international journal of hydrogen energy 33 (2008) 4387–4396

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Catalytic steam reforming of acetic acid in a fluidized

bed reactor with oxygen addition

J.A. Medrano, M. Oliva, J. Ruiz, L. Garcia*, J. Arauzo

Thermochemical Processes Group (GPT), Aragon Institute for Engineering Research (I3A), University of Zaragoza,
Marı́a de Luna 3, 50018 Zaragoza, Spain

article info abstract

Article history: Catalytic steam reforming of bio-oil is a promising process for producing hydrogen in
Received 31 October 2007 a sustainable environmentally friendly way that can improve the utilization of local
Received in revised form resources (natural sources or wastes). However, there remain drawbacks such as coke
11 April 2008 formation that produce operational problems and deactivation of the catalysts. Coprecipi-
Accepted 3 May 2008 tated Ni/Al catalysts are here used in a fluidized bed for reforming at 650  C of acetic acid as
Available online 12 August 2008 a model compound of bio-oil–aqueous fraction. Different strategies are applied in order to
study their effects on the catalytic steam reforming process: modification of the catalyst by
Keywords: increasing the calcination temperature or adding promoters such as calcium. The addition
Steam reforming of small quantities of oxygen is also tested resulting in an optimum percentage to achieve
Acetic acid a high carbon conversion process with less coke and without a hydrogen yield penalty
Pyrolysis liquids production. The results for catalytic steam reforming are compared with other ones
Oxygen addition from literature.
Fluidized bed ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
Nickel catalyst reserved.

1. Introduction energy carriers of the future [1], is a feasible and renewable

Interest in the hydrogen economy is increasing because of its
chemical uses and its utilization as a clean fuel in high ener-
getic efficiency systems such as fuel cells in stationary, mobile
or portable applications that can be used in vehicles.
Currently, hydrogen is produced through non-environ-
mentally friendly ways, such as steam reforming of natural
gas and petroleum derived compounds or coal gasification,
that deplete fossil fuels, producing corresponding CO2 emis-
sions. However, hydrogen from biomass can replace fossil
fuels, reducing greenhouse gases and other contaminants,
contributing to a better utilization of available local natural
resources, diversifying energy sources and reducing external
dependence. Waste-to-hydrogen processes are also attracting
increasing interest. Hydrogen, one of the most promising
alternative for sustainable development.
There are several methods for obtaining hydrogen from the
conversion of biomass classified in two main areas: biological
or thermochemical. The latter includes steam reforming, one
of the most suitable ways to produce a hydrogen rich gas.
Substantial research has been done on steam reforming
from biomass or wastes, including bioethanol [2,3], trap grease
[4], vegetable oils [5], glycerol [6] or bio-oil [7–9].
Steam reforming of pyrolysis liquids (bio-oil) is a promising
path for achieving hydrogen production. Lignocellulosic
biomass is thermochemically processed (fast pyrolysis) to
obtain bio-oil. As bio-oil suffers from ageing during storage
[10,11] and is a complex mixture of a large number of
compounds, including aldehydes, alcohols, ketones, and acids,
as well as more complex carbohydrate- and lignin-derived

* Corresponding author. Tel.: þ34 976 762194; fax: þ34 976 761879.
E-mail address: luciag@unizar.es (L. Garcia).
0360-3199/$ – see front matter ª 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2008.05.023
4388 international journal of hydrogen energy 33 (2008) 4387–4396
oligomeric materials emulsified with water, an aqueous frac-
tion is separated in order to achieve a higher stability of pyrol-
ysis liquids. The aqueous phase contains some organic
compounds such as acids, alcohols, aldehydes, ketones and
sugars. The ligninic fraction, insoluble in water, can be used
to produce highly valued fine chemicals [12], such as phenolic
resins that improve the economic viability of the process.
Research into steam reforming of model compounds of
bio-oil [13–22] is needed in order to develop efficient and stable
catalysts to perform this process. Generally, acetic acid (HAc),
which is soluble in water, is chosen as a model compound
because it has a significant presence and is one of the most
representative constituents of the water soluble fraction of
bio-oil [18].
Some disadvantages have been found when steam reform-
ing bio-oil and other liquids derived from biomass in fixed-bed
reactors due to problems caused by the formation of carbona-
ceous deposits limiting the operating time and requiring
a long regeneration process. A fixed bed is inadequate for pro-
cessing the non-stable organic liquids derived from biomass
[23]. Therefore, it is necessary to use a fluidized bed because
of one of its main advantages: carbon deposits on catalyst are
better exposed to contact with steam and are consequently
more easily removed allowing more continuous operation.
Another operational problem is that the bio-oil is not totally
vaporized when feeding, so significant amounts of residual
solids block the feeding line and the reactor [8]. Thus, a spray
system and a cooling jacket are necessary to feed bio-oil or its
fractions instead of a simple injection system.
The review of Sutton et al. [24] presents various types of
catalysts that have been employed in the gasification of
biomass. Nickel catalysts, both research and commercial,
play a significant role. Noble metals [15,17,20] and nickel cata-
lysts [7–9,13,18–20,22] have been used in research into steam
reforming reactions of oxygenates derived from biomass. In
this paper we have selected nickel catalysts because they
are effective, commercially available and relatively cheap.
In order to develop the appropriate nickel catalyst for
a process, some variables must be considered such as the
preparation method and conditions (calcination and activa-
tion), metal content and the presence of promoters. Ni/Al
coprecipitated catalysts have shown a good performance in
fluidized bed in biomass steam gasification [25] and in steam
reforming of model compounds of bio-oil, HAc [18] and acetol
[26], and therefore they have been selected as the catalysts in
this work. The calcination temperature of Ni/Al coprecipitated
catalysts significantly influences final properties of the cata-
lyst such as, inter alia, surface area and crystalline phases,
and this variable must be considered. In previous work, the
influence of calcination temperature showed a significant
effect on catalytic biomass pyrolysis [27]. Therefore the effect
of this variable on steam reforming of acetic acid is studied in
this paper.
Metal loading is also an important parameter in catalyst
activity. Bangala et al. [28] tested impregnated nickel–alumina
catalysts with different nickel contents (5, 10, 15 and 20 wt%),
and found that the conversion and gas yield increased with
metal loading up to 15%. On the other hand the coke yield
also increased continuously up to 20% as it is related with
metal loading. These results were attributed to the lower
metal dispersion as the metal loading increased. Bimbela
et al. [22] worked with coprecipitated Ni/Al catalysts with
different nickel contents in HAc steam reforming (23, 28 and
33% atomic ratio Ni/(Ni þ Al)) and reported that the highest
hydrogen yield was obtained using 28% nickel content. In
this work this has been the nickel content selected.
Steam reforming catalysts are often doped with promoters.
Arauzo et al. [29] researched magnesium addition to a Ni/Al
catalyst that resulted in an improvement in catalyst strength
but gave a lower gas yield. Bangala et al. [28] reported that
chromium inhibited the formation of nickel carbide, La2O3
led to a decrease in coke formation, MgO improved the robust-
ness and TiO2 addition decreased the conversion and yield of
gas. Galdámez et al. [18] concluded that the addition of
lanthanum in the nickel catalyst diminishes the hydrogen
yield. Garcia et al. [7] explained that magnesium and
lanthanum can enhance steam adsorption that facilitates
the gasification of surface carbon; on the other hand cobalt
and chromium can modify the metal sites forming alloys
with nickel and possibly reducing the crystallite size.
Another promoter is calcium. Some nickel catalysts
employed in the partial oxidation of methane that incorpo-
rates this element have demonstrated a good performance
against coke formation. Morioka et al. [30] prepared Ni/Al
catalysts with calcium. The spc-Ni/Ca–Al catalyst (prepared
by solid phase crystallization) showed the highest activity
and selectivity to gas production as well as the highest
sustainability against coke formation due to the stable and
highly dispersed Ni metal particles and the basic properties
of the support. Lu et al. [31] reported the design of a modified
Ni/Al catalyst introducing a CaAl2O4 spinel compound that
stabilized tiny nickel crystallites improving the resistance to
coke. This work shows a first attempt to incorporate calcium
in coprecipitated Ni/Al catalysts in order to know the influ-
ence on steam reforming of acetic acid.
A common problem in the steam reforming of hydrocar-
bons reported by many authors is coke formation, which is
a serious operational problem and produces catalyst deactiva-
tion. Three types of coke can be formed during steam reform-
ing: a highly reactive one constituted probably of atomic
carbon, that is mostly gasified [32]; an amorphous type from
the polymerisation of the former, that is less active and may
be dissolved in the nickel crystallite leading to whisker forma-
tion; and graphitic carbon. Coke can be eliminated by the use
of promoters or, as some authors have reported, by oxygen
addition [33]. One strategy that can be used is the incorpora-
tion of small quantities of oxygen that can help to gasify
coke precursors on the catalyst surface. The incorporation of
oxygen in steam reforming reactions also has a beneficial
effect on the energy balance decreasing the heat supply [34].
Therefore, small quantities of oxygen were added to steam
reforming of acetic acid as a novelty of the research work
that is being carried out.
This work studies the influence of the addition of small
quantities of oxygen to the catalytic steam reforming of HAc
as well as the influence of the calcination temperature and
the addition of calcium as a promoter on the catalyst activity
and stability. The experiments were performed at 650  C in
a fluidized bed reactor using coprecipitated Ni/Al catalysts
with a nickel content of 28% atomic ratio Ni/(Ni þ Al).
 international journal of hydrogen energy 33 (2008) 4387–4396
2. Experimental
2.1. Experimental system
The experimental system is shown in Fig. 1. This is a bench-
scale installation with a tubular 1 inch (2.54 cm) quartz fluid-
ized bed reactor. The reactor is externally heated by an electric
furnace. The feeding system consists of a quartz coaxial injec-
tion nozzle producing a spray and is refrigerated by an
external cooling jacket. The aqueous solution of HAc is intro-
duced through the inner tube and is sprayed into the fluidized
bed by a secondary nitrogen flow coaxial to the inner tube.
This reactor was designed in order to process bio-oil or its
fractions. As mentioned above, bio-oil cannot be totally vapor-
ized and a significant amount of residual solids can be formed
because of thermal decomposition blocking the feeding line,
so a spray system with external cooling is needed.
The aqueous solution of HAc is delivered by a peristaltic
pump. The product gas goes out through a recovering cooling
system (two special condensers with an ice bath) where
excess steam and non-reacted organic liquids are trapped by
condensation. A cotton filter is also placed after the
condensers to retain small solid particles of catalyst or carbo-
naceous residues.
The CO and CO2 concentrations of the exit gas were contin-
uously measured by an infrared (IR) analyzer. An Agilent P200
Micro GC gas chromatograph equipped with thermal conduc-
tivity (TC) detectors was used to determine concentrations of
the gas products: CO2, CO, CH4, C2 (C2H4, C2H6, C2H2), N2 and H2.
The experimental system was operated at atmospheric
pressure. All the experiments were performed using
a 23 wt% HAc aqueous solution, which corresponds to an S/C
molar ratio of 5.58. The reactor operated as a fluidized bed at
u/umf ¼ 10.
The catalytic steam reforming experiments were per-
formed at 650  C. The reactor bed contained a well mixed
Fig. 1 – Schematic of the experimental system.
4389
mixture of sand and the nickel catalyst that did not show
any segregation problems during the experiments. The
particle size of sand and catalyst used was 160–320 mm and
the particle density of these solids is similar. The bed was
of 7 cm height with a nickel catalyst weight content of
1.1 g. The inlet liquid (HAc aqueous solution) flow rate was
0.68–0.77 ml/min. The catalyst weight/HAc mass flow ratio
(W/mHAc) was around 6 g catalyst min/g HAc, corresponding
to GC1HSV values of around 6800 h1. GC1HSV was defined
as the volume of C1-equivalent species in the feed at stan-
dard temperature and pressure (STP) per unit volume of
catalyst (including the void fraction) per hour. Oxygen
addition experiments were carried out ranging from 0 to
8% oxygen (percentage of oxygen necessary for the stoi-
chiometric combustion of HAc). In these experiments air
was used to add the oxygen.
The experimental procedure involved in situ reduction of
the catalyst prior to the steam reforming reaction, with
hydrogen diluted in nitrogen (10%, v/v) at 650  C for 1 h.
2.2. Catalysts
Two research catalysts were prepared by coprecipitation. One
contains nickel and aluminium and the other also contains
calcium. The preparation method was similar to that
described by Al-Ubaid and Wolf [35]. The nickel content of
these catalysts is 28% atomic ratio Ni/(Ni þ Al).
One of the catalysts (Ni/Al) was synthesised by adding
ammonium hydroxide (NH4OH) to a solution of Ni(NO3)2$6H2O
and Al(NO3)3$9H2O in distilled water until the pH attained
a value of 7.9. The precipitation medium was maintained at
40  C and moderately stirred. The precipitate obtained was
filtered and washed at 40  C and dried overnight at 105  C.
The precursors thus obtained were ground and sieved to
a particle size ranging from 160 to 320 mm and calcined at
low heating rate in air atmosphere up to the final calcination
4390 international journal of hydrogen energy 33 (2008) 4387–4396
temperature for 3 h. Final calcination temperatures of 750, 850
and 900  C were employed.
The other catalyst (Ni/Al/Ca), modified with calcium, was
synthesised with the following molar ratios: Ca/Al ¼ 0.50,
Ca/Ni ¼ 1.29. It was prepared by adding ammonium hydroxide
(NH4OH) to a solution of Ni(NO3)2$6H2O, Ca(NO3)2$4H2O and
Al(NO3)3$9H2O in distilled water until the pH attained a valued
of 7.9. The precipitation medium was maintained at 40  C and
moderately stirred. The colloid was not filtered because Ca2þ
could not be precipitated at the pH value and was thus dried
overnight at 70  C to evaporate the water. The precursor
obtained was ground and sieved to a particle size ranging from
160 to 320 mm and calcined in air atmosphere at low heating
rate up to a temperature of 750  C that was maintained for 3 h.
In order to know various properties of the catalysts, the
calcined catalysts were characterized by X-ray diffraction
(XRD) and nitrogen adsorption. Several catalyst samples
were also characterized by XRD and scanning electronic
microscopy (SEM) after their use in reforming.
Fig. 2 shows the results obtained for the XRD analyses (D-
Max Rigaku) of the calcined catalysts. Two different phases
are detected: NiO and NiAl2O4 (spinel compound) for the Ni/
Al catalyst calcined at different temperatures. As the calcina-
tion temperature increases a higher proportion of spinel
phase is observed. Higher crystallinity is also obtained when
increasing the calcination temperature of the catalyst. Similar
Fig. 2 – XRD patterns of Ni/Al and Ni/Al/Ca fresh catalysts.
(a) Ni/Al calcined at 750 8C, (b) Ni/Al calcined at 850 8C, (c) Ni/
Al calcined at 900 8C and (d) Ni/Al/Ca calcined at 750 8C.
trends were observed previously for the coprecipitated Ni/Al
catalyst with 33% atomic ratio Ni/(Ni þ Al) [27]. The compar-
ison of the XRD patterns of Ni/Al and Ni/Al/Ca catalysts
(both calcined at 750  C) shows that the NiO phase is clearly
present in the calcium modified catalyst in contrast to the
Ni/Al catalyst where two phases are found (NiO and NiAl2O4).
Surface areas of the different modified catalysts were
measured in a Micromeritics ASAP 2020 by nitrogen adsorp-
tion. The values of surface area determined were 175 m2/g
for the catalyst calcined at 750  C, 112 m2/g for the catalyst
calcined at 850  C and 88 m2/g at 900  C of calcination temper-
ature. When increasing the calcination temperature
a decrease in surface area is obtained because of the catalyst
support sintering. A 50% of surface area is lost by increasing
the calcination temperature from 750 to 900  C.
2.3. Chemicals
The model compound selected for the tests (HAc) was
supplied by PANREAC (99.5% purity). Other chemicals used
included commercial high purity gases (>99.999%): hydrogen,
nitrogen, air, helium and argon, as well as standard gas
mixtures of CO, CO2 and nitrogen for calibration of the CO-
CO2 analyzer and H2, N2, CO, CO2, CH4, and C2 for the calibra-
tion of the gas chromatograph.
3. Results and discussion
3.1. Influence of the calcination temperature
of the catalyst
The activity and stability of the catalyst can be modified by its
calcination temperature, so steam reforming experiments
were carried out to study this influence. Table 1 shows the
experimental conditions and the overall results obtained for
the experiments using the Ni/Al catalyst at different calcina-
tion temperatures (750, 850 and 900  C). The table shows the
values of some experimental variables such as the liquid
feeding rate, W/mHAc ratio and GC1HSV. Some results are also
shown such as the carbon conversion (percentage of carbon
contained in the HAc that is converted to gases: CO, CO2, CH4
and C2), yields to different gases (expressed as g gas/g HAc),
and the gas composition (% mol, N2 and H2O free).
The results indicate that the recovery for all the experi-
ments is 1.00  0.02. The gas composition (% mol, N2 and
H2O free) shows that H2 content is around 65%, CO content
around 6%, CO2 content around 27% and CH4 content up to
0.22%. Fig. 3a–d shows in more detail the influence of the calci-
nation temperature of the catalyst on gas yields and carbon
conversion. The hydrogen yield (Fig. 3a) decreases when
increasing the calcination temperature of the catalyst. This
effect is more noticeable when the catalyst is calcined at
900  C. Fig. 3b shows the same behaviour for the CO2 yield as
for H2. In contrast, an increase in the CO yield (Fig. 3c) is
observed when the calcination temperature increases. These
figures allow the study of the evolution of different gas yields
with time. A low decrease in the H2 and CO2 yields and a very
slight decrease in the CO yield are observed with time for the
catalyst calcined at 750 and 850  C. These tendencies could be
 international journal of hydrogen energy 33 (2008) 4387–4396 4391

Table 1 – Experimental results at 650 8C, with a catalyst

weight of 1.1 g and 2 h reaction time with modified
catalysts
Run # 1 2 3 4

Catalyst Ni/Al Ni/Al Ni/Al Ni/Al/Ca

Calcination temperature 750 850 900 750
( C)
Ca/Al molar ratio 0 0 0 0.50
Liquid feeding rate 0.76 0.75 0.68 0.76
(ml/min)
W/mHAc (g catalyst 6.152 6.181 6.830 6.085
min/g HAc)
GC1HSV (h1) 6772 6741 6100 6847
Gas yield (g/g liquid fed) 0.343 0.338 0.292 0.347
Liquid yield (g/g liquid fed) 0.672 0.669 0.712 0.651
Recovery 1.014 1.007 1.004 0.998
Carbon conversion (%) 98.87 98.33 87.15 100.97

Gas yields (g/g HAc)

H2 0.1303 0.1239 0.1062 0.1314
CO 0.1533 0.1655 0.1884 0.1697
CO2 1.2053 1.1784 0.9737 1.2069
CH4 0.0014 0.0014 0.0028 0.0026

Gas composition (% mol, N2 and H2O free)

H2 66.42 65.40 64.64 66.14
CO 5.58 6.24 8.20 6.10
CO2 27.92 28.27 26.93 27.60
CH4 0.09 0.09 0.22 0.16

due to catalyst deactivation probably caused by coking.

However, for the catalyst calcined at 900  C a fast decrease
in H2 and CO2 yields and a lower decrease of CO yield are
observed as the experiment evolves.
Fig. 3 – Influence of the calcination temperature on the
In Fig. 3d complete carbon conversion is observed for the
evolution of gas yields and carbon conversion with time.
catalyst calcined at 750 and 850  C but not at 900  C.
(a) H2 yield, (b) CO2 yield, (c) CO yield and (d) carbon
The main reactions involved are steam reforming (Eq. (1))
conversion; (-) 750 8C, (B) 850 8C and (6) 900 8C.
and water gas shift (Eq. (2)) that occur simultaneously:

CH3 COOH þ 2H2 O / 2CO2 þ 4H2 (1)

CO þ H2 O 4 CO2 þ H2
The decrease in the H2 and CO2 yields and the increase in
the CO yield when the calcination temperature increases
can be explained by the water gas shift reaction. However,
the lower carbon conversion observed with the catalyst
calcined at 900  C indicates a lower reforming activity, espe-
cially with time. The experiment carried out with the catalyst
calcined at 900  C also shows a higher methane yield, which
could be related to a lower reforming activity. Galdámez
et al. [18] explained the participation of the catalyst in the
steam reforming of methane (Eq. (3)).
CH4 þ H2 O 4 CO þ 3H2
XRD analyses (Fig. 2) showed that at higher calcination
temperatures a larger proportion of crystalline spinel
(NiAl2O4) phase appears. This phase is more difficult to reduce.
The lower reforming activity of the catalyst calcined at 900  C
could be due to the fact that the catalyst was not properly
reduced and harder reduction conditions were needed in
order to obtain metallic nickel [27]. The reaction atmosphere,
H2 and CO, is not capable of reducing the phases present in the
(2)
catalyst either. In addition, the surface area of the catalyst
decreases when the calcination temperature increases, and
this fact can influence reforming activity.
3.2. Influence of calcium addition as a promoter
These experiments were carried out in order to find out if the
addition of calcium as a modifier of the Ni/Al catalyst has
some significant effect on the process. The experimental
conditions and the overall results obtained for the experiment
with calcium addition as a promoter are shown in Table 1. A
comparison of the results obtained with the Ni/Al catalyst
(3)
(run 1) and Ni/Al/Ca catalyst (run 4), both calcined at the
same temperature, indicates very similar values of H2 and
CO2 yields, while CO and CH4 yields are slightly higher for
the calcium promoted catalyst.
Fig. 4 shows a comparison of the evolution of the H2 yield
with time for the Ni/Al and Ni/Al/Ca catalysts. The same deacti-
vation tendency with time is observed for both catalysts, so the
same resistance to coke deactivation is probably taking place.
4392 international journal of hydrogen energy 33 (2008) 4387–4396

In addition, coke could be the cause of catalyst deactivation

Fig. 4 – H2 yield evolution with time, influence of calcium
addition. Calcination temperature of 750 8C; (-) Ni/Al
catalyst and (,) Ni/Al/Ca catalyst.
Although the results of XRD characterization (Fig. 2a and d)
indicate different crystalline phases in the Ni/Al and Ni/Al/Ca
catalysts, both calcined at 750  C, the performance in steam
reforming is similar in activity and stability. It may perhaps
be necessary to test these catalysts in other operational condi-
tions in order to know of any positive effects produced by the
addition of calcium.
3.3. Influence of oxygen addition to the steam reforming
process
Coke is a serious operational problem that is endemic to
steam reforming and depends on the nature of the feed [32].
in steam reforming of pyrolysis oil–aqueous fraction [23].
Therefore, an addition of oxygen in small quantities can
provide less coking to the process as well as slightly helping
to compensate for the endothermicity of the steam reforming
reactions. These experiments were thus performed in order to
study the effect of oxygen addition to the steam reforming.
Table 2 shows the experimental conditions and the overall
results obtained for these experiments. The Ni/Al catalyst
calcined at 750  C was used in all cases and different concen-
trations of oxygen were fed ranging from 0 to 8% (percentage
of oxygen necessary for the stoichiometric combustion of
HAc).
As shown in Fig. 5a, the H2 yield decreases when the
percentage of oxygen addition increases. This decrease is
moderate at lower inlet oxygen concentrations (2 and 4%)
but there is no difference when comparing these two experi-
ments. In contrast, with 8% oxygen an important decrease in
the H2 yield occurs. The same tendency is observed for the
CO2 yield (Fig. 5b) at short reaction time. However, for times
longer than 1 h reaction CO2 yields for 2 and 4% oxygen are
higher than 0% oxygen. The opposite performance to that of
the H2 yield is observed for the CO yield (Fig. 5c). This is prob-
ably because partial oxidation (Eq. (4)) is taking place at higher
oxygen concentrations.
CH3 COOH þ O2 / 2CO þ 2H2 O (4)
On the other hand, for the experiment conducted with no
oxygen addition the carbon conversion decreases with time
(Fig. 5d). The addition of oxygen has a favourable effect
because it keeps the carbon conversion of the process
constant up to a value of 100%.
These results seem to be of interest since the O2 presence
on the one hand maintains a constant activity over time but,
on the other hand, decreases the yield of hydrogen. This

Table 2 – Experimental results at 650 8C, with a catalyst weight of 1.1 g of Ni/Al catalyst calcined at 750 8C with oxygen
addition
Run # 1 5 6 7 8 9

Reaction time (h) 2 2 2 2 6 6

O2 addition (%) 0 2 4 8 0 4
Liquid feeding rate (ml/min) 0.76 0.76 0.77 0.75 0.75 0.74
W/mHAc (g catalyst min/g HAc) 6.152 6.096 6.026 6.179 6.205 6.246
GC1HSV (h1) 6772 6835 6914 6743 6715 6670
Gas yield (g/g liquid fed) 0.343 0.344 0.344 0.330 0.339 0.351
Liquid yield (g/g liquid fed) 0.672 0.620 0.667 0.693 0.689 0.688
Recovery 1.014 0.964 1.011 1.024 1.028 1.039
Carbon conversion (%) 98.87 99.83 100.27 100.52 98.09 102.64

Gas yields (g/g HAc)

H2 0.1303 0.1224 0.1203 0.1096 0.1255 0.1233
CO 0.1533 0.1595 0.1704 0.2467 0.1546 0.1775
CO2 1.2053 1.2134 1.2028 1.0764 1.1908 1.2246
CH4 0.0014 0.0000 0.0000 0.0037 0.0017 0.0007

Gas composition (% mol, N2 and H2O free)

H2 66.42 64.78 64.30 62.07 65.75 64.28
CO 5.58 6.03 6.50 9.97 5.78 6.65
CO2 27.92 29.19 29.20 27.70 28.36 29.03
CH4 0.09 0.00 0.00 0.26 0.11 0.05
 international journal of hydrogen energy 33 (2008) 4387–4396 4393

Fig. 6 – Influence of the oxygen addition for 6 h of reaction

time. (a) H2 yield and (b) carbon conversion; (-) O% O2, (,)
4% O2. Ni/Al catalyst calcined at 750 8C.

Fig. 5 – Influence of the oxygen addition on the evolution of

gas yields and carbon conversion with time. (a) H2 yield, (b)
CO2 yield, (c) CO yield and (d) carbon conversion; (,) 0% O2,
(C) 2% O2, (6) 4% O2 and (;) 8% O2. Calcination
temperature of 750 8C.

decrease is moderate at lower inlet oxygen concentrations (2

and 4%). It follows that better operation conditions, in terms
of O2 concentration, are a compromise between keeping
high and constant levels of catalyst activity over time and
high levels of hydrogen yield. Therefore 4% of oxygen is a suit-
able value that can give a process with less coke, maintaining
the carbon conversion up to 100% with high hydrogen yield.
In order to prove if catalyst activity is maintained over the
operation time, some reforming experiments have been per-
formed for longer reaction times (6 h) in the absence and pres-
ence of O2 (0 and 4%). Results of these experiments are shown
in Table 2 (runs 8 and 9). The hydrogen yield is similar for the
two experiments, while the CO and CO2 yields are slightly
higher with 4% O2. Fig. 6a and b shows the evolution of the
H2 yield and carbon conversion with time.
The hydrogen yield (Fig. 6a) obtained with 4% O2 is kept
constant during 6 h of reaction time while a decrease at the
beginning of the experiment is observed when oxygen is not
added. The H2 yield is very similar for both runs after 2 h of
experiment, indicating almost no hydrogen penalty with Fig. 7 – SEM images of Ni/Al catalyst after 6 h reaction: (a)
oxygen addition. with no oxygen addition and (b) with 4% oxygen addition.
4394 international journal of hydrogen energy 33 (2008) 4387–4396
Fig. 8 – XRD patterns for the Ni/Al catalyst after 6 h reaction:
(a) with no oxygen addition and (b) with 4% oxygen
addition.
On the other hand, the carbon conversion (Fig. 6b) is for the
majority of time slightly higher when 4% O2 is added. This
may be due to the positive effect of oxygen on coke removal.
SEM images (Fig. 7a and b) were taken of Ni/Al catalyst after
6 h reaction in absence and presence of 4% oxygen, respec-
tively. These images showed a major presence of filamentous
Fig. 9 – Literature comparison of acetic acid catalytic steam reforming: (a) acetic acid conversion and (b) H2 yield.
carbon on the surface of the catalyst when no oxygen was
added to the reaction and a clearer surface when oxygen
was added.
In order to know the crystalline phases present in the cata-
lyst after reaction, XRD analyses have been performed. Fig. 8
shows the results of the catalysts after 6 h of reaction. Higher
proportions of NiO and NiAl2O4, the oxidized phases, are
observed when 4% O2 is added, but metallic Ni is detected
with similar peak intensity. This analysis also indicates the
presence of coke in the two samples.
3.4. Literature comparison of acetic acid catalytic
steam reforming
Fig. 9a and b shows acetic acid conversion and H2 yield,
respectively, versus the inverse of space velocity, expressed
as W/mHAc, for catalytic steam reforming experiments carried
out at a reaction temperature close to 650  C (from 600 to
665  C). Some works, such as this, do not calculate acetic
acid conversion. Therefore carbon conversion has been
assimilated to acetic acid conversion.
In Fig. 9b a theoretical thermodynamic equilibrium for
hydrogen yield of acetic acid steam reforming was simulated
at the operational conditions of this work. The analysis of
these figures must be done carefully because authors use
different operating conditions (S/C molar ratio, temperature,
catalyst and fixed or fluidized bed).
In Fig. 9a the acetic acid conversion for the majority of the
studies is between 90 and 100%. This work shows an acetic
acid conversion close to 100%, which is one of the best results
of the literature survey.
In Fig. 9b it is observed that the H2 yield obtained by many
authors is close to equilibrium and among them the results of
this work. The H2 yield of the study carried out by Galdámez et al.
[18] for a W/mHAc ¼ 2.0 g catalyst min/g HAc is similar to the H2 yield
obtained in this work for a W/mHAc ¼ 6.2 g catalyst min/g HAc, both
 international journal of hydrogen energy 33 (2008) 4387–4396
using fluidized bed reactor. The best result obtained in the work of
Galdámez et al. can be explained by the wall effect, because the
reactor is made of stainless steel. The study of Galdámez et al.
also shows lower values of H2 yield that can be explained by the
lower W/mHAc values used. H2 yields obtained by Rioche et al. [15]
and Basagiannis and Verykios [20] must be a consequence of the
lower S/C molar ratio used, although the latter did not reach
complete acetic acid conversion. Takanabe et al. [17], who worked
with a Pt/ZrO2, also obtained an H2 yield close to equilibrium at
similar operation conditions (S/C ¼ 5 and 602  C reaction tempera-
ture) but at higher W/mHAc values.
4. Conclusions
Coke is a serious operational problem that produces the deac-
tivation of catalysts, especially those nickel based catalysts
used in steam reforming. When organic feedstocks such as
bio-oil or its fractions are reformed, there is a greater tendency
for the system to be fouled by coking. Therefore, different
strategies are needed in order to avoid these problems, and
fluidized beds are found to perform better than fixed ones.
The effects of various factors have been studied in fluidized
bed steam reforming with acetic acid as a model compound
at 650  C. First of all, calcination temperatures of 750, 850
and 900  C have been studied. A lower reforming activity
and stability has been observed when using the catalyst
calcined at 900  C, probably due to the increase in spinel phase
that is harder to reduce. The effect of calcium as a promoter of
the catalyst was studied. The incorporation of a Ca/Al ratio of
0.50 under the experimental conditions did not result in an
improvement in reforming activity and stability. Finally, the
influence of oxygen addition to the steam reforming process
indicated that an excess of oxygen (8%) can lead to a lower
reforming activity decreasing the H2 and CO2 yields and
increasing the CO and CH4 yields. On the other hand, 4%
oxygen resulted in almost no penalty in hydrogen yield
production providing a process with a probability of less
coke because the carbon conversion was maintained up to
100%.
Acknowledgments
The authors express their gratitude to the Spanish Ministry of
Education and Science (MEC) (Research Project Ref. No.
CTQ2004-06279) and to the Government of Aragon (Research
Project Ref. No. PIP185/2005) for providing financial support
for the work.
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