Fuel 287 (2021) 119547

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Fuel
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Full Length Article

Investigation of coke deposition inside catalyst with heterogeneous active

component distribution
Xuesong Yang , Shuai Wang *, Kai Zhang , Yurong He
School of Energy Science and Engineering, Harbin Institute of Technology, Harbin 150001, China

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

Keywords: Coke deposition over catalytic particles is not only associated with pore structure and pore distribution, but also
Active component distribution depends on the active component distribution. A particle-resolved model is employed to explore the coke
Coke deposition deposition process inside catalyst particles with heterogeneous active component distribution. The spatial and
Catalyst
instantaneous distribution of coke deposition and its influence on catalytic performance in a single particle and a
Particle-resolved model
packed bed are evaluated. The results show that there is a weaker internal resistance of mass and heat transfer
inside the egg-shell type catalyst so as to lead to a faster coke accumulation and catalyst deactivation, compared
to the egg-yolk type catalyst. Meanwhile, the wall effect on coke accumulation is more significant for egg-yolk
type catalysts.

introduced metal nanoparticles into the framework of oxide carriers and

designed a nanocomposite catalyst. It was shown that the catalyst par­
1. Introduction
ticle with high porosity could significantly reduce the coke formation.
From the above mentioned, most concerns concentrate on catalytic
Catalytic reforming technology has been widely applied to hydrogen
performance and coke resistance of catalyst particles with the uniform
production form hydrocarbon and alcohol fuel owing to its advantage in
distribution of active substances.
reducing carbon dioxide emission and promoting hydrogen yield [1–3].
The spatial distribution of active substances in catalyst particles has
Whereas in the catalytic reforming process, coke deposition can not be
been confirmed to greatly influence the catalytic performance and coke
avoided, considerably influencing on reaction performance [4–6]. On
deposition behaviors [16–18]. The catalysts with uneven active
the one hand, coke will cover the active site and make it isolated from
component distribution have been widely applied since 1960 s, such as
the reactant. On the other hand, internal pores in catalyst particles will
automobile tail gas purifier [19], catalytic reforming[20,21] and
be narrowed or blocked with coke deposition so as to increase the
Fischer-Tropsch process[22,23]. Generally, the catalyst with egg-shell
diffusion resistance [7]. Hence, a deep insight into the generation mode,
type distribution is more popular for its lower mass transfer resistance
distribution and control strategy of coke deposition is essential for the
[24]. On the contrary, the egg-yolk type can effectively prevent the
design of catalyst and regulation of catalytic reforming process.
thermal runaway behavior[25]. Recently, Cho et al. [26] experimentally
In order to explore the chemical pathway for carbon deposition and
compared the catalytic performance and coke resistance of the egg-shell
deactivation behaviors, some kinetic experiments have been carried out
type and homogeneous type tube-shaped Ni/MgAl2O4 catalyst during
[8,9]. It was found that the coke formation is mainly included in the
the methane steam reforming process. The results showed that the cat­
methane cracking, boudouard and carbon monoxide reduction reactions
alytic performance of the two type catalysts were similar while the long-
[10,11]. In particular, methane cracking process is considered as the
term stability of egg-shell type catalyst was more excellent than that of
main reason for coke formation [12,13]. Furthermore, the impacts of
the homogeneous type catalyst. Besides experiments, numerical simu­
pore structure and distribution in catalyst particles on carbon deposition
lation is regarded as an efficient tool and has been applied in the study of
have drawn a great deal of concerns. Li et al. [14] prepared a hy­
the active substance spatial distribution effect. Zimmermann et al. [27]
droxyapatite supported nickel catalyst and tested its coke resistance
adopted a heterogeneous particle-reactor model to optimize the design
during the methane dry reforming process. It was stated that increasing
of catalyst particles in a fixed-bed coke dioxide methanation reactor. The
the mesopore proportion could lead to small Ni nanoparticles so as to
results demonstrated that a good dynamic and flexible reactor operation
improve the activity and long-term stability of catalyst. Li et al [15].

* Corresponding author.
E-mail address: shuaiwang@hit.edu.cn (S. Wang).

https://doi.org/10.1016/j.fuel.2020.119547
Received 28 July 2020; Received in revised form 25 September 2020; Accepted 16 October 2020
Available online 5 November 2020
0016-2361/© 2020 Elsevier Ltd. All rights reserved.
X. Yang et al. Fuel 287 (2021) 119547

Nomenclature T temperature [K]

u velocity [m s− 1]
a activity [–] x molar fraction [–]
Cp specific heat capacity [J kg− 1 K− 1]
d particle diameter [m] Greek letters
D diffusivity [m2 s− 1] μ viscosity [Pa.s]
F volume force[N/m3] ε porosity [–]
g gravity [m s− 2] ρ density [kg m− 3]
k thermal conductivity [W m− 1 K− 1] β forchheimer coefficient [kg m4]
M molar weight [kg/mol] κ permeability [m2]
P pressure [Pa] τ tortuosity [–]
rp averaged pore diameter [nm] Subscripts
R reaction source [kg/m3/s] cat catalyst
Sm Mass source [kg/ m3/s]

behavior could be achieved with egg-yolk type particles. where the molecular diffusion is calculated by the Fuller equation. The
In order to better understand the catalyst deactivation mechanisms Knudsen diffusion can be calculated as below:
of heterogeneous type catalyst particles, this paper aims to evaluate coke
( )12
deposition behaviors over the catalyst with different types of active T
component distribution via numerical simulation. A particle-resolved Di,k = 97rp (2)
Mi
model is employed to investigate the performance of egg-shell type
and egg-yolk type catalyst particles in a single particle and packed bed It is worth noting that the effect of coke deposition on the pore
reactor. The change of activity caused by coke deposition is further structure inside the catalyst particle is implemented by the change of
compared. The reaction and mass transfer performance are further porosity, which can be expressed as below:
examined. r⋅Mc
ε = ε0 − Δt (3)
ρc
2. Mathematical model

2.1. Governing equations

Table 2
In this work, the particle-resolved model developed by Karthik et al. Governing equations in the particle-resolved model.
[28] is applied to simulate coke deposition behaviors over catalyst Continuity equation
particles in a single particle and a packed bed reactor. The governing ∂ερ (T2-1)
+ ∇⋅(ρu) = Sm
equations are expressed in Table 2. The entire computing region is ∂t
∂ρ (T2-2)
divided into the free fluid region and the porous particle region. For the + ∇⋅(ρu) = 0
∂t
free fluid region, the laminar flow is employed to avoid the complexity
Momentum conservation equation
of transient flow field under reaction condition, as described in the work 1 ∂u 1 u
(
Sm
)
(T2-3)
+ ρ(u⋅∇) = − ∇⋅[ − pI + K] − κ− 1 μ + βu + 2 u + F
of Dixon et al. [29]. In terms of the porous particle region, the brinkman ρ
ε ∂t ε ε ε
equation is adopted to describe the momentum transfer inside the ∂u (T2-4)
ρ + ρ(u⋅∇)u = − ∇⋅[ − pI + K] + F
∂t
catalyst, where an infinitely small permeability κ is chosen. In this way, a
Species transportation equation
large momentum source is applied so that the convective flux across the ( )
∑ Mi (T2-5)
fluid–solid interface can be suppressed [30].
∂ω eff ∇Mn
ερ i − ∇ ρDeff ∇ ω i + ρ D − ρω i D eff
∇x k = Ri
∂t i i
Mn Mn k
For the species transportation inside the porous particle region, the (
k
)
∂ω ∇Mn ∑ Mi (T2-6)
effective diffusion coefficient Deff ρ i − ∇ ρDi,j ∇ωi + ρDi,j Di,j ∇xk + ρ(u⋅∇)ωi = 0
i depends on the porosity ε and tortu­
− ρωi
∂t Mn k
Mn
osity τ, which can be calculated by the Knudsen diffusion Di,k and mo­ Energy conservation equation
lecular diffusion Di,j : ∂T ( ) (T2-7)
(ρCp)eff + ∇⋅ − keff ∇T = Q
∂t
ε Di,j ⋅Di,k ∂T (T2-8)
Deff
i = (1) ρCp + ρCpu⋅∇T + ∇⋅( − k∇T) = 0
τ Di,j + Di,k ∂t

Table 3
Table 1 Reaction kinetic model and parameters.
Main operating parameters in the simulation. P2H2 (T3-1)
PCH4 −
Description Simulation Unit Kp
r = a⋅k ( √̅̅̅̅̅̅̅̅ )2
1 + kH PH2
Particle diameter 5 mm ( )
104200 (T3-2)
Particle density 1974 kg/m3 k = exp 20.492 −
Rg T
Particle initial porosity 0.45 – ( )
Particle average pore diameter 10 nm 163200 (T3-3)
kH = exp − 22.426
Coke density 4000 kg/m3 Rg T
( )
Coke molar mass 12 g/mol 91200 (T3-4)
Kp = 5.088⋅105 ⋅exp −
Inlet fuel gas velocity 0.1 m/s Rg T
da (T3-5)
Inlet gas composition(CH4/H2) 4:1 – = − ka r2max ca
dt
Inlet fuel gas temperature 773 K (
135600
)
(T3-6)
Pressure outlet 0.1 MPa ka = exp − 32.077
Rg T

2
X. Yang et al. Fuel 287 (2021) 119547

Fig. 1. Sketch of geometry domains (a) single catalyst particle; (b) fixed bed reactor; (c) catalysts with heterogeneous distribution of active components.

where Mc, ρc and r denote the molar weight, density and formation rate
of coke.
Finally, a local thermal equilibrium model is applied to simulate the
energy conservation process inside the porous particle region where the
temperature difference between the gas phase and porous medium is
neglected [31]. The adiabatic boundary condition is adopted to obtain a
well-developed temperature distribution in the relatively short pipe
length [29]. The effective heat capacity and thermal conductivity are
associated with coke accumulation.
(ρCp)eff = (ε0 - ε)⋅(ρCp)carbon + (1 − ε0 )⋅(ρCp)catalyst + ε⋅(ρCp)gas (4)

keff = (ε0 - ε)⋅kcarbon + (1 − ε0 )⋅kcatalyst + ε⋅kgas (5)

For the interface between these two regions, the velocity and pres­
sure are continuous with continuous mass and heat fluxes, while the
stress jump condition is realized.

(a) Egg-shell type

(b) Egg-yolk type

Fig. 3. Transient variations of hydrogen concentration in a single particle.

Fig. 2. Comparison of model predictions and experimental data.

3
X. Yang et al.
(a) Egg-shell type
(b) Egg-yolk type
Fig. 4. Transient variations of temperature in a single particle.
2.2. Reaction kinetics model
Here, the methane cracking reaction as a simple one-step reaction is
selected to evaluate coke formation behaviors and catalyst deactivation.
Besides that, the oxidative dehydrogenation, isomerization, hydroge­
nation, Fischer-Tropsch synthesis and reforming also greatly affect the
coke formation [32,33], which will be our further concern. The detailed
reaction rate can be found in Table 3[34]. It is worth noting that the
effect of coke deposition on realistic reaction rate depends on the ac­
tivity and the deactivation rate, which is associated with the coke
accumulation and formation rate.
2.3. Model implementation and system description
In this work, the coke deposition performance inside a single catalyst
particle and a randomly stacked packed bed reactor is investigated with
the catalyst density of 1974 kg/m3 and the particle diameter of 5 mm, as
shown in Fig. 1(a) and (b). The catalysts with heterogeneous distribution
of active components are displayed in Fig. 1(c). It is worth noting that
the randomly stacked packed bed reactor is established by means of the
DEM and the particle diameters are reduced to 99% in order to improve
the mesh quality and convergence [35,36]. In a packed bed reactor, the
tube to particle diameter ratio of 3.5 and the stack height to particle
diameter of 5 are selected. Meanwhile, there are empty pipe zones to
reduce the influence of the inlet and outlet on the flow in the filling
structure. The detailed operating conditions and physical properties are
4
Fuel 287 (2021) 119547
(a) Egg-shell type
(b) Egg-yolk type
Fig. 5. Transient variations of coke accumulation in a single particle.
listed in Table 1.
A particle-resolved model is established based on the COMSOL
Multiphysics, where the predefined element size of “finer” is adopted via
a grid-independent analysis. Meanwhile, the maximum residual of
0.0001 is selected for the species and energy transportation equations
and the maximum residual for other parameters is set to be 0.001.
3. Results and discussion
In order to validate the fixed bed structure generated by the DEM
method, the simulated local bed porosity is compared to the experiment
data [37] and the empirical correlations of Mueller [37] and De klerk
[38], as shown in Fig. 2. It can be recognized that the simulation results
can give a better prediction on the measured data in contrast to the
empirical correlations. Meanwhile, the reaction kinetic model has been
also verified in the previous work [39]. Therefore, the present model can
be used for the prediction of coke deposition behaviors of catalyst.
The transient variations of hydrogen concentration at different lo­
cations inside the egg-shell type and egg-yolk type catalyst particles and
the instantaneous contour plots of hydrogen concentration are shown in
Fig. 3(a) and (b). We can find that the hydrogen concentrations usually
decrease as the time goes on owing to catalyst deactivation. However,
the concentration at the center of the egg-yolk type catalyst firstly in­
creases and then decreases, which is attributed to the fact that the
deactivation effect of coke deposition in the core is weak at first. In
X. Yang et al.
(a) Egg-shell type
(b) Egg-yolk type
Fig. 6. Transient variations of activity in a single particle.
addition, a non-uniform distribution inside the catalyst particle can be
observed that a high hydrogen concentration region in the egg-shell type
catalyst occurs near the top junction, resulting from the gas flow di­
rection and the lower internal diffusion resistance. For the egg-yolk type
catalyst, a high hydrogen concentration appears at the junction and then
moves to the center as a result of catalyst deactivation.
Fig. 4 displays the transient variation of temperature inside the two
types of catalyst particles. It can be found that the temperature increases
and eventually approaches the inlet gas temperature, because the coke
accumulation hinders the methane decomposition reaction. Meanwhile,
a non-uniform distribution of temperature inside the two types of
catalyst particles can be observed. A low temperature occurs near the
top junction point of the egg-shell type particle owing to the gas flow
direction. For the egg-yolk type catalyst, the endothermic coke forma­
tion reaction occurs at the center. This indicates that the heat is trans­
ferred from the shell to the center. In addition, the gas flow direction
leads to a wider zone of high temperature at the bottom section of the
shell.
The transient distribution of coke accumulation in the two types of
catalyst particles is displayed in Fig. 5. It can be recognized that coke
deposition only occurs at the active component region. In addition, a
strong internal diffusion resistance in the egg-yolk type will lead to a
5
Fuel 287 (2021) 119547
(a) Egg-shell type
(b) Egg-yolk type
Fig. 7. Transient variations of reaction rate in a single particle.
more uneven distribution of coke deposition and the coke accumulation
moves toward the center direction inside these two types. Compared to
the egg-yolk type, the rising rate of the egg-shell type is faster and the
average coke accumulation is lower, which is related to the reaction rate
in the next discussion.
The coke deposition leads to a change in activity, as shown in Fig. 6.
We can observe that the catalytic activity declines with time as a result
of continuous coke accumulation. For the egg-shell type particle, the
descending degree of the activity near the bottom is more significant. In
contrast, the descending degree of activity near the bottom junction is
more significant inside the egg-yolk type particle, which is in accordance
with the distribution of coke accumulation in Fig. 5. Additionally, the
deactivation rate of the egg-shell type particle is faster and more uniform
than that of the egg-yolk type particle, which is related to the coke
deposition rate. In other words, the egg-shell type particle is suitable for
short-time operation before regeneration.
The catalyst activity determines the reaction rate, as displayed in
Fig. 7. It can be observed that the reaction rate tends to decrease as the
time goes on owing to the catalyst deactivation. Meanwhile, the distri­
bution of the reaction rate is obviously non-uniform owing to the uneven
distribution of gas component, temperature and activity. To be specific,
a higher reaction rate appears near the bottom of the egg-shell type
X. Yang et al. Fuel 287 (2021) 119547

Fig. 8. Transient variations of effective factor in a single particle.

particle at the initial stage as a result of low hydrogen concentration and

high temperature, which also indicates that a fast coke deposition will
lead to a high reaction rate towards the top junction. Similarly, a high
reaction rate occurs near the top and below the junction of the egg-yolk
type particles at the initial stage and then moves to the center. In
addition, the deactivation rate of the egg-shell type particle is faster and
more uniform than that of the egg-yolk type particle.
In order to further evaluate the impact of the internal mass transfer
on reaction rates, an effective factor is introduced, as shown in Fig. 8.
The profiles of effective factors are similar to those of reaction rates.
Comparing the two types of catalyst particles, we can recognize that the
effective factor of the egg-shell type is higher than that of the egg-yolk
type owing to a weaker internal diffusion resistance at the initial
stage. However, a higher coke accumulation rate results in a faster decay
rate of the effective factor so that the effective factor of the egg-yolk type
catalyst becomes greater than that of the egg-shell type. In general, the
operation time before regeneration should be optimized according to the
transient variation of the effective factor.
In a randomly stacked packed bed reactor with a low tube to particle
diameter ratio, the bed porosity varies dramatically near the wall, which
Fig. 10. Variation of surface-averaged reaction rate and coke accumulation
influences gas flow behaviors so as to act on the coke deposition. Fig. 9
with time.
illustrates the instantaneous contour plots of hydrogen concentration at

(a) Egg-shell type (b)Egg-yolk type

Fig. 9. Transient variations of hydrogen concentration in a fixed bed reactor.

6
X. Yang et al.
Fig. 11. Radial distributions of local bed porosity, area-averaged activity, area-averaged coke accumulation and area-averaged reaction rate in packed beds.
t = 2000 s. It can be found that the hydrogen concentration rises as the
endothermic reaction goes on. Meanwhile, the non-uniform distribution
of bed porosity causes the discrepancy of reaction and diffusion so that
the gas species concentration distribution inside the catalyst particle is
different. Compared to the egg-shell type, the non-uniform distribution
of concentration of the egg-yolk type is more obvious owing to stronger
internal diffusion resistance.
Fig. 10 displays the variation of the surface-averaged coke accumu­
lation and reaction rate with time. It can be seen that different axial
surface-averaged coke accumulations increase and the reaction rates
decrease as the time goes on. By comparing the two types of catalyst
particles, we can also find that the reaction rates of the egg-shell type at
different heights are higher than those of the egg-yolk type at the start
stage. Then the reaction rate of the egg-shell type becomes lower than
that of the egg-yolk type so that the final coke accumulation of the egg-
yolk type is more obvious than that of the egg-yolk type. Meanwhile,
there exists some difference in coke accumulation at different reactor
heights, that is, the coke deposition rates at low locations are faster at
the initial stage, which is attributed to higher reaction rates under higher
temperature and lower hydrogen concentration. As coke deposition
continues to be accumulated, the activity and internal diffusion of mass
and temperature are hindered so that the reaction rates at low locations
become lower than those at high locations. In this way, the final coke
accumulations at high locations are more evident than those at low lo­
cations for both the egg-shell type and egg-yolk type catalyst particles.
Fig. 11 shows instantaneous radial distributions of local bed
porosity, area-averaged activity and coke accumulation and reaction
rate. It can be recognized that the wall effect on radial distribution of
7
Fuel 287 (2021) 119547
activity, coke accumulation and reaction rate is stronger for the egg-yolk
type catalyst particle. An obvious rising trend of bed porosity will lead to
more coke accumulated so as to decrease the catalyst activity. However,
the influence is not significant for the egg-yolk type, resulting from the
weak diffusion of mass and heat.
4. Conclusion
Coke deposition inside a single catalyst particle and a fixed bed
reactor with different active component distributions is numerically
studied via a particle-resolved model. The coke accumulation moves
toward the center direction inside the two types of particles. Low in­
ternal diffusion resistance of mass and heat inside the egg-shell type
catalyst leads to a more uniform distribution and a faster rate of coke
deposition. Hence, the egg-shell type catalyst particle is suitable for
short-time operation before regeneration.
The wall effect on coke accumulation and reaction rate is confirmed
to be stronger for the egg-yolk type than that for the egg-shell type owing
to a higher diffusion resistance. Additionally, an obvious rising trend of
bed porosity will lead to more coke accumulated and decrease the
catalyst activity.
CRediT authorship contribution statement
Xuesong Yang: Investigation, Writing - original draft, Data curation.
Shuai Wang: Supervision, Methodology. Kai Zhang: Visualization.
Yurong He: Writing - review & editing.
X. Yang et al.
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.
Acknowledgment
This research is conducted with financial support from the National
Natural Science Foundation of China (52076060).
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