Applied Catalysis A: General 251 (2003) 131141

Novel supported Rh, Pt, Ir and Ru mesoporous aluminosilicates as

catalysts for the hydrogenation of naphthalene
Mlanie Jacquin a , Deborah J. Jones a, , Jacques Rozire a , Simone Albertazzi b ,
Angelo Vaccari b , Maurizio Lenarda c , Loretta Storaro c , Renzo Ganzerla c
a

Laboratoire des Agrgats Molculaires et Matriaux Inorganiques, UMR CNRS 5072, Universit Montpellier II,
2 Place Eugne Bataillon, 34095 Montpellier Cedex 5, France
b Dipartimento di Chimica Industriale e dei Materiali, Universit degli Studi di Bologna, INSTM UdR di Bologna,
Viale del Risorgimento 4, 40136 Bologna, Italy
Dipartimento di Chimica, Universit Universit di Venezia, INSTM UdR di Venezia, Via Torino 155/B, 30173 Venezia-Mestre, Italy
Received 17 January 2003; accepted 9 April 2003

Abstract
Rh, Pt, Ir and Ru have been directly incorporated in mesoporous aluminosilicates prepared using direct liquid crystal
templating with a non-ionic surfactant via addition of the corresponding metal complexes to the synthesis gel. In this approach,
the non-ionic surfactant plays the role both of porogen and dispersant for the metal ions throughout the aluminosilicate,
leading to controlled metal particle formation. Chemicalphysical characterisation, simulated coking and regeneration tests,
and catalytic behaviour towards naphthalene hydrogenation and ring opening are described. The catalyst activity in the
hydrogenation of naphthalene has been studied at atmospheric pressure at 200 and 300 C, and at 6 MPa between 220 and
340 C. At atmospheric pressure, all four catalysts give a naphthalene conversion in the range of 9596% at 200 C, while
at 300 C, the Rh and Ru catalysts have the highest selectivity to high molecular weight (HMW) hydrogenolysis and/or
ring-opening products, as shown by the relatively high formation of alkylbenzenes and decadiene. The effect of parameters
such as temperature, contact time and H2 /naphthalene ratio on conversion and selectivity to partially or fully hydrogenated
products, HMW products and low molecular weight gases, was investigated under 6 MPa for the supported Rh catalyst. It
provides a naphthalene conversion up to 9899% and interesting selectivity, with a high proportion of HMW products between
260 and 300 C, and a good thermal stability.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Mesoporous aluminosilicates; Noble metal supported catalysts; Naphthalene hydrogenation/ring opening/hydrogenolysis

1. Introduction
There is an increasing demand for friendly hydrocarbons and clean-burning high performance fuels and, particularly, for a decrease of particulate
Corresponding author. Tel.: +33-4-67-14-33-30;
fax: +33-4-67-14-33-04.
E-mail address: debtoja@univ-montp2.fr (D.J. Jones).

emission in diesel exhaust gases [1]. To satisfy increasingly stringent regulations, the improvement of
petroleum fractions such as middle distillates has become one of the main objectives of the refining industry. These middle distillate fuels have a high content
of multi-ring aromatic compounds which leads to a
low cetane quality, and the conversion of these aromatics into hydrocarbons of higher cetane number is
today a key process in the modern refining industry.

0926-860X/$ see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0926-860X(03)00314-4

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M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

Current processes for dearomatisation use catalysts

combining the acidity of a support and the hydrogenation and hydrogenolysis/ring-opening activity of an
incorporated metal. Hydrogenation/hydrocracking is
most often practised on cyclic molecules over primarily acidic zeolite, alumina or silico-alumina-supported
noble and other Group VIII metal catalysts. Different
processes have used catalysts such as NiMo, CoMo,
NiW, Pt and or Pd on various supports [212]. Key
mechanisms controlling product distributions in hydrogenolysis and hydrocracking reactions have been
reported previously [1315]. The dominance of the
acid function can lead to excessive cracking and thus,
a primary focus is the optimisation of the acid function, and it has been shown recently that significant
enhancements in ring opening selectivity are made by
focusing on the metal function. The metal function
is usually provided by Pt and/or Pd but it has been
shown that Ir, Ru and Rh also have exceptional activity and selectivity for the target reaction of selective
ring opening [1618].
In this paper, we describe the preparation of new
mesoporous catalytic materials containing highly and
homogeneously dispersed particles of Rh0 , Pt0 , Ir0 or
Ru0 after reduction, and investigate their activity for
hydrogenation and hydrogenolysis and/or ring opening of aromatic compounds under various reaction
conditions, using naphthalene as a model substrate
(Fig. 1). The metal particle size of supported metal
catalysts is an important factor affecting the catalytic
behaviour and the support, in particular, the pore

structure, can affect the metal dispersion. We have

investigated a novel preparation method leading to a
mesoporous matrix using direct liquid crystal templating with a non-ionic surfactant and have previously
reported [19] the use of this method to obtain materials with surface acidity of strength lower than that of
zeolites [20]. The pore dimension of the channel system can be tailored by selecting the Si/Al ratio and the
nature of the non-ionic template. This preparation of
the mesoporous silico-aluminate matrix differs from
that used for MCM-41 type materials [2123], in particular by the concentration range of surfactant used
and the ready formation, by controlling the kinetics of
the reaction, of monolithic blocks instead of powders.
Several different methods for metal incorporation
in porous supports are described in the literature. One
approach is the direct addition of metal salts, alkoxides
or complexes to the solgel mixture, which enables
introduction of the metal into the silico-aluminate
body and/or the pores [24,25]. Such an approach has
been used to directly prepare rhodium functionalised
MCM-41 [26,27]. Other methods include impregnation or ion-exchange, the former generally of a
calcined support, but also of surfactant containing
mesophases [28]. Metal nanoparticles have also been
prepared in the micelle pores of block copolymers,
then used as templates for porous silica [29]. We
concentrate here on the direct incorporation of metals
(Rh, Pt, Ir or Ru) into the synthesis gel followed by
thermal treatment to remove surfactant porogen and
reduction under hydrogen.

Fig. 1. Proposed reaction pathway for the vapour-phase hydrogenation of naphthalene, including parallel and consecutive reactions.

M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

2. Experimental
The first step of catalyst preparation is the dispersion of 4.5 g of a non-ionic C11 C15 (EO)9 surfactant (Aldrich) in 4.5 g of a dilute HNO3 solution (a
65% nitric acid solution was obtained from Aldrich).
To this solution are added 13.0 g of tetraethoxysilane (TEOS, Fluka) and 1.17 g of aluminium nitrate (Al(NO3 )3 9H2 O, Merck). Rh(NO3 )3 solution
(0.80 g) (Strem chemicals), is then incorporated for
the rhodium catalyst, and Pt(CH3 COCHCOCH3 )2
(0.16 g), Ir(CH3 COCHCOCH3 )3 (0.25 g) or Ru(CH3
COCHCOCH3 )3 Alfa Aesar (0.21 g) for the Pt, Ir and
Ru containing materials, respectively. The solution
is stirred until the total dissolution of the reagents is
reached. The system is then maintained under vacuum
for 2 h and left in a closed vessel at room temperature
for 3 days after which time a transparent solidified gel
is recovered. The surfactant is then removed by calcination at 560 C for 4 h using a ramp rate of 1 C/min.
The catalysts are denoted 2RhSiAl20, 2PtSiAl20,
2IrSiAl20 and 2RuSiAl20 in the following.
To determine the specific surface area and the
porosity of the materials, adsorptiondesorption of
nitrogen at 77 K was performed using an automated
volumetric Analsorb 9011 instrument. Samples were
outgassed overnight at 200 C under vacuum prior to
these experiments. The surface area was determined
using the BET formalism [30] and the pore diameter
was estimated using the s method. Various methods
were used to estimate the size of the metal particles
and the metal dispersion, including H2 chemisorption,
X-ray powder diffraction (XRD) and transmission
electron microscopy (TEM) on the reduced materials.
XRD data were recorded on an automated Philips
XPert diffractometer with Cu K radiation, in an
interval of 1827 2 which corresponds to the region of the metal (1 1 1) reflection. The breadth of
this line (full width at half height) allowed a first estimation of the average metal particle size by use of
the Scherrer relation [31], considering contributions
from particle stress and instrumental broadening to be
negligible. The validity of this hypothesis is justified
by the closely similar values for the average metal
particle size obtained from XRD and TEM. TEM
observations were made on samples prepared as extractive replicas using a JEOL 1200 EX operating at
100 kV. The accessible metal surface was measured

133

by H2 chemisorption using a Micromeritics instrument (ASAP 2010C). Samples were first flushed in a
flow of helium, and then evacuated before chemisorption with H2 at 300 C. The metal dispersion value so
derived is directly related to the metal particle size by
the relation: D = 1000/d, where D (%) is the metal
dispersion and d the metal particle diameter in .
Simulation of coking and oxidative regeneration of
the 2RhSiAl20 catalyst enables an assessment of the
stability under these conditions. A saturated solution
was prepared with 0.1 g of anthraquinone in 20 ml
of THF, and the reduced catalyst impregnated with a
quantity of this solution. The catalyst was left to dry for
12 h in a closed vessel at 30 C, then dried at 65 C for
1 h. Three impregnation/drying cycles were employed
to assure a high level of adsorption of carbonaceous
material. To simulate coking, the carbon-containing
catalyst was then heated under nitrogen at 100 C for
2 h and at 400 C for 2 h (ramp rate 2 C/min) and
then regenerated in air at 120 C for 2 h and at 560 C
for 2 h (ramp rate 2 C/min). The coked/regenerated
catalyst was re-analysed by H2 chemisorption, so allowing any changes in the metal particle size and the
textural properties of the material to be followed. In
addition, the surface area and pore characteristics were
re-determined by N2 adsorption.
The activity of the four catalysts in the hydrogenation of naphthalene was first investigated in a
fixed bed lab-scale microreactor, operating at atmospheric pressure, at 200 C and 300 C. The bed,
containing 200 mg of the catalyst first reduced under
H2 /N2 , is in contact with a 10 ml naphthalene/He
(0.1 g/10 ml) continuous flow. The reaction products
were analysed on-line by a Hewlett-Packard 5890 gas
chromatograph.
Following this evaluation at atmospheric pressure,
the catalytic activity was fully investigated at 6.0 MPa
using 2RhSiAl20. Here, the set-up made use of a stainless steel tubular reactor (i.d. 8 mm; length 54 cm),
heated by an electric. The catalyst was crushed and
sieved to 1420 mesh and 6 cm3 were placed in the
isothermal zone of the reactor. Before the tests, the
catalyst was activated in a 200 ml/min H2 flow, using a programmed increase of the temperature from
room temperature up to 350 C. The catalyst temperature was determined during the tests using a 0.5 mm
J-thermocouple sliding in a stainless steel capillary
tube inside the catalytic bed. A 10 wt.% naphthalene

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M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

solution in n-heptane was fed by a Jasco pump, in a

gas flow of H2 /N2 . After an initial 1.5 h period under reaction conditions to allow steady state activity
to be reached, each catalytic test was performed for
5 h, and the products collected in a trap cooled at
10 C. Reaction conditions including temperature,
contact time and H2 /organic feed ratio were varied.
The reaction products were first identified using an
HP GCD 1800A system, equipped with a column of
5 wt.% methylphenylsilicone (30 m 0.25 mm, film
width 0.25 m), comparing the experimental GCMS
patterns with those present in the instrument library.
Quantitative analysis was performed by a Carlo Erba
6000 GC, equipped with FID and a PS 264 column
(5 wt.% methylphenylsilicone, 25 m 0.53 mm, film
width 1.5 m), comparing the GC patterns with those
obtained for pure reference compounds. For the main
reagent/products (decalins, tetralin and naphthalene),
GC calibration factors were obtained using pure reference compounds, while for the other molecules
(mainly high molecular weight (HMW) products)
calculated average GC factors were adopted.

3. Results and discussion

3.1. Catalyst characterisation
Chemical analysis for silicon, aluminium and metal
contents (CNRS elemental analysis service at Vernaison, France) indicated the Si/Al ratios and the metal
content to be close to those used in the synthesis.

Fig. 2. Nitrogen adsorption isotherm at 77 K of 2RhSiAl20 before

catalytic tests (the isotherm is fully reversible, and the desorption
isotherm is not given).

Precipitation is avoided in the direct liquid crystal

templating approach, and all components of the catalysts are recovered in the product. The BET surface
area and the pore diameter were determined for the
four fresh catalysts, and were re-determined after simulated coking/regeneration and catalytic test at 6 MPa
for 2RhSiAl20. The fresh catalysts all showed fully
reversible adsorption isotherms (example provided
by 2RhSiAl20 in Fig. 2) with a quasi-linear region
from 0.1 to 0.3 indicative of super-microporosity. The
derived surface areas are between 641 and 760 m2 /g,
and the mean pore diameter of 2.2 nm, is around the
lower limit of mesoporosity (Table 1). These values

Table 1
Textural properties, dispersion and metal particle size of 2RhSiAl20, 2PtSiAl20, 2IrSiAl20 and 2RuSiAl20
2RhSiAl20

Surface area (m2 /g)

Pore diameter (nm)
Metal dispersion (%)
Metal surface area (m2 /g metal)
Particle diameter (nm)

From metal dispersion.

From XRD.
c From TEM.
b

2PtSiAl20

2IrSiAl20

2RuSiAl20

Fresh

Regenerated

Used

Fresh

Fresh

Fresh

660
2.2
18
78

670
2.2
15
66

610
2.1
1
4.4

760
2.2
34.4
85

653
2.2
50
121

641
2.2
29
120

5.5a
4.0b
4.0c

6.7a
5.0b

4.0b

2.9a
3.0b
3.0c

2.2a
2.8b
2.0c

3.6a
3.0c

M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

can be compared to those for silico-aluminates described in previous work [19] pertaining to materials free from additional metal components. The
SiO2 /Al2 O3 (Si/Al = 20) system had a specific surface area of 999 m2 /g and a pore diameter of 2.6 nm.
The incorporation of a metal in the structure therefore leads to a slight decrease in the surface area
but the pore diameter and the mesoporous character
are maintained. These textural properties can also be
compared to those for other reported Rh-, Pt-, Ir- and
Ru-containing catalysts prepared by solgel methods.
RhSiO2 and RhSiO2 /Al2 O3 systems have surface
areas of 550700 and 375 m2 /g, respectively [32,33],
while those for Ru/Al2 O3 , Ru/SiO2 , Ir/Al2 O3 and
Pt/Al2 O3 systems vary from 100 to 304 m2 /g [3437].
Importantly, in the context of catalytic application,
the specific surface area and pore diameter of the
2RhSiAl20 catalyst are unaffected by the simulated
coking and regeneration process, and the textural properties are essentially identical to those of the fresh material. Finally, following catalytic testing at 6 MPa and
up to 340 C, the surface area was re-determined and
found to have decreased by ca. 7%, while the nature
of the porosity remains unchanged (Table 1).
The extractive replica TEM of Rh particles from
2RhSiAl20 is shown in Fig. 3, and the X-ray diffraction pattern over the region of diffraction from (1 1 1)
planes of rhodium metal in Fig. 4. The 2% Rh-, Pt-,
Ir- and Ru-containing materials are characterised by
metal dispersions of 18, 34, 50 and 29% and metal
surface areas (per gram of metal) of 78, 85, 121 and
120 m2 /g, respectively, Table 1. The metal particle size
calculated from these dispersion values, is 5.5 nm for
Rh, 2.9 nm for Pt, 2.2 nm for Ir and 3.6 nm for Ru.
Measurement of the diameter of >500 particles in the
TEM micrograph of RhSiAl20 provided an indication of the distribution of particle size. The method
employed is that described by Gallezot and Leclercq
[38] and leads to the histograms shown in Fig. 5.
The first of these provides
in diameter

a distribution


with a mean diameter of ni di / ni , while the second
is a quadratic
distribution with a mean diameter


of
ni di3 / ni di2 (ni : number of particles and di :
mean diameter, in each successive interval). The second distribution is probably the most pertinent since
the catalyst activity is directly linked to the metal surface area. The distribution is narrow, with 46% of the
rhodium metal particles of size between 3 and 4 nm

135

Fig. 3. Transmission electron micrograph (extractive replica) of

the Rh, Pt, Ir and Ru particles in 2RhSiAl20 (a), 2PtSiAl20 (b),
2IrSiAl20 (c) and 2RuSiAl20 (d) (reduced form).

(76% between 3 and 5 nm), and a mean diameter of

3.6 nm. Eighty-one percent of the metal surface area
results from particles between 3 and 5 nm in diameter.
The mean surface diameter, 4.1 nm, is in good agreement with that estimated from XRD (4 nm) while both

Fig. 4. XRD pattern in the region of the Rh(1 1 1) and (4 0 0)

reflections of 2RhSiAl20 after reduction with H2 .

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M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

of around 20% in metal particle size. This probably corresponds to metal sintering caused by particle
ripening and aggregation, and could contribute to a
loss of active surface area of the catalyst, which could
in turn exert an influence on the catalytic reactivity
[49]. Experimental observations demonstrate that the
stability of metals and hence their resistance to sintering, increases with increase in melting point of the
metal. It has been shown, for example, that stability
increases in the sequence nickel, palladium, platinum
and rhodium, which concurs with the sequence of
increasing melting point [50]. In the present case,
the sintering is linked to the different thermal treatments used during catalyst regeneration. However, the
results obtained are promising since without any optimisation, the textural properties remain unchanged
and the dispersion value shows only a slight decrease.
After catalytic reaction with naphthalene, the metal
particle size estimated from width of the X-ray diffraction line is unchanged (Table 1). However, hydrogen
chemisorption measurements provided an unrealistically low dispersion, which certainly is a result of the
deposition of heavy products on the catalyst surface
that prevent access to the metal by H2 .
Fig. 5. Number and area distribution of rhodium particles in
2RhSiAl20.

are slightly lower than that estimated from chemisorption of hydrogen (5.5 nm). However, the values concord sufficiently well to allow us to conclude that all
the metal is accessible to hydrogen, and that no side
phases are formed. The metal particle sizes of the
four catalysts may be compared to others previously
reported systems containing Rh, Pt, Ir and Ru such
as Rh/SiO2 , Rh/Al2 O3 or Rh/SiO2 /Al2 O3 , containing
from 0.5 to 5 wt.% of Rh: 1.35 nm [32,33,3944],
such as zeolites containing Pt incorporated by impregnation: 7.311.3 nm [45], or Ir/-Al2 O3 and Ir/SiO2 :
1.63 nm [46] or Ru/Al2 O3 : 2.1 and 3 nm [47,48]. In
summary, in these various rhodium metal-containing
systems, the metal particle size depends on the metal
content, the support, the surfactant and the method of
incorporation.
After impregnation with anthracene, reduction
and oxidative regeneration, the dispersion results on
2RhSiAl20 show a decrease, linked to an increase

3.2. Hydrogenation/ring opening of naphthalene

3.2.1. Catalytic activity at atmospheric pressure
Preliminary tests to assess hydrogenation and hydrogenolysis and/or ring-opening activity of the materials prepared were carried out at atmospheric
pressure. The reaction is thermodynamically limited at this pressure, and the conversion decreases
rapidly as the temperature is increased. At 200 C,
none of the catalysts prepared show appreciable ringopening activity, while at 300 C the hydrogenation
conversions are low (9014.1%) because of thermodynamic limitations leading to low yields to ringopening products (0.83.0%). The conversion and
selectivity to decalin (decahydronaphthalene), tetralin
(1,2,3,4-tetrahydronaphthalene), hydrogenolysis/ringopening products (e.g. cyclohexane, toluene, xylene,
alkylbenzenes, decadiene) and light (C1 C4 ) products are shown in Table 2. At 200 C, the naphthalene conversion values of all four materials is in the
range 95100% while at 300 C, the conversion by
2RhSiAl20 and 2PtSiAl20 (13.514.0%) is significantly higher than that of the Ir and Ru functionalised

M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

137

Table 2
Conversion and product distribution at 200 and 300 C and atmospheric pressure given by mesoporous silico-aluminates containing dispersed
Rh, Pt, Ir and Ru
Catalyst

Yield (%)a

Conversion Selectivity (%)

(%)
Decalin
Tetralin

Cyclohexane

C1 C4

Toluene,
o-xylene

Alkyl- Decadiene
benzenes

At 200 C
2RhSiAl20
2PtSiAl20
2IrSiAl20
2RuSiAl20

96.3
100
95.2
95.0

2.3
97.4
16.5
2.8

97.7
0.7
83.3
97.0

0.2
0.2

0.2
0.2

At 300 C
2RhSiAl20
2PtSiAl20
2IrSiAl20
2RuSiAl20

14.1
13.5
9.6
9.0

2.1

75.3
94.0
83.4
77.9

1.4

1.0
1.1

3.5

1.0
1.1

5.6

2.1
5.5

7.1
3.0
7.3
8.8

7.1
3.0
3.1
5.6

3.0
0.8
1.3
1.9

HMW hydrogenolysis
and/or ring-opening
products

Sum of cyclohexane, toluene, o-xylene, alkylbenzenes and decadiene.

catalysts (910%). Further, at 200 C the presence of

Pt, Rh and Ru gives pronounced selectivity to decalin
(Pt: 97.4%) or tetralin (Rh and Ru: 9798%) while
the iridium-containing sample provides a mixture of
decalin (17%) and tetralin (83%). Tetralin is also
the main product of the naphthalene hydrogenation
over Pd-containing catalysts at 100 C [51], and this
observation has been interpreted in terms of interaction of Pd with naphthalene similar to the 2 -olefin
co-ordination in a mononuclear transition metal complex. Indeed, it has been suggested that naphthalene
may adsorb on different precious metals (Ru, Rh,
Pt, Pd) as an olefin or an aromatic [52] and this will
influence the rates of product formation. By analogy
with the above, it may be that in the present catalysts,
the adsorption interaction of Rh and Ru with the
substrate is more olefinic (giving tetralin), and that
of the Pt catalyst more an aromatic type interaction
(leading to decalin).

Most interesting is the change in product distribution observed at 300 C, with a significant degree of
formation of molecules resulting from ring-opening
reaction, representing ca. 20% of the reaction products given by supported Rh and Ru catalysts, 13% of
those given by the Ir functionalised sample and 6%
given by material containing Pt. The high selectivity
in high molecular weight products (mainly decadiene) of the 2RhSiAl20 to decadiene is of particular
interest in the context of increase of cetane number
of diesel by hydrodearomatisation, and the reactivity towards hydrogenation and hydrogenolysis/ring
opening of naphthalene by this catalyst was thus investigated more completely at high pressure, using
various reaction conditions.
3.2.2. Catalytic activity at 6 MPa
At 6 MPa and at temperatures between 260 and
340 C (Table 3), a naphthalene conversion of 9899%

Table 3
Catalytic activity as a function of temperature of 2RhSiAl20 towards hydrogenation and ring opening of naphthalene at 6 MPa
T ( C)

Conversion
(%)

Tetralin
(yield %)

Decalin trans
(yield %)

Decalin cis
(yield %)

HMW products
(yield %)

C balance
( %)

220
260
300
340
260

95.6
98.0
98.7
95.1
98.3

84.2
79.2
29.3
23.2
78.6

2.1
6.3
28.1
9.1
6.0

5.9
8.5
6.5
1.5
8.5

1.6
3.6
30.8
33.7
3.6

1.8
0.4
4.0
27.6
1.6

Contact time: 6.8 s; H2 /naphthalene: 21 mol/mol.

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M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

was observed. Formation of tetralin is predominant

at low temperatures. This preference was already
identified at atmospheric pressure and is clearly conserved at high pressure. Using Pt- and Pd-supported
zeolites, the selectivity to cis or trans decalin from
naphthalene at 200 C, 10 MPa has been reported to
depend on the nature of the metal, the zeolite and its
surface acidity [53]. An increase in trans isomer was
observed over Pd and at higher Si/Al ratios, i.e. with
an increase in weak acid sites. In the present case, decalin is never the dominant product over either tetralin
or HMW products, but a change in selectivity of the
minor amounts formed from cis to trans decalin is
observed as the reaction temperature increases above
260 C, in agreement with the higher thermal stability
of the latter [53]. Corma has related the selectivity
to the naphthalene conversion, with hydrogenation
of the second ring occurring to a significant extent
only at very high conversions using Al-MCM-41 supported Pt. Under 5 MPa and at 225275 C, <0.1%
of ring opening and isomerisation products were
observed [54]. In contrast, in the present work, a
high proportion of hydrogenolysis/ring-opening products is also observed. At 300 C, the yield in such
high molecular weight products reaches 31%, while
the carbon balance indicates a loss by formation
of light gases of only 4%. Moreover, very similar
activity is observed on repeating the test at 260 C
after that at 360 C, indicating good stability with
temperature.
Complete hydrogenation of naphthalene to decalin
requires, in principle, a ratio of 5 moles of hydrogen per mole of naphthalene. Investigation was made
here of the influence at two temperatures (260 and
300 C) of the H2 /naphthalene ratio on the conversion and selectivity (flow was maintained constant
by completing with N2 ). The results are represented
graphically in Fig. 6. The detailed effects of the
change in ratio are compounded with the influence of
the different temperatures, but common trends may
be identified. Firstly, the conversion value falls as the
ratio H2 /naphthalene is lowered from 21 to 5 mol/mol.
This effect becomes particularly significant below
ca. 10 mol/mol, and it is slightly compensated by increasing the temperature to 300 C. Such lowering of
the H2 /naphthalene ratio also modifies the selectivity.
Fig. 6 shows that below a value of 21 mol H2 /mol
naphthalene, the yield of HMW hydrogenolysis and/or

Fig. 6. Influence of the H2 /naphthalene molar ratio on conversion and product selectivity at 260 C (a) and 300 C (b), using
2RhSiAl20. () Conversion; (+) carbon balance; () tetralin; ()
decalin trans; ( ) decalin cis; () HMW.

ring-opening products drops suddenly, while that of

tetralin increases. This effect is all the more notable
at 300 C, where the yield of high molecular products decreases from 30.8 to 5.4% on reducing the
H2 /naphthalene ratio from 21 to 15 mol/mol. Since
the carbon balance also generally worsens under these
conditions, it may be concluded that it is essential
to operate with a large excess of hydrogen over the
stoichiometric quantity in order to favour formation
of high molecular weight products, and avoid partial

M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

hydrogenation, and loss of yield by formation of low

molecular weight products (light gases). In the reaction pathway of Fig. 1, high molecular weight compounds are formed mainly by consecutive reactions
of hydrogenolysis and/or ring opening on decalin (cis
and trans). Such reaction is more strongly favoured
by a higher excess of hydrogen, than is hydrogenation, compatible with the experimentally observed
high H2 excess requirement, and the decrease in the
yield in HMW products observed at the first decrease
of the H2 /naphthalene molar ratio.
In a further attempt to identify the most appropriate
operating conditions for catalytic hydrogenation/ring
opening of naphthalene with this catalyst, the contact time was varied between 3.4 and 22.5 s, and the
conversion and selectivity at 260 and 300 C were
monitored (Fig. 7). TA maximum in the yield of high
molecular weight products and cis and trans decalin,
and a minimum in the carbon balance are observed
with a contact time of 6.8 s (operating temperature
300 C). At longer contact times, the yield of LMW
light gases is excessive (>50%), while at lower contact times the reaction does not proceed beyond the
formation of the partially hydrogenated tetralin. These
data clearly indicate that a contact time of 6.8 s is the
most favourable in terms of overall product yield, and
selectivity to high molecular weight compounds, and
are further compatible with the hypothesis that the
latter are formed via isomerisation/hydrogenolysis of
decalin.
The efficiency of Rh-supported catalysts towards
hydrogenation and hydrogenolysis/ring opening of
naphthalene has also been demonstrated by others.
For example, in the selective ring opening of n-pentylcyclopentane (PCP) with 0.5 wt.% Rh-Al2 O3 , there is
68.3% PCP conversion with a full ring disappearance
and a selectivity of 87% in ring-opened paraffins [20].
The catalytic activity of Rh-supported on -Al2 O3
at 300 C and 63 MPa towards benzene, naphthalene
and biphenyl hydrogenation has also been examined. The specific reaction rate constant shows that
biphenyl is the most reactive over Rh metal, followed
by benzene and naphthalene, with pseudo first-order
rate constants of, respectively, 11.6, 2.2 and 0.42
106 (ml/(min g mol) Ms ) [43]. The activity of
rhodium-supported catalysts in toluene hydrogenation
in the presence also of a sulphur-containing poison at
100 C was studied for two different supports (SiO2

139

Fig. 7. Influence of the contact time on conversion and product

selectivity at 260 C (a) and 300 C (b), using 2RhSiAl20. ()
Conversion; (+) carbon balance; () tetralin; () decalin trans;
( ) decalin cis; () HMW.

and Al2 O3 ) and two different precursors (RhCl3 and

Rh(acac)3 ) with greater sulphur tolerance on the two
supports impregnated with the latter [44].

4. Conclusion
Highly dispersed metal particles embedded within
a supermicroporous/mesoporous silicoaluminate support may be prepared by an approach exploiting

140

M. Jacquin et al. / Applied Catalysis A: General 251 (2003) 131141

the pore forming and metal dispersant properties

of non-ionic surfactants. In the direct liquid crystal
templating route to porous materials, precipitation is
avoided through control of hydrolysis conditions and
kinetics, and since all inorganic components added to
the synthesis gel are recovered, none of the precious
metal is lost to a solution. Metal particles increase
in size in the order platinum and iridium (23 nm),
ruthenium (34 nm) and rhodium (45 nm) and provide a metal surface area of up to ca. 120 m2 /g metal.
Of the four catalysts, it has been shown by reaction
with naphthalene at 300 C and 1 atm that rhodium,
ruthenium and iridium show higher selectivity towards hydrogenolysis and/or ring-opening products
than the platinum-containing catalyst. This observation agrees with recent reports on the activity of
alumina and zeolites impregnated with metals such as
rhodium, iridium, platinum, palladium and ruthenium
[1618]. Further, it should be related to the nature of
the metal and not to the SiAl ratio, identical in each
case, nor to the metal particle size, which is generally
larger for ruthenium and rhodium than for platinum.
Such hydrogenolysis/ring-opening activity must be
compounded with an effective amount of controlled
acidity to give catalysts of optimally high activity
and with limited loss of yield through non-selective
cracking to light products. Under the less thermodynamically limited conditions of operation at 6 MPa,
the rhodium-containing catalyst at 300 C leads to
significant amounts of high-molecular weight and
fully hydrogenated (cis, trans decalin) products from
naphthalene, with a favourable carbon balance, in
particular, under conditions of a high excess of hydrogen and adequate contact time. Moving towards
the stoichiometric value of the hydrogen/naphthalene
ratio, the conversion undergoes a sudden drop, while
conversion is relatively insensitive to the contact
time. Conversion is also unchanged in the presence
of dibenzothiophene (remaining at 9899% at up
to 3000 ppm of DBT) although the hydrogenation
and hydrogenolysis activities decrease resulting in a
poorer carbon balance.

Acknowledgements
Financial support under Brite-EuRam Project
BRPR-CT97-0560 is gratefully acknowledged.

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