam. This observation is verified
with the pycnometric analysis that resulted in a higher PACC open-cell content of 88%
compared to the 75% open-cell content of blank PU. Moreover, the microphotographs of
PACC as shown in Figure 2(b.1,b.2) reveal larger cell sizes compared to the blank PU’s
microphotographs in Figure 2(a.1,a.2). In the lens of PACC’s potential as Pb2+ adsorbent,
these observations could further translate to the enhancement of PACC’s ability for Pb2+
sequestration [28]. The inclusion of larger open-cell matrices in the composite foam en-
hances the accessibility of Pb2+ to the PACC adsorbent [29]. Furthermore, the presence of
numerous small channels in the open-cell design of the PACC foam is advantageous, as it
facilitates the rapid dispersion of Pb2+ across the surface. Moreover, the substantial porosity
of the material establishes an interconnected three-dimensional (3D) environment, provid-
ing accessibility and ample storage capacity for Pb2+ [29]. As shown in Figure 2(c.1,c.2), the
microphotographs of PACC after subjecting to Pb2+ adsorption revealed no significant phys-
stainability 2023, 14, x FOR PEER REVIEW
ical changes as compared to the microphotographs of unused PACC in Figure 2(b.1,b.2).
These findings demonstrate the structural durability and stability of PACC during its
employment for Pb2+ adsorption.

Figure 2. SEM images of blank polyurethane foam (a.1,a.2), polyurethane-activated carbon composite
Figure 2. polyurethane-activated
(b.1,b.2), SEM images of blank polyurethane
carbon composite after foam (a.1,a.2),
lead adsorption polyurethane-activated ca
(c.1,c.2).
site (b.1,b.2), polyurethane-activated carbon composite after lead adsorption (c.1,c.2).

Table 2. Elemental composition comparison of blank PU (a), PACC (b), and PACC after
tion (c).
Sustainability 2023, 15, 14344 8 of 23

Table 2 presents the elemental composition analysis of blank PU and PACC using EDX.
After the integration of activated carbon (AC) into the polyurethane (PU) matrix, there was
an observed rise in carbon content by 1.85% and oxygen content by 9.87%. Conversely, the
nitrogen content displayed a relative decrease of 2.00%. Enhanced levels of O/C and (O +
N)/C values correspond to an increased degree of negative polarity in the material [30]. As
presented in Table 2, PACC demonstrates notably elevated O/C ratio and (O + N)/C ratios
of 35.55% and 17.65%, respectively, in comparison to the blank PU. This finding implies the
creation of a higher number of sorption sites within PACC, which enhances its potential for
the sequestration of Pb2+ ions. These observed variations in composition can be attributed
to the intrinsic hydroxyl groups in AC, resulting in an enhanced oxygen concentration in
the PACC. PACC exhibits a significant presence of oxygen-containing functional groups,
which have been previously reported to facilitate the adsorption of Pb2+ [31]. After the
adsorption process, the O/C ratio and (O + N)/C ratios experienced a reduction of 37.70%
and 31.25%, respectively. This is ascribed to the depolarization of the participating amino
and oxygen-containing groups during their interaction with Pb2+ , therefore reducing the
PACC’s negative polarity during the Pb2+ adsorption process [32]. Thus, this observation
relates to the successful interaction of Pb2+ to the PACC’s active sorption sites.

Table 2. Elemental composition comparison of blank PU (a), PACC (b), and PACC after lead adsorption (c).

Element Wt%
Difference Difference
a b c
(b−a) (c−b)
CK 53.28 ± 1.13 55.13 ± 1.05 56.11 ± 1.03 1.85 −4.02
NK 12.58 ± 1.00 10.58 ± 0.81 9.56 ± 0.79 −2.00 3.98
OK 23.73 ± 1.19 33.60 ± 1.22 21.27 ± 1.20 9.87 −4.33
SiK 1.31 ± 0.01 0.60 ± 0.01 0.51 ± 0.01
PtK 3.10 ± 0.80 0.09 ± 0.11 0.18 ± 0.09
PbK 0.00 0.00 12.37 ± 0.16
O/C 0.45 0.61 0.38 35.55% −37.70%
(O+N)/C 0.68 0.80 0.55 17.65% −31.25%

3.1.2. FTIR Analysis

In addition to their physical characteristics, the adsorption capacity of PU and AC
can also be influenced by their chemical composition. Although the porous structure
is important, the chemical structural attributes of these materials (i.e., their functional
groups) can also have an impact on their adsorption capacities [32,33]. FTIR spectroscopy
was used to analyze the chemical characteristics of PU and PACC adsorbent foams, as
illustrated in Figure 3. The significant peak at 3311 cm−1 is associated with the O-H
bonds present in the foam samples. Additionally, the heightened intensity of the peak at
3311 cm−1 in PACC is ascribed to the inherent OH (hydroxyl) groups existing in its AC
constituent. This suggests that PACC harbors a greater abundance of OH groups compared
to the blank PU, consequently manifesting a more negatively polar chemical structure.
Furthermore, the identified peak at 1740 cm−1 is associated with the stretching vibrations
of C=O, which are linked to the urethane component within the foam samples [34]. The
peaks at 1601 cm−1 correspond to the bending vibrations of C=O, which can be linked to
the urethane components, and the stretching vibrations of C-O in carboxylic acids present
on the AC surfaces [35]. The peaks at 1521 cm−1 correspond to the bending of N-H and
the stretching vibrations of C=O, which can be ascribed to the existence of urethane bonds
and carboxyl groups within the PACC matrices. It is worth highlighting that the significant
increase in the mentioned peaks found in PACC compared to the blank PU can be attributed
to the presence of AC in the PACC matrix. Furthermore, the observed reduction of the
oxygen- and nitrogen-related peaks on the FTIR spectrum of PACC after adsorption reveals
the reduction of functional sites, as indicated by the peak intensity reductions found at
3311 cm−1 , 1740 cm−1 , 1601 cm−1 , 1521 cm−1 , due to the interaction of Pb2+ ions. These
 and carboxyl groups within the PACC matrices. It is worth highlighting that the signifi-
cant increase in the mentioned peaks found in PACC compared to the blank PU can be
attributed to the presence of AC in the PACC matrix. Furthermore, the observed reduction
of the oxygen- and nitrogen-related peaks on the FTIR spectrum of PACC after adsorption
Sustainability 2023, 15, 14344 9 of 23
reveals the reduction of functional sites, as indicated by the peak intensity reductions
found at 3311 cm−1, 1740 cm−1, 1601 cm−1, 1521 cm−1, due to the interaction of Pb2+ ions.
These observations agree with other research on the role of these peaks in the reaction
observations
with Pb2+ [2,36].agree with other research on the role of these peaks in the reaction with
Pb 2+[2,36].

Figure 3. Fourier transform infrared (FTIR) spectra of blank polyurethane foam, polyurethane-
Figure 3. Fourier transform infrared (FTIR) spectra of blank polyurethane foam, polyurethane-acti-
activated carbon composite (PACC), and PACC after Pb adsorption.
vated carbon composite (PACC), and PACC after Pb adsorption.
3.1.3. Surface Area Analysis
3.1.3. Surface Areacharacteristics
The textural Analysis of both blank PU and PACC, encompassing specific surface
area
The and pore dimensions,
textural were of
characteristics examined utilizing
both blank a surface
PU and PACC, area analyzer via nitrogen
encompassing specific sur-
adsorption-desorption isotherms. The
face area and pore dimensions, were examined outcomes unveiled that the Brunauer–Emmett–Teller
utilizing a surface area analyzer via nitro-
(BET) surface area of PU, quantified at 1.1817 m2 g−1 , exhibited a notable disparity in com-
gen adsorption-desorption isotherms. The outcomes unveiled that the Brunauer–Emmett–
parison to PACC before adsorption, which demonstrated a 2measurement of 10.8949 m2 g−1 .
Teller (BET) surface area of PU, quantified at 1.1817 m g⁻ 1, exhibited a notable disparity
This discrepancy underscores that the integration of activated carbon into the PU matrix
in prompted
comparison to PACC upsurge
a substantial before adsorption, which
In surface area, demonstrated
approximately a measurement
ten-fold, of 10.8949
therefore yielding
m ag⁻
2 1 . This of
plethora discrepancy
binding sitesunderscores that the integration
for effective sequestration 2+ of activatedthe
of Pb . Furthermore, carbon
averageinto
porethe PU
matrix prompted
sizes for a substantial
PU and PACC upsurgeasIn2.3406
were determined surface
nm area, approximately
and 0.9825 ten-fold,
nm, respectively. therefore
Reduced
pore dimensions
yielding a plethora lead
oftobinding
an enlarged
sitessurface area andsequestration
for effective an increased surface-to-volume ratio. the
of Pb2+. Furthermore,
This phenomenon
average pore sizes explains
for PU and the observed
PACC were augmentation
determined in the
asPACC’s
2.3406 surface
nm andarea [37]. nm, re-
0.9825
spectively. Reduced pore dimensions lead to an enlarged surface area and an increased
3.1.4. XRD Analysis
surface-to-volume ratio. This phenomenon explains the observed augmentation in the
Figure 4 portrays the X-ray diffraction (XRD) pattern of both the blank PU and PACC
PACC’s surface area [37].
samples. The diffraction patterns exhibit a diffuse and subtle diffraction peak observed at
approximately 19◦ and 43◦ 2θ angles. These angles correspond to the distinctive diffraction
patterns associated with the amorphous carbon structure aligned with the (0 0 2) and
(1 0 0) crystallographic planes, respectively [38]. Furthermore, the presence of these peaks
at a subdued intensity implies a limited extent of graphitization, therefore implying the
presence of a carbonaceous structure with relatively low crystallinity [39].
 Figure 4 portrays the X-ray diffraction (XRD) pattern of both the blank PU and PACC
samples. The diffraction patterns exhibit a diffuse and subtle diffraction peak observed at
approximately 19° and 43° 2θ angles. These angles correspond to the distinctive diffrac-
tion patterns associated with the amorphous carbon structure aligned with the (0 0 2) and
(1 0 0) crystallographic planes, respectively [38]. Furthermore, the presence of these peaks
Sustainability 2023, 15, 14344 at a subdued intensity implies a limited extent of graphitization, therefore implying the 10 of 23
presence of a carbonaceous structure with relatively low crystallinity [39].

Figure 4. XRD profile of a blank polyurethane (PU) and polyurethane-activated carbon composite
Figure 4. XRD profile of a blank polyurethane (PU) and polyurethane-activated carbon composite
(PACC).
(PACC).
3.1.5. Thermogravimetric Analysis
3.1.5. Thermogravimetric Analysis
Figure 5 illustrates the thermal properties of blank PU, PACC, and PACC after adsorp-
Figure 5 illustrates the thermal properties of blank PU, PACC, and PACC after ad-
tion. The black lines represent the weight loss graph, whereas the red line corresponds to
sorption. The black lines represent the weight loss graph, whereas the red line corre-
the derivative thermogravimetry graph. In Figure 5a, the DTG graph of PU displays two
sponds to the derivative thermogravimetry graph. In Figure 5a, the ◦DTG graph of◦ PU dis-
notable
plays endothermic
two notable peakspeaks
endothermic located at approximately
located at approximately 184184C°C andand406
406 C.
°C.The
The mentioned
peaks suggest
mentioned the thermal
peaks suggest degradation
the thermal of the unique
degradation rigid and
of the unique rigidflexible segments
and flexible seg- of PU. The
rigid
ments of segments
PU. The rigidcansegments
be linked cantobethe presence
linked of urethane
to the presence bonds, bonds,
of urethane whereas the introduction
whereas
theof fatty acid chains
introduction into chains
of fatty acid the PUinto matrix
the PU affects
matrixthe flexible
affects segments
the flexible [17]. In
segments contrast, the
[17].
DTG examination
In contrast, of PACCofbefore
the DTG examination PACC and before following adsorption
and following adsorption discloses
disclosesthe
thepresence of
presence
severalofpeaks
severallocated
peaks located at approximately
at approximately 220 ◦ C, °C, ◦310
220310 ◦ C, °C,
°C, 400
C, 400 andand ◦ C,
440440 °C,
asasdisplayed in
displayed
Figure in Figure
5b,c. 5b,c. to
Similar Similar
pure to
PU, pure
thePU,peaksthe identified
peaks identified ◦
at 220at 220
C and 400 ◦400
°C and °C
C correspond to
correspond
the thermalto the thermal breakdown
breakdown of the urethane
of the urethane segmentssegments
and the andfatty
the fatty
acid acid com-
components within
ponents withinFurthermore,
the PACC. the PACC. Furthermore,
the extra peak the extra
canpeak can be ascribed
be ascribed to the thermal
to the thermal dis-
disintegration of the
integration of the activated carbon constituents incorporated into the composite [40]. Ad-
activated carbon constituents incorporated into the composite [40]. Additionally, the TGA-
Sustainability 2023, 14, x FOR PEER ditionally,
REVIEW the TGA-DTG curve of PACC following adsorption, as depicted in Figure 5c,
DTG curve of PACC following adsorption, as depicted in Figure 5c, displays comparable 11 of 25
displays comparable thermal degradation peaks to those of PACC in Figure 5b. This ob-
thermal degradation peaks to those of PACC in Figure 5b. This observation implies that
servation implies that the thermal stability of PACC was not compromised during the ad-
the thermal
sorption process.stability of PACC was not compromised during the adsorption process.

Figure 5. Cont.
Sustainability 2023, 15, 14344 11 of 23

Figure 5. TGA-DTG curves of (a) polyurethane (PU), (b) polyurethane-activated carbon composite
Figure
(PACC),5.and
TGA-DTG curves ofafter
(c) PACC composite (a) adsorption.
polyurethane (PU), (b) polyurethane-activated carbon com
(PACC), and (c) PACC composite after adsorption.
3.2. Effect of Dynamic Adsorption Parameters
Table 3 displays the data parameters obtained from the column under varying Pb con-
3.2. Effect of Dynamic Adsorption Parameters
centrations, bed heights, pH, and flow rates while maintaining a constant room temperature.
Table 3 displays the data parameters obtained from the column under varyin
Table 3. Data parameters
concentrations, bed attained at different
heights, pH, and bedflow
heights, pH, flow
rates rates,
while and inlet Pb concentrations
maintaining a constant room
(T = 28 ± 1 ◦ C).
perature.
Data parameters attained at different bed heights with constant initial concentration (50 mg L−1 ),
flow rate (4 mL min−1 ), and pH (6)
Total mass Equilibrium
Bed height Total time Effluent volume
adsorbed, qtotal uptake, qeq
(mm) (min) (mL)
(mg) (mg g−1 )
50 190 35.85 7.17 760
100 240 106.3 10.63 960
150 300 125.7 8.38 1200
Sustainability 2023, 15, 14344 12 of 23

Table 3. Cont.

Data parameters attained at different initial concentrations with constant bed height (100 mm),
flow rate (4 mL min−1 ), and pH (6)
Initial Total mass Equilibrium
Total time Effluent volume
Concentration adsorbed, qtotal uptake, qeq
(min) (mL)
(mg L−1 ) (mg) (mg g−1 )
10 290 94.6 9.46 1100
50 240 106.6 10.66 960
100 180 135.4 13.54 270
Data parameters attained at different flow rates with constant bed height (100 mm),
initial concentration (50 mg L−1 ), and pH (6)
Total mass Equilibrium
Flow rate Total time Effluent volume
adsorbed, qtotal uptake, qeq
(mL min−1 ) (min) (mL)
(mg) (mg g−1 )
4 250 106.6 10.66 1000
6 195 105.6 10.56 1170
8 150 86.6 8.66 1200
Data parameters attained at different pH with constant bed height (100 mm),
initial concentration (50 mg L−1 ), and flow rate (4 mL min−1 )
Total mass Equilibrium
Total time Effluent volume
pH adsorbed, qtotal uptake, qeq
(min) (mL)
(mg) (mg g−1 )
2 265 220.3 22.03 1060
4 300 280.0 28.00 1200
6 250 107.0 10.70 1000

3.2.1. Effect of Bed Height

Figure 6 shows the breakthrough curve for Pb2+ adsorption on PACC at three distinct
bed heights (50 mm, 100 mm, and 150 mm). The flow rate was held steady at 6 mL min−1 ,
pH at 6, and the inlet concentration of Pb2+ was kept constant at 50 mg L−1 . The experi-
mental results show that elevating the bed height from 50 mm to 150 mm resulted in an
extended time for the bed to achieve saturation. This observation implies a correlation
between the breakthrough curve and the bed height, indicating an expansion in the zones
of mass transfer [41]. Additionally, Figure 6 demonstrates that reducing the bed height
resulted in a more rapid saturation. Meanwhile, increasing the bed height to 150 mm
improved the removal efficiency. Similar studies have observed that these findings are
influenced by the augmentation of active sorption sites and the prolongation
Sustainability 2023, 14, x FOR PEER REVIEW 13 of 25 of duration of
2+
contact between PACC and Pb [42,43].

Figure
Figure 6. Breakthrough
6. Breakthrough curves
curves for for Pb2+ on
Pb2+ adsorption adsorption on polyurethane-activated
polyurethane-activated carbon composite carbon composite
(PACC) at different bed heights.
(PACC) at different bed heights.
3.2.2. Effect of Flow Rate
To examine the influence of flow rate on Pb2+ adsorption using PACC, the flow rate
was subjected to variation (4, 6, and 8 mL min−1), keeping a consistent adsorbent bed
height of 100 mm, a pH level of 6, and a constant inlet concentration of Pb2+ at 50 mg L−1.
The outcomes of this investigation are presented in Figure 7, where the breakthrough
Sustainability 2023, 15, 14344 13 of 23

Figure 6. Breakthrough curves for Pb2+ adsorption on polyurethane-activated carbon composite

3.2.2. Effect of Flow Rate
(PACC) at different bed heights.
To examine the influence of flow rate on Pb2+ adsorption using PACC, the flow rate
3.2.2. Effect of Flow Rate
was subjected to variation (4, 6, and 8 mL min−1 ), keeping a consistent adsorbent bed
To examine the influence of flow rate on Pb2+ adsorption using PACC, the flow rate
height of 100 mm, a pH level of 6, and a constant inlet concentration of Pb2+ at 50 mg L−1 .
was subjected to variation (4, 6, and 8 mL min−1), keeping a consistent adsorbent bed
The outcomes
height of 100 mm, a ofpHthis
levelinvestigation areinlet
of 6, and a constant presented in Figure
concentration of Pb2+ at7,50where
mg L−1. the breakthrough curve
The outcomes of The
is depicted. this investigation are presented
findings indicate in Figure 7, enhancement
a significant where the breakthrough
in breakthrough occurrence
curve is depicted. The findings indicate a significant enhancement in breakthrough occur-
with the escalation of flow rate. Conversely, along with the
rence with the escalation of flow rate. Conversely, along with the decreasing flow rate,
decreasing flow rate, there is
a significant extension of the duration required to reach saturation.
there is a significant extension of the duration required to reach saturation. At lower flow At lower flow rates,
there was more time for the interaction between Pb and PACC, resulting in an augmented
rates, there was more time for the interaction between Pb and PACC, resulting in an aug-
mented removal of Pb 2+ in the column.
removal of Pb2+ in the column.

Figure 7. Breakthrough
Figure curves forcurves
7. Breakthrough for Pb2+
Pb2+ adsorption on adsorption
polyurethane-activated carbon composite
on polyurethane-activated carbon composite
(PACC) at different flow rates.
(PACC) at different flow rates.

The fundamental concepts of mass transfer clarify the variations noticed in the steep-
ness of the breakthrough curve and the adsorption capacity. Increased flow rates induce
a reduction in the hindrance to mass transfer posed by the external film at the surface of
the adsorbent, leading to an escalated rate of mass transfer and a decreased residence time.
Consequently, saturation is achieved more quickly, leading to decreased removal efficiency.
This implies that the amount of heavy metal adsorbed per unit of bed height, known as the
mass transfer zone, enlarges with higher flow rates, resulting in a more rapid attainment
of saturation capacity [22,44]. In contrast, inadequate solute residence time in the column
results in a decline in the adsorption capacity, as the solute exits the column before reaching
equilibrium. Similar patterns have been noted by other investigators [45–47].

3.2.3. Effect of Initial Concentration

Figure 8 portrays the influence of varying the initial Pb2+ concentration on the break-
through curve, all the while sustaining a constant adsorbent bed height (100 mm), pH value
of 6, and solution flow rate of 6 mL min−1 . The graphical representation indicates that an
elevation in the initial Pb2+ influent concentration prompts a more rapid achievement of
saturation in the adsorption process, subsequently leading to a reduction in breakthrough
time. It is noteworthy that at lower Pb2+ inlet concentrations, the breakthrough curves
exhibited increased dispersion, resulting in a more gradual manifestation of breakthrough.
Conversely, sharper breakthrough curves were observed upon increasing the influent con-
centration of Pb2+ . This phenomenon can be ascribed to the higher concentration gradient,
which resulted in swifter movement attributed to the mass transfer coefficient.
An elevated influent concentration results in a more pronounced incline of the break-
through curve and a shorter breakthrough time, in accordance with findings from previous
studies [48]. These results suggest that the concentration affects the level of saturation
and breakthrough time, implying that the dispersion mechanism is influenced by the
influent concentration. An increase in the influent concentration led to an increase in
the driving force for mass transfer, leading to a decrease in the length of the adsorption
 3.2.3. Effect of Initial Concentration
Figure 8 portrays the influence of varying the initial Pb2+ concentration on the break-
through curve, all the while sustaining a constant adsorbent bed height (100 mm), pH
value of 6, and solution flow rate of 6 mL min−1. The graphical representation indicates
that an elevation in the initial Pb2+ influent concentration prompts a more rapid achieve-
Sustainability 2023, 15, 14344 ment of saturation in the adsorption process, subsequently leading to a reduction in break- 14 of 23
through time. It is noteworthy that at lower Pb2+ inlet concentrations, the breakthrough
curves exhibited increased dispersion, resulting in a more gradual manifestation of break-
through. Conversely, sharper breakthrough curves were observed upon increasing the in-
zoneconcentration
fluent [22,49]. Theseof Pb2+findings are congruent
. This phenomenon withtoprior
can be ascribed studies
the higher conducted
concentration on numerous
fixed-bed
gradient, adsorption
which frameworks
resulted in swifter movement [47,50].
attributed to the mass transfer coefficient.

Figure
Figure8. Breakthrough
8. Breakthroughcurves curves for Pb2+ adsorption
for Pb2+ adsorption on polyurethane-activated carbon composite
on polyurethane-activated carbon composite
(PACC) at different initial concentrations.
(PACC) at different initial concentrations.
An Effect
3.2.4. elevatedof
influent
pH concentration results in a more pronounced incline of the break-
through curve and a shorter breakthrough time, in accordance with findings from previ-
The[48].
ous studies pHThese
values exert
results a critical
suggest that theinfluence onaffects
concentration various aspects
the level of heavy metal behavior
of saturation
within the environment. Beyond its influence on the dissociation of
and breakthrough time, implying that the dispersion mechanism is influenced by theheavy
in- metal sites, pH
fluent concentration.
exerts a An
substantial increase
impact in the
on influent
solution concentration
chemistry led
by to an increase
contributing in the
to various processes,
Sustainability 2023, 14, x FOR PEER REVIEW 15 of 25
driving force for mass transfer, leading to a decrease in the length of the adsorption zone
including redox reactions, hydrolysis, complexation with organic
[22,49]. These findings are congruent with prior studies conducted on numerous fixed-
and/or inorganic ligands,
and precipitation. The pH
bed adsorption frameworks [47,50]. significantly governs these mechanisms and consequently has
3.2.4. Effect of pH
a notable effect on the availability of heavy metals for biosorption [51]. To assess how
The pH values exert a critical influence on various aspects of heavy metal behavior
pH levels
within affectBeyond
the environment. the efficiency
its influence onofthePb
2+ adsorption
dissociation bysites,
of heavy metal PACC,
pH a series of pH values ranging
exerts a substantial impact on solution chemistry by contributing to various processes,
from 2 to 6 were utilized for investigation. Throughout
including redox reactions, hydrolysis, complexation with organic and/or inorganic lig-
this experimentation, the bed
height (100 mm), flow rate (4 mL min ), and initial concentration (50 mg L−1 ) remained
ands, and precipitation. The pH significantly governs these − 1
mechanisms and consequently
has a notable effect on the availability of heavy metals for biosorption [51]. To assess how
constant. As shown in Figure 9, the breakthrough curve at pH = 2 shifted towards the left,
pH levels affect the efficiency of Pb2+ adsorption by PACC, a series of pH values ranging
indicating
from 2 to 6 were autilized
shorter breakthrough
for investigation. Throughout time. This occurrence
this experimentation, the bed can be explained by the higher
height (100 mm), flow rate (4 mL min−1), and initial concentration (50 mg L−1) remained
concentration of hydronium ions at lower pH levels, which competes effectively with Pb2+
constant. As shown in Figure 9, the breakthrough curve at pH = 2 shifted towards the left,
ions for
indicating interaction
a shorter breakthrough with the occurrence
time. This active sites of PACC
can be explained [52].
by the higher Although at pH values greater
concentration of 2+hydronium ions at lower pH levels, which competes effectively with Pb2+
than 6, Pb ions undergo solvation, hydrolysis, and
ions for interaction with the active sites of PACC [52]. Although at pH values greater than
lead oxide precipitation [53]. These
6,precipitates
Pb2+ ions undergo are unable
solvation, to be
hydrolysis, adsorbed
and lead by the
oxide precipitation PACC
[53]. foam, leading to a decrease in the
These precip-
itates are unable to be adsorbed by the PACC foam, leading to a decrease in the break-
breakthrough time, which occurred at 240 min. Hence, at a moderate pH (pH = 4), these
through time, which occurred at 240 min. Hence, at a moderate pH (pH = 4), these circum-
circumstances
stances can be mitigated,can be mitigated,
resulting resultingtime.
in the longest breakthrough in the longest breakthrough time.

Figure 9. Breakthrough curves for Pb2+ adsorption on polyurethane-activated

Figure 9. Breakthrough curves for Pb2+ adsorptioncarbon
(PACC) at different pH values.
composite
on polyurethane-activated carbon composite
(PACC) at different pH values.
3.3. Modeling of Column Data
Mathematical modeling is of crucial importance in upscaling techniques from labor-
atory experiments to pilot plants and industrial scales. It acts as a valuable instrument for
examining and explaining experimental information, recognizing significant process
mechanisms, foreseeing the outcomes of different operational circumstances, and enhanc-
ing the total effectiveness of the process [18].
Sustainability 2023, 15, 14344 15 of 23

3.3. Modeling of Column Data

Mathematical modeling is of crucial importance in upscaling techniques from labora-
tory experiments to pilot plants and industrial scales. It acts as a valuable instrument for
examining and explaining experimental information, recognizing significant process mech-
anisms, foreseeing the outcomes of different operational circumstances, and enhancing the
total effectiveness of the process [18].

3.3.1. Thomas Model

The theoretical framework suggested by the Thomas model suggests that the flow
pattern inside the bed adheres to a plug flow configuration. Additionally, the model in-
corporates the Langmuir isotherm to describe the equilibrium behavior and second-order
reversible reaction kinetics [24]. This simulation is extensively accepted and commonly
employed to characterize sorption processes in fixed-bed columns. It is especially ap-
plicable in situations where external and internal dispersion has minimal impact on the
overall process.
Table 4 demonstrates that the Thomas model exhibited a remarkable fit, with R2 values
of 0.96 to 0.98. Based on the model, the total adsorption capacity (qo ) rises as the inlet
concentration of Pb2+ increases. This phenomenon can be attributed to the fundamental
driving force of adsorption, which primarily originates from the difference in Pb2+ concen-
tration between the solution and the adsorbent composite [54]. Furthermore, a surge in
flow rate leads to a decreased total adsorption capacity (qTh ). Similar findings have been
reported in other studies [43,46].

Table 4. Thomas model parameters at different conditions using linear regression analysis.

kTh qTh
Parameter R2
(L mg−1 min−1 ) × 10−4 (mg g−1 )
Flow rate 4 2.11 0.3774 0.8801
(mL min−1 ) 6 3.13 0.3866 0.8764
8 4.32 0.9725 0.9122
Bed height (mm) 50 3.50 0.7106 0.9354
100 2.11 0.3774 0.8801
150 1.73 0.3690 0.8284
2 1.50 0.8267 0.8801
pH 4 1.80 1.8025 0.9784
6 2.11 0.3774 0.8801
Initial metal 10 3.53 0.2706 0.9301
concentration 50 2.11 0.3774 0.8801
(mg L−1 ) 100 1.64 0.7356 0.8664

3.3.2. Bohart–Adams Model

Bohart and Adams introduced an equation derived from surface reaction theory to
establish a relationship relating to Ct /C0 and t in a continuous system [25]. This equation
can be used in illustrating the initial portion of the breakthrough curve, as it postulates that
equilibrium is not immediately attained.
The data presented in Table 5 reveals that higher effluent Pb2+ concentration and flow
rate are associated with decreased values of kAB , while increased bed height corresponds to
an increase in kAB . These trends are consistent with findings from prior research [55,56],
indicating that surface mass transfer plays a significant function in the kinetics of the overall
system, particularly throughout the preliminary phase of column adsorption [57].
Sustainability 2023, 15, 14344 16 of 23

Table 5. Bohart–Adams model parameters at different conditions using linear regression analysis.

KAB N0
Parameter R2
(L mg−1 min−1 ) × 10−5 (mg L−1 )
Flow rate 4 2.44 0.6023 0.6781
(mL min−1) 6 2.93 0.7181 0.5621
8 2.30 0.7503 0.7032
Bed height (mm) 50 2.25 0.9150 0.8164
100 2.44 0.6023 0.6781
150 1.83 0.5035 0.6132
2 3.10 0.7041 0.6789
pH 4 2.89 0.8278 0.8954
6 2.44 0.6023 0.6781
Initial metal 10 4.05 0.4037 0.8381
concentration 50 2.44 0.6023 0.6781
(mg L−1 ) 100 1.33 0.8980 0.6964

Although the Bohart–Adams model is widely utilized and valuable for conducting and
analyzing adsorption-column experiments, it is crucial to acknowledge that its applicability
is limited to certain experimental conditions [41,43]. The model’s correlation coefficient
falling below 0.96 indicates that it is not sufficient for fully capturing the adsorption
behavior of the column. Instead, it is exclusively suitable for depicting the initial portion of
the breakthrough curve [5].

3.3.3. Yoon–Nelson Model

Yoon–Nelson postulated that the decline in the likelihood of adsorbate molecule bind-
ing is intricately linked to both the probability of adsorbate adsorption and the occurrence
of breakthrough phenomena within the adsorbent medium [27] (Table 6).

Table 6. Yoon–Nelson model parameters at different conditions using linear regression analysis.

kYN Tcalc
Parameter R2
(mg−1 min−1 ) × 10−2 (min)
Flow rate 4 2.11 9.4382 0.8801
(mL min−1 ) 6 3.13 6.4445 0.8764
8 4.32 5.8982 0.9122
Bed height (mm) 5 3.50 8.8842 0.9354
10 2.11 9.4382 0.8801
15 1.73 13.8422 0.8284
2 1.50 20.6706 0.8801
pH 4 1.77 45.0641 0.9784
6 2.11 9.4382 0.8801
Initial metal 10 1.72 13.5244 0.9301
concentration 50 2.11 9.4382 0.8801
(mg L−1 ) 100 3.24 9.1965 0.8664

The Yoon–Nelson model demonstrated its applicability to the current system, as

indicated by R2 values surpassing 0.96. According to the model, the 50% breakthrough
extended as the bed height increased, but decreased when higher concentrations and flow
rates were employed. These observations align with earlier research findings [43,46].
The Thomas and Yoon–Nelson models proficiently described the adsorption patterns
of Pb2+ within a fixed-bed column, as demonstrated by high R2 values and well-matched
breakthrough curves.

3.4. Comparative Analysis of Breakthrough Curves Fitting

It is worth emphasizing that despite their distinct assumptions, derivations, and
simplifications, the Thomas, Bohart–Adams, and Yoon–Nelson models (Equations (5)–(7))
Sustainability 2023, 15, 14344 17 of 23

may be expressed using the subsequent formula, where the ‘lumped’ variables a and b are
defined in Table 5:
C 1
= (7)
CO 1 + exp(b − at)
Based on Equation (7), it can be concluded that the Thomas, Bohart–Adams, and Yoon–
Nelson models are fundamentally equal. The breakthrough curve predictions obtained
from Equation (7) depict the breakthrough curve that would be achieved using any of the
three previously mentioned models (Equations (5)–(7)). The three sets of parameters (kTh ,
qTh ; kBA , N0 ; and kYN , t) can be determined from constants ‘a’ and ‘b’ (Table 7) and are thus
interchangeable [56].

Table 7. Parameters of “a” and “b” of generic model (Equation (7)) formulated using variables of
different models.

Thomas Bohart–Adams Yoon–Nelson

a kTh Co kBA Co kYN
b kTh qTh M/Q kBA No Z/u kYN τ

The merits and limitations of the models utilized in this study were assessed and
summed up in Table 8 based on the analysis and relationship of the experimental data. The
results show that the three models were well-suited to describe the column data, especially
in instances of columns with higher bed heights, where a consistent and even depletion
process was observed [57]. Hence, these models can be effectively used to forecast the
performance of columns and aid in designing considerations and future enhancement
endeavors. The applicability of the three utilized models in this study was observed for
adsorption in distinct component systems. The utilization of the Thomas model offered
valuable insights into the dynamics of mass transfer between the adsorbent material and
metal solutions. This allowed for a better understanding of the driving forces behind these
processes under various conditions. The experimental data collected from the Pb2+ columns
showed a promising alignment with the theoretical predictions generated by the Thomas
and Yoon–Nelson models. This alignment indicated the presence of hindrances to mass
transfer within the columns. Each of the three models employed in this study necessitated
distinct parameters for their respective theoretical calculations.

Table 8. Merits and limitations of column models employed in this study in relation to PACC.

Merits Limitations
• Appropriate for sizeable bed
depth adsorbent of Pb2+ • Insufficient representation
Thomas model columns for Pb2+ columns with
• Best fitted for columns with shorter bed lengths
mass transfer resistance
• Require additional
parameters for the model
to be utilized
• Offered an estimation of the • Insufficiently described the
Bohart–Adams equilibrium concentration of the behaviors of the metal
adsorbate columns
• Only applicable to
adsorption processes
involving surface reactions
• Requires fewer parameters for
• Inadequate for Pb2+
computation
Yoon–Nelson model columns with a shallow
• The projected 50% breakthrough
bed depth of adsorbent
time was realistic
Sustainability 2023, 15, 14344 18 of 23

Among the three models utilized in this study, the Yoon–Nelson model stood out
for its simplicity, requiring fewer parameters and theoretical calculations. It provided
valuable information on the 50% breakthrough of the column, enabling the prediction of
the saturation period without requiring extensive experimental duration [58]. In contrast,
the widely used Bohart–Adams model has proven useful in predicting the sorption capacity
of adsorbents in various studies, particularly for the design of large-scale effluent treat-
ment systems. By analyzing experimental breakthrough data, the Bohart–Adams model
can estimate breakthrough time and maximum adsorption capacity, which are crucial
for efficient system design and operation [54]. However, this model imposes additional
parameters and computations to derive predicting data. It primarily focuses on adsorption
through surface reactions, the presence of sorption sites, and the starting portion of the
breakthrough curve [59]. In the case of removing Pb2+ using PACC, involving the inte-
gration of ion exchange and adsorption, the Bohart–Adams model is not an ideal fit for
accurately and comprehensively representing column behaviors and mechanisms in this
study. Although the employed models exhibited a good fit for certain column parameters,
certain parameters were not accurately captured, likely due to the presence of mass transfer
resistance and the intricate mechanisms involved in the removal process [59].
The findings suggest that enhanced adsorption efficiency is attained through increased
bed heights, reduced flow rates, and higher initial concentrations. Furthermore, Table 9
offers a concise overview of how various adsorbents perform under similar circumstances.
This investigation has affirmed that the adsorption capability of PACC is on par with, and
conceivably superior to, the capacities of alternative adsorbents noted in contemporary
scientific literature.

Table 9. Summary of capacity uptake of other adsorbents used for Pb2+ adsorption.

Adsorbent qeq (mg g−1 ) Reference

PACC 28.00 Present study
Rice husk ash 12.6 [60]
Coir 18.9 [61]
Papaya wood 17.4 [62]
Hazelnut shell 16.23 [63]
Olive pomace 7.0 [62]
Jute 17.8 [63]
Olive stone waste 14.5 [64]

Given the absence of prior published research specifically focusing on fixed-bed

column studies in relation to the biosorption of Pb2+ by PACC, this study can be compared
to similar investigations that have examined either the same metal or biosorbents with
similar characteristics.

3.5. Regeneration Studies and Implications to Industrial Wastewater Treatment

In line with the comprehensive concept of sustainability, which encompasses economic,
social, and environmental factors, the achievement of sustainable industrial development
relies heavily on the adoption of viable technologies that generate positive socio-economic
and environmental outcomes [65]. This progress extends not only to novel strategies but
also to the enhancement of protocols that offer optimal results while minimizing resource
utilization, thus providing significant benefits such as environmental safety and yield
improvement. In addition to possessing effective adsorption capability, the convenient
reusability of the adsorbent without substantial reduction in adsorption capacity and its
long-term reusability are crucial considerations for practical applications.
In this study, the PACC material, having undergone Pb2+ adsorption, was subjected
to desorption experiments utilizing a 0.1 M NaOH solution as the desorbing agent. The
regeneration cycle encompassed the passage of the desorbing agent through the column at
a flow rate of 2.5 mL min−1 for a duration of 30 min. Subsequently, a rinsing phase with
 yield improvement. In addition to possessing effective adsorption capability, the conven-
ient reusability of the adsorbent without substantial reduction in adsorption capacity and
its long-term reusability are crucial considerations for practical applications.
In this study, the PACC material, having undergone Pb2+ adsorption, was subjected
to desorption experiments utilizing a 0.1 M NaOH solution as the desorbing agent. The
Sustainability 2023, 15, 14344 19 of 23
regeneration cycle encompassed the passage of the desorbing agent through the column
at a flow rate of 2.5 mL min−1 for a duration of 30 min. Subsequently, a rinsing phase with
deionized water was carried out for an additional 30 min before initiating a successive
deionized
cycle of Pb2+ water was carried
adsorption. out forfollowing
Furthermore, an additional 30 min
four (4) before
cycles initiating a successive
of adsorption-desorption,
cycle of Pb 2+ adsorption. Furthermore, following four (4) cycles of adsorption-desorption,
the PACC exhibited a consistent removal efficiency surpassing 80% of its initial capacity,
asthe PACC exhibited
illustrated in Figurea 10.
consistent removal efficiency
This observation signifies surpassing 80%
the potential of of
theitscomposite
initial capacity,
mate-as
illustrated in Figure 10. This observation signifies the potential of the composite
rial for repeated utilization in proficiently eliminating Pb ions from wastewater streams.
2+ material
for repeated utilization in proficiently eliminating Pb2+ ions from wastewater streams.

Figure 10. Regeneration performance of polyurethane-activated carbon composite (PACC) in seques-

Figure 10. 2+
Regeneration performance of polyurethane-activated carbon composite (PACC) in se-
tering Pb in fixed-bed column.
questering Pb2+ in fixed-bed column.
Figure 11 displays the FTIR spectra of PACC during distinct phases: pre-adsorption,
Figure 11 displays
post-adsorption, the FTIR
and after spectra of In
regeneration. PACC during distinct phases:
the pre-adsorption stage, thepre-adsorption,
FTIR spectrum
post-adsorption, and after regeneration. In the pre-adsorption stage,
reveals pronounced and intense peaks associated with certain functional groups, the FTIR spectrum
specifically
reveals pronounced
-OH, C=O, C-O, and and intense
N-H bonds. peaks
Upon associated withthe
regeneration, certain
FTIRfunctional
spectrum of groups,
PACCspecifi-
displays
cally -OH,
comparable
Sustainability 2023, 14, x FOR PEER REVIEW
C=O, C-O,
peak and N-H
intensities to bonds.
its Upon
pre-adsorptionregeneration,
state, the
resemblingFTIR
the spectrum
initial of
FTIR PACC
spectrum
21 of 25
displays
of PACCcomparable peak to
before exposure intensities
2+ to its pre-adsorption
Pb adsorption. This observation state, resemblingthe
demonstrates the initial
successful
FTIR spectrumofofthe
regeneration PACC before sites
adsorption exposure
showingto Pb 2+ adsorption. This observation demon-
PACC’s reusability feature.
strates the successful regeneration of the adsorption sites showing PACC’s reusability fea-
ture.

Figure 11.11.
Figure Fourier transform
Fourier infrared
transform (FTIR)
infrared spectra
(FTIR) spectraof of
polyurethane-activated carbon
polyurethane-activated composite
carbon composite
(PACC), PACC
(PACC), PACC after PbPb
after adsorption, and
adsorption, andPACC
PACCafter regeneration.
after regeneration.

A proposed industrial setup for wastewater treatment is depicted in Figure 12. To

showcase the practicality of a continuous adsorptive water treatment method, a rotating
pattern of two parallel columns can be utilized for wastewater treatment, as illustrated in
 Sustainability 2023, 15, 14344 20 of 23

A proposed industrial setup for wastewater treatment is depicted in Figure 12. To

showcase the practicality of a continuous adsorptive water treatment method, a rotating
pattern of two parallel columns can be utilized for wastewater treatment, as illustrated
in Figure 12. Each column can be filled with 50 g of PACC adsorbent and utilized for
uninterrupted processing. Once 2.5 L of wastewater has been treated in Column A, the
wastewater feed will be directed to Column B, while Column A undergoes simultaneous
regeneration using the elution solvent. This method offers the advantage of simultaneous
adsorption-desorption processes, therefore circumventing the drawbacks associated with
conventional adsorbents, which necessitate costly operating and manufacturing methods,
resulting in potential secondary pollution. The suggested approach is expected to mitigate
Sustainability 2023, 14, x FOR PEER REVIEWenvironmental and health risks in comparison to alternative methods. A comprehensive
22 of 25 life
cycle assessment (LCA) can provide further evaluation and assessment of the environmental
impact and sustainability aspects of this approach.

Figure Figure 12. Continuous

12. Continuous adsorption
adsorption unit process
unit process diagramdiagram using polyurethane-activated
using polyurethane-activated carbon carbon
com- com-
posite (PACC)
posite (PACC) as a sorbent
as a sorbent material.
material.
4. Conclusions
4. Conclusions
In conclusion, this study has thoroughly investigated the potential of coconut oil-based
In conclusion, this study has thoroughly investigated the potential of coconut oil-
porous activated carbon composites (PACC) as a sustainable and cost-effective alternative
based porous activated carbon composites (PACC) as a sustainable and cost-effective al-
to conventional sorbents. Our findings reveal that PACC exhibits robust adsorption ca-
ternative to conventional
pabilities sorbents.
for the removal Our
of Pb 2+ findings reveal solutions,
from aqueous that PACCasexhibits robust adsorp-
demonstrated by fixed-bed
tion capabilities for the in
column studies, removal of Pb with
accordance
2+ fromtheaqueous
Thomas solutions, as demonstrated
and Yoon–Nelson by fixed- curve
breakthrough
bed column
models.studies, in accordance
These remarkable with thecharacteristics
performance Thomas and can Yoon–Nelson
be attributedbreakthrough
to the outstanding
curve physicochemical
models. These remarkable performance characteristics can be attributed
properties of PACC, including its high porosity, substantial to the
cellout-
size, and
standing physicochemical properties of PACC, including its high porosity, substantial
enhanced negative polarity. Furthermore, PACC stands out for its remarkable reusability, cell
size, and enhancedanegative
maintaining significantpolarity. Furthermore,
adsorption PACCupholding
capacity while stands outdurability
for its remarkable
and structural
reusability, maintaining
stability, a significant
as confirmed by i-depthadsorption
analyses capacity while upholding
of its physicochemical anddurability and
thermal properties.
structural stability, as confirmed by i-depth analyses of its physicochemical and
Consequently, the exceptional attributes of PACC make a compelling case for its potential thermal
properties. Consequently,
superiority the exceptional
and comparability to otherattributes of PACC
biosorbents. Themake a compelling
successful synthesiscase for un-
of PACC
its potential superiority and comparability to other biosorbents. The successful synthesis
of PACC underscores its promise as an economically viable, environmentally friendly,
and sustainable biosorbent for the large-scale removal of heavy metals, particularly Pb2+,
from wastewater. This study paves the way for further exploration and application of
Sustainability 2023, 15, 14344 21 of 23

derscores its promise as an economically viable, environmentally friendly, and sustainable

biosorbent for the large-scale removal of heavy metals, particularly Pb2+ , from wastewater.
This study paves the way for further exploration and application of PACC in addressing
critical challenges associated with heavy metal pollution in aquatic environments.

Author Contributions: Conceptualization, R.M.D.F.; Data curation, R.J.R.E., T.R.B.T. and A.A.L.
(Alona A. Lubguban); Formal analysis, R.G.D.J.; Funding acquisition, G.G.D., A.C.A. and A.A.L.
(Arnold A. Lubguban); Methodology, R.J.R.E. and T.R.B.T.; Resources, R.M.D.F.; Software, R.M.D.F.,
R.J.R.E. and T.R.B.T.; Supervision, R.M.M., H.P.B. and A.A.L. (Arnold A. Lubguban); Writing—review
and editing, R.F.A.J., R.Y.C., R.M.M., A.C.A., H.P.B. and A.A.L. (Arnold A. Lubguban). All authors
have read and agreed to the published version of the manuscript.
Funding: The Department of Science and Technology—Accelerated Science and Technology Human
Resource Development Program provided support for this study as part of the primary author’s
scholarship program.
Informed Consent Statement: Not applicable.
Data Availability Statement: The datasets utilized and/or analyzed during the current study are
available from the corresponding author upon reasonable request.
Acknowledgments: The authors wish to express their gratitude for the financial assistance provided
by the Department of Science and Technology through the Niche Centers in the Region (NICER)—
R&D Center for Sustainable Polymers.
Conflicts of Interest: The authors declare no conflict of interest.

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