Chemical Engineering Journal 278 (2015) 62–78

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Review

Kinetic and mechanistic aspects for CO2 reforming of methane over Ni

based catalysts
Yasotha Kathiraser, Usman Oemar, Eng Toon Saw, Ziwei Li, Sibudjing Kawi ⇑
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117576, Singapore

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Kinetic and mechanistic review for

CO2–methane reforming over Ni
based catalyst.
 Langmuir–Hinshelwood type models
with rate determining steps of each
model.
 Characterization techniques and
insights for postulation of
mechanism.

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

Article history: In recent decades, CO2 utilization has become increasingly important in view of the escalating global
Available online 12 January 2015 warming phenomenon. In view of this, conversion of CO2 to syngas via CO2 (dry) reforming of methane
(DRM) reaction has been gaining prominent research interest. This paper presents a review on the kinetic
Keywords: and mechanistic aspects for DRM reaction with focus on Ni based catalysts. Ni-based catalysts are com-
CO2 reforming of methane mercially attractive due to the low cost and wide availability of Ni metal. Kinetic studies over the Ni
Ni catalyst based catalysts are vital in scaling up of the DRM process in order to assess its industrial viability. Many
Reaction kinetics
differing opinions have been formed for the rate determining steps (RDS) of the reaction kinetics. In this
Rate determining steps
Characterization techniques
review, a survey of the differing RDS presented in literature based on the widely used Langmuir Hinshel-
wood Hougen Watson (LHHW) models for Ni-catalyzed DRM reactions are categorized and presented
along with the importance of experimental techniques for justifying mechanistic formulation.
Ó 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2. Overview of CO2 reforming of methane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
3. Influence of process variables on reaction rates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
4. General applicable models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4.1. Power-law model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.2. Eley–Rideal (ER) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4.3. LHHW models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

⇑ Corresponding author at: Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576, Singapore.
Tel.: +65 65166312; fax: +65 6779 1936.
E-mail address: chekawis@nus.edu.sg (S. Kawi).

http://dx.doi.org/10.1016/j.cej.2014.11.143
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78 63

4.3.1. Brief history on kinetic studies for DRM–LHHW models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

4.3.2. Summary of possible elementary reactions from simulated studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3.3. Summary of kinetic reaction models from experimental studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4.3.4. Postulated LHHW models based on different RDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5. Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76

1. Introduction
During the past decade, there has been increasing global con-
cern over rise of anthropogenic CO2 emissions into Earth’s atmo-
sphere, estimated to be circa 25.7 Gt CO2 per annum [1]. The
reaction of CO2 with methane, which are also greenhouse gases,
into more valuable compounds is one of the important subjects
in catalysis, energy and environmental research since it provides
a pathway to reduce and recycle the greenhouse gases (CH4 and
CO2) [2–4]. In fact, CO2 reforming can also be used to convert
and utilize CO2-rich natural gas to increase the commercial value
[5]. In addition, CO2 (dry) reforming of methane (DRM) is regarded
as the basis for upgrading the calorific value of hydrocarbons for
the solar reforming of natural gas process, which has been termed
the most promising ‘‘solar thermochemical process’’ [6]. In addi-
tion, the generation of syngas via methane is one of the most tech-
nically advanced route for natural gas utilization [7].
The DRM reaction produces syngas can be converted into
hydrocarbons for specialty chemicals production via the Fischer–
Tropsch synthesis. Increase of environmental restrictions forcing
the reduction of exhaust emissions and interest in diminishing
dependence on petroleum, associated with the continuous increase
of probed natural gas reserves and the large scale conversion of
fresh organic waste into biogas, are factors that justify the great
deal of attention given to methane reforming processes [8]. DRM
is seen as an attractive alternative for steam reforming of methane
(SRM) as besides utilization of greenhouse gases, the lower H2/CO
product ratio than in conventional SRM is suitable for further usage
in the Fischer–Tropsch synthesis of long chain hydrocarbons [9].
DRM is highly endothermic and requires energy input for the
reaction to take place. Due to its requirement of external heat
exchange, it is a slow process involving long resident times and
hence poor transient responses [10]. Furthermore, a serious prob-
lem in the DRM reaction especially over Ni-based catalyst is the
rapid carbon deposition on the catalyst by CO disproportionation
(2CO ? CO2 + C) and/or methane decomposition (CH4 ? 2H2)
[11,12]. These two side reactions which occur and generate the
carbon deposits, eventually would destroy the catalyst particles
and block the reactor. Thereby, this leads to catalytic deactivation
[13,14]. As explained in greater detail by Liu et al. [15], coke forma-
tion by CO disproportionation is less favored at high temperatures
(700 °C and above), which are the DRM operating conditions. Dis-
sociation of methane occurs on Ni surface to generate highly reac-
tive Ca, which can be further gasified by reactions with H2O, CO2 or
H2. However, some are converted to the less reactive Cb which may
encapsulate on the surface or may dissolve in or encapsulate the
nickel crystallite based on kinetic balance of various reactions.
The dissolution of carbon in Ni is a key step for growth of carbon
whiskers, which can destroy the catalyst or block the reactor
[15,16]. However, with the recent development of solar energy or
other CO2-free energy, the energy requirements for the DRM reac-
tions can be supplemented and thereby minimize the high costs
required to meet the energy requirements. Hence, this paves way
for continuous interest in the DRM reaction to combat CO2
emissions and at the same time producing valuable syngas for
chemical industries.
Several reviews have been carried out in terms of DRM reac-
tions however so far, there is no review focusing solely on the
kinetic and mechanistic pathways especially with regards to the
RDS involved for the Ni based catalysts. Bradford and Vannice
[17] reviewed the DRM reaction in terms of the chemistry involved
and delved into the mechanism for activation of each of the reac-
tants. Details on mechanistic and kinetic aspects for studies done
on several types of catalysts for the DRM process were also pre-
sented. This was followed by Rostrup-Nielsen et al. [18] who con-
ducted an extensive review on syngas and H2 production via both
the DRM and SRM reactions industrially as well as the catalysts
involved with their corresponding issues and several kinetic and
mechanistic aspects. More recently, Fan et al. [19] gave an exten-
sive review on the catalyst in terms of metal and support used
for DRM and several CO2-co reforming of CH4 reactions. They also
touched on some kinetic studies and gave an overview of the DRM
process technologies currently in place. Liu et al. [15] have recently
covered a very important and relevant review on the preparation of
coke resistant Ni catalyst for SRM and DRM processes. In their
review, they have presented the different forms of catalyst as well
as highlighted the importance of plasma in the preparation of cat-
alyst. Furthermore, they highlighted the importance of density
functional theory study which can lead to improved design and
synthesis of coke resistant Ni-based catalysts. Most recently, Pak-
hare and Spivey [20] covered an extensive review on noble metals
for DRM reactions which includes some kinetic and mechanistic
aspects.
Hence, in this review, it is our aim of this review to give the
reader an overview into the reaction mechanism and kinetics per-
taining to DRM reactions for Ni based catalysts. The importance of
kinetics in terms of adsorption and desorption of reactive species
cannot be understated since it paves way for determining reliable
surface reaction mechanism of complex catalytic reaction schemes.
Kinetic studies are basically chemical steps performed in order to
identify a suitable mechanism model by correlating with experi-
mental data, giving a best-fit which most closely describes the rate
of reaction and defines the chemical process [21]. The reaction
kinetics which correlate to the developed mechanism can further
be used for optimization of the catalyst design and chemical sys-
tems (as this data is an important input in reactor modelling soft-
ware packages) [22] which can further lead to development of a
more cost-effective DRM technology. Ni based catalysts shall be
the priority of this review owing to its more economically viable
implementation industrially as well as its wide availability. This
review shall cover on the different proposed models and rate
determining steps and several experimentally proven mechanisms.
The differing opinions and findings for the RDS based on proposals
and experimentally proven techniques are presented as these are
salient features which can confirm the postulated mechanism
involved for the DRM reaction over certain catalyst configuration.
Some important characterizations shall also be covered as they
play a crucial role in confirming the postulated reaction pathway.
64 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78

2. Overview of CO2 reforming of methane

DRM involves a highly endothermic reaction (Eq. (1)). In fact,

the thermodynamics and equilibrium characteristics of CO2
reforming of methane are similar to the widely employed steam
reforming of methane (Eq. (2)) except that the former reaction pro-
duces synthesis gas with lower H2/CO ratio [17]:
1
CO2 þ CH4 ! 2CO þ 2H2 DH298 ¼ 247 kJ mol ð1Þ

1
CH4 þ H2 O ! CO þ 3H2 DH298 ¼ 228 kJ mol ð2Þ
Reverse water gas shift (RWGS) reactions which are likely to
occur simultaneously (Eq. (3)) influences the product syngas ratio
(H2/CO), pushing it to less than 1, since CO is produced more in this
reaction. The steam produced enables steam/carbon gasification
reaction to take place (Eq. (4)):
Fig. 1. Spontaneity of reactions occurring in DRM at different temperatures.
1
CO2 þ H2 ! CO þ H2 O DH298 ¼ 41 kJ mol ð3Þ
3. Influence of process variables on reaction rates
1
C þ H2 OðgÞ ! CO þ H2 DH298 ¼ 131 kJ mol ð4Þ
Extensive investigations have been initiated to study the influ-
Carbon deposition is the main reason for catalyst deactivation
ence of process variables on the catalyst performance for DRM
originating from methane cracking (Eq. (5)) and Boudouard reac-
reaction. In order to gauge the dependence of the reaction rates
tion (Eq. (6)):
for process parameters, these studies have been primarily aimed
1 at designing and developing suitable catalysts and at the elucida-
CH4 ! Cads þ 2H2 DH298 ¼ 75 kJ mol ð5Þ
tion of the intrinsic kinetics of the DRM reaction. Laboratory exper-
iments and derivation of intrinsic reaction rates are the initial steps
1
2CO ! Cads þ CO2 DH298 ¼ 75 kJ mol ð6Þ required to develop industrial reactors (see Fig. 2). On the other
hand, catalyst property is a pre-requisite for efficient DRM opera-
DRM poses the problem of severity in catalyst condition as
tions. In order to achieve a compromise between economic feasi-
there is no O2 directly involved in gasifying the carbon deposited
bility and efficiency in process, it is of primary importance to
on the catalyst surface [23] In order to reduce the carbon present,
accurately formulate the intrinsic kinetic models of the appropriate
carbon formed should be consumed by the reverse Boudouard
catalyst based on elementary steps, keeping in mind the influence
reaction (Eq. (6)) [24]. Otherwise there will be a net carbon depo-
of transport of reactants on reaction kinetics. Therefore, reaction
sition which in practice would lead to catalyst deactivation and
kinetics is essential for optimizing the catalyst design based on
reactor blockages. Furthermore the formation of carbon (Eqs. (5)
the knowledge of the rate determining steps and kinetic trends.
and (6)) are more favorable at low temperatures. Therefore the
In order to eliminate external mass transport resistance, differ-
DRM reaction temperature below 800 °C mainly forms carbon-
ent gas hourly space velocities (GHSV) have to be tested in order to
derived from both methane decomposition and Boudouard reac-
confirm that the conversions have reached a steady state value,
tions. The formation of carbon eventually leads to the suppression
such that a further increase in GHSV can still maintain the reactant
of catalyst activity. In addition, the occurrence of RWGS reaction
conversions. Regardless of temperature, various contact times do
decreases the mole ratio of H2/CO in the product stream. When
play an important part in CO2 and methane conversions. Only at
the DRM reaction temperature is above 800 °C, the deposition of
a higher value of contact time does the conversion of CO2 or meth-
carbon generated during CH4/CO2 reforming mainly originates
from CH4 decomposition and the carbon species is more reactive
than that generated from Boudouard reaction. Therefore, due to
the presence of CO2 in reforming process, the carbon formed can Intrinsic kinetic Catalyst
be easily oxidized [25]. RWGS reaction also contributes to the laboratory data design &
slightly higher CO2 conversion than CH4 in DRM reaction. optimization
Fig. 1 shows the spontaneity of main and side reactions occur-
ring in DRM at different temperatures ranging between 500 and
Intrinsic chemical kinetics
900 °C using a CO2/CH4 feed ratio of l/l at 1 atm pressure. It is note-
based on elementary
worthy to point out that at the reaction temperature of 700 °C, the
mechanistic steps
rate of methane decomposition is more spontaneous than the rate
of carbon oxidation by CO2, suggesting that the DRM reaction at
high CO2/CH4 ratios (>1) and high temperatures can minimize car- Transport phenomenon
bon formation in DRM reaction. However the CO2/CH4 ratio is gen- influence
erally close to 1 to ensure that side reactions which may occur
parallel to the DRM reaction such as Boudouard and RWGS, could
be minimized in order to produce syngas with the desirable H2/ Reactor design and
CO ratio. These calculated equilibrium conversions suggest that optimization for
kinetic experiments should be performed within the thermody- industrial level
namically feasible regions in order to minimize carbon formation
due to side reactions. Validation of the mechanistic model based Fig. 2. Catalytic process development from intrinsic kinetic laboratory experiments
on these kinetic data can then be conducted. to industrial reactor design.
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78 65

Table 1
EA values over different catalysts for the DRM reaction.

Catalyst Reactor type Total flow Cat Cat. ECH4 ECHx O decomposition ECO2 EH2 ECO Refs.
rate amount particle (kJ/mol) (kJ/mol) (kJ/mol) (kJ/mol) (kJ/mol)
(mL/min) (mg) size (lm)
Nickel supported catalyst
Ni/Al2O3 (773–973 K) Fixed Bed ID: (10 mm) 360 1–5 60 50.9 – 56.1 – 80.5 [26]
Ni/Al2O3 (673–773 K) Tubular U-shaped 100 10–50 – 70.6 – 69.0 98.1 74.0 [27]
Ni/SiO2 (673–773 K) Tubular U-shaped 100 10–50 – 62.3 – 69.8 93.9 68.9 [27]
Ni/Al2O3 (673–923 K) Fixed Bed Microreactor (8 mm) 28 500 – – – 64.4 – – [28]
Ni/Al2O3 (773–973 K) Fixed Bed (ID: 10 mm) 360 1–5 60 50.9 – 56.1 – 80.5 [29]
Ni/TiO2 (673–923 K) Fixed Bed Microreactor (8 mm) 28 500 – – – 59.8 – – [28]
4.82Ni–Al2O3 (1023–1123 K) Fixed Bed Microreactor 100–980 – – 242.67 – 115.86 – – [30]
Ni/C (673–823 K) Fixed Bed 20 5–100 210–360 121.4 – 92.1 134.0 100.5 [31]
Ni/SiO2 (673–823 K) Fixed Bed 20 5–100 210–360 96.3 – 79.6 113.0 83.7 [31]
Ni/MgO (673–823 K) Fixed Bed 20 5–100 210–360 92.1 – 87.9 146.5 87.9 [31]
Ni/TiO2 (673–823 K) Fixed Bed 20 5–100 210–360 108.9 – 87.9 134.0 96.3 [31]
Ni/La2O3 (923–1023 K) Fixed Bed (ID: 4 mm) 300 5–10 180–220 55.3 – – – – [32]
Ni/La2O3 (1023 K) Fixed Bed (ID: 4 mm) 200–400 5–10 40 Initial apparent activation energy: 80.0 kJ/mol [33]
After 2–5 h reaction: 62.7 kJ/mol
Ni/ZrO2 (723 K) Fixed Bed (ID: 4 mm) 170 300 300–600 58.62 – 41.87 – 50.244 [34]
Ni/MgOSiO2 (723 K) – – – – 41.87 – – – – [35]
Promoted nickel supported catalyst
Ni/CaO–Al2O3 (893–963 K) Fixed Bed (ID: 9 mm) 100 20–40 100–150 106.8 – 98.8 147.4 103.0 [36]
Ni/CeO2–Al2O3 (773–973 K) Fixed Bed (ID: 10 mm) 360 1–5 60 50.5 – 77.0 – 87.0 [29]
13.5Ni–2K/10CeO2–Al2O3 Fixed Bed (ID: 16 mm) 400 50 200–1000 113.8 119.3 – – – [37]
(823–1073 K)
Ni/La2O3 from LaNiO3 Fixed Bed (ID: 6 mm) 100–300 2–10 – 68 – 77 – – [38]
(773–973 K)
Bimetallic Ni-based catalyst
5Co–15Ni/Al2O3 Fixed Bed (ID: 4.57 mm) – – 140–250 56.4 – – – – [39]
2.5Ce–5Co–15Ni/Al2O3 Fixed Bed (ID: 4.57 mm) – – 140–250 54.52 – – – – [39]
Ni–Co/Al–Mg–O Fixed Bed (ID: 6 mm) 300 10 165 69.4 – 25.9 85.1 61.8 [40]
0.3Pt–10Ni Fixed Bed (ID: 6 mm) 100 5 250–425 26.9 – 23.6 24.9 35.8 [41]
0.2Pt–15Ni Fixed Bed (ID: 6 mm) 100 5 250–425 26.6 – 16.9 21.0 35.2 [41]
Other Ni-based catalyst
LaSrNiO4 (633–713 K) Fixed Bed (ID: 10 mm) 60 200 – 41.8 – 12.4 – – [42]

ane remain unaffected. Hence, by eliminating effect of mass trans-
port, the conversions observed can be directly attributed to the
intrinsic kinetics of the catalysts. Since the particle size of a cata-
lyst is also known to play an important role in affecting the internal
mass transport resistance, the particle size should be as small as
possible such that a further decrease in size does not affect the
conversions.
Since DRM is an endothermic reaction, higher CH4 conversion
can be obtained with an increase in temperature due to the
enhanced reaction rate at higher temperatures. Therefore, reaction
temperature is an important process variable in determining the
reactant conversions as well as controlling the side reactions which
may occur parallel to the main reforming reactions.
Table 1 shows the activation energy, EA values of different reac-
tants and products in DRM reaction obtained over different types
of Ni-based catalysts. The variation in the obtained activation
energy values indicate that different type of catalyst support, pro-
moter as well as bimetallic interactions of the catalyst play an
important role in influencing the activation energy.
Table 1 also shows that the activation energies for DRM reaction
over different Ni-supported catalysts vary from 26 to 243 kJ/mol.
Most of the higher values were obtained for the formation of H2
and CO products as well as for CH4 decomposition. The EA for H2
formation for most of the studies was higher than those for CO for-
mation, implying the significance of the occurring RWGS reaction
which affects the apparent activation energies during DRM. This
observation shows that the initial activation of methane alone does
not determine the rate for most of the catalysts, as the activation
energy for final decomposition of its intermediates to hydrogen
(as observed by EH2 ) was quite high for several catalysts. High EA
for CO formation (either via C oxidation or reverse Boudouard reac-
tion) was also observed for several other catalysts.
Typically, a high flow rate and low catalyst amount with small
particle size play a role in minimizing the amount of external and
internal mass transfer limitations. Low GHSV is expected to lead to
serious mass transfer limitations. Surprisingly, Table 1 shows that
the Ea values obtained for several studies utilizing low mass flow
rates (i.e. low GHSV) were still high [28,31] in contrast to the
expected low Ea values caused by mass transfer effect. For example,
Kim et al. [28] explored the usage of CO2-photoacoustic signal
(PAS) to kinetically analyze the DRM reaction. A photoacoustic sig-
nal is created when a material absorbs a modulated laser beam and
generates heat periodically. Therefore, this is the possible reason
for the utilization of low mass flow rates. They stressed that it is
important not to miss any particular features of kinetic curves such
as the point of the inflection, a short induction period or break-
points, etc. which serve as finger-prints of the reaction mechanism.
PAS has been found to be a suitable technique for in situ monitor-
ing of catalytic reactions since direct measurement of absorption
characteristics of samples can be observed [43,44]. Therefore, the
outcome from all the data compiled shows that there is no specific
GHSV that can be fixed and this asserts the importance of prelimin-
ary studies in order to eliminate the effect of mass transfer limita-
tion on the development of the intrinsic kinetic models.
4. General applicable models
In this section, we shall cover the following models which are
typically used for DRM reactions:
66 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78

(i) Power law model. Eley–Rideal (ER) type of models and Langmuir Hinshelwood–Hou-
(ii) Eley Rideal (ER). gen–Watson (LHHW) are used. Nevertheless, the power law model
(iii) Langmuir Hinshelwood–Hougen Watson (LHHW). can be used for initial guess estimates in order to solve more com-
plex models which require larger amount of data.
Among these models, LHHW models have received greater
attention (as shall be seen in Section 4.3) due to the conformity 4.2. Eley–Rideal (ER) model
of most of the mechanistic steps proposed with experimental tech-
niques for confirmation. In this section, * shall be used to represent Mark et al. [50] have shown the models based on the ER mech-
unoccupied active sites for all the mechanistic steps. anism (ER I or ER II) as shown in following equations:
Basic reaction (B):
4.1. Power-law model kRef
ðaÞ CH4 þ CO2 () 2CO þ 2H2
Power-law models support the kinetic rate for DRM reaction in !
the form of: P2CO P2H2
rRef ¼ kRef PCH4 PCO2 
K Ref
r ¼ k½PCH4 m ½PCO2 n
Generally this simple model provides a rough estimation of the Eley–Rideal model I (ER 1):
parameters required and do not represent the kinetics of the reaction KCH
4 ½CH4  
inawholesomemannerapplicabletoawiderangeofcatalysts.Table2 ðaÞ CH4 þ  () CH4   KCH4 ¼
PCH4 ½
shows the value of these power-law rate coefficients for Ni-based cat-
alysts based on the rate of CH4 consumption.
kRef
It can be seen from Table 2 that, even though similar supports ðbÞ CH4 þ CO2 () 2CO þ 2H2 þ  RDS
were used for some of the Ni-based catalyst, such as Ni/SiO2
 
[35,45,46], the power constants that were obtained differ in values. P2CO P2H
For most of the catalysts, the power constant for methane partial kRef KCH4 PCH4 PCO2  K 2
Ref

pressure (m) is close to unity, indicating that more methane is rRef ¼

1 þ KCH4 PCH4
adsorbed on the species thus dominating the reaction. Whereas
the power constant for CO2 partial pressure (n) is generally much Eley–Rideal model II (ER II):
less, indicating the presence of CO2 adsorptive term in the denom- KCO
2 ½CO2  
inator. Based on the Pulse Surface Reaction Analysis (PSRA) results ðaÞ CO2 þ  () CO2   KCO2 ¼
PCO2 ½
reported by Osaki et al. [48], Ni/SiO2 catalysts were found to be
hydrogen deficient on the surface, indicating its affinity to carbo-
kRef
naceous formation, i.e. fast decomposition of methane. PSRA is an ðbÞ CO2   þ CH4 () 2CO þ 2H2 þ  RDS
interesting analysis which can reveal the structure of the reaction
intermediate as it enables measurement of the reaction dynamics  
P2CO P2H
of reactant or product molecule [49].Their results which are sup- kRef KCO2 PCH4 PCO2  K 2
Ref
ported by PSRA technique shows that the presence of carbon due rRef ¼
1 þ KCO2 PCO2
to the fast formation rate of carbon plays a part in suppressing
the obtained orders of the DRM reaction. In ER model, one reactant is assumed to be associatively
Therefore the main advantage of these power-law models is the adsorbed on the catalyst surface at adsorption equilibrium. The
simplicity in application and parameter estimation. However, from slow and rate-determining step (RDS) is the reaction of the
different mechanistic schemes and over a wider range of partial adsorbed species with the other reactant from the gas phase lead-
pressure data, these models cannot sufficiently explain the various ing directly to the products. As both reactants can theoretically be
reaction mechanistic steps which take place on the catalyst sur- the adsorbed species, both resulting models (ER I and II) can be
face. Since it is crucial to understand the mechanistic aspects of considered, i.e. gaseous CO2 reacting with adsorbed CH4 or gaseous
the DRM reforming reaction, more rigorous models such as CH4 reacting with adsorbed CO2.

Table 2
Kinetic rate law constants for Ni based catalysts in DRM reaction.

Catalyst r CH4 r CO2 r CO r H2 Refs.

m n m n m n m n
Ni/SiO2 0.44 0.15 0.27 0.64 0.18 0.44 0.49 0.11 [31]
Ni/SiO2 0.8 – – – – – – – [35]
Ni/SiO2 0.02–0.05 0.5–0.6 – – – – – – [45]
Ni/SiO2 0.30 0.16 – – – – – – [46]
Ni/Al2O3 – – 0.48 0.45 – – – – [28]
Ni/Al2O3 0.9–1.08 0.83–1.77 – – – – – – [29]
Ni/CeO2–Al2O3 1.04–1.12 0.55–0.97 – – – – – – [29]
Ni/MgO 0.61–0.72 0.01–0.05 0.52–0.60 0.27–0.36 0.57–0.64 0.15–0.21 1.16–1.22 0.36–0.54 [29]
Ni/TiO2 0.13–0.4 0.18–1.55 0.43–0.86 0.22–0.41 0.44–0.67 0.1–0.3 0.9–1.76 0.61–0.15 [29]
Ni/TiO2 – – 0.38 0.32 – – – – [28]
Ni/C 0.72 0.77 0.45 0.54 0.33 0.43 1.03 0.05 [31]
13.5Ni–2K/10CeO2–Al2O3 0.91–1.0 0.32–0.45 0.42–0.45 0.32–0.46 0.44–0.57 0.18–0.29 0.88–0.96 0.08–0.2 [37]
La2xSrxNiO4 0.89–0.41 0.18–0.10 0.18–0.23 0.93–1.04 – – – – [42]
Pt–Ni/Al2O3 1–1.09 0.87–1.40 – – – – – – [41]
Ni–C – – – – 0.17 0.43 0.39 0.06 [47]
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78 67

There are not many literatures for ER formulated models for CH4 þ  $ CHx  þð4  xÞ=2H2
DRM reaction over Ni-based catalysts. Among the few, Akpan
et al. [51] have conducted DRM studies over Ni/CeO2–ZrO2 catalyst CHx  þCO2 $ 2CO þ x=2H2 þ 
in a packed bed tubular reactor. The kinetic model that best pre-
Here, the CO2 gas phase was assumed to react directly with the
dicted their experimental rates was developed based on the ER for-
adsorbed methyl species to form syngas. They derived their kinetic
mulation, assuming the methane dissociative adsorption as the
equations based on the above mechanism, whereby reaction rate 1,
rate-determining step. The validity of their ER kinetic model was
r1 refers to the reforming step and reaction rate 2, r2 as shown
tested against the experimental data and a satisfactory agreement
below refers to the RWGS reaction which was included as an inde-
between the model prediction and measured results was obtained.
pendent side reaction:
The reaction mechanism that they postulated was based on rele-
 
vant literature data that they have compiled and are given as P2 P2H
k1 KCH4 PCH4 PCO2  COK1 2
follows:
r1 ¼  
1 þ KCH4 PCH4
CH4 þ 2 $ CH3ðÞ þ HðÞ
 
PCO PH2 O
CH3ðÞ þ  $ CH2ðÞ þ HðÞ r2 ¼ k2 PCO2 PH2 
K2
CH2ðÞ þ  $ CHðÞ þ HðÞ The EA values obtained for the reforming and RWGS reactions
were 107 and 64.8 kJ/mol, respectively. Their results appear to con-
CHðÞ þ  $ CðÞ þ HðÞ form to some of the LHHW model values available in the literature
as there are only scarce reported data for ER models.
CðÞ þ Ox $ CO þ Ox1 þ  Based on the findings of ER models for DRM reactions above for
Ni based catalysts, we can see that the findings of Akpan et al. [51]
CO2 þ Ox1 $ Ox þ CO and Becerra et al. [53] both follow ER model 1, whereby gaseous
CO2 is found to react with adsorbed CH4.
4HðÞ $ 2H2 þ 4 In the case of noble metal catalysts, it has been reported by
Erdohelyi et al.[54] that Al2O3-supported Rh catalysts undergo ER
H2 þ Ox $ Ox1 þ H2 O type of mechanism, whereby CH4 is adsorbed and decomposed
on the metal (Rh) to H2 and adsorbed C and the carbon on the cat-
where * and Ox represent unoccupied active sites and lattice oxygen alyst then reacts directly with the CO2 from the gas phase to yield
on their support surface, respectively. Akpan et al. [51] also devel- CO as follows:
oped four rate equations based on different rate determining steps
as follows: CH4 þ 2 $ CH3ðÞ þ HðÞ
Model 1: Adsorption and/or dissociation of CH4:
  CH3ðÞ þ  $ CH2ðÞ þ HðÞ
N2 N2
k0 eE=RT NA  KCP NBD
Model#1 : rA ¼  5
N2 1 CH2ðÞ þ  $ CHðÞ þ HðÞ
1 þ KA NCB þ KB N2D
CHðÞ þ  $ CðÞ þ HðÞ
Model 2: Surface reaction of solid carbon with lattice oxygen:
 
N2
k0 eE=RT NN2A  KP NC B CðÞ þ CO2 $ 2CO þ 
Model#2 : rA ¼  D
1

N2 From the below sets of equations, it can be seen that hydrogen
1 þ KA NCB þ KB N2D
can enhance the rate of CO2 dissociation. In fact, if there is a surface
Model 3: Surface reaction of reduced site with CO2: CH2 species, CO2 was proposed to directly gasify the surface spe-
! cies to CO and H2O. Furthermore, the presence of OH group was
NA NB NC postulated to react with CH to form CO and H2 as follows:
Model#3 : r A ¼ k0 eE=RT 
NC N2D KP
CO2 þ HðÞ $ COðÞ þ OHðÞ
Model 4: Surface reaction of two adsorbed hydrogen atoms:
  CH4 þ OðÞ $ CH3ðÞ þ OHðÞ
N2
k0 eE=RT NNA N2 B  KDP
Model#4 : rA ¼  C
1
4 CHx þ OðÞ $ COðÞ þ xHðÞ
N2
1 þ KA NCB þ KB N2D
2OHðÞ $ H2 O þ OðÞ
Based on their calculations, Akpan et al. [51] suggest CH4 disso-
ciation to be the RDS, as their obtained EA for CH4 dissociation is in
CH2 þ CO2 $ CO þ H2 O
the similar range as reported by previous studies using LH model
[52]. Thus, they finalized their rate equation as follows:
CH þ OH $ CO þ H2
 
N2 N2 However, prior to the findings of Erdohelyi et al. [54], Richard-
2:1  1017 e222800=RT NA  KCP NBD
r A ¼  5 son et al. [55] found that a simplified LH mechanism was sufficient
1
1 þ 34:3N2D based on the rate determining reaction between adsorbed CH4 and
CO2 to final products over Rh/Al2O3. From here, we can see that
Becerra et al. [53] did DRM reaction kinetic study for Ni/Al2O3 even for noble metal catalysts, the proposed kinetic models differ
and found that their reaction kinetics fitted better into the ER from different investigations over the same catalyst-support
model using the following reaction steps: combination.
68 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78
In order to analyse the differences between ER and LHHW mod-
els, Mark et al. [50] have conducted a comparison test study based
on the ER and LHHW rate models for Ir/Al2O3 catalysts with 1:1
CH4 and CO2 mixture within 700–850 °C. Their results show that
the fitting quality of the parameters for the models followed the
order of ER 1 < LH < ER II. Fitting of the experimental rata based
on the basic reaction equation (B) as shown in the beginning of this
section, leads to an apparent activation energy of 230 kJ/mol (with
only small standard deviation). From their model, Mark et al. [50]
proposed that the reaction rate of DRM is determined by the disso-
ciative adsorption of CH4 due to the formation of active carbon and
hydrogen species. However, in the fast second reaction step, which
is thermodynamically controlled, the carbon species undergoes
Reverse Boudouard reaction to form CO. Under higher reaction
temperature region, it was confirmed that methane decomposition
was the RDS. On the other hand, for the other temperature regions,
neither the LH model nor the ER model could adequately describe
the kinetics of CO2 reforming over the whole temperature range.
Among these 2 models, they postulated that the LH model
appeared to provide a more-realistic reaction kinetic model of
comparable fitting quality especially in the low temperature range
of <720 °C since methane decomposition controls at higher reac-
tion temperature regime.
It is incidental that there is less literature coverage on ER mod-
els for Ni-based catalysts and even further lack of experimental
evidence in some studies pertaining to ER models which pose the
ambiguity of gas phase reactions with a surface adsorbed reactant
for DRM reaction. On the other hand, LHHW models appear to have
wider coverage in literature with greater applicability to Ni based
catalysts and are therefore discussed more adequately in the next
subsection.
4.3. LHHW models
Most of the reaction mechanisms proposed for the DRM reac-
tion are based on the LHHW formalism. In the LHHW model it is
assumed that one reaction step is slow and rate determining while
the others are in thermodynamic equilibrium [50]. LHHW based
kinetic models are usually derived from reaction mechanisms
involving dissociative adsorption of the reactants CH4 and CO2 fol-
lowed by rate-determining surface reaction of the adsorbed species
to the final products, H2 and CO.
4.3.1. Brief history on kinetic studies for DRM–LHHW models
Although the first reaction mechanism for DRM was proposed
by Bodrov and Apel’baum [56] in 1967, however, in recent years
most of the investigations for reaction mechanism were derived
based on LH model which were referenced from the extensive LH
steps presented by Xu and Froment [57] for their study on Ni/
MgAl2O4 catalyst for steam reforming of methane (SRM) reactions.
The important postulations applicable for the DRM reaction
based on the LHHW model of Xu and Froment [57] for SRM are
as follows:
CH4 þ  $ CH4 
CH4  þ $ CH3  þH
CH3  þ $ CH2  þH
CH2  þ $ CH  þH
CH  þ $ C  þH
CH2  þO $ CH2 O  þ
CH2 O  þ $ CHO  þH
CHO  þ $ CO  þH  ðRDSÞ
CO  þO $ CO2  þ  ðRDSÞ
CHO  þO $ CO2  þH  ðRDSÞ
CO $ CO þ 
CO2  $ CO2 þ 
2H $ H2  þ
H2  $ H2 þ 
However Rostrup-Nielsen [18] countered on the proposed mecha-
nism by Xu and Froment [57] by stating that methane dissociation
is shown not to proceed via the adsorbed precursor state. Rostrup-
Nielsen’s [18] argument appeared to be more realistic as it is gener-
ally accepted that the activation of methane is rate determining.
Using the postulation that CH4 dissociation is the rate determining
step, a LHHW model for DRM was developed by Zhang and Verykios
[58] based on the investigation of DRM reaction kinetics over
17 wt% Ni/CaO–Al2O3 catalyst. Furthermore, Xu and Froment [57]
found that their result has negative heat of adsorption of steam
which appears to deviate from the acceptable trend, however, its
value is not significant. This shows that there is generally no mutual
agreement on the rate determining steps for LHHW models which
shall be further described in the following sections.
4.3.2. Summary of possible elementary reactions from simulated
studies
According to Jones et al. [59], various reactions which proceed
via the dissociation of diatomic molecules can have drastically dif-
ferent over-all reaction energies, DEA. They have reiterated the use-
fulness in expressing microkinetics in terms of the approach to
equilibrium instead of using the product pressure and reaction
energy to describe the given reaction. Reactions with drastically
different reaction energies all follow the same microkinetic model
for a given approach to equilibrium, but a given approach to equi-
librium will correspond to very different product pressures for the
various reactions. This concept greatly applies to DRM as well due
to the heterogeneous metal–support nature of the catalysts.
Table 3, as compiled by Zhu et al. [60] shows the simulated ele-
mentary reactions involved in the DRM reaction calculated using
DFT modeling. Based on previous investigations [31,46] and as
summarized in Table 4, the reaction mechanism for DRM reaction
over Ni based catalysts involves: (1) Adsorption of methane on
active metal nickel sites in a dissociative form to produce hydrogen
and hydro-carbonate species CHx (0 6 x < 4); this process is nor-
mally regarded as a slow kinetic step. (2) Adsorption of CO2 on
either metal nickel sites or basic support surface to form carbonate
(CO2 
3 )/bicarbonate species (HCO2 ), followed by direct CO2 dissoci-
ation to CO and O which combines with H to form OH groups, or H-
assisted decomposition to produce CO and OH groups, respectively.
The later process participates in the reaction mechanism through
the RWGS reaction. (3) The surface OH groups on the support react
with adsorbed CHx intermediates to yield a formate-type interme-
diate, CHxO, which decomposes to yield H2 and CO. In this case, the
support may serve as a sink for surface hydroxyl groups, such that
the active site for the formation and subsequent decomposition of
CHxO may be at the metal–support interface. (4) These CHxO spe-
cies can also be created by the reaction of adsorbed CHx intermedi-
ates with O which originates either from CO2 direct dissociation or
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78 69

Table 3
Possible elementary reactions involved in DRM reaction [60].

Elementary reaction Ea,f (eV) Ea,r (eV) Reaction pathway

1 CH4(g) + * M CH4* 0 0.02 CH4 adsorption
2 CH4* M CH3* + H* 0.91 0.90 CH4 dissociation on metal
3 CH3* M CH2* + H* 0.70 0.63
4 CH2* M CH* + H* 0.35 0.69
5 CH* M C* + H* 1.33 0.81
6 H* + H* M H2* 0.92 0.06 Desorption of H2
7 H2* M H2(g) 0.22 0
8 CO2(g) + * M CO2* 0 0.02 CO2 adsorption
9 CO2* M CO* + O* 0.67 1.65 CO2 direct dissociation
10 CO2* + H* M COOH* 1.13 0.85 H-assisted CO2 activation and dissociation
11 COOH* M CO* + OH* 0.57 1.65
12 O* + H* M OH* 1.35 1.16 Surface OH groups involved oxidation of adsorbed CHx fragments and subsequent decomposition
13 CH3* + OH* M CH3OH* 2.20 1.61
14 CH3OH* M CH2OH* + H* 0.88 0.69
15 CH2* + OH* M CH2OH* 1.32 0.60
16 CH2OH* M CHOH*+H* 0.53 0.90
17 CH* + OH* M CHOH* 1.48 0.80
18 CHOH* M COH* + H* 0.15 0.86
19 C* + OH* M COH* 1.46 2.01 Surface carbon hydroxylation and subsequent decomposition
20 COH* M CO* + H* 0.98 1.97
21 CH3* + O* M CH3O* 1.59 1.31 Surface O atom oxidation of adsorbed CHx fragments and subsequent decomposition
22 CH3O* M CH2O* + H* 0.93 0.64
23 CH2* + O* M CH2O* 1.45 0.95
24 CH2O* M CHO* + H* 0.36 0.74
25 CH* + O* M CHO* 1.53 1.08
26 CHO* M CO* + H* 0.20 1.48
27 C* + O* M CO* 1.59 2.94
28 CO* M CO(g) 1.92 0 Desorption of CO
29 OH* + H* M H2O* 1.33 0.92 Desorption of H2O
30 H2O* M H2O(g) 0.29 0

Ea,f: activation energy for forward elementary reaction

Ea,r: activation energy for reverse elementary reaction.

the cleavage of OH groups; this step is also considered as a rate-
determining step.
Although the rate-determining steps involved in the DRM to
synthesis gas over supported Ni catalysts have been studied exten-
sively [61–64] however they were mainly focused on CH4 dissoci-
ation and the surface reaction of CHx and O. Moreover, the model
developed by Aparicio [56] indicated that there is no single rate-
determining step in methane reforming. The inconsistency among
these reaction mechanisms originated from the nature of the cata-
lysts (such as the particle size of Ni, the properties of support and
the interaction between metal nickel and support) and the reaction
conditions they applied.
4.3.3. Summary of kinetic reaction models from experimental studies
Table 4 as follows shows a summary of kinetic reaction models
with the associated rate constants determined from experimental
data obtained from DRM reaction. Therefore, in the following sec-
tions, we shall look further into each reaction step which has been
experimentally proven for some of the kinetic models developed in
recent years, followed by a brief summary of the classical experi-
mental techniques for model validation.
4.3.4. Postulated LHHW models based on different RDS
Below are the key steps involved in DRM reaction:
a. Dissociation/activation of CH4 and CO2.
b. Adsorption of elemental and intermediate C, H and O species
on active sites.
c. Formation of product species via surface reaction.
d. Desorption of product species, i.e. CO, H2, H2O.
Among these steps, CH4 and CO2 dissociation or activation are
often considered to be the RDS. However, as we can see in the
following sub-sections, several investigations done in recent years
have unravelled various different steps to be the RDS. Some of
these were assumed from literature and several advanced charac-
terization techniques (which are elaborated further in this section)
which prove beneficial in determination of the reaction mecha-
nism. Among the characterization technique used, the more com-
mon techniques are the in situ DRIFTS analysis, XPS, XRD,
temperature programmed techniques, SSITKA techniques and
TGA. One technique which deserves special mention but is not
widely used in publications pertaining to kinetic and mechanistic
study for DRM reaction is the X-ray absorption spectroscopy which
includes: (a) X-ray Absorption Near Edge Structure (XANES) which
provides crucial information of the metal particle size and metal
support interaction; and (b) Extended X-ray Absorption Fine Struc-
ture (EXAFS) which provides evidence of the metal oxidation state
[71]. This is one of the most incisive methods for characterization
of supported metal nano-catalysts. By performing the appropriate
curve fitting technique, the important information of EXAFS can
be processed [72]. The main information which can be elucidated
from the EXAFS analysis are the (i) distances between central
and neighboring atoms (bond length); (ii) the number of neighbor-
ing atoms (coordination number); (iii) the nature of neighboring
atoms (their approximate atomic number) and (iv) changes in cen-
tral-atom coordination with changes in experimental conditions
[72,73]. Another important EXAFS feature is that structures can
be studied in non-crystalline forms (including liquid and frozen
solutions) and where small particles of chemically active elements
are dispersed on a suitable support. The specific requirements for
these experiments necessitate special in situ cells in which the
experiments can be performed. Wang et al. [73] studied the mech-
anism of metal particle growth during reduction of the monome-
tallic Ni or Co and the bimetallic Ni–Co catalysts for DRM
reaction using XANES and EXAFS analysis. They could elucidate
70 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78

Table 4
Summary of kinetic reaction models developed for CO2 reforming of methane.

Catalyst Rate model Temp range (°C) Refs.

CH4 activation by metal Ni as RDS

Ni/Al2O3, Ni/CaO–Al 2O3 aPCH4 P2CO 500–850 [58]
r ref ¼  2
2
aþbP2CO þcPCH4
2

RDS: *–CH4 ? *–C + 2H2

Surface reaction between adsorbed CH3 and adsorbed CO2 as RDS
 
Ni–Rh–Al2O3 pCH pCO
4 2
p1:5 p2
H2 CO
505–625 [65]
k1 KCH4 KCO2  Kref
p0:5
H2
r ref ¼  2
pCH
1þ 4 þpCO KCO2
p0:5 KCH 2
H2 4
332:0452:40
k1 ¼ 3:59  1021 exp RT
 
KCH4 ¼ 2:89  108 exp 109:6857:53
RT
8 125:3939:11
KCO2 ¼ 3:53  10 exp RT
RDS: *–CH3 + *–CO2 ? 2CO + 2H2 + 2*
Surface reaction between CHx and adsorbed O as RDS
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Ni/SiO2, MoS2 and WS2 kref KCH4 KCO2 PCO2 PCH4 600–800 [66]
r ref ¼  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2
1þ KCH4 PCH4 þ KCO2 PCO2

RDS: CHx.–* + O–* ? CO + x/2H2 + 2*

C oxidation as RDS
Ni/SiO2 k3 K 1 K 2 PCH4 PCO2 PCO P2H 680–720 [67]
r ref ¼  2
2
PCO P2H þK1 PCH4 PCO þK2 PCO2 P2H
2 2

K1 = 108
K2 = 22.66
K3 = 4.850  104 (mol s1 g cat1)
RDS: C–* + O–* ? CO + 2*
Ni/La/Al2O3 r ref ¼
kref PCH4 PCO2 700–900 [68]
ð1þK 1 PCH4 þK 2 PCO Þð1þK 2 PCO2 Þ
Kref = 0.00445 mol s1 g1 catalyst atm
2
, K1 = 0.52 atm1, K2 = 10 atm1, K3 = 27 atm1
RDS: C–* + O–* ? CO + 2*
Ni/Al2O3, Ni/CeO2–Al2O3 r ref ¼
kref PCH4 PCO2 500–700 [29]
ð1þKCH4 PCH4 Þð1þKCO2 PCO2 Þ
Ni/Al2O3 :
k1 = 0.2–0.32 (lmol gcat s kPa), K1 = 8.2  104–3.5  10–2 kPa, K2 = 0.43–4.3 kPa
Ni/CeO2–Al2O3:
k1 = 0.21–1 (lmol g cat s kPa), K1 = 1.3  1010–7.6  10–10 kPa, K2 = 0.9–22.8 kPa
RDS: C–* + O–* ? CO + 2*
pffiffiffiffiffiffiffiffipffiffiffiffiffiffiffiffi
Ni–Co/Al2O3, Ce–Co–Ni/Al2O3 krxn PCH PCO2 650–750 [39]
rCH4 ¼  pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi4 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1þ KCH4 PCH4 1þ KCO2 PCO2
E 
krxn ¼ A exp RTa
DHads;CH
KCH4 ¼ expðDSadsR;CH4 Þ expð RT 4 Þ
DS  DHads;CO
ads;CO2
KCO2 ¼ exp R expð RT 2 Þ
RDS: C–*1 + O–*2 ? CO–*2 + *1
Reverse Boudouard reaction as RDS
Ni/Al2O3 r CH4 ¼ ð1þK 1 PCH
k1 PCH4 PCO2 500–700 [26]
4
Þð1þK 2 PCO2 Þ
2
k1 = 0.2–0.32 lmol/g cat s kPa
K1 = 0.00082–0.035 kPa1
K2 = 4.3–0.43 kPa1
RDS: *–C + *–CO2 ? 2CO + 2*
Ni–Co/Al–Mg–O aPCH4 PCO2 650–750 [40]
rCH4 ¼ bPCH þcPCO2 þdPCH4 PCO2
4

a = CMTCSTK1k2K3k4
b = K1k2
c = CSTK3k4
d = CSTK1K3k4
RDS: *–CO2 + M–C ? 2CO + M + *
2 step-single site RDS: CH4 activation by metal Ni and CHxO decomposition as RDS
Supported Ni r ref ¼  
k1 PCH4 PCO2
h   i 400–450, 500–550 [31]
k1 K ð4xÞ=2 k1
k7
PCO PH þ 1þ k7
PCH4 PCO2
2

ki = kiL, L = total number of active sites and K is a lumped equilibrium constant:

K ¼ ðK 2 KK 84 K 6 Þ
Ni/TiO2: k1 = 0.003–0.042, k7 = 0.77–5.35, k1 K = 0–5.38
Ni/MgO: k1 = 0.031–0.085, k7 = 20.45–33.58, k1 K = 0.153–0.167
RDS: methane dissociation and CHxO decomposition
Ni–K/CeO2–Al2O3 r CH4 ¼ h  4  k1L PCH
i 600–800 [69]
1
ðk1L PCH4 PCO =k7L K a PCO2 Þþ K b PCO2 P2H2 =PCO þðk1L PCH4 =k7L Þþ1
 g mol 
k1L ¼ 1292  465 exp 12894366 T gcat s atm
22025g mol 
k7L ¼ ð3:8  0:1Þe  3 exp T gcat s

K a ¼ ð7:4  4:4Þ expð4145663

T Þðatm2 Þ
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78 71

Table 4 (continued)

Catalyst Rate model Temp range (°C) Refs.

159982808 2:5
8605
K b ¼ 2:3e7 exp T ðatm Þ And c ¼ 5:8exp T
RDS1 : *–CH4 ? *–C + 2H2
RDS2: CHxO,s ? CO,s + xH,s
2 step-single site RDS: CH4 activation and C gasification by adsorbed CO2 on metal Ni as RDS
Ni/La2O3 K 1 k2 K 3 k4 PCH PCO
r CH4 ¼ K 1 k2 K 3 PCH PCO þK 1 k24PCH 2þK 3 k4 PCO 650–750 [32]
4 2 4
  1
K 1 k2 ¼ 2:61  103 exp 4300 T ðmol g sÞðkPaÞ
5 8700 1
K 3 ¼ 5:17  10 exp T ðkPaÞ
 
K 4 ¼ 5:35  101 exp 7500 T ðmol=g sÞ
RDS1: *–CH4 ? *–C + 2H2
RDS2: La2O2CO3 + C–* ? La2O3 + 2CO + *
Dual site RDS: CH4 activation by metal Ni and C gasification by adsorbed CO2 on support site as RDS
La2xSrxNiO4
( )
360–440 [42]
KCH4 PCH4 KCO2 PCO2
r CH4 ¼ k  P K
 PK
1þ PI ð1þ PJ Þ
I J

Where I are all the species adsorbed on metal and J all the species adsorbed on oxidic surface:
Under constant PCO2 :
KCH PCH4
r CH4 ¼ k3 fð1þKCH
4
P g k3: 4.1–25.6; KCH4 = 0.1–10.1
4 CH4

Under constant PCH4

KCO PCO2
r CH4 ¼ k4 fð1þKCO
2
P g k4: 36.4–49.4; KCO2 = 44.7–82.5
2 CO2

RDS: -Surface reaction between adsorbed CH4 and adsorbed CO2 on distinct and discrete size
CH4.*1 + CO2.*2 ? 2H2 + 2CO + *1 + *2
2-step dual site RDS: CH4 activation by metal Ni and C gasification by adsorbed CO2 on support site as RDS
LaNiO3 r CH4 ¼ K 3 k4 ½CH4K½CO
1 k2 K 3 k4 ½CH4 ½CO2  650–750 [70]
þK k ½CH þK k ½CO 
2 1 2 4 1 3 4 2
K 1 ¼ 297:55exp 7502:5 T
  kPa
k2 ¼ 12:27exp 10;219:2 T
mol
ðgcat sÞ
6968:2 1
K 3 k4 ¼ 0:034exp T ðkPa mol gcat sÞ
RDS1: *CH4 ? 2*C + 2H2
RDS2: La2O2CO3 + *C ? 4 La2O3 + 2CO + *
Ni/La2O3 produced from LaNiO3 r CH ¼ K 1 k2 K 3 k4 ½CH4 ½CO2  500–700 [38]
4 K 3 k4 ½CO2 þK 1 K 3 k4 ½CH4 ½CO2 þK 1 k2 ½CH4 þK 1 k2 K 3 ½CO2 
At 700 °C, K1 = 141  103 kPa
k2 = 0.22326  103 mol g1 s1
K3 = 15.98  103 kPa
k4 = 13.22  103 mol g1 s1
RDS1: *1–CH4 ? *1–C + 2H2
RDS2: La2O2CO3(*2–CO2) + *1C ? *2 + 2CO + *

significant information on the nature of reduction of the bimetallic
Ni–Co catalyst which showed that addition of Co as second metal
results in mitigation of Ni reduction and enhancement of Co reduc-
tion which results in small and evenly dispersed metal nanoparti-
cles during catalyst reduction. The first derivate of XANES analysis
can accurately confirm the Ni–Co alloy formation. In fact, it is not
an easy task to confirm features such as chemical state or forma-
tion especially for Ni nanocatalysts. In this aspect, EXAFS technique
has been successfully used in several studies to prove key informa-
tion such as alloy formation [74,75] and chemical state of Ni [76]
especially for nanocatalyst. Hence, extension of this technique in
determination of reaction kinetic pathways would certainly be a
good complement to other widely used techniques which are cov-
ered together with the discussion on various rate determining
steps in the following subsections
4.3.4.1. CH4 activation by metal–Ni as RDS. The initial and often rate
determining step is dissociative chemisorption of CH4 on the metal
catalyst, i.e. breaking of one of the CAH bonds on CH4 [77]. Kuijpers
et al. [78] studied CH4 dissociation and explained that it is a struc-
ture sensitive phenomenon, which may be a consequence of a
change in the geometric active site distribution on the different
metal surface structures. It was reported that the different faces
of Ni crystallite surface indeed play an important role in the rate
of CH4 decomposition, whereby CH4 decomposition decreases in
the order of Ni(1 1 0) > Ni (1 0 0) > Ni (1 1 1) [79].
Several researchers, such as Zhang and Verykios [58] and Wang
and Au [62], have proposed that CH4 decomposition to be the rate
determining step. Wei and Iglesia [80] also conducted a kinetic and
isotopic assessment to investigate the mechanism of DRM reaction
on Ni/MgO catalysts. Their turnover rates and first order rate con-
stant and activation energies were found to be similar to those
measured for CH4 decomposition, leading them to assert that
CAH bond activation is the sole kinetically-relevant step in this
reaction. Wei and Iglesia [80] further concluded that the mechanis-
tic features on Ni surface resemble those previously established for
supported noble metal catalysts (Rh, Pt, Ir).
It has been reported that hydrogen can be adsorbed on the Ni
catalysts to form Ni-H species during the reforming reaction.
Therefore, CH4 dissociation is considered reversible since H2 and
Ni–H species can reach rapid equilibrium during the reforming
reactions [81]. Hence, the subsequent sections shall further
describe the different proposed RDS which differs from the gener-
ally accepted CH4 decomposition.
4.3.4.2. Surface reaction between adsorbed O or OH (from CO2 or
support surface. Although there are several researchers suggesting
that adsorbed O atoms are the key intermediate [82,83] in the oxi-
dation of adsorbed CHx species, however surface OH groups are
gaining more and more attention [84]. Li et al. [85] performed
the investigation of methane adsorption on alumina by FT-IR spec-
troscopy and found that two hydroxyls with IR bands at 3750 and
72 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78
3665 cm1 were perturbed evidently by the adsorbed CH4, hence
resulting in two red shifted bands at 3707 and 3640 cm1. This
result suggests that there is a weak interaction between methane
and surface hydroxyls. This H-bridged bonding between the sur-
face OH groups and the methane interaction has also been
observed on Ir catalysts during CH4 decomposition [86].
This is especially the case when the supporting materials are
basic since the basic supports are expected to enhance the adsorp-
tion of CO2. The principal pathway for CO2 reduction occurs by the
initial non-dissociative adsorption of CO2 under reaction condi-
tions on the basic support in the form of carbonates or bicarbon-
ates, followed by H atom-assisted dissociation to produce CO and
OH. By increasing the concentration of adsorbed OH species, the
enhancement of the oxidation of surface adsorbed CHx species
from CH4 decomposition can be achieved.
4.3.4.3. Surface reaction between CHx and O as RDS. When CH4 disso-
ciates on the metallic Ni site, various forms of CHx species will be
present, depending on the structure and property of the catalyst
and the interaction of these species with the support. Osaki et al.
[48] have proposed possible CH4 dissociation steps during DRM
based on PSRA technique. From their observation and proposed
mechanistic steps, CO2 firstly dissociates on the metal site as
adsorbed CO and adsorbed O. CH4, on the other hand, dissociates
on the metallic Ni site and the adsorbed CHx species reacts with
adsorbed O, forming adsorbed CO and adsorbed H which later des-
orbs in the gas phase. Osaki et al. [63] also performed an ab initio
molecular orbital calculation for the PSRA calculation. Upon obser-
vation of rapid sharp H2 response, they therefore excluded CH4 dis-
sociation as a rate determining step. They thus concluded from
their PSRA study that the surface reaction between CHx and O is
rate determining and found that the two steps responsible for H2
production are: (i) dissociative adsorption of CH4 to produce 2H2
and CHx, followed by (ii) subsequent production of 2H2 together
with CO by the surface reaction between CHx and atomic O. For
their study, an isotopic effect on the reaction of adsorbed hydrocar-
bon species with atomic oxygen was observed.
4.3.4.4. Carbon oxidation as RDS. Several studies have proposed that
the surface reaction between carbon and oxygen species to be the
RDS [29,39,67,68]. Kroll et al. [67] using Ni/SiO2 in their study
found that the coke formation on their catalyst was highly depen-
dent on the pre-treatment conditions whereby they found that
reduction under reaction conditions produced less toxic filamen-
tous carbon, whilst a pre-reduction under H2 flow produced toxic
encapsulating carbon. They conducted experiments to determine
the kinetic isotopic effect (KIE) at 700 °C (to minimize temperature
gradient) and atmospheric pressure using predeuterated (CD4)
instead of light methane (CH4) to measure KIEs. Their reaction
mechanism scheme is proposed as follows:
CAH Activation : CH4 þ 1 $ Cads þ 2H2
This step was considered fast as no significant accumulation of CHx
or Hads species was found, therefore leading to accumulation of
dehydrogenated carbon monomers.
CO2 Activation : CO2 þ C ads $ 2CO þ 1
This activation step consists of two elementary steps shown
below:
a: CO2 þ 2 $ CO þ Cads
b: Cads þ Oads ! CO þ ads RDS
The former elementary step was considered to be fast due to the
observed isotopic equilibrium between CO2 and CO. On the other
hand, Kroll et al. [67] deduced from techniques such as Steady
State Isotopic Transient Kinetic Analysis (SSITKA), Temperature
Programmed Hydrogenation (TPH) and Temperature Programmed
Oxidation (TPO) that the latter step to be rate determining as it
required surface migration of species like adsorbed O and C. Using
CH4/CD4 equilibration experiments, they also found evidence of
isotopic H/D scrambling, leading them to suggest that water mol-
ecules interact reversibly with the catalytic surface, in the same
manner as CO2, as shown in the reaction step below:
H2 O þ S2 $ Oads þ H2
Schuurman et al. [87] utilized transient kinetics to unravel the
mechanisms of methane activation over Ni/SiO2, Ni/a-Al2O3, Ru/
SiO2 and Ru/c-Al2O3. They coupled SSITKA with in-situ Diffuse
Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)
and utilized Temporal Analysis of Product (TAP) to correlate their
findings. From methane pulsing using TAP, they found the release
of hydrogen which was confirmed by Kroll et al. [62] The SSITKA
and TAP experiments clearly revealed that CO was formed from
direct and fast activation of CO2 and oxidation of C monomer from
CH4 activation. The tailing response of CO gas phase in TAP reveals
and further confirms that the reaction of surface C monomers with
surface O atoms was rate determining.
Complementing reaction mechanisms with techniques such as
SSITKA and TAP are certainly beneficial in determining true kinet-
ics of the reaction. Since SSITKA generates isotopic step function
which lets the overall surface occupancy unperturbed, therefore
it has been used to give access to true time constants of reactive
intermediates and their concentrations [87]. Generation of tran-
sient input signals, such as step functions in gas concentrations,
lead to observation of product yields. These attributes of SSITKA
[87], encouraged various researchers to utilize it [88,89] in order
to elucidate the reaction mechanism for DRM reaction. On the
other hand, in terms of TAP technique, small and known amounts
of reactants are pulsed through a catalyst bed and the pulse expan-
sion and relaxation at the reactor exit are analyzed [89] This tech-
nique has been successfully used to investigate the adsorption and
reaction characteristics of CH4, CO2, CO and H2 for DRM [90]
whereby the interdependence between the dissociation mecha-
nisms can be obtained. In addition, the aforementioned tempera-
ture programmed techniques such as Temperature Programmed
Oxidation (TPO) and Temperature Programmed Hydrogenation
(TPH) are used to determine the type of surface carbon present
in the catalyst after DRM reaction. The carbon present on the cat-
alyst is generally oxidized during TPO analysis to detect the tem-
perature for formation of CO2 and CO (if present), whereas the
carbon present on the catalyst is hydrogenated during TPH analysis
to detect the temperature required for the formation of CH4. This
information can validate the source of carbon formed during reac-
tion and distinguished based on its reactivity [91,92]. For example,
the amorphous types of carbon originate from CO disproportion-
ation; however these types of carbon encapsulate the catalyst,
leading to the deactivation of catalyst. On the other hand, the gra-
phitic types of carbon, although they are more stable, originate
from CH4 decomposition. Hence, this information is useful in cor-
relating the types of carbon formed with the proposed mechanism
steps during DRM reaction.
4.3.4.5. Reverse Boudouard reaction as RDS. Generally CH4 activation
is often regarded as a first order reaction. Wang and Lu [26] did a
comprehensive study on DRM over Ni/c-Al2O3 catalyst and showed
that CH4 or CO2 first involved chemisorption in the reaction and
the CO formation step is the rate determining step from the reverse
Boudouard reaction, as proposed in the following reaction mecha-
nistic steps [26]:
CH4 þ  ! CH4 
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78
CO2 þ  ! CO2 
CH4  ! CH3  þH
CH3  ! CH2  þH
CH2  ! CH  þH
CH ! C  þH
C  þCO2  ! 2CO þ 2  ðRDSÞ
Wang and Lu [26] had observed that, with respect to the reac-
tion rate on CH4 or CO2 partial pressure, methane showed first
order and CO2 exhibited first-order at lower partial pressures and
zero order at high pressures. This observation shows that at higher
partial pressures, CO2 may not be the rate determining factor.
According to Gibson [93], one of the most powerful ways to
activate inert CO2 molecule for chemical reactions, is to form an
active site-CO2 complex via direct coordination method. CO2 con-
sists of C which is a Lewis acid center and O is a weak Lewis base.
Therefore, a support with a strong Lewis base has the potential to
form the active site-CO2 complex. Therefore, using this criterion,
Zhang et al. [40] conducted DRM kinetic study over Ni–Co/Al–
Mg–O bimetallic catalyst and postulated that CO2 was activated
due to the presence of Lewis base center in their catalyst support,
i.e. MgO. This activated CO2 was assumed to undergo a slow reac-
tion with the carbon from CH4 decomposition. Zhang et al. [40] also
proposed that reaction of activated CO2 with surface hydrogen spe-
cies to form CO and adsorbed hydroxyl group (from RWGS reac-
tion), could also be rate determining. However, in their final
modeling, reverse Boudouard reaction was taken as the sole RDS
to correlate with their kinetic data. In fact, formation of bimetallic
alloy is reported to improve catalyst stability by improving resis-
tance to active metal oxidation [94–96], hence it should be noted
that different metal alloyed with Ni may contribute different prop-
erties which may lead to different reaction kinetics.
4.3.4.6. Two (2) step-single site RDS: CH4 activation by metal Ni and
CHxO decomposition as RDS. There are many studies reporting the
formation of CHxO species as the Most Abundant Reaction Interme-
diate (MARI) species, leading to postulation that CHxO decomposi-
tion is the kinetically relevant step [88]. The following rate
equation has been proposed by Bradford and Vannice [31]:
k1 PCH4 PCO2
r CH4 ¼   h i
k1 K ð4xÞ=2
k7
PCO PH2 þ 1 þ ðkk17 ÞPCH4 PCO2
where ki = kiL, L = total number of active sites and K is a lumped
equilibrium constant:
 
K8
K¼
K2K4K6
The addition of promoters, such as alkali or alkaline oxides, onto
catalyst surface has been used to improve the performance of cat-
alysts by increasing the basicity of the supporting materials. The
kinetic results showed that the added metal oxides changed the
reaction order in CH4 from negative to positive and that in CO2
from positive to negative. This observation implies that the surface
of a nickel catalyst incorporating basic metal oxides is abundant in
adsorbed CO2, whereas the surfaces devoid of these oxides are
abundant in adsorbed CH4 [97]. The coverage of nickel with CO2
is most likely unfavorable to CH4 decomposition and, as a result,
the carbon deposition is decreased.
Nandini et al. [69] performed the DRM reaction over 13.5Ni–2K/
10CeO2–Al2O3 catalyst and found that their reaction sequence
involved methane adsorption and dissociation, non-dissociative
73
carbon dioxide adsorption, promotion of carbon dioxide dissocia-
tion by adsorbed hydrogen atoms, interaction of the adsorbed
CHx fragments with surface hydroxyl groups, and irreversible CHxO
decomposition. The proposed irreversibility of CHxO was valid
under circumstances of no net methane formation, and hence, this
formed the basis of their claims to be the RDS.
Luo et al. [88] investigated the mechanism of DRM reaction over
Ni supported on La2O3/5A catalyst based on CH4/CD4 kinetic isoto-
pic studies as well as Thermal Gravimetry Analysis–Differential
Thermal Analyzer (TGA–DTA) techniques. They observed that
encapsulated carbon was formed in a CH4/N2 atmosphere and
whisker carbon was formed in a CO/N2 or CO2/CH4/N2 atmosphere
[88]. In addition, they observed that CAH cleavage was found to be
O assisted and further confirmed that decomposition of CHxO to CO
and H2 to be the rate determining step. Based on these findings,
Luo et al. [88] deduced three possible ways for CAH cleavage in
DRM:
i: CH4 $ Cx þ 4H
ii: CHx þ O ! CO þ xH
iii: CHx O ! CO þ xH RDS
Luo et al. [88] suggested that step (i) was reversible since they
did not observe IR bands circa 3000 cm1 which indicated the
absence of CHx adsorbed species, and hence postulated that this
could be a result of fast CHx interaction with surface oxygen spe-
cies. Step (ii) was postulated to be rather facile based on their
observation from the isotopic CH4 pulsing with CO2. They also
observed CD3CHO in the CD3I chemical trapping, which indicates
presence of HCO on the sample surface, which was further con-
firmed by the presence of broad and weak IR bands in the range
of 2700–3000 cm1 characterizing CHxO species (where x = 1–3).
Hence, based on these observations, they concluded that CHxO
decomposition is the RDS and proposed the following mechanism:
CH4;g ! CH4 ; 
CO2;g ! CO þ 2; 
CH4;s ! CHx ;  þ ð4  xÞH;
CO2 ;  ! CO;  þO;
HCOO; ! HCO;  þO
HCOO; ! CO;  þOH
CHx ;  þ O; ! CHx O;
CH4 ;  þ O; ! CHx O;  þð4  xÞH;
CHx ;  þ OH; ! CHx O;  þH;
CHx O; ! CO;  þxH;  RDS
H;  þOH; ! H2 O;
Based on these mechanistic steps, they have shown that CHx
decomposition on Ni metal is postulated to be assisted by oxygen
generated in CO2 dissociation via CHxO formation (x = 1, 2). The
CO2 adsorbed on basic sites dissociates with or without H species
from CH4 decomposition to give CO and O or CO and OH. Therefore,
the RDS is the decomposition of CHxO to CO and H.
4.3.4.7. Two (2) step-single site RDS: CH4 Activation and C gasification
by adsorbed CO2 on metal Ni as RDS. Generally 2-step kinetic
74 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78
models refer to two different rate determining steps that control
the reaction rate. The most general 2-step model applies to carbon-
ate formation especially on slightly basic sites, whereby C-H acti-
vation and CO2 dissociation play a major role in the rate
determining steps. Extensive investigations were conducted by
Zhang et al. [98] as well as Tsipouriari and Verykios [99] in order
to prove the formation of oxycarbonate species based on the prop-
erties of La2O3 which contribute to the rate mechanism. This shall
be explored further below.
4.3.4.8. La2O2CO3 formation. Zhang et al. [98] proposed a kinetic
model for Ni/La2O3 catalyst using a range of techniques to eluci-
date the reaction mechanism. Based on their Diffuse Reflectance
Fourier Transform Infrared Spectroscopy (DRIFTS) and X-ray Pho-
toelectron Spectroscopy (XPS) and studies, they observed the for-
mation of the stable La2O2CO3 compound, which was formed
from the interaction between La2O3 with CO2 partially covering
Ni particles. The catalytic activity occurred at the interface of Ni
and La2O2CO3 species. The benefits of using in situ DRIFTS to detect
reaction intermediates during surface reactions are multifold since
real-time analysis of the reaction can be monitored as the pulse
input can generate results for analysis. Besides, the database for
the infrared characteristic group frequencies can be readily
obtained from literature such as Socrates [100]. Several studies
for the DRM reaction have successfully employed this technique
to elucidate the reaction mechanism [31,98,101,102] by distin-
guishing the roles played by the reactant species during DRM reac-
tion. In addition, using this technique, Ni et al. [103] could observe
the nature of the catalyst support in terms of surface hydrophilic-
ity, to gauge the contribution of hydroxyl group species in DRM
reaction mechanism. Another function of in-situ DRIFTS analysis
is the flexibility to study the adsorption property of different gas-
eous species such as CO and CO2. CO chemisorption on metal is
essential information which can be obtained from this DRIFTS
analysis in order to determine the bonding of the metallic active
site to the CO, i.e. linear and/or bridged. This information is crucial
in order to determine the surface property of the catalyst and the
dispersion of the metallic Ni on the catalyst surface. The key infor-
mation of the working surface can be obtained, such as presence of
adsorbed CO or OH vibrations indicating formation of NiACO and
NiAOH ad-species which can then form significant pools under
reforming conditions on the reacting surface [91].
On the other hand, XPS can be used to elucidate the changes in
the binding energy of the catalyst and to obtain relationship
between metal-–support interactions. Besides deducing the forma-
tion of oxycarbonate species (based on binding energy changes in
La (3d) and C (1s), XPS is also a powerful tool which can be used
to claim the presence of mobile surface oxygen species. From
XPS analysis, Sutthiumporn et al.[104] could prove the presence
of mobile surface oxygen in Sr-doped Ni/La2O3 catalyst; and found
that this oxygen species was responsible for the activation of CAH
bond as well as reaction with CO2 to form the bidentate oxycarbon-
ate species, hence aiding in carbon gasification process and stabi-
lizing the catalytic activity during DRM reaction.
On the other hand, Tsipouriari and Verykios [99] utilized SSITKA
method to compare the DRM reaction between Ni/Al2O3 and Ni/
La2O3 catalysts; they detected smaller quantities of reversibly
adsorbed CH4 and active carbon-containing species from CH4 mol-
ecule. Based on these techniques, they confirmed that the forma-
tion of La2O2CO3 played an important role in imparting the
special catalyst stability. The oxycarbonate species was also found
to participate directly in the DRM reaction by reacting with the
deposited carbon. Therefore, the carbon deposition was less
and the activity of Ni sites was restored. Tsipouriari and
Verykios [99] also reported that the methane decomposition on
Ni sites and the surface reaction between deposited carbon and
oxycarbonate species are the rate determining steps. Based on
these observations, a few mechanistic steps were proposed. The
detection of reversibly adsorbed CH4 under reaction conditions
indicate that the activation of CH4 may be considered a slow step
over the Ni/La2O3 catalyst. On the other hand, the strong interac-
tion between CO2 and La2O3 support to form La2O2CO3 was consid-
ered a fast step at equilibrium. However, the step where
oxycarbonate species react with carbon deposited onto Ni particles
was also considered to be a slow step. The mechanism and the
kinetic model were proposed based on the above observations
and presented as follows [98,99]:
CH4 þ  $ -CH4
CO2 þ La2 O3 $ La2 O2 CO3 ðRDSÞ
-CH4 ! -C þ 2H
La2 O2 CO3 þ C- ! La2 O3 þ 2CO þ  ðRDSÞ
From the above steps, we can break down the 2 major steps to be
related to CAH activation and CO2 reaction to correlate with other
researches [105].
(a) CAH activation
Similar to other reported studies – activation on metallic Ni site
was one of the RDS as shown below:
CH4 þ  $ CH4 
CH4  ! C  þ2H2 ðRDSÞ
(b) CO2 reaction
Similar to other reported studies – C gasification by CO2 (in this
case, adsorbed CO2 in the form of oxycarbonate species) as the
other RDS as shown below:
CO2 þ La2 O3 $ La2 O2 CO3
La2 O2 CO3 þ C ! La2 O3 þ 2CO þ  ðRDSÞ
H2 þ 2 $ 2H
La2 O2 CO3 þ H $ La2 O3 þ CO þ OH
OH  þC $ CO  þH
OH  þH $ H2 O þ 2
CO $ CO þ 
As for the reaction between La2O2CO3 and H* spillover from the
Ni crystallites, the elemental reaction may involve formate group
formed on the support, which upon interaction with another H*,
decomposes into H2O and CO as the following mechanism [99].
The elemental reaction between La2O2CO3 and H* spillover from
the Ni crystallites may involve formate group formation on the
support, whereby upon interaction with another H*, decomposi-
tion of the formate species into H2O and CO takes place as shown
in the following equations.
CO2 ðaÞ þ Hþ ! HCOO ðsupportÞ
HCOO þ Hþ ! H2 O þ CO
The above 2 steps can be considered as fast RWGS occurring on
metal support interfacial area [99]. Therefore, the produced H2O
may react with C on Ni to form H2 and CO, thus offering increased
favourability to remove C on the Ni crystallites from both H2O and
CO2.
 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78
Slagtern et al. [106] performed High Resolution Transmittance
Electron Microscope (HRTEM) along with in situ DRIFT, SSITKA
and TAP investigations to further elucidate reaction mechanisms
on Ni/La2O3. Using X-ray Diffraction (XRD) and High Resolution
Transmission Electron Microscopy (HRTEM), they could also detect
the presence of small amounts of La2O2CO3 species for the used Ni/
La2O3 catalyst after DRM reaction at 750 °C. In fact, in-situ XRD
(coupled with heating chamber) technique can be used to study
the crystalline structural change at different conditions during cat-
alyst calcination process and DRM reactions. XRD technique is
especially beneficial when the catalyst structure undergoes struc-
tural and morphological changes, such as during the reduction of
perovskite to mixed oxides. In a different study, Slagtern et al.
[107] have successfully employed this technique to study the
phase changes in La-Ni-Al-O type catalyst during DRM reaction.
They were able to identify the crystalline structure change during
reduction of perovskite. From their analysis, La2O2CO3 formation
(formed by the reaction of CO2 with La2O3) was not observed but
they noted that CO2 aided in the re-dispersion of metallic Ni during
reaction. They also detected the presence of Ni3C at 2h = 45.5° to
elucidate the active phase formed during DRM reaction since
Ni3C has been reported by to be the active catalytic site for DRM
[107]. However, on their study on Ni/La2O3 catalysts, the formation
of lanthanum oxycarbonates were also supported with their obser-
vation using in situ DRIFT, SSITKA and TAP analysis.
Furthermore, their TAP analysis indicated that when CH4 was
pulsed into the system, CO production was inhibited. This means
that cracking of CH4 on the metallic Ni step is in competition with
lanthanum oxycarbonate decomposition into CO which also occurs
on the metallic Ni site. Therefore, they proposed a mechanistic
scheme using Ni as the site as follows:
CH4 þ Ni ! NiC þ 2H2
La2 O2 CO3 þ Ni ! CO þ NiO þ La2 O3
NiC þ NiO ! CO þ 2Ni
CO2 þ La2 O3 ! La2 O2 CO3
Moradi et al. [70] performed an investigation on perovskite cat-
alyst, LaNiO3 and found that the kinetic behavior resembled that of
Ni/La2O3 and Rh/La2O3 which were investigated by Tsipouriari and
Verykios [99] and Munera et al. [108] respectively.
All studies pertaining to La2O3 support generally are in agree-
ment with the mechanism tabulated in Table 4. By comparing
the studies of 3 different La2O3 supported catalysts, Moradi et al.
[70] summarized that Rh/La2O3 was more active than Ni/La2O3
and LaNiO3 due to the higher values of CH4 adsorption and meth-
ane decomposition rate, which was probably due to the different
surface properties between Rh and Ni.
4.3.4.9. Multiple rate determining steps. Cui et al. [81] concur that
operating temperature zone plays an important part in the deter-
mination of RDS. They employed transient kinetic methods to
prove their claim. They found that the Ea for CH4 and CO2 were
31.1 and 40.5 kJ/mol respectively below 650 °C, and 89.1 and
88.6 kJ/mol respectively above 650 °C. These results suggest that
the reforming mechanism might be varied below 650 °C and con-
stant above 650 °C. They concluded that the activation energies
of CH4 dissociation and CO2 conversion, together with the reaction
orders of CH4, CO2, H2, and CO, showed that the reaction mecha-
nism can be divided into three regions: 550–575 °C, 575–650 °C,
and 650–750 °C. The reaction was constant in the low and high
temperature regions but varied with temperature in the middle
region. The dissociation of CH4 into CHx species and hydrogen spe-
cies on the Ni active sites reached equilibrium state above 650 °C.
75
It was found that the surface oxygen species originating from CO2
dissociation became removable and they moved to Ni active sites
to react with CHx species above 575 °C. The reaction rate of CHx
with CO2 was lower than that of CH4 dissociation above 650 °C,
leading to the durative carbon deposition on the Ni/a-Al2O3 cata-
lyst throughout the DRM reaction. CO competed with CH4 on the
Ni active sites and inhibited the dry reforming below 650 °C; and
CO was desorbed rapidly above 650 °C. Since the formation of
hydrogen was a rapid step due to the equilibrium with Ni–H in
the reforming reaction, therefore CH4 dissociation was the RDS in
the temperature region of 550–575 °C. The reaction between CHx
and CO2 became the RDS in 650–750 °C. The restraining steps were
switched from the former two steps to the latter one in the tem-
perature region of 575–650 °C. Therefore, based on their observa-
tions, the reaction temperature obviously altered the reaction
steps, including the amount of Ni–H on catalyst, the removability
of the oxygen species, and desorption of CO from catalysts. The var-
iation of the reaction steps with the temperature lead to the alter-
nations of the reforming mechanism and the RDS in the different
temperature regions.
5. Outlook
Kinetic modeling for DRM reaction requires extensive experi-
mental data for validation, especially when the effect of side prod-
ucts (such as H2O) formed from side reactions (such as RWGS) play
an important role in DRM reaction. This is especially true when the
interaction of different support with the catalyst alter the reaction
pathway, hence contributing to differences in the reaction mecha-
nistic steps. The prospects for improvement and more cohesive
understanding on the mechanistic aspects lies in the advancement
of powerful experimental techniques to probe and detect the reac-
tion intermediates and pathways and to confirm postulations. The
development of transient pulse techniques (SSITKA and TAP) in
probing the nature of the reactants and products during DRM reac-
tion via pulse perturbations or in situ DRIFT analysis is especially
powerful for detection of intermediate species. Coupling with in
situ MS can further confirm proposed reaction mechanism steps.
Fast analysis responses are a key requirement and present day
technologies should cater for complete in situ studies such as
RAMAN, TEM, XPS, TPR-MS, FTIR-MS, in order to determine the fac-
ile intermediates present on the catalyst surface during DRM reac-
tion. Other key features include improvement of the analysis via
introduction of products to the reacting components, whereby
more coherent effect of the partial pressures of product-reactant
on the reactions can be effectively obtained to optimize assump-
tions and the proposed model. Synchroton EXAFS technology for
analysis of bi-metallic catalyst coupled with RAMAN technology
can provide information of metal–metal or metal–support interac-
tions, therefore elucidating deeper understanding of the role of cat-
alyst on the reaction mechanism during DRM.
A complete microkinetic, ab initio and Density Functional The-
ory (DFT) analysis approach should be conducted in order to obtain
a comprehensive database for the various kinetic models. This con-
solidated table could provide immediate reference for catalyst-
reactor design calculation for DRM reaction. Henceforth, a wide
array of reaction pathways can be simulated and compared
experimentally.
The carbon deposition issue in DRM reaction, has also promoted
other reaction concepts such as oxidative CO2 reforming, steam-
CO2 reforming of methane and tri-reforming of methane, whereby
by both O2 and steam act as co-reactants for the DRM reaction. Tri-
reforming of methane, a novel concept developed by Song et al.
[5,109,110], offers an interesting possibility of producing useful
syngas with desired H2/CO ratios without carbon formation
76 Y. Kathiraser et al. / Chemical Engineering Journal 278 (2015) 62–78
problem as it involves the synergetic combination of the CO2
reforming, steam reforming and partial oxidation of methane reac-
tions. In addition, the flue gas from power plants can directly be
used for reforming reaction, without necessitating additional
downstream CO2 separation steps. It would certainly be an inter-
esting future development if kinetic studies pertaining to these
mixed reforming reactions account are intensively researched in
order to promote the commercial potential of CO2 reforming. How-
ever, the nature of the complex multiple pathways, most certainly
warrant implementation of the in situ analysis techniques to pro-
vide substantial justification and enlightenment on the mechanis-
tic pathways and the rate determining steps involved, as there may
be potential for more than 1 RDS which control the reaction under
the mixed reforming environment. Thus, research on these areas
offer promising avenues to further expand the applicability of
DRM reactions as well as the on the design and synthesis of opti-
mal Ni based catalyst to achieve this goal.
6. Conclusion
This paper presents a comprehensive review on different pro-
posed reaction mechanisms and kinetics based on their respective
RDS steps involved in DRM reaction on Ni based catalysts. A survey
of the differing RDS presented in literature based on the widely
used Langmuir Hinshelwood Hougen Watson (LHHW) models for
Ni-catalyzed DRM reactions are categorized and presented. These
steps include CAH activation from CH4 on metallic Ni, CO2 dissoci-
ation on metallic Ni or support, intermediate species formation and
decomposition, carbon oxidation as well as several other side reac-
tions. The importance of experimental techniques for justifying
mechanistic formulation is highlighted as well, wherein techniques
such as EXAFS, DRIFTS, SSITKA, MS with their critical functions per-
tinent to gain in-depth understanding on the possible mechanisms
involved in the DRM reaction are elaborated. Ultimately, the goal
from investigation reaction kinetics is greatly beneficial in optimi-
zation of catalyst design and synthesis to improve the commercial-
ization viability of the DRM process for Ni based catalysts.
Acknowledgments
The authors gratefully thank the National University of Singa-
pore and National Research Foundation – Proof of Concept grant
(NRF-POC 001-055, RP No. 279-000-397-281) for generously sup-
porting this work. The authors thank Professor Michele Aresta for
his valuable suggestions and Dr. Ni Jun for his kind assistance in
this manuscript.
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