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International Journal of Hydrogen Energy 29 (2004) 187 – 193

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Hydrogen production by catalytic decomposition of methane

over activated carbons: kinetic study
Myung Hwan Kima , Eun Kyoung Leea , Jin Hyuk Juna , Sang Jun Konga ,
Gui Young Hana , Byung Kwon Leeb , Tae-Jin Leec , Ki June Yoona;∗
a Departmentof Chemical Engineering, Sungkyunkwan University, Suwon 440-746, South Korea
b CFC Alternative Research Center, Korea Institute of Science and Technology, Seoul 136-791, South Korea
c School of Chemical Engineering & Technology, Yeungnam University, Kyongsan 712-749, South Korea

Received 13 February 2003; received in revised form 26 March 2003; accepted 3 April 2003

Abstract
Several domestic activated carbons were tested as the catalyst for decomposition of methane. All the activated carbons
showed similar deactivation pattern. Mass transport e9ect in the catalyst particles was observed and the pore mouth blocking
appeared to occur noticeably especially in large particles. Between di9erent kinds of the activated carbons, no discernible
trend was observed between the initial activity and the surface area, and the initial activities lay in a relatively narrow range.
The reaction orders were 0.5 and the same for di9erent samples of the activated carbon. The activation energies were also
about the same, ca. 200 kJ=mol, regardless of the kind and suppliers. These results indicate that the reaction mechanism is the
same for all the activated carbons. Ashes in the activated carbons do little a9ect the catalytic activity.
? 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Activated carbon; Ash; Deactivation; Hydrogen; Kinetic parameters; Mass transport e9ect; Methane decomposition

1. Introduction signiFcantly. When concentrated solar–thermal energy is

Hydrogen is regarded as the ultimate clean power source
of the future. Its application to fuel cells is a typical exam-
ple. However, conventional processes of hydrogen produc-
tion, such as the steam reforming and partial oxidation of
natural gas and other fossil fuels, accompany simultaneous
production of CO2 , which is to be reduced due to the green-
house e9ect. Clean production of hydrogen, e.g. by water
electrolysis using renewable energy, is not competitive with
current energy costs. On the other hand, decomposition of
methane produces no CO2 [1–4].
Noncatalytic thermal decomposition of methane requires
quite a high temperature (1500 –2000 K) in order to obtain
a reasonable hydrogen yield. If the heat is supplied by burn-
ing a fossil fuel, overall CO2 emission may not be reduced
∗ Corresponding author. Tel.: +82-31-290-7244; fax: +82-31-
290-7272.
E-mail address: kijyoon@skku.edu (K.J. Yoon).
used, the CO2 emission will be considerably reduced [5],
but the area where the solar–thermal energy can be utilized
suIciently may be restricted. There have been several at-
tempts to use catalysts in order to reduce the temperature
of methane decomposition. Some transition metals, such as
Ni, Fe and Co, showed remarkable activity in methane de-
composition, but rapid catalyst deactivation associated with
carbon build-up induces other problems such as reactor
blocking and accompanying catalyst regeneration [6–10].
Catalyst regeneration by burning the coke produces CO2
again. Another approach is a plasma process without release
of CO2 to the atmosphere [1,3,4]. It is proposed that this
process could be economical depending on the revenues
from the carbon black product, even though the cost of
electricity occupies a quite high portion.
Recently, CO2 -free production of hydrogen via catalytic
decomposition of methane and other hydrocarbons over car-
bon catalysts has been proposed as a viable alternative to
the conventional steam reforming and partial oxidation [10–
13]. When carbon is used as the catalyst, the clean carbon

0360-3199/03/$ 30.00 ? 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/S0360-3199(03)00111-3
188 M.H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 187 – 193

diamond, carbon Fbers and carbon nanotubes. Among these,

Nomenclature ACs and carbon blacks showed reasonable activity and sta-
bility at around 1123 K. Carbon blacks exhibited relatively
kp rate constant, mmol=min g-cat atm0:5
lower initial activity but deactivated more slowly, while ACs
pA partial pressure of methane, atm
exhibited higher initial activity but deactivated more rapidly.
r0 initial methane decomposition rate, mmol=min
However, many are not well understood about the nature of
g-cat
the catalytic action of the carbons, such as the structure of
r(t) rate at a given time t, mmol=min g-cat
the active sites, e9ects of ashes in the carbons, the kinetic
W mass of catalyst, g
parameters, and so on.
WC amount of deposited carbon at t per g catalyst,
In this work, several samples of domestic ACs (in Korea)
g C deposit./g-cat
were tested for the catalytic activity in methane decomposi-
WCM the maximum amount of deposited carbon per
tion, and some of them were screened for further evaluation.
g catalyst, g C deposit./g-cat
The factors a9ecting the catalyst activity and stability, such
Greek letters as the surface area and particle size, were investigated. The
kinetic parameters such as the reaction order and the activa-
volumetric Kow rate of reactant gas,
tion energy were determined. E9ects of ashes in the carbons
cm3 (STP)=s
were also investigated.

D time constant for deactivation, min

produced can be utilized as a valuable byproduct and it elim-
inates the need for catalyst regeneration and CO2 removal,
which signiFcantly simpliFes the process. The heat required
for the decomposition of methane, which is an endothermic
reaction, can be supplied by burning 10 –15% of the pro-
duced hydrogen, thus no CO2 emission occurring. Muradov
[10–13] investigated various kinds of carbon, such as acti-
vated carbons (ACs), carbon blacks, glassy carbon, graphite,
2. Experimental
Methane (99.99%) was used without further puriFcation.
A variety of ACs made from coconut shell and coal were
supplied from various domestic producers in granular or
powder form. They are shown in Table 1. They were tested in
the form as supplied for preliminary screening, and some of
them were tested in smaller sizes after crushing and sieving
for further evaluation. Just before the reaction test and

Table 1
Activated carbons used

Type Designated name Avg. part. size (m) SA (m2 =g) Method of activ.

Coconut CCN-CI 1485 498 Steam

CCN-DR 1140 725 NAa
CCN-HD 2035 759 Steam
CCN-NA 1140 647 NA
CCN-SCR 1140 966 Steam
CCN-SG1 265 261 Steam
CCN-SG2 325 811 H3 PO4
CCN-SG3 1140 1071 H3 PO4
CCN-SG4 1485 978 H3 PO4
CCN-SG5 1485 244 Steam

Coal CL-CI 1485 950 Steam

CL-DR 1485 670 NA
CL-HD 1485 1077 Steam
CL-OS1 75 1009 Steam
CL-OS2 75 860 H3 PO4
CL-OS3 335 1065 Chemical
CL-OS4 1055 998 Steam
CL-SCR 1140 912 Steam
CL-UN 1485 285 Steam
a Not available.
 M.H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 187 – 193 189

characterization, the sample was dried at 573 K for 1 h

in air. The decomposition reaction was carried out in a
Fxed-bed, quartz-tube Kow reactor heated by an electric
tube furnace. The catalyst charge ranged from 0.2 to 0:8 g.
The reaction temperature ranged from 1023 to 1173 K and
the volumetric hourly space velocity (VHSV) ranged from
about 2 to 15 l=g h. The standard reaction conditions were
the catalyst charge of 0.2 g, the temperature of 1123 K,
the methane Kow rate of 50 cm3 (STP)=min and VHSV of
15:0 l=g h. The product gas was analyzed by gas chromatog-
raphy, using Ar carrier and a TCD. The concentration of hy-
drogen or the methane conversion was determined by using
calibrated data. The Frst sampling and analysis was usually
done at 5 min after the methane was Kowed, since it took
some time for the reaction system to reach the steady state
in order to Kush the argon gas initially present. Because the
stainless-steel sheath of the thermocouple is a good cata-
lyst for hydrocarbon decomposition, the thermocouple was
removed before the reaction experiments after the desired
temperature was adjusted.
The N2 BET surface areas (SA) were measured before
and after the reaction. The amounts of ashes in the ACs Fig. 1. Methane conversion vs. time over as-supplied ACs from
were determined by completely burning the carbons in air at coconut shell (temp: = 1123 K; VHSV = 15:0 l=g h).
873 K for a suIcient time and then measuring the weight of
solid residues. The ashes were dissolved in aqua regia and
hydroKuoric acid and then analyzed by ICP-MS (inductively
12
coupled plasma-mass spectroscopy). To obtain ash-removed
samples, the ACs were immersed in 2 M nitric acid, Fltered
and washed a few times and then dried. 10 CL-CI 1485 µm
CL-DR 1485 µm
CL-HD 1485 µm
CH4 Conversion [%]

3. Results and discussion 8 CL-SCR 1140 µm

3.1. Preliminary testing 6

Some representative reaction data are presented in Fig. 1

for ACs made from coconut shell and in Fig. 2 for those from 4
coal. No gaseous products other than hydrogen were de-
tected. This has been conFrmed to be true below ca. 1400 K
2
by a thermodynamic analysis [14]. It was also conFrmed that
no homogeneous gas phase decomposition occurred below
1173 K. 0
No large di9erence was observed between di9erent sam- 0 20 40 60 80 100 120
ples of the ACs in each group. There were no signiFcant Time [min]
di9erences in activity and deactivation pattern between the
two groups either. All the carbons deactivated quite rapidly. Fig. 2. Methane conversion vs. time over as-supplied activated
After 1 h, the activity became around 0.1– 0.25 of the initial carbons from coal (temp: = 1123 K; VHSV = 15:0 l=g h).
activity. This is in good agreement with an earlier work on
other ACs, where the ratios of activity at 1 h to the initial
activity were in a range from 0.05 to 0.32 at the same tem-
Because the catalyst deactivated quite rapidly, the initial
perature [11]. The data for the other ACs are not presented
activity at 0 min was estimated by extrapolation. The rate of
here for brevity, since they showed somewhat lower activ-
deactivation by carbon deposition can often be represented,
ity but the same deactivation trend. After 2 h of reaction,
as a good approximation, by the following empirical expres-
most of the carbons had 20 –60 m2 =g of the surface area and
sion [15]:
some had less than 10 m2 =g. This indicates that the ACs are
deactivated due to pore blocking by deposited carbon. r(t) = r0 exp(−t=
D ); (1)
190 M.H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 187 – 193
Fig. 3. Initial methane decomposition rate against surface area of
fresh ACs as supplied (temp: = 1123 K; VHSV = 15:0 l=g h).
where r0 and r(t) are the initial rate and the rate at a
given time, t the time on-stream, and
D the time con-
stant for deactivation. By plotting ln r(t) against t, the
initial rate can be estimated by extrapolating to the zero
time.
For all the catalyst investigated the initial rate was plotted
against the surface area. As shown in Fig. 3, no discernible
trend was observed and the activities lay in a relatively nar-
row range. This result is contrasted with that of an earlier
work. Muradov [11] reported that the activity appeared to be
proportional to the surface area when various kinds of car-
bons, including carbon blacks, graphite and acetylene black
whose surface area ranged from 3 to 1500 m2 =g, were com-
pared. However, when only the ACs, whose surface area
ranged from 650 to 1650 m2 =g, were compared, it was not
clear that any linear relationship was observed. Neverthe-
less, the result in this work shows that the ACs exhibit sim-
ilar activities regardless of the surface area or of the type
and suppliers. This suggests that the entire surface is not
the active surface (or the active site) for the decomposition
of methane but only a portion of the surface is active; this
portion in each AC may be di9erent so that the active sur-
face area is not considerably di9erent each other. The ini-
tial rates over ACs reported by Muradov [11] ranged from
1.6 to 2:0 mmol=min g-cat at 1123 K with the space time
of about 1 s. The initial rates in this work ranged from 0.7
to 1:5 mmol=min g-cat with the space time of about 0:6 s
(note: the space time based on the mass of catalyst, W= ,
was 0:24 s g-cat=cm3 , and the apparent catalyst bed density
was ca. 0:4 g-cat=cm3 ). Considering the di9erence in the
space time, the activities reported by the two works can be
regarded to be about the same.
Fig. 4. Methane conversion vs. time over CL-SCR with di9erent
particle size (temp: = 1123 K; VHSV = 15:0 l=g h).
3.2. E9ect of particle size
Since the particle size as supplied was usually large,
the ACs were crushed and sieved to get smaller sizes. The
activities were measured over the samples of CL-SCR with
di9erent particle size and the results are shown in Fig. 4. As
the particle size decreased, the activity increased. This in-
dicates that a mass transfer e9ect may exist. In other words,
as the particle size increases, it takes some more time for
methane to reach the inside surface of the particle due to a
limited rate of reactant transport and thus the overall reac-
tion rate becomes lower. Other ACs showed a similar trend.
The higher decomposition rate means the larger amount
of deposited carbon. Even though the decomposition rate
was higher over the smaller particles, the rate of deactiva-
tion was not higher. This indicates that the carbon produced
from methane decomposition deposits preferentially at the
outer shell of the carbon particles, resulting in pore mouth
blocking and leaving the inner core intact especially for large
particles. It seems that the pore mouth blocking is alleviated
as the particle size decreased and the inner surface can be
utilized to a much greater extent. Since the activity and sta-
bility were found to depend on the particle size, the reaction
experiments hereafter were carried out with the particles of
137 m or smaller.
3.3. The reaction order
To determine the reaction order, the rate was measured
with varying partial pressure of methane and using argon
as the diluent. The results are shown in Fig. 5 of a log–
log graph. The initial rates were estimated by extrapolation.
 M.H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 187 – 193 191

Fig. 6. Methane conversion vs. time over CCN-DR(127 m) at

Fig. 5. Initial rate of methane decomposition over ACs as a function
di9erent temperatures (VHSV = 15:0 l=g h).
of methane partial pressure (temp:=1123 K; VHSV =15:0 l=g h).

The reaction orders, or the slopes, over CCN-DR(127 m)

and CL-SCR(137 m) were 0.51 and 0.49, respectively.
Therefore, the reaction order of methane decomposition over
ACs may be said to be practically 0.5. The rate equation is
r0 = kp pA 0:5 : (2)
This may be the Frst report on the reaction order of
methane decomposition over ACs. A half-order reaction
is often observed for a heterogeneous catalytic reaction
where a reactant adsorbs with dissociation requiring two
surface-active sites and the rate determining step (r.d.s.)
is a subsequent elementary reaction involving an adsorbed
intermediate [16]. By comparison, the reaction order over
Ni, Co and Fe catalysts was reported to be the Frst order
[10]; Muradov [17] assumed that the reaction order over
carbon catalysts was the Frst order, particularly for a carbon
black.

3.4. E9ect of temperature

The activities vs. time were measured over CCN-DR
(127 m) at di9erent temperatures and the results are pre-
sented in Fig. 6. As the temperature increased, the initial ac-
tivity increased but the deactivation occurred more rapidly.
Other catalysts showed the same behavior. The initial rates
were again estimated by the extrapolation. The rate constants
were calculated by using the half-order reaction rate equation
and the integral method. The activation energies were deter-
mined from the Arrhenius plot shown in Fig. 7. The activa-
tion energies over CCN-DR(127 m), CCN-SCR(137 m)
and CL-SCR(137 m) were 194, 198 and 186 kJ=mol,
respectively. The activation energy obtained by another
Fig. 7. Arrhenius plot for methane decomposition over ACs.
work was reported to be 200 kJ=mol [17], which is prac-
tically the same as ours. This indicates that the activation
energy is all the same regardless of the type of ACs. This
activation energy is much lower than the methane C–H
bond energy of 440:0 kJ=mol. This further suggests that
the structure of active surface or the active sites in those
ACs and the reaction mechanism may be the same. A more
detailed and elaborated study may be needed to determine
the structure of the active sites and the mechanism.
192 M.H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 187 – 193

Table 2
Analysis of ashes

Carbon type Name Ash content Ash composition (wt%, excluding O)

(wt%)
Na K Al Si Fe Mg Ca Others

Coconut CCN-CI 3.10 24 44 3 11 3 9 5 1

CCN-DR 2.97 20 39 3 18 5 9 4 2
CCN-SCR 1.84 9 41 2 34 4 4 3 3
CCN-UN 4.37 17 45 2 18 3 9 4 2

Coal CL-CI 6.29 9 1 37 37 8 1 3 4

CLSCR 10.20 6 1 37 44 5 2 2 3

It has been suggested that the total rate of methane decom- Table 3
position is the sum of the rates of carbon nuclei formation The BET surface area of original and ash-removed activated car-
and carbon crystallite growth, and it has also been reported bons
that the activation energy of the carbon nuclei formation is Surface area (m2 =g)
316:8 kJ=mol and that of the carbon crystallite growth is
227:1 kJ=mol [10,12,13]. Thus, the rate of carbon crystal- AC CCN-DR CCN-SCR CL-SCR
Original 725 966 912
lite growth tends to be higher than the rate of carbon nuclei
Ash-removed 278 821 116
generation. The activation energy over ACs is more close
to that of the carbon crystallite growth, and hence this may
be considered to be a major controlling step in the methane
decomposition mechanism. Although the carbon nuclei for-
mation may occur rapidly especially in high-surface-area
carbons such as ACs [12], this seems to be terminated in a
very short initial period of time owing to the exhaustion of
the nucleation sites and then the carbon crystallite growth
takes over the proceeding of the reaction.

3.5. E9ects of ash

ACs usually contain 1–12% of ashes. The ashes in some

samples were analyzed and the results are presented in
Table 2. The ash content in the ACs from coconut shell
was in a range from 1.8 to 4:4 wt%, while that in the ACs
from coal from 6.3 to 10:2 wt%, considerably higher than
the former. The major elements in the former were K, Na,
Si and Mg, while in the latter were Al and Si. These ele-
ments are known to be almost inactive by themselves for
the decomposition of methane. Fe is known to be active.
But its content is so small that it is not considered to a9ect
the activity to a noticeable extent.
When the ashes in the original activated carbons were re- Fig. 8. Comparison of the activities between the original and
ash-removed samples (temp: = 1123 K; VHSV = 15:0 l=g h).
moved, the granules of 1–2 mm size were broken into Fne
particles, most of them being smaller than 75 m. As shown
in Table 3, the surface areas of two ash-removed samples
were reduced greatly and one was reduced by about 15%. The deactivation pattern was very similar between the two
This is probably due to breakdown of the porous struc- groups. Among the ash-removed samples, no relationship
ture. Fig. 8 compares the activities between the original and was seen between the initial activity and the surface area
ash-removed samples. Although the surface areas were re- either. This again indicates that the entire surface is not
duced to about 13 and 18 for CCN-DR and CL-SCR, respec- active but only a fraction is active, and that a majority of the
tively, the initial activities decreased by only about 20%. active surface or sites still remain even after the ash removal.
 M.H. Kim et al. / International Journal of Hydrogen Energy 29 (2004) 187 – 193
4. Conclusions
All the ACs tested deactivated rapidly and showed sim-
ilar deactivation pattern. Smaller particles exhibited higher
activity than larger particles, indicating that the intraparti-
cle mass transport e9ect exists. Since the smaller particles
deactivated somewhat more slowly, the pore mouth block-
ing seemed to occur especially in large particles. Between
di9erent kinds of the ACs, any discernible trend was not
observed between the initial activity and the surface area.
The initial activities, including those from the earlier works,
lay in a relatively narrow range. This suggests that the en-
tire surface is not active but only a portion of the surface is
active with di9erent proportions for di9erent samples. Since
the reaction orders (0.5) and the activation energies (ca.
200 kJ=mol) were about the same regardless of the kind and
suppliers, the reaction mechanism or the structure of active
sites is considered the same on any AC. Ashes in the ACs
do little a9ect the catalytic activity.
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