Aromatics Hydrogenation On Silica-Alumina Supported Palladium-Nickel Catalysts
Aromatics Hydrogenation On Silica-Alumina Supported Palladium-Nickel Catalysts
Aromatics Hydrogenation On Silica-Alumina Supported Palladium-Nickel Catalysts
Department of Chemical and Environmental Engineering, School of Engineers, University of the Basque Country,
Alameda Urquijo s/n, 48013 Bilbao, Spain
b Institute of Catalysis and Petrochemistry, Spanish Council for Scientific Research (CSIC),
Campus de la UAM, Cantoblanco 28049 Madrid, Spain
Received 8 June 2002; received in revised form 29 August 2002; accepted 2 September 2002
Abstract
Nickel- and palladiumnickel catalysts supported on silicaalumina have been studied in the simultaneous hydrogenation of naphthalene and toluene. These catalysts were characterised by means of X-ray diffraction, CO chemisorption,
temperature-programmed reduction, NH3 temperature-programmed desorption, diffuse reflectance spectroscopy, Fourier
transform infrared spectroscopy of adsorbed CO and X-ray photoelectron spectroscopy techniques. All the catalysts studied
showed higher initial intrinsic activity in the hydrogenation of toluene than of naphthalene. Regarding the hydrogenation of
toluene, the 1Pd8Ni/SA sample displayed the strongest resistance to deactivation by coke precursors as compared with the
Ni-free 1Pd/SA catalyst. For the 1Pd8Ni catalyst, the characterisation data pointed not only to a high degree of reducibility
of nickel but also the greatest exposure of Pd species. Both findings appear to be related to the development of nickel hydrosilicate species at the support interface. Indeed, a better resistance towards deactivation was obtained by Pd incorporation
and by increasing Ni-loading.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Aromatics hydrogenation; Nickel and palladium catalysts; Silicaalumina support
1. Introduction
Owing to environmental and clean-fuel legislation
[13], deep hydrodearomatisation of diesel fuel has
been the focus of many recent studies. Supported
noble metal catalysts are well known for their high
hydrogenation activity for deep hydrodearomatisation
Corresponding author. Tel.: +34-94-6017282;
fax: +34-94-6014179.
E-mail addresses: iapbacav@bi.ehu.es (V.L. Barrio),
jlgfierro@icp.csic.es (J.L.G. Fierro).
1 Tel.: +34-91-5854769; fax: +34-91-5854760.
at low reaction temperatures and moderate hydrogen pressures, although in general they show low
resistance to sulphur poisoning [4]. Due to the low
cost and acceptable resistance to sulphur poisoning,
Ni-based systems are good alternatives to noble metal
hydrogenation catalysts [5,6]. These catalysts are particularly suited to the production of middle distillates
through the hydroconversion of hydrocarbons derived
through the FischerTropsch process.
Most studies on Ni-based catalysts have been carried out using silica or alumina supports. The use of
silicaalumina as a support has received less attention. Recently, Guimon et al. [5] reported that the
0926-860X/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 4 8 9 - 1
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2. Experimental procedure
2.1. Catalyst preparation
A commercially available support, SiO2 Al2 O3
(SMR 5-473, Grace Davison Chemical, hereafter referred to as SA) containing 28 wt.% alumina was
calcined in air at 773 K for 3 h prior to catalyst preparation. Ni/SA and Pd/SA catalysts were prepared by
wet impregnation of the support with aqueous solutions of Ni(NO3 )2 4H2 O (Carlo Erba, 99%) and
Pd(NO3 )2 2H2 O (Fluka, >98%), respectively. Once
adsorption equilibrium had been reached, excess
water was removed in a rotary evaporator. Then,
the impregnates were dried at 383 K in air for 12 h
and calcined in air at 723 K for 2 h. The bimetallic
PdNi/SA catalysts were prepared by impregnation
of calcined Ni/SA catalysts with the Pd(NO3 )2 2H2 O
(Fluka, >98%) solution, followed by drying and calcination as above. The metal contents of the catalysts,
as determined by plasma analysis, are reported in
Table 1. For all the catalysts, the nominal palladium
composition was 1 wt.%. Monometallic and bimetallic systems are referred to xNi and 1PdxNi, respectively, where x denotes the nominal nickel percentage.
It can be observed in Table 1, that x can be 4 or 8,
and implies a Ni content of 4 or 8 wt.%.
2.2. Catalyst characterisation
The chemical compositions of the catalysts were determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using a Perkin-Elmer
Table 1
Chemical compositiona , textural propertiesb and metal dispersionc of Pd/SA, Ni/SA and NiPd/SA catalysts
Catalyst
SA
1Pd
4Ni
8Ni
1Pd4Ni
1Pd8Ni
a
Metal contenta
Ni (wt.%)
Pd (wt.%)
4.0
8.3
3.9
8.2
0.9
0.8
0.8
Dc (%)
dp b (nm)
26.6
14.6
21.7
16.1
394
372
389
375
324
326
7.5
6.9
6.6
5.5
6.9
5.7
118.4
102
107
103
89
89
Optima 3300DV instrument. Samples were solubilised in a mixture of HF, HCl and HNO3 at 363 K
and homogenised in a microwave oven. Diffuse reflectance UV-Vis spectroscopy was performed on
the calcined samples using a Shimadzu-UV-2100
spectrophotometer. The calcined samples were also
characterised by X-ray diffractometry according to
the step-scanning procedure (step size 0.02 ), using a
computerised Seifert 3000 diffractometer, with Cu K
( = 0.15406 nm) radiation, and a PW 2200 Bragg
Brentano /2 goniometer equipped with a bent
graphite monochromator and an automatic slit. Scanning 2 angles ranged from 10 to 70 . Line-broadening
measurements were carried out using the NiO peak
(43.35 in 2). The full-width at half-maximum
(FWHM) of these peaks was corrected for instrumental broadening (b). Diffuse reflectance spectra (DRS)
of the finely ground calcined samples were recorded
in the 240800 nm range with a Shimadzu UV-2100
spectrophotometer, using BaSO4 as a reference and
converted to the SchusterKubelkaMunk function.
The textural properties of the calcined catalysts
were evaluated from the N2 (air liquide, 99.994%)
adsorptiondesorption isotherms obtained at 77 K
over the whole range of relative pressures, using a
Micromeritics ASAP-2000 apparatus, for samples
previously outgassed at 413 K for 18 h. A value of
0.1620 nm2 was taken for the cross-section of the
physically adsorbed N2 molecule. BET specific areas
were computed from these isotherms by applying
the BET method over the 0.0050.25 P/P0 range. In
all cases, correlation coefficients above 0.999 were
obtained.
Volumetric CO chemisorption isotherms at 303 K
were obtained in order to estimate metal dispersion.
Before measurements, the sample was reduced under
H2 at 673 K for 1 h and then outgassed at 105 mbar.
In order to avoid sintering of the Pd0 particles, the
1Pd sample was reduced at 573 K. After cooling the
sample to room temperature, CO was admitted and
the adsorption isotherm was measured. The monolayer
adsorption capacity was obtained by extrapolation to
zero-pressure the linear part of the isotherm. In the
calculation of the dispersion, the stoichiometry of CO
to either Pd or Ni was assumed to be unity.
Temperature-programmed reduction profiles were
obtained on a semiautomatic Micromeritics TPD/TPR
2900 apparatus interfaced with a computer. Since PdO
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3. Results
3.1. Chemical and textural properties of oxidic
catalysts
Although under hydrogenation conditions the catalysts are in reduced state, it is relevant to study their
oxidic precursors because there is a direct relationship
between the properties of calcined catalysts and the
corresponding reduced samples.
The chemical composition and textural properties of
the NiPd/SA catalysts as revealed by chemical analysis and nitrogen adsorptiondesorption isotherms, respectively, are given in Table 1. For all samples, the
shape of the N2 adsorptiondesorption isotherms (not
shown) and their hysteresis loops were similar to the
bare SA. As expected, the sorption capacity of the
SA decreased after Ni and/or Pd incorporation. The
drop in the adsorbed volumes of N2 at a relative pressure of P/P 0 = 0.2, and consequently in the BET
area and porosity, indicate that some of the micropores and/or the smaller mesopores become occupied
or blocked by nickel and/or palladium species. Noticeably, the 8Ni/SA catalyst shows a similar BET area to
that of the 1Pd/SA sample. The similar BET specific
area of the 1Pd4Ni and 1Pd8Ni catalysts shows that
the decrease in the BET specific area is mainly governed by the second impregnation step with the Pd
salt. According to the X-ray profiles (not shown), all
the calcined catalysts exhibited only one peak coming from the support (2 = 24.16), but none from the
Pd or Ni phases. Thus, it was inferred either the formation of well-dispersed amorphous PdO/NiO phases
or solid state reaction between NiO and support to
form an ill-crystallized surface compound (Ni aluminate/silicate) [12].
3.2. CO chemisorption
Data on the metal dispersion of catalysts obtained
by the chemisorption method are given in Table 1.
Metal dispersion follows the trend: 4Ni > 1Pd4Ni >
1Pd8Ni > 8Ni. As the metal dispersion of a given
metal usually increases in consecutive impregnations
[13], for 1Pd8Ni sample some re-dispersion of the
Ni species after impregnation of 8Ni catalyst with
the palladium solution could be expected. However,
for the1Pd4Ni sample, in which Ni-loading is much
lower and Ni species interact strongly with the support surface, re-dispersion of the nickel phase during
consecutive impregnation with the palladium salt did
not occur.
3.3. UV-Vis diffuse reflectance analysis
In order to confirm the identity of the nickel
species and the formation of nickel hydrosilicate, the
UV-Vis diffuse reflectance spectra of Ni/SA catalysts are obtained. Fig. 1 shows the UV-Vis diffuse
reflectance spectroscopy profiles for the representative 4Ni and 8Ni catalysts in the visible range. Both
catalysts showed two distinctive major bands at 370
and 650 nm, and a minor one at around 530 nm.
Since a similar band was observed for NiO obtained
by decomposition of nickel nitrate [12], the band at
370 nm was attributed to the octahedral coordinated
Ni2+ ions. Considering the diffuse reflectance spectroscopy study of Houalla and Delmon [12] on the
Ni/silicaalumina catalyst with several alumina contents, we ascribed a band at 650 nm as being due to
Ni2+ in a tetrahedral environment, and the band at
530 nm as being due to Ni3+ (the excess of oxygen
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Bare SA
1Pd
4Ni
8Ni
1Pd4Ni
1Pd8Ni
a
T601650 K
T702711 K
5.3
3.8
3.1
2.9
1.0
0.7
3.4
4.3
1.0
1.5
5.8
23
Fig. 3. Normalised NH3 temperature-programmed desorption profiles of reduced 1Pd/SA, Ni/ASA, 1PdNi/SA catalysts and bare support.
For the sake of comparison, profiles have been deconvoluted.
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Table 3
Binding energies (eV) of core electrons and surface atomic ratios of reduced (fresh) and used Pd/SA, Ni/SA and PdNi/SA catalystsa
Catalyst
Ni 2p3/2
Pd 3d5/2
335.0
335.8
0.010
0.005
1Pd
Fresh
Used
4Ni
Fresh
852.7
855.3
852.8
855.3
(18)
(82)
(40)
(60)
0.029
852.7
855.3
852.8
855.3
(25)
(75)
(37)
(63)
0.040
852.6
855.1
852.7
855.2
(31)
(69)
(54)
(46)
335.0
0.029
0.015
335.8
0.016
0.008
852.6
855.2
851.5
854.6
(30)
(70)
(41)
(59)
335.2
0.049
0.023
335.8
0.048
0.013
Used
8Ni
Fresh
Used
1Pd4Ni
Fresh
Used
1Pd8Ni
Fresh
Used
0.032
0.039
26
catalysts decreased with time on stream. For the hydrogenation of toluene, the 8Ni/SA and 1Pd8Ni/SA
samples show higher activity as compared to the
1Pd/SA sample during the first 7 h on-stream. Considering the run time without deactivation, the
1Pd8Ni/SA sample shows an approximately two-fold
higher resistance to deactivation than its Pd-free
8Ni/SA catalyst. Similar behaviour has previously
been reported for PdNi alloys supported on silica;
these underwent less deactivation than the Pd-free Ni
catalyst [8]. According to the steady-state data shown
in Fig. 5, only the 1Pd/SA sample is active in the
hydrogenation of toluene whereas the activity of the
other catalysts resembles that of bare SA. Contrary to
toluene hydrogenation, the steady-states of the naphthalene hydrogenation activities of all the catalysts
are much more active than bare SA. The activities of
both 1Pd/SA and 1Pd8Ni/SA catalysts are highest
and are very close each other. Interestingly, unlike
the hydrogenation of toluene, these two catalysts
do not undergo deactivation in the hydrogenation of
naphthalene.
Fig. 7. Effect of the reaction time on selectivity in the hydrogenation of naphthalene (tetralin and trans-decalin formation) and toluene
conversion on the 1Pd4Ni/SA catalyst. Reaction conditions as in Fig. 5.
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Fig. 8. Effect of the reaction time on selectivity in the hydrogenation of naphthalene (tetralin and trans-decalin formation) and toluene
conversion on the 1Pd8Ni/SA catalyst. Reaction conditions as in Fig. 5.
As seen in Fig. 7, the main product in the hydrogenation of naphthalene over the 1Pd4Ni/SA catalyst is tetralin. A similar type of behaviour is observed
for the 4Ni/SA catalyst (data not shown). Under the
Fig. 9. Effect of the reaction time on selectivity in the hydrogenation of naphthalene (tetralin and trans-decalin formation) and toluene
conversion on the 1Pd/SA catalyst. Reaction conditions as in Fig. 5.
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4. Discussion
In order to avoid the influence of deactivation and
to establish some catalyst structureactivity correlations, Fig. 10(a) and (b) compare the initial activity (calculated at zero-time conversion) expressed in
gToluene/Naphthalene /(gcat h) and the turnover frequencies (TOFs), respectively. Considering the latter, the
major feature is that, irrespectively of the reacting
molecule, the 1Pd sample showed larger TOFt=0 than
other Ni catalysts. This is because Ni has a weaker
Fig. 10. Comparison of the intrinsic activity (a) and turnover frequencies (TOFs) at zero-time conversion (s1 ) (b) for simultaneous toluene (Tol) and naphthalene (NP) hydrogenation over Pd/SA,
Ni/SA and PdNi/SA catalysts. Reaction conditions as in Fig. 5.
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