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Fuel Processing Technology 91 (2010) 16551661

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Fuel Processing Technology


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Enhancement of PdPt/Al2O3 catalyst performance in naphthalene hydrogenation by


mixing different molecular sieves in the support
Mingxian Du, Zhangfeng Qin, Hui Ge, Xuekuan Li , Zhanjun L, Jianguo Wang
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan, Shanxi 030001, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The hydrogenation of naphthalene in hexane was carried out over the catalyst PdPt supported on alumina
Received 25 March 2010 mixed with different molecular sieves including ZSM-5, Beta, USY and SAPO-11. The catalyst was
Received in revised form 24 June 2010 characterized by N2 sorption, NH3TPD, TPR, and H2O2 titration. The results indicated that the catalyst
Accepted 2 July 2010
performance for naphthalene hydrogenation is related to its acid property, pore structure, PdPt dispersion,
and metal-support interaction, which may be well regulated by mixing proper molecular sieves in the
Keywords:
alumina support. The catalyst PdPt supported on a two-component support of Al2O3SAPO-11 is provided
Naphthalene
Hydrogenation
with proper acidity, large pores and moderate metal dispersion; it exhibits excellent performance in the
PdPt catalyst saturated hydrogenation of naphthalene to decalin (over it a complete conversion of naphthalene is
Mixed support observed and the selectivity to decalin exceeds 90% at 260300 C).
Molecular sieves 2010 Elsevier B.V. All rights reserved.

1. Introduction on the acidity and SiO2/Al2O3 ratio of the zeolites [12]. The catalytic
performance was related to the zeolite topology and acidity; proper
It is generally desirable to reduce the content of aromatics along pore structure and acidity favored the dispersion of the active metal
with sulfur compounds in the diesel fuel to enhance its quality. High phases [13]. For the hydrogenation of aromatics in diesel fuels, Pt/
content of aromatics in the diesel fuel may result in poor burning MCM-41 with mesoporous structure exhibited high activity and sulfur
quality and smog pollution; reducing the aromatic content can tolerance, which may be attributed to the high metal dispersion and
increase the cetane number signicantly and then improve the proper interaction of the small Pt clusters with the Brnsted acid sites
combustion characteristics [1]. This may become necessary in the near of mild acidity present in AlMCM-41 [14]. Using tetralin and decalin
future to meet the increasingly stringent regulations on the transport as probe molecules and a set of zeolites with medium-sized (ZSM-5,
fuel quality. MCM-22, ITQ-2), large (USY, Beta), and ultra-large (UTD-1) pores, as
Aromatics can be saturated through the catalytic hydrogenation. well as a mesoporous MCM-41 as catalyst supports, Corma et al. [16]
The deep hydrogenation of aromatics is favored thermodynamically at further proved that for the hydrotreating of the light cycle oil fraction,
low temperature due to its exothermic characteristic. Noble metals the pore size and topology of zeolites have a strong inuence on the
with high activity are the candidate catalysts for the hydrogenation of diffusion, and consequently, on the activity and selectivity of the
aromatics at low temperature to attain high equilibrium conversion reactions like ring opening, dealkylation, transalkylation, hydride
and to avoid further cracking of the diesel fuel components [28]. As transfer and coke formation. For the hydrogenation of aromatics over
such a process generally demands a catalyst with certain sulfur the supported PdPt catalysts, although the activity was enhanced by
tolerance, high product diffusivity and selectivity for aromatics the acid sites of the zeolite via the hydrogen spill-over effect, coke
hydrogenation, molecular sieves with high surface area as well as formation and excessive cracking of products were promoted
proper pore size and acidity are potential catalyst supports [917]. For simultaneously on the acid sites [17]. On the other hand, alumina
example, the hydrogenation of methylnaphthalene over Pt/USY was with high strength, high surface area and proper acidity are
inuenced signicantly by the zeolite acidity, whereas the acidic extensively used as the support for the hydrogenation catalysts. It
properties of the zeolite were modied by regulating both the was then supposed that the performance of the PdPt catalyst for the
framework and extra-framework compositions [11]. For the hydro- deep hydrogenation of aromatics can be enhanced by regulating its
genation of tetralin over PdPt/HY and PdPt/USY, the hydrogenation metal dispersion, pore structure and acidic properties through mixing
activity, selectivity, and the sulfur tolerance were strongly dependent proper molecular sieves in the alumina support.
Therefore, in this work, the hydrogenation of naphthalene in
hexane was carried out over the catalyst PtPd supported on the
Corresponding authors. Tel.: + 86 351 4046092; fax: + 86 351 4041153. mixed support of Al2O3 and the molecular sieves (ZSM-5, Beta, USY
E-mail addresses: lxk@sxicc.ac.cn (X. Li), iccjgw@sxicc.ac.cn (J. Wang). and SAPO-11). The effects of support composition, pore structure, acid

0378-3820/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2010.07.001
1656 M. Du et al. / Fuel Processing Technology 91 (2010) 16551661

property as well as the reaction conditions on the hydrogenation of by absorbing the desorbed NH3 into a boric acid solution that was later
naphthalene were then investigated. titrated with sulfuric acid.
TPR and H2O2 titration were also performed on the adsorption
apparatus TP 5000-II. About 200 mg of the catalyst sample (calcined)
2. Experimental
was loaded for each run. The measurement was made according to the
following procedures: (1) The catalyst sample was rstly calcined on-
2.1. Catalyst preparation
line for 60 min at 450 C in air ow (30 ml/min), followed by purging
it with N2 stream (30 ml/min) at 450 C for 30 min; after that, it was
To prepare the mixed support, pseudo-boehmite (Shandong
cooled down to 30 C in the N2 stream. (2) A mixture of 6 vol.% H2 in
Alumina Corporation, China) and the molecular sieves (ZSM-5, Beta,
N2 (30 ml/min) was then switched into the reactor to start the TPR
USY or SAPO-11, from the Catalyst Plant of Fushun Third Renery,
measurement; the sample stayed in the H2N2 mixture at 30 C for
China) were grinded and sieved to powders ner than 200 mesh. They
30 min, heated from 30 C to 450 C at 10 C/min and kept at 450 C
were blended at a given proportion with the addition of a certain
for 60 min. After that, the sample was purged with the N2 stream at
amount of dilute nitric acid (1.0 ml of 2 wt.% HNO3 aqueous solution
450 C for 30 min and then cooled down to 70 C. (3) A mixture of
for per gram dry powder mixture). The pseudo-boehmite was
10 vol.% O2 in N2 (30 ml/min) was switched into the reactor at 70 C
partially dissolved by the dilute nitric acid, which may enhance the
for 30 min to turn the noble metals from the reduced state into the
glutinosity, adherence and distribution of particles of different
oxidized form. The physical adsorbed O2 was removed by purging it
materials. The mixture was stirred intensively for 1 h and then the
with the N2 stream at 70 C for another 30 min. (4) H2 was introduced
doughy material obtained was extruded into trifolium bars with a
into the reactor by impulse of pure H2 with N2 as carrier gas through a
diameter of about 2 mm. The trifolium support was further dried and
calibrated sample tube. This injection of pulse H2 was repeated until
calcined at 550 C for 4 h and then crushed and sieved to 2040 mesh.
the signal of H2 detected by TCD leveled off. The amount of chemically
The supported PdPt catalysts were obtained through the wet co-
adsorbed H2 was then determined by the H2 consumption during the
impregnation with aqueous H2PtCl6 and PdCl2 solution. The impreg-
H2O2 titration.
nation lasted for 24 h; after that, the catalyst sample was dried at
110 C for 12 h and calcined at 450 C for 4 h in air. In this way, the
2.3. Catalytic activity measurements
catalysts PtPd supported on Al2O3 and the mixed supports of Al2O3
and molecular sieves such as ZSM-5, Beta, USY and SAPO-11 were
A solution of naphthalene (8.5 wt.%) in n-hexane was used as the
prepared; the composition of support and loading of Pd and Pt of the
feedstock. The catalytic test was carried out in a stainless steel tubular
catalyst prepared are listed in Table 1. For the catalysts when the
ow microreactor with an internal diameter of 8.0 mm. About 6 cm3
loadings of Pt and Pd are 0.3 wt.% and 1.0 wt.%, respectively, the
of catalyst sample (2040 mesh) was used per run; the catalyst bed
atomic ratio of Pd/Pt is about 6.1.
was in the constant temperature zone of the microreactor and
embedded between glass wool plugs and quartz beads. A thermo-
2.2. Catalyst characterization couple was immersed in the catalyst bed to measure the reaction
temperature and a back pressure regulator was used to regulate the
The surface area and pore parameters of the catalysts (calcined reaction pressure. Prior to the hydrogenation reaction, the catalyst
samples) were determined by nitrogen sorption at 77.4 K with a was rst reduced with hydrogen at 400 C and 4.0 MPa for 4 h, and
Surface Area and Porosimetry Analyzer (ASAP2000, Micromeritics then the reactor was cooled down to the reaction temperature. The
Instrument Co., USA). The catalyst samples were degassed at 200 C feedstock was then pumped into the reactor. The mole ratio of H2/oil
and 5 Pa for 45 h prior to the measurement. (naphthalene + hexane) in the feed was 50 and the liquid hourly
NH3TPD measurement was conducted on a multiple adsorption space velocity (LHSV) was 2.0 h 1. The reaction was conducted under
apparatus TP 5000-II (Tianjin Xianquan Corporation of Scientic 4.0 MPa and 220340 C. The reaction temperature was elevated step-
Instruments, China). The measurement was performed in a quartz wisely with an interval of 20 C and held for 24 h at each stage. At each
micro reactor and about 100 mg of the calcined catalyst sample (40 temperature stage, the reaction was rstly stabilized for 12 h, and
60 mesh) was loaded for each run. The sample was rst pretreated in then the oil sample was collected in the next 12 h; after that, the
an argon ow (30 ml/min) at 550 C for 1 h and cooled down to temperature was increased by 20 C in 0.5 h under hydrogen to enter
100 C. The catalyst sample was then saturated with NH3 by pulse the next stage, during this period the reaction feed is uninterrupted.
injection of pure NH3, followed by purging it with the argon ow at The liquid samples were collected in a trap with ice-water bath
120 C for 1 h to remove the physically adsorbed NH3. After that, the and analyzed with an FID gas chromatograph (Shimadzu GC-9A)
sample was heated in the argon ow from 120 C to 550 C at a ramp equipped with an FFAP column (0.3 mm 30 m) at 180 C and argon
of 10 C/min; the signal of NH3 desorption was monitored by a as carrier gas. The conversion of naphthalene and the selectivities to
thermal conductivity detector (TCD) at the outlet. The peak area of tetralin, decalin and other products for naphthalene hydrogenation
NH3 desorption was numerically integrated by using the operating under steady-state operation are then determined on the basis of the
software incorporated in the TP 5000-II adsorption apparatus; it was naphthalene content in the feed.
further calibrated to the amount of NH3 chemisorption (in mmol/g)
3. Results and discussion
Table 1
Composition of the PdPt catalysts supported on the mixed supports of Al2O3 and 3.1. Pore structure
various molecular sieves.
Naphthalene is converted to tetralin and decalin through hydro-
Catalyst Zeolite Si/Al Zeolite Al2O3 Pt loading Pd loading
mole ratio content content (wt.%) (wt.%) genation; the molecular sizes of these substances are in the range of
(wt.%) (wt.%) 0.500.71 nm. The molecules of reactants and products can penetrate
PdPt/Al2O3 none 0 100 0.3 1.0
easily in the channel of 12-membered ring zeolites, but the channel of
PdPt/Al2O3ZSM-5 79.2 70 30 0.3 1.0 10-membered ring zeolites may bring certain diffusion resistance.
PdPt/Al2O3-Beta 17.5 70 30 0.3 1.0 Therefore, two kinds of 10-membered ring zeolites (ZSM-5, SAPO-11)
PdPt/Al2O3USY 23.5 15 85 0.3 1.0 and two kinds of 12-membered ring zeolites (Beta, USY) were used in
PdPt/Al2O3SAPO-11 1.1 70 30 0.3 1.0
this work as support constituents to examine the effects of pore
M. Du et al. / Fuel Processing Technology 91 (2010) 16551661 1657

structure on naphthalene hydrogenation [18]. 12-membered ring


zeolite Beta has a three-dimensional interconnecting pore system with
pores of 0.55 0.64 0.76 nm, whereas USY has a three-dimensional
interconnecting pore system with supercages of 1.18 nm connected by
circular 12-membered ring windows of 0.74 nm. 10-membered ring
zeolite ZSM-5 has two kinds of interconnecting pore system, one is
elliptical straight channels (0.51 0.57 nm), the other is almost circle Z
channels (0.54 nm), with an intersection size of 0.9 nm. SAPO-11 is
also a 10-membered ring zeolite, with one-dimensional elliptical
straight channels of 0.39 0.63 nm.
The pore textures of the catalysts PtPd supported on the mixed
supports of Al2O3 and the molecular sieves are listed in Table 2. It is
obvious that the mean pore size of PtPd/Al2O3 is decreased
signicantly by mixing the molecular sieves in the support and the
porosity of the resultant catalyst is related with the type of the
molecular sieves added. PtPd/Al2O3-Beta and PtPd/Al2O3ZSM-5,
Fig. 1. NH3TPD proles of the catalysts (a) PdPt/Al2O3, (b) PdPt/Al2O3ZSM-5, (c)
especially, exhibit small mean pore size, while PdPt/Al2O3USY and
PdPt/Al2O3-Beta, (d) PdPt/Al2O3USY, and (e) PdPt/Al2O3SAPO-11.
PdPt/Al2O3SAPO-11 show moderate mean pore size. Generally,
large pore in the catalysts is in favor of the diffusion of large reactant
molecules. Navarro et al. [22] found that there was a strong PdPt interaction in
the PdPt bimetallic catalysts and PdO was well reduced at 22 C.
3.2. Acidity With the increase of temperature from 30 C to 450 C, the reduction
peak of Pt is indistinct. It may be attributed to that the content of Pt
NH3TPD proles of different catalysts were shown in Fig. 1 and was much lower than that of Pd and Pd is enriched on the surface. Pd
the analysis results of the acidity determined are listed in Table 3. The Pt/Al2O3 displays a broad shoulder peak, which may correspond to the
NH3 desorption temperature represents the strength of the acidic sites Pd species interacted with Al2O3 support [23]. PdPt/Al2O3ZSM-5
and the peak area is related with the quantities of acidic sites; the NH3 and PdPt/Al2O3USY show mild shoulder peaks, suggesting that
desorption temperature ranges of 20200, 200350 and 350550 C there are still certain amounts of noble metal species strongly
correspond to weak, moderate, and strong acid sites, respectively [19]. interacted with Al2O3. However, there is no such shoulder reduction
The acidity quantity of different catalysts follows the sequence of Pd peak observed for PdPt/Al2O3-Beta and PdPt/Al2O3SAPO-11,
Pt/Al2O3USY N PdPt/Al2O3-Beta N PdPt/Al2O3 N PdPt/Al2O3SAPO- indicating that the metal species on these catalysts is well and rapidly
11 N PdPt/Al2O3ZSM-5. PdPt/Al2O3USY and PdPt/Al2O3 are sim- reduced at 30 C. These suggest that the reducibility of metal species is
ilar in the shape of NH3TPD proles; both of them present two peaks promoted by mixing proper molecular species in the alumina support.
in the NH3TPD proles, a low temperature one for weak to moderate Because of H2 spill-over, the quantity of H2 chemically adsorbed on
acidic centers and a high temperature one for strong acidic sites. This the supported catalysts are often higher than the stoichiometric
is probably due to that the content of USY zeolite here in the mixed quantity calculated on the basis of surface metals [24]. H2-chemi-
support Al2O3USY is only 15 wt.%, much lower than that in other sorption is effective to characterize the status of noble metal catalyst;
mixed supports. PdPt/Al2O3ZSM-5, PdPt/Al2O3-Beta and especially however, it is not appropriate to determine the dispersion of noble
PdPt/Al2O3SAPO-11 contain mainly moderate acidic sites. The metals by using H2-chemisorption. The dispersion of noble metals are
amount and strength of acid sites are related not only to the activity usually determined by H2O2 titration, in which Pd or Pt oxides on the
of naphthalene hydrogenation but also to the extent of concomitant catalyst surface are reduced to the hydrids (Eqs. (1) and (2)).
further cracking and coke disposition.
PdO 3=2H2 PdH H2 O 1
3.3. TPR and H2O2 titration
PtO 3=2H2 PtH H2 O 2
The H2TPR proles of the catalysts PtPd supported on the
different mixed supports are shown in Fig. 2. Upon switching from N2 The metal dispersion was then obtained with formula (Eq. (3))
to H2 at 30 C, for all the catalysts, the reduction starts immediately;
3 V0 M
H2 consumption here is mainly attributed to the reduction of PdO [20]. 2
R= 3
The negative peak after the rst reduction peak is ascribed to the H2 22400WP
release from PdH and the broad peak after the H2 release may
correspond to Pd species interacted with Pt or the support [21,22]. For where R is metal dispersion, V0 is H2 volume used for the titration, M is
the hydrogenation of aromatics in the presence of dibenzothiophene mean atomic weight of PtPd (118.9 g/mol), W is weight of catalyst
(DBT) on the catalysts Pt, Pd and PdPt supported on silicaalumina, loaded (0.2 g) and P is metal loading in the catalyst (1.3 wt.%).

Table 2
Surface area and pore texture of the PtPd catalysts supported on the mixed supports of Al2O3 and various molecular sieves.

Catalyst Surface area (m2/g) Pore volume (cm3/g) Mean diameter (nm) Pore distribution (nm,%)

b5 510 1020 2030 N30

PdPt/Al2O3 216 0.68 12.0 7.0 33.2 41.5 14.1 4.3


PdPt/Al2O3ZSM-5 323 0.27 3.4 16.6 44.8 25.5 9.1 3.9
PdPt/Al2O3-Beta 270 0.37 5.4 3.8 25.6 28.9 13.6 28.1
PdPt/Al2O3USY 289 0.62 8.5 5.5 36.1 30.7 17.5 10.2
PdPt/Al2O3SAPO-11 154 0.30 7.7 3.5 22.9 35.9 16.4 21.4
1658 M. Du et al. / Fuel Processing Technology 91 (2010) 16551661

Table 3
Analysis results of acidity and metal dispersion of the PtPd catalysts supported on the mixed supports of Al2O3 and various molecular sieves.

Catalyst Total acidity (mmol/g) NH3-TPD peak temperature (C) and Metal dispersion Particle size (nm)
area percentage in parenthesis

PdPt/Al2O3 0.294 193 (34%); 377 (66%) 0.62 1.5


PdPt/Al2O3ZSM-5 0.191 256 (100%) 0.35 2.7
PdPt/Al2O3Beta 0.338 266 (100%) 0.36 2.6
PdPt/Al2O3USY 0.358 193 (31%); 377 (69%) 0.78 1.2
PdPt/Al2O3SAPO-11 0.236 326 (100%) 0.54 1.7

The average metal particle size (d) was estimated with the metal SAPO-11 exhibits a moderate metal dispersion and particle size, while
dispersion. The particles of noble metals are assumed to be cubic with PdPt/Al2O3ZSM-5 and PdPt/Al2O3-Beta show very low metal
one face contacted with the support, the mean surface area and dispersion and large particle size.
volume of the metal particles are 5d2 and d3, respectively [25]. The
metal dispersion R can also be expressed as the ratio of atoms on 3.4. Catalytic performance of PdPt supported on the mixed support of
surface over total atoms in a particle (Eq. (4)). Al2O3 with different molecular sieves

5d2 = 5M For the hydrogenation of naphthalene, the rst step to tetralin is


R= = 4
d = MN
3 dN generally much easier than the next step to decalin; the reaction rate
for the hydrogenation of naphthalene to tetralin is about 30 times of
where is the density ( values of Pt and Pd are 21.5 and 12.0 g/cm3, that to decalin, and decalin is only formed when the conversion of
respectively) and is the cross-section area of the metal atom ( values naphthalene exceeds 80% [13]. Over the catalysts with strong acidity
of Pd and Pt are assumed as 0.0787 and 0.0800 nm2, respectively). N is and/or very small channels, tetralin and decalin may be further cracked
the Avogadro constant. From Eq. (4), the average metal particle size d into butyl-benzene and butyl-cyclohexane, and sometimes even
can then be obtained (Eq. (5)). methyl-cycloheptane and isobutene, which result in relatively low
liquid yields [26,27]. As the saturated hydrogenation is strongly
5M expected for the hydrogenation of aromatic compounds in the diesel
d= 0:94 = R 5
NR fuel, the selectivity to decalin at given temperature is then used as the
main criterion to evaluate the performance of a catalyst for naphthalene
The mean dispersion and particle size of PdPt metals estimated in hydrogenation. For this reason, the selectivities to tetralin, decalin and
this way are listed in Table 3. It suggests that the metal dispersion and other products for naphthalene hydrogenation over various catalysts
particle size are strongly dependent on the interaction between the are shown in Fig. 3. It should be noted that the conversions of
metals and the support. The TPR results show that Al2O3 has stronger naphthalene over all these catalysts under current conditions are close
interaction with the metal species than the mixed supports. to 100%, and therefore, they are not specially mentioned in this work.
Meanwhile, large pore favors the movement of Pt and Pd species The effects of mixing different molecular sieves in the support on the
towards the pore channels [13], thus the dispersions of PdPt in Pd catalyst performance are then mainly investigated by comparing the
Pt/Al2O3USY and PdPt/Al2O3 are higher than that in other catalysts, selectivities to decalin, tetralin and cracking products over various
meanwhile the metal particle sizes are also smaller. PdPt/Al2O3 catalysts under equivalent reaction conditions.
As shown in Fig. 3(a), the catalyst PtPd supported on pure Al2O3
support (PdPt/Al2O3) exhibits poor selectivity to decalin. Below
300 C, the main product is tetralin; over 300 C, the cracking
products are increased signicantly and the selectivity to decalin is
only about 4045%. The selectivity to decalin at 340 C is lower than
that at 320 C, while the change in the selectivity to tetralin with
temperature is in the opposite direction; this is probably due to the
limit of chemical equilibrium, because naphthalene hydrogenation is
thermodynamically unfavorable at high temperature.
As shown in Tables 2 and 3, PdPt/Al2O3 is provided with large
pore volume and mean pore diameter, its metal dispersion and total
acidity are also relatively high, but it performs poorly in the saturated
hydrogenation of naphthalene. PtPd/Al2O3 exhibits the low density
of weak acidic sites along with certain amounts of strong acidic sites;
the strong acidic sites may give rise to the cracking of hydrogenation
products and then results in the decrease of the selectivity to tetralin
and decalin. In addition, the Lewis acidity of Al2O3 support is less
active in hydrogenation reaction than the Brnsted acidity of zeolites
or SiO2Al2O3. Fujikawa et al. found that PtPd/SiO2Al2O3 catalyst is
more active for aromatic hydrogenation than Pt/Al2O3 [28]. For the
hydrogenation of toluene over the bifunctional catalysts, Chupin et al.
also found that Pt/Al2O3 was less active than Pt/HFAU(zeolite)Al2O3
[29]. These are consistent with current results; the poor performance
of PdPt/Al2O3 for the saturated hydrogenation of naphthalene may
be attributed to its Lewis acidity and the relatively high acidity
Fig. 2. TPR proles (against time) of the catalysts (a) PdPt/Al2O3, (b) PdPt/Al2O3ZSM-5,
(c) PdPt/Al2O3-Beta, (d) PdPt/Al2O3USY, and (e) PdPt/Al2O3SAPO-11 (line f
strength.
represents the temperature of the catalyst sample along with the time during the TPR By using the mixed supports, the catalyst PdPt/Al2O3ZSM-5
measurement). exhibits high selectivity to tetralin at 260340 C and the selectivity to
M. Du et al. / Fuel Processing Technology 91 (2010) 16551661 1659

a larger dimension of pore channels than Beta, the diffusion of


reactants and products is much easier. The selectivity to decalin
reaches the highest value of 60.0% at 280 C, while above this
temperature the amounts of cracking products is increased drastical-
ly; this tendency is similar to that using PtPd/Al2O3-Beta as catalyst.
This may be ascribed to the high acidity and high metal dispersion in
the catalyst PdPt/Al2O3USY. It should be noted that the content of
USY zeolite in the mixed support here is only 15 wt.%. A higher USY
content will result in the formation of large amounts of ring opening
products and poor material balance because of the intense cracking
property of USY zeolite.
In contrast to the above-mentioned catalysts, PdPt/Al2O3SAPO-
11 exhibits the highest catalytic activity for the saturated hydroge-
nation of naphthalene to decalin, the selectivity to decalin exceeds
90% at 260300 C, while the selectivity to cracking products is kept at
a low level, as shown in Fig 3(e). The formation of cracking products
only becomes signicant at a temperature higher than 320 C.
The high activity of PtPd/Al2O3SAPO-11 for the saturated
hydrogenation of naphthalene may be ascribed to its proper pore
channel and moderate acidity and metal dispersion. As shown by
NH3-TPD in Fig. 1, the catalyst PdPt/Al2O3SAPO-11 owns high
density of weak acidic sites, which favors the hydrogenation of
aromatics and the suppression of further product cracking. In contrast
to Al2O3, SAPO-11 owns large amounts of Brnsted acidic sites.
Aguayo et al. [30] found that the ratio of Brnsted acid sites to Lewis
one increased from 1.09 to 3.99 with the increase of the Si/Al of SAPO-
11 from 0.17 to 0.25 and the Brnsted acid sites could promote the
hydrogenation of aromatics. Corma et al. [14] claimed that the strong
Brnsted acid sites could enhance the dispersion of Pt and promote
the formation of electron-decient Pt species, which was in favor of
the hydrogenation activity. Wang et al. [31] also found that the
support with more Brnsted acid sites could improve the catalyst
activity for the hydrogenation of benzene and promote the production
of methylcyclopentane. Moreover, SAPO-11 has elliptical straight
channels with a dimension of about 0.63 nm, which enables the
Fig. 3. Selectivities of tetralin, decalin and other products for naphthalene hydroge-
nation over different catalysts: (a) PdPt/Al2O3, (b) PdPt/Al2O3ZSM-5, (c) PdPt/ reactants and the products to diffuse easily in the zeolite channels.
Al2O3-Beta, (d) PdPt/Al2O3USY, and (e) PdPt/Al2O3SAPO-11. Mean value for the SAPO-11 zeolite is a good catalyst for the hydroisomerization of long-
reaction duration of 1224 h; Feed, 8.5 wt.% naphthalene in n-hexane; 4.0 MPa, chain alkanes [32]. This work suggests that an excellent support can
LHSV = 2.0 h 1, H2/oil = 50. The conversions of naphthalene over all these catalysts be obtained by mixing the molecular sieve SAPO-11 in Al2O3 to
here under current reaction conditions are close to 100%.
prepare the PdPt catalyst for the saturated hydrogenation of
naphthalene.
decalin and other products stays at a low level for the naphthalene
hydrogenation, as shown in Fig. 3(b). Less cracking products over Pd 3.5. Effect of SAPO-11 content in the mixed support on the naphthalene
Pt/Al2O3ZSM-5 are formed than that over PdPt/Al2O3. This may be hydrogenation
attributed to that the zeolite ZSM-5 used here is in high Si/Al ratio (Si/
Al = 79.2) and the acidity of resultant catalyst is relatively low, which As illustrated above, the catalyst PtPd/Al2O3SAPO-11 performs
can alleviate the undesired cracking reaction. As listed in Tables 2 and excellently in the saturated hydrogenation of naphthalene. To
3, PdPt/Al2O3ZSM-5 exhibits much smaller pores and lower metal determine the optimal composition of the mixed support, the effect
dispersion. The three-dimensional 10-membered ring channel of of SAPO-11 content in the mixed support on the performance of the
ZSM-5 zeolite has a pore size of about 0.55 nm. Such a small pore catalyst PtPd/Al2O3SAPO-11 (the loadings of Pt and Pd are 0.3 wt.%
dimension may restrain the reactants naphthalene and tetralin from and 1.0 wt.%, respectively) for naphthalene hydrogenation was
diffusion to the active sites in the zeolite channel. As a result, tetralin is further examined, as shown in Fig. 4.
formed as the main product, since the rst step hydrogenation of At 320 C, a complete conversion of naphthalene is achieved over
naphthalene to tetralin is much easier than the next step to decalin. all these catalysts. The selectivity to decalin increases markedly but
For naphthalene hydrogenation over PdPt/Al2O3-Beta, tetralin is the selectivity to tetralin decreases correspondingly with the increase
also the main product at 260320 C and the selectivity to tetralin of SAPO-11 content in the mixed support; while little change in the
decreases with increasing the reaction temperature, as shown in Fig. 3 amounts of cracking products with the SAPO-11 content is observed.
(c). The selectivity to decalin is at a low level and reaches a maximum The catalytic tests at 280 C and 300 C also exhibit the same
value of 26.4% at 280 C. Above 280 C, the cracking of the products tendency. Such a result may be attributed that the amounts of weak
becomes increasingly crucial with the increase of reaction tempera- Brnsted acidic sites increase with the SAPO-11 content in the mixed
ture. The low selectivity to decalin and high selectivity to cracking support, which is able to enhance the saturated hydrogenation of
products over the catalyst PdPt/Al2O3-Beta may be ascribed to the naphthalene. With a SAPO-11 content of 70 wt.% in the mixed
low metal dispersion, high acidity, and small mean pores. Such a support, the selectivity to decalin already exceeds 90%. However, a
result is in accordance with the report of Pawelec et al. [17]. higher content of SAPO-11 in the mixed support may inuence the
For naphthalene hydrogenation over PdPt/Al2O3USY, decalin mechanic strength of the nal catalyst. The strongly acidic solution for
becomes the main products, as shown in Fig. 3(d). Because USY owns the impregnation of active metals may also cause notable damages to
1660 M. Du et al. / Fuel Processing Technology 91 (2010) 16551661

catalyst for the saturated hydrogenation of naphthalene. This is in


accordance with the report of Fujikawa et al. that the optimal catalytic
activity could be attained when the loadings of noble metals Pd and Pt
meet the formula Pd / (Pt + Pd) = 0.7 [28].

4. Conclusions

To search for proper catalysts for the deep hydrogenation of


aromatics in diesel fuel, the hydrogenation of naphthalene in hexane
was conducted over the catalysts PtPd supported on the mixed
supports of Al2O3 and a series of molecular sieves like ZSM-5, Beta,
USY and SAPO-11. The results indicated that the catalytic performance
for saturated hydrogenation of naphthalene is related to the acidic
property, metal dispersion, interaction of metals and support, and
pore texture of the catalyst, which may be well regulated by mixing
proper molecular sieves in the alumina support.
Fig. 4. Effects of SAPO-11 content in the mixed support on the performance of the The molecular sieve SAPO-11 mixed with Al2O3 provides an
catalyst PtPd/Al2O3SAPO-11 (the loadings of Pt and Pd are 0.3 wt.% and 1.0 wt.%, excellent support for preparing the catalyst for the saturated
respectively) for naphthalene hydrogenation (320 C, mean value for the reaction hydrogenation of naphthalene. The catalyst PdPt (the loadings of
duration of 1224 h. The conversion of naphthalene under current reaction conditions
Pt and Pd are 0.3 wt.% and 1.0 wt.%, respectively) supported on the
is 100%).
two-component support of Al2O3SAPO-11 (the SAPO-11 content in
the mixed support is 70 wt.%) is provided with proper acidity, large
the framework of molecular sieves in the mixed support with a higher pores and moderate metal dispersion. The catalyst PtPd/Al2O3
SAPO-11 content. Therefore, a SAPO-11 content of 70 wt.% in the SAPO-11 exhibits excellent performance in the saturated hydrogena-
mixed support is preferred for preparing PtPd/Al2O3SAPO-11 tion of naphthalene to decalin; over it a complete conversion of
catalyst for the saturated hydrogenation of naphthalene. naphthalene is observed and the selectivity to decalin exceeds 90% at
260300 C.
3.6. Effect of metal loading on the naphthalene hydrogenation
Acknowledgments
To determine the optimal loading of noble metal, the effect of Pd
loading on the performance of the catalyst PtPd/Al2O3SAPO-11 The authors are grateful for the nancial support of the National
(SAPO-11 content in the mixed support is 70 wt.%, and Pt loading is Basic Research Program of China (2006CB202504), the National
0.3 wt.%) for naphthalene hydrogenation is further examined, as Natural Science Foundation of China (20873174, 10979068), the
shown in Fig. 5.
Natural Science Foundation of Shanxi Province (2008011014-2), and
The conversions of naphthalene over these catalysts at 320 C are the Knowledge Innovation Program of the Chinese Academy of
also close to 100%. The selectivity to decalin increases markedly but Sciences (KJCX2.YW.H16, YZ200933).
the selectivity to tetralin decreases correspondingly with the increase
of Pd loading from 0.25 wt.% to 1.0 wt.%. With a Pd loading of 1.0 wt.%,
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