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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
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,%)
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
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
4. Conclusions
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