International Journal of Hydrogen Energy 32 (2007) 4821 – 4829

www.elsevier.com/locate/ijhydene

Production of hydrogen and carbon nanofibers by thermal decomposition

of methane using metal catalysts in a fluidized bed reactor
J.L. Pinilla a , R. Moliner a , I. Suelves a,∗ , M.J. Lázaro a , Y. Echegoyen a , J.M. Palacios b
a Instituto de Carboquímica, CSIC, Miguel Luesma 4, 50018 Zaragoza, Spain
b Instituto de Catálisis y Petroleoquímica, CSIC, Campus Universidad Autónoma, Cantoblanco, 28049 Madrid, Spain

Received 27 December 2006; received in revised form 6 July 2007; accepted 11 August 2007
Available online 24 October 2007

Abstract
Thermo catalytic decomposition (TCD) of methane using Ni–Cu–Al catalyst in a pilot scale fluidized bed is studied. The conventional
method of catalyst preparation based on co-precipitation is compared versus an easier preparation method based on the fusing of the metallic
nitrates. Catalysts prepared by both methods shown similar behavior. Fluidodynamic studies have shown that TCD can be carried out in a
fluidized bed reactor without reactor clogging provided that a methane velocity of two times the minimum fluidization velocity is used. This
high spacial velocity resulted in a reduction of the fraction of methane converted, but not in the quantity of carbon deposited per gram of
catalyst. The optimum gas velocity should be chosen in terms of hydrogen production rates and fluidization quality. A semi-continuous fluidized
bed installation has been started up and operated to produce at the scale of 60 l h−1 of hydrogen and 15 g h−1 of carbon nanofibers.
䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydrogen production; Carbon nanofibers; Thermal decomposition of methane; Fluidized bed reactor

1. Introduction hydrogen and carbonaceous materials by methane decomposi-

Hydrogen is an emerging alternative to conventional fuels
to reduce CO2 emissions. It is generally accepted, that in the
near-to-medium term hydrogen production will rely on fossil
fuels, primarily natural gas. Thermo catalytic decomposition
(TCD) of natural gas, with carbon being captured as a solid of
added value product appears an interesting alternative to steam
reforming [1] for hydrogen production.
Feasibility of TCD in economical terms is very sensible to
the carbon selling price which depends on the properties of the
carbon obtained. The quality of carbon produced from TCD
largely depends on the operation conditions and the type of cat-
alyst used. Using metal-based catalysts lead to the production
of carbon forms of high quality whose high selling price would
compensate the high cost of the catalyst. TCD of methane us-
ing Ni and Ni–Cu catalysts to produce hydrogen and novel car-
bonaceous materials has been reported by many authors [2–8].
The use of solar heating has also been reported to produce
∗ Corresponding authors. Tel.: +34 976733977; fax: +34 976733318.
E-mail address: isuelves@icb.csic.es (I. Suelves).
0360-3199/$ - see front matter 䉷 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2007.08.013
tion [9,10].
TCD of methane using nickel catalysts has been extensively
studied by our group using a fixed bed reactor. In the first
approach [11], a commercial Ni catalyst (Ni content 65% wt),
was used in TCD of methane to gain knowledge on the influence
of the operating conditions on the catalyst deactivation and on
the properties of the deposited carbon. It was shown, that the
higher the methane flow rate used the shorter the catalyst life.
At temperature of 700 ◦ C, the concentration of hydrogen in the
outlet gas was close to the thermodynamic value. SEM and
TEM examinations showed that the deposited carbon appeared
either as large filaments a few nanometres in diameter emerging
from Ni particles or as uniform coatings. XRD, FT-Raman and
XPS revealed that in all cases the deposited carbon was highly
ordered graphite whose structure apparently did not depend on
the operating conditions.
In the second stage [12,13], Ni and Ni–Cu catalysts were
prepared using different methods to evaluate the influence of
the amount of nickel as catalyst, the role of copper as a possible
alloying element with Ni and the catalyst preparation procedure
on methane conversion and on the properties of the produced
4822 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829
carbon. The prepared catalysts showed a similar behaviour to
the commercial one, even better when a small concentration
of copper was introduced in its composition. At 700 ◦ C the
catalyst’s activity did not decay after 8 h on-stream (except
for the catalyst with a percentage of nickel below 30%) and a
weight ratio of carbon to nickel between eight and eleven was
obtained without catalyst deactivation.
Among the different methods of catalyst preparation de-
scribed in the literature, co-precipitation and impregnation are
the most used. These methods include washing and filtering
steps which are time and energy consumed and involve the use
of huge amounts of water. These could be important drawbacks
for their use at an industrial scale. For that reason an easier
preparation method based on the fusing of the metallic nitrates
was also studied at the same operating conditions [12,13]. Per-
formance tests showed that the hydrogen production was not
highly dependent on the preparation method used. The cata-
lyst deactivation was never reached at the fixed times used in
the reactivity tests for any of the preparation methods studied.
Ni:Cu:Al catalysts promoted the formation of a well-ordered
graphitic carbon with relative large crystal domain sizes. Ni:Al
catalysts, however, promoted the formation of turbostratic
carbon.
Different aspects of the catalyst preparation procedure have
been studied in more detail [14]. First of all the effects of cat-
alyst calcination temperature on the hydrogen yield and on the
carbon obtained have been analyzed. A wide range of calci-
nation temperatures have been studied in order to simulate the
regeneration step of an industrial installation where catalyst is
submitted to high temperatures to burn the carbon layer coat-
ing the catalyst particle. The higher hydrogen yields were ob-
tained using catalysts calcined at 600 ◦ C. This behaviour is at-
tributed to the fact that at 450 ◦ C the conversion of the nitric
salts into oxides is not complete, while at temperatures higher
than 600 ◦ C there is an increment in the metal crystal size. Con-
sistently, the efficiency for methane decomposition decreases.
The work presented above was carried out in a fixed-bed
quartz reactor 2 cm i.d., 60 cm height, using pure CH4 as feed-
ing gas and following the experimental procedure previously
described [11–14]. One of the main problems associated to the
fixed bed operation is that the reactor was completely filled
with produced carbon and the flow path for the reactant gas
was blocked. This behavior has been reported by Lee et al. [15]
where carbonaceous catalysts were used and by [16–18] where
metal catalyst were used. Therefore, in a continuous process
of catalytic methane decomposition, the carbon produced must
be removed from the reactor in order to maintain the reaction
activity and to avoid plugging by the carbon produced. The
issues related to the development of a reactor suitable for cat-
alytic methane decomposition with continuous withdrawal of
carbon product were treated by Muradov [19], using carbona-
ceous catalyst. The fluidized bed reactor (FBR) was selected as
the most promising reactor for a large-scale operation. FBRs
are used successfully in a multitude of processes both catalytic
and non-catalytic. A FBR system provides constant flow of
solids through the reaction zone, which makes it particularly
suitable for the continuous addition and withdrawal of carbon
particles from the reactor. In an FBR, the bed of catalyst parti-
cles behaves as a well mixed body of liquid giving rise to high
particle-to-gas heat and mass transfer. The FBR was proposed
in order to overcome the reactor plugging problem due to car-
bon deposition, which resulted in the shut down of the FBR.
More recently different works have been published on the
behavior of the active carbons [15] and carbon blacks [20] as
catalysts and the modelling and scaling up [21] of a FBR for
TCD of natural gas.
The FBR has also been proposed as an alternative for the
large-scale nanotubes production from high hydrogen content
gases and not methane by CVD [22–25]. Morançais et al. have
recently reported the large-scale nanotubes production from
ethylene using a FBR [26]. Methane decomposition with si-
multaneous hydrogen and nanotubes production has been pro-
posed by Quian et al. [27] using a two staged FBR. Despite this,
scarce information is available in literature in which hydrogen
and carbon nanofibers are simultaneously produced in an FBR
[28] and so that, one of the main objectives of the present paper
is to demonstrate the feasibility of the simultaneous production
of carbon nanofibers and hydrogen in an FBR, avoiding the
clogging problems associated to the fixed bed operation when
using the Ni:Cu:Al catalysts previously tested.
2. Experimental
2.1. Catalysts
Two types of catalyst have been prepared following the
procedures previously described for the FBR experiments
[12–14]:
(1) Co-precipitation: a catalyst with Ni:Cu:Al of 78/6/16 ratio
was prepared by co-precipitation from an aqueous so-
lution of the respective nitrates with sodium carbonate.
The precipitates were then washed, dried and calcined
at 450 ◦ C.
(2) Fusion: a catalyst with Ni:Cu:Al of 78/6/16 ratio was
prepared by fusing nitric salt of nickel and copper nitrate
with nitric salt of aluminium followed by decomposi-
tion of the mixtures at 350 ◦ C and subsequent calcination
at 450 ◦ C.
All samples were ground to fine powder (particle size lower
than 100 m).
2.2. Experimental apparatus
Experiments were carried out in the experimental apparatus
schematically shown in Fig. 1. The FBR (with i.d. of 0.065
and 0.8 m in height) was made of kanthal. Kanthal is a metal
alloy treated to form an oxides layer which is very stable at
high temperature, avoiding material drop during the reaction. A
horizontal perforated plate with 3 mm holes is used to divide the
reactor in two stages. Quartz glass is used to prevent material
from plugging the holes.
 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829
Fig. 1. Scheme of the experimental apparatus employed.
All process variables (pressures, temperatures and flow rates)
are recorded in continuous mode by a personal computer. The
gas enters the reaction zone using a stainless steel tube heated at
550 ◦ C by an electric furnace Watlow with a maximum power
of 888 W. The reactor is heated to the desired reaction tem-
perature using an electric furnace Watlow, (maximum power
1775 W). Thermocouples type K (Thermocoax) were used for
monitoring pre-heater (by one thermocouple placed into the
stainless steel tube) and reactor temperatures (by two thermo-
couples, one fixed on the outer reactor wall and the other placed
in the FBR, 3 cm above the perforated plate). Hydrogen and
methane flow rates were controlled by mass flow controllers
(Bronkhorst).
The combined pressure drop across the distributor and flu-
idized bed was measured with a differential pressure transducer.
The pressure drop through the distributor and quartz glass was
separately measured, so that the pressure drop across the flu-
idized bed by itself could be calculated from Eq. (1):
Pbed = Pbed+perforate plate − Pperforate plate .
4823
2.3. Operating procedure
All experiments were conducted at atmospheric pressure.
Prior to activity tests, all catalysts were subjected to a reduction
treatment using a flow rate of pure hydrogen of 80 l/h for 3 h at
550 ◦ C. Then, pure methane (99.99%) was fed into the reactor
and decomposed by the catalyst. The catalyst mass used was
fixed to a value of 20 g. The composition of the outlet gas
was determined by gas chromatography: two packed columns,
Molecular Sieve 13× and Porapack, and TCD detector were
used. Methane conversion was calculated from the following
expression:
%H2
CH4 = . (2)
200 − %H2
The carbon deposited during each run (Cdep ) was determined by
direct weight. Moreover, an estimation of the evolution of the
(1) carbon product generated can be accomplished by the following
4824 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829

correlation: Table 1
 t
Properties of the carbon product generated during long TCD run (16 h)
MC
Cdep.calc = Finlet · CH4 · dt, (3) Catalysts preparation Apparent density Mean particle diameter Catalyst
 0
method (g/cm3 ) (m) (%)a
where  is the standard molar volume, MC is the atomic weight
Co-precipitation 0.646 209 8.30
of carbon, Finlet is the methane flow rate fed to the reactor Fusion 0.604 206 8.84
(l(SPT)/min), CH4 is the methane conversion and t is the total
run time. T = 700 ◦ C; catalyst: 20 g; methane flow rate = 70 l/h.
a calculated by ash analysis.
The minimum fluidization velocity (umf ) has been deter-
mined experimentally using nitrogen gas at the reaction tem-
perature (700 ◦ C), by measuring the pressure drop caused by a
7
known mass of carbonaceous product (200 g) generated during ΔPmax=W/S
the TCD of methane. The method used the extrapolation of the 6
linear part of the pressure drop curve (p) versus gas velocity
plot up to the value corresponding to the maximum theoretical 5
pressure drop (pmax = W/S, where W is the mass of carbon
product (g) and S is the cross-sectional area in m2 ). An inert

gas was used to avoid changes and agglomeration problems.
The experimental umf value obtained with N2 has been cor-
rected to account the effect of using CH4 , using the ratio be-
tween the theoretical umf at the reaction conditions calculated
for CH4 and N2 by the method proposed by Wen and You [29],
using as constant those proposed by Adánez and Abadanes [32]
for carbonaceous material (umf -CH4 /umf -N2 = 1.4).
The mean particle diameter of the carbon product obtained
by TCD of methane used for the determination of the minimum
fluidization velocity was determined by hand sieving a repre-
sentative sample and recording the weight fraction retained on
each sieve. The particle mean diameter is then calculated by
the following equation:
1
dp =  , (4)
all i /dpi )
(x
where xi is the weight fraction in the interval, dpi is the mean
particle diameter in the interval.
Bulk density, b , was determinate by measuring the mass of
a known volume of particles placed inside a graduated cylinder,
without packing down the particles.
3. Results and discussion
3.1. Fluidodynamic study: determination of the minimum
fluidization velocity
As previously mentioned, in TCD, carbon is deposited
mainly on the catalyst as filaments emerging from the nickel
particles. As a consequence, density and shape of the particles
in the reactor, and so, their fluidodynamic behaviour dramat-
ically change as growing of carbon filaments progresses. In
addition, agglomerations of particles resulting in reactor plug-
ging have been observed at bench scale [15–18]. All these
phenomena demonstrated that fluidization of this system is
not an easy work. In order to gain information about the
fluidodynamic behaviour of the system, a set of fluidization
experiments were conducted.
First, the minimum fluidization velocity umf of the carbon
product generated during TCD of methane was determined ex-
ΔP (mbar)
4
fusion
co-precipitation
3
2
1
umf-pb umf-eb 2 x umf-eb
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
uo (cm(STP)/s)
Fig. 2. Pressure drop P across the bed vs. superficial fluidization velocity
u. Fluidization gas: nitrogen; temperature: 700 ◦ C.
perimentally. Carbon product generated in long run experiments
(16 h) carried out using the same spactial velocity as in the FBR
experiments [11–14], and with the catalysts prepared by the
two methods previously mentioned was selected conservatively
as model compound to the determination of the umf , though
the conditions for the fluidization at the early stage of the reac-
tion are lower. During TCD reaction, particles got bigger and
bigger, increasing mean particle diameter. It was also observed
that the apparent density diminished after the experiment, due
to the lower density of the carbon materials deposited. Carbon
product was sieved and the mean particle diameter was deter-
minate from Eq. (4). A wide particle size distribution, between
50 and 1000 m was observed. The mean particle diameters
from the particle size distribution obtained from sieve analysis
were found to be 208 m. Important features of the particles
are given in Table 1. We can conclude that the carbon product
particles belong to the Geldart Group A. These solids fluidize
easily, with smooth fluidization at low gas velocities and con-
trolled bubbling with small bubbles at high gas velocities. FCC
(fuel catalytic cracking) catalyst is representative of these types
of solids [30].
The experimental values of p measured for increasing val-
ues of u are shown in Fig. 2. A characteristic curve is ob-
tained, typical of the solids with wide particle size distribution,
which indicates that a partial fluidization phenomena occurs
[31]. When the gas velocity u0 is increased through these beds
 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829
Table 2
Gas velocity, flow rate and space velocity for the different fluidization velocities tested
u0 N2 (cm(STP)/s) u0 CH4 (cm(STP)/s)
umf -pb 0.47 0.66
umf -eb 0.72 1.01
2xumf -eb 1.44 2.02
of solids, the smaller particles are able to slip into the void space
between the larger particles and be fluidized while the larger
particles remain stationary. The partial fluidization occurs, giv-
ing an intermediate pressure drop p. When increasing gas
velocity, p approaches to W/S, showing that all the solids
eventually are fluidized. The fluidizing gas velocity which re-
sults of the extrapolation of the linear part of the p versus
gas velocity plot up to the value corresponding to the maxi-
mum theoretical pressure drop is referred to as the minimum
fluidization velocity for the partial bed (umf -pb ). This value cor-
responds to a nitrogen gas velocity of 0.47 cm (STP)/s. At this
p, the bed was partially fluidized. As the fluidizing gas ve-
locity was further increased, the pressure drop again increased
and a greater fraction of the bed was fluidized. From a value
of 0.72 cm (STP)/s and beyond, the pressure drop becomes al-
most constant and did not change with further increase in the
gas velocity. At this stage the entire bed was fluidized. The ni-
trogen gas velocity at which P = W/A is referred here as
the minimum fluidization velocity for the entire bed (umf -eb ).
The gas velocity was further increased up to a value of 1.44 cm
(STP)/s, which corresponds to two times the minimum fluidiza-
tion velocity for the entire bed, 2 × umf -eb . Table 2 shows the
experimental umf with N2 , the umf corrected to account the ef-
fect of using CH4 , the methane flow rate necessary to operate
at the three fluidization velocities selected as well as the space
velocity used.
3.2. Effect of the catalyst preparation method
Two types of catalyst were used in the pilot plant described
above in order to study its behaviour in the TCD of methane
in an FBR. Fig. 3 shows the hydrogen evolution in the outlet
gas for Ni:Cu:Al catalysts prepared by co-precipitation and by
fusion using a methane flow rate corresponding to the mini-
mum fluidization velocity for the partial bed umf -pb at 700 ◦ C.
In bench scale experiments [11–14], the hydrogen production
was closed to the maximum thermodynamic value, finding no
difference between both catalysts. In pilot plant scale reactor,
just small differences were found, observing the catalyst pre-
pared by co-precipitation showed a slight better behaviour. For
the co-precipitation catalysts, the average hydrogen concentra-
tion in the outlet gas is around 65%, which corresponds to a
CH4 conversion of 48%. For the fusion catalyst, the average
hydrogen concentration in the outlet gas is around 60%, which
corresponds to a CH4 conversion of 43%. For both samples,
catalysts deactivation did not occur after a 16 h run. In fact,
catalyst activity is only slightly decreasing in spite of the high
increase of the amount of deposited carbon with time. At the
4825
CH4 flow rate (l(STP)/h) Space velocity (l(STP)/h/gcat )
78 3.9
120 6
240 12
80
70
60
50
%H2 (vol.)
40
Co-precipitation
30 Fusion
20
10
0
0 100 200 300 400 500 600 700 800 900 1000
Time (min)
Fig. 3. Hydrogen production (%vol) for co-precipitation and fusion catalyst
in pilot plant scale. T = 700 ◦ C, catalyst: 20 g, methane flow rate = 70 l/h.
end of the test, more than 200 g of carbon product were ob-
tained. Table 3 shows the main parameters of umf -pb TCD test
in the long run experiments featured for co-precipitation and
fusion catalysts: the reaction time, the amount of carbon de-
posited calculated from Eq. (3), the carbon formation rate the
volumetric hydrogen production as well as the average methane
conversion. Similar results were obtained with both catalyst
preparation method used. In the TCD of methane, the catalyst
is a consumable expensive material contributing substantially
to the final cost of the hydrogen produced. Co-precipitation
method for catalyst preparation involves filtration and washing
processes that could increase the overall production costs an
industrial scale. Consequently, a method for catalyst prepara-
tion as simple as possible, like salt fusing, is highly desirable
[12,13]. The catalyst prepared by the fusion method was se-
lected for rest of the fluidization experiments.
It is worth to mention that the pressure drop measured dur-
ing the experiments showed an exponential increase after a few
hours of reaction (figures not shown). This is attributed to the
poor fluidization quality of the particle bed as the particle in-
ventory in the bed increased.
3.3. Effect of the fluidization conditions
3.3.1. Kinetics measurements
It is well known that gas velocity is the most important pa-
rameter in the FBR operation because the fluidization quality
of the gas–solid contacting pattern is strongly dependent on gas
4826 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829

Table 3
Hydrogen and carbon production and methane conversion for the FBR experiments

Fluidization velocity Reaction time Space velocity Carbon deposited Cdep /h H2 production Conversion
(h) (l/gcat h) (l/h)

umf -pb a 16 4 241 15.06 76.8 0.48

umf -pb b 15 4 226 15.07 68.8 0.43
umf -eb b 8 6 118 14.75 50.4 0.21
2xumf -eb b 8 12 131 16.38 57.6 0.12
a Co-precipitation catalyst.
b Fusion catalyst.

80 3.0

70 umf-pb

reaction rate (mmol CH4/min/gcat)

2.5 umf-pb

60 2 x umf-pb

umf-pb
2.0
50 umf-eb
% H2 (vol.)

2 x umf-eb
40 1.5

30
1.0
20

10 0.5

0 0.0
0 100 200 300 400 500 0 100 200 300 400 500
Time (min) Time (min)

Fig. 4. Effect of gas velocity on the hydrogen production over fusion Ni:Cu:Al Fig. 5. Effect of gas velocity on the methane reaction rate over fusion
catalyst at the temperature of 700 ◦ C. Ni.Cu:Al catalyst at the temperature of 700 ◦ C.

velocity [15]. Fig. 4 shows the effect of the gas velocity on the
hydrogen production over Ni:Cu:Al fusion catalyst at the oper-
ating temperature of 700 ◦ C. As can be observed in Fig. 4, the
effect of gas velocity on the hydrogen production was signifi-
cant in the FBR. As we have mentioned before, for the umf -pb ,
which corresponds to a space velocity of 4 l/gcat /h, the hydro-
gen production was 60%, and not deactivation was observed
during the 16 h run. For the umf -eb and 2 × umf -eb , which cor-
respond respectively to a space velocity of 6 and 12 l/gcat /h,
a different pattern was observed: the hydrogen concentration
remains constant during 150 min, obtaining a hydrogen con-
centration of 40% and 30%, respectively, and from this point
onwards a progressive deactivation begins. At the end of the
run, a hydrogen production of 25% and 15%, respectively, was
observed for the umf -eb and 2 × umf -eb experiments.
Unlike the fixed bed operation, in the fluidized bed opera-
tion it is assumed that all the gas in excess of that required
for the minimum fluidization passed through the bed as bub-
bles. Therefore, the higher gas velocity increased the number
of bubbles and the size of them and these bubbles may exit the
reactor without effective contacting the catalyst. Thus, the in-
creasing gas velocity reduced the residence time in the reactor
and lowered the contacting efficiency between gas and metal
catalyst due to bubble formation [15]. The above mentioned
hydrodynamic characteristic of fluidized bed explains why the
gas velocity effect on the methane conversion was significant.
It is worth to mention that a higher methane conversion can be
achieved by an increase in the bed height. Fluidization of the
bed can be carried out by the hydrogen produced. The fact that
the theoretical umf for hydrogen calculated by the method pre-
viously mentioned is 40% higher than the umf for methane is
balanced by the increase of the volume during the methane de-
composition (2 mol of H2 are produced for each mol of methane
converted). Fig. 5 shows the methane reaction rate for the runs
featured at the three fluidization velocities. The same pattern
as in Fig. 4 is observed. However, the three curves fall in a
narrow range meaning that negligible mass resistance occurs,
and the gasin excess does not have an effective contact with the
metal catalyst. As we have mentioned before, this gas in ex-
cess improves the mixing of the bed and prevents the clogging
problems observed when low fluidization velocities are used.
Table 3 shows the carbon deposited after each run, the car-
bon deposition per hour, the average methane conversion as
well as the average hydrogen production. As can be observed
in Table 3, close values of carbon deposition ratio and hydro-
gen production ratio are observed. It can be observed that the
 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829 4827

magnification of the Fig. 6a. Pcalc was also plotted for a bet-
50 ter comparison of the fluidization quality (to see if the reactor
umf-pb clogging occurs). Due to the same ratio of carbon deposited for
umf-pb the three conditions studied, the same curve has been plotted
40 2 x umf-pb for all of them.
ΔPcalc Figs. 6a and b show that for the three fluidization velocities
30 tested, the Pmeasured was in good agreement with the Pcalc
ΔP (mbar)

during the first stage of the reaction (until 150 min). For the
umf -pb and umf -eb an exponential increase in the Pmeasured was
20 observed. However, when 2 × umf -eb is used, the Pmeasured
correlates fairly well with the Pcalc . That clearly indicates that
10 it is necessary to operate with a vigorous fluidization regime,
at least two times the minimum fluidization for the entire bed.
Otherwise, defluidization occurs leading to clogging problem
0 during the runs.
0 50 100 150 200 250 300 350 400 450 500 It is known that for binary mixtures where the particles
Time (min) differ in size only, larger particles segregate preferentially to-
ward the bottom of the bed (near the distributor plate), while
10 the smaller particles accumulate near the free surface. For
umf-pb continuous particle size distribution, the mean particle diam-
9
umf-pb eter decreases from the bottom of the bed to the free sur-
8 2 x umf-pb face [33]. The fluidization experiments were carried out with
7 ΔPcalc a carbon product with a wide particle size distribution, as we
6 have seen from hand sieved analysis. Thus, we propose as ex-
ΔP (mbar)

5
4
3 of the bigger particles. Then defluidization occurs, leading to
2 the agglomeration of the particles that finally provokes the
1
0 relative big sized carbon particles. The agglomeration of the
0 50 100 150 200
Time (min)
Fig. 6. (a) Variation in the pressure drop of the particle bed for different gas
velocities and (b) magnification of (a).
fluidized bed installation has been operated to produce at the
scale of 60 l/h of hydrogen and 15 g/h of carbon nanofibers.
3.3.2. Fluidization quality
Scarce information about the hydrodynamic behavior of the
bed of particles during the TCD is found in literature. In order
to confirm the correct fluidization of the bed of particles, the
pressure drop across the particles bed was continuously mon-
itorized, Pmeasured . As we have seen before, the evolution of
the amount of carbon deposited Cdep-calc as a function of the
reaction time can be calculated from Eq. (4). From pressure
drop definition, we can calculate the evolution with time of the
pressure drop of the fluidized bed Pcalc as the carbon is de-
posited in the catalyst and thus, increasing the mass particle in-
ventory. By comparing Pmeasured and Pcalc we can determi-
nate the quality of the fluidization: a good correlation between
both curves means that the bed fluidizes correctly.
Fig. 6a plots the Pmeasured across the bed for different flu-
idization regimes: umf -pb , umf -eb , 2 × umf -eb . Fig. 6b shows a
planation that, as the particle diameter gets higher, the big-
ger particles tend to occupy the low region of the bed, and
the gas velocity is not sufficient to maintain the fluidization
shut down of the reactor. In addition, the fluidization regime
leads to the attrition of the particles, avoiding the formation of
solid is a problem in catalytic fluidized bed reactors. In most
cases high relative velocities (u/umf ) are employed to avoid
defluidization [34].
At an industrial scale, the carbon product can be withdraw
from the bottom of the fluidized bed, grinded to a desired par-
ticle size, and recirculated, assuring a good fluidization of the
particle bed.
Thus, we can conclude that the lowering in methane con-
version is balanced with good fluidization behaviour. So the
optimum gas velocity should be chosen in terms of hydrogen
production rates and fluidization quality.
3.4. Characterization of the carbon product
Fig. 7a shows the SEM images for the carbon deposited from
the co-precipitation catalyst, Fig. 7b shows the SEM images
for the carbon deposited from the fusion catalyst. They show
that nanofibers are present, appearing as long filaments emerg-
ing from Ni particles coexisting with uniform coatings on the
Ni particles. Although the relative concentration of these two
carbons forms cannot be achieved, a simple examination of the
respective images evidences that long filaments are more abun-
dant than uniform coatings as it had been observed in the work
carried out using a small fixed bed reactor [11–14].
4828 J.L. Pinilla et al. / International Journal of Hydrogen Energy 32 (2007) 4821 – 4829
Fig. 7. SEM micrograph of the Ni:Cu:Al-78:6:16 catalysts after an 16 h run. Reaction T : 700 ◦ C; (a) co-precipitation and (b) fusion. left, 8000×, right, 20 200×.
4. Conclusions
Performance tests showed that the hydrogen production was
not highly dependent on catalyst preparation method and so
that an easier and cheaper one as the fusion of salts can be used
at an industrial scale.
Fluidodynamic studies have shown that TCD can be carried
out in a fluidized bed reactor without reactor clogging provided
that a methane velocity of two times the minimum fluidization
velocity is used.
A semi-continuous fluidized bed installation has been started
up and operated to produce at the scale of 60 l h−1 of hydrogen
and 15 g h−1 of carbon nanofibers.
Acknowledgments
The authors would like to thank CDTI for financial support
through the contract with Gas Natural to carry out the SPHERA
Project included in the CENIT Program 2006. Y.E. the Spanish
MEC for the FPI Grant.
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