International Journal of Hydrogen Energy 32 (2007) 4792 – 4799

www.elsevier.com/locate/ijhydene

Microwave-assisted catalytic decomposition of methane over activated

carbon for CO2 -free hydrogen production
A. Domínguez, B. Fidalgo, Y. Fernández, J.J. Pis, J.A. Menéndez ∗
Instituto Nacional del Carbon, CSIC, Apartado 73, 33080 Oviedo, Spain

Received 6 February 2007; received in revised form 14 June 2007; accepted 17 July 2007
Available online 10 September 2007

Abstract
The aim of this work was to combine microwave heating with the use of low-cost granular activated carbon as a catalyst for the production
of CO2 -free hydrogen by methane decomposition in a fixed bed quartz-tube flow reactor. In order to compare the results achieved, conventional
heating was also applied to the catalytic decomposition reaction of methane over the activated carbon. It was found that methane conversions
were higher under microwave conditions than with conventional heating when the temperature measured was lower than or equal to 800 ◦ C.
However, when the temperature was increased, the difference between the conversions under microwave and conventional heating was reduced.
The influence of volumetric hourly space velocity (VHSV) on the conversion tests using both microwave and conventional heating was also
studied. In general, there is a substantial initial conversion, which declines sharply during the first stages of the reaction but tends to stabilise
with time. An increase in the VHSV has a negative effect on CH4 conversion, and even more so in the case of microwave heating. Nevertheless,
the conversions obtained in the microwave device at the beginning of the experiments are, in general, better than the conversions reported in
other works which also use a carbonaceous-based catalyst. Additionally, the formation of carbon nanofibres in one of the microwave experiments
is also reported.
䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Methane; Hydrogen; Microwave; Catalytic decomposition; Carbon nanofibres

1. Introduction • Partial oxidation: CH4 + 21 O2 ⇔ 2H2 + CO, H298 =

The alarm generated by climatic change has motivated a
search for alternative clean power sources and for a way to min-
imize the emission of greenhouse gases. Hydrogen is consid-
ered the ideal fuel of the future because its combustion product
is H2 O. Methane is a good source of hydrogen due to its high
hydrogen-to-carbon ratio [1–3].
There are several catalytic processes for the production of
hydrogen from methane:
• Steam reforming of methane: CH4 + H2 O ⇔ 3H2 + CO,
H298 = +206 kJ/mol.
• Dry reforming of methane: CH4 + CO2 ⇔ 2H2 + 2CO,
H298 = +247 kJ/mol.
∗ Corresponding author. Tel.: +34 985118972.
E-mail address: angelmd@incar.csic.es (J.A. Menéndez).
0360-3199/$ - see front matter 䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.07.041
−8.5 kJ/mol.
• Thermal decomposition of methane: CH4 ⇔ C + 2H2 ,
H298 = +75 kJ/mol.
Catalytic steam reforming is currently used for the production
of several chemicals via synthesis gas. A critical parameter for
the subsequent reaction of the syngas is the H2 /CO ratio which
must be adjusted close to unity for some syntheses, implying
further post-reformer reactions [4]. These steps could be elim-
inated by carbon dioxide reforming, which is more endother-
mic than steam reforming but yields syngas with lower H2 /CO
ratios.
From an environmental point of view, dry reforming [5]
would lead to a mitigation of CO2 emissions and contribute to
the consumption of CH4 , both of which are undesirable green-
house gases.
Despite these advantages, there is still no commercially feasi-
ble process for CO2 reforming. The high temperatures required
 A. Domínguez et al. / International Journal of Hydrogen Energy 32 (2007) 4792 – 4799
to attain high conversions favour carbon deposition which de-
activates the tested conventional catalysts [4–6]. In the steam
reforming reaction, this problem is avoided by increasing the
steam concentrations. This improves the selectivity towards hy-
drogen but also increases the energy consumed in the process.
An alternative process for the production of syngas which
avoids the disadvantages of the use of steam is partial oxidation.
This gives a H2 /CO ratio of 2; it is an exothermic reaction and
it may proceed at much moderate temperatures [7]. However,
the partial oxidation of methane to synthesis gas is very difficult
to achieve.
Recently, a process that has attracted considerable attention
is a combination of partial oxidation and steam reforming (au-
tothermal reforming) due to its higher energy efficiency com-
pared to other endothermic processes [7,8].
All these conventional processes give rise to the simulta-
neous production of CO2 , which needs to be reduced due to
the greenhouse effect. A viable alternative is the catalytic ther-
mal decomposition of methane, which produces hydrogen in
a single-step process without CO/CO2 emission, eliminating
the need for a water gas-shift reaction and the CO2 removal
stages [9]. In addition, CO2 emissions could be reduced if
the energy needed for methane decomposition was supplied
by burning 15–20% of the hydrogen produced in the pro-
cess [2]. Moreover, the carbon obtained as a by-product from
methane decomposition is potentially more valuable than CO2
in the current market, and could reduce the cost of the overall
process [10].
The main drawback of thermal decomposition as an operat-
ing process is the deactivation of the catalyst associated with
the carbon deposited on the catalyst surface. In order to re-
generate the original catalytic activity, the gasification or com-
bustion of the carbon deposits has been proposed. These pro-
cesses, however, would result in the production of CO2 as a
by-product [11].
Muradov et al. [11–14] have proposed the use of carbon-
based catalysts instead of metal catalysts due to their availabil-
ity, durability and low cost. These catalysts offer some advan-
tages over metal catalysts such as high temperature resistance
and tolerance to sulphur as well as other potentially harmful
impurities in the feedstock.
On the other hand, the operation of endothermic catalytic re-
actors is limited by the transfer of radial heat through the packed
bed. This results in a pronounced temperature profile, and
affects the rate of reaction [15]. The effect of microwave heat-
ing on several heterogeneous catalytic reactions has been stud-
ied since the late 1980s, with enhanced reaction rates, higher
yields and improved product selectivities. The reactions com-
pared above are among these tested systems. Zhang et al. [4]
studied the application of microwaves to the carbon dioxide
reforming of methane, comparing its performance with con-
ventional heating. The steam reforming of methane and water
gas-shift reactions were investigated by Wan et al. [16]. Even-
tually, Cooney et al. [17] compared microwave heating and
conventional heating applied to the production of hydrogen by
means of the decomposition of pure methane over a coal char
catalyst.
4793
The microwave heating of a dielectric material, which oc-
curs through the conversion of electromagnetic energy into
heat within the irradiated material, offers a number of advan-
tages over conventional heating such as (i) noncontact heating;
(ii) energy transfer, no heat transfer; (iii) rapid heating; (iv)
selective material heating; (v) volumetric heating; (vi) quick
start-up and stopping; (vii) the heating starts from the interior
of the material body; (viii) a higher level of safety and automa-
tion and (ix) it can be transported from the source through a
hollow nonmagnetic metal tube [18,19].
The purpose of this work is to study the reaction of methane
decomposition when activated carbon is used as a catalyst and
conventional heating is replaced by microwave heating. The de-
composition is carried out at various temperatures and reaction
times, focusing on catalyst activity and methane conversion,
which differ depending on the heating system used.
2. Experimental
A commercial activated carbon (Filtracarb FY5), made from
coconut shell and activated with steam, was used as a catalyst in
the methane decomposition experiments. The surface area and
the bulk density of the FY5 were 826 m2 /g and 0.49 g/cm3 ,
respectively, and the size of particles ranged within 0.5–2 mm.
Proximate analysis (moisture, ash and volatile matter content)
and elemental analysis (C, H, O, N, S) were carried out in a
LECO TGA-601 thermo-balance and in a LECO CNHS-932
apparatus, respectively; the oxygen content was calculated by
the difference. Table 1 shows the main chemical characteristics
and the ash composition of the activated carbon.
Table 2 shows the conditions employed for each test. The
CH4 decomposition reactions were carried out in a quartz re-
actor (45 cm length ×2.2 cm i.d.) charged with a variable mass
of catalyst, previously dried overnight at 110 ◦ C, and heated in
an electrical furnace (EF) or a single mode microwave oven
(MW). Details of this equipment setup have been described pre-
viously [20]. Before the reactant gas was introduced, nitrogen
was used as inert gas at a flow rate of 82 mL/min for 20 min
after which the system was heated up to a pre-set temperature
under inert atmosphere. In order to determine the best operat-
ing temperature, runs from A to F were conducted. To study the
long-term behaviour of the catalyst and the influence of volu-
metric hourly space velocity (VHSV) on the conversion, tests
G to N were carried out. As can be seen in Table 2, some VHSV
and mass of catalyst values for the tests carried out in the MW
differ slightly from the values obtained in the electric furnace.
This is because the volume of the catalyst was used as a refer-
ence instead of the catalyst mass since microwave heating is a
volumetric heating process [21].
The outflow gas was collected in 0.5, 1 or 3 L Tedlar䉸 sam-
ple bags. During the first 30 min, each bag was filled with the
outflow gases for 3 min. After the first half an hour, each sam-
ple bag was filled with the gases for 10 min. The gases were
analysed in a gas-chromatograph Perkin-Elmer Sigma 15 fitted
with a TCD detector. A Teknokroma 10FT Porapak N, 60/80,
and a Teknokroma 3FT Molecular Sieve 13X, 80/100, columns
were also used. The oven temperature was pre-set at 50 ◦ C and
4794 A. Domínguez et al. / International Journal of Hydrogen Energy 32 (2007) 4792 – 4799

Table 1
Main chemical characteristics of the activated carbon used as a catalyst for methane decomposition

Chemical characteristics

Proximate analysis (wt%) Ultimate analysis (wt%)a

Moisture Asha Volatile mattera C (%) H (%) N (%) S (%) O (%)b H/C

6.7 2.8 3.0 95.7 0.5 0.5 0.2 0.3 0.068

Inorganic composition of the ashes (expressed as wt% of metal oxides)a

SiO2 K2 O Al2 O3 Fe2 O2 CaO Na2 O SO3 MgO TiO2 Ni Co

39.79 25.40 9.06 9.04 6.40 3.01 2.77 2.71 1.18 n.d.c n.d.c
a Dry base.
b Calculated by difference.
c n.d., non detected.

Table 2
Test conditions
Run Temperature (◦ C) Heating device VHSVa (L/g h) Space timeb (s) CH4 flow rate (mL/min) Mass of catalyst (g) Time (min)

A 900 MW 0.16 46 36 13.5 30

B 900 EF 0.16 46 36 13.5 30
C 800 MW 0.16 46 36 13.4 30
D 800 EF 0.16 46 36 13.5 30
E 700 MW 0.16 46 36 13.6 30
F 700 EF 0.16 46 36 13.5 30
G 800 MW 0.16 46 36 13.6 120
H 800 EF 0.16 46 36 13.5 120
I 800 MW 0.31 24 65 12.6 120
J 800 EF 0.31 24 65 12.5 120
K 800 MW 0.31 24 44 8.6 120
L 800 EF 0.31 24 36 6.9 120
M 800 MW 0.72 10 98 8.2 120
N 800 EF 0.71 10 98 8.3 120
a Volumetric hourly space velocity, defined as VHSV = flow rate of CH4 (L h−1 )/mass of catalyst (g).
b Space time is defined as the ratio between the volume of catalyst (L) and the flow rate of CH4 (L s−1 ), i.e., space time = 3600/[VHSV (L g−1 h−1 )* bulk
density (g L−1 )].

the carrier gas flow rate (He) was 20 mL/min. The injector and Table 3
detector temperatures were 100 and 150 ◦ C, respectively. The Textural properties of fresh and selected used catalysts
TCD was calibrated with a standard gas mixture at periodic Sample SBET (m2 /g) a Vtotal (cm3 /g)a,c Vmic (cm3 /g)a Vmic (cm3 /g)b
intervals.
FY5 826 0.341 0.320 0.255
The conversion of methane was calculated employing the
C 530 0.224 0.206 0.205
concentrations of hydrogen and methane in the effluent gas, D 748 0.308 0.289 0.231
which were determined by chromatography: G 227 0.096 0.089 0.100
H 527 0.222 0.209 0.224
CH4 conversion, %
a Calculated from isotherms of nitrogen at 77 K.
= 100 × [(H2 )out /2]/[(CH4 )out + (H2 )out /2], b Calculated from isotherms of carbon dioxide at 273 K.
c Calculated by means of the Gurvitsh rule [29].
where (CH4 )out and (H2 )out are the methane and hydrogen con-
centrations in the effluent gas (% by volume), respectively.
Textural characterisation of fresh and some used samples The carbon deposits formed on the activated carbon surface
of catalyst was carried out by CO2 adsorption–desorption were studied by a Scanning Electron Microscope DSM 942
isotherms at 0 ◦ C and N2 adsorption–desorption isotherms at from Zeiss, equipped with an EDX detector (OXFORD LINK-
−196 ◦ C in the pressure range of 0–1 bar in a Micromeritics ISIS).
Tristar 3000 apparatus. The Dubinin–Raduskevich method was
applied to the CO2 and N2 adsorption isotherms to determine 3. Results and discussion
the volume of micropores, while the BET equation was ap-
plied in the case of the N2 adsorption isotherms. The results Before the methane decomposition was studied using acti-
for each sample are shown in Table 3. vated carbon as a catalyst, blank tests were carried out in the
 A. Domínguez et al. / International Journal of Hydrogen Energy 32 (2007) 4792 – 4799 4795

100

gas composition (vol %)

100

80 80 blank (a)
blank (a)

CH4 conversion (%)

blank (b) 60 blank (b)

60 blank (c) 40
20

40 0
CH4 H2 C2H4

20

0
0 5 10 15 20 25 30
time (min)

Fig. 1. Conversion of methane for blank tests carried out at different conditions: (a) 900 ◦ C with a thermocouple; (b) 900 ◦ C without a thermocouple and
(c) 800 ◦ C with a thermocouple.

electric furnace in order to find out if thermal decomposition of A C E

methane was possible at the operating temperature. These tests
consisted in passing a 36 mL/min flow rate of CH4 through a
quartz wool bed at 800 and 900 ◦ C, using an experimental pro-
cedure similar to the one described previously to evaluate the
conversion of CH4 . Fig. 1 shows the results obtained for these
experiments. Interestingly, at 800 ◦ C there was no CH4 con-
version at all, while at 900 ◦ C about 7% of CH4 was mainly
converted to H2 , a small proportion of ethene (C2 H4 ) also be-
ing found. Moreover, the results of this experiment were repro-
duced both with and without a thermocouple, which rules out
any possible catalytic effect from the thermocouple. In sum, a
small fraction of CH4 can be thermally decomposed at 900 ◦ C
but not at 800 ◦ C.
In order to study the performance of the activated carbon
as a catalyst under different temperatures and to compare mi-
crowave and electrical heating, experiments from A to F (see
Table 2) were carried out. It was found that, unlike thermal de-
composition, C2 H4 was not produced in the presence of acti-
vated carbon. Thus, the gases detected by gas chromatography
were H2 , N2 and CH4 as well as some small (< 1%) amounts
of CO and CO2 in the first bags collected (< 9 min). The pres-
ence of N2 is due to remnants of the inert gas used during the
warming up of the catalyst, whereas CO and CO2 are attributed
both to the decomposition of oxygen-containing surface groups
present on the surface of the activated carbon and to the air
occluded in micropores, since these carbon samples were not
degasified.
The results of these experiments are plotted in Fig. 2. In gen-
eral it can be seen that, as expected, the conversion increases
with the temperature. On the other hand, with the exception
of experiment F, the conversion decreases with time, which
points to a loss of catalytic activity due to blockage of the ac-
tive centres by the carbon deposits produced in the decompo-
sition of CH4 (chemical vapour deposition, CVD). In addition,
as can be inferred from the textural parameters summarised in
Table 3, the catalysts used in runs C and D undergo a significant
decrease in their BET surface areas and micropore volumes.
This agrees with the fact that carbon deposits block part of the
porosity, preventing the CH4 molecules from gaining access to
B D F
100
CH4 conversion (%)
80
60
40
20
0
0 5 10 15 20 25 30
time (min)
Fig. 2. Effect of the reaction temperature on methane conversion, under
microwave heating (solid symbol) or conventional heating (empty symbol).
Runs A and B: 900 ◦ C; runs C and D: 800 ◦ C; and runs E and F: 700 ◦ C.
VHSV = 0.160 L/g h.
this part of the surface area of the carbon. As a result catalytic
activity is reduced. Moreover, when the micropore volumes ob-
tained from the N2 and CO2 isotherms are compared, it can
be observed that, while the differences between these two pa-
rameters are relatively important in the case of the fresh cata-
lyst (FY5), indicating a broad micropore size distribution, these
differences are very small in the samples obtained from runs
C and D, pointing to a narrower micropore size distribution
[22]. Thus, it seems that carbonaceous deposits which modify
the pore structure of the carbon are formed from CH4 decom-
position, i.e., these carbon deposits appear to be preferentially
located at the pore mouths narrowing them (in a similar way
than that used to obtain carbon molecular sieves by CVD). The
decrease in the textural parameters is greater in the case of the
sample from run C, which was performed in the microwave, in
accordance with the results of Fig. 2. Thus, microwave heating
was more effective in decomposing CH4 to H2 than the electric
furnace (run D) and gave rise to a greater number of carbon
deposits.
In fact, it can be observed that at the same temperature,
all the experiments performed in the microwave resulted in a
higher CH4 conversion than those carried out in the electric
4796 A. Domínguez et al. / International Journal of Hydrogen Energy 32 (2007) 4792 – 4799
furnace. These differences are particularly significant at lower
temperatures, becoming smaller as the temperature of the ex-
periment increases. Similar results were reported by Zhang
et al. [4] when comparing the CO2 reforming of CH4 using
microwave and conventional heating. These results can be at-
tributed to the different way the materials are heated in the
microwave. Thus, in the case of MW heating, the catalyst
(activated carbon) is heated directly by the action of the mi-
crowaves, and so is at a much higher temperature than the
surrounding atmosphere, whereas in the EF the heat trans-
fer proceeds through the surface of the catalyst, resulting in
a totally different temperature gradient. Moreover, during mi-
crowave heating numerous small sparks can be observed prac-
tically throughout the entire experiment. These sparks are hot
spots which, in a way, can be considered as “micro-plasmas”,
both from the point of view of time (since they only last for a
fraction of a second) and space (since they are located in a very
tiny spot). Therefore, whereas the overall temperature corre-
sponds to the one measured by the optical pyrometer, the tem-
perature in these “micro-plasmas” must be much higher. Such
a situation can be expected to favour heterogeneous reactions
between the solid catalyst and the gaseous CH4 , enhancing
CH4 decomposition.
From Fig. 2 it can be seen that at 700 ◦ C the differences be-
tween the two methods (EF and MW) are quite large but the
conversion of CH4 is relatively small in both cases. At 900 ◦ C,
however, both conversions are quite high, whereas the differ-
ences between the two methods employed are relatively small.
Thus, 800 ◦ C was selected as the most appropriate temperature
to study the long-term behaviour of the catalyst and the influ-
ence of VHSV on conversion (Fig. 3). In order to check the
repeatability of the experients, runs G and H have been plotted
along with runs C and D in Fig. 3a. As can be seen, the ex-
periments are completely reproducible in the EF, whereas the
repeatability of the experiments in the MW is worse, although
still reasonably good. This could be due to the hot spots referred
to above, which are generated in a random way for each sam-
ple, thereby adding uncertainty to the temperature values given
by the pyrometer. If the 120 min-long experiments (G and H)
are compared, it can be observed that, although the conversion
is higher in the MW at the beginning of the experiment, the de-
crease is also more pronounced than in the EF, so that after 2 h
both conversions are practically the same. In fact, the decom-
position of CH4 to H2 by MW treatment is more efficient than
in the EF, although the unavoidable carbon deposition results in
a greater loss of catalytic activity. Again the textural properties
summarised in Table 3 illustrate that there is a substantial de-
crease in the textural properties after 120 min-long treatments,
this decrease being much more significant in the MW than in
the EF. In sum, MW treatments favour CH4 conversion, but at
the same time CVD is also favoured so that, although the cat-
alyst works more efficiently, it is for a shorter time than in the
case of the EF treatments.
Fig. 3b shows the conversion obtained in runs I to L. In these
experiments, the flow rate of CH4 and the mass of catalyst were
varied in such a way that the VHSV remained the same (see
Table 2). In runs I to K (MW) and runs J to L (EF), a good
repeatability was achieved (although once again the result was
better in the EF than in the MW). This indicates that, when
the rest of the operating conditions are kept constant, it is the
ratio between these two parameters (VHSV) that controls the
CH4 conversion rather than the flow or the amount of catalyst
evaluated as individual variables.
On the other hand, a comparison of Figs. 3a–c suggests that
an increase in the VHSV leads to a smaller conversion of CH4 .
In fact, an increase in the VHSV reduces the capacity of the cat-
alyst to process the feeding of CH4 . In other words, it reduces
the contact time between the CH4 molecules and the active cen-
tres present on the catalyst, thereby impairing the conversion.
However, it should be noted that the MW treatments seem to
be much more affected by the increase in VHSV than the EF
treatments. Thus, although at the beginning of the experiments
the conversion is always higher in the MW, the decay in this
conversion is also greater, leading to an earlier crossover be-
tween the conversion curves of the MW and EF.
The results collected in this work can be compared with oth-
ers found in the bibliography. Various studies on CH4 decom-
position have been carried out over metal-based catalysts, such
as Ni or Cu [23–26]. It has been found that CH4 initial conver-
sions are often higher when activated carbons are used as cata-
lyst, but it is the metallic catalyst that shows the best long-term
behaviour, high conversions being achieved even after 5–10 h.
Taking into account that these tests were run at lower tem-
peratures, it can be inferred that, in general, activated carbon
displays a worse performance as a catalyst than metal-based
catalysts. This could be due to either a higher concentration
of active centres on the metallic catalysts or a greater facility
for carbon deposition on the active centres of the carbon cat-
alysts. Other works which used carbonaceous-based catalysts
for CH4 decomposition were also consulted but the results can-
not be directly compared with the ones of this work because
the VHSV chosen are not similar (see Table 4). Even so, a de-
creasing trend in CH4 conversion with time can be observed,
except when carbon blacks are used as catalysts [3]. In fact,
after 90–120 min, there is usually no CH4 conversion, the high-
est conversion being no higher than 10%. Thus, the operating
conditions chosen for the tests carried out in this work provide
better conversion results (see Table 4). Moliner et al. [28] stud-
ied the decomposition of methane at 850 ◦ C over several com-
mercial activated carbons, whose BET surface was larger than
the BET surface of FY5, using a space time of 25 s, as in runs
I to L in this work (see Table 2). Their initial H2 production
was in the range of 65–35 vol% and around 45–30 vol% after
120 min. Hydrogen production for runs I to L was in the range
of 65–59 vol% for the first few minutes and about 40–27 vol%
after 120 min, which implies that their results were similar to
ours, although in the present work the temperature was lower
and the surface area of the FY5 was not so large.
The nature and characteristics of the carbon deposits formed
on the catalyst surface after CH4 decomposition also need to
be discussed. SEM microphotographs reveal that the nature of
these carbon deposits is very heterogeneous. Both for MW and
EF heating, most of the carbon is deposited on the surface
of the active carbon where it forms discrete deposits, which
 A. Domínguez et al. / International Journal of Hydrogen Energy 32 (2007) 4792 – 4799 4797

100

G
80

CH4 conversion (%)

H
C
60
D

40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130
time (min)

100

80
CH4 conversion (%)

I
J
60
K
L
40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130
time (min)

100

80
CH4 conversion (%)

60
M
N
40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120 130
time (min)

Fig. 3. Effect of the VHSV on methane conversion, under microwave heating (solid symbol) conventional heating (empty symbol): (a) VHSV = 0.16 L/g h;
(b) VHSV = 0.31 L/g h and (c) VHSV = 0.72 L/g h. T = 800 ◦ C.

can be seen in Fig. 4a. Eventually, these deposits coalesce and
develop a uniform layer of carbon, which cannot be seen by
SEM. However, in the specific case of run M, in addition to
the discrete carbon deposits, the formation of several skeins
of nanofibres with heterogeneous shapes (some nanofibres are
relatively straight, whereas others are twisted into spirals) and
sizes ranging from a few nanometres to about 200 nm was ob-
served. Fig. 4b shows an example of these skeins, which are
found scattered over the surface of the catalysts. The nanofibres
are formed under conditions unfavourable for the CH4 conver-
sion, i.e., the largest VHSV value, which implies a low H2 /CH4
ratio in the outflow gases. This result seems to contradict the
general trend found in the literature, where it is reported that a
higher proportion of nanotubes vs. amorphous carbon deposits
is favoured by the presence of H2 . On the other hand, these
nanofibres are only formed under MW heating, suggesting that
“micro-plasmas” (hot spots which do not appear in EF heating)
may play a decisive role in their formation. Some authors have
studied the synthesis of nanostructures (nanotubes and nanofi-
bres) under microwave heating, using different operating con-
ditions, i.e., acetylene as a hydrocarbon source and Co, Ni and
Fe supported over carbon black (a microwave absorber) or Co
4798 A. Domínguez et al. / International Journal of Hydrogen Energy 32 (2007) 4792 – 4799

Table 4
Summary of CH4 conversions using carbonaceous-based catalysts at different conditions

Reference Catalyst Temperature range (◦ C) VHSV (L/g h) XCH4 rangea (%) XCH4 rangeb (%)

Present work Activated carbon 800 0.16–0.72 100–49 29–7

Kim et al. [27] Activated carbon 750–900 15 14–2 3–0
Bai et al. [1] Activated carbon 750–900 3 35–5 9–2.5
Muradov [14] Activated carbon 850 10 27–21 2–0.5
Carbon black 6–1 3.5–0.5
Lee et al. [3] Carbon black 750–1050 15 50–0 60–2
Bai et al. [2] Coal char 750–900 3 34–5 6–0
a CH initial conversion evaluated during the first 5 min. b CH final conversion evaluated after 90 min.
4 4

Fig. 4. SEM images of the FY5 obtained after the reaction at 800 ◦ C and 0.72 L/g h for 2 h: (a) carbon deposits on the surface active carbon, obtained after
CH4 decomposition in the EF ; (b) detail of the nanofibres obtained after CH4 decomposition in the MW.

on a SiO2 support (a microwave insulator) [30], directly heat-
ing samples of graphite and sucrose, calcined sucrose or boric
acid and collecting the condensed material on a fused silica tar-
get [31], or decomposing ferrocene molecules on the surface
of Fe nanoparticles [32]. Interestingly, among these metals that
catalyse the growth of nanofibres, Fe is present in the ashes of
the activated carbon used in this work. These issues, however,
require a more complete study and they will be addressed in
more detail in a future study.
4. Conclusions
In this work it has been pointed out that the thermal decom-
position of CH4 to H2 and C2 H4 , with a very low but notice-
able CH4 conversion, takes place at 900 ◦ C, while below this
temperature CH4 does not decompose. However, when an ac-
tivated carbon is used as catalyst, CH4 decomposes selectively
to H2 with much higher conversions. It was found that mi-
crowave heating gives rise to higher conversions than electric
heating (conventional heating), probably due to the formation of
hot spots (micro-plasmas) inside the catalyst bed, which favour
CH4 decomposition. Experiments conducted for 30 min have
established that the differences between these heating methods
are much greater at lower temperatures. In addition, although
an increase in the temperature has a positive effect on the CH4
conversion for both methods, at temperatures around 900 ◦ C
these differences become smaller. Experiments conducted for
2 h at 800 ◦ C showed that there is a decrease in conversion with
time, associated with a drop in the activity of the catalyst due
to carbon deposits entering the pores, and reducing the surface
area and pore volume. Thus, the more efficient the process is,
the more carbon is deposited, this effect being even more detri-
mental in the case of microwave heating. Therefore, although
for a given temperature the conversion in the microwave at
the beginning is higher than in the electric furnace, with time
they both become similar, and microwave conversion eventu-
ally falls below the one obtained by conventional heating. An
increase in the volumetric hourly space velocity (VHSV) has
a negative effect on CH4 conversion, which is more noticeable
for microwave heating. Comparison of these results with those
of other works revealed that, for a similar space time, the per-
formance of the activated catalyst used as a catalyst for CH4
decomposition is similar to activated carbons which have larger
surface areas and are heated to a higher temperature. Under
certain experimental conditions, microwave heating gave rise
to carbon nanofibres on the activated carbon surface.
Acknowledgements
B. Fidalgo and Y. Fernández are grateful to CSIC of Spain
and the European Social Fund (ESF) for financial support under
thesis Grant I3P-BDP-2006.
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