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Catalysis Communications 3 (2002) 305311

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Hydrogenation of aromatics over PtPd Metals supported on


a mixed c-ZrPsilica carrier promoted with lithium
S. Murcia-Mascar
os, B. Pawelec, J.L.G. Fierro *

Instituto de Cat
alisis y Petroleoqumica, CSIC, Campus UAM, Cantoblanco, E-28049 Madrid, Spain
Received 18 March 2002; accepted 22 May 2002

Abstract

PtPd and LiPtPd catalysts were prepared by incipient wetness impregnation of the solgel prepared mixed c-Zr
phosphateSiO2 carrier. The catalytic behavior of the Li-modied and its Li-free PtPd/ZPS systems was compared in
the simultaneous hydrogenation (HYD) of toluene and naphthalene (NP) in the presence of dibenzothiophene (DBT).
Irrespective of the reacting molecule, the Li-modied sample showed higher activity at zero time than its Li-free
counterpart. The binding energies of Pt4f 7=2 and Pd3d5=2 levels for the LiPtPd sample were lower than for the PtPd
counterpart. This observation suggests that the enhancement in activity at short times on-stream of the LiPtPd catalyst
might be due to the interaction of Li with the support surface that then weakens the metalsupport interaction. At times
on-stream operation longer than 1 h, the H2 S produced in the hydrodesulfurization of dibenzothiophene tends to
eliminate the benecial eect of Li. 2002 Elsevier Science B.V. All rights reserved.

Keywords: Aromatics hydrogenation; Li-promotion; PdPt bimetallic catalysts; Mesoporous layered materials.

1. Introduction that additional active sites can exist in the metal


support interface region, which is also able to
In aromatic hydrogenation reactions it has been participate in the hydrogenation of aromatic hy-
shown that noble metals on acidic supports display drocarbons [3]. This latter possibility has been
higher TOF and greater resistance to S-poisoning conrmed at our laboratory for noble metals
than when they are supported on non-acidic car- (PtPd) supported on zeolite Beta [4]. The dual-site
riers. This has been related either to the polariza- behavior was also observed for Ni and Mo sup-
tion of the metal particles by nearby cations [1], or ported on alumina-pillared a-zirconium phosphate
to a metalsupport interaction, which may induce catalysts [5], which showed good performance in
a partial electron transfer between the metal tetralin hydrogenation in the presence of 1000 ppm
and the substrate [2]. An alternative explanation is of DBT (45% yield) and, simultaneously, good
activity in the ring-opening reaction.
Initially, the incorporation of lithium to the
*
Corresponding author. Tel.: +34-1-585-47-69; fax: +34-91-
supported noble metals appears to be benecial in
585-4760. the target reactions because alkali compounds are
E-mail address: jlgerro@icp.csic.es (J.L.G. Fierro). currently added in order to inhibit coking [6,7].

1566-7367/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 1 5 6 6 - 7 3 6 7 ( 0 2 ) 0 0 1 3 2 - 2
306 S. Murcia-Mascaros et al. / Catalysis Communications 3 (2002) 305311

Kang [8] observed that lithium addition to Pd loading, the ZPS carrier was rst impregnated with
supported on silica markedly improves 1-butene 0.04 g of PdCl2 . After adsorption equilibrium had
selectivity and activity for the hydrogenation of been reached, the excess of water was removed in a
1,3-butadiene without isomerization and over-hy- rotary evaporator after which the impregnate was
drogenation of the 1-butene. It was assumed that dried at 383 K in air for 4 h followed by calcina-
Li favors 1-butene desorption. Parvulescu et al. [9] tion in air at 573 K for 4 h (heating rate 4 K/min).
observed that the hydrogenation of indene over In order to obtain PtPd/ZPS catalyst, the calcined
PdLi/g-Al2 O3 occurs both in indane and hydrin- Pd/ZPS catalyst was impregnated with 0.320 ml of
dane while on the Li-free catalyst (Pd/g-Al2 O3 ) a 0.51 M H2 PtCl6 solution. The LiPtPd/ZPS
hydrogenation occurs only in indane. This be- catalyst was prepared by simultaneous impregna-
havior was assigned to the presence of lithium, tion of the calcined Pd/ZPS substrate with H2 PtCl6
which generates basic sites that chemisorb indene and lithium acetate solution. For both catalysts,
and on which the hydrogenation occurs with hy- the drying and calcination steps were performed
drogen spilled over from palladium. For phenol under the same conditions as described for the Pd/
hydrogenation, an increase in the intrinsic activity ZPS samples.
of the palladium site on Li-promotion has been Chemical analysis of the calcined samples was
attributed to the alteration of the net charge den- performed by inductively coupled plasma atomic
sity at the reactive site (Pd) induced by lithium due emission spectroscopy and their textural properties
to a strong interaction between the surface metal were explored using the N2 adsorptiondesorption
atoms and positively charged Li ions. This conse- isotherms obtained at 77 K. The chemical and
quently aects the strength of bonding between the textural data obtained are reported in Table 1. The
oxygen atom and the phenolate ring and the sup- reduced catalysts (563 K for 1 h) were character-
port, thereby enhancing product desorption [10]. ized by volumetric CO chemisorption isotherms at
However, the authors of this article failed to report 303 K and temperature-programmed desorption
evidence of the alternation of the electronic prop- (TPD) proles of ammonia using a Micromeritics
erties of the Pd=Al2 O3 system. TPD/TPR 2900 apparatus. Photoelectron spectra
Our aim in the present communication is to of used catalysts were recorded on a VG Escalab
clarify the inuence of the Li promoter on the 200R electron spectrometer equipped with a
overall performance of the mixed PtPd/c-ZrP hemispherical electron analyzer, using a MgKa
SiO2 catalyst system, in which the acidity of the (hm 1253:6 eV) X-ray source.
carrier and the hydrogenation capacity of the Hydrogenation of aromatic compounds was
metals coexist, for the simultaneous hydrogenation performed in a continuous-down-ow catalytic re-
of toluene and naphthalene model reactions in the actor. The model feed (DBT, naphthalene, and
presence of dibenzothiophene. toluene dissolved in hexadecane) was prepared.
Activity tests were performed using 0.25 g of cata-
lyst diluted with SiC. Catalyst reduction was carried
2. Experimental out at 573 K in an H2 =N2 mixture (ratio 1:10 vol, a
ow rate 55 ml/min) at atmospheric pressure for 2
For support preparation, the original c-ZrP h. Catalytic activities were measured at T 498 K,
c-ZrPO4 O2 POH2  2H2 O was exfoliated in a 50 bar total pressure, weight hourly space velocity
wateracetone mixture according to the procedure (WHSV) of 49.8 h1; and a H2 /feed ratio of 202
described elsewhere [11]. The gel thus obtained was L(N)/L. Liquid samples were analyzed by GC with
dried at 353 K and nally calcined in air at 873 K FID (Varian chromatograph Model Star 3400 CX)
for 2 h. The two PtPd/ZPS and LiPtPd/ZPS cat- equipped with a 30 m  0.53 mm DB-1 column (J &
alysts used in this work were prepared by consec- W Scientic). In this study the naphthalene was
utive wet impregnation of the mixed c-ZrPSiO2 hydrogenated to decalin and tetralin only (the sum
(hereafter, ZPS) substrate, prepared by following was 100%), and for HYD of toluene the MCH was
the method reported previously [11]. For metal the unique product detected (conversion of toluene
S. Murcia-Mascaros et al. / Catalysis Communications 3 (2002) 305311 307

Table 1
Catalytic ativitya mol h1 g1 , TOFb , and percentagec of activity decay for simultaneous toluene and naphthalene hydrogenation in
the presence of DBT over Li-promoted and unpromoted PtPd/ZPS catalysts
LiPtPd/ZPS PtPd/ZPS
HDS of DBT
r4h  104 mol h1 g1 b 0.7 0.7
TOFt0  103 s1 b 2.4 0.7
Activity decay (%)c 57.7 37.7
HYD of toluene
r4h  104 mol h1 g1 b 49 59
TOFt0  103 s1 b 157 13.9
Activity decay (%)c 95.3 77.8

HYD of naphthalene
r4h  104 mol h1 g1 b 776.5 737.8
TOFt0  103 s1 b 11.9 7.0
Trans-to-cis-decalin ratioc 2.0 2.1
Activity decay (%)d 13.1 5.6
a
Specic reaction rate for DBT, toluene and naphthalene conversions at 4 h on-stream. Reaction conditions were: T 498 K,
P 50 bar, WHSV 49:8 h1 .
b
TOF at zero-time conversion.
c
Trans-to-cis-decalin ratio at fourth hour on-stream.
d
Percentage of activity loss between rst and fourth hour on-stream as calculated from conversion values.

was equal to selectivity toward methylcyclohexane the presence of DBT (S-113 ppm) was studied over
(MCH) formation). On the other hand, after HDS PtPd supported on the mixed ZPS substrate. This
of DBT, cyclohexylbenzene (CHB) and biphenyl model reaction was chosen because: (i) on any gi-
(BF) were the only products detected by GC. Ac- ven catalyst it is possible to compare the relative
tivity is described in terms of total DBT, toluene reactivity of the hydrocarbons, which depends on
and naphthalene conversions, and using a specic their molecular structure, (ii) additional informa-
reaction rate according to tion can be obtained about the surface structure of
the catalyst itself, and (iii) both model compounds
ri Xi  F =mcat ; 1
resemble the structure of aromatic compounds
where ri is the specic rate mol=g s, Xi is the found in the diesel fraction (typical light gas oil
conversion of reactant i (i DBT, toluene or (LGO)).
naphthalene), F is the molar ow rate of the re- The total conversions of toluene, DBT and NP
actant i (mol/s), and mcat is the catalyst weight (g). vs time on steam are shown in Fig. 1(a)(c), re-
Turnover frequency (TOF: molecules converted/ spectively. Intrinsic activities at fourth hour on-
atom s) data were obtained on the basis of exposed stream and TOF at zero-time conversion
metal atoms, calculated from dispersion values (TOFt0 ), together with deactivation percentages,
obtained from CO chemisorption data. Activity are shown in Table 1. TOFt0 was calculated from
decay was expressed as the percentage of the cat- conversion data extrapolated to zero run time. As
alyst deactivation calculated from the ratio [(initial can be seen, irrespective of the reacting molecule
activity at fourth hour on-stream)/initial activity]. the Li-modied sample (LiPtPd/ZPS) was much
more active than its Li-free counterpart (PtPd/
ZPS). In line with previous ndings [4], the in-
3. Results and discussion trinsic activity of both catalysts at steady-state
conversion (Table 1) followed the sequence:
In the present study, the simultaneous hydro- NP toluene > DBT. This is because hydroge-
genation of toluene (T) and naphthalene (NP) in nation of toluene is more dicult than that of NP
308 S. Murcia-Mascaros et al. / Catalysis Communications 3 (2002) 305311

low sites and the distortions and binding energy


depend on the back-donation to the adsorbate, in
turn controlled by the electronic properties of
metals [13].
Table 2 summarizes the main physico-chemical
characteristics of both PtPd/ZPS and LiPtPd/ZPS
catalysts. Fig. 3 shows TPD proles of NH3 de-
sorption of both LiPtPd and PtPd samples and
the bare ZPS support. As expected, the acidity of
support decreased after metal incorporation and
this decrease (stronger acid sites) is larger for the
LiPtPd catalyst. From the results presented in
Table 2, it is clear that neither the metal content
nor the acidity nor the surface area can account
for the higher activity of the LiPtPd/ZPS catalyst.
From the CO chemisorption data, LiPtPd/ZPS
shows a poorer metal dispersion than its Li-free
counterpart (16% vs 24.4%), in turn in agreement
with the data reported by Mahata et al. [10]. This
low metal dispersion suggests the presence of lar-
ger particles of noble metal (5.2 vs 3.4 nm). Ad-
ditionally, comparison of the Pt/(Zr + Si) and Pd/
(Zr + Si) ratios derived from XPS (Table 3) and
chemical analyses (Table 2) suggest that the pres-
ence of a large amount of Li ions (Li 0:68 A )
on the catalyst surface favors the surface exposure
of noble metals. Fig. 4 shows the Pd3dZr3p core-
level energy region for both LiPtPd and PtPd
catalysts. The BE of the Pd 3d5=2 and Pt 4f 7=2
peaks of the LiPtPd/ZPS sample were 0.5 and 0.3
eV, respectively, lower in comparison with the Li-
free PtPd/ZPS sample (Table 3). Thus, a higher
metallic character of Pd(Pt) particles for the Li-
promoted sample is evident. Since for the Li 1s
core-level a BE of 55.6 eV is indicative of LiO [14],
Fig. 1. Total conversion of toluene (a), DBT (b) and NP (c). this Li species may to a certain extent neutralize
Reaction conditions were: T 498 K; P 50 bar; WHSV the acidity of the ZPS substrate, thus increasing
49:8 h1 .
the metallic character of Pd/Pt atoms in the
metal particles. Accordingly, the stronger initial
as a result of the dierences in the p-electron reactivity of the Li-promoted sample as compared
density in the aromatic rings. For HYD of NP, the to the unpromoted one can be explained in terms
preferential formation of the trans-decalin isomer of the indirect eect of lithium on the carrier sur-
rather than the cis-isomer (see trans-to-cis decalin face. Since in this study both Pt and Pd particles
ratio in Table 1) points out to the edgewise ad- behave as separate phases, our results agree with
sorption of the NP, which allows H-addition from the observations of Rousset et al. [15] who found
opposite sites [12]. In contrast with NP, on noble that neighbouring Pt atoms have no inuence on
metals, toluene is probably adsorbed in a cong- the reactivity of Pd atoms in tetralin hydrogena-
uration parallel to the surface over threefold hol- tion.
S. Murcia-Mascaros et al. / Catalysis Communications 3 (2002) 305311 309

Table 2
Chemical composition,a textural properties,b acidityc and metal dispersiond of the calcined PtPd/c-ZrPSiO2 catalysts
LiPtPd/ZPS PtPd/ZPS
ZrP (wt%) 25.56 27.52
SiO2 (wt%) 64.13 67.38
Pt (wt%)a 2.88 3.10
Pd (wt%)a 1.73 1.99
Li (wt%)a 1.08
BET specic area m2 g1 b 335 521
Average pore diameter (nm)b 4.5 3.6
Acid amount (mmol NH3 g1 cat
c
0.27 0.47
Metal particle diameter (nm)d 5.2 3.4
Metal particle dispersion (%)d 16.0 24.4
a
From chemical analysis.
b
From N2 adsorptiondesorption isotherms at 77 K.
c
From TPD of NH3 .
d
From CO chemisorption measurements.

Fig. 2. Eect of reaction time on tetralin and MCH formation


Fig. 3. NH3 temperature desorption proles for the LiPtPd/
on LiPtPd/ZPS catalyst in the HYD of naphthalene and tol-
ZPS and PtPd/ZPS catalysts.
uene, respectively, in the presence of DBT. Reaction conditions
were: T 498 K; P 50 bar; WHSV 49:8 h1 .
LiPtPd/ZPS catalyst underwent a sudden drop in
Fig. 2 shows the tetralin and MCH formation in MCH formation in the HYD of toluene (Fig. 2).
HYD of NP and toluene, respectively. Interest- This decrease in MCH formation was accompa-
ingly, after the rst hour on-stream reaction the nied by an opposite increase in selectivity toward
310 S. Murcia-Mascaros et al. / Catalysis Communications 3 (2002) 305311

Table 3
Binding energies (eV)a and surface atomic ratios of core electrons of LiPtPd/ZPS and PtPd/ZPS catalysts usedb
LiPtPd/ZPS PtPd/ZPS
BE of Li 1s (eV) 55.6
BE of P 2p (eV) 134.0 134.1
BE of Pd 3d5=2 eVc 335.1 335.6
BE of Pt 4f 7=2 (eV) 70.8 71.2
Zr/Si at 103 59 71
P/Zr at 103 2120 2240
Li=Zr Si at  103 325
Pd=Zr Si at  103 8 14d 3 (15)d
Pt=Zr Si at  103 3 (14)d 2 (13)d
a
The C 1s peak at a BE of 284.9 eV was taken as internal standard.
b
Reaction conditions were: T 498 K, P 50 bar, WHSV 49:8 h1 .
c
As the Pd 3d5=2 peak overlaps with the Zr 3p3=2 peak, the BE of Pd 3d5=2 was obtained by subtracting a value of 5.25 eV from the Pd
3d5=2 peak.
d
Bulk Me/(Zr + Si) at ratio (Me Pt, Pd) calculated from chemical analysis of oxidic samples are in parentheses.

tetralin formation in the HYD of NP (Fig. 2). The


dramatic inhibition in activity for the HYD of
toluene did not appear to be related exclusively to
coke deposition. This was conrmed in a run
performed by feeding the reactor with an S-free
toluene + NP mixture, under the same experimen-
tal conditions, in which MCH conversion de-
creased in the second hour on-stream by only 61%.
Thus, these data suggest that S enhances the se-
lectivity of hydrogenation reactions toward par-
tially hydrogenated products [6] and that
electronegative S originating from DBT conver-
sion could be adsorbed on Li [6]. Thus, the strong
decay in activity during the second hour on-stream
is more likely due to a suppression of the primary
eect of lithium on the substrate. It may, therefore,
be concluded that Li-modied noble metal cata-
lysts can be successfully used in the hydrogenation
of S-free streams of aromatic compounds.

4. Conclusions

PtPd-loaded mesoporous ZPS systems are ac-


tive in the saturation of aromatic compounds.
Activity was enhanced when lithium was incor-
porated in the catalyst formulation. From the
measurement of the BE of core-levels of the tran-
Fig. 4. Pd3dZr3p core level spectra for the LiPtPd/ZPS and
PtPd/ZPS catalysts. Note that the most intense Pd 3d5=2 peak is
sition metals, it appears that the higher initial ac-
overshadowed by the strong Zr 3p3=2 peak of the c-ZrP sub- tivity of the LiPtPd/ZSP as compared with the Li-
strate. free PtPd/ZPS sample can be explained as being
S. Murcia-Mascaros et al. / Catalysis Communications 3 (2002) 305311 311

due to the modication of the ZPS substrate by [4] B. Pawelec, R. Mariscal, R.M. Navarro, S. van Bokhorst,
lithium incorporation. The strong inhibition of S. Rojas, J.L.G. Fierro, Appl. Catal. A: General 225 (2002)
223.
toluene hydrogenation, which was not observed in [5] R. Hernandez-Huesca, J. Merida-Robles, P. Maireles-
the absence of an S compound in the feed stream, Torres, E. Rodrguez- Castell on, A. Jimenez-L opez, J.
is related to the poisoning of lithium by the H2 S Catal. 203 (2001) 122.
produced in the HDS of DBT. [6] G.A. Martin, in: B. Imelik, C. Naccache, C. Coudurier, H.
Praliaud, P. Meriaudeau, P. Gallezot, G.A. Martin, J.C.
Vedrine (Eds.), MetalSupport and Metal Additives Eects
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One of us (B.P.) acknowledges nancial support
[9] V.I. Parvulescu, V. Parvulescu, S. Gobolos, E. Talas, J.M.
from the Spanish Ministry of Science and Tech- Margitfalvi, Rev. Roum. Chim. 44 (1112) (2000) 1113.
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[11] G. Alberti, C. Dionigi, E. Giontella, S. Murcia-Mascar os,
R. Vivani, J. Colloid Interface Sci. 188 (1998) 27.
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