Chemical Engineering Research and Design 183 (2022) 274–284

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Chemical Engineering Research and Design

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Dynamic simulation of adsorption desulfurization

from diesel fuel over activated carbon in the
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]]]]]]
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fixed bed
⁎
Mingling Ren a, Feichao Fan a, Bing Zhou a, Xiaoyi Liang a, Zhen Yang a,b,
a
State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science
and Technology, Shanghai 200237, China
b
Key Laboratory of Specially Functional Polymeric Materials and Related Technology (Ministry of Education),
School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

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

Article history: A fixed bed for adsorption desulfurization (ADS) from a typical diesel fuel is designed via
Received 20 January 2022 dynamic simulation, taking into account the hindering effects of polyaromatics
Received in revised form 9 April 2022 (PAHs) and nitrogen compounds. Experimental results reveal the order of these com­
Accepted 20 April 2022 pounds in term of adsorption affinity as dibenzothiophene > indole > quinoline >
Available online 22 April 2022 methylnaphthalene > naphthalene. At equimolar concentrations, the inhibitory effect of
nitrogen compounds is substantially larger than that of PAHs. The simulations of mul­
Keywords: ticomponent breakthrough curve based on the ideal adsorbed solution theory and the
Dynamic simulation linear driving force model match the experimental data. The mass transfer process is
Diesel desulfurization controlled using a combination of liquid film diffusion and pore diffusion. For adsorbate
Polyaromatics molecules with a critical diameter of approximately 0.7 nm, the mass transfer process
Nitrogen compounds possibly occurs from the liquid phase into macro- or mesopores before being adsorbed in
Activated carbon micropores. The designed fixed bed for ADS from a typical diesel fuel shows a good
negative linear relationship between the liquid hourly space velocity and the ratio of
dibenzothiophene to the total adsorption amount (maximum value of 9.82%).
© 2022 Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.

150 ppm, respectively (Xiong et al., 2017). Therefore,

1. Introduction
achieving ultra-deep desulfurization of commercial diesel is
a vital research topic for many countries to fulfil the demand
Sulphur in diesel fuel is converted to SOX during combustion,
for clean diesel.
which not only poisons the catalytic converter for exhaust
Currently, refineries typically remove sulphur-containing
emission treatment but also causes acid rain and air pollu­
compounds from crude oil via hydrodesulphurisation (HDS).
tion (Song and Ma). Owing to health and environmental
However, it is challenging to completely remove aromatic
concerns, many countries are imposing restrictions on the
sulphur compounds through conventional HDS because the
sulphur content of diesel fuel through strict regulations,
lone electron pairs on sulphur atoms can form a stable
limiting the sulphur concentration in diesel to 10 parts per
electron system with the π-electrons of the aromatic ring,
million (ppm) (Shafiq et al., 2020; Tanimu and Alhooshani,
resulting in poor reactivity with hydrogen (Tan et al., 2018).
2019). However, in most commercial diesel fuel available in
Aromatic sulphur compounds such as thiophene, ben­
the European Union and China, the sulphur content is 50 and
zothiophene, dibenzothiophene (DBT), and their derivatives,

⁎
Corresponding author at: State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of
Science and Technology, Shanghai 200237, China.
E-mail address: yangzhen@ecust.edu.cn (Z. Yang).
https://doi.org/10.1016/j.cherd.2022.04.029
0263-8762/© 2022 Published by Elsevier Ltd on behalf of Institution of Chemical Engineers.
 Chemical Engineering Research and Design 183 (2022) 274–284
comprise majority of the sulphur-containing compounds in
commercial diesel fuel. HDS requires specific conditions to
remove these compounds such as high temperature and
pressure, hydrogen content, and large reactors, resulting in
increased cost and energy consumption. To remove aromatic
sulphur compounds in an energy-efficient and effective
manner, several new approaches have been rapidly devel­
oped such as oxidative desulfurization (Wu et al., 2020),
biological desulfurization (Chen et al., 2021), and adsorption
desulfurization (ADS) (Saha et al., 2021). Among these, ADS is
considered one of the most competitive methods because it
can selectively adsorb aromatic sulphur compounds at room
temperature and atmospheric pressure, achieving ultra-deep
desulfurization without lowering the octane value of diesel
fuel (Luo et al., 2019). Additionally, it uses activated carbons,
zeolites, or activated alumina as adsorbents, which is ad­
vantageous as these compounds are cheap, abundant, and
renewable (Saleh et al., 2018; Yaseen et al., 2021; Hessou
et al., 2021). ADS can therefore be used as a post-treatment
process for HDS, enabling energy-efficient and effective ul­
tradeep desulfurization of diesel fuel.
Among many adsorbents, activated carbon has out­
standing adsorption capacity for aromatic sulphur com­
pounds owing to its unique pore structure and highly specific
surface area, and it can be easily modified. The adsorption
affinity of aromatic sulphur compounds is primarily based on
π-π interactions between the aromatic ring and the surface of
activated carbon (Saleh et al., 2017). In real diesel fuel, the
aromatics and nitrogen compounds as well as aromatic sul­
phur compounds have similar aromatic skeletons, which
poses a challenge to the selectivity of ADS (Qu et al., 2016;
Wen et al., 2010). Aromatics are typically classified as
monoaromatics (15–25 wt%) and polyaromatics (PAHs)
(5–10 wt%). Xiao et al. (Xiao et al., 2012) revealed that mono­
aromatics at a concentration of 10 wt% have a negligible ef­
fect on ADS, while PAHs at a concentration of 1 wt% have a
significant hindering effect. Among nitrogen compounds,
indole and quinoline exhibit higher adsorption capacity than
DBT on modified activated carbon (Arcibar-Orozco et al.,
2019). Kim et al. (Kim et al., 2006) reported that in a fixed bed,
4,6-dimethyldibenzothiophene (4,6-DMDBT) was partially
replaced by nitrogen compounds. In model diesel fuel (MDF),
activated carbon has excellent adsorption capacity for aro­
matic sulphur compounds; however, in real diesel fuel, ac­
tivated carbon does not exhibit satisfactory adsorption. This
is because in MDF, the effect of PAHs and nitrogen com­
pounds on ADS is not taken into account (Bu et al., 2011; Shi
et al., 2015). Thus, activated carbon should have high ad­
sorption capacity as well as high adsorption selectivity.
Moreover, for ADS using real diesel fuel, the effect of PAHs
and nitrogen compounds should be considered when evalu­
ating the sulphur uptake of activated carbon.
In industrial applications, ADS is usually performed using
a fixed bed. For designing fixed beds, adsorption capacity and
the mass transfer rate are crucial because they define the
breakthrough curve (Wilkins et al., 2020). Iruretagoyena et al.
(Iruretagoyena et al., 2020) simulated ADS in a fixed bed and
fitted the mass transfer rates of DBT and 4,6-DMDBT on ac­
tivated carbon treated with different activation methods
based on the experiment results of breakthrough curves.
However, none of the studies have conducted dynamic si­
mulations considering the effects of PAHs and nitrogen
compounds on ADS, which makes an accurate systematic
assessment of the desulfurization performance from real
275
diesel fuel in fixed bed challenging. The dynamic adsorption
process is complex; thus, to design adsorption models, linear
algebra, ordinary differential equations, or even partial dif­
ferential equations are required (Sotelo et al., 2014). To meet
the needs of simulation and design of adsorption processes,
Aspen has developed Aspen Adsorption software. It com­
prises a flowsheet operating system with various models and
does not require the user to be well versed in advanced
programming skills. In a study on removing C5-C6 compo­
nents to improve the gasoline octane value, Bárcia et al.
(2010) used this software to simulate multicomponent
breakthrough curves, and these matched the experimental
data. Ncube et al. (2018) simulated the adsorption behaviour
of benzene, toluene, and m-xylene in a packed bed and de­
signed a commercial-scale packed bed (internal diameter =
3 m, height = 10 m). Ahmed et al. (2020) designed a mass
transfer model for adsorption of melanoidins in the packed
bed and optimised the operating parameters, including inlet
concentration, flow rate, and bed height. Hence, in this
study, Aspen Adsorption software was used for performing
multicomponent adsorption simulations and optimising op­
erating conditions.
Herein, Aspen Adsorption software is used to conduct the
dynamic simulation of ADS, considering the hindering ef­
fects of PAHs and nitrogen compounds. The adsorption iso­
therms and breakthrough curves of PAHs, nitrogen
compounds, and aromatic sulphur compounds are obtained
to establish the adsorption isotherm and mass transfer
models. The effects of PAHs and nitrogen compounds on ADS
are investigated, and the multicomponent adsorption iso­
therm model and the mass transfer model are developed.
Dynamic simulations are applied to further analyse the ef­
fects of varying concentrations of PAHs and nitrogen com­
pounds on ADS as well as to design a fixed bed for ADS from
a typical diesel fuel.
2. Experiments
2.1. Adsorbent and analytical methods
The adsorbent used herein is styrene-based spherical acti­
vated carbon (ACs, Taiyuan Cuihong Technology Co. Ltd.
Taiyuan, China). The nitrogen adsorption of ACs was de­
termined using Micromeritics ASAP 2020 automated nitrogen
adsorption apparatus at 77 K. Specific surface area was cal­
culated based on the Brunauer-Emmett-Teller method
(Brunauer et al., 1938). Pore volume was estimated using
density functional theory, and the average pore size was
obtained using the Barrett-Joiner-Halenda (BJH) method
(Barrett et al., 1951). The pH of the sample suspension was
determined.
2.2. Preparation of model diesel fuel
The composition of real diesel fuel is rather complex and not
suitable for investigating the adsorption mechanism. Thus,
MDF samples are prepared with naphthalene (NA) and me­
thylnaphthalene (MNA) as PAHs; quinoline (QUI) and indole
(IDL) as nitrogen compounds; DBT as the aromatic sulphur
compound; and n-octane as the solvent. Single-component
MDF with X (X in the order of NA, MNA, QUI, IDL and DBT)
was prepared to test adsorption isotherms, and 10 μmol/g of
sample was selected for breakthrough curve measurements.
Details of the concentrations of the one-component MDF for
276 Chemical Engineering Research and Design 183 (2022) 274–284
isotherm determination are shown in Table S1 of
Supplementary material. Two-component MDF containing
10 μmol/g DBT and 10 μmol/g X (X in the order of NA, MNA,
QUI, and IDL) was prepared to investigate the effects of PAHs
and nitrogen compounds on ADS in the fixed bed. NA, QUI,
and n-octane are purchased from Shanghai Lingfeng Che­
mical Reagent Co. Ltd. MNA, IDL, and DBT are purchased
from Alfa Aesar Chemical Co. Ltd. Their concentrations are
99%, 98%, 95%, 96%, 99%, and 98% in that order and are used
without further purification.
2.3. Adsorption experiments
Batch adsorption experiments were conducted at 30 ℃ in a
constant temperature water bath shaker at 100 rpm. In a
series of experiments, 0.1 g of ACs was mixed thoroughly
with 10 g MDF in a 20 mL brown conical flask for 48 h. The
concentration of the treated MDF was analysed using GC-
2014 C. The adsorption isotherms of NA, MNA, QUI, IDL, and
DBT were determined sequentially to identify the isotherm
model, which was essential for simulation. The adsorption
amount qe was calculated using Eq. (1).
M (C0 Ce )
qe = m (1)
where C0 is the initial concentration, Ce is the equilibrium
concentration (μmol/g-MDF), M is the weight of MDF (g), and
m is the amount of adsorbent (g).
The fixed-bed adsorption experiments were conducted in
a stainless steel column (inner diameter = 4.6 mm, length =
150 mm) with a packed amount of 0.6 g at 30 ℃. The inlet flow
rate was 0.1 mL/min, and the treated MDF samples were
collected using an automatic sampler. The concentration of
the treated MDF was analysed using GC-2014 C. A simple
experimental apparatus of fixed bed is shown in Fig S1 of the
supplementary material. Experimental results of the break­
through curve are used to confirm rationality of the simula­
tion. The adsorption amount of the fixed bed is calculated
using Eq. (2).
q=
V*
m (C L
0
L
0
C (L ) dL ) (2)
where V is flow rate (mL/min), is the density of MDF (g/mL),
and L is the amount of treated MDF (g).
3. Modelling of fixed-bed adsorption
3.1. Adsorption isotherm model
The adsorption isotherm is essential for fixed-bed adsorption
simulations because it reflects the relationship between the
saturation adsorption capacity and the residual concentra­
tion. Langmuir and Freundlich models, expressed using Eqs.
(3) and (4), respectively, are typically used to describe ad­
sorption isotherms.
qm KL Ce
qe = (3)
1 + KL Ce
where Ce is the equilibrium concentration of adsorbate in the
liquid phase (μmol/g-MDF), KL is the Langmuir constant (g-
MDF/μmol), and qm is the maximum adsorption capacity
(μmol/g-ACs).
qe = KF Ce1/ n (4)
where KF , (μmol/g-ACs) (g-MDF/μmol)1/n, and 1/n are Freun­
dlich constants.
The parameters are determined by fitting the isotherm
model to adsorption equilibrium data. Isotherm parameters
are obtained using a nonlinear method in the Static Isotherm
model of Aspen Adsorption software (Wang and Guo, 2020).
Furthermore, these parameters are used to predict the mul­
ticomponent adsorption isotherm based on the ideal ad­
sorbed solution (IAS) theory.
3.2. Mass transfer model in fixed beds
To simplify calculations, the mass transfer model is based on
the following assumptions:
(1) Consistent with plug flow, the axial and radial diffusion is
ignored.
(2) The bed operates in isothermal conditions without con­
sidering the heat of adsorption.
(3) The superficial velocity is constant, and pressure drop is
neglected.
(4) The mass transfer process is approximated by the linear
driving force (LDF) model, where the main resistances are
combined in a lumped parameter.
These assumptions are made for several reasons. The
practical value of the Reynolds number, Pe (Pe Hb / Rp), is 404,
which is much larger than 20; thus, the effect of axial dis­
persion is minimal, and the assumption of plug flow is jus­
tified (Raghavan and Ruthven, 1983). The concentration of
adsorbates in MDF is at the ppm scale; thus, the adsorption
process in the fixed bed is a purification process. In a pur­
ification process, when the concentration of the adsorbate
is < 1%, the influence of the fluid flow rate and radial diffu­
sion as well as the heat are negligible (Gutiérrez Ortiz et al.,
2019). According to the Kozeny-Carman equation, in this
case, the pressure decreased by 0.723 kPa/m, and the effect of
this decrease on the breakthrough curve is negligible (Fig. S2).
The LDF model is often used to characterise the mass
transfer kinetics in adsorption columns (Shafeeyan et al.,
2014). It is validated to be suitable for describing the parabolic
concentration profile within the particle, and it is in good
agreement with the simulation results of the homogeneous
surface diffusion model (HSDM) (Liaw et al., 1979; Sperlich
et al., 2008). The model is popular because of its simplicity
and fast calculation speed. Therefore, herein, the mass
transfer kinetics of adsorbates in MDF are approximated
using the LDF model described using Eq. (5).
q
s t = ki (ci ci* ) (5)
where ki is the effective mass transfer coefficient (s−1), ci de­
notes the equilibrium concentration of adsorbate in the li­
quid phase, and ci* is the average concentration of adsorbate
within the particle.
Jeon et al. (Jeon et al., 2009) reported that the adsorption
capacities of aromatic sulphur compounds on activated
carbon had a strong positive linear relationship with the pore
volumes of 0.63–1.2 nm micropores. Ania et al. (Ania and
Bandosz, 2005) demonstrated that a high number of meso­
pores can significantly increase the adsorption rate. During
the adsorption process of aromatic sulphur compounds on
activated carbon, macropores or mesopores serve as chan­
nels, whereas micropores serve as the main adsorption sites.
 Chemical Engineering Research and Design 183 (2022) 274–284 277

Fig. 1 – Sample structural characteristics: (a) N2 adsorption isotherm and (b) pore size distribution of ACs.

Therefore, pore diffusion resistance should be considered. values of the breakthrough curve (Siahpoosh et al., 2009;
Taking into account liquid film resistance and pore diffusion Lucas et al., 2004). It is calculated using Eq. (11):
resistance, the value of ki is calculated using Eq. (4)
1 n Cexp Cmodel
(Siahpoosh et al., 2009). LDF approximation is successfully AAD = n i=1 C0 (11)
applied to the dynamic simulation of acetaminophen ad­
sorption (Juela, 2020). where n is the number of experimental points. When AAD <
0.05, the result is highly consistent; when 0.5 < AAD < 0.1,
1 Rp Rp2
ki
= 3kfi
+ 15 p Dpi (6) the result is probably consistent; and when AAD > 0.1, the
result is not consistent.
where i represents adsorbates, kfi is the liquid film mass
transfer coefficient (cm/s), Dpi is the effective pore diffusion
4. Results and discussion
coefficient (cm2/s), p is the particle porosity, and Rp is the
particle radius (cm).
4.1. Characteristics of ACs
The value of kfi is calculated using Carberry's empirical
equation (Carberry, 1960):
Fig. 1 shows the nitrogen adsorption isotherm and pore size
0.5
( )
2/3
( )
kfi b µ dp v distribution. Nitrogen adsorption mainly occurs at a low-
v Dmi
= 1.15 µ (7)
pressure range, and it exhibits an obvious hysteresis circle at
the relative pressure p/p0 of approximately 0.8, indicating the
where b is the bed porosity, and Dmi is the molecular diffu­
presence of a large number of micropores and some meso­
sion coefficient, which is calculated using the Wilke-Chang
pores. The pore structure characteristics of ACs are presented
equation.
in Table S2. The pore volumes of micropores, mesopores, and
The value of Dpi is obtained using Eq. (8) (Lucas
et al., 2004): macropores account for 75%, 12%, and 13% of the total pore
volume, respectively. The average pore diameter calculated
1
Dpi
=
p
( 1
Dmi
+
1
Dki ) (8) by the BJH method is 10.8 nm. The pH of the sample sus­
pension is 4.0, implying the presence of a large number of
where τ is the curvature factor, and Dki is the Knudsen dif­ acidic sites on the surface of ACs (Seredych et al., 2009).
fusion coefficient. The value of τ is calculated using Eq. (9)
(Siahpoosh et al., 2009): 4.2. Adsorption isotherm
= p + 1.5(1 p) (9)
The adsorption isotherms of PAHs, nitrogen compounds, and
The Biot number (Bi) can be used to determine the control DBT are presented in Fig. 2. The adsorption amount increases
step in the mass transfer process, which is defined using with increasing equilibrium concentration. MNA has larger
Eq. (10): adsorption capacity than NA, and thus, the presence of me­
kfi Rp thyl groups facilitates adsorption. The adsorption isotherms
Bii = (10) of DBT and IDL are similar, implying that strong competitive
p Dpi

adsorption may occur during coexistence.

When Bi < 1, external diffusion is the control step; when
1 < Bi < 100, the mass transfer process is controlled by ex­
ternal diffusion and pore diffusion; and when Bi > 100, pore
diffusion is the control step.
3.3. Modelling validation
Absolute average deviation (AAD) is used to quantify the
deviation of the simulation results from the experimental
To further explore the adsorption performance, experi­
mental data of adsorption isotherms are fitted using
Langmuir and Freundlich models based on the nonlinear
method, and their parameters are listed in Table 1. The ad­
sorption isotherm better fits the model when the correlation
coefficient R2 is closer to 1. NA and QUI are more consistent
with the Langmuir model than with the Freundlich model,
whereas DBT, IDL, and MNA are more consistent with the
Freundlich model (R2 > 0.99). Without maximum adsorption
278 Chemical Engineering Research and Design 183 (2022) 274–284

Fig. 2 – Adsorption isotherms of adsorbates over ACs fitted using (a) Langmuir and (b) Freundlich models.

more significant for DBT and IDL due to their stronger acid-
Table 1 – Langmuir and Freundlich model parameters of
base interactions.
adsorbates.
Adsorbate Langmuir Freundlich

qm KL R2 KF 1/n R2 4.3. Single-component breakthrough curve

NA 646 0.147 0.989 105 0.521 0.967

MNA 730 0.149 0.933 151 0.441 0.991
Quin 1182 0.158 0.991 211 0.503 0.982
IDL 1133 0.379 0.971 367 0.367 0.997
DBT 1141 0.410 0.951 405 0.341 0.996
capacity, the Freundlich model implies the existence of
multilayer adsorption for DBT, IDL, and MNA (Wen et al.,
2010). The adsorption capacity KF increases in the order
NA < MNA < QUI < IDL < DBT. This indicates that the ad­
sorption affinity increases in the order NA < MNA < QUI <
IDL < DBT (Misra et al., 2017).
The adsorption of compounds with aromatic skeletons
mainly occurs via π-π interactions between aromatic rings
and the surface of activated carbon (Bu et al., 2011). Ad­
sorbate molecules with larger π electron numbers (sum of the
number of C(sp2) and S/N atoms) possibly have stronger ad­
sorption affinities (Qu et al., 2016). As shown in Table 2, the
increasing order of these molecules in terms of π electron
number is IDL < NA = MNA = QUI < DBT. The methyl group
provides electrons to the aromatic ring, increasing the elec­
tron density of the π-system. Consequently, the π-system of
MNA is slightly larger than that of NA, and MNA has a
stronger adsorption affinity than NA, implying that adsorp­
tion is mainly based on π-π interactions. Thus, aromatic
sulphur compounds with methyl groups, particularly 4, 6-
DMDBT, may be easier to remove over ACs. The pH of a
sample suspension reflects the acidity or basicity of a surface
(Ania and Bandosz, 2005). The pH of 4.0 indicates that many
acidic sites are present on ACs surface (Lucas et al., 2004).
Heterocyclic compounds such as DBT, IDL, and QUI are basic
compounds, and thus, their adsorption is based on π-π in­
teractions and acid-base interactions (Qu et al., 2016; Arcibar-
Orozco et al., 2019; Ania and Bandosz, 2005). The Freundlich
model is applicable to heterogeneous surfaces. The surface is
more heterogeneous when 1/n is closer to 0. The 1/n values of
DBT and IDL are 0.341 and 0.367, respectively, which are
smaller than those of other adsorbates, implying that the
sample surface is heterogeneous and the heterogeneity is
To investigate the adsorption capacity of PAHs, nitrogen
compounds, and aromatic sulphur compounds in the fixed
bed and to examine the validity of the dynamic simulation,
single-component breakthrough curves are measured. The
initial concentration of adsorbates in MDF is 10 μmol/g. The
single-component breakthrough curves are presented in
Fig. 3, where the dots represent the experimental values and
the solid lines represent the simulation values. With the
same mass transfer model and Langmuir and Freundlich
models as the isotherm models, their simulation results are
shown in Fig. 3(a) and (b), respectively.
The breakthrough capacity increases in the order
NA < MNA < QUI < IDL < DBT, and the corresponding values
are 37.4, 40.6, 61.1, 75.2, and 77.6 g-MDF/g-ACs, respectively.
The breakthrough capacity is consistent with the adsorption
affinity. Hence, the adsorption capacity of DBT over ACs is
the largest, followed by nitrogen compounds and then PAHs.
Parameters of the simulation in the fixed bed are listed in
Table S3. Fig. 3(a) shows that the simulated NA breakthrough
curve shows a lower capacity than the experimental values
obtained using the Langmuir model. Fig. 3(b) shows similar
phenomena for NA, MNA, and QUI by using the Freundlich
model. In order to explain the modelling error sources, the
saturation adsorption amounts of the MDF sample at a con­
centration of 10 μmol/g are listed in Table 3. Compared with
the experimental values in fixed-bed adsorption, the batch
adsorption amounts estimated by the isotherm models are
smaller, which is the main reason for the lower saturation
amount in dynamic adsorption simulation. The fixed-bed
experimental value is close to the batch value, indicating that
the simulated breakthrough curves are highly consistent
with their experimental values. For example, DBT and IDL
with AAD values of only 0.17 and 0.16 by using the Freundlich
model. As shown in Table 3, AAD values are all less than 0.1,
and this error is within the acceptable range. In addition,
their AAD values are < 0.05, except for NA, showing good
agreement with the experimental results. Therefore, the
Langmuir or Freundlich models for the adsorption isotherm
and the LDF model approximation for the mass transfer
process in the dynamic simulation of single-component
 Chemical Engineering Research and Design 183 (2022) 274–284 279

Table 2 – Properties of adsorbate molecules.

Chemicals Chemical structure Molecular weight Molecular sizea Number of
C (sp2) + S/N atoms

NA 128.17 7.40 × 9.16 10

MNA 142.20 8.13 × 9.58 10

QUI 129.16 7.40 × 9.16 10

IDL 117.15 7.77 × 9.48 9

DBT 184.26 7.05 × 11.54 13

a
Molecular size is calculated based on the density functional theory (Jae et al., 2011).

adsorption are appropriate choices. Furthermore, when the
Freundlich model is used as the isotherm model, the values
of AAD for DBT and IDL are only 0.017 and 0.016, respectively,
suggesting that the Freundlich model is more consistent with
their adsorption isotherms.
The breakthrough curves are steep, but their slopes are
governed by the adsorption isotherm and the mass transfer
rate (Fig. 3). It is hard to know the mass transfer rate of the
adsorption process. The calculated values of the effective
mass transfer coefficient ki are listed in Table S4. The Bi va­
lues of PAHs, nitrogen compounds, and DBT are in the range
of 40–50, suggesting that their mass transfer processes in
fixed beds are influenced by a combination of liquid film
diffusion and pore diffusion (Xue et al., 2018). Therefore, their
mass transfer process occurs from the liquid phase into the
macropores or mesopores and are finally adsorbed into the
micropores. Iruretagoyena et al. (Iruretagoyena et al., 2020)
reported that the value of mass transfer rate for DBT on ac­
tivated carbon samples was in the range 0.0001–0.0005 s−1.
Mass transfer rate for DBT on ACs is 0.0860 s−1. The mass
transfer rate using ACs is 150 times larger than that with
their samples. Their samples contain more micropores with
an average pore size of approximately 3.5 nm, while ACs has
more mesopores and macropores with an average pore size
of 10.8 nm, because of which the mass transfer rate using ACs
is accelerated. Therefore, an ideal activated carbon sample
should contain a large number of micropores as well as some
mesopores and macropores to have high adsorption capacity
and fast mass transfer rate.
4.4. Effect of aromatics and nitrogen compounds on ADS
Two-component breakthrough experiments in the fixed bed
are performed to investigate the effect of PAHs and nitrogen
compounds on ADS and to examine the rationality of mul­
ticomponent dynamic simulation. Fig. 4 shows the two-
component breakthrough curves, where the dots represent
the experimental values, and the dashed and solid lines re­
present the simulation values when the isotherm models are
chosen as the IAS-Langmuir and IAS-Freundlich model, re­
spectively. The mass transfer model uses the LDF model with
the same ki as in Section 4.3.
The MDF at the inlet contains equimolar concentrations
of NA and DBT (Fig. 4(a)). NA reaches the breakthrough point
first, and then, its C/C0 value increases rapidly until it reaches
1.4. After DBT reaches the breakthrough point, the C/C0 of NA

Fig. 3 – Single-component breakthrough curve in fixed bed.

280 Chemical Engineering Research and Design 183 (2022) 274–284

Table 3 – Saturation adsorption amount for one-component MDF (µm olg

/ ).
Adsorbate Experiment Langmuir model estimation Freundlich model estimation

Fixed-bed Batch Fixed-bed AAD Batch Fixed-bed AAD

NA 427 384 373 0.055 348 338 0.085

MNA 454 437 424 0.033 417 405 0.049
QUI 710 724 697 0.022 672 648 0.034
IDL 855 896 864 0.028 854 823 0.016
DBT 870 917 884 0.030 888 854 0.017

gradually decreases and finally decreases to 1.0. As shown in
Fig. 4(b)-(d), a similar phenomenon occurs for MNA, QUI, and
IDL when coexisting with DBT, for example, their break­
through amount becomes smaller, and C/C0 is greater than 1.
From Fig. 4(a) to (d), it can be seen that the breakthrough
amount of DBT progressively becomes smaller and the
breakthrough curve becomes flat. In MDF, adsorbates with
different adsorption affinities may be partially adsorbed on
the same adsorption sites. The adsorbates that break
through later usually have stronger adsorption affinities.
Hence, they can replace adsorbates with weaker affinities
adsorbed at the same site, resulting in a higher exit con­
centration of adsorbates than import concentration (Qu
et al., 2016). This indicates that the adsorption affinity of DBT
on ACs is significantly stronger than that of the other four
adsorbates. The adsorption capacities of adsorbates in the
two-component breakthrough experiments are listed in
Table 4. Under equimolar concentrations of NA, MNA, QUI,
and IDL, the breakthrough amount of DBT decreases by 2, 44,
70, and 159 μmol/g, respectively. This indicates that the
presence of PAHs and nitrogen compounds hinders the ad­
sorption of DBT, and the hindrance effect is in the order
IDL > QUI > MNA > NA. The hindering effect of IDL is the
strongest, because of which DBT has smaller breakthrough
amount (2.3 times higher than that of QUI). The pKa of IDL is
21.0, which is why it may have larger adsorption affinity
through stronger acid-base interactions. Coexisting with
DBT, the net adsorption capacities of NA, MNA, QUI, and IDL
decreased by 70%, 77%, 54%, and 34%, respectively, indicating
the weak replacement ability of DBT for nitrogen com­
pounds. The net adsorption capacities of QUI and IDL are 325
and 567 μmol/g, which indicates that ACs can remove ni­
trogen compounds and aromatic sulphur compounds si­
multaneously.
According to the IAS-Langmuir model, the breakthrough
points of simulated DBT breakthrough curves are advanced

Fig. 4 – Two-component breakthrough curve in fixed bed:(a) DBT-NA, (b) DBT-MNA, (c) DBT-QUI, (d) DBT-IDL.
 Chemical Engineering Research and Design 183 (2022) 274–284 281

Table 4 – Adsorption capacity of PAHs, nitrogen compounds, and DBT in the two-component breakthrough experiments
(μmol/g-ACs).
Adsorbate NA+DBT MNA+DBT QUI+DBT IDL+DBT

NA DBT MNA DBT QUI DBT IDL DBT

Breakthrough 229 774 309 732 391 706 540 617

Saturation 313 846 348 811 508 825 619 711
Netb 129 845 105 801 325 816 567 712
b
Difference between the total adsorbate in the feed and the total adsorbate at the output until the end of the experiment.

investigate the effect of different concentrations of PAHs and

Fig. 5 – Effect of PAHs and nitrogen compounds on ADS.
and adsorption capacities are significantly smaller than ex­
perimental values (Fig. 4. (a)-(d)). The adsorption affinity in­
creases as follows NA < MNA < QUI < IDL < DBT, and the
hindrance effect is ranked as NA < MNA < QUI < IDL. This re­
sult indicates that the closer the adsorption affinity, the
stronger is the competition with DBT for adsorption. Fig. 4(a) to
(d) indicates that this problem is progressively worse, in­
dicating that the simulation becomes less effective when the
competition between the adsorbates is strong. Fortunately, the
application of the IAS-Freundlich model helped efficiently
overcome this problem, significantly reducing the error be­
tween the simulated breakthrough curve of DBT and the ex­
perimental value. According to the IAS-Freundlich model, the
simulation results are satisfactory for the coexistence of DBT
and PAHs. And they are slightly poor for the coexistence of
DBT and nitrogen compounds due to the intensive competi­
tion between nitrogen compounds and DBT. The AAD values
of dynamic simulation based on the IAS-Langmuir model and
IAS-Freundlich model are presented in Table S5. Obviously, the
AAD values of the former are smaller than that of the latter.
Thus, multicomponent adsorption isotherms are more con­
sistent with the IAS-Freundlich model, implying the occur­
rence of heterogeneous adsorption.
According to the adsorption isotherm, the adsorption ca­
pacity of the sample increases with increasing adsorbate
concentration in MDF. Therefore, it is necessary to
nitrogen compounds on ADS. To reduce effort, we explore
this aspect using simulations with the IAS-Freundlich model
and the LDF model. The simulation results are presented in
Fig. 5. The simulation results show that the breakthrough
amount of DBT decreases with an increase in the con­
centration of PAHs and nitrogen compounds, but the de­
creasing trend gradually plateaus. The rate of decrease is in
the order IDL > QUI > MNA > NA, implying that nitrogen
compounds have a stronger hindering effect than PAHs. The
adsorption affinities of PAHs and DBT are governed by π-π
interactions; with increasing concentration, PAHs are more
likely to occupy the same adsorption sites as DBT, leading to
an increasingly obvious hindrance to DBT (Qu et al., 2016).
The reduction rate gradually tends to become 0 because of
the limited adsorption sites for PAHs and DBT. The un­
occupied adsorption sites of DBT may be based on acid-base
interactions. When the concentration of PAHs reaches 10%,
the breakthrough amount of DBT decreases by approxi­
mately 85%. Under different concentrations, PAHs and ni­
trogen compounds have considerably different hindering
effects; thus, it is essential to consider their concentrations
when assessing the ADS performance of a diesel fuel sample.
4.5. Designing fixed bed reactors using typical diesel
In a typical diesel fuel, the concentration of nitrogen com­
pounds and aromatic sulphur compounds is usually at the
ppm scale, while it is 5–10 wt% for PAHs. In this study, a fixed
bed is simulated (inner diameter = 0.2 m) for ADS from diesel
as well as to determine optimal operating conditions. The
hindering effect of PAHs and nitrogen compounds on ADS
are taken into account; then, the sample contains 10 μmol/g
DBT, 3 μmol/g IDL, 3 μmol/g QUI, 3 wt% MNA, and 3 wt% NA.
The optimal operating conditions are determined by chan­
ging the stacking height and the flow rate. The operating
parameters of the fixed bed are presented in Table 5.
Bi > 100 indicates that pore diffusion is the control step.
The simulation results show that a low flow rate and a large
stacking height leads to more DBT breakthrough amount per
unit weight of samples (Table S6). Furthermore, the adsorp­
tion capacity of ACs for each component when DBT reaches
the breakthrough point is analysed (Fig. 6). Selectivity of ADS
is defined as the ratio of DBT adsorption amount to the total

Table 5 – Operating parameters of the fixed bed.

Run 1 2 3 4 5 6 7 8 9

Stacking height (m) 2 2 2 3 3 3 4 4 4

Flow rate (L/min) 1.6 4.8 14.4 1.6 4.8 14.4 1.6 4.8 14.4
LHSV (/h) 1.53 4.59 13.76 1.02 3.06 9.17 0.76 2.29 6.88
282 Chemical Engineering Research and Design 183 (2022) 274–284

Fig. 6 – Simulation results: (a) adsorption amount when DBT reaches the breakthrough point, (b) relationship between LHSV
and selectivity of ADS.

adsorption amount. Fig. 6(a) shows that the low flow rate and
large stacking height increase selectivity of ADS. Thus,
clearly, a fixed bed with low flow rate and large stacking
height has a large LHSV. Fig. 6(b) shows a strong negative
linear relationship between the LHSV value and selectivity of
ADS, and the intercept of the straight line is 0.0982, implying
that the maximum value of selectivity of ADS is 9.82%. This
value decreases from 9.68% to 6.29% with increasing LHSV,
implying that large LHSV is not suitable to the selectivity of
ADS. Fig. 7(a)-(c) shows the breakthrough curves of a fixed

Fig. 7 – Simulation of breakthrough curve in typical diesel fuel at (a) 1.6 L/min, (b) 4.8 L/min, (c) 14.4 L/min, and (d) the effect of
PAHs and nitrogen compounds on ADS.
 Chemical Engineering Research and Design 183 (2022) 274–284
bed with a stacking height of 4 m under different flow rates.
The order of breakthrough is NA < MNA < QUI < IDL < DBT,
which is consistent with the ranking of the adsorption affi­
nities. This indicates that the ranking of the competitive
adsorption ability is NA < MNA < QUI < IDL < DBT. At large
flow rates, the breakthrough curves become smoother and
the amount of replacement is reduced. The low LHSV with a
long residence time of the MDF in the fixed bed leads to an
adequate contact between the adsorbate and the adsorbent.
With the strongest adsorption affinity and competitive
ability, adsorption of DBT is favoured when the contact is
adequate.
When the stacking height is 4 m and the flow rate is 1.6 L/
min, the selectivity reaches 9.68%, which represents the ideal
state; its breakthrough curve in the fixed bed is shown in
Fig. 7(d). The breakthrough amount of DBT is 1600 L, and its
breakthrough curve is relatively smooth. The breakthrough
amount of DBT without considering the effect of PAHs and
nitrogen compounds is 6736 L, and its breakthrough curve is
steeper. This shows that the effects of PAHs and nitrogen
compounds on ADS are significant and should be considered
when designing fixed beds for ADS from diesel fuel. The
modelling results show that with an inner diameter of 0.2 m,
stacking height of 4 m, and an inlet flow rate of 1.6 L/min, the
fixed bed can treat 1600 L of typical diesel fuel to accomplish
ultra-deep desulfurization.
A large number of activated carbon materials have been
synthesised and modified. Dynamic adsorption simulations
allow rapid screening of qualified adsorbent materials for
ADS from diesel fuel in industry by simulating the hindering
effects of PAHs and nitrogen compounds and optimising the
fixed bed operating conditions. The composition of real
diesel fuel is rather complex. Dynamic simulations of two-
component breakthrough curves show the simulation be­
comes less effective when the competition between the ad­
sorbates is strong. Therefore, we plan to conduct multi-
component adsorption experiments to further investigate
the feasibility of dynamic simulations in the future.
5. Conclusions
The competitive adsorption ability is ranked as
NA < MNA < QUI < IDL < DBT. The relatively developed me­
sopores of ACs result in a fast mass transfer rate. For com­
petitive adsorption, simulation results of the IAS-Freundlich
model are better. Simulation results show nitrogen com­
pounds and PAHs can severely inhibit ADS at 1 and 5 wt%
concentrations, respectively. Due to the strongest adsorption
affinity and competitive ability of DBT, low LHSV with more
residence time is beneficial to ADS selectivity.
Declaration of Competing Interest
The authors declare the following financial interests/per­
sonal relationships which may be considered as potential
competing interests.
Acknowledgements
This work is partly supported by the National Nature Science
Foundation of China (No: 21978097) and the Fundamental
Research Funds for the Central Universities (No:
JKD01211701). The Aspen Adsorption software provided by
283
East China University of Science and Technology is ac­
knowledged. The authors would like to thank the anon­
ymous reviewers for their constructive suggestions that have
improved the quality of this work.
Appendix A. Supporting information
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.cherd.2022.04.029.
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