Applied Catalysis A: General 185 (1999) L199L201

Letter
Sulfur-tolerant PdPt/Al2 O3 B2 O3 catalyst for aromatic hydrogenation
Hiroyuki Yasuda a, , Takashi Kameoka b , Toshio Sato a , Norihito Kijima a , Yuji Yoshimura a
a National Institute of Materials and Chemical Research, 1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
b Catalysts & Chemicals Ind. Co., Ltd., 13-2 Kitaminato-Machi, Wakamatsu-Ku, Kitakyushu, Fukuoka 808-0027, Japan
Received 9 April 1999; received in revised form 19 May 1999; accepted 19 May 1999

Abstract
Hydrogenation of tetralin was done over a bimetallic PdPt catalyst supported on amorphous Al2 O3 B2 O3 at a hydrogen
pressure of 3.9 MPa at 553 K in the presence of dibenzothiophene (sulfur content of 500 ppm by weight). The resulting
activity and selectivity were compared with those for PdPt supported on amorphous SiO2 Al2 O3 , -Al2 O3 , SiO2 , and USY
zeolites. PdPt/Al2 O3 B2 O3 had high sulfur tolerance; it showed higher activity than PdPt/SiO2 Al2 O3 , PdPt/-Al2 O3 ,
PdPt/SiO2 , or PdPt/USY (SiO2 /Al2 O3 = 680), but slightly lower activity than PdPt/USY (SiO2 /Al2 O3 = 40). Furthermore,
PdPt/Al2 O3 B2 O3 showed excellent hydrogenation selectivity. This catalytic system, therefore, is promising for practically
reducing the aromatics in diesel fuels. 1999 Elsevier Science B.V. All rights reserved.
Keywords: PdPt; Amorphous Al2 O3 B2 O3 ; Tetralin hydrogenation; Sulfur tolerance

1. Introduction MCM-41 [12], or amorphous SiO2 Al2 O3 [12,14],

The increasingly more stringent environmental reg-
ulations for diesel emissions in exhaust gases demand
new diesel-fuel specifications, including lower lev-
els of sulfur and aromatics and higher cetane number
[13]. Such specifications require the development of
new catalysts and processes that can reduce the aro-
matics in diesel fuels. Noble metal catalysts generally
exhibit excellent activity for aromatic hydrogenation,
but they are easily poisoned by small amounts of sulfur
in the feedstock [4]. In recent years, for the hydrogena-
tion of aromatics in diesel fuels, sulfur-tolerant no-
ble metal catalysts, such as Pd, Pt or bimetallic PdPt
supported on -Al2 O3 [59], acidic zeolites [1013],
Corresponding author. Tel.: +81-298-54-4530; fax:
+81-298-54-4532; e-mail: yasuda@nimc.go.jp
have attracted much attention. However, the sulfur tol-
erance of these catalysts is still insufficient, and further
improvement of sulfur tolerance is needed for increas-
ing the tolerant-sulfur levels and extending the cata-
lyst life. Moreover, the choice of the supports is also
important for the development of aromatic hydrogena-
tion catalysts; for example, when strongly acidic sup-
ports are used, excessive hydrocracking of the feed-
stock occurs and this decreases the middle-distillate
yields.
In this study, we chose the hydrogenation of tetralin
in the presence of dibenzothiophene (DBT) as a
model reaction, and investigated the catalytic prop-
erties of bimetallic PdPt supported on amorphous
Al2 O3 B2 O3 . The results were compared with PdPt
supported on amorphous SiO2 Al2 O3 , -Al2 O3 ,
SiO2 , and USY zeolites.

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L200 H. Yasuda et al. / Applied Catalysis A: General 185 (1999) L199L201
2. Experimental
The bimetallic PdPt catalysts were prepared
by incipient wetness impregnation of amorphous
Al2 O3 B2 O3 (Catalysts & Chemicals Ind. Co., Ltd.
(CCIC), 15 wt.% B2 O3 , 228 m2 g1 ), amorphous
SiO2 Al2 O3 (CCIC, 13 wt.% Al2 O3 , 516 m2 g1 ),
-Al2 O3 (CCIC, 204 m2 g1 ), SiO2 (Fuji Silysia
Chemical Ltd., CARiACT G-10, 239 m2 g1 ) with
a mixed aqueous solution of [Pd(NH3 )4 ]Cl2 and
[Pt(NH3 )4 ]Cl2 . The total amount of metal loading
was 1.21.3 wt.%, and the mole ratio of Pd to Pt was
fixed at 4. The impregnated samples were dried in
vacuum at 333 K for 6 h, and calcined in an oxygen
stream at 573 K for 3 h. The calcined samples were
reduced in-situ in a hydrogen stream at 573 K for 3 h
before being used in the reaction.
Metal dispersion of the PdPt catalysts was deter-
mined from the amount of chemisorbed CO measured
by a pulse method. In the calculation of the dispersion,
we assumed the stoichiometry of CO to either Pd or Pt
to be unity. Acid strength and amount of the supports
were determined by microcalorimetric measurements
of the differential heat of adsorption of ammonia at
303 K after the supports were evacuated at 673 K for
4 h.
Hydrogenation of tetralin was carried out in a
high-pressure fixed-bed continuous-flow reactor, as
described previously [11]. The liquid feed consisted
of tetralin (30 wt.%), DBT (0.3 wt.%, sulfur con-
tent of 500 ppm by weight), and n-hexadecane (for
balance). The reaction conditions were a hydrogen
pressure of 3.9 MPa, reaction temperature of 553 K,
weight hourly space velocity (WHSV) of 16 h1 , and
a volume ratio of hydrogen (NTP) to feed of 500.
The feed and products were analyzed by using a GC
(Shimadzu, GC-17A) equipped with an FID and a
capillary column (Hewlett-Packard, Ultra 1).
3. Results and discussion
Fig. 1 shows the time-course of the conversion
of tetralin over PdPt supported on Al2 O3 B2 O3 ,
SiO2 Al2 O3 , and -Al2 O3 . The conversion decreased
with time on stream (t) when DBT was present in
the feed, but the degree of deactivation significantly
Fig. 1. Time-course of tetralin conversion in the hydrogenation
of tetralin in the presence of DBT over PdPt/Al2 O3 B2 O3 (),
PdPt/SiO2 Al2 O3 () and PdPt/-Al2 O3 (4) catalysts.
differed among the catalysts. PdPt/Al2 O3 B2 O3
showed a small deactivation and a high conversion
(54.5%), even at t = 24 h. Although PdPt/SiO2 Al2 O3
showed the highest initial conversion (83.4%), the
level decreased rapidly with time on stream to 35.8%
at t = 24 h. PdPt/-Al2 O3 showed a low conversion
even at the initial stage of the reaction.
We evaluated the tetralin hydrogenation activity and
the selectivity to decalins (trans- and cis-decalin) at
t = 24 h (Table 1). Products other than decalins (trans-
and cis-decalin) were decalin isomers, alkylcycloalka-
nes, gaseous hydrocarbons, and tetralin dimers and
their hydrogenated derivatives. We also evaluated the
degree of deactivation by residual conversion, which
we defined as the ratio of the tetralin conversion at
t = 24 h to that at t = 1 h (Table 1). PdPt/Al2 O3 B2 O3
had the smallest deactivation among the catalysts
studied here, and showed higher conversion and se-
lectivity than PdPt/SiO2 Al2 O3 or PdPt/-Al2 O3 .
Furthermore, PdPt/Al2 O3 B2 O3 was more ac-
tive than PdPt/SiO2 Al2 O3 , PdPt/-Al2 O3 , or
PdPt/SiO2 , even when the activity is compared by
TOF, which represents the number of tetralins con-
verted into decalins per hour per surface Pd and Pt
atoms. The conversion of DBT at t = 24 h was 100%
for either PdPt/Al2 O3 B2 O3 or PdPt/SiO2 Al2 O3 ,
whereas it was 73.3% for PdPt/-Al2 O3 and 63.7%
for PdPt/SiO2 . The tetralin hydrogenation activity
and selectivity of PdPt/USY depend strongly on the
 H. Yasuda et al. / Applied Catalysis A: General 185 (1999) L199L201 L201

Table 1
Tetralin hydrogenation activity and selectivity over supported PdPt catalystsa
Catalyst Dispersion Conversion of tetralin (%) Selectivity to decalinsb (%) TOF (102 h1 ) Residual conversion

PdPt/Al2 O3 B2 O3 0.57 54.5 99.2 3.6 0.87

PdPt/SiO2 Al2 O3 0.38 35.8 86.1 3.1 0.43
PdPt/-Al2 O3 0.56 7.5 97.4 0.5 0.75
PdPt/SiO2 0.17 3.1 100 0.7 0.55
PdPt/USY-40c 0.48 63.5 78.9 3.9 0.67
PdPt/USY-680d 0.43 25.7 99.7 2.2 0.36
a Time on stream of 24 h.
b Products other than decalins (trans- and cis-decalin) were decalin isomers, alkylcycloalkanes, gaseous hydrocarbons, and tetralin dimers
and their hydrogenated derivatives.
c Cited from [13].
d Cited from [11].

SiO2 /Al2 O3 ratio of USY [11,13]; the activity is max-
imum in the SiO2 /Al2 O3 range of 1540, whereas the
selectivity reaches almost 100% at the SiO2 /Al2 O3
ratio of 680. In this study, PdPt/Al2 O3 B2 O3 was less
active than PdPt/USY (SiO2 /Al2 O3 = 40, abbreviated
as USY-40), but much more active than PdPt/USY
(SiO2 /Al2 O3 = 680, abbreviated as USY-680). On the
other hand, the selectivity of PdPt/Al2 O3 B2 O3 was
higher than that of PdPt/USY-40, and was similar to
that of PdPt/USY-680.
It is well-known that the sulfur tolerance of no-
ble metals increases when they are supported on
acidic supports [2,3,1517]. However, strong acid
sites on the supports cause undesirable reactions,
such as hydrocracking and coke formation. The
initial heat of adsorption of ammonia was about
129 kJ mol1 for SiO2 Al2 O3 , 109 for Al2 O3 B2 O3 ,
and 107 for -Al2 O3 . On the other hand, for a heat
of adsorption greater than 70 kJ mol1 [18], the
amount of adsorbed ammonia was 0.61 mmol g1
for SiO2 Al2 O3 , 0.70 for Al2 O3 B2 O3 , and 0.23
for -Al2 O3 . These results indicate that the acid
strength of the supports was, in decreasing order,
SiO2 Al2 O3  Al2 O3 B2 O3 > -Al2 O3 , whereas the
acid amount was Al2 O3 B2 O3 > SiO2 Al2 O3  [14] M. Vaarkamp, W. Dijkstra, B.H. Reesink, P.H. Berben, Am.
-Al2 O3 . Thus, when supported on Al2 O3 B2 O3 ,
bimetallic PdPt showed high sulfur tolerance and
high activity, maintaining a high hydrogenated yield,
possibly because of large amounts of acid sites that
had moderate acid strength on Al2 O3 B2 O3 .
In conclusion, the PdPt/Al2 O3 B2 O3 catalyst
showed high sulfur tolerance for the hydrogenation of
tetralin in the presence of DBT, and showed excellent
hydrogenation selectivity. These results demonstrate
the promise of using this catalytic system for practi-
cally reducing the aromatics in diesel fuels.
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