catalysts

Article
Kinetic Monte-Carlo Simulation of Methane Steam
Reforming over a Nickel Surface
Palawat Unruean 1,2 , Teetuch Plianwong 1,2 , Sirawit Pruksawan 1 , Boonyarach Kitiyanan 1,2, *
and Robert M. Ziff 3
1 The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok 10330, Thailand;
palawat_tay@hotmail.com (P.U.); ohmbaby03@gmail.com (T.P.); beam_03148@hotmail.com (S.P.)
2 Center of Excellence on Petrochemical and Materials Technology, Chulalongkorn University,
Bangkok 10330, Thailand
3 Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, USA; rziff@umich.edu
* Correspondence: boonyarach.k@chula.ac.th




Received: 31 August 2019; Accepted: 5 November 2019; Published: 11 November 2019


Abstract: A kinetic Monte-Carlo model was developed in order to simulate the methane steam
reforming and kinetic behavior of this reaction. There were 34 elementary step reactions that were
used, based on the Langmuir–Hinshelwood mechanism, over a nickel catalyst. The simulation was
investigated at a mole fraction of methane between 0.1 and 0.9, temperature of 600 to 1123 K, and total
pressure of up to 40 bar. The simulated results were collected at a steady state and were compared
with the previously reported experiments. The fractional coverages of the adsorbed species and the
production rates of H2 , CO, and CO2 were evaluated, and the effects of the reaction temperature,
feed concentration, and total pressure of reactants were also investigated. The simulation results
showed a similar trend with previous experimental results, and suggested the appropriate conditions
for this reaction, which were a total pressure of 10 bar, with the mole fraction of methane in a range of
0.4–0.5.

Keywords: methane steam reforming; kinetic Monte-Carlo simulation; kinetic behavior; nickel catalyst

1. Introduction
Reforming is one of the most important processes to produce hydrogen (H2 ) and/or syngas (H2
and CO), which can be further used in downstream processes [1–3]. Three main reactions widely
studied in H2 or syngas production from methane (CH4 ) are partial oxidation, dry reforming, and
steam reforming [4,5]. These three reactions provide the H2 to CO ratio differently. Typically, partial
oxidation produces syngas with a H2 :CO ratio of 2:1. Dry reforming provides a CO-rich syngas with an
H2 :CO ratio of 1:1, while steam reforming produces an H2 -rich syngas with an H2 :CO ratio of 3:1 [4,5].
Methane steam reforming is generally used to produce an H2 -rich syngas from methane [6,7].
The process uses steam (H2 O) to react with CH4 in the presence of a catalyst. H2 is formed by the
dissociation of H2 O and CH4 . After that, the remaining oxygen atom from H2 O reacts with the
remaining carbon atom from CH4 to form CO and CO2 . During the steam reforming of methane, three
main reversible reactions can take place involving two strongly endothermic reactions of methane
steam reforming, as shown in Equations (1) and (2), and the moderately exothermic water–gas shift
reaction, as shown in Equation (3) [7–9].

CH4 (g) + H2 O(g) ↔ CO(g) + 3H2 (g) ∆H◦ 298 = +206 kJ/mol (1)

CH4 (g) + 2H2 O(g) ↔ CO2 (g) + 4H2 (g) ∆H◦ 298 = +165 kJ/mol (2)

Catalysts 2019, 9, 946; doi:10.3390/catal9110946 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 946 2 of 12

CO(g) + H2 O(g) ↔ CO2 (g) + H2 (g) ∆H◦ 298 = −41 kJ/mol (3)

Various metals have been studied as the catalyst for this reaction, such as palladium (Pd) [10],
nickel (Ni) [11], platinum (Pt) [12], ruthenium (Ru) [13], rhodium (Rh) [14], and iridium (Ir) [15]. Among
these metals, nickel is typically investigated, owing to its moderate cost, good catalytic performance,
and high stability at relatively high temperatures [16,17]. Nevertheless, the rapid deactivation on the
nickel surface by carbon deposition or coking has been reported [18], as well as by the formation of an
NiAl2 O4 spinel in the Ni/Al2 O3 catalyst, leading to the reduction of the active Ni [19].
The kinetic behavior of methane steam reforming and water–gas shift reactions over a Ni/MgAl2 O4
catalyst was investigated using microkinetic modelling based on the Langmuir–Hinshelwood (LH)
mechanism, with purposed elementary reaction steps. The reactions were carried out in rows of
tubular reactors, with the reaction temperature between 675 and 1000 K and a pressure of 30 bar [20].
The activation energy and pre-exponential factor of each elementary reaction were estimated by
using the unity bond index-quadratic exponential potential (UBI-QEP) and density functional theory
(DFT) calculations [21]. In addition, the kinetics of the methane steam reforming with the water–gas
shift reaction were studied over a commercial Ni/α-Al2 O3 catalyst, and the results indicate that
hydrogen and syngas are favorably produced at a high steam-to-methane ratio with a low reaction
temperature, and both CO and CO2 are formed as primary products [22]. Moreover, the steam
reforming of methane is performed over a Ni/NiAl2 O4 catalyst, with a steam-to-carbon ratio in the
range of 0.2–7.1, at temperatures of 843, 858, and 873 K. A Langmuir–Hinshelwood model is satisfied
for these experimental data [23]. The model is then developed by considering carboxyl species (COOH)
and active carbon as intermediates [24].
Kinetic Monte-Carlo (kMC) is one of the most effective tools for investigating the complex kinetic
behavior of catalytic reactions [25]. The kMC simulations connect the gap between the microscopic
scale and macroscopic scale information [26]. The kMC simulations combine the statistical and
elementary reaction steps to predict the adsorption on the surface of the catalyst, surface composition,
site blocking, and reaction on the surface catalyst [27,28]. The kMC of CO oxidation on the catalyst
surface was modeled by Ziff, Gulari, and Barshad, and is called the ZGB model [29]. This model has
been successfully applied for studying complex phenomena on the surface of a catalyst [30–34]. A
two-dimensional lattice is used to represent the catalyst surface, which contains all of the catalytic
sites, by evenly distributing the active sites on the lattice [25]. One of the advantages of using kMC is
that some effects, such as the diffusion and lateral interactions of adsorbed species, can be included.
However, the diffusion of the adsorbed species is not included in this study because, based on our
previous work [34], the diffusion has only a slight effect on the production rates. Furthermore, the
kMC simulations of the water–gas shift reaction show that the CO lateral interactions do not play an
important role, because of almost no CO coverage at the final steady-state [35]. Therefore, the lateral
interactions are also not included.
The purpose of this work is to develop a kMC model for methane steam reforming over a
nickel catalyst, based on the LH mechanism, under an isothermal condition. The simulations were
performed under various operating conditions at a steady state, and the results were compared with
the experimental results reported in the literature. The effects of the lattice site, feed concentration,
reaction temperature, and total pressure of reactants are revealed.

2. Results
In this simulation, lattice sizes of 64 × 64, 128 × 128, and 256 × 256 sites were examined under the
same operating conditions, and it could be observed that the lattice size had no significant effect on the
fractional coverages and rates of product formation, which is similar to the other works [34,36–38].
Therefore, the lattice size of 64 × 64 sites was selected in this simulation study.
To find the reaction time to reach the steady state, the fractional coverages and the production
rates were simulated as a function of time. Generally, the required computational time of the kMC
depends on the number of elementary step reactions and the model complexity [37]. Figures 1 and 2
 38]. Therefore, the lattice size of 64 × 64 sites was selected in this simulation study.
To find the reaction time to reach the steady state, the fractional coverages and the production
on the fractional coverages and rates of product formation, which is similar to the other works [34,36–
rates were simulated as a function of time. Generally, the required computational time of the kMC
38]. Therefore, the lattice size of 64 × 64 sites was selected in this simulation study.
depends on the number of elementary step reactions and the model complexity [37]. Figure 1,2
To find the reaction time to reach the steady state, the fractional coverages and the production
illustrate the fractional coverages and the production rates as a function of time, respectively. The
rates were
Catalysts 2019, simulated
9, 946 as a function of time. Generally, the required computational time of the3kMC
of 12
steady state was reached within 0.04 milliseconds.
depends on the number of elementary step reactions and the model complexity [37]. Figure 1,2
illustrate the fractional coverages and the production rates as a function of time, respectively. The
illustrate the fractional coverages and the production rates as a function of time, respectively. The
steady state was reached within 0.04 milliseconds.
steady state was reached within 0.04 milliseconds.

Figure 1. Fractional coverages as a function of time; time (T) = 850 K, pressure (P) = 1 bar, and 𝑦 =
0.5.

Figure1.1.Fractional
Figure Fractionalcoverages
coveragesasasa function of of
a function time; time
time; time = 850
(T)(T) K, pressure
= 850 (P) =(P)
K, pressure 1 bar, yCH4 𝑦= 0.5.=
and and
= 1 bar,
0.5.

Figure2.2.Production
Figure Productionrates
ratesasasaafunction time;TT==850
functionofoftime; K,PP== 11 bar,
850K, and y𝑦CH4 ==0.5.
bar,and 0.5.

The
Theresults
results fromfromthis this
simulation were compared
simulation were comparedto those to of previous
those ofexperiments. At a temperature
previous experiments. At a
oftemperature Figure
850 K and total 2. Production
pressure of 1 rates
bar, theasHa2function
:CO of time;
product T = from
ratio 850 K,this
P = work and 𝑦
1 bar, was 10:1, =while
0.5. the H2 :CO
of 850 K and total pressure of 1 bar, the H2:CO product ratio from this work was 10:1,
product
while the ratio
H2:COfromproduct
the experiment
ratio from reported by Delgado
the experiment et al. by
reported [24]Delgado
was approximately
et al. [24] was 6:1. In addition,
approximately
both The results
theaddition,
simulated from
andthethis simulation
experimental were
results compared
show that results to those
the productions of previous experiments. At a
6:1. In both simulated and experimental show thatofthe COproductions
and CO2 were nearly
of CO and
temperature
similar at these of 850 K and
conditions. total pressure of 1 bar, the H 2 :CO product ratio from this work was 10:1,
CO2 were nearly similar at these conditions.
while the H2:CO product
Moreover, ratio from the experiment reported by Delgado et al. [24] wasratio
approximately
Moreover,the therelationship
relationship between
between COCO 2 selectivity and the steam-to-carbon inlet
2 selectivity and the steam-to-carbon inlet ratio (S/C)
(S/C) from
6:1.
this In addition, both the simulated and experimental results show that the productions of CO 873
and
from this work was compared to that reported by Sprung et al. [39], at temperatures of 843, and
work was compared to that reported by Sprung et al. [39], at temperatures of 843, 853, 853, and
COThe
K. 2 were nearly
results similar at these
demonstrate that COconditions.
2 selectivity increases with the increasing S/C ratio, and both the
Moreover, the relationship
simulated and experimental results were about between CO2 theselectivity
same atand the steam-to-carbon inlet ratio (S/C)
all temperatures.
fromThethisHwork was compared to that reported by Sprung et al. [39], at temperatures of 843, 853, and
2 :CO ratio as a function of temperature predicted by this work was also compared to that
reported by Maier et al. [40] at temperatures of 1023, 1123, and 1223 K. The results show that the
H2 :CO ratio decreases with the increasing temperature. The H2 :CO ratios obtained by this simulation
exhibited values of 9.7, 7.5, and 4.5, while the H2 :CO ratios obtained by the experiment were 9, 7.1,
behavior for all of the temperatures.

2.1. Effect of Feed Concentration

Figure 3,4 illustrate the effect of the feed (CH4 and H2O) concentration on the fractional coverages
and production
Catalysts 2019, 9, 946
rates by varying the mole fraction of methane (𝑦 ) between 0.1 to 0.9 at a constant 4 of 12
temperature and pressure. It can be noticed that the reaction takes place and all of the products are
formed even at a very low methane concentration (𝑦 = 0.1). As shown in a snapshot of the nickel
surface (Figure 5a), the surface is almost entirely covered experimental
and 5.5, respectively. Therefore, both the simulated and by O* and H* at 𝑦 show
results = 0.2, about
and alsotheby
samethe
behavior for all of the temperatures.
other active species such as the active vacant site, and C* and CHx* intermediates, leading to the
reaction taking place.
2.1. Effect of Feed Concentration
The high yield (high rate of production) of H2 and CO is around 0.4 < 𝑦 < 0.5 (H2: 2500–2700
Figures 3 and 4 illustrate
molecules/site/second and CO: the≈220
effect of the feed (CH4 andfor
molecules/site/second H2 O) concentration
CO). However, CO on 2the fractional
reaches the
maximum yield at 𝑦
coverages and production rates by varying the mole fraction of methane
of 0.4 (382 molecules/site/second). The snapshot in (yCH4Figure 5b is also 0.9
) between 0.1 to in
at a constant
agreement thattemperature
the surfaceand pressure.
of the It can beisnoticed
nickel catalyst mainlythat the reaction
covered by C* andtakes
H*,place and all
together of O*,
with the
products
CO*, andare COformed
2*. These even at aspecies
active very low aremethane concentration
also exhibited, along with = 0.1).
yCH4 the As shown
vacant in a snapshot
active sites, which are of
the nickel to
necessary surface
carry (Figure 5a), the surface
on the reactions in orderisto
almost entirely
generate CO* covered
(steps 23,by24,
O*26,
and
and at yCH4 = 0.2, and
H*28).
also by
Above 𝑦 active
the other = 0.5,species such as the rates
the production activeofvacant site, and
H2, CO, and C*COand CHx * intermediates,
2 gradually decrease and leading
the
production rates of both CO and CO2 products are extremely low at 𝑦
to the reaction taking place. = 0.9 (4
The high yield (high
molecules/site/second for CO rateandof 42
production) of H2 and CO
molecules/site/second is around
for CO 0.4 < inyCH
2). As shown < 0.5
Figure
4 5c, (H
the 2:
surface of the nickel catalyst is mainly covered by C* and CH3* at 𝑦
2500–2700 molecules/site/second and CO: ≈220 molecules/site/second = 0.7. Moreover, at 𝑦
for CO). However, CO 2 reaches
= 0.9,
the CO
no maximum
2* and O* yield at yCH
active of 0.4are
species
4
(382observed
molecules/site/second).
on the snapshot. The snapshot in
According to Figure 5b is also
these results, it inis
agreement to
interesting that thethat
note surface of the nickel
the optimum catalystrates
production is mainly
of H2 covered
and CO areby C* and H*,
obtained whentogether
CH4 andwithHO*,2O
CO*,fed
are and CO2 *. (𝑦
equally These=active species
0.5). The are also
vacant activeexhibited,
sites arealong with the vacant
also important active sites,
for allowing new which
adsorbed are
necessary
species as to carry
well on the
as new reactions reactions.
elementary in order to generate CO* (steps 23, 24, 26, and 28).

Figure
Catalysts 9, xFractional
2019, 3. FOR PEERcoverages
REVIEW as a function of the mole fraction of methane; T=
methane; T = 823 K and P == 11 bar.
bar.
5 of 12

Figure 4. Production rates as a function of the mole fraction of methane; T = P ==11bar.

823 K and P
= 823 bar.
Catalysts 2019, 9, 946 5 of 12

Figure 4. Production rates as a function of the mole fraction of methane; T = 823 K and P = 1 bar.

Figure 4. Production rates as a function of the mole fraction of methane; T = 823 K and P = 1 bar.

(a) (b) (c)

Figure
Figure 5. 5. Snapshotsofofthe
Snapshots thesurface
surface of
of the
the nickel catalyst:(a)(a)𝑦 yCH=4 0.2;
nickelcatalyst: = 0.2; 𝑦 yCH
(b)(b) = 0.5;
4
(c) 𝑦(c) yCH
= 0.5; = 0.7;= T0.7;
4

T == 823
823 K, P = 1 bar (□ = Empty, ■ = H*, ■ = C*, ■ = O*, ■ = CH4*,4 ■ = CH3*,3 ■ = CH2*,2■ =
= 1 bar ( = Empty,  = H*,  = C*,  = O*,  = CH *,  = CH *,  = CH *, = CH*,
 CH*,
 =■CO= CO *, =■CO*,
2 *, 2  =■OH*,
= CO*,  =■H=
= OH*, 2 O*,  =■H=2 *,H2*,=■COOH*).
H2O*, = COOH*).

2.2.Above yCH
Effect of = 0.5,Temperature
Reaction
4
the production rates of H2 , CO, and CO2 gradually decrease and the production
rates of both CO and CO2 products are extremely low at yCH4 = 0.9 (4 molecules/site/second for CO
and 42 To observe the effect of the
molecules/site/second
(a) for reaction
CO2 ). As temperature,
shown the fractional coverages and production rates
(b) in Figure 5c, the surface of the(c)nickel catalyst is
are investigated by varying the reaction temperature from 600 to 1123 K. The results are plotted as
mainly covered by C* and CH3 * at yCH4 = 0.7. Moreover, at yCH4 = 0.9, no CO2 * and O* active species
shown
Figure in5.Figure 6. When
Snapshots CH
of the 4 adsorbs
surface asnickel
of the CH4* catalyst: (a) 𝑦 surface,
on the nickel = 0.2; it 𝑦 = 0.5; (c)
(b)dissociates 𝑦 3* and
to CH = 0.7;CH
T 2*
are observed on the snapshot. According to these results, it is interesting to note that the optimum
CO are■obtained
= H*, ■ when
= C*, ■ and■H=2 O 4*, ■ = CH3*, ■ = CH2*, ■ = CH*,
intermediates. The CH 4* and CH3* coverages on the surface are high at 600 K, and as the temperature
= 823 K,rates
production P = 1of H(2□and
bar = Empty, CH=4O*, CHare fed equally yCH = 0.5). The vacant
increases, both the CH4* and CH3* on the surface decrease. For O*, a similar 4trend of surface
active■sites
= COare2*, ■ = CO*,
also ■ = OH*,
important ■ = H2O*,new
for allowing ■ =adsorbed
H2*, ■ = COOH*).
species as well as new elementary reactions.
concentration is also observed. As the reaction temperature increases from 600 to 700 K, the surface
2.2.coverages
2.2. Effect of
Effect
of C* andTemperature
of Reaction
Reaction H* increase and then decrease after 700 K.
Temperature
To observe
To observe the
the effect
effect of
of the
the reaction
reaction temperature,
temperature, thethe fractional
fractional coverages
coverages andand production
production rates
rates
are investigated
are investigated by
by varying
varying thethe reaction
reaction temperature
temperature fromfrom 600
600 to
to 1123
1123 K.
K. The
The results
results are
are plotted
plotted as
as
shown in Figure 6. When CH
shown in Figure 6. When CH4 adsorbs 4 adsorbs as CH
as CH4* on * on the nickel surface, it dissociates to CH
4 the nickel surface, it dissociates to CH3* and3 CH2* * and
CH2 * intermediates.
intermediates. The CHThe4* andCH 4 * 3and
CH CH3 * coverages
* coverages on the
on the surface aresurface
high at are
600 high
K, and atas
600
theK,temperature
and as the
increases, both the CH4* and CH3* on the surface decrease. For O*, a similar trend of trend
temperature increases, both the CH 4 * and CH 3 * on the surface decrease. For O*, a similar of
surface
surface concentration is also observed. As the reaction temperature increases from
concentration is also observed. As the reaction temperature increases from 600 to 700 K, the surface 600 to 700 K, the
surface coverages
coverages of H*
of C* and C* increase
and H* increase
and then and then decrease
decrease after 700after
K. 700 K.

Figure 6. Fractional coverages as a function of te reaction temperature; P = 1 bar and 𝑦 = 0.4.

Figure 6. Fractional coverages as a function of te reaction temperature; P =

Fractional coverages = 11 bar and y𝑦CH4 =
bar and = 0.4.

Figure 7 demonstrates the production rates as a function of the reaction temperature. The results
suggest that the production rates of H2 and CO2 are the highest at 750–800 K, whereas the production
rate of CO exhibits the highest values at a temperature range of 800–900 K. Therefore, at around
800 K, the reaction should provide the highest yield of syngas (3439 molecules/site/second for H2
and 161 molecules/site/second for CO). From the simulation, at a temperature higher than 750 K, the
the formation of CO from the adsorbed C* and O* active species. Moreover, the 𝐸 of the CO2
formation (step 32) is also lower than that for the CO desorption (step 33). Therefore, the rate of CO2
formation is higher than the rate of CO formation.
Another possible reason is that the produced CO is strongly adsorbed on the nickel catalyst at
lower
Catalyststemperatures
2019, 9, 946 [41]. From Figure 6, as the temperature increases, the CO* on the nickel surface6 of 12
decreases. Furthermore, the adsorbed O* can possibly form a non-stoichiometric nickel oxide at a
temperature around 523 and 623 K, and a nickel oxide around 723 K [42], leading to less O* to oxidize
fractional
CO* to formcoverages of C* and
CO2 at higher H* decrease,
temperatures. Forasthese
well reasons,
as O*, possibly
the CObecause of the increasing of the H2 ,
2 production rate is higher at lower
CO, and CO
temperatures, formation rates.
2 while CO production prefers a higher temperature.

Figure 7. Production rates as a function of the reaction temperature; P =

= 11 bar and y𝑦CH4 =
bar and = 0.4.

It is interesting
2.3. Effect of the Totalto note that
Pressure CO2 has a higher rate of production than CO, even though CO* can be
of Reactants
generated by several elementary reactions (steps 23, 24, 26, and 28). However, the CO2 * formation
As expected, when the total pressure increases from 1 to 5 bar, the surface coverages of the
(steps 25 and 30) by the adsorbed active O* and the CO* on the surface is easier (lower energy) than the
intermediates, especially CH3* and C*, increase, whereas the vacant sites significantly decrease.
formation of CO from the adsorbed C* and O* active species. Moreover, the Ea of the CO2 formation
Above a total pressure of 5 bar, the surface coverages of all of the species are relatively constant.
(step 32) is also lower than that for the CO desorption (step 33). Therefore, the rate of CO2 formation is
As mentioned in the previous study [43], the steam reforming reaction is not favored
higher than the rate of CO formation.
thermodynamically at high pressures. The effect of the total pressure is studied by varying the total
Another possible reason is that the produced CO is strongly adsorbed on the nickel catalyst at
pressure from 1 to 40 bar at 𝑦 = 0.5. As shown in Figure 8, the production rates are remarkably
lower temperatures [41]. From Figure 6, as the temperature increases, the CO* on the nickel surface
increased with increasing the total pressure up to 10 bar. However, when the total pressure is higher
decreases. Furthermore, the adsorbed O* can possibly form a non-stoichiometric nickel oxide at a
than 10 bar, the production rates are notably decreased.
temperature around 523 and 623 K, and a nickel oxide around 723 K [42], leading to less O* to oxidize
CO* to form CO2 at higher temperatures. For these reasons, the CO2 production rate is higher at lower
temperatures, while CO production prefers a higher temperature.

2.3. Effect of the Total Pressure of Reactants

As expected, when the total pressure increases from 1 to 5 bar, the surface coverages of the
intermediates, especially CH3 * and C*, increase, whereas the vacant sites significantly decrease. Above
a total pressure of 5 bar, the surface coverages of all of the species are relatively constant.
As mentioned in the previous study [43], the steam reforming reaction is not favored
thermodynamically at high pressures. The effect of the total pressure is studied by varying the
total pressure from 1 to 40 bar at yCH4 = 0.5. As shown in Figure 8, the production rates are remarkably
increased with increasing the total pressure up to 10 bar. However, when the total pressure is higher
than 10 bar, the production rates are notably decreased.
Catalysts 2019, 9, 946 7 of 12
Catalysts 2019, 9, x FOR PEER REVIEW 7 of 12

pressure; TT = 823 K and y𝑦CH4 =

Figure 8. Production rates as a function of the total pressure; = 0.5.

3. Model and
3. Model and Simulation
Simulation Procedure
Procedure

3.1. Model
3.1. Model
The kinetics of the nickel-catalyzed methane steam reforming were first studied, based on the
The kinetics of the nickel-catalyzed methane steam reforming were first studied, based on the
LH mechanism, by Xu and Froment [20]. The elementary reactions can be described by the following
LH mechanism, by Xu and Froment [20]. The elementary reactions can be described by the following
three main steps: adsorption, reaction, and desorption. After that, the microkinetic mechanism was
three main steps: adsorption, reaction, and desorption. After that, the microkinetic mechanism was
applied to study the steam reforming of methane over the Ni/NiAl2 O4 catalyst, and 24 elementary
applied to study the steam reforming of methane over the Ni/NiAl2O4 catalyst, and 24 elementary
reactions with 12 reversible reactions were proposed [39]. CH4 was adsorbed on the surface of the
reactions with 12 reversible reactions were proposed [39]. CH4 was adsorbed on the surface of the
catalyst by dissociating into C* and H*, while H2 O was dissociated into O* and H*. Moreover, a kinetic
catalyst by dissociating into C* and H*, while H2O was dissociated into O* and H*. Moreover, a kinetic
model on the nickel catalyst, including methane reforming and oxidation processes described by
model on the nickel catalyst, including methane reforming and oxidation processes described by 54
54 elementary-step reactions, was studied by Delgado et al. [24]. Among these elementary steps,
elementary-step reactions, was studied by Delgado et al. [24]. Among these elementary steps, 34 steps
34 steps were described as steam reforming of methane. Based on the elementary reaction steps
were described as steam reforming of methane. Based on the elementary reaction steps described
described above, Table 1 summarizes the elementary reactions as followed by the adsorption of
above, Table 1 summarizes the elementary reactions as followed by the adsorption of reactants (steps
reactants (steps 1–2), activation of methane without oxygen (steps 3–10), activation of methane with
1–2), activation of methane without oxygen (steps 3–10), activation of methane with oxygen (steps
oxygen (steps 11–18), dissociation of steam (steps 19–22), reaction (steps 23–31), and desorption of
11–18), dissociation of steam (steps 19–22), reaction (steps 23–31), and desorption of products (steps
products (steps 32–34).
32–34)
Our kinetic model was developed using the adsorption parameters from Sprung et al. [39], and
the surfaceTable
reaction and desorption
1. Elementary reactions parameters from Delgado
and corresponding kineticetparameters
al. [24], asusedshown in Table
in this work 1.
a. Steps 3, 4,

5, 6, 7, 8, 9, 11, 12, 14, 17, 20, 22, 24, 25, 26, 28, 30, 31, and 34 are assumed to be instantaneous (possibility
𝑬
of an event = 1), as(i)
Steps a result Elementary
of their very fast reaction
Reaction or 𝒌𝟎𝒊 kinetic
𝑨𝒊 (the (s−1 or Parate
−1s−1) is higher
β than𝒂𝒊 2.02 × 109 s−1 at
(kJ/mol)
858 K). 1 H2O(g) + [*] → [H2O*] 2.70 × 103 (𝑘 ) 0 0
According to2 these data, CHthe 4(g)adsorption
+ [*] → [CH4*]parameters2.87 of CH× 1043 and
(𝑘 ) H2 O are 0 2870 and 0 2700 Pa−1 sec−1 ,
3 b [CH *] + [*] → [CH *] + [H*] 4.10 × 10 12
respectively, at an average temperature of 858 K, and the adsorption rate (ki ) in steps 1–2 can be
4 3 0.087 55.8
4b [CH3*] + [H*] → [CH 4*] + [*] 3.83 × 1013 −0.087 63.4
calculated using Equation (4), where ki0 is the adsorption coefficient, yi is the mole fraction of CH4 or
5b [CH3*] + [*] → [CH 2*] + [H*] 4.10 × 1015 0.087 98.1
H2 O in the gas phase,6b and P 2is
[CH *] +the
[H*]total
→ [CHpressure.
3*] + [*] 8.22 × 1014 −0.087 57.2
7b [CH2*] + [*] → [CH*] + [H*] 9.84 × 1015 0.087 95.2
8b [CH*] + [H*] → [CH2*] + [*] ki = ki0 yi P 2.60 × 1016 −0.087 81.0 (4)
9b [CH*] + [*] → [C*] + [H*] 2.63 × 1012 0.500 21.9
The reaction10rate and[C*] + [H*] → [CH*]
desorption rate+ (k
[*] ) in steps 4.52
3–34× can −0.500 using
1015 be calculated 157.9 the Arrhenius
i
11 b [CH4*] + [O*] → [CH3*] + [OH*] 1.49 × 1016 −0.101 92.7
equation [28,44–47]
12 b
(Equation (5)), where Ai is+ [O*]
[CH3*] + [OH*] → [CH4*]
the pre-exponential
7.93 × 1013
factor, β 0.101
is the temperature
25.8
exponent,
Eai is the activation
13 energy,
[CH3*]R +is[O*]
the→gas 2*] + [OH*] and T is
[CHconstant, the× reaction
3.25 1016 temperature.
−0.101 134.6
14 b [CH2*] + [OH*] → [CH3*] + [O*] 3.70 × 1012 0.101 19.0
β

15 [CH2*] + [O*] → [CH*]
ki =+ A T
[OH*]
i exp −E /RT
3.25
ai × 10 16 −0.101 131.3 (5)
16 [CH*] + [OH*] → [CH2*] + [O*] 1.17 × 1014 0.101 42.4
17 b [CH*] + [O*] → [C*] + [OH*] 6.57 × 1012 0.312 57.7
18 [C*] + [OH*] → [CH*] + [O*] 6.46 × 1012 −0.312 118.9
19 [H2O*] + [*] → [H*] + [OH*] 9.76 × 1012 −0.086 92.9
Catalysts 2019, 9, 946 8 of 12

Table 1. Elementary reactions and corresponding kinetic parameters used in this work a .

Steps (i) Elementary Reaction Ai or k0i (s−1 or Pa−1 s−1 ) β Eai (kJ/mol)
1 H2 O(g) + [*] → [H2 O*] 2.70 × 103 (ki0 ) 0 0
2 CH4 (g) + [*] → [CH4 *] 2.87 × 103 (ki0 ) 0 0
3b [CH4 *] + [*] → [CH3 *] + [H*] 4.10 × 1012 0.087 55.8
4b [CH3 *] + [H*] → [CH4 *] + [*] 3.83 × 1013 −0.087 63.4
5b [CH3 *] + [*] → [CH2 *] + [H*] 4.10 × 1015 0.087 98.1
6b [CH2 *] + [H*] → [CH3 *] + [*] 8.22 × 1014 −0.087 57.2
7b [CH2 *] + [*] → [CH*] + [H*] 9.84 × 1015 0.087 95.2
8b [CH*] + [H*] → [CH2 *] + [*] 2.60 × 1016 −0.087 81.0
9b [CH*] + [*] → [C*] + [H*] 2.63 × 1012 0.500 21.9
10 [C*] + [H*] → [CH*] + [*] 4.52 × 1015 −0.500 157.9
11 b [CH4 *] + [O*] → [CH3 *] + [OH*] 1.49 × 1016 −0.101 92.7
12 b [CH3 *] + [OH*] → [CH4 *] + [O*] 7.93 × 1013 0.101 25.8
13 [CH3 *] + [O*] → [CH2 *] + [OH*] 3.25 × 1016 −0.101 134.6
14 b [CH2 *] + [OH*] → [CH3 *] + [O*] 3.70 × 1012 0.101 19.0
15 [CH2 *] + [O*] → [CH*] + [OH*] 3.25 × 1016 −0.101 131.3
16 [CH*] + [OH*] → [CH2 *] + [O*] 1.17 × 1014 0.101 42.4
17 b [CH*] + [O*] → [C*] + [OH*] 6.57 × 1012 0.312 57.7
18 [C*] + [OH*] → [CH*] + [O*] 6.46 × 1012 −0.312 118.9
19 [H2 O*] + [*] → [H*] + [OH*] 9.76 × 1012 −0.086 92.9
20 b [H*] + [OH*] → [H2 O*] + [*] 4.92 × 1011 0.086 41.5
21 [H*] + [O*] → [OH*] + [*] 1.05 × 1015 −0.188 104.3
22 b [OH*] + [*] → [H*] + [O*] 5.99 × 1011 0.188 29.6
23 [C*] + [O*] → [CO*] + [*] 9.04 × 1014 0 148.1
24 b [C*] + [OH*] → [H*] + [CO*] 1.03 × 1017 0.188 62.5
25 b [CO*] + [O*] → [CO2 *] + [*] 5.32 × 1010 0 123.6
26 b [CO2 *] + [*] → [CO*] + [O*] 1.23 × 1015 −1.000 89.3
27 [CO*] + [OH*] → [COOH*] + [*] 1.60 × 1013 0.213 97.6
28 b [COOH*] + [*] → [CO*] + [OH*] 3.88 × 1015 −0.213 54.3
29 [CO2 *] + [H*] → [COOH*] + [*] 1.66 × 1016 −0.475 117.2
30 b [COOH*] + [*] → [CO2 *] + [H*] 9.92 × 1011 0.475 33.6
31 b [H*] + [H*] → H2 (g) + [*] + [*] 6.76 × 1011 0 95.2
32 [CO2 *] → CO2 (g) + [*] 1.71 × 10−1 0 25.9
33 [CO*] → CO(g) + [*] 9.47 × 102 0 111.2
34 b [H2 O*] → H2 O(g) + [*] 9.92 × 103 0 60.7
Note: [*] = active site, [X*] = adsorbed X species. a Referenced from [24,39]. b Assumed instantaneous.

3.2. Simulation Procedure

In the simulation, the kMC model defines the surface of the catalyst as a two-dimensional square
lattice of L × L sites with periodic boundary conditions [34,48]. The lattice is in contact with an infinite
reservoir of methane (CH4 ) and steam (H2 O), with fixed feed concentrations. The kMC algorithm
consists of the following steps [33,36,45,49]:
(a) Set the lattice site and initial configuration for the simulation.
(b) Select one of the lattice sites randomly.
(c) Perform the instantaneous event (steps 3, 4, 5, 6, 7, 8, 9, 11, 12, 14, 17, 20, 22, 24, 25, 28, 30, 31, and
34). If the conditions for the selected site and its neighboring are satisfied, the surface reaction
will spontaneously take place.
(d) Calculate the possibility of an event i (pi ), as defined by Equation (6), where ki corresponds to the
rate constant of step i. An event i is chosen from the possible events, except for the instantaneous
event (steps 1, 2, 10, 13, 15, 16, 18, 19, 21, 23, 27, 29, 32, and 33). The possibility of each event
is between 0 and 1. This procedure is known in different sources as the Bortz–Kalos–Lebowitz
(BKL), the Gillespie algorithm, or the Random Selection method [50,51].

k
pi = P i (6)
ki

(e) Perform the reaction event i selected in step (d) according to the following processes:
Catalysts 2019, 9, 946 9 of 12

(e-1) Adsorption

• If the adsorption of H2 O (step 1) selected with a random number is 0 ≤ n ≤ p1 and

the selected site is vacant (*), the event is successful, and steam then adsorbs into the
site (H2 O*). If the site is occupied, the attempt is terminated.
• If the adsorption of CH4 (step 2) selected with a random number is p1 ≤ n ≤ p1 + p2 ,
the procedure will be similar to that of the adsorption of H2 O.
(e-2) Surface reaction

• If the surface reaction (steps 10, 13, 15, 16, 18, 19, 21, 23, 27, and 29) is selected with
a selection number is p1 + p2 ≤ n ≤ p1 + p2 + pevent , and the selected site in step (b)
is occupied by one of the reactants, a neighboring site next to the first site is then
chosen randomly. The event is successful when the latter site is occupied by the other
species of the same reaction. After that, the corresponding reaction is carried out, and
both sites are then replaced by the products or one other is empty. If both sites are
not occupied by the appropriate reactants, the attempt is terminated
(e-3) Desorption

• If the desorption of H2 , CO, or CO2 (step 31, 32, or 33, respectively) is selected with a
random number is p1 + p2 + preaction ≤ n ≤ p1 + p2 + preaction + . . . + pdesorption and the
selected site in step (b) is occupied by the product, the event is successful and the
product then desorbs from the site. The site is empty again because of the leaving of
the product. If the site is not occupied by product, the attempt is terminated.

(f) Update the time from t to t + ∆t by using Equation (7), where r is a uniformly distributed random
P
number between 0 and 1, L is lattice length, and ki is the summation of all of the reaction
constants, excluding the instantaneous events.

− ln(r)
∆t = (7)
L2 ki
P

(g) Repeat the algorithm from step (b) until the steady state is obtained.

The simulation was carried out over 80,000 Monte-Carlo cycles so as to avoid the non-equilibrium
behavior where one Monte-Carlo cycle equals L × L times for the events of adsorption, reaction, and
desorption. The production rate (Ri ), fractional coverage (θi ), and selectivity (Si ) were computed under
isothermal conditions, by taking the averages over the subsequent 80,000 Monte-Carlo cycles. The
production rates of produced H2 , CO, and CO2 were calculated by the numbers of product molecules
per lattice site in a unit of time.

4. Conclusions
The kinetic behavior of methane steam reforming on a nickel surface was studied using kMC
simulation. This technique could provide a better understanding of the reaction comprising of several
elementary steps. The snapshots at each reaction condition could hint at the events taking place on the
catalyst surface.
The simulation results were in good agreement with previous experimental results, and clearly
demonstrated that the reaction took place at both a low mole fraction of methane (yCH4 = 0.1) and a
high mole fraction of methane (yCH4 = 0.9), as a result of the high coverages of H* and O* at low yCH4 ,
and the high coverage of C* and CH3 * at high yCH4 , respectively. The methane mole fraction in a range
of 0.4–0.5 showed the maximum production rates of H2 and CO. At these mole fractions, the oxidation
of CHx * intermediates (steps 11, 13, and 15) became the crucial reactions allowing for the subsequent
elementary reactions to be carried out. The reaction temperature also played an important role on both
Catalysts 2019, 9, 946 10 of 12

the production rates and surface coverages. The catalyst surface was filled with CHx intermediates and
O* at the reaction temperature of 600 K. The catalyst surface was then almost completely covered by C*,
H*, and O* at 700 K. Furthermore, the effect of the total pressure illustrated that the production rates of
H2 and CO significantly increased from a total pressure of three bar, and reached a maximum at 10 bar.
Above 10 bar, the production rates of both H2 and CO remarkably dropped. All of the results described
above suggest the reaction conditions for obtaining the highest yield of hydrogen and/or syngas.

Author Contributions: Conceptualization, T.P. and B.K.; methodology, T.P.; software, T.P. and R.M.Z; validation,
P.U., S.P., B.K., and R.M.Z.; formal analysis, P.U.; investigation, T.P.; resources, T.P.; data curation, T.P.; writing
(original draft preparation), P.U.; writing (review and editing), P.U., S.P., B.K., and R.M.Z.; visualization, P.U.;
supervision, B.K.; project administration, P.U. and B.K.; funding acquisition, B.K.
Funding: This research was partially supported by the Center of Excellence on Petrochemical and Materials
Technology, Chulalongkorn University.
Acknowledgments: P.U. expresses his thanks to the Center of Excellence on Petrochemical and Materials
Technology, Chulalongkorn University, for his scholarship.
Conflicts of Interest: The authors declare no conflict of interest.

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