Fuel 310 (2022) 122427

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Effects of zeolite molecular sieve on the hydrocarbon adsorbent and

diffusion performance of gasoline engine during cold start
Lehan Chen a, Yuanwang Deng a, d, Wei Han b, Jiaqiang E. a, d, *, Chunhua Wang c, *, Dandan Han a,
Changling Feng a
a
College of Mechanical and Vehicle Engineering, Hunan University, Changsha 410082, China
b
Technical Center, Dongfeng Motor Corporation, Wuhan 430056, China
c
College of Energy and Power Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
d
Institute of New Energy and Energy-Saving & Emission-Reduction Technology, Hunan University, Changsha 410082, China

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, adsorption characteristic of the MOR, MFI, and CON zeolites used in hydrocarbon catcher and
HC adsorber diffusion properties of hydrocarbon (HC) molecules on them were studied for hydrocarbon emission control
Cold start HC emission during cold start. To find adsorbents with promising adsorption performance for hydrocarbon catcher, the nu­
Adsorption simulation
merical simulation was carried out by using Material studio software with benzene (C6H6) and ethylene (C2H4) as
Diffusion efficiency
the probes, the Grand Canonical Monte Carlo (MC) method was used in the adsorption simulation, and Molecular
Dynamics (MD) method was used to simulate the diffusion of hydrocarbon molecules. The isotherms, adsorption
sites, heats of adsorption, and interaction energy distribution of hydrocarbon single-component and multi-
component molecules on three different zeolites were studied at various low temperatures and pressures.
Based on the simulation results, the most suitable type of molecular sieve was found from the three molecular
sieves when the type and quantity of components were different. Results of adsorption simulation show that CON
molecular sieve has batter adsorption performance for benzene component. The adsorption amount is 65/uni­
te cell (UC) benzene molecules per cell, which is about twice of MFI molecular sieve. MFI molecular sieve has
batter adsorption performance for ethylene component. The adsorption amount is 130/UC ethylene molecules
per cell, which is about 2 and 1.5 times of MOR and CON, respectively of MOR molecular sieve. The adsorption
simulation results of mixed hydrocarbon components show that the adsorption capacity of each component on
the three molecular sieves was ranked as follows: C6H6 > C3H6 > C2H4 > C3H8 > H2O > CH4, collectively. The
results of diffusion simulation show that the single component of ethylene molecule has relatively small diffusion
coefficient on MFI molecular sieve about 2.2×10− 10m/s and good adsorption performance at low temperature,
and the largest diffusion coefficient on CON molecular sieve about 3.4×10 − 10m/s. The single component of
benzene molecules has the smallest diffusion coefficient on the CON molecular sieve 5.9×10− 11m/s about and
the largest diffusion coefficient on the MOR molecular sieve about 1.76×10− 10m/s. In multicomponent diffusion.
In multicomponent diffusion. The diffusion degree of each component molecule in the MFI and CON molecular
sieve from strong to weak is about: H2O, CH4, C2H4, C3H8, C3H6 and C6H6. The diffusion pattern within the MOR
molecular sieve from strong to weak approximately: C3H8, C6H6, C3H6, C2H4, CH4 and H2O. The results show that
the high temperature had an obvious effect on the adsorption capacity of zeolite. As temperature rises the
molecular diffusion coefficient increases and the molecular motion becomes more intense. After about 500 K, the
adsorption capacity is at a very low level.

1. Introduction internal combustion engines is increasing. The widespread use of in­

ternal combustion engines has brought great convenience to our pro­
As people’s living standards improve, purchasing power increases duction life, but the problem of exhaust pollution from internal
rapidly, and society and industry develop at a rapid pace the demand for combustion engines has also become one of the most serious

* Corresponding authorsat: College of Mechanical and Vehicle Engineering, Hunan University, Changsha 410082, China (E. Jiaqiang).
E-mail addresses: ejiaqiang@hnu.edu.cn (J. E.), chunhuawang@nuaa.edu.cn (C. Wang).

https://doi.org/10.1016/j.fuel.2021.122427
Received 1 October 2021; Received in revised form 19 October 2021; Accepted 27 October 2021
Available online 5 November 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
L. Chen et al.
environmental pollution problems [1–3]. Energy saving and emission
reduction has become one of the most significant approaches to achieve
green sustainable development [4], and there is an increasing amount of
study[5,6] into how to use clean energy and renewable energy [7,8]
effectively. At the same time, along with the increasingly stringent
emission regulations [9–11], how to reduce the emission of pollutants in
exhaust gas and achieve environmentally sustainable development
[12,13] has become an urgent issue for all countries [14–16] and in­
ternal combustion engine companies.
It has been found hydrocarbon emissions [17] from internal com­
bustion engines account for about 70–80% [18] of total hydrocarbon
emissions from gasoline engines during cold starts, which is about ten
times [19] more than hydrocarbon emissions during hot starts, while HC
and CO emissions from [20,21] petrol engines equipped with three-way
catalytic converters (TWC) account for about 50–80% of total hydro­
carbon emissions [21] from gasoline engines, so it has become necessary
to control hydrocarbon emissions from gasoline engine exhaust during
cold starts. Many new technologies have arisen to address this problem.
There are two types of approaches for reducing hydrocarbon emissions
during cold star of engines [22,23], pre-treatment measures and post-
treatment measures. Engine preheating [24], improved air intake
[25], electrically heated catalysts [26], novel alternative fuels [27], and
reducing hydrocarbon emissions during cold starts by enhancing fuel
atomization and adjusting timing parameters (valve timing, fuel injec­
tion timing, ignition timing, etc. [28,29]) are all examples of pre-
treatment measures.
Preheating intake can increase evaporation rate, and in the first 40 s,
average emissions of HC and CO were reduced. The emissions of CO and
HC were reduced respectively, under the action of the preheating [30].
Besides the intake temperature, the oxygen concentration in the intake is
also an important factor affecting the cold start HC emission. The effects
of different concentrations of oxygen on the combustion and emissions
of gasoline engines during cold starts were studied. In the first 60 s after
starting, many parameters were tested in air with 25% and 21% O2
cases. Related experiment results demonstrated that combustion could
be optimized using oxygen-enriched air, with higher exhaust tempera­
ture, lower HC and CO emissions, and less time reaching TWC light-off
temperature at the same time [31]. Then 21%, 23%, 25%, 27% and 29%
O2 concentrations were selected for cold start experiments. As the O2
concentration in the intake air increased, the ignition angle increased,
the combustion in the cylinder was complete, and the peak pressure and
combustion temperature increased, a good combustion environment
was created and HC emissions were reduced[25]. Meanwhile, emission
of polycyclic aromatic HCs [32] and soot were be significantly reduced
by adjusting injection parameter (injection pressure increase) and using
EGR [33]. Apart from traditional pre-treatment measures, research on
the addition of alternative fuels [34,35] is also increasing. Pending cold-
start part of FTP-75, ethanol mixed fuel vehicles showed lower CO and
HC content[36]. Combustion and emission in four ethanol gasoline fuels
conditions were studied in the range of 10–85% ethanol. E10, E20, E45
can start stably. However, for E85 engines, the race of engine was
shocked because of leaner burn [37]. In addition to ethanol, methanol
fuel [38] is also used as engine fuel [39,40] widely. Studies about
emission and combustion behaviors of methanol/gasoline engines dur­
ing warm-up and cold start had shown that the HC of methanol gasoline
fuels lower during cold starts, but the amount of methanol does not seem
to have an effect on the degree of HC reduction [41]. Investigations of
the effects of methanol injection time and LPG ratio [42] on cold start
behaviors of methanol engines had shown that proper methanol injec­
tion timing provided reliable engine ignition and minimal HC emissions
[43]. With the proposal of hydrogen fueled engine, more and more in­
vestigations on hydrogen blending combustion appears [44,45]. A
comparative study of only gasoline, only hydrogen and hydrogen/gas­
oline injection during cold start presented that mixed injection had
better combustion and emission performance, and emission of CO and
HC were all decreased [46]. Cold start process in European driving cycle
2
Fuel 310 (2022) 122427
for hydrogen/gasoline fueled engine showed similar results, and its
cumulative emission amount of CO and HC were significantly lower than
that of conventional one [47]. There are other fuels that are also being
used to improve cold-start emissions. Adding a certain proportion of
alcohol, dimethyl ether, hydrogen, etc. to the fossil fuel can improve the
combustion and reduce emissions, while also alleviates the energy crisis
to a certain extent [48]. However, due to the complex operating con­
ditions of gasoline engines, exhaust emissions are difficult to control
precisely [28]. Experts and scholars have gradually shifted their
research focus to off-engine purification technology, such as the use of
TWC, as pre-treatment measures has become increasingly difficult and
costly and the use of pre-treatment measures alone cannot meet the
increasingly stringent emission standards, in recent years. TWC is one of
the most effective pre-treatment measures technologies for reducing
exhaust emissions from internal combustion engines [49,50]. The TWC,
on the other hand, takes 60–120 s to warm up from cold start to working
temperature. As a result, the traditional TWC [51] cannot solve the cold-
start emission problem of a gasoline engine, and extra post-treatment is
required to reduce hydrocarbon emissions in gasoline engine exhaust at
250–300 K. HC adsorber, a more convenient post-processing device
appeared [52,53]. The HC capture technology [54] was first introduced
by Engelhard in 1995 and is currently the most effective technology for
controlling hydrocarbon emissions from gasoline engines during cold
starts. When the exhaust gas temperature is low, an adsorbent applied to
the HC catcher carrier adsorbs hydrocarbon molecules, which are then
released when the temperature rises to the TWC starting ignition tem­
perature, and then oxidized with a catalyst, or introduced into the intake
pipe into the cylinder for combustion. The HC catcher is reliable and
convenient in reducing HC emission, and the schematic [55] is shown in
Fig. 1.
The HC catcher can reduce total hydrocarbon [56] emissions by
45–75% compared to a conventional three-way catalytic converter. The
sorbent material is crucial to the HC catcher’s capture performance at
cold start and has a direct impact of control effect on hydrocarbon
emissions[57,58].
Zeolite molecular sieve is a kind of crystalline silico-aluminate con­
taining alkali metal and alkaline earth metal oxides. It is considered to
be an excellent molecular adsorbent because of its strong adsorption
capacity for small polar molecules such as water molecules and its se­
lective adsorption ability for different molecules such as critical diam­
eter, shape, polarity and saturation. The adsorption characteristics of
molecular sieves are derived from several aspects: (1) The molecular
sieves have large specific surface area and micropore volume. The pores
of molecular sieves are small and uniform. The adsorption molecules
receive the superimposed adsorption force of pore wall in the pores, and
the adsorption mechanism is similar to that of microporous filling. (2)
Zeolite molecular sieves have a unique pore channel and pore cage (pore
cavity with a guest molecule) structure [59], and only molecules smaller
than or approximately equal to the pore size may be adsorbed. (3)
Exchangeable metal cations in the pores of molecular sieves have special
effects on the adsorption of certain molecules. (4) Molecular sieves have
chemical adsorption on a few molecules. Therefore, zeolite molecular
sieves have been widely used in drying, purification, catalysis and other
fields, especially in adsorption and separation [60–62].
In this paper, zeolite molecular sieve was selected as adsorbent for
adsorption of hydrocarbon molecules in exhaust gas, and the adsorption
and diffusion characteristics of hydrocarbon molecules on zeolite mo­
lecular sieve were studied. Different molecular sieve types, preparation
conditions [63,64] and coating procedures [65] might affect properties
of molecular sieve, resulting in different HC emission control effects.
Kustov et al. [17] modified ZSM-5 (SiO2/Al2O3 = 35) molecular sieves
with Li+, K+, and Na+ cations, and the results showed that these cations
could enhance the ability of ZSM-5 zeolite to adsorb toluene at high
temperatures, with 2.3% Na-ZSM-5 modified zeolite having the best
adsorption effect. The 5%LiZSM-5 and 2.3%Na-ZSM-5 zeolites charac­
terized by toluene desorption temperatures about 200–400 degrees C
L. Chen et al.
Fig. 1. Schematic of adsorption system [55].
are very promising to control the cold-start hydrocarbon emissions.
Under cold start conditions, Lopez et al. [66] investigated the capture
effect of Silicalite-1, BETA, ZSM-5, Mordenite, SAPO-41, and SAPO-5 on
HC analog molecules (propene). The experimental results points out that
materials with high equilibrium propene adsorption capacity at 30 de­
grees C, where propene is mainly chemisorbed and, which presents some
kinetics restrictions, seem to be the best for a propene trap under cold
start conditions. BETA and ZSM-5 zeolites, as well as SAPO-5 molecular
sieve, were shown to be more promising materials for propene capture.
Elangovan et al. [67] investigated the adsorption of toluene by SSZ-33
(CON) zeolite molecular sieves using the temperature-programmed
desorption (TPD) method and compared the results to those of A, Y,
mordenite, and ZSM-5 molecular sieves. It is clear from the data shown
that the capacity of SSZ-33 is about 1.25 times larger than that of β. The
capacity and the desorption temperature of SSZ-33 are superior to those
of zeolite β when considering the requirements in the HC cold trap
application. The findings demonstrate that SSZ-33 (CON) has a larger
adsorption capacity and better hydrothermal stability than other zeo­
lites, making it a potential hydrocarbon catcher material for cold start
emission management. Wesson et al. [68] and Serra et al. [69] used an
optimized TPD method to test the adsorption characteristics of hydro­
carbon catcher using Cs mordenites (MOR) during cold start of a vehicle
utilizing a mixture of toluene, propane, and water. The results showed
that toluene adsorption capacity and interaction strength could be
increased using Cs mordenites. The diffusion coefficients vary in the
10− 14-10− 17cm2/s range with activation energies between 55 and 65
kJ/mol. The value of diffusivity increases with the Cs loading, probably
due to the increase of external surface area [68–70].
To develop excellent HC capture catalysts, Park JH et al. synthesized
over 100 zeolite samples and performed toluene adsorption in­
vestigations on them, in which FAU and BEA type zeolites demonstrated
great toluene adsorption performance under dry conditions. Over Li, K
and Ag-exchanged Beta zeolites with an Si/Al ratio of ca 13.5, the
amount of toluene adsorbed was partially maintained up to 60%
compared to that initially adsorbed at 25C, even after temperature
ramping under wet condition. It was also noted that Li, K, or Ag-Beta
zeolites were particularly promising HC capture catalysts [71]. In
addition to the cold-start simulation experiment, there were some time-
saving, low-cost research and widely used approaches on the perfor­
mance of the trapping material: molecular simulation study [72]. The
adsorption of propane (simulated HC molecules) on FAU zeolite was
simulated using a grand canonical Monte Carlo (GCMC) simulation
[73,74]. They had performed molecular simulations of the FAU zeolites
X and Y with varying content of exchange cations at a pressure range
from 102 to 106 Pa at a temperature of 299 K. For a given ratio of Si/Al,
the adsorption of propane in both sodium and calcium FAU increases
with the increasing nonframework cation number density, suggesting
that an increase in the number of cations produces extra adsorption sites
and leads to a higher amount of adsorption [75]. Beerdsen et al. [76]
investigated the adsorption of simulated HC molecules (methane,
ethane, and propane) on MFI and MOR zeolites with different frame­
work Al densities and non-framework Na on MFI and MOR zeolites. The
3
Fuel 310 (2022) 122427
results show that increasing the nonframework sodium density in MFI-
type zeolites increasingly blocks the intersections and thereby in­
creases the selectivity of MFI-type zeolites for adsorbing linear alkanes.
By contrast, increasing the nonframework sodium density in MOR-type
zeolites increases the number of sites favorable for adsorbing small
linear alkanes.
The researchers next utilized Configuration bias Monte Carlo
(CBMC) simulation to investigate the adsorption of alkanes (methane,
ethane, propane, and so on) on MFI zeolites with different densities and
non-framework cation characteristics. For a MFI structure containing
four Al/UC, the highest selectivity is obtained for the structure with four
Cs+/UC. A lower and almost similar selectivity is observed for the
structures with four K+/UC and two Ba2+/UC, and it decreases even
more for the structures with two Ca2+, four Na+, and four Li+/UC. The
simulated alkanes’ adsorption ability in the MFI increased as the non-
framework cation density decreased when the non-framework cation
was known [77]. The adsorption of simulated HC molecules (propylene
and toluene) on ZSM-5 zeolites was simulated by García et al. and the
effect of high concentrations of water in the exhaust gas on the
adsorption of propylene and toluene was taken into account. The sim­
ulations revealed that the specific adsorption sites of guest molecules
like propylene and toluene, as well as water molecules, can explain
multi-location materials’ unique features [78]. This demonstrates that
molecular simulation is an effective and accurate method for simulating
adsorption.
At present, most of the research on hydrocarbon trap materials is
focused on the adsorption performance of a modified molecular sieve for
single component and binary component molecules, but there is little
research on the adsorption and diffusion of pure silica molecular sieve
and multicomponent. In this paper, the adsorption and diffusion be­
haviors of ethylene, benzene and the mixed components of six main
exhaust molecules on MOR, MFI and CON molecular sieves were sys­
tematically simulated, and the appropriate molecular sieves corre­
sponding to different exhaust components were selected as adsorbents
for HC trap.
In this work, the isotherms, adsorption sites, heats of adsorption, and
interaction energy distribution of hydrocarbon single-component and
multi-component molecules on three different zeolites at various low
temperatures and pressures are studied using the Monte Carlo method.
The Monte Carlo method has been shown to provide accurate and reli­
able simulations over a wide range of temperatures and pressures, which
compensates for the absence of experimental research to some extent
[79,80] and analyzes the state features of molecular adsorption by
zeolite at the atomic level. In addition, the molecular dynamics (MD)
method was used to analyze the motion of various hydrocarbon mole­
cules on the three molecular sieves and to analyze the diffusion prop­
erties of single- and multi-component molecules on the three molecular
sieves.
2. Adsorption simulation
Hydrocarbons have more than 200 components. The main
L. Chen et al.
components of hydrocarbons in automobile exhaust are aldehydes and
polycyclic aromatic hydrocarbons. Formaldehyde and propylene are the
most common aldehydes, while benzene is the most common polycyclic
aromatic hydrocarbon [81]. The other hydrocarbon component of the
exhaust gas is mainly composed of methane (CH4), ethane (C2H6),
acetylene (C2H2), ethylene (C2H4), propane (C3H8), butylene (C4H6) and
benzene (C6H6). In the single-component simulation of this paper, the
most commonly used benzene (C6H6) and ethylene (C2H4) molecules
[58,82] are selected as probe molecules, and methane (CH4), ethylene
(C2H4), propylene (C3H6), propane (C3H8), benzene (C6H6) and water
(H2O) molecules are selected for the multi-component simulation. MOR,
MFI, and CON zeolite are selected as adsorbent materials in this paper,
among which MOR and MFI zeolite are considered to be the most suit­
able for cold start applications as MOR and MFI structures appear to be
the less selective for any type of hydrocarbon [83].
2.1. Simulation method
An HC catcher is designed as shown in Fig. 2. The gasoline engine HC
catcher is on the middle cylinder, and the inlet and the outlet are on the
front and rear ends, respectively. The cylinder is the core part of the HC
catcher, which is filled with a honeycomb packed bed coated with ad­
sorbents. This structure is helpful for the full contact between the gases
and the adsorbents.
The molecular sieve structures of the adsorbents selected in this
paper vary. The mordenite molecular sieve MOR is a one-dimensional
structure with large pores, which is formed by 3–5 structural units
sharing one side and further forming a chain. It has a one-dimensional
straight channel of 12-membered ring and 8-membered ring channel
connected with it. The 8-membered ring is located between the 12-
membered ring. The 12-membered ring window is oval with a diam­
eter of 0.65×0.56 nm and the 8-membered ring window is 0.26×0.57
nm. Due to the small size of the 8-membered ring annular channel that
crossing the 12-membered ring annular channel, it is not easy for gen­
eral molecules to through. MOR zeolite has high thermal stability and
suitable acidity, which is widely used in gas or liquid mixture separation
[84–86] and important catalytic reactions. MFI molecular sieve is an
orthogonal crystal system with the general chemical formula |Mex (­
H2O)m| [AlxSi96-xO192] (x < 27), where × and m are the number of Al
and hydrated ions, respectively.
The MFI molecular sieve is a three-dimensional mesoporous struc­
ture with two microporous channels contained. On the Y-axis, one is a
straight channel parallel to each other, while on the X-axis, the other is a
zigzag Z-shaped sinusoidal channel. The straight channel is around
0.53×0.56 nm in diameter, while the Z-shaped channel is about
Fig. 2. HC catcher of gasoline engine.
4
Fuel 310 (2022) 122427
0.51×0.55 nm. The 10-membered ring straight channel and sinusoidal
channel are cross-linked. CON molecular sieve has 12×12×10 three-
dimensional pore channels, the pore diameter of the 10-membered
ring is 0.45×0.51 nm, and the pore diameter of the 12-membered ring
is 0.64×0.70 nm. Channels of 10-membered ring and 12-membered ring
pore cross each other to form a larger cross pore, and adsorbent mole­
cules can enter the molecular sieve through them. Due to this nature
makes CON molecular sieve has recognized good adsorption perfor­
mance. To ensure the accuracy of the calculation results, the size of the
three directions of the cell box must be twice larger than the radius of the
cut-off segment.
Considering that too large model will cause the calculation time
consuming too long, all the adsorbent models in this paper adopt the
2×2×2 supercell model, i.e. 8 unite cells(UC). Framework model of pure
silicon supercell molecular sieves are shown in Fig. 3.
In order to verify the correctness of the model used in this paper, the
X-ray diffraction (XRD) patterns of MOR, MFI and CON molecular sieve
models are calculated using the Reflex module in Materials Studio, and
are compared with the standard XRD patterns in the database of the
International Zeolite Association. The results are shown in Fig. 4.
It can be seen from the figure that the positions of the characteristic
peaks of the three molecular sieve models used in this article are basi­
cally consistent with the positions of the characteristic peaks in the
standard spectrum. It is proved that the three molecular sieve frame­
work models built by Materials Studio is reasonable, and they can be
used in the following simulation analysis.
Considering the limitations of computer computing power i.e., the
number of atoms in the simulation system is usually far less than the real
system, so periodic boundary conditions are usually set, the finite size of
the boxes are copied in infinite space so that the simulation system can
more realistically reflect the actual system. The electrostatic interaction
and van der Waals force between molecular sieve and adsorbate,
adsorbate and adsorbate are calculated by Ewald method and Atom
based method, respectively, and the configuration deviation is Metrop­
olis. In this paper, the COMPASS force field has been chosen. The
COMPASS force field is widely used to simulate the adsorption and
diffusion properties [85] of various molecules in zeolite since it can
predict the properties of most gas and solid substances, and simulate
complex systems such as carbon and carbon-free structures, and some
non-framework heavy cations ions, due to its wide range of application
systems (including commonly used polymer and inorganic molecules,
some metal ions, metals and metal oxides, and surface, blending, and
other complex systems). The equations of Lennard-Jones potential (also
known as L-J potential, 9–6 potential) in the COMPASS force field for
electrostatic interaction in non-bonding form and van der Waals
L. Chen et al. Fuel 310 (2022) 122427

Fig. 3. Framework model of pure silicon 2×2×2 supercell molecular sieve ([001] direction): (a)MOR; (b)MFI; (c)CON.

Fig. 4. Simulation XRD and standard XRD of MOR, MFI and CON Molecular Sieve Model.

interaction could be expressed as follows [87]: bonding form and van der Waals interaction, respectively; qi is the
∑qi qj partial charge applied to sites i, qj is the partial charge applied to sites j,
Eele = (1) rij is the distance between the centers of the two interaction sites i and j,
rij
rij0 is the position diameter, Eij is the potential energy parameter of
i>j

⎡ ( )9 ( )6 ⎤ different atoms.
∑ rij0 rij0 Because the potential energy of molecules decays rapidly with the
Evdw = ⎣
Eij 2 − 3 ⎦ (2)
rij rij distance between molecules, the potential energy can be roughly cutoff
to a suitable distance for computing the Lennard-Jones interaction en­
where Eele and Evdw represent the electrostatic interaction in non- ergy. As the interaction between molecules decays rapidly with the

5
L. Chen et al.
distance between molecules increases, the cutoff radius in this paper is 1
nm.
In order to verify the effectiveness of the adsorption model, the
adsorption isotherm of ethylene on a 2×2×2 supercell MFI (silicalite)
molecular sieve is simulated and compared with the results in the
literature [88,89]. To obtain more general and macroscopic results, the
periodic boundary conditions are applied to the X, Y and Z directions of
the simulation box. The grand canonical Monte Carlo (GCMC) method is
used in the simulation, and the simulation length is 9×106 steps with the
first 3×106 steps are used for adsorption equilibrium. The simulation
point is set to 20 and saved a conformation every 400 steps. The simu­
lation temperature is 253 K, 298 K and 348 K, and the relative pressure is
0–50 kPa to simulate the cold start conditions of gasoline engine. The
whole simulation process is carried out on Materials Studio molecular
simulation software, and the Sorption module in the software is used for
adsorption simulation.
GCMC and experimental results of ethylene adsorption on MFI (sil­
icalite) molecular sieve are shown in Fig. 5. Fig. 5 shows that the
simulated adsorption isotherm law is basically consistent with the
experimental results, which both belongs to theIadsorption isotherm.
The adsorption amount increases with the increase of pressure. When
the pressure reaches a certain value, the adsorption amount gradually
reaches saturation. The simulated adsorption isotherm plots fit well with
the adsorption isotherm plots obtained from literature experiments at
temperatures around 250 K, 300 K, and 350 K.
Table 1 shows the errors of the simulation results in this paper and
the experimental results in the literature. Overall, it seems that the
simulation results and experimental results of this paper are in good
agreement, which proves the correctness of the model and GCMC
method used in this paper. The relative errors of the saturation
adsorption amount between the simulations in this paper and the liter­
ature experiments were 1.2%, 5.8%, and 9.6% at temperatures of about
250 K, 300 K, and 350 K, respectively. However, gasoline engine tail gas
composition was complex, and the zeolite had a large surface roughness,
etc., which was different to the simulated perfect crystal form. These
differences would increase the interaction between beta zeolite and the
components in the exhaust gas, and the current simulation force field
model had certain limitations, and there was no field to parameterize
this interaction.
In addition to the adsorption amount, the adsorption heat is also an
important parameter for studying the adsorption process. The strength
of the interaction between molecular sieve and adsorbate can be known
Fig. 5. GCMC and experimental results of ethylene adsorption on MFI (silica­
lite) molecular sieve [88,89].
6
Fuel 310 (2022) 122427
by the adsorption heat, which provides an important reference for the
study of selective adsorption of molecular sieve. Under the conditions of
constant temperature, constant pressure and constant adsorbent surface
area, the enthalpy of adsorption of 1 mol gas becomes isosteric heat of
adsorption Qst, which can be expressed as follow [90]:
( )
∂ΔH
Qst = (3)
∂N
where ΔH is the enthalpy change of adsorbate as it changes from gas
phase to adsorption phase, and the unit is kJ/mol. N is the adsorption
capacity, namely the number of adsorbed molecules.
According to Clausius-Clapeyron equation, the equivalent adsorp­
tion heat can be expressed as follow [90]:
( )
∂lnp
Qst = RT 2 (4)
∂T Γ
where the subscript Г on the right side of the equation indicates that the
adsorption capacity is constant; R is the molar gas constant; T is the
absolute temperature; p is the pressure.
Integrating the above equation and assuming that the adsorption
heat is independent of absolute temperature T, the following equation
can be obtained [90]:
Qst
lnp = −
RT
+ const
The adsorption heat Qst under different adsorption capacities can be
calculated when the adsorption capacity is constant according to the
slope of the straight line obtained by this formula. Choudhary et al.
measured the adsorption isotherms of ethylene molecules at 305 K and
353 K by using a gravimetric adsorption apparatus and obtained their
average adsorption heat of 26 kJ/mol for low coverage[91]. The average
adsorption heat of ethylene molecules in MFI (silicalite) is 26.862 kJ/
mol at the simulated temperature of 298 K. Pascual et al. used a simu­
lation to obtain the adsorption heat of different olefins at 300 K and the
average adsorption heat of ethylene molecules was 26 kJ/mol[92]. The
value is in good agreement with the above literature results, which again
proved the correctness of the model in this work.
2.2. Adsorption of single component
The adsorption effects of benzene (C6H6) and ethylene (C2H4) on
MOR, MFI and CON molecular sieves are simulated by using the grand
canonical Monte Carlo method (GCMC) in the single-component
adsorption simulation. The adsorption isotherms, the distribution of
the most probable interaction energy and the distribution of adsorption
site at different temperatures are obtained at the relative pressure of
0–50 kPa. The results are shown in Figs. 6-8.
Fig. 6 is the adsorption isotherms at different temperatures. Fig. 6
(a–c) are the adsorption isotherms of benzene molecules on the three
molecular sieves. Fig. 6(d–f) are the adsorption isotherms of ethylene
molecules on the three molecular sieves. The six adsorption isotherms
show that the molecular sieve can begin to adsorb molecules at low
pressure when the temperature is constant, and the adsorption capacity
increases gradually with the increase of pressure. When the pressure
increases to a certain value, the adsorption capacity gradually tends to
be stable and no longer changes. Because zeolites are microporous and
adsorption forms a monolayer, all adsorption isotherms are typical type I
isotherms.
Because of the interaction between adsorbate molecules and the
molecular sieve framework structure, molecular sieves can adsorb at low
pressure. However, due to the pore diameter and specific surface area
limitations of molecular sieves, as well as the interaction between
adsorbate molecules, hydrocarbon molecules must be injected at a high
pressure to completely fill molecular sieve holes. As a result, when the
pressure reaches a specific level, the molecular sieve pores are filled, and
L. Chen et al. Fuel 310 (2022) 122427

Table 1
Errors of the simulation results in this paper and the experimental results in the literature.
Approximate Saturated adsorption amount of Saturated adsorption amount of Minimum relative Maximum relative Relative error of saturated
temperature/K the experiment this simulation error error adsorption amount

250 16.39 16.19 1.2% 14.7% 1.2%

300 12.73 13.47 5.8% 24.3% 5.8%
350 8.22 9.01 0.6% 23% 9.6%

Fig. 6. Adsorption isotherms of benzene (C6H6) and ethylene (C2H4) single-component molecules on MOR, MFI, and CON molecular sieves at different temperatures.

the adsorption capacity is reached. The adsorption isotherms at different downward trend, indicating that the adsorption performance of molec­
temperatures show a pattern of right shift with increasing temperature ular sieves is highly dependent on temperature. This is caused by the
at the same pressure, and the adsorption capacities show a considerable arrangement of molecules inside the molecule. With the increase of

7
L. Chen et al. Fuel 310 (2022) 122427

Fig. 7. The most probable interaction energy distribution of pure benzene and pure ethylene molecules on three zeolites at different temperatures.

Fig. 8. Probability density distribution of benzene and ethylene molecular in MOR, MFI, and CON molecular sieves at 298 K and a relative pressure of 40 kPa.

8
L. Chen et al.
temperature, the attraction between molecules is not so obvious. The
arrangement of molecules will become scattered from the original order,
and the interval between molecules will become larger, which makes the
molecules have enough space and position to move. At 253 K, the MOR,
MFI, and CON molecular sieves have the highest adsorption capabilities.
At the time, benzene has adsorption capacities of 29, 64, and 64 on the
three zeolites, while ethylene has adsorption amount of 66.8, 129.5, and
86.1, respectively.
The results shows that the adsorption capacities are the smallest
when the temperature is raised to 498 K. The amounts of benzene
molecules that adsorb on the three zeolites are 13.6, 24.3, and 32.6,
respectively, while the amounts of ethylene molecules are around 2, 6.8,
and 3. Low temperature and high pressure are both favorable to
adsorption, as can be observed. However, because of the low exhaust
pressure simulated in this paper, the impact of pressure is not obvious,
and the change in exhaust temperature has a considerable impact on the
adsorption process. The primary explanation is that when the temper­
ature rises, molecular motion becomes more vigorous, reducing the
adsorption force of molecular sieves on adsorbate molecules and
resulting in a decrease in adsorption capacity. Thus, better capture
performance can be obtained under cold start conditions.
When the temperature is higher than 498 K, the adsorption capacity
of adsorbate molecules in the molecular sieve is very small, and the
molecular behavior in the molecular sieve is dominated by diffusion
desorption, that is, the molecular sieve will release the adsorbed hy­
drocarbon molecules. At this temperature, the TWC has basically
reached the ignition temperature, so it is not significant to study the
adsorption characteristics of molecular sieve when the temperature is
higher than 498 K. When comparing Fig. 6(a–c), it can be seen that at a
low temperature of 253 K, the saturated adsorption capacity of the MOR
molecular sieve for benzene molecules is about half that of the MFI and
CON molecular sieves, which is due to the large cross-sectional area of
benzene molecules and the small pore size of the 8-membered ring pore
in MOR molecular sieve, which makes it difficult for benzene molecules
to penetrate, resulting in a low adsorption capacity.
In addition, at 253 K, the saturation adsorption capacity of MFI and
CON molecular sieves is nearly identical, at about 64/uc. CON molecular
sieve may also obtain saturated adsorption capacity under lower pres­
sure than MFI molecular sieve. The saturated adsorption capacity of
CON molecular sieve is consistent with that of MFI and MOR molecular
sieve at 298 K and 348 K and is greater than that of MFI and MOR
molecular sieve at those temperatures. It demonstrates that there is a
stronger interaction between CON molecular sieve and benzene mole­
cules contact with benzene molecules and the CON molecular sieve has a
better capture impact on benzene molecules. Overall, the saturated
adsorption capacities of the three zeolite molecular sieves for benzene
molecules are relatively substantial due to the peculiar pore structure.
The adsorption capabilities of zeolites for guest molecules are
affected by differences in basic components, pore topological topologies,
and pore volumes of zeolites. CON zeolite, on the other hand, has a pore
structure that is better suited to the adsorption of benzene molecules,
resulting in superior benzene adsorption performance.
Fig. 6(d–f) are the adsorption isotherms of ethylene molecules on the
three molecular sieves. The adsorption law of ethylene molecules on the
three molecular sieves is the same as that of benzene molecules, as
shown in these pictures. The adsorption isotherms are all belong to the I
adsorption isotherm and the amount of adsorption decreases with the
temperature rises. The adsorption capacity of ethylene on MOR, MFI,
and CON molecular sieves is about 66.8/UC, 129.5/UC, and 86.1/UC,
respectively, at a low temperature of 253 K. It can be seen that MFI
molecular sieve has a much larger adsorption capacity on ethylene than
the other two molecular sieves, and that the saturated adsorption ca­
pacity of MFI molecular sieve is still the largest among the three mo­
lecular sieves at other temperatures, indicating MFI molecular sieve has
a good trapping effect on ethylene molecules.
When comparing the adsorption isotherms of benzene and ethylene
9
Fuel 310 (2022) 122427
molecules on the same molecular sieve, it can be shown that ethylene
molecules adsorb much more on all three molecular sieves than benzene
molecules. The saturated adsorption amount on MOR molecular sieve at
253 K is approximately 2.3 times that of benzene molecules. On MFI, the
saturation adsorption capacity is almost 1.9 times that of a benzene
molecule. The saturation adsorption capacity of MFI is approximately
1.3 times that of benzene, showing that ethylene is more easily absorbed
by MFI molecular sieve than benzene. This is due to the stronger inter­
action between ethylene molecules and MFI molecular sieves.
Fig. 7 is the most probable interaction energy distribution of pure
benzene and pure ethylene molecules on three zeolites at different
temperatures. Fig. 7 shows that the lower the temperature on the same
molecular sieve, the less the most likely interaction energy, indicating
that the adsorption is more stable. The peaks of the action energy curve
shift right as the temperature rise, indicating that as the temperature
rise, the adsorption of benzene molecules in molecular sieves gradually
shift from the lower-energy adsorption sites to the higher-energy
adsorption sites, resulting in a decrease in adsorption amount. The
result drawn from the adsorption isotherms above is the same.
As shown in Fig. 7(a–c), the most probable interaction energies of
benzene molecules on MOR, MFI, and CON molecular sieves are − 68.45
kJ/mol, − 70.55 kJ/mol, and − 73.90 kJ/mol, respectively, at the same
simulation temperature of 253 K, and the smallest one is CON molecular
sieve. As a result, benzene adsorption on the CON molecular sieve is
more stable and has a higher adsorption capacity than the other two
molecular sieves. The results of the most probable interaction energy
distribution support the conclusions made above again.
The most probable interaction energy of ethylene molecules is also
investigated in this paper, as shown in (c), (d), and (e) in Fig. 7. In MOR,
MFI, and CON molecular sieves, the most probable interaction energies
of ethylene molecules are − 29.51 kJ/mol and − 40.83 kJ/mol, − 35.38
kJ/mol, and − 30.35 kJ/mol, respectively. At low temperatures,
ethylene molecules emerged as peaks on the MOR molecular sieve,
showing that the molecular sieve possesses two ethylene adsorption
sites. This is one of the reasons why molecular sieve has better adsorp­
tion performance at low temperature. The distribution curve of action
energy gradually changes to the right as temperature rises. The peak at
–22.19 kJ/mol energy increases with the temperature rising, but the
other peak fall dramatically, showing that ethylene molecules gradually
transfers to the same high-energy adsorption site. This is due to the fact
that as the temperature increases, the thermal movement of molecules
becomes more intense, and the adsorption sites of adsorbable molecules
are gradually converted from two to one because of the subtle change in
the skeleton structure of molecular sieve, and the interaction force be­
tween molecules and molecular sieve is reduced. Therefore the
adsorption amount will be relatively decreases. The peak separation
phenomena happens at higher temperatures on the MFI and CON mo­
lecular sieves, indicating that as the temperature rises, two types of
ethylene molecular adsorption sites gradually developed in the molec­
ular sieve, which has better for ethylene molecule adsorption.
When comparing the most likely interaction energies of benzene and
ethylene molecules on the same molecular sieve, it is discovered that
under the same conditions, the interaction energy of ethylene molecules
with molecular sieve is always significantly lower than that of benzene
molecules with molecular sieves. As a result, ethylene molecules have a
higher chance of being adsorbed by molecular sieve, and the adsorption
effect of molecular sieve on ethylene molecules is better than that of
benzene molecules since the diameter of benzene molecules is bigger
than that of ethylene molecules.
It is vital to know the adsorption positions of hydrocarbon molecules
on molecular sieves during cold start of gasoline engines in order to
more intuitively understand their adsorption distribution. In this study,
GCMC is used to simulate the adsorption configuration at various tem­
peratures and pressures, and then statistical calculations are utilized to
get the probability density distribution of adsorbed particles, as shown
in Fig. 8. The probability density distribution map clarifies and
L. Chen et al.
intuitively depicts the adsorption site distribution of hydrocarbon mol­
ecules on molecular sieves. The diagram illustrates benzene and
ethylene molecular probability density distribution in the three molec­
ular sieves at 298 K and a relative pressure of 40 kPa, with red dots
indicating probable adsorbate molecule sites. The probability density of
benzene molecules at different molecular sieve pore positions are shown
in Fig. 8 (a), (b), and (c). The image shows that benzene molecules are
only adsorbed in the 12-membered ring pores of MOR and CON mo­
lecular sieves, with the probability density of distribution increasing as
one gets closer to the pore center. It can be seen that the main adsorption
sites of benzene molecules adsorbed by MOR and CON are the 12-
membered ring pores. The distribution range of benzene molecules is
wider and more scattered in the MFI molecular sieve, with most of it
adsorbed in the 10-membered ring straight channel and a little amount
in the sinusoidal channel. It can be seen that the main adsorption sites of
benzene molecules adsorbed by MFI is 10-membered ring straight
channels. Fig. 8 (d), (e), and (f) show the probability density of ethylene
molecules at different molecular sieve pore positions. Ethylene mole­
cules are distributed in the three channels of the 12-membered ring and
the 10-membered ring window in MOR and CON molecular sieves, and
their probability density is substantially higher than that of benzene
molecules on the three molecular sieves. It shows that the same mo­
lecular sieve has different adsorption sites for different molecules, which
is related to the pore size and molecular diameter of molecular sieve,
molecular polarity, and the interaction force between molecules and
molecular sieve. The conclusions are also in line with the previous one.
By the GCMC, the adsorption of methane, ethane, propane, and
butane in MOR zeolites at 300 K and 330 K was studied by Chen et al.
Fig. 9. Adsorption isotherms of hydrocarbon mixtures on the three molecular sieves at 253 K.
10
Fuel 310 (2022) 122427
The results showed that at 300 K, the adsorption capacities of pure
components CH4, C3H6, C3H8 and C4H10 are about 8.8/UC, 7.8/UC, 3.6/
UC, 3/UC, respectively. In this study, when the temperature is 298 K, the
adsorption capacities of MOR zeolite for C2H4 and C6H6 are 6.88/UC and
3.13/UC respectively[93]. It can be seen that the simulation results are
basically consistent with the numerical value of the literature results,
and the adsorption properties of hydrocarbon molecules on MOR mo­
lecular sieve are supplemented.
2.3. Adsorption of multicomponent
Fig. 9, Fig. 10, Fig. 11, Fig. 12 show the competitive adsorption
isotherms of hydrocarbon mixtures on different molecular sieves when
the exhaust temperature of cold start is 253 K, 298 K, 398 K, 498 K and
the exhaust pressure is 0–50 kPa. The room temperature is generally
considered as 25 ± 1–5℃ [94] (about 298 K), and the range of the
exhaust gas temperature during the cold start phase of the gasoline
engine is about 0–650℃ [94,95] in the first five minutes. The simulation
results also show that when the temperature is higher than 498 K, the
adsorption amount of adsorbate molecules in the molecular sieve is very
small, and the molecular behavior in the molecular sieve is mainly
desorption. On the other hand, at this temperature, the TWC has basi­
cally reached the ignition temperature, so it is not significant to study
the adsorption characteristics of molecular sieve when the temperature
is higher than 498 K. Considering the above factors, it was decided to use
several representative temperatures including room temperature, i.e.
253 K, 298 K, 398 K, 498 K.
When the molecular sieve is the same and the adsorbate is a mixed
L. Chen et al.
Fig. 10. Adsorption isotherms of hydrocarbon mixtures on the three molecular sieves at 298 K.
component, the adsorption isotherm still maintains the action law of
theItype of adsorption isotherm, that is, with the increase of exhaust
temperature, the adsorption amount of various components in the
mixture is significantly decreases, and is far less than that under the
same conditions when the pure component is used. This is due to
competitive adsorption between components. The adsorption isotherms
of hydrocarbon mixtures at different temperatures on the same molec­
ular sieve showed the same adsorption characteristics: When the exhaust
temperature is 253 K, the adsorption amount of each component is the
largest, and the adsorption amount of propylene on the three molecular
sieves is greater than that of other hydrocarbons, followed by propane
and ethylene molecules. The adsorption amount of propylene on MFI
zeolite is the largest, about 50/UC.
At the exhaust temperature of 298 K, the adsorption amount of each
hydrocarbon component decreases. The higher adsorption on the MFI
molecular sieve is still propane and propylene molecules, but at this
temperature, the MOR and CON molecular sieves adsorb significantly
more benzene molecules than the others, with the number of benzene
molecules on the CON molecular sieve is about 40/UC. When the
exhaust temperature is 398 K, the adsorption amount of each component
further decreases. At this time, the adsorption amount of benzene mol­
ecules on the three molecular sieves is far more than that of other
molecules. Among them, the benzene molecules on CON are the most,
about 40/UC, and the propylene and propane molecules on MFI mo­
lecular sieve larger than those on the other two zeolites, about 15/UC.
When the exhaust temperature is 498 K, the adsorption amount of
each component reaches the minimum. In addition to benzene mole­
cules, the adsorption amount of molecular sieve for other hydrocarbon
molecules is very small, almost 0. The adsorption amount of benzene
molecules on the three kinds of molecular sieves is similar, and the
11
Fuel 310 (2022) 122427
adsorption amount on CON molecular sieve is slightly more, about 12/
UC. The simulation results of hydrocarbon mixed component adsorption
show that when the adsorbate molecule is a variety of components, there
is a competitive adsorption phenomenon between different components,
which is especially obvious at high temperatures. This is because the free
volume of molecular sieves is limited and other molecules are difficult to
enter when the adsorption sites are filled with enough molecules.
Overall, the adsorption amount of each component of the hydro­
carbon mixture changes greatly with the increase in temperature. The
adsorption amount on the three zeolites is ranked as follows: C6H6 >
C3H6 > C2H4 > C3H8 > H2O > CH4. Dispersion force and orientation
force affect molecular adsorption. Dispersion force is the force between
instantaneous dipoles of molecules, and its size is related to the
deformability of molecules and other factors. Generally, the larger the
molecular weight, the more electrons contained in the molecule, the
greater the deformability of the molecule, and the greater the dispersion
force. Orientation force is the force between the inherent dipoles of
molecules, and its size is related to the polarity and temperature of the
molecules. The greater the dipole moment of the polar molecule, the
greater the orientation force; the higher the temperature, the smaller the
orientation force.
At a lower temperature of 253 K, MOR molecular sieve has a good
capture effect on propane and ethylene, and MFI molecular sieve has a
good capture effect on propane and propylene. The adsorption effect of
the MFI molecular sieve on propane and propylene is twice stronger than
that of the other two molecular sieves. Propene is a polar molecule. The
molecular sieve polarizes the polarizable molecules through the elec­
trostatic induction of the dispersion force and the electrostatic force on
the surface, resulting in adsorption. MFI molecular sieve can be
considered the promising material for HC catcher when the exhaust
L. Chen et al.
Fig. 11. Adsorption isotherms of hydrocarbon mixtures on the three molecular sieves at 398 K.
temperature is low and the emissions of propane and propylene are
large.
At other temperatures, the trapping effect of the three molecular
sieves on benzene molecules is significantly better than that of other
hydrocarbon molecules. CON molecular sieve especially has the largest
adsorption capacity and the best trapping performance among the three
molecular sieves at 298–398 K. When the exhaust temperature is higher
than 300 K, the adsorption capacity of the three molecular sieves for
each component is greatly reduced, but they have mainly adsorbed
benzene molecules.
Therefore, selecting the collector material and adjusting the exhaust
temperature can be tried to directional capture, segmented capture, and
accurate capture of several molecules in the hydrocarbon mixture, so as
to improve the capture efficiency of the HC catcher.
The three figures in Fig. 13 show the probability density distribution
of hydrocarbon mixtures on different molecular sieves at 298 K and 50
kPa. The adsorption amount and adsorption site distribution of hydro­
carbon components in molecular sieves can be seen intuitively from the
diagram. When the temperature is 298 K, the adsorbate is distributed in
the 12-membered ring supercages and the 8-membered ring channels in
the MOR molecular sieve. The number of benzene molecules is the
largest, mainly concentrated in the 12-membered ring channels, and
concentrated in the center of the channel. The hydrocarbon mixture in
MFI molecular sieve is widely distributed. It is adsorbed in the 10-
membered ring straight channel parallel to the Y-axis and the sinusoi­
dal channel along the X-axis. The hydrocarbon mixture in CON molec­
ular sieve is mainly distributed in the pores of the 10-membered ring and
the 12-membered ring, and the window position is less distributed.
Similarly, the number of benzene molecules is the largest, followed by
water molecules.
12
Fuel 310 (2022) 122427
(Deep blue is methane molecule. Light blue is ethylene molecule. Red
is propylene molecule. Green is propane molecule. Orange is water.
Purple is benzene molecule)
Fig. 14 shows the relationship between the adsorption heat of hy­
drocarbon molecules on MFI zeolite and the adsorption amount at
different temperatures. When the temperature is constant, the adsorp­
tion heat increases with the increase of adsorption amount, which is
because the molecular sieve adsorption is an exothermic process. As the
temperature increased, the adsorption decreased. With the increase of
pressure, the adsorption amount is increasing, and the heat released is
also increasing, so the adsorption heat increases. In general, the
adsorption heat of physical adsorption is about 40 kJ/mol, and that of
chemical adsorption is 84–417 kJ/mol. It can be seen from the figures
that the adsorption heat of each molecule is about 60 kJ/mol. Through
experiments and simulations, June et al. obtained the relationship be­
tween the adsorption heat of alkanes on MFI zeolite and the number of
carbon atoms in alkanes [89], it can be expressed as follow:
Qst = 9.5nc + 9.3 (6)
where nc is the number of carbon atoms and the adsorption heat unit is
kJ/mol. The calculation results of this paper are basically consistent
with that of June et al.[96], and the reliability of the simulation results
in this paper are verified again.
Fig. 14 shows the change of adsorption heat of hydrocarbon mixture
molecules on three molecular sieves with adsorption amount. It is
obvious from the figure that the heat of adsorption shows a linear in­
crease with the increase of the adsorption amount on the same molec­
ular sieve, and the growth rate remains basically the same. In the same
molecular sieve, the adsorption heat gradients of different molecules are
different. It can be seen the slope of benzene molecule is larger than that
L. Chen et al. Fuel 310 (2022) 122427

Fig. 12. Adsorption isotherms of hydrocarbon mixtures on the three molecular sieves at 498 K.

Fig. 13. Probability density distribution of hydrocarbon mixtures on different molecular sieves at 298 K and 50 kPa.

of other molecules, indicating that the interaction effect between ben­
zene molecule and molecular sieve is the strongest, followed by about
C3H6, C3H8, C2H4 and CH4. That means the adsorption heat is not only
related to the number of carbon atoms of adsorbate molecules, but also
related to the number of hydrogen atoms. The larger the molecular
weight, the more electrons in the molecule, the greater the deformation
capacity of the molecule, the greater the dispersion force, the stronger
the adsorption, and the more the adsorption heat.
3. Diffusion simulation
In order to explore the molecular characteristics of various states,
molecular dynamics (MD) simulation is carried out on molecular sieve.
The statistical average value of the system and the diffusion coefficient

13
L. Chen et al.
Fig. 14. Adsorption heat of hydrocarbon mixture on the three molecular sieves.
are calculated. The diffusion coefficient characterizes the diffusion rate
of gas molecules, thus determining the equilibrium time of adsorption
and desorption of gas molecules. In this study, MD simulations are used
to calculate the diffusion of hydrocarbons in molecular sieves, and the
diffusion coefficients are expressed in terms of the mean square
displacement (MSD). Based on the study of adsorption properties, the
14
Fuel 310 (2022) 122427
diffusion properties of hydrocarbon mixtures in zeolites are systemati­
cally simulated with the help of Material Studio simulation software,
using MOR, MFI and CON zeolite molecular sieves as adsorbents. The
simulation obtains the self-diffusion coefficients of different gas mole­
cules in three types of zeolites, and the factors affecting the diffusion
behavior.
3.1. Simulation method
The diffusion is simulated using the canonical NVT system synthesis
with 2×2×2 cells as the basic unit of the simulation, and periodic
boundary conditions are used for the simulation. For the calculation, the
molecules are first randomly placed into the molecular sieve channel,
followed by energy optimization to obtain the initial configuration.
Finally, 100 ps simulation is carried out. The Nose method is used for
temperature control during the simulations, and a cut-off value of 10 Å is
used for van der Waals interactions and Ewald addition method is
applied for electrostatic interactions during the calculation of the non-
bonded interactions of the system. The simulation step is 0.5 fs, and a
research system conformation is preserved every 200 steps.
Diffusion describes the average displacement of gas molecules
without chemical potential difference. The mean square displacement
could be obtained after the molecular dynamic simulation is balanced.
The mean square displacement MSD and the Einstein equation is as
follows [97,98]:
〈 〉 1 ∑∑
X 2 (t) = [Xi (t + t0 ) − Xi (t0 ) ]2 (7)
Nm Nt0 m t0
〈 〉
X 2 (t) = 6Dt + B (8)
where < X2(t) > is value of the mean square displacement; t is the
simulation time, and t0 represents the initial time; m is ­
the number of molecules at time t0, Nm is the number of adsorbate
molecules; Nt0 is the number of reference time when calculating the
average; Xi is the coordinate of the centroid of the molecule i; D is the
diffusion coefficient, B is the thermal factor of atomic vibration. The
relationship between diffusion coefficient D and absolute temperature T
can be described by Arrhenius [99] equation:
[ ]
Ea
D = D0 × exp − (9)
RT
where D0 is diffusion pre-exponential factor, Ea is the diffusion apparent
activation energy.
From Eq. (8), it can be seen that 1/6 of the slope of the mean square
displacement as a function of time, MSD-t, is the diffusion coefficient of
the molecule in the molecular sieve. It can be seen that the diffusion
coefficient is related to the temperature and the activation energy from
Eq. (9).
3.2. Diffusion of single component
To get a clear picture of the motion of hydrocarbon molecules inside
the molecular sieve, a canonical system synthesis (NVT) molecular dy­
namics (MD) method is used to probe molecules of ethylene (C2H4) and
benzene (C6H6) molecules on three molecular sieves, MOR, MFI and
CON, at temperatures of 253 K, 298 K, 498 K, 698 K, 898 K and 1098 K.
The diffusion properties are simulated and their MSD-t curves are ob­
tained. To better visualize the effect of temperature on diffusion coef­
ficient, fitting functions of temperature and diffusion coefficient are
obtained by processing the mean square displacement data, as shown in
Figs. 15-17. Their diffusion coefficients on the three molecular sieves are
subsequently obtained statistically by calculating the Einstein relation
for the root-mean-square displacement, and the results are shown in
Tables 2-4.
L. Chen et al. Fuel 310 (2022) 122427

Fig. 15. Mean square displacement curves of single components of ethylene and benzene on MOR zeolite.

Fig. 16. Mean square displacement curves of single components of ethylene and benzene on MFI zeolite.

Fig. 17. Mean square displacement curves of single components of ethylene and benzene on CON zeolite.

15
L. Chen et al. Fuel 310 (2022) 122427

Table 2 Table 4
The MSD-t fitting linear equation and diffusion coefficient of single component The MSD-t fitting linear equation and diffusion coefficient of single component
on MOR molecular sieves. on CON molecular sieves.
Temperature Ethylene Benzene Temperature Ethylene Benzene
(K) (K)
Fitting Diffusion Fitting Diffusion Fitting Diffusion Fitting Diffusion
linear coefficient linear coefficient linear coefficient linear coefficient
equation (m2⋅s− 1) equation (m2⋅s− 1) equation (m2⋅s− 1) equation (m2⋅s− 1)
10 10 10 11
253 y= 2.6475×10− y= 1.7577×10− 253 y= 3.4162×10− y= 5.8817×10−
0.15885x 0.10546x 0.20497x 0.03529x
+ 0.75823 + 1.13671 + 1.23024 + 1.52818
10 10 10 11
298 y= 3.6168×10− y= 2.2682×10− 298 y= 6.1498×10− y= 6.2733×10−
0.21701x 0.13609x 0.36899x 0.03764 x
+ 0.76137 + 1.24167 + 1.17895 + 1.62031
10 10 10 11
498 y= 5.0228×10− y= 7.5022×10− 498 y= 9.6165×10− y= 6.2433×10−
0.2652x + 0.45013x 0.57699x 0.03746 x
1.84543 + 0.25067 + 0.88892 + 2.24999
9 10 10 11
698 y= 1.3282×10− y= 8.0405×10− 698 y= 9.012×10− y= 7.145×10−
0.79693x- 0.48243x 0.54072x 0.04287x
1.17584 + 1.70299 + 2.75185 + 2.51428
9 9 9 11
898 y= 1.6812×10− y= 1.0236×10− 898 y= 1.4979×10− y= 4.765×10−
1.00869x- 0.61417x 0.89874x 0.02859 x
1.29673 + 2.3527 + 3.10665 + 2.72979
9 10 9 11
1098 y= 1.9878×10− y= 8.5596×10− 1098 y= 1.5898×10− y= 5.0683×10−
1.19266x- 0.51358x 0.95386x 0.03041 x
0.54829 + 0.75823 + 2.70166 + 1.23024

different temperatures. According to the graphs and tables, the MSD

Table 3
graphs of molecules basically show a pattern of steepening with
The MSD-t fitting linear equation and diffusion coefficient of single component
increasing temperature. The relationship between diffusion coefficient
on MFI molecular sieves.
and temperature generally shows the law that the diffusion coefficient
Temperature Ethylene Benzene increases with the increase of temperature. This is because with the
(K)
Fitting Diffusion Fitting Diffusion increase of temperature, the molecular thermal motion intensifies, the
linear coefficient linear coefficient vibration frequency in the molecular sieve cage increases, the interac­
equation (m2⋅s− 1) equation (m2⋅s− 1)
tion between the guest molecule and the adsorption site of the molecular
sieve weakens, and the gas molecules are more likely to break away from
10 11
253 y= 2.2092×10− y= 1.6916×10−
0.13255x 0.01015x the bondage of the adsorption site and diffuse.
+ 1.09897 + 0.4118
298 y= 2.0118×10− 10
y= 1.55×10− 11 At 253 K, the diffusion coefficient of ethylene molecules on CON is
0.12071x 0.0093x + 3.42×10− 10 m2/s, about 1.5 times of that on the MOR and MFI. Overall,
+ 1.51421 0.46991 the diffusion coefficient of ethylene molecules is the largest on the CON
10 11
498 y= 5.986×10− y= 1.6317×10− molecular sieve. The diffusion coefficients on the MOR and MFI mo­
0.35916x 0.00979x
lecular sieves are similar, with a slightly smaller diffusion coefficient on
+ 0.81385 + 0.70321
698 y= 5.61×10− 10
y= 2.0867×10− 11 the MFI molecular sieve. It indicates that the diffusion of ethylene
0.3366x + 0.01252x molecules on CON molecular sieve is the most intense and difficult to
1.84331 + 0.82079 capture. MFI molecular sieve has relatively good capture performance.
9 11
898 y= 1.1664×10− y= 1.515×10− The diffusion coefficient of benzene molecule is generally smaller than
0.69983x 0.00909x
+ 0.7188 + 0.90069
that of ethylene molecule. Different from ethylene molecule, the diffu­
1098 y= 9.3877×10− 10
y= 2.4467×10− 11 sion coefficient of benzene molecule on CON molecular sieve is the
0.56326x- 0.01468x smallest, about 5.8817×10− 11m2/s, and that on MOR molecular sieve is
0.54829 + 1.09897 the largest, about 1.7577×10− 10 m2/s. This is because MOR molecular
sieve is a one-dimensional macroporous structure with 12-membered
ring supercages. According to the study of Chen. Y et al., the diffusion
As can be seen from the table, the values of the diffusion coefficients
of benzene molecules mainly occurs in the 12-membered ring superc­
of ethylene and benzene molecules on the three molecular sieves are in
the range of literature data 10− 8–10− 12 m2/s[97], indicating that the ages, so the diffusion coefficient of benzene molecules on MOR molec­
ular sieve is relatively large, which is consistent with the conclusion of
simulation results in this study are correct.
As for the three zeolites shown in Figs. 15-17 and Tables 2-4, the the literature [100]. In addition, it can be seen from the figure that,
unlike ethylene molecules, the diffusion coefficient of benzene molecule
diffusion coefficients of ethylene and benzene molecules at low tem­
peratures of 253 K and 298 K are small, indicating that the molecular is large in the first 5 pm, and then decreases significantly. This is because
in the first 5 pm, the benzene molecule is rapidly filled with molecular
diffusion behavior is not intense, and it is most likely to be adsorbed at
this time. Comparing the displacement and diffusion coefficient of sieve channels due to thermal motion. After the adsorption sites are
basically occupied, the molecular motion is slowed down due to the
ethylene and benzene molecules on different molecular sieves at the
same temperature, it can be seen that the diffusion coefficient of large diameter and molecular weight, so the diffusion coefficient de­
creases rapidly.
ethylene molecules is higher than that of benzene molecules, indicating
that the diffusion behavior of ethylene molecules is more intense, and it
is more difficult to be captured by molecular sieves. 3.3. Diffusion of multicomponent
The diffusion simulation shows that under the same temperature
conditions, the diffusion coefficients are different with different gas Fig. 18 shows the MSD of multicomponent hydrocarbon mixtures on
types. For the same gas, the diffusion coefficients are different for the MOR molecular sieve at temperatures of 253 K, 298 K, and 498 K.
Table 5 shows the diffusion coefficients of components at different

16
L. Chen et al. Fuel 310 (2022) 122427

Fig. 18. Mean square displacement curve of multicomponent hydrocarbon mixture on MOR zeolite at 253 K, 298 K and 498 K.

them, propane and benzene molecules diffuse fast, while at 298 K the
Table 5
diffusion coefficient are about 1.11×10− 9 m2/s and 1.08×10− 9m2/s,
Diffusion coefficient of multicomponent on MOR molecular sieve at different
respectively. The diffusion of methane and water molecules on MOR
temperatures (m2⋅s− 1)
molecular sieves is much smaller than that of other molecules. It shows
253 K 298 K 498 K
that MOR molecular sieve has better capture performance for methane
CH4 1.9933×10 − 11
1.7667×10 − 11
2.2033×10− 11
and water molecules at low temperature (253 K), while propane and
C2H4 3.2373×10− 10 7.2235×10− 10 3.8513×10− 9
benzene molecules have stronger diffusion performance on MOR mo­
C3H6 5.053×10− 10 8.3823×10− 10 5.7365×10− 9

C3H8 4.7428×10− 10 1.1096×10− 9 6.0745×10− 9 lecular sieve, about 4.74×10− 10 m2/s and 4.4×10− 10 m2/s, respectively.
H2O 1.83×10− 11 5.115×10− 11 2.5208×10− 10 This result is consistent with the above multi-component adsorption
C6H6 4.441×10− 10 1.0849×10− 9 2.4369×10− 9
simulation conclusion.
Fig. 19 shows the distribution of hydrocarbon diffusion on MOR
molecular sieve when the exhaust temperature is 298 K. It can be seen
temperatures. Comparing (a), (b), (c) in Fig. 18 and Table 5, it can be
from the figure that hydrocarbon molecules distribute in the 12-
found that with the increase of simulated exhaust temperature, the mean
membered ring supercages and 8-membered ring channels of MOR
square displacement of each component molecule in the molecular sieve
molecular sieve. Benzene molecules basically only distribute in the
increased, and the diffusion coefficient is significantly increased, indi­
center of the 12-membered ring channels, and other molecules
cating that the degree of molecular diffusion becomes more intense with
distribute in the 12-membered ring supercages and 8-membered ring
the increase of temperature. It is more difficult to be captured by mo­
channels.
lecular sieve.
Fig. 20 shows the MSD of multicomponent hydrocarbon mixtures on
The simulation results show that the displacement of each compo­
the MFI molecular sieve at temperatures of 253 K, 298 K, and 498 K.
nent in the molecular sieve basically presents a linear change trend, and
Table 6 shows the diffusion coefficients of components on the MFI
the diffusion degree of each component is significantly different. At
molecular sieve at different temperatures. Comparing (a), (b), (c) in
lower temperature, the order of diffusion degree of each component
Fig. 20 and Table 6, it can be found that with the increase of exhaust
from strong to weak is C3H8, C6H6, C3H6, C2H4, CH4, H2O, which is due
temperature, the mean square displacement of each component mole­
to the different intermolecular forces and intermolecular forces. Among
cule in the molecular sieve increased, and the diffusion coefficient also

17
L. Chen et al. Fuel 310 (2022) 122427

of methane and water molecules on MFI molecular sieve is stronger at

low temperature. The diffusion degree of propylene and benzene mol­
ecules are the smallest, about 3.92×10− 10m2/s and 1.76×10− 10m2/s,
indicating that the MFI molecular sieve has better capture performance
for propylene and benzene molecules.
Fig. 21 shows the distribution of hydrocarbon diffusion on MFI
molecular sieve when the exhaust temperature is 298 K. As shown in the
diagram, the hydrocarbon mixture in MFI molecular sieve is widely
distributed. There is adsorption in the straight channel of the ten-
membered ring parallel to the Y-axis and the sinusoidal channel along
the X-axis. It can be seen that benzene molecules are also concentrated in
the 10-membered ring of the largest pore of the molecular sieve, and
other molecules such as propylene and propane are basically distributed
in the 6-membered ring window connected to the 10-membered ring.
Fig. 22 shows the MSD of multicomponent hydrocarbon mixtures on
the MFI molecular sieve at temperatures of 253 K, 298 K, and 498 K.
Table 7 shows the diffusion coefficients of components on the CON
molecular sieve at different temperatures. Comparing (a), (b), (c) in

Table 6
Fig. 19. Distribution of hydrocarbons on MOR molecular sieve at 298 K.
Diffusion coefficient of multicomponent on MFI molecular sieve at different
temperatures (m2⋅s− 1)
increases significantly. The simulation results show that, the diffusion
253 K 298 K 498 K
degree of each component from strong to weak at low temperatures is
roughly arranged as follows: H2O, CH4, C2H4, C3H8, C3H6, C6H6. The CH4 1.3880×10− 9 1.5051×10− 9 1.3599×10− 9
C2H4 5.3548×10− 10 6.753×10− 10 1.5687×10− 9
diffusion rate of propylene and benzene molecules is slow. The diffusion
C3H6 3.9202×10− 10 5.196×10− 10 1.5138×10− 9
degree of methane and water molecules on MFI molecular sieve are C3H8 3.6833×10− 10 6.4493×10− 10 1.6057×10− 9
much greater than that of other molecules, about 1.39×10− 9m2/s and H2O 2.3055×10− 9 2.3083×10− 9 3.5662×10− 9
2.31×10− 9m2/s, respectively, indicating that the diffusion performance C6H6 1.759×10− 10 2.0127×10− 10 1.109×10− 10

Fig. 20. Mean square displacement curve of multicomponent hydrocarbon mixture on MFI zeolite at 253 K, 298 K and 498 K.

18
L. Chen et al. Fuel 310 (2022) 122427

temperature, the diffusion performance of methane and water molecules

on CON molecular sieve is stronger. The capture performance of
ethylene, propylene, propane and benzene molecules is better, which is
consistent with the multicomponent adsorption simulation results
above.
Fig. 23 shows the distribution of hydrocarbon diffusion on CON
molecular sieve when the exhaust temperature is 298 K. It can be seen
from the figure that the hydrocarbon mixture in the CON molecular
sieve is mainly distributed in the 10-membered ring channel and the12-
membered ring channel. The window position is less distributed. Most of
the benzene molecules are in the 12-membered channel, and other
molecules are distributed in the 12-membered ring channel, 10-
membered ring channel and the connected window.
In general, the diffusion coefficients of ethylene and benzene mole­
cules on all kinds of molecular sieves are larger than those of pure
components. This phenomenon is mainly caused by two aspects. One is
Fig. 21. Distribution of hydrocarbons on MFI molecular sieve at 298 K.
Table 7
Fig. 22 and Table 7, it can be found that at low temperatures, the Diffusion coefficient of multicomponent on MFI molecular sieve at different
diffusion degree of each component from strong to weak is roughly ar­ temperatures (m2⋅s− 1)
ranged as follows: H2O, CH4, C2H4, C3H8, C3H6, and C6H6. Similar to 253 K 298 K 498 K
that on MFI molecular sieve the difference of molecular motion intensity
CH4 4.8367×10− 9 2.7246×10− 9 5.7627×10− 9
is due to the difference in the magnitude of the force between the C2H4 3.8097×10− 10 5.3218×10− 10 9.341×10− 10
molecule and the molecular sieve. At low temperature (253 K), the C3H6 2.9762×10− 10 2.3627×10− 10 8.474×10− 10
diffusion coefficient of methane and water molecules on CON molecular C3H8 3.3743×10− 10 3.36×10− 10 6.9398×10− 10
sieve are about 4.84×10− 9m2/s and 3.19×10− 9m2/s ,respectively, H2O 3.1893×10− 9 3.4956×10− 9 5.1040×10− 9
C6H6 2.563×10− 10 1.679×10− 10 4.6278×10− 10
much higher than that of other molecules, indicating that at low

Fig. 22. Mean square displacement curve of multicomponent hydrocarbon mixture on CON zeolite at 253 K, 298 K and 498 K.

19
L. Chen et al.
Fig. 23. Distribution of hydrocarbons on CON molecular sieve at 298 K.
that the temperature increases while the energy of ethylene and benzene
molecules increases, and the thermal movement is more intense. On the
other hand, due to the different diffusion coefficients of ethylene and
benzene molecules, when the molecules with more intense movement
diffuse outwards to the molecular sieve, the free volume in the molec­
ular sieve pore will increase, thus promoting the diffusion of other
molecules.
It is found that there is a competitive diffusion between the com­
ponents at 253 K, 298 K and 498 K by comparing the mean square
displacement curves of competitive diffusion of multicomponent mix­
tures on MOR, MFI and CON molecular sieves. In contrast, the diffusion
coefficients of each component on the same molecular sieve are
different, which is mainly due to the different interactions between
different molecules and molecular sieves, and the different interactions
between molecules. Comparing the diffusion coefficients of each
component on different molecular sieves, it can be seen that the diffu­
sion laws of each component molecule in MFI and CON molecular sieves
are similar in general. In contrast, the diffusion law of hydrocarbon
molecules in MOR molecular sieve is opposite to that of the above two
types of molecular sieves. The order from strong to weak is about C3H8,
C6H6, C3H6, C2H4, CH4 and H2O. It shows that the intensity of molecular
movement in MOR molecular sieve is still related to the number of
carbon atoms and hydrogen atoms. Since the total diffusion space is the
same, the weight and the volume smaller, the molecular diffusion
freedom larger and the diffusion easier.
4. Conclusions
In this work, the adsorption and diffusion of two single component
and six hydrocarbon mixtures on MOR, MFI and CON molecular sieves
at different temperatures are simulated. Results can be concluded as
follows:
1. Compared with pure silicon MOR and MFI molecular sieves, the CON
molecular sieve has better adsorption performance for benzene
component. MFI molecular sieve has better adsorption performance
for ethylene component. At the same temperature and on the same
molecular sieve, the adsorption capacity of ethylene molecule is
obviously more than benzene molecule on the three molecular
sieves. Compared with benzene molecules, ethylene molecules are
more easily adsorbed by molecular sieve.
2. The adsorption simulation results of mixed hydrocarbon components
show that when the adsorbent molecules are multiple components,
the competition between different components appears, and this
phenomenon is especially obvious at higher temperatures. The
adsorption amount of each component of the hydrocarbon mixture
changes significantly with increasing temperature. Collectively, the
20
Fuel 310 (2022) 122427
adsorption capacity of each component on the three molecular sieves
is ranked as follows: C6H6 > C3H6 > C2H4 > C3H8 > H2O > CH4.
However, under the cold start condition at low temperature (around
253 K), the MOR molecular sieve has a better adsorption perfor­
mance for C3H6 and C2H4, and the MFI molecular sieve has a better
adsorption performance for C3H6 and C3H8. At higher temperatures,
all three molecular sieves have significantly better trapping effect
adsorption performance for C6H6 than other hydrocarbon molecules.
At the temperature below 300 K, MFI molecular sieve has a larger
adsorption capacity for C3H6 and C3H8, which is twice that of the
other two molecular sieves. MFI molecular sieve could be considered
to adsorb C3H6 and C3H8 emissions when the exhaust temperature is
under 300 K. In the cold start condition, when the exhaust temper­
ature is around 300 K-400 K, the CON molecular sieve has the largest
adsorption of benzene molecules among the three molecular sieves.
When the exhaust temperature is higher than 300 K, the adsorption
of each component of the three molecular sieves is greatly reduced,
but they all mainly adsorb benzene molecules. At this time, the
adsorption performance of benzene molecules is greatly reduced.
3. The single component of ethylene molecule has relatively small
diffusion coefficient on MFI molecular sieve and good adsorption
performance at low temperature, and the largest diffusion coefficient
on CON molecular sieve, which is the least adsorbed. The pure
fraction of benzene molecules shows the smallest diffusion coeffi­
cient on the CON molecular sieve and the largest diffusion coefficient
on the MOR molecular sieve. In multicomponent diffusion, the
diffusion coefficients of ethylene and benzene molecules on each
molecular sieve are larger than those on single components. The
diffusion pattern of each component molecule in the MFI molecular
sieve is more similar to that of the CON molecular sieve. The results
show that the number of carbon atoms and hydrogen atoms of the
adsorbent molecules, the molecules weight and the molecules size all
have an effect on the degree of diffusion.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work is supported by the National Natural Science Foundation
of China under the research grant number of 51776062.
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