Korean J. Chem. Eng.

, 24(4), 674-678 (2007)

SHORT COMMUNICATION
Hydrogen production by catalytic decomposition of methane
over carbon catalysts in a fluidized bed
Jae Uk Jung, Wooseok Nam, Ki June Yoon and Gui Young Han †

Department of Chemical Engineering, Sungkyunkwan University, Suwon 440-746, Korea

( )
Received 19 October 2006 • accepted 23 January 2007

Abstract−A fluidized bed reactor made of quartz tube with an I.D. of 0.055 m and a height of 1.0 m was employed
for the thermocatalytic decomposition of methane to produce CO - free hydrogen. The fluidized bed was used for con-
2

tinuous withdrawal of the carbon products from the reactor. Two kinds of carbon catalysts - activated carbon and car-
bon black - were employed in order to compare their catalytic activities for the decomposition of methane in the flu-
idized bed. The thermocatalytic decomposition of methane was carried out in a temperature range of 800-925 C, using o

a methane gas velocity of 1.0-3.0 Umf and an operating pressure of 1.0 atm. Distinctive difference was observed in the
catalytic activities of two carbon catalysts. The activated carbon catalyst exhibited higher initial activity which de-
creased significantly with time. However, the carbon black catalyst exhibited somewhat lower initial activity compared
to the activated carbon catalyst, but its activity quickly reached a quasi-steady state and was sustained over time. Sur-
faces of the carbon catalysts before and after the reaction were observed by SEM. The effect of various operating pa-
rameters such as the reaction temperature and the gas velocity on the reaction rate was investigated.
Key words: Hydrogen, Activated Carbon, Carbon Black, Fluidized Bed, Methane

INTRODUCTION without additional CO2 removal stages commonly required in con-

ventional technologies (e.g., steam reforming, partial oxidation).
Hydrogen is expected to be an important energy source of the The energy required to produce one mole of hydrogen, 37.8 kJ, is
future because of its environmentally acceptable characteristics. How- somewhat less than that of other conventional processes such as
ever, hydrogen cannot be naturally produced so that it is not a pri- the steam reforming (63.3 kJ/mol H2). The methane decomposition
mary fuel. Hydrogen must be generated from other natural resources is an endothermic reaction which occurs above 700 oC [5-7].
on the earth, of which water is the most abundant one. The elec- There have been many attempts to improve catalysts in order to
trolysis of water has been widely used so far to produce hydrogen reduce the temperature of the thermal decomposition of methane.
from water even though its energy efficiency is quite low [1,2]. The Metal catalysts possessing Ni, Fe, Co and others have been com-
steam reforming of natural gas is a well-known process to produce monly used for this purpose. However, the catalysts were deacti-
hydrogen efficiently. Only 40.75 kJ is required for producing one vated by carbon buildup on the surface [8-10]. The metallic catalysts
mole of hydrogen in this process. However, the total CO2 emission were periodically burned off in order to remove the carbon depos-
from the process reaches up to 0.43 moles of CO2 per mole of H2 ited on the surface. As a result, the amount of CO2 produced dur-
produced. Therefore, the thermal decomposition of methane has ing the regeneration is comparable with that of the conventional
been studied in order to produce H2 without any associated CO2 processes. The oxidative regeneration of metal catalysts causes an-
emission [3]. other problem related to the unavoidable contamination of hydro-
Natural gas can be thermally decomposed into carbon and hy- gen with carbon oxides, which brings on an additional purification
drogen, and the resulting carbon can be sequestered or sold as a ma- step. Our technical approach is based on the thermocatalytic decom-
terial commodity. Thus, hydrogen can be cleanly produced by the position of hydrocarbons over carbon-based catalysts in an air/water-
thermal decomposition of natural gas without production of CO2 free environment. The use of carbon catalysts offers the following
[4,5]. Thermocatalytic decomposition of natural gas is an alterna- advantages: (i) no need of regenerating catalysts by burning the de-
tive method for producing hydrogen with the accompanying seques- posited carbon off, (ii) no contamination of hydrogen with carbon
tration of carbon. The thermocatalytic decomposition of methane oxides and, consequently, no need of additional gas purification,
occurs at an elevated temperature and results in the formation of and (iii) the production of a valuable by-product, namely elemental
hydrogen and elemental carbon. carbon.
CH4=C+2H2 ∆Ho=75.6 kJ/mol (1)
To produce CO2-free hydrogen from natural gas, a fluidized bed
reactor was employed. A fluidized bed reactor provides a constant
Due to the absence of oxidants (e.g., H2O and/or O2), no carbon flow of solids through the reaction zone, which makes it particu-
oxides are formed in the reaction. This approach also proposes re- larly suitable for the continuous addition and withdrawal of carbon
markable advantages. Hydrogen can be produced in a single step particles from the reactor. In fluidization, the bed of carbon cata-
lysts behaves like a well-mixed body of liquid, giving rise to high
To whom correspondence should be addressed.
†
particle-to-gas heat and mass transfer rates [11]. The carbon cata-
E-mail: gyhan@[Link] lysts are allowed to spend a certain time in the reaction zone, which
674
 Hydrogen production by catalytic decomposition of methane over carbon catalysts in a fluidized bed 675
can easily be controlled by adjusting the ratio of the feed rate and RESULTS AND DISCUSSION
the weight of the bed. The bed can also buffer any instability that
may arise during the continuous operation. In this study, the char- Catalytic activities of the activated carbon and the carbon black
acteristics of the thermocatalytic decomposition of methane in a for the decomposition of methane were examined under various
fluidized bed reactor were investigated. operating conditions in a fluidized bed.
1. Activated Carbon
EXPERIMENTAL Catalytic activity of the activated carbon was measured at vari-
ous temperatures. The activity changes along time on stream are
Methane (99.95 vol%) was used without further purification. Sam- plotted in Figs. 2 and 3. The activated carbon showed high activity
ples of carbon catalysts were obtained from carbon manufacturers
in Korea in the form of fine powders. The particle size of activated
carbon was 106 µm, and the effective particle size of carbon black
was about 153 µm due to the agglomeration of fine particles which
were of 30-40 nm in primary size. The effective particle size of car-
bon black was determined by measuring the minimum fluidization
velocity in the fluidized bed.
A schematic diagram of the fluidized bed reactor used is shown
in Fig. 1. The fluidized bed reactor was made of quartz tube with
an I.D. of 0.055 m and a height of 1.0 m. The initial catalyst load-
ings of the activated carbon and the carbon black were 20 g and
100 g, respectively. The methane flow rate was controlled by means
of a mass flow controller. A feed stream of methane which was pre-
heated to 400 oC entered the reactor from the bottom and passed
through the fluidized bed of carbon catalysts at the operating tem-
perature where the thermocatalytic decomposition of methane oc-
curred. The temperature of the bed was monitored by a thermocou-
ple situated in the middle. Hydrogen-containing gas exited from
the top of the reactor via a cyclone and a bag filter. The products
were analyzed by gas chromatography (TCD detector) and the char-
acterization of the carbon catalysts and the carbon products was
performed by SEM. The conversion of methane was determined
by GC and checked by weighing the fluidized bed materials (car-
bon catalysts and by-product carbons in the reactor). Fig. 2. The effect of reaction temperature on the CH conversion
over activated carbon at a gas velocity of 1.0 Umf .
4

Fig. 1. A schematic diagram of the fluidized bed reactor.

1. Mass flow controller 07. Cyclone
2. Preheater 08. Data logger
3. Distributor 09. Temperature controller
4. Fumace 10. Bag filter
5. Fluidized bed reactor 11. GC Fig. 3. The effect of reaction temperature on the CH decomposi-
tion rate over activated carbon at a gas velocity of 1.0 Umf .
4

6. Thermocouple
Korean J. Chem. Eng.(Vol. 24, No. 4)
676 J. U. Jung et al.
at the beginning of the reaction and became rapidly deactivated re- of the minimum fluidization velocity, Umf, so that the flow regime
gardless of the reaction temperature. This indicated that the deacti- of the fluidized bed can be easily understood. A gas velocity of 1.0
vation of the active carbon resulted from the blocking of the mouths Umf in the fluidized bed of activated carbon is equivalent to a space
of the pores by the deposited carbon. As the temperature increased, velocity of 1.10 L/gcat hr. As can be seen in Figs. 4 and 5, the effect
the initial activity increased, but the deactivation occurred more rap- of the gas velocity on the CH4 conversion was significant in the flu-
idly. The activation energy determined from the Arrhenius plot was idized bed reactor. Unlikely in a fixed bed reactor, all gases exceed-
about 140 kJ/mol CH4 and was much lower than the methane C-H ing the amount required for the minimum fluidization seemed to
bond energy of 440 kJ/mol. The effect of the methane gas velocity pass through the bed as bubbles. In addition, the increase of the gas
on the methane conversion is given in Figs. 4 and 5. In the case of velocity reduced its residence time in the reactor as well as low-
a fluidized bed, it is convenient to express the gas velocity in terms ered the contact efficiency between the gas and the carbon cata-
lysts due to the formation of large bubbles. SEM images of the sur-
faces of activated carbon before and after the reaction are given in
Figs. 6 and 7, respectively. They showed the carbon was deposited
on the surface of activated carbon catalyst and it was believed that
this carbon deposition blocked the mouths of the pores of activated
carbon, thus causing rapid deactivation of the catalyst.

Fig. 4. The effect of gas velocity on the CH conversion over acti-

vated carbon at a temperature of 850 C.
4
o

Fig. 6. SEM images of the surfaces of the activated carbon before

the reaction.

Fig. 5. The effect of gas velocity on the CH decomposition rate over Fig. 7. SEM images of the surfaces of the activated carbon after
activated carbon at a temperature of 850 C. the reaction.
4
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July, 2007
 Hydrogen production by catalytic decomposition of methane over carbon catalysts in a fluidized bed 677
due to the merging of protrusions or the agglomeration of particles,
while others may be generated at the edges or defects of the grow-
ing graphite layer in the carbon black. One plausible explanation
for the catalytic activity sustained at the quasi-steady state may there-
fore be that the overall number of active sites remains almost con-
stant during the reaction. The effects of the methane gas velocity
on the methane conversion and the decomposition rate are given in
Figs. 10 and 11. A minimum fluidization velocity of 1.0 Umf is equi-
valent to a space velocity of 0.16 L/gcat hr in this case. As can be
seen in Fig. 10, the effect of the gas velocity on the CH4 conver-

Fig. 8. The effect of reaction temperature on the CH conversion

over carbon black at a gas velocity of 1.0 Umf .
4

Fig. 10. The effect of gas velocity on the CH conversion over car-
bon black at a temperature of 900 C.
4
o

Fig. 9. The effect of reaction temperature on the CH decomposi-

tion rate over carbon black at a gas velocity of 1.0 Umf .
4

2. Carbon Black
Catalytic activity of the carbon black was measured at various
temperatures, and it is plotted as a function of time on stream in
Figs. 8 and 9. The carbon black catalyst showed a relatively lower
activity compared to the activated carbon catalyst at the beginning
of the reaction. However, the activity of the carbon black quickly
reached a quasi-steady state and remained constant for more than 8
hrs regardless of the reaction temperatures. It is believed that since
the carbon morphology changes continuously due to the deposition Fig. 11. The effect of gas velocity on the CH decomposition rate
of carbon (as shown in Fig. 13), some active sites may disappear over carbon black at a temperature of 900 C.
4
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Korean J. Chem. Eng.(Vol. 24, No. 4)

678 J. U. Jung et al.
ane conversion. It may be proposed that extensive investigation of
the characteristics of the reaction rate in conjunction with hydrody-
namics in the fluidized bed is required for the optimal operation of
the fluidized bed reactor. SEM images of the surfaces of carbon
black before and after the reaction are given in Figs. 12 and 13. The
fresh carbon black particles shown in Fig. 12 are mostly round and
their surfaces look smooth. As observed in Fig. 13, the deposited
carbon formed many cone- or pillar-shaped protrusions on the sur-
faces, and the particles looked like sea squirts. As the carbon de-
position proceeded, the particles tended to become larger and more
particles became stuck together.
CONCLUSIONS
The characteristics of the thermocatalytic decomposition of meth-
ane in a fluidized bed reactor with activated carbon and carbon black
catalysts were investigated experimentally. Distinctive difference
Fig. 12. SEM images of the surfaces of the carbon black before the was observed in the catalytic activities of the two carbon catalysts.
reaction. The activated carbon catalyst exhibited high initial activity which
decreased significantly with time. It seemed mainly attributed to
the deposition of carbon on the surfaces of the activated carbon cat-
alyst, thereby decreasing the number of active sites inside the pores.
However, the carbon black catalyst exhibited somewhat lower ini-
tial activity compared to the activated carbon catalyst, but its ac-
tivity was sustained for more than 8 hrs. The difference in the reac-
tion activity was examined by studying SEM images of the used
carbon catalysts. The effect of the operating parameters such as the
reaction temperature and the gas velocity on the reaction rates was
investigated.
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July, 2007