Applied Catalysis A: General 381 (2010) 17

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Review

Catalytic features of Rh and Ni supported catalysts in the steam reforming of

glycerol to produce hydrogen
V. Chiodo a, , S. Freni a , A. Galvagno b , N. Mondello a , F. Frusteri a
a
b

CNR-ITAE Nicola Giordano, Via S. Lucia sopra Contesse, 598126 - Messina, Italy
DIIM, Universit degli Studi di Catania, Viale A. Doria, 695125 - Catania, Italy

a r t i c l e

i n f o

Article history:
Received 9 December 2009
Received in revised form 17 March 2010
Accepted 18 March 2010
Available online 25 March 2010
Keywords:
Rh and Ni catalysts
H2 production
Glycerol steam reforming
Coke formation

a b s t r a c t
Glycerol steam reforming on Rh and Ni supported catalyst was investigate in view to produce syn-gas to
feed a high temperature fuel cell system (SOFC-MCFC). Results obtained revealed that glycerol is subjected
to pyrolysis phenomena and at temperature higher than 720 K drastically decomposes before to reach
the catalyst surface. Rh/Al2 O3 catalyst resulted to be more active and stable than Ni supported catalysts
but independently from the catalyst used (Rh or Ni) and temperature investigated, the reaction is affected
by coke formation mainly promoted by the large presence of olens formed by glycerol thermal decomposition. Even if for thermodynamic reasons the hydrogen production should be favored by operating
at high temperature, results obtained demonstrate that it is more convenient to operate at temperature
not higher than 923 K, since higher reaction temperature promotes the formation of encapsulated carbon
which negatively reects on catalyst stability.
2010 Elsevier B.V. All rights reserved.

Contents
1.
2.

3.
4.
5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Catalyst preparation and characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Catalytic measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
The increasing commercial interest on diesel production by
transesterication of vegetable oil aimed several research groups to
investigate innovative routes to improve the economic balance of
the overall process. For this purpose, most emphasis has been also
addressed towards the development of processes that can convert
the glycerol, the main by-product of FAME process, into added value
chemicals like bio-fuels or hydrogen.
The amount of glycerol produced in the bio-fuel production process, which use vegetable oil as renewable source, is about the

Corresponding author. Tel.: +39 090 624219.

E-mail address: vitaliano.chiodo@itae.cnr.it (V. Chiodo).
0926-860X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2010.03.039

1
2
2
2
3
5
7
7

17 wt% of the bio-diesel mass produced. The glycerol separated

from bio-fuel contain about 20 wt% of water.
One promising way to use glycerol as carbon source is the production of hydrogen or syn-gas by steam reforming (SR) process
in order to supply a solid oxide or molten carbonate fuel cells to
produce electricity and heat [1,2].
Theoretical feasibility of the steam reforming process of glycerol has been demonstrated by different authors [3,4] in terms of
hydrogen yield as a function of process temperature, pressure and
steam/carbon ratio.
Steam reforming process of hydrocarbons is, as well known, a
strongly endothermic reaction usually performed on Ni based catalysts that allow to obtain a hydrogen rich gas mixture containing H2 ,
CO2 , CH4 , CO and H2 O. However, the composition of reformed gas
change as a function of operative conditions (temperature, pressure

V. Chiodo et al. / Applied Catalysis A: General 381 (2010) 17

and steam/carbon ratio), while catalyst life is depending upon several deactivation phenomena that usually affect steam reforming
reaction [57].
Ni/based catalysts, typically used for methane SR have been
recently investigated to produce H2 by SR of glycerol. In particular, Ni based catalysts investigated in aqueous phase reforming
(AFR) of glycerol resulted to be affected by signicant deactivation
phenomena [5]. Ni appear more suitable for application on steam
reforming of glycerol if supported on bare alumina [6] or modied with promoters [5,7]. These studies indicate that Ni catalysts
are sufciently active and selective to syn-gas production but coke
formation represents a serious problem to overcame since glycerol
give rise to the formation of several intermediate products that
promote coke formation. Pt/alumina catalysts were also investigated in SR of glycerol [8] but, even if, higher reaction temperature
enhances the overall reforming process, reaction pathways is characterized by several side reactions (like dehydration) that leads to
carbon formation that negatively affects catalyst stability. Carbon
formation has been also observed on La2 O3 supported Ru catalysts
[9].
On the basis of a preliminary experience acquired in the use of
Rh and Ni catalysts to produce syn-gas by ethanol steam reforming
[10,11], in this paper we have focused our attention to evaluate
the behavior of such catalysts in the glycerol steam reforming.
The study was focused to investigate the deactivation phenomena
occurring on such systems with the objective to nd technological solutions to design an active and stable catalyst for glycerol
conversion into syn-gas.
2. Experimental

Table 1

Rh/Al2 O3
Ni/Al2 O3
Ni/MgO
Ni/CeO2

Metal loading (wt%)

MSA (m2 Me/gcai )

BETSA (m2 /g)

ds (nm)

5
30
21
30

8.1
12
6.3
6.2

163
44
45
27.2

2.1
7
8.1
22.8

der; SA (BET): 27 m2 g1 ) as carriers. Before impregnation MgO

was stabilized in steam atmosphere at 973 K for 12 h. Using a
RhCl2 aqueous solution for the preparation of 5% Rh/Al2 O3 and
Ni-acetate for the synthesis of 21% Ni/MgO. An aqueous solution
of Ni(NO3 )2 6H2 O was used to synthesize 30% Ni/CeO2 and 30%
Ni/Al2 O3 catalysts. All samples were dried at 353 K for 24 h and
then air calcined at 673 K for 12 h. Catalysts were pressed at 400 bar,
crushed and sieved and the 4070 mesh fraction was used for the
catalytic tests.
The BET surface area and porosity of carriers have been determined in a conventional volumetric apparatus at 77 K with Carlo
Erba Sorptomatic 1990 series instrument.
The metal particle size distribution of catalyst was evaluated
by TEM analysis, using a Philips CM12 instrument provided with
a high resolution camera which allow acquisition and elaboration
of images. The samples were ultrasonically dispersed in isopropyl
alcohol and deposited on a carbon supported lm.
Carbon deposed during reaction was evaluated using a CHNS
ThermoFlash EA 1112 Series instrument. Catalyst samples were
treated at high temperature in air and the CO2 produced by oxidation with oxygen was determined by a high sensitivity TC detector.
The main chemicalphysical properties of the catalyst prepared
according to the above procedure are reported in Table 1.

2.1. Catalyst preparation and characterization

2.2. Catalytic measurements
Catalyst were prepared by impregnation (incipient wetness)
using -Al2 O3 AKZO-NOBEL 001-3P (SA (BET) 260 m2 g1 ), MgO
Martin Marietta (SA (BET) 120 m2 g1 ) and CeO2 (smoke pow-

The ow-sheet of glycerol steam reforming process is shown

Fig. 1. Catalytic experiments were performed at atmospheric

Fig. 1. Experimental set up used to perform the glycerol steam reforming reaction.

V. Chiodo et al. / Applied Catalysis A: General 381 (2010) 17

Fig. 2. Blank test. Glycerol conversion and product selectivity as a function of reaction time: TR = 1073 K; S/C molar ratio = 3.

pressure in a xed-bed linear quartz micro-reactor (i.d. = 4 mm;

Hbed = 1.02.0 cm). 0.020.06 g of catalyst (grain size: 4070 mesh)
diluted with 200 mg of similar sized inert material (SiC) were used
for the catalytic tests. Before each test run, catalysts were reduced
in situ at T = 1073 K for 1 h under hydrogen ow. Water/glycerol
mixture (steamcarbon molar ratio; S/C = 3) was fed by isocratic HP
1100 pump and vaporized in a N2 ow in a stainless steel reactor
held at 493 K.
Experiments were performed a temperature raging from 723
to 1073 K and gas hourly space velocity (GHSV) raging from
5000 to 30,000 mlC3H8O3 h1 mlcat 1 . The total ow corresponding at the GHSV of 30,000 h1 was 130 ml min1 and the reaction
stream composition was: 23.08 vol% N2 ; 69.23 vol% H2 O; 7.69 vol%
C3 H8 O3 ).
Before analysis, the gas reaction stream was cooled at 275 K and
separated into liquid and gas phases. The gas phase was analyzed on
line by gas-chromatography (HP Agilent 6890) equipped with three
columns (Molecular Sieve 5A, Porapack QS and Hysep Q) system
and conductivity detector (TCD); GC data were acquired and elaborated by HP-IB interfaced computer system (HP Chemistation). The
liquid phase was analyzed by GC-MS Agilent 5975C provided with
capillary column HP Innowax. The following equations were used
to calculate the glycerol conversion, selectivity and H2 productivity
(mol of H2 produced per mol of glycerol converted):
Glycerin conversion to gas =

C atoms in gas products

total C atoms in the feedstock
100

C selectivity =

C atoms in species
100
C atoms produced in gas phase

where species is CO, CO2 , CH4 , C2 H4 , C2 H6 and C3 H6 ,

H2 selectivity =

H2 moles produced
1
100
R
C atoms produced in gas phase

where R is H2 /CO2 ratio (7/3 in the case of glycerol steam reforming

reaction).
3. Results
The steam reforming is the most commonly used method for
producing hydrogen in the chemical industry. In case of oxygenated
organic compounds use, the following stoichiometry of reaction

should be considered:
Cn Hm Ok + (n k)H2 O nCO + [(n +

m
)]H2
2k

Nevertheless, for an appropriated evaluation of catalytic phenomena occurring during SR of such compounds, should take into
account that, at high temperature they could decompose in primary and secondary pyrolysis products before to reach the catalyst
surface.
Glycerol (C3 H8 O3 ) is an oxygenated organic compounds containing three alcoholic groups. On the base of theoretical evaluation
the following reactions should occur in the steam reforming of
glycerol:
C3 H8 O3 + 3H2 O 7H2 + 3CO2
C3 H8 O3 4H2 + 3CO

(Glycerol steam reforming)

(Direct decomposition)

CO + H2 O H2 + CO2
CH4 + H2 O CO + 3H2

(WGS)
(CH4 steam reforming)

However, taking into account that glycerol is not a thermally

stable molecule its could decomposes, then a preliminary test without catalyst has been carried out to ascertain the extent of pyrolysis
phenomena that could contribute to negatively affects the catalyst
resistance and the evolution of steam reforming process.
In Fig. 2 a blank test performed at 1073 K using a reaction stream
containing 7% of glycerol, under steam reforming conditions is
shown in terms of glycerol conversion and products selectivity.
Results indicate that glycerol signicantly decomposes (conversion close to 65 mol%) giving rise to the production of a series of
products like CO (upper 50 mol%), CO2 (1 mol%), olens (ethylene
and propylene about 25 mol%), CH4 (13 mol%) and H2 (10 mol%).
In addition the analysis of the condensed phase of reaction stream
(30 mol%), performed by gas-chromatography GC/MS, revealed the
presence of several unsaturated compounds (not well quantied)
such as acetone, acetaldehyde, ethanol, propanol, acetic acid and
2,3-dyhydroxylpropanal.
Therefore, taking into account that the real composition of reaction stream that reach the catalyst surface is strictly depending
upon the extent of glycerol decomposition, a preliminary test a
TR = 1073 K to compare the performance of different catalysts investigated in this study was carried out feeding the reactor with a

V. Chiodo et al. / Applied Catalysis A: General 381 (2010) 17

Fig. 4. Coke formation rate observed using different metal supported catalysts:
TR = 1073 K; GHSV = 30,000 h1 ; S/C molar ratio = 3.

Fig. 3. H2 yield (mol of hydrogen produced per mol of glycerol converted) vs time
on stream: TR = 1073 K; GHSV = 30,000 h1 ; S/C = 3 mol/mol.

reaction mixture containing 23.08 vol% N2 , 69.23 vol% H2 O and

7.69 vol% C3 H8 O3 . The results obtained are shown in Fig. 3 in terms
of H2 yield (mol of H2 produced/mol of glycerol converted) as a
function of reaction time. It can be seen that a signicant difference
among catalysts exist both in terms of initial activity and deactivation trend. Rh/Al2 O3 catalyst showed the best performance both
in terms of H2 yield and stability while, among nickel supported
catalysts, the Ni/Al2 O3 resulted to be the most active ones. What
it is very important to underline is that all catalysts drastically
deactivate during the rst 2 h of reaction. For Ni catalysts activity
was completely lost after 6 h of reaction, but a residual hydrogen
production remain due to thermal decomposition of glycerol (see
results reported in Fig. 2).
To ascertain if the difference in the Rh and Ni catalysts behavior
could depend upon the extent of coke formation, CHNS elementary
analysis was carried out on spent catalysts. The results obtained (see
Fig. 4) clearly indicated that coke forms on all catalytic systems with
signicant rate but on Rh/Al2 O3 catalyst the coke formation take
place with lower rate (about 2.2 mgC/gcat h) respect to the Ni catalysts. The rate of carbon formation was calculated considering the
amount of coke formed in 20 h of reaction. On differently supported
Ni catalysts, coke formation can be considered to occurs with similar rate (46 mgC/gcat h) independently of carrier employed (Al2 O3 ,
MgO or CeO2 ). The small difference observed can be justied on the
basis of the different initial conversion level.
In order to investigate the inuence of reaction temperature
on hydrogen yield a series of experiments have been performed
using Rh/Al2 O3 catalyst. Results show in Fig. 5 reveal a progressive decreasing of hydrogen production during the rst 5 h of the
reaction at all temperatures investigated. Furthermore, by comparing the results in terms of initial H2 yield as a function of reaction
temperature a not linear trend was observed. This is more evident
from data show in Fig. 6. Hydrogen production increase from 1.8
to 5 mol% as the temperature increases from 723 to 923 K, but for
temperatures higher than 923 K, on the contrary of what foreseen
from thermodynamic equilibrium, a sudden decreasing of hydrogen yield is observable.

CHNS analysis of Rh catalyst used at different reaction temperature (Fig. 7) revealed that coke forms at low rate (1.9 mgC/gcat h) at
723 K, while a comparable coke formation rate was observed at 823
and 1073 K (about 2.3 mgC/gcat h). The highest coke formation rate
was observed at 923 K (4.2 mgC/gcat h). By comparing the results
reported in Figs. 6 and 7 it can be deduced that the trend of coke
formation follow the same trend of H2 productivity.
According to our previously experience [10,11,13] to shed light
on the behavior of catalysts used at different temperatures we have
focused our attention to investigate the metal sintering phenomena
eventually occurring during reaction and the nature of coke formed.
TEM analysis of used catalysts (see images shown in Fig. 8)
highlights a substantial morphological difference between catalysts used at different temperature. In terms of metal sintering it
can be observed that up to 923 K the Rh particles size distribution
does not change signicantly, while at 1073 K the presence of several Rh particles larger than 15 nm are diagnostic of the occurrence
of a drastic sintering. As regard the coke formation, it seems enough
clear that up to 923 K (see Fig. 8AC) the type of coke formed is of
lamentous nature while at higher temperature (1073 K) encapsulating carbon forms prevalently.

Fig. 5. H2 yield (mol of hydrogen produced per mol of glycerol converted) as a

function of time on stream on Rh/Al2 O3 catalyst. GHSV = 30,000 h1 ; S/C = 3 mol/mol.

V. Chiodo et al. / Applied Catalysis A: General 381 (2010) 17

Fig. 6. H2 yield (mol of hydrogen produced per mol of glycerol converted) vs

temperature on Rh/Al2 O3 catalyst. GHSV = 30,000 h1 ; S/C = 3 mol/mol. Dashed line
represent H2 yield at different temperatures according to thermodynamic analysis
[3].

The resistance of Rh towards sintering ad coke formation phenomena was also investigated by an endurance test performed at
923 K and low GHSV (5000 h1 ). As it can be seen from the Fig. 9,
the glycerol conversion remain almost constant up to 8 h of reaction after that it drastically decreases with a progressive trend. A
similar behavior is observable also for the H2 yield.
TEM images of catalyst used in the endurance test (see Fig. 10)
revealed that even at 923 K the catalyst surface appear to be covered

Fig. 7. Coke formation rate on Rh used catalysts: tests performed at

GHSV = 30,000 h1 ; S/C molar ratio = 3 mol/mol.

by amorphous coke (see Fig. 10A) and some particles (see the high
magnication imageFig. 10B) result to be encapsulated by coke.
4. Discussions
Blank test shown in Fig. 2 indicate that at 1073 K, glycerol
is not stable and decomposes giving rise to the formation of

Fig. 8. TEM images of Rh/Al2 O3 catalysts used at (A) 723 K; (B) 823 K; (C) 923 K; (D) 1073 K.

V. Chiodo et al. / Applied Catalysis A: General 381 (2010) 17

Fig. 9. Endurance test performed using Rh/Al2 O3 catalyst: TR = 923 K; GHSV = 5000 h1 ; S/C molar ratio = 3.

several compounds. Ethylene is prevalent as a consequence of

the initial CC bond cleavage which leads to the formation of
CH2 (OH)CH(OH) and CH2 OH radicals that subsequently evolve
towards the formation of C2 H4 ,H2 and CH4 [1422]. Furthermore,
considering that the radical decomposition mechanism foresee the
formation of acetaldehyde (dehydrogenation reaction) the large
presence of CO and CH4 can be associated to its decomposition
(CH3 CHO CH4 + CO). Instead, the low presence of CO2 is an index
of the fact that water gas shift reaction (WGS) does not occur and
the presence of 10% of H2 is imputable to the occurrence of dehydrogenation reactions.
Experiments performed in the presence of catalysts evidenced
that the hydrogen yield increases from 6.8 mol% (blank test) to
40 mol% using Rh/Al2 O3 and to 19 mol% for Ni/Al2 O3 catalysts.
By considering the chemicalphysical characterization data
reported in Table 1, Ni/Al2 O3 catalyst has a MSA higher that Rh
catalyst, therefore, at least at the beginning of reaction, since Ni is
a excellent steam reforming catalyst, a higher or similar catalytic
behavior was expected, instead Rh was found to be more active. This
is because in the steam reforming of glycerol what should primarily
be considered is that the composition of reaction stream is complex
and depends upon the extent of glycerol decomposition. By operating at high temperatures (see Fig. 2) it is demonstrated that glycerol
easily decomposes into CO, CO2 , olens, water hydrogen and oxygenates before to reach the catalytic surface, therefore, the catalytic
consideration should be done take into account the ability of active

metal to activate CO (typical of oxygenated compounds), CC and

C C bonds.
Several papers concerning H2 production from glycerol mainly
by steam reforming process have been recently published
[19,12,15]. Performance of both rhodium and nickel supported
catalysts has been evaluated in terms of activity and hydrogen
productivity, but not clear evidences have been reported to establish the most suitable catalyst system for glycerol steam reforming
[7,12,15]. Even though, short time experiments in its self could
not be representative to denitively establish what catalytic system is more active and stable in the studied reaction, on the basis
of both literature evidences and results here reported, there are
valid reasons to believe that Rh catalysts are more adequate to perform glycerol steam reforming. The reasons of such result are to
be searched in the composition of reaction stream that, depending
on reaction temperature dramatically changes since glycerol easily
decomposes before to reach the catalyst surface.
Olens (C2 H4 , C3 H6 ) and carbon monoxide are the main chemical species reaching the catalyst surface, therefore, it can be
deduced that catalytic performance is straight depending upon the
tendency towards: (i) C C cleavage, (ii) coke formation inhibition
by polymerization of CHx species and/or CO dissociation (Bouduard
reaction) [11,13,23,24].
It is well known that Rh catalysts are active in C C bond
activation and furthermore they are more resistance than Ni catalyst towards coke formation because Rh is a very active metal in

Fig. 10. TEM image of Rh/Al2 O3 catalyst used in the endurance test: TR = 923 K; GHSV = 5000 h1 ; S/C molar ratio = 3.

V. Chiodo et al. / Applied Catalysis A: General 381 (2010) 17

hydrogenation reactions that, in case of removal of unsaturated

compounds from catalyst surface, is a fundamental properties to
depress the coke formation. The results shown in Fig. 4 clearly
demonstrate that on Rh supported catalyst a lower amount of coke
forms respect to Ni/Al2 O3 catalyst.
From results reported in Fig. 6 it can be observe that, on the
contrary of what the thermodynamic foresees, at the highest temperature (1073 K) the catalyst activity is lower than that observed
at 923 K. As a rst hypothesis we have thought that the reason of
such result was due to the metal sintering phenomenon that as
well know normally occurs at high reaction temperature, but TEM
investigation have revealed that particle size distribution of used
catalyst does not change signicantly respect to the fresh reduced
sample. In particular the particle size distribution increases from
12 to 15 nm not sufcient to justify the deactivation observed, then
our attention was addressed to investigate the morphology of coke
formed during reaction in order to try to nd a relationship between
catalyst behavior and reaction temperature.
TEM images shown in Fig. 8 clearly demonstrate that as the reaction temperature increases the coke formation mechanism change,
in particular at temperature of 923 and 973 K is prevalent the formation of lamentous carbon while at 1073 K the carbon formed
is mainly of encapsulating type. This is the key factor that could
explain why at high temperature the catalyst performance worse
notwithstanding the steam reforming process is favored. The formation of encapsulating coke is deleterious for the Rh catalyst that
loses activity quickly and H2 yield result to be lower even when
the steam reforming is carried out at high temperature even if
the reaction is carried out in favorable thermodynamic conditions.
Why at high temperature the formation of encapsulating carbon is
prevalent it was well described in a previous paper [2327]. What
governs the carbon formation mechanism is the elementary carbon rate diffusion through the metal particle: an high diffusion
rate favors the formation of lamentous carbon while a low diffusion rate of carbon favors the formation of encapsulating carbon
species. Naturally, when metal particle is encapsulated by coke
immediately deactivates.
The endurance test result performed at low GHSV (5000 h1 )
and 923 K revealed that Rh catalyst is not so resistant in glycerol
steam reforming and as the coke accumulates on the surface it
deactivates on the time. What is important to underline in such
test is that, even the prevailing amount of coke formed is of lamentous nature (see Fig. 10A) even at such temperature, but with
lower extent respect to the experiment performed at 1073 K, some
Rh particles resulted to be encapsulated by amorphous carbon with
negative consequence on catalyst stability.
5. Conclusions
From the results here reported the following conclusions can be
drown:

- Glycerol is subjected to pyrolysis phenomena and at 1073 K

drastically decomposes giving rising to the formation of CO,
CO2 , olens, water, hydrogen, acetone, acetaldehyde, ethanol,
propanol, acetic acid and 2,3-dyhydroxylpropanal;
- Rh/Al2 O3 catalyst is more active and stable than Ni supported
catalysts;
- The steam reforming of glycerol, independently from the catalyst used (Rh or Ni) and temperature investigated, is affected by
coke formation due to the large presence of olens in the reaction stream, formed by glycerol thermal decomposition, in the
reaction stream;
- Even if for thermodynamic reasons the hydrogen production
should be favored by operating at high temperature results
obtained suggest that it is more convenient to operate at temperature not higher than 923 K;
- High reaction temperature promotes the formation of encapsulating carbon which negatively reects on catalyst stability.
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