Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101

https://doi.org/10.1007/s11144-020-01767-y

Kinetics of steam reforming of methane on Rh–Ni/MgAl2O4

catalyst

Sanjay Katheria1 · Deepak Kunzru2 · Goutam Deo1

Received: 15 January 2020 / Accepted: 11 March 2020 / Published online: 17 March 2020
© Akadémiai Kiadó, Budapest, Hungary 2020

Abstract
The kinetics of the steam reforming of methane was studied on 0.5 wt% Rh–15
wt% Ni/MgAl2O4 catalyst. The variation of methane conversion with contact time
( W∕FCH4 ,0 ) was recorded in the temperature range of 450 to 600 °C, at three differ-
ent pressures of 1, 4 and 6 bar, and at steam to carbon ratio (S/C) of 2, 5 or 6. Before
the kinetic experiments, a check for external and internal mass transfer limitations
was also performed. The experimentally obtained data was tested for different ear-
lier proposed kinetic models, and parameters were calculated using non-linear least
square optimization. Among the different kinetic models tested, the kinetic model
proposed by Al-Ubaid and Wolf was found to be the most suitable. Reaction order
of 0.21 for methane and 0.16 for water with an apparent activation energy of 75.3 kJ/
mol was obtained.

Keywords  Methane steam reforming · Kinetic modeling · Rh-Ni/MgAl2O4 catalyst ·

Parameter optimization · Hydrogen production · Noble metal

Introduction

The steam reforming of methane (SRM) is a widely used industrial process for
hydrogen production. Even though SRM is an old process, but due to its commercial
importance, a number of recent investigations have analysed this reaction to further
improve its efficiency [1–3]. To understand the process and model the reactor, it is

Electronic supplementary material  The online version of this article (https​://doi.org/10.1007/s1114​

4-020-01767​-y) contains supplementary material, which is available to authorized users.

* Goutam Deo
goutam@iitk.ac.in
1
Department of Chemical Engineering, Indian Institute of Technology Kanpur, Uttar Pradesh,
Kanpur 208016, India
2
School of Engineering & Applied Science, Ahmedabad University, Navrangpura, Ahmadabad,
Gujarat 380009, India

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 92 Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101

essential to study the kinetics of the SRM reaction. Kinetics of steam reforming of
methane on different catalysts has been investigated by several researchers and vari-
ous kinetic models have been proposed for the different catalysts [4–6]. The three
main reactions, which can account for formation of all the products during SRM are
the following:
CH4 + H2 O ↔ 3H2 + CO, (i)

CO + H2 O ↔ CO2 + H2 , (ii)

CH4 + 2H2 O ↔ CO2 + 4H2 . (iii)

Due to its low cost and easy availability, nickel is one of the most studied active
metals for steam reforming reaction. Several kinetic models for different nickel cata-
lysts, based on different aspects, such as rate controlling step, major reaction prod-
uct and different reaction pathways etc., have been reported by various researchers
[7]. Among these, the kinetic model proposed by Xu and Froment [5] is a widely
accepted model for SRM reaction. Although this model was developed for Ni/
MgAl2O4 catalyst, various researchers have verified this model for different catalytic
systems [4, 8, 9]. The major drawback of this model is that it is not applicable at
zero hydrogen partial pressure condition.
Although, a number of studies have been reported on nickel-based catalysts, still
catalyst deactivation because of carbon formation over the catalyst surface and sin-
tering of active metal particles remains a challenging problem [10, 11]. Several stud-
ies have also shown that addition of a small amount of a noble metal can signifi-
cantly improve the performance of nickel-based catalysts [12]. These studies have
shown that addition of a small amount of noble metal changes the physio-chemical
properties of the catalyst, and it is possible that this addition also results in a change
in reaction kinetics. However, limited information is available on the kinetic study
of noble metal promoted nickel supported catalysts for SRM reaction. The only
detailed kinetic modeling study using noble metal promoted nickel supported cat-
alysts has been reported by Obradovic et  al. [13]. In their work, Obradovic et  al.
[13] investigated the kinetics of steam reforming reaction using Ni/Al2O3 and Pt/Ni/
Al2O3 catalysts. For both catalysts, the model suggested by Xu and Froment [5] was
found to be satisfactory. In another recent work, Rocha and co-workers have studied
Au doped Ni/Al2O3 catalyst for the SRM reaction and calculated the apparent acti-
vation energy [14].
As earlier studies have shown that Rh noble metal is one of the most active noble
metals and Ni/MgAl2O4 is a widely used industrial catalyst for steam reforming of
methane, studies on Rh promoted Ni/MgAl2O4 catalyst for the SRM reaction have
drawn attention from various researchers [12]. However, there is no study on the
kinetic modeling of Rh promoted nickel supported catalyst. In our earlier work, we
developed a synthesis procedure for Rh promoted Ni/MgAl2O4 catalyst to maximize
the conversion over this catalytic system [15]. In this present work, we investigate
the kinetics of the synthesised Rh/Ni/MgAl2O4 catalyst and explain the reactivity
data obtained for the SRM reaction.

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Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101 93

Experimental

Catalyst preparation

Rh-Ni/MgAl2O4 catalyst was prepared by mixing the required amount of Rh precur-

sor salt solution to a previously prepared Ni/MgAl2O4 catalyst by sequential impreg-
nation method. For this purpose, the 15% Ni/MgAl2O4 catalyst was initially pre-
pared by addition of required amount of aqueous solution of nickel precursor salt,
Ni(NO3)2·6H2O (Loba Chemicals, India), to M ­ gAl2O4 spinel powder, which was the
support. After drying this slurry in a rotary evaporator at 90 °C and subsequently in
an oven at 120 °C, the catalyst powder was calcined at 600 °C for 3 h. Addition of
Rh was done by impregnating the required amount of rhodium nitrate solution (10
wt% Rh in ­HNO3 solution, Alfa Aesar) to the Ni/MgAl2O4 catalyst prepared above.
Similarly to the process followed after nickel impregnation, the catalyst powder
was again dried and calcined at 600 °C. This catalyst has been referred to as Rh-Ni/
MgAl2O4. Detail of this synthesis procedure is described in our earlier work [15].

Activity test

The experimental data used for determining the kinetics was obtained on a vertical
down-flow packed bed reactor. Prior to the activity test, a blank experimental run
(without catalyst) was performed at different experimental conditions. Details about
the experimental setup have been discussed in our earlier work [16]. During these
experiments, ­N2 was used as an internal standard and added at the reactor exit, such
that ­CH4:N2 was always kept as 1:1. However, to cover a wider range of inlet partial
pressures, in a few experiments, ­N2 was added with the feed gases.
It was observed that there was no methane conversion in the blank runs. In addi-
tion, catalyst stability test at different operating conditions as well as preliminary
runs to check for internal and external mass transfer limitations were performed.
The catalyst size for the kinetic runs was kept in the range of 0.250 to 0.300  mm
(average size, ­dp = 0.275 mm) to avoid internal mass transfer limitation. For activity
tests, 50 mg of the catalyst was mixed with 150 mg of quartz particles of the same
size and packed in a 4.4 mm i.d. stainless-steel tube. The length of the catalyst bed
(L) was around 1.5 cm. Table 1 shows the range of experimental conditions used to
study the kinetics of the SRM reaction on the Rh-Ni/MgAl2O4 catalyst. Analysis
of the product gases was performed using two gas chromatographs (GC). The first

Table 1  Experimental Catalyst Tempera- Pressure(bar) H2O/methane

conditions for Rh-Ni/MgAl2O4 ture (°C) molar ratio
catalyst (S/C)

Rh/Ni/MgAl2O4 450 2, 5 1
500 1, 4, 6 2, 5
550 1, 4, 6 2, 5,6
600 1, 4, 6 2, 5

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 94 Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101

GC, equipped with a thermal conductivity detector (TCD), was used for the analysis
of all the products, while the second GC, equipped with a methanator and a flame-
ionization detector (FID), was used to measure the concentrations of CO and ­CO2 at
low concentrations. In both GCs, the separation of product gases was performed on
a 3-m Carbosphere column.

Model discrimination and parameter estimation

Several kinetic models proposed by earlier investigators were tested for Rh-Ni/
MgAl2O4 catalyst (Table S2). The integral method of analysis was used to determine
the best kinetic model. For this, the variation of conversion with W∕FCH4 ,0 (W is the
weight of the catalyst; FCH4 ,0 is the inlet molar flow rate of methane) was calculated
by integrating the following equation for each model:
dX
d(W∕FCH4 ,0 )
= rCH4 . (1)

Equation 1 was integrated using the ordinary differential equation solver ODE45
of MATLAB (Version R2007a), which uses a variable step-size Runge–Kutta
method for its computation. For the calculation of rate and adsorption parameters,
re-parameterization of the rate and equilibrium constants was done as given by
Eqs. 2 and 3:
( ( ))
Ei 1 1
ki = ki,Tr × exp − − , (2)
R T Tr

( ( ))
ΔHi 1 1
Ki = Ki,Tr × exp − − , i = CH4 , H2 O, H2 , CO and CO2 . (3)
R T Tr

Here ­Tr is the reference temperature (848  K), ­Ei is activation energy, ­Ki is the
adsorption equilibrium constant for component i and ∆Hi is the heat of adsorption.
After calculation of rate and adsorption parameters, pre-exponential factors, A,
were calculated from the following equations:
( )
Ei
(4)
( )
A ki = ki × exp ,
RT

ΔHj
( )
(5)
( )
A Kj = Kj × exp .
RT

As the rate of methane disappearance is a function of the partial pressures of the

different components, therefore to solve Eq. 1, the partial pressures of the different
species were correlated with contact time ( W∕FCH4 ,0 ) using second or third order
polynomials. Similar partial order dependency with contact time has also been used
previously [8, 17]. For each set of rate data, the dependence of partial pressures, p­ i

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Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101 95

(calculated from product distribution data) was correlated with contact time in the
following manner:
( ) ( )2 ( )3
W W W
p i = ai × + bi × + ci × . (6)
FCH4 o FCH4 o FCH4 o

Here, i = CH4 , H2 O, H2 , CO or CO2 and a, b and c are constants.

The kinetic parameters of any model were estimated by minimizing the sum of
square of the errors (resnorm) calculated from the difference between the methane
conversions obtained from solving the rate equation for a given model ­(Xcal) and the
experimentally measured methane conversion ­(Xexp). The error minimization was
done using a nonlinear least square optimization tool solver (lsqnonlin) of MAT-
LAB. Results obtained from the optimization were tested using different criteria.
The criteria for model validation and applicability was the parity plot between calcu-
lated ­(Xcal) and experimental values ­(Xexp) and resnorm (sum of squares or errors).

Results and discussion

Check for mass transfer limitations

Preliminary runs were made to confirm the absence of internal and external
mass transfer limitations with Ni/MgAl2O4 catalyst. As can be observed from
Fig.  1, increasing the average catalyst particle size from 0.115 to 0.326  mm did
not affect the methane conversion for Ni/MgAl2O4 catalyst, while a decrease in
methane conversion was observed when the average catalyst particle size was
increased to 0.638  mm. These results show that for the conditions used, pore

Fig. 1  Check for pore diffusion (internal mass transfer) limitation for 15% Ni/MgAl2O4 (S/C = 4,
W∕FCH4 ,0 = 0.35 ­gcat h/mol, T = 700 °C and P = 1 atm)

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 96 Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101

diffusional resistance did not affect the rate for an average catalyst particle size
below 0.326 mm. To check for external mass transfer limitations, the effect of super-
ficial velocity on methane conversion at a constant W∕FCH4 ,0 was investigated (refer
Fig. 2). It was found out that increasing the superficial velocity from 2.2 to 3.0 m/s,
did not affect the methane conversion. However, a decrease in methane conversion
was observed at a lower superficial velocity of 1.48 m/s. Since a very small amount
of Rh (0.5 wt%) was added in Ni/MgAl2O4 catalyst, the parameters obtained from
Ni/MgAl2O4 catalyst for mass transfer limitation study were also used for Rh-Ni/
MgAl2O4 catalyst. Thus, for all the kinetic runs, the superficial velocity was kept
more than 2.2 m/s and the particle size was kept in a range of 0.250 to 0.300 mm for
Rh–Ni/MgAl2O4 catalyst.

Kinetic modeling of SRM reaction for Rh–Ni/MgAl2O4 catalyst

Fig. 3 represents the variation of methane conversion with W∕FCH4 ,0 at different

temperatures, pressures and S/C ratios for the Rh–Ni/MgAl2O4 catalyst. Sym-
bols in all the figures have been shown as Tt–Pp–Ss, which represent the experi-
mental conditions of temperature (T °C), pressure (p bar), and S (S/C ratio).
For a better understanding of the experimental results, trend lines using poly-
nomial curve fitting have also been shown in Fig.  3. To study the variation of
methane conversion with partial pressures of different product species, all the
experiments were performed well below the equilibrium methane conversion.
To study the effect of change in partial pressures of methane and water, experi-
ments were performed at S/C 2, 5 or 6. From the figures, the expected increase
in methane conversion with the increase in contact time ( W∕FCH4 ,0 ) and temper-
ature was observed. Moreover, methane conversion decreased with an increase
in total pressure. Values of partial pressures at different operating conditions for

Fig. 2  Check for external mass transfer limitation for 15%Ni/MgAl2O4 (S/C = 4, W∕FCH4 ,0 = 0.35 ­gcat h/
mol, T = 700 °C, P = 1 atm and average catalyst particle size, ­dp = 0.275 mm)

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Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101 97

Fig. 3  Variation of methane conversion with W∕FCH4 ,0 for Rh–Ni/MgAl2O4 catalyst at different operating
conditions (average catalyst particle size, ­dp = 0.275 mm)

all products of SRM reaction using Rh–Ni/MgAl2O4 catalyst are presented in

Supplementary Information, Table S1.
The kinetic data obtained for Rh–Ni/MgAl2O4 catalyst was tested against the
earlier published models. Comparison of experimental and calculated methane
­2
conversions (parity plots) from different earlier proposed kinetic models and R
values are presented in Table  S2 and Figs. S1, S2, S3, S4, S5 and S6 of Sup-
plementary Information. Among the various models screened, the kinetic model
proposed by Al-Ubaid and Wolf [18] (Model 15) was found to be the most satis-
factory. The kinetic model obtained for Rh–Ni/MgAl2O4 catalyst was:

dX k × P0.21 0.16
CH4 × PH2 O
= , (7)
d(W∕FAo ) 1 + 15.6 × P0.59
H 2

−75.3×103
mol.bar−0.37
where k = 53.9 × 104 × e R×T
gcat h
.
Fig. 4 shows the parity plot of the experimental methane conversions and the
conversions calculated using Eq. 4. As can be seen from Fig. 4, this model fits
the data satisfactorily over the whole range of conversion.

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 98 Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101

0.7

0.6 R² = 0.9755

0.5

0.4
Xexp

0.3

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Xcal

Fig. 4  Parity plot for methane conversion obtained from Al-Ubaid and Wolf model and experimental
methane conversion (solid line represents the best fit line passing through origin)

Discussion

Besides the Langmuir–Hinshelwood type models, power law models have also been
used by various researchers for kinetic modeling of SRM reaction on different cata-
lysts [19–21]. Studies have shown that power law kinetics can be used as a start-
ing model for assessment of the rate data. In our work, similar to the method sug-
gested by the Shacham and Brauner [21], the rate data was tested with the following
equation:
dX
= k × P𝛼CH × P𝛽H O × P𝛾H × P𝛿CO × HT1 . (8)
d(W∕FCH4 ,0 ) 4 2 2

P3H ×PCO
Here HT1 = PCH4 × PH2 O − 2
K1
  , ­K1 is the equilibrium constant for reaction (i)
and α, β, γ and δ are reaction order with respect to methane, water, hydrogen and
carbon mono-oxide.
Besides the above equation, the following equation considering ­CO2 as the pri-
mary product was also tested:
dX
= k × P𝛼CH × P𝛽H O × P𝛾H × P𝛿CO × HT2 . (9)
d(W∕FCH4 ,0 ) 4 2 2

PH2 4 ×PCO2
Here HT2 = PCH4 × (PH2 O )2 − K2
and ­K2 is the equilibrium constant for
reaction (iii).
The applicability of the power law models given by Eqa. 5 and 6 was tested for
the rate data obtained for Rh–Ni/MgAl2O4 catalyst. It was found that the contribu-
tion of ­PCO, PCO2 , and PH2 was not significant as the values of c and d were very
small in comparison to the values of a and b.

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Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101 99

In the light of above, power law model as given by Eq.  10 was also tested for
Rh–Ni/MgAl2O4 catalyst. However, satisfactory results were not obtained.
dX
= k × P𝛼CH × P𝛽H O . (10)
d(W∕FCH4 ,0 ) 4 2

Among the different models screened for Rh–Ni/MgAl2O4, the Al-Ubaid and
Wolf [18] model shown in Eq. 7 was found to be the most satisfactory. Contrary to
the earlier published studies, which show a first-order rate dependence with respect
to methane and zeroth order dependence with respect to water, the kinetic model
for Rh–Ni/MgAl2O4 showed positive orders of 0.21 ± 0.06 and 0.16 ± 0.05 for meth-
ane and water, respectively. Al-Ubaid and Wolf [18] also reported positive reaction
orders of 0.24 and 0.28 for Ni/NiAl2O4 with respect to methane and water, respec-
tively. Table 2 summarizes the results obtained for Rh–Ni/MgAl2O4 catalyst (with
an upper and lower limit of 95% confidence interval) and shows a comparison with
the results reported by Al-Ubaid and Wolf [18]. Similar to their results, the adsorp-
tion equilibrium constant for hydrogen was found to be independent of temperature.
As can be seen from Table  1, lower orders with respect to methane, water and
hydrogen have been observed. Although in both studies different catalysts were
used, a similar apparent activation energy was found. In their work, Sprung et al. [7]
have shown that reaction order with respect to methane and water depends on the
partial pressure of methane and water or S/C ratio. It was shown that the order with
respect to methane and water varied in the range of 0 to 0.7 and − 0.2 to 0.7. These
observations support our findings of lower order with respect to both methane and
water.
As can be seen from Eq.  7, apart from methane and water, hydrogen also sig-
nificantly affects the rate of the reaction. This observation indicates that hydrogen
formed during the steam reforming process also occupies the active sites present on
the catalyst surface. Earlier studies have indeed demonstrated that noble metals, like
Rh and Pt, show hydrogen spillover effect, which can also promote the absorption
of hydrogen on active metal [22]. Furthermore, Jakobsen et al. [23] also suggested
that the hydrogen and carbon monoxide can significantly affect the rate of the reac-
tion particularly for reaction temperatures below 600 °C, which might subsequently

Table 2  Parameters estimated Rh–Ni/MgAl2O4 Ni/NiAl2O4 catalyst

from the kinetic study of catalyst (Al-Ubaid and Wolf
Rh–Ni/MgAl2O4 catalyst and [18])
comparison with the parameters
obtained for Ni/NiAl2O4 from αa 0.21 ± 0.06 0.24
Al-Ubaid and Wolf [18] work
βa 0.16 ± 0.05 0.28
γa 0.59 ± 0.21 1.86
Activation energy 75.2 ± 3.9 69.0
(kJ/mol)
a
 α, β and γ reaction orders with respect to methane, water and hydro-
gen, respectively (Model 15, Table S2, Supplementary File)

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 100 Reaction Kinetics, Mechanisms and Catalysis (2020) 130:91–101

result in lower order with respect to methane and water. Thus, the kinetic parameters
obtained in the present study can be effectively rationalized.

Conclusions

Kinetic study of steam reforming of methane reaction was performed using Rh–Ni/
MgAl2O4 catalyst. Among the different models screened, the model proposed by Al-
Ubaid and Wolf was found to be the most satisfactory for the given experimental
conditions. Kinetic study of Rh added Ni/MgAl2O4 catalyst shows that there was a
positive order of 0.21 and 0.16 for both methane and water with an activation energy
of 75.3 kJ/mol. This kinetic model also suggests that hydrogen adsorbs on the active
sites present on the catalyst surface. The orders with respect to the methane and
water and activation energy were similar to the results reported by Al-Ubaid and
Wolf [18].

Acknowledgements  The financial support provided for this study by Science and Engineering Research
Board (SERB), Government of India under Grant No. SB/S3/CE/066/2013 is gratefully acknowledged.

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