4864 Ind. Eng. Chem. Res.

2004, 43, 4864-4870

Kinetic Studies on Catalytic Decomposition of Methane to Hydrogen

and Carbon over Ni/TiO2 Catalyst
Sharif Hussein Sharif Zein, Abdul Rahman Mohamed,* and P. Sesha Talpa Sai
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
14300 Nibong Tebal, S.P.S, Pulau Pinang, Malaysia

Experiments were conducted in a fixed-bed catalytic reactor to study the decomposition of

methane to hydrogen and carbon over 13 wt % Ni/TiO2-based catalyst. The variables include
the volumetric flow rate of reactant (relative partial pressures of methane and argon of 0.5 each)
(100 < v0 < 450 mL/min) and reaction temperature (823 < T < 1173 K). The experimental data
of conversion versus time were subjected to the integral method of analysis, and the rate law of
the decomposition reaction was found to be first-order. An activation energy of 60 kJ/mol was
obtained. A possible reaction sequence for methane decomposition was validated against experi-
mental data. An analysis of the rate equations indicated that the adsorption of methane on the
surface is the rate-controlling step. This observation was same as that obtained from an analysis
of data by both integral and differential methods. Using the design equation for a packed plug-
flow reactor, predictions were made to obtain the conversion profiles at various operating condi-
tions. Good agreement was obtained upon comparison of the experimental and simulated data.

Introduction In this paper, kinetic studies were carried out using

Hydrogen is predicted to become an efficient source
of clean fuel and has been described as a long-term
replacement for natural gas. With increasing interest
in fuel cells and progress in hydrogen storage technolo-
gies, the use of hydrogen as a source of clean fuel is
likely to increase in the future.1 There is substantial
interest in developing novel methods for the production
of hydrogen, and one such process is the catalytic
decomposition of methane.2-8
Many experimental studies have been conducted to
gain a better understanding of the kinetics of methane
decomposition. The majority of the research has been
focused on determination of the reaction mechanism,
identification of the primary decomposition products,
and estimation of the activation energy for methane
decomposition. The activation energy for methane de-
composition using a tubular reactor without catalyst
was found 370 kJ/mol over the temperature range
1770-2270 K.9 Steinberg10 reported an activation en-
ergy of 131 kJ/mol for methane decomposition over the
temperature range 973-1173 K, which is considerably
lower than the value for methane decomposition without
catalyst. However, he performed the reaction at pres-
sures of 28-56 atm. Dahl et al.11 reported an activation
energy of 208kJ/mol for methane decomposition using
a fluid-wall graphite aerosol flow reactor over the
temperature range 1533 < T < 2144 K.
The activation energy of the decomposition of meth-
ane with a mixture of hydrogen over nickel catalysts
was found to be 90 kJ/mol over the temperature range
723-863 K12 and 97 kJ/mol over the temperature range
803-863 K.13 Muradov14 studied the decomposition of
methane over carbon catalysts, reporting activation
energies of 236 kJ/mol (valid for a temperature range
of 1023-1223 K) and 201 kJ/mol (valid for a tempera-
ture range of 873-893 K) for a carbon black catalyst
and an activated carbon catalyst, respectively.
* To whom correspondence should be addressed. E-mail:
chrahman@eng.usm.my
10.1021/ie034208f CCC: $27.50 2004 American Chemical Society
Published on Web 07/08/2004
13 wt % Ni/TiO2-based catalyst for the catalytic decom-
position of methane for the production of hydrogen. The
rate equation was obtained and the activation energy
was estimated. A model, which uses the obtained rate
equation for the decomposition of methane to hydrogen,
was simulated to predict the methane conversion pro-
files.
Experimental Section
Methane decomposition was studied using 13 wt %
Ni catalyst doped onto different supports, viz., TiO2,
Al2O3, MgO, and SiO2. The catalysts were prepared
using the impregnation method. Desired amounts of the
transition metal oxides were dissolved in deionized
water. The dopant concentrations are actually relative
to the molar quantity of the support. The resulting paste
was then dried in an oven and subsequently calcined
in a ceramic crucible at 900 C. The catalysts were then
sieved to a size of 400-500 m.
The experiments were carried out at atmospheric
pressure in a stainless steel fixed-bed reactor system.
A schematic diagram of the reactor system is shown in
Figure 1. The reactor was fabricated from a stainless
steel tube (o.d. ) 12.7 mm, i.d. ) 10.92 mm, and length
) 600 mm). A thermocouple of type K in an inconel tube,
3 mm in diameter and 600 mm long, was used to
measure the temperature of the catalyst bed in the
reactor. The catalyst layer was situated in the center
of the reactor. The free space before and after the
catalyst layer was filled with quartz particles (RDH) to
minimize the reactor dead volume. The furnace used
was a single zone (model Carbolite VST 11) with a
temperature controller and was supplied by Carbolite,
Hope Valley, U.K. A pressure gauge (Ashcroft, Stratford,
CT) located just above the reactor was used to read the
inlet pressure.
Methane (supplied by Malaysian Oxygen Sdn. Bhd.)
with a purity of 99.999% and argon (supplied by Sitt
Tatt Industrial Gases Sdn Bhd.) with a purity of
99.999% were mixed in ratio of 1:1 before entering the

Figure 1. Schematic diagram of the reactor system.
reactor, i.e., a mole fraction of 0.5 for methane was used
for all of the experiments. Argon was used as a diluent
as nitrogen might react with the hydrogen at high
temperatures. The flow of methane was regulated using
a mass flow controller (MKS), and the argon flow was
regulated with Brooks mass flow controllers (model
5850E). The outlet gas flow was monitored by a gas flow
meter (Alexander Wright DM3 B).
For the kinetics study, a total of 64 experiments were
conducted with fresh catalyst in each run. One gram of
catalyst was packed in the reactor. The furnace was
switched on, and pure argon was allowed into the
reactor to create an inert atmosphere in the reactor. To
activate the fresh catalyst, it was subjected to methane
for 5 min at 998 K and 2700 h-1 gas hourly space
velocity (GHSV). When the furnace had attained the
required temperature, methane of known concentration
was admitted into the reactor. The concentrations of the
product gases were analyzed, and the experiment was
stopped when the concentration of the product gases
attained a steady value. The experiment was repeated
for different volumetric flow rates (100-450 mL/min)
and temperatures (823-1173 K).
The product gases were analyzed using an on-line gas
chromatograph (GC) (Hewlett-Packard Series 6890,
Hewlett-Packard, Wilmington, DE). The GC was con-
trolled on-line using HP ChemStation Rev. A. 06.01.-
[403] software. Porapaq N and molecular sieve 5 (1/
8-in. diameter, 6-ft length) stainless steel columns,
situated in series with the Porapaq N column located
in front were used. The Porapaq N column was used to
separate carbon dioxide, ethane, ethylene, and propy-
lene and the molecular sieve 5 column for hydrogen,
oxygen, carbon monoxide, nitrogen, and methane. Be-
cause higher hydrocarbons and carbon dioxide can ruin
the molecular sieve 5 column, two valves operated at
temperature 333 K were used to control the outlet gas
from the Porapaq N column to the detectors to avoid
passing it through the molecular sieve 5 column.
Valve 1 functioned as a sampling mechanism, and valve
2 was used to control the flow of the product through
the molecular sieve 5 column. When the valve is off,
gas is allowed to flow through the molecular sieve 5
Ind. Eng. Chem. Res., Vol. 43, No. 16, 2004 4865
column. The gas chromatograph injector temperature
was set at 313 K. The initial and the final temperatures
of the oven were set to 313 and 473 K, respectively. A
heating rate of 5 K/min was used. The detector tem-
perature was kept at 473 K. Pure argon gas (99.999%)
was used as a carrier gas. The total analysis time was
25 min for each injection. Standard gas was injected into
the gas chromatograph, and the area of each of the
components in the standard gas was determined. The
standard gas mixture was supplied by BOC Gases,
Guilford, U.K. Chromatograms of hydrocarbons such as
methane, ethylene, ethane, and propylene were obtained
using a flame ionization detector (FID), whereas hydro-
gen, oxygen, carbon monoxid,e and carbon dioxide were
detected using a thermal conductivity detector (TCD).
A carbon balance of 100 ( 2% was obtained for every
run over the catalyst.
Pore volume and surface area measurements of the
different samples were determined via nitrogen adsorp-
tion/desorption isotherms at liquid nitrogen tempera-
ture (77 K) using an automated gas sorption system
(Autosorb I, QuantaChrome Corporation, Boynton Beach,
FL). All samples were degassed at a temperature of 573
K for 3 h prior to the measurements. Computer pro-
grams (Micropore, version 2.46) allowed for rapid nu-
merical results for the surface area and pore texture
from the adsorption-desorption isotherm. Spent cata-
lysts were analyzed using a transmission electron
microscope (Philips TEM CM12). In preparation for
TEM experiments, a few samples of the spent catalyst
were dispersed in distilled water, and then a drop of
the dispersion was deposited on a coated copper grid.
Results and Discussion
A blank reaction (i.e., decomposition of methane
without catalyst) study was carried out in the stainless
steel reactor filled with quartz sand with a feed consist-
ing of methane and argon in a ratio of 1:1 at a total
flow rate of 80 mL/min and in the temperature range
of 673-1173 K (the range used in the present study).
The conversion of methane was less than 1% in all of
4866 Ind. Eng. Chem. Res., Vol. 43, No. 16, 2004
Table 1. Physical Properties of the Fresh Ni Supported
on Different Supports
surface area total pore volume
catalyst (m2/g) (Vp) (cm3/g)
Ni on SiO2 11.45 0.003
Ni on Al2O3 5.28 0.010
Ni on TiO2 8.05 0.005
Ni on MgO 7.53 0.007
Table 2. Details of Conversions Obtained in the Present
Study with Different Supports at 998 K and 2700 h-1
GHSV
conversion (%)
catalyst 2 min 5 min 60 min 120 min
13 wt % Ni on SiO2 97.41 74.12 48.67 PBa
13 wt % Ni on Al2O3 99.54 72.98 PB PB
13 wt % Ni on TiO2 99.18 64.57 61.34 62.44
13 wt % Ni on MgO 99.23 52.23 15.84 8.05
a PB ) pressure buildup.
these experiments, indicating that the decomposition of
methane without catalyst in the temperature range of
673-1173 K was negligible. Thus, the material stainless
steel of type 316 used in this study is a suitable material
for the construction of a reactor for the decomposition
of methane.
Selection of Support Material. Table 1 shows the
physical properties of 13 wt % Ni/TiO2 doped onto
different supports, viz., SiO2, Al2O3, TiO2, and MgO. The
surface areas of Ni on SiO2, Al2O3, TiO2, and MgO were
11.45, 5.28, 8.05, and 7.53 m2/g, respectively. The total
pore volumes show the same trend as the surface areas
with values of 0.003, 0.010, 0.005, and 0.007 cm3/g for
Ni on SiO2, Al2O3, TiO2, and MgO, respectively. This
can be attributed to the change of the structure or
electronic state of the metal species due to the interac-
tion with the supports.15
To select a suitable support material, experiments
were conducted for methane dissociation into hydrogen
and carbon with 13 wt % NiO catalyst supported on
different supports, viz., TiO2, Al2O3, MgO and SiO2, at
998 K and 2700 h-1 gas hourly space velocity (GHSV).
The results obtained are listed in Table 2. After 2 min
on stream, methane conversion of 100, 100, 100, and
97% and COx yield of 60, 62, 65, and 62% were
obtained using 13 wt % Ni/SiO2, 13 wt % Ni /Al2O3, 13
wt % Ni/TiO2, and 13 wt % Ni/MgO, respectively. The
rest of the yield was hydrogen. No higher hydrocarbons
were detected. The COx production probably occurs via
the reaction of chemisorbed carbon and hydrogen,
produced by the decomposition of methane with the
lattice of metal oxides.4 Methane reactions were con-
ducted over catalysts without any added oxygen. There-
fore, any methane oxidation in these experiments must
be derived from oxygen originating from the catalyst.
The surface oxygen present on the catalyst was respon-
sible for the formation of COx as no oxygen was present
in the feed gas. The reaction takes place between gas-
phase or weakly adsorbed methane and strongly ad-
sorbed oxygen or lattice oxygen. Surface OH groups and/
or oxygen from the support and/or promoter and/or the
active metal, in this case NiO, might have participated
in the conversion of methane to COx. Previously, it was
concluded that the surface OH groups were involved in
the conversion of methane to CO.16 On the basis of Table
2, it was estimated that 2-4 min is sufficient for
reducing the fresh catalyst. As the time increased, the
number of methane pulses over the catalyst increased,
Table 3. Repeatability and Analytical Reproducibility of
the Catalytic Data Obtained in the Present Study at 998
K for 60 Min on Stream Using 13 wt % Ni on TiO2
trial conversion (%)
1 61.34
2 60.08
3 62.11
and only hydrogen was detected because the catalyst
was reduced further. After 5 min on stream, hydrogen
and methane were the only components detected in the
product stream for the all types of catalysts. The ratio
of methane conversion and hydrogen formation was
found to be 1:2. In fact, hydrogen was the only gas
detected after 5 min on stream. The methane decom-
position obtained within the first 5 min of reaction
decreased in the order SiO2 > Al2O3 > TiO2 > MgO
support. After 60 min on stream, the order of activity
changed to TiO2 > SiO2 > MgO support, and a pressure
buildup (PB) was observed on the Al2O3 support. At 120
min on stream, the TiO2 system maintained its activity,
and the MgO decreased from 16 to 8%, whereas a
pressure buildup occurred in the SiO2-supported cata-
lyst system. Thus, it can be concluded that TiO2 is the
best support. This is in line with the observations of
Takenaka et al.,17,18 who concluded that TiO2 is the best
support for either repeated cycles of methane decom-
position or high catalytic activity of Ni/TiO2 for repeated
reactions. The results of the present study also confirm
that deactivation is not occurring up to 120 min on
stream over TiO2-supported Ni catalyst. Because fresh
catalyst was used each time, the deactivation can be
neglected in the present study. Carbon samples obtained
from Ni catalysts loaded onto various supports were
further studied using TEM. The results obtained showed
that the introduction of the support markedly influenced
the carbon morphology. The TEM micrographs of carbon
synthesized on Ni supported on SiO2, Al2O3, TiO2, and
MgO support are shown in parts a-d, respectively, of
Figure 2. The TEM image of the carbon formed on Ni
on SiO2 and Al2O3 supports seems to be undeveloped
carbon nanotubes, whereas the carbon formed on Ni on
MgO looks like small tubes connected to each other. On
the other hand, the TEM image of the carbon formed
using Ni on the TiO2 support (Figure 2c) was the best
among the supported catalysts. Thus, the catalytic
activity depended strongly the kind of support.
To test the repeatability and analytical reproducibility
of the raw catalytic data, activity tests for the newly
prepared 13 wt % Ni on TiO2 catalyst were conducted
three times at 998 K for 60 min on stream using new
catalyst each time, and the results are reported in Table
3. The ratio of methane conversion to hydrogen forma-
tion was found to be 1:2. In fact, hydrogen was the only
gas detected. The results indicate that the reproduc-
ibility of the data is satisfactory.
Kinetics of the Reaction. Among the catalysts
studied in this work, 13 wt % Ni on TiO2 support was
found to be the most effective catalyst for the production
of hydrogen and carbon through the decomposition of
methane. Kinetic studies were carried out using this
catalyst. The experimental program for obtaining the
kinetics of the reaction consisted of runs at different
mole ratios and temperatures with a constant weight
of the 13 wt % Ni/TiO2, and the results are presented
in Table 4. The conversion of methane versus time data
were subjected to the integral method for the derivation
of a suitable rate law.
 Ind. Eng. Chem. Res., Vol. 43, No. 16, 2004 4867

Figure 2. Transmission electron microscope images of the carbon produced on Ni supported on the different supports (a) SiO2, (b) Al2O3,
(c) TiO2, and (d) MgO at 998 K and GHSV of 2700 h-1.

Table 4. Details of Methane Conversions (%) Obtained in

the Present Study at Various Operating Conditionsa

temperature volumetric flow rate (mL/min)

(K) 100 150 200 250 350 450
823 15.82 11.42 7.04 6.52 - -
873 27.41 20.65 16.55 14.03 7.03 -
923 41.56 33.81 27.43 24.87 16.21 9.87
973 53.99 45.10 37.21 31.58 24.99 17.88
1023 59.07 49.66 39.48 33.24 26.04 21.97
1073 70.54 59.63 49.02 35.10 24.43 21.07
1123 82.49 69.08 54.32 48.77 37.67 24.33
1173 92.03 76.88 65.87 53.46 47.01 34.68
a Catalyst weight ) 1 g.
Figure 3. Plot of conversion as a function of weight time at
For a first-order reaction in a packed-bed reactor, the different temperatures.
relation between conversion and weight time is as
follows19

k ) (1 + ) ln ( 1
1 - Xout )
- AXout (1)

For the present reaction, the above equation reduces to

k ) 1.5 ln
( 1
1 - XCH4 )
- 0.5XCH4 (2)

From the plots of the function on the right-hand side of
eq 2 versus (w/v0), shown typically in Figure 3 for a
1-g sample of catalyst, it follows that the data fall on a
reasonably straight line through the origin. Hence, the
decomposition reaction is of first order.
From the values of the specific reaction rate constant,
k, calculated from the slopes at different reaction
temperatures, the activation energy obtained in the
present study is 60 kJ/mol following the Arrhenius
equation. The plot is shown in Figure 4. Reported
activation energies for methane decomposition without
Figure 4. Plot of values of logarithmic specific reaction rate
constant against the reciprocal of the reaction temperature.
catalyst range from 356 to 402 kJ /mol,9,11 and those
with catalyst range from 90 to 236 kJ/mol.12-14 Thus,
the activation energy obtained in this study using 13
wt % Ni/TiO2-based catalyst is considerably the lower
than others.9-14
Reaction Mechanism. Experimental observations
of the present study indicate that the reaction is
elementary. However, the reaction mechanism and the
4868 Ind. Eng. Chem. Res., Vol. 43, No. 16, 2004

decomposes on the front surface of certain active sites

of the Ni/TiO2-based catalyst, and the carbon thus
formed diffuses through the metal and precipitates at
the rear surface. The driving force that pushes the
carbon diffusion was suggested to originate from the
concentration gradient of dissolved carbon between the
two interfaces, i.e., the metal-gas interface to the
metal-nanocarbon interface. Therefore, for high values
of diffusivity, the concentration of carbon dissolved
in nickel is almost uniform and small (therefore, CNi
0).
When the adsorption of methane is the rate-limiting
step, the expression relating the rate of reaction and
the concentrations of various species is

CTK1PCH4
Figure 5. Transmission electron microscope image of carbon
formation on the catalyst particle.
-rCH4 ) (10)
1 + K71/2PH21/2
identification of rate-controlling steps were attempted
in the present study following the mechanism proposed
by Snoeck et al.20 They proposed the following mecha- Initially, the concentration of hydrogen is zero, so eq
nism for methane decomposition 10 becomes

k+1
CH4 + S {\
k
} CH4S (3) -rCH4,0 ) CTK1PCH4 (11)
-1

k+2
CH4S +S {\
k
} CH3S + HS (4)
-2 If the methane decomposition is an adsorption-limited
reaction, then the initial rate will be linear with the
k+3
CH3S + S {\ } CH2S + HS (5) initial partial pressure of methane. This is what was
k -3 observed experimentally in the present study. However,
the individual rate laws and individual initial rate plots
k+4
CH2S + S {\ } CHS + HS (6) with the other steps in the mechanism as rate-limiting
k -4 step are also derived below and checked to confirm
whether the methane decomposition reaction is really
k+5
CHS + S {\ } CS + HS (7) adsorption limited.
k -5
When the removal of the first hydrogen atom from
k+6 molecularly adsorbed methane is the rate-limiting step,
CS {\
k
} CNi + S (8) it follows that
-6

k+7
2HS {\ } H2 + 2S (9)
k -7
Whereas eq 3 represents the adsorption of methane
on the surface of the catalyst, eqs 4-7 represent the
surface reaction to form adsorbed methyl radicals and
adsorbed hydrogen atoms on the catalyst surface. Equa-
tions 8 and 9 represent the deposition of carbon on the
catalyst surface and the desorption of hydrogen from
the catalyst surface, respectively.
For the mechanism shown in eqs 3-9, the rate-
limiting step is identified as follows: It is assumed that
one of the equations is the rate-limiting step, and then
the rate law is formulated in terms of the partial
pressures of the methane and hydrogen. From the
equation obtained, the variation of the initial reaction
rate with the initial partial pressure of methane is
checked. If the theoretical rate varies with pressure in
the same way as observed experimentally, it will be
assumed that the mechanism and the rate-limiting step
are correct.
A mechanistic interpretation of the growth of carbon
on the catalyst has been proposed in the literature.21,22
Figure 5 supports the proposed mechanism for the
growth of carbon nanotubes on the catalyst. Methane
CTK1k+2PCH4
-rCH4S ) (12)
(1 + K1PCH4 + K71/2PH21/2)2
Initially, the concentration of hydrogen is zero, and
hence eq 12 becomes
CT2K1k+2PCH4
-rCH4S,0 ) (13)
(1 + K1PCH4)2
If the removal of the first hydrogen atom from molecu-
larly adsorbed methane limits the methane decomposi-
tion, the rate will increase at low initial partial pres-
sures of methane and then decrease at high initial
partial pressures of methane. This conclusion is not
consistent with the experimental observations of the
present study.
When the removal of second, third, and fourth hy-
drogen atoms from molecularly adsorbed methane is
the rate-limiting step, the expressions relating the rate
 Ind. Eng. Chem. Res., Vol. 43, No. 16, 2004 4869

of reaction and concentrations of various species are as Initially, the concentration of hydrogen is zero, and
follows eq 19 becomes

-rCH3S )
( C2TK1K2k+3PCH4
K71/2PH21/2 )/(1 + K1PCH4 +
-rHS ) 0 (20)

Because the reaction rate cannot be zero, desorption of

)
2 hydrogen from the surface cannot be the rate-limiting
K1K2PCH4 step.
+ K71/2PH21/2 (14)
K71/2
PH2 1/2 An analysis of the above rate equations indicates that
the rate equation with the adsorption of methane on

( )/(
the surface as the rate-controlling step exhibited a linear
CT2K1K2K3k+4PCH4 relationship with the concentration of methane. This
-rCH2S ) 1 + K1PCH4 + observation is same as that obtained from the analysis
K7PH2 of data by the integral method. Hence, the assumed

)
2
mechanism with the adsorption of methane rate-
K1K2PCH4 K1K2K3PCH4 controlling is consistent with the experimental observa-
1/2 1/2
+ + K7 PH2 (15) tions. This can be expected, as the surface reaction is
K71/2PH21/2 K7PH2
unlikely to control the rate because the reaction occurs

( )/(
at relatively high temperatures.
CT2K1K2K3K4k+5PCH4 Simulation. Conversion profiles along the length of
-rCHS ) 1 + K1PCH4 + the reactor were obtained following the design equation
K73/2PH23/2 for packed-bed reactor. Isothermal and plug-flow condi-
tions (the ratio of bed diameter to catalyst particle
K1K2PCH4 K1K2K3PCH4 K1K2K3K4PCH4 diameter is around 25) were assumed in the reactor.
+ + + Because the flow rates were sufficiently high, heat- and
K71/2PH2 1/2 K7PH2 K73/2PH23/2 mass-transfer limitations were assumed to be negligible,

1/2
K7
Initially, the concentration of hydrogen is zero, and
the numerators and denominators of eqs 14-16 ap-
proach infinity. Therefore, the limit of these expressions
approaches zero. Because the reaction rate cannot be
zero, the removal of the second, third, or fourth hydro-
gen atom from molecularly adsorbed methane cannot
be the rate-limiting step.
)
2
and the reaction was assumed to be kinetically con-
1/2
trolled. Experiments were conducted with different flow
PH2 (16) rates keeping all of the other variables constant, and
the conversion (H2 yield) was found to be almost same
in all of these experiments (there was a slight increase
at lower flow rates).
The packed-bed reactor is assumed to have no radial
gradients in concentration, temperature or reaction rate.
When the pressure drop through the reactor and
catalyst decay are neglected, the relation between
conversion and weight time is

( )
When the deposition of carbon on the catalyst is rate-
limiting step, one obtains kW 1
) 1.5 ln - 0.5 XCH4 (21)
1 - XCH4

( )/(

CTK1K2K3K4K5k+6PCH4
-rCS ) 1 + K1PCH4 + The above equation can be used to determine the
K72PH22
amount of catalyst needed to obtain a specified conver-
K1K2PCH4 K1K2K3PCH4 K1K2K3K4PCH4 sion at a given temperature and volumetric flow rate.
+ + + Similarly, it can also be used to obtain the conversion
1/2
K7 PH2 1/2 K7PH2 K73/2PH23/2

)
for a given amount of catalyst at a particular temper-
K1K2K3K4K5PCH4 ature and volumetric flow rate. The above equation is
+ K71/2PH21/2 (17) valid for 823 < T < 1173 K and 100 < v0 < 450 mL/
K72PH22 min, as these were ranges in which the experiments
were performed in the present study.
Initially, the concentration of hydrogen is zero, and the The model predictions for the conversion of methane
numerator and denominator of eq 17 approach infinity. under conditions of variable volumetric flow rates (100
Therefore, the limit of this expression gives < v0 < 450 mL/min) and variable temperatures (823 <
T < 1173 K) agree well with the experimental observa-
tions. The predictions of the model for methane conver-
-rCS ) CTk+6 (18)
sion are compared to the experimental values at all
temperatures and volumetric flow rates. Figure 6 shows
Because, the reaction rate cannot be CTk+6, the deposi- a satisfactory comparison between the experimental and
tion of carbon on the catalyst cannot be rate-limiting predicted (using eq 21) conversions. The standard
step. deviation (SD) of (0.13 was obtained using the equation
When desorption of hydrogen from the surface is the
rate-limiting step, one finds

x
N (Exp - Cal)
2
CT k-7PH2 Exp
-rHS ) - (19) SD )
i)1
) (0.13 (22)
(1 + K1PCH4)2 N-1
4870 Ind. Eng. Chem. Res., Vol. 43, No. 16, 2004
Figure 6. Comparison of theoretically and experimentally de-
termined conversions of methane.
As consequence, the experimental values are well fitted
by the model at low temperature.
Conclusions
For the decomposition of methane to hydrogen and
carbon using 13 wt % Ni/TiO2 catalyst, it was found in
the present study that the decomposition reaction is of
first order with an activation energy of 60 kJ/mol. This
activation energy is the lowest activation energy re-
ported in the literature for this reaction. It was also
found that the adsorption of methane on the surface is
the rate-controlling step. The model developed indicates
the volumetric flow rate, catalyst weight, and temper-
ature to be decisive parameters in scale-up consider-
ations and in the extrapolation of laboratory-scale ex-
perimental results. The model predictions for the con-
version agree well with the experimental observations.
Acknowledgment
The authors acknowledge for the financial support
provided by Ministry of Education, Malaysia and Uni-
versiti Sains Malaysia under Fundamental Research
Grant Scheme (Project: A/C No: 6070014).
Nomenclature
CA ) concentration of substance A (mol/mL)
CA0 ) initial concentration of substance A (mol/mL)
CCH4 ) concentration of methane (mol/mL)
CNi ) concentration of carbon dissolved in nickel
CT ) total concentration of sites
CV ) concentration of vacant sites
k+1, k-1, k+2, k-2, k+3, k-3, k+4, k-4, k+5, k-5, k+6, k-6, k+7,
k-7 ) rate coefficients of the forward (+) and the reverse
(-) reactions
k ) specific reaction rate constant [mL/(gcat s)]
K1, K2, K3, K4, K5, K6, K7 ) equilibrium coefficients
N ) number of experiments
PCH4 ) partial pressure of methane
-rA ) rate of species A decomposition [mol(gcat s)]
-rCH4 ) rate of methane decomposition [mol/(gcat s)]
S ) surface active site
T ) Temperature (K)
v0 ) entering volumetric flow rate
Vp ) total pore volume (cm3/g)
W ) Weight of catalyst
XA ) conversion of species A
XCH4 ) conversion of methane
Xout ) conversion at the outlet
Greek Symbols
 ) fractional change in volume per mole of A reacted
resulting from the change in total number of moles
) weight time (g s/mL)
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Received for review October 25, 2003
Revised manuscript received March 25, 2004
Accepted May 4, 2004
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