Dynamic Simulation of Lead (II) Metal Adsorption From Water On Activated Carbons in A Packed Bed Column

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Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-022-03079-8

ORIGINAL ARTICLE

Dynamic simulation of lead(II) metal adsorption from water


on activated carbons in a packed‑bed column
Areeba Hameed1 · Bassim H. Hameed1 · Fares A. Almomani1 · Muhammad Usman2 · Muneer M. Ba‑Abbad3 ·
Majeda Khraisheh1

Received: 22 March 2022 / Revised: 23 June 2022 / Accepted: 11 July 2022


© The Author(s) 2022

Abstract
In this work, lead(II) adsorption on activated carbons, tire-derived activated carbon (TAC), and commercial activated carbon
(CAC), in a packed-bed column, was simulated using the Aspen Adsorption® V11 flowsheet simulator. The simulator was
used to model the fixed-bed adsorption column and to establish the breakthrough curves by varying the initial concentration
of lead(II) ions (500 mg/L, 1000 mg/L, 2000 mg/L, and 3000 mg/L), the bed height (0.2 m, 0.3 m, 0.4 m, 0.5 m, and 0.6 m),
and the flow rate (9.88 × ­10−4 ­m3/s, 1.98 × ­10−3 ­m3/s, 2.96 × ­10−3 ­m3/s, 3.95 × ­10−3 ­m3/s, and 4.94 × ­10−3 ­m3/s), at constant
temperature and pressure of 25 °C and 3 bar, respectively. At the optimum conditions of 500 mg/L lead(II) concentration,
0.6 m bed height, and 9.88 × ­10−4 ­m3/s flow rate, the breakthrough times were 488 s and 23 s for TAC and CAC, respectively.
Under the same conditions, the adsorption capacity obtained at t0.5 was 114.26 mg/g for TAC and 7.72 mg/g for CAC. The
simulation results indicate the potential of TAC for the adsorption of lead(II) in comparison to CAC.

Keywords Activated carbon · Adsorption · Lead(II) · Breakthrough curve · Aspen adsorption simulator

1 Introduction non-biodegradable metal that is harmful to people and other


species and can cause major health problems like anemia
During oil and gas operations, large volumes of wastewa- [4]. It can enter the food chain, be absorbed, and can accu-
ter are produced, which is referred to as produced water mulate in body tissues [2]. Because of its toxicity, the extent
(PW). This water is by far the most generated by industry of its contamination in aquatic systems, the potential for
and includes a variety of pollutants such as oil compounds, major health hazards, and tight requirements, lead must be
dissolved minerals, chemical compounds, and dissolved tested, monitored, and removed from PW before disposal. Pb
particles [1]. Zinc, lead, manganese, iron, and barium are levels in wastewater and agricultural soils should not exceed
among the frequent metals detected in PW [2]. The removal 0.01 ppm, according to WHO guidelines [5].
and recovery of toxic heavy metals have received a lot of Electrochemical techniques [6], chemical precipitation
attention in recent years. Discarding PW without sufficient [7], chemical coagulation [8], membrane filtration [9], ion
treatment can cause serious environmental damage, includ- exchange [10], bioremediation [11], and adsorption [12]
ing the death of water and plant life, as well as soil deterio- have all been used to remove heavy metals in the past. How-
ration that will affect humans [3]. Lead, for example, is a ever, the majority of these treatments are inefficient, have
limited large-scale operation capability, and are expensive,
all of which limit their application. Adsorption is recognized
* Bassim H. Hameed
[email protected] as the most successful physicochemical strategy for heavy
metal removal among the other procedures due to its simple
1
Department of Chemical Engineering, College operation, cost-effectiveness, and regeneration nature of the
of Engineering, Qatar University, P.O. Box 2713, Doha, adsorbents [13].
Qatar
The adsorbents that have been investigated for removal of
2
Center for Environmental Studies and Research, Sultan heavy metals include activated carbon [14], cellulose nanofib-
Qaboos University, Al‑Khoud 123, Seeb, Oman
ers [15], biochar [16], zeolites [17], carbon nanotubes [18],
3
Gas Processing Center, College of Engineering, Qatar agro-industrial waste materials [19], clay minerals [20], and
University, P.O. Box 2713, Doha, Qatar

13
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Biomass Conversion and Biorefinery

modified activated carbon [21]. Activated carbon is a desir- version 11 software. The property method used was non-
able adsorbent for heavy metal removal because of its unique random two-liquid (NRTL). The NRTL model calculates
features, such as high pore volume and vast surface area [22]. liquid activity coefficients and is recommended for highly
Although a variety of carbon-rich materials can be used to non-ideal chemical systems for both vapor–liquid and liq-
make activated carbon, charcoal is the most common mate- uid–liquid equilibrium applications and uses the advanced
rial used in commercial activated carbon manufacturing [23]. equation-of-state mixing rules [4].
Charcoal has a high adsorption efficiency, but it requires a
high initial capital cost for large-scale applications. As a 2.2 Feed and product stream simulation
result, more focus has been placed on locating inexpensive
and unconventional precursors for the manufacture of effective An input stream, an adsorption tower, or packed-bed col-
activated carbons, such as agricultural and industrial wastes. umn, and a product stream are all part of the process. Fig-
The significant increase in the production and distribution of ure 1 depicts an activated carbon packed-bed column devel-
tires over the past two decades initiated the idea of recycling oped for the simulation. The feed requirements, such as flow
and using the tires in the pyrolysis process to allow for the pro- rates (9.88 × ­10−4 ­m3/s, 1.98 × ­10−3 ­m3/s, 2.96 × ­10−3 ­m3/s,
duction of char as a side product, under certain conditions [23]. 3.95 × ­10−3 ­m3/s, and 4.94 × ­10−3 ­m3/s) and initial concentra-
Char is a very carbonaceous substance that may be utilized as tion of lead(II) ions (500 mg/L, 1000 mg/L, 2000 mg/L, and
a precursor to create activated carbon for heavy metal adsorp- 3000 mg/L), were utilized as inputs for the input stream. For
tion, which is a win–win approach to solve the problem of the the adsorption column setup, the required input values such
waste tire and produce a cost-effective adsorbent. as the internal diameter of the adsorbent layer and the inter-
Although the adsorption tests are considered simple to particle voidage were provided as 0.025 m and 0.4, respec-
perform and are carried out in the laboratory, they require a tively. The feed stream enters at a temperature of 25 °C and
high number of tests and a long time to create the kinetic and a pressure of 3 bar. The product concentration was checked
isotherms. Using simulation software is beneficial as it saves to ensure it was set to zero to establish the breakthrough
time and cost, and allows us to find the appropriate operating curves for the adsorption column. The reversible model was
range by varying different parameters. Software such as Aspen selected as the process model type [4]. The feed flow rate
Adsorption® V11 offers the chance of conducting different tri- was set at the feed block, resulting in a consistent flow rate
als under a wide variety of conditions to determine the optimal throughout the adsorption process. This holds true for dilute
conditions. Carrying out simulations at various conditions is liquids in which the effect of ions binding to the adsorbent
safer as parameters such as high concentrations of lead can is minimal [4].
be studied, whereas in a lab, such experiments are considered
to be unsafe. These software programs are particularly useful 2.3 Properties of the adsorbents
for small and medium firms that cannot afford more advanced
heavy metal wastewater treatment due to running costs [4]. Two types of activated carbons were used for the simula-
The aforementioned literature review suggests that a new tion: CAC and TAC [22]. The BET surface area, cumulative
inexpensive and sustainable adsorbent is required to treat
industrial PW. There is a crucial need to develop and use
simulation protocol to test the removal efficiencies of such
adsorbents, and there is a gap in knowledge regarding the
feasibility of using software to scale up and optimize the
adsorption process. Therefore, the objectives of this work are
to simulate a fixed-bed column for the adsorption of lead(II)
using two types of activated carbons, tire-derived activated
carbon (TAC) and commercial activated carbon (CAC), and
to determine their performances by establishing the break-
through curves using Aspen Adsorption® V11.

2 Methodology

2.1 Physical and chemical properties of lead

The physical and chemical properties of the contami- Fig. 1  Simulation flowsheet of liquid-phase adsorption on Aspen
nant, lead, are readily available in the Aspen Properties® Adsorption.® V11

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Biomass Conversion and Biorefinery

pore volume, pore size, and density for CAC were 1241 𝜕wi ( �
(3)
)
­m2/g, 0.445 ­cm3/g, 2.781 nm, and 2050 kg/m3, respec- = MTCsi wi − wi
𝜕t
­ 2/g, 0.302 c­ m3/g,
tively, whereas for TAC, they were 82 m
3
19.756 nm, and 1940 kg/m , respectively [23]. where wi represents the equilibrium solid loading for com-
ponent i and MTCsi is a constant provided by the user, or
they can vary and, in that case, are either estimated by the
2.4 Packed‑bed column specification software’s correlations [24]. Because the mass transfer driv-
ing force is represented as a function of the solid-phase con-
The adsorption process was simulated using Aspen Adsorp- centration, the solid film was chosen under the film model
tion® V11 with a set of equations that were configured using assumption. The Langmuir adsorption isotherm models
the tabs, namely the general tab, the material/momentum were obtained from previous experimental studies [23]. The
balance tab, the kinetic model tab, and the isotherm tab. The Langmuir model equation [25] is
following theoretical assumptions were made for the bed [4]: qL KL Ce
(1) discretization model (upwind differencing scheme-first qe = (4)
1 + KL Ce
order (UDS 1)), (2) material balance assumption (convec-
tion with estimated dispersion), (3) pressure drop assump- where qL represents the maximum monolayer adsorption
tion (none), (4) velocity assumption (constant), (5) film capacity (mg/g), qe is the equilibrium adsorption capacity
model assumption (solid), (6) kinetic model assumption (mg/g), and KL (L/mg) is Langmuir constant. The Langmuir
(linear lumped resistance), (7) form of mass transfer coef- model parameters, qmax and KL, for both the adsorbents were
ficient (constant), (8) isotherm assumed for layer (Langmuir obtained as 476.2 mg/g and 0.015 L/mg for TAC and as
1 model), and (9) energy balance assumption (isothermal). 42.5 mg/g and 0.008 L/mg for CAC, respectively [23].
The UDS 1 was chosen as the discretization method under
the general tab because it is an excellent all-around per-
former, non-oscillatory in all possible situations, and uncon- 2.5 Mass transfer coefficient
ditionally stable; takes less time to simulate; and has fair
accuracy. The UDS 1 is a first-order upwind differencing The external mass transfer coefficient of particles in a fixed
scheme based on the Taylor expansion of the first order [4]. column was calculated using the following equation [26]:
This equation depicts the first-order convection term:
(5)
1
Sh = 2 + 1.1Re0.6 Sc 3
𝜕Γi Γ Γ
= i− i−1 (1) where Sh = Kc Dp ∕DAB, Re = Dp u𝜌∕𝜇 , and Sc = 𝜇∕𝜌DAB.
𝜕z Δz
Substituting these parameters results to
whereas the second-order dispersion term is shown using a )0.6
second-order differencing scheme: Kc Dp Dp u𝜌
( 1
𝜇 3
= 2 + 1.1 ( ) (6)
2
DAB 𝜇 𝜌DAB
𝜕 Γi Γi+1 − 2Γi + Γi−1
= (2)
𝜕z2 Δz2 where Dp is the average particle diameter in cm, DAB is the
mass diffusivity of solute A in solvent B, u is the fluid veloc-
where Γ is the dependent variable and z is the independent ity in m/s, 𝜌 is the density of the solution, and μ is the solu-
spatial variable. tion viscosity [4]. The particle size was 0.02 mm, and the
The number of nodes was kept as the default in the pro- viscosity of the solution was 8.94 × ­10−4 kg/ms at 25 °C. The
gram and was set as 20. The essential assumptions regarding density of the solution was calculated at each concentration
material dispersion in the liquid phase for the ion exchange of lead ranging from 1000.5 to 1003 kg/m3.
process are provided in the material/momentum balance tab. The total mass diffusivity of the electrolyte Pb ­(NO3)2
Convection with estimated dispersion was used as the mate- in water was calculated. The diffusion coefficient obtained
rial/momentum balance assumption. The dispersion term for was 9.45 × ­10−10 ­m2/s for DPb2+ and 19.02 × ­10−10 ­m2/s for
the material balance of the bed is included in this assump- DNO3 − ­DNO3 [27]. This resulted in the overall DAB value
tion. Within the length of the bed, the dispersion coefficient being 1.4175 × ­10−9 ­m2/s.
varies. The program, in this situation, is capable of combin- The mass transfer coefficient in the adsorption tower
ing all of the resistances to an overall mass transfer single was adjusted to be constant across the bed. However, due
component. The linear lumped resistance model was chosen to the relationship between fluid velocity and fluid flow rate
from the kinetic model tab. The mass transfer driving force with the mass transfer coefficient, a change is seen in the
for component i is represented as a linear function of the mass transfer coefficient when the fluid flow rate is altered
solid phase loading: [28]. Table 1 provides a list of flow rates as well as the

13
Biomass Conversion and Biorefinery

corresponding mass transfer coefficients that were used for Lastly, the feed flow rate was changed in each trial to
the simulation. observe its effect on the breakthrough time, keeping the
concentration and bed height at their optimum values
2.6 Process simulation as obtained in the previous trials. Different velocities for
the liquid stream flowing (2 m/s, 4 m/s, 6 m/s, 8 m/s, and
After completing the bed configuration and identifying all 10 m/s) were used. The mass transfer coefficient was then
necessary parameters, the system was ready to be simulated. calculated for each flow rate and was used each time the flow
Aspen Adsorption® V11 was used to simulate the adsorp- rate was changed.
tion of lead(II) ions in the packed-bed column (Fig. 1). The These steps were first carried out for the TAC adsorbent
effect of different parameters such as the initial lead(II) followed by the CAC adsorbent.
concentration, the bed height, and the flow rate was studied The optimum produced breakthrough curves for both the
to observe each parameter’s influence on the breakthrough adsorbents were then compared.
time.
The simulation began with the process being initialized
and then switched to dynamic mode. The breakthrough 3 Results and discussion
curve was generated as time progressed in the dynamic
model. The adsorption process was simulated with a total of 28 runs
The initial concentration of the contaminant was first with varying lead(II) ion concentrations, flow rates, and bed
changed, keeping a constant flow rate (4.94 × ­10−4 ­m3/s) and heights. This was done using a trial-and-error technique,
bed height (0.4 m). The initial concentrations of lead(II) ions which demonstrated that the chosen values of the parameters
were 500 mg/L, 1000 mg/L, 2000 mg/L, and 3000 mg/L. were within the range to produce a successful breakthrough
The optimum initial concentration of the lead(II) ions curve. A greater or lower value from the range of values
was determined by studying the breakthrough curves and indicated that the adsorption process would no longer be effi-
choosing the concentration which produced a curve with the cient due to the breakthrough curves not being successful.
longest breakthrough time. Next, the height of the bed was
changed to observe its effect on the breakthrough time by 3.1 Effect of lead(II) initial concentration
changing the height in each trial from 0.20 to 0.60 m, with
increments of 0.10 m. The optimum concentration of the By changing the initial concentration of lead(II) from 500 to
contaminant found previously was used and kept constant, 3000 mg/L at a constant bed height of 0.4 m and flow rate
along with the flow rate at 4.94 × ­10−4 ­m3/s. of 4.94 × ­10−4 ­m3/s, the effect of the initial concentration on
the system was evaluated. Figure 2 depicts the breakthrough
curves for both the adsorbents (TAC and CAC) for the col-
Table 1  Mass transfer coefficients at different flow rates
umn. The initial concentrations used for the lead(II) were
Velocity (m/s) Flow rate ­(m3/s) Kc (1/s) 500 mg/L, 1000 mg/L, 2000 mg/L, and 3000 mg/L.
−4 It can be seen from Fig. 2 that the outlet concentration
1 4.94 × ­10 0.342
of lead(II) increases as the adsorption process proceeds,
2 9.88 × ­10−4 0.519
ultimately reaching the inlet concentration value. It was
4 1.98 × ­10−3 0.786
observed that the breakthrough curves obtained are steeper
6 2.96 × ­10−3 1.00
at high initial concentrations and the curves lost their steep-
8 3.95 × ­10−3 1.19
ness at low initial concentrations of 500 mg/L, 1000 mg/L,
10 4.94 × ­10−3 1.36
and 2000 mg/L when considering the curves at a constant

Fig. 2  Comparison of the break-


through curves at 25 °C and
3 bar with a constant flow rate
of 4.94 × ­10−4 ­m3/s and a bed
height of 0.4 m, with varying
initial concentrations. a TAC.
b CAC​

(a) (b)

13
Biomass Conversion and Biorefinery

flow rate and bed height for both adsorbents. The break- produce a much steeper curve. Increasing the initial concen-
through times for a concentration of 3000 mg/L were trations of heavy metal ions increases the driving force at
obtained as 639 s and 30 s for TAC and CAC, respectively. the solid–liquid interface, resulting in increased adsorption
At the same concentration, the saturation times obtained for capacity until the adsorption sites were saturated. Thus, a
TAC and CAC were 1643 s and 143 s, respectively. Since shorter breakthrough time is observed for the steeper curves.
TAC has a longer breakthrough and saturation time, a larger With a lower initial concentration, a breakthrough curve
volume of the solution could be treated and therefore can be with a longer breakthrough time was produced, suggest-
considered the better adsorbent. As seen in Table 2, at an ing that a larger volume of solution could be treated. This
initial concentration of 3000 mg/L, the adsorption capacity is because a lower concentration gradient causes a slower
at t0.5 were 681.13 mg/g and 45.82 mg/g for TAC and CAC, transport due to a decrease in diffusion coefficient or mass
respectively. This suggests that for the same length of time, transfer coefficient [29]. Therefore, the optimum lead(II)
the adsorption capacity (q0.5) is higher for TAC and, in this initial concentration was 500 mg/L.
case again, implies that TAC is a better adsorbent due to Studies carried out previously depict a similar trend of
its higher adsorption capacity. In general, a breakthrough increasing the contaminants’ initial concentration on the
curve reflects how much of an adsorbent bed’s capacity was breakthrough time [30]. It was determined that the adsorp-
used. The column saturates faster during the adsorption pro- tion capacity of heavy metal ions increased, and the removal
cess if the breakthrough curve is steeper, while a less steep efficiency decreased with the increasing initial concentra-
breakthrough curve implies low saturation of the column at a tions of heavy metal ions.
low initial metal concentration as there are fewer metal ions When plotting C/C0 vs. time, the simulation data over-
present in the solution. This indicates that when the concen- laps. This means there is no correlation between initial
tration of lead flowing down the column was increased, the lead(II) concentration and breakthrough or saturation time.
pores of the adsorbent will be saturated much quicker and However, according to Alhamed [31], this is not the true

Table 2  Column adsorption Adsorbent Initial lead(II) Bed height (m) Flow rate ­(m3/s) Mass (g) t0.5 (s) Adsorption
capacity at different initial concentration capacity, q0.5
lead(II) concentrations, bed (mg/L) (mg/g)
heights, and flow rates for both
adsorbents (TAC and CAC) TAC​ 500 0.4 4.94E − 04 2.30 1055 113.52
at t0.5
1000 0.4 4.94E − 04 2.30 1054 226.83
2000 0.4 4.94E − 04 2.30 1055 454.09
3000 0.4 4.94E − 04 2.30 1055 681.13
500 0.2 4.94E − 04 1.15 517 111.26
500 0.3 4.94E − 04 1.73 786 112.77
500 0.5 4.94E − 04 2.88 1324 113.97
500 0.6 4.94E − 04 3.45 1593 114.27
500 0.6 9.88E − 04 3.45 798 114.26
500 0.6 1.98E − 03 3.45 399 114.49
500 0.6 2.96E − 03 3.45 268 114.96
500 0.6 3.95E − 03 3.45 201 115.06
500 0.6 4.94E − 03 3.45 161 115.26
CAC​ 500 0.4 4.94E − 04 2.43 75 7.64
1000 0.4 4.94E − 04 2.43 75 15.27
2000 0.4 4.94E − 04 2.43 75 30.55
3000 0.4 4.94E − 04 2.43 75 45.82
500 0.2 4.94E − 04 1.22 37 7.54
500 0.3 4.94E − 04 1.82 56 7.60
500 0.5 4.94E − 04 3.04 94 7.66
500 0.6 4.94E − 04 3.65 113 7.67
500 0.6 9.88E − 04 3.65 57 7.72
500 0.6 1.98E − 03 3.65 29 7.87
500 0.6 2.96E − 03 3.65 20 8.12
500 0.6 3.95E − 03 3.65 15 8.13
500 0.6 4.94E − 03 3.65 12 8.13

13
Biomass Conversion and Biorefinery

phenomenon. Another possibility is that the kinetic model’s breakthrough curve with the longest breakthrough time and
assumption of linear lumped resistance may not properly the least steep curve.
reflect the entire mechanism of phenol adsorption onto acti- A similar trend was obtained by Firdaus et al. [33] when
vated carbon particles. studying the effect of changing the bed height on the adsorp-
tion process of copper(II) from wastewater using corncob-
based activated carbon (CCAC) at room temperature. It was
3.2 Effect of bed height seen that increasing the bed height enhanced the break-
through and exhaustion time. This is because as the bed
Using the best initial lead(II) concentration of 500 mg/L height was increased, the total surface area of the adsorbent
obtained from the previous simulations, the bed height increased as well. The functional groups present such as
was varied from 0.2 to 0.6 m, in increments of 0.1 m, at a carboxyl and hydroxyl groups on the surface of the adsor-
constant flow rate of 4.94 × ­10−4 ­m3/s. Figure 3 shows the bent CCAC also show good coordination with heavy metals
breakthrough curves obtained for the column at different which is enhanced with a larger surface area. As a result,
bed heights. an increase in the adsorption binding sites can be seen with
As the bed height was increased, the breakthrough curve an increase in bed height, causing a better metal absorption
became less steep. This can be seen as the breakthrough capacity and a longer breakthrough time.
time was obtained as 237 s for TAC and 11 s for CAC at a
bed height of 0.2 m. On the other hand, at the bed height of 3.3 Effect of feed flow rate
0.6 m, a breakthrough time of 994 s and 52 s was obtained
for TAC and CAC, respectively. With a higher bed height, The used flow rates (9.88 × ­10−4 to 4.94 × ­10−3 ­m3/s) and the
the breakthrough time increased, resulting in a greater breakthrough curves for a column system with a bed height
lead(II) removal efficiency because there is good contact of 0.6 m and metal ion initial concentration of 500 mg/L are
time between the metal ions and the adsorbent. A greater bed depicted in Fig. 4. It can be observed from the breakthrough
height provides more binding sites for the adsorption process curves that increasing the flow rate resulted in a steeper
and a larger surface area, resulting in a longer breakthrough curve. A breakthrough time of 89 s and 3.5 s was obtained
time and, as a result, a higher removal rate of lead(II). A for TAC and CAC, respectively, at a flow rate of 4.94 × ­10−3
lower bed height indicates that the bed has a reduced abil- ­m3/s. Similarly, the saturation time obtained for TAC and
ity to adsorb metal ions from the solution due to its smaller CAC at the same flow rate was 260 s and 30 s, respectively.
surface area, resulting in the binding sites being occupied This implies that greater fluid movement resulted in
more quickly and therefore having a shorter breakthrough quicker saturation of the adsorbent pores, as the velocity
time. In addition, at lower bed heights, axial dispersion is of the contaminant entering the pores of the adsorbent also
the primary mass transfer process, reducing metal ion diffu- increased. At higher flow rates, the contact time between the
sion [32]. Using Table 2, it can be seen that at a bed height adsorbent and the lead ions is reduced, resulting in a shorter
of 0.6 m, the adsorption capacity at t0.5 was 114.27 mg/g contract period. As a result, a thin film forms around the
and 7.67 mg/g for TAC and CAC, respectively. Since a adsorbent which causes the rate of mass transfer to increase,
longer breakthrough and saturation time is obtained for the and the quantity of lead adsorbed onto the bed to increase as
adsorbent TAC which, in turn, results in having a higher well, resulting in faster saturation at higher flow rates [34]. It
adsorption capacity (q0.5), this suggests that TAC is a bet- can be seen in Table 2 that at a flow rate of 4.94 × ­10−3 ­m3/s,
ter adsorbent due to having a higher adsorption capacity at the adsorption capacity at t0.5 was 115.26 mg/g and 8.13 mg/g
the same conditions compared to CAC. The best bed height for TAC and CAC, respectively. A longer breakthrough and
was, therefore, determined to be 0.6 m, which resulted in a saturation time is obtained for the adsorbent TAC which, in

Fig. 3  Comparison of the


breakthrough curves at 25 °C
and 3 bar with a constant flow
rate of 4.94 × ­10−4 ­m3/s and
lead(II) initial concentration
of 500 mg/L, at different bed
heights. a TAC. b CAC​

(a) (b)

13
Biomass Conversion and Biorefinery

Fig. 4  Comparison of the


breakthrough curves at 25 °C
and 3 bar with a constant initial
concentration of 500 mg/L and
a bed height of 0.6 m, with
varying flow rates. a TAC. b
CAC​

(a) (b)

turn, has a higher adsorption capacity, suggesting that TAC is


a better adsorbent due to its higher adsorption capacity under
the same conditions compared to CAC.
A breakthrough time of 488 s was obtained for TAC and
23 s for CAC at a flow rate of 9.88 × ­10−4 ­m3/s. The external
film mass resistance at the adsorbent’s surface rose as the
flow rate decreased, as did the residence time. As a result,
the time required for saturation increased, suggesting good
absorption and a longer time for a breakthrough. Therefore,
the optimum flow rate for the removal of lead from produced
water was 9.88 × ­10−4 ­m3/s.
Experiments carried out by Kavand et al. [35] explain
a similar trend to what was obtained through our simula- Fig. 5  Comparison between TAC and CAC breakthrough curves at
tions. The results from their studies show that as the flow optimum conditions
rate increases from 1 to 5 ml/min, the time to reach the
breakthrough point decreases from 450 to 100 min. This
is because when the flow rate increases, the residence time higher surface area to allow more of the lead to be adsorbed
of the solute in the bed reduces, leaving insufficient time from the PW; however, this is not seen from the results of
for adsorption equilibrium to be established, resulting in the simulation. From the FT-IR results obtained from previ-
decreased bed utilization and the adsorbate solution leaving ous studies, it is determined that both CAC and TAC show
the column before equilibrium. peaks forming at wavelengths corresponding to carboxylic,
hydroxyl, and phenolic groups. Higher intensities of these
3.4 Comparison between TAC and CAC groups are seen for TAC, suggesting an increase in the coor-
performances dination of TAC with heavy metals. Another reason for TAC
to be the better adsorbent may be due to its better accessibil-
The results of the simulations revealed that the most opti- ity because of its higher pore size. As a result, TAC has a
mum conditions were found to be the initial lead concentra- higher affinity towards the lead(II) than CAC.
tion of 500 mg/L with a bed height of 0.6 m and a flow rate These generated breakthrough curves can offer a basic
of 9.88 × ­10−4 ­m3/s. This was the case for both the adsor- overview of which adsorbent is preferable. However, in order
bents, TAC and CAC. At these optimum conditions, the to determine the numerical values for adsorption capacities,
breakthrough curves of both the adsorbents were plotted to computations are required to validate the accuracy of the
compare their breakthrough times as shown in Fig. 5. assumptions made. The mass of the adsorbent is estimated
It can be seen that the breakthrough time obtained for by determining the volume of the packed-bed column and
CAC was 7 s, whereas for TAC, it was 391 s, depicting that then using 60% of that value as the volume that is packed
it takes much longer for TAC to get saturated with lead. with the adsorbent to calculate the adsorption capacity.
This suggests that TAC is a better adsorbent at these opti- The amount of lead(II) adsorbed at q0.5 (mg/g) is calcu-
mum conditions to adsorb lead from PW for the longest lated using the following equation [36]:
period. The adsorption capacities calculated at the varying
t0.5 × F × C0
conditions for both the adsorbents in Table 2 also suggest q0.5 = (7)
that TAC is a better adsorbent due to its higher adsorption madsorbent
capacities. The BET surface area suggests that CAC has a

13
Biomass Conversion and Biorefinery

where F ­(m3/s) is the volumetric flow rate of lead(II), m (g)

4.94E − 03
is the mass of adsorbent in the adsorption column, C0 is the
inlet concentration of lead(II), and t0.5 is half of the total

0.242
0.004
0.455
0.360
0.191
0.062
0.485
0.451
adsorption time.
Due to the values of the adsorption capacity at break-

3.95E − 03
through and saturation time, a method developed by Chowd-

0.242
0.004
0.455
0.450
0.191
0.062
0.485
0.602
hury et al. [29] was adopted to compute the adsorption
capacities at t0.5.
Using the results generated above, further dynamic

2.96E − 03
adsorption parameters such as length of mass transfer zone

0.241
0.004
0.455
0.601
0.191
0.062
0.485
0.899
(MTZ), empty bed contact time (EBCT), degree of sorbent
used (DoSU), and sorbent usage rate (SUR) were obtained
from the breakthrough data through the equations used by

1.98E − 03
Nwabanne et al. [37]. The param eters obtained are listed in

0.240
0.004
0.456
0.898
0.185
0.064
0.489
1.802
Table 3. It can be seen from Table 3 that as the concentration
increases, the DoSU increases. The reason is connected to a

9.88E − 04
higher concentration of the lead(II) present in the wastewater
which, in turn, allows more of the pollutant to be adsorbed.

0.240
0.004
0.456
1.800
0.182
0.065
0.491
3.604
In terms of the bed height, it can be seen that as the bed

Flow rate ­(m3/s)


height increases, both MTZ and DoSU increase as well. A

4.94E − 04
greater bed height indicates a larger amount of adsorbent and

0.240
0.004
0.456
3.600
0.180
0.065
0.492
3.002
mass transfer zone, which increases the amount of sorbent
used and the volume of effluent treated. With the increase in
flow rate, the MTZ value decreases for both the adsorbents.

0.240
0.004
0.456
3.600
0.180
0.065
0.492
3.002
An increased flow rate indicates a reduction in the residence

0.6
time of lead, and because lead did not have enough time

0.239
0.004
0.380
3.005
0.180
0.065
0.410
1.797
to diffuse into the active pores of the adsorbent, it leaves
0.5
the column unadsorbed and therefore has a smaller mass
transfer zone. 0.238
0.004
0.305
2.400
0.180
0.066
0.328
0.341
0.4
Table 3  Breakthrough parameters for the adsorption of lead(II) onto TAC and CAC​

Bed height (m)

0.229
0.004
0.229
1.805
0.179
0.066
0.246
1.205
4 Conclusion
0.3

Simulations were carried out using Aspen Adsorption® V11


0.153
0.005
0.153
1.200
0.177
0.067
0.165
2.400
0.2

to imitate a fixed packed-bed column, and the breakthrough


curves were analyzed for different parameters such as ini-
1.430
0.004
0.172
2.400
1.078
0.066
0.031
2.400
3000

tial lead(II) concentration, bed height, and produced water


flow rate. A prolonged breakthrough time indicated a high
0.954
0.004
0.019
2.400
0.719
0.066
0.112
2.400
2000

adsorption capacity. Increasing the initial lead concentration


Concentration (mg/L)

and flow rate both resulted in a quicker breakthrough time


Column adsorp- Process variables

since the adsorbent saturated faster and there was a decrease


0.476
0.004
0.209
2.400
0.359
0.066
0.256
2.400
1000

in contact time between the contaminant and the adsorbent.


Increased bed height had the opposite effect, resulting in
0.238
0.004
0.305
2.400
0.180
0.066
0.328
0.341

more binding sites for adsorption and hence a slower break-


500

through time. With a flow rate of 9.88 × ­10−4 ­m3/s, an initial


contaminant concentration of 500 mg/L, and a bed height of
tion parameters

EBCT (min)

EBCT (min)

0.6 m, the slowest breakthrough time was 488 s for TAC and
SUR (g/L)

SUR (g/L)
MTZ (m)

MTZ (m)

23 s for CAC. The results indicated that the performance of


DoSU

DoSU

the TAC was better in adsorbing lead(II) ions compared to


the commercial activated carbon. It may be concluded that
tire-derived activated carbon has a significant potential as a
Adsorbent

cost-effective alternative adsorbent material for heavy metal


CAC​
TAC​

removal, thereby reducing waste tire disposal problems.

13
Biomass Conversion and Biorefinery

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