www.elsevier.com/locate/apcata
Instituto Mexicano del Petroleo, Ingeniera Molecular, Eje Central Lazaro Cardenas 152, C.P. 07730, Mexico, D.F., Mexico
b
Division de CBI, Universidad Autonoma Metropolitana-Iztapalapa, 09340 Mexico, D.F., Mexico
Received 23 November 2004; received in revised form 16 May 2005; accepted 18 May 2005
Available online 27 June 2005
Abstract
The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)Pt (0.3 wt.%) catalysts supported on ZrO2 (70, 85 wt.%)Al2O3
(15, 0 wt.%)WOx (15 wt.%) prepared by solgel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N2
physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by solgel
favored the high dispersion of WOx and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of
monoclinic-WO3 bulk phase. The catalysts increased their SBET for about 15% promoted by Al2O3 addition. Various oxidation states of WOx
species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WOx species is constituted mainly
of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in
the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW
catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated
to the coexistence of W6+ and reduced-state WOx species (either W4+ or W0). The addition of Pt to the Pd/ZrAlW catalyst does not modify
significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.
# 2005 Elsevier B.V. All rights reserved.
Keywords: Bimetallic PdPt catalysts; ZrO2Al2O3WO3 ternary oxide; Solgel method; Structure; Reducibility; XPS; Raman; NMR; Acidity;
Isomerization of n-hexane
1. Introduction
In recent years the catalytic processes to promote the
skeletal isomerization of light n-alkanes such as n-hexane
(n-C6H14) have played an important role in order to increase
the octane number of gasoline [1,2]. The industrial catalysts
used for the isomerization of alkanes are those based in Pt
supported on chlorinated alumina and Pt or Pd supported on
mordenite [1,2]. However, the former catalyst results in
serious environmental problems related to the recovery of
corrosive acids and it is sensitive to moisture and sulfur
impurities, while Pt or Pd supported on mordenite is less
* Corresponding author. Tel.: +52 55 91 75 8375; fax: +52 55 95 75 6239.
E-mail address: amontoya@imp.mx (J.A. Montoya).
0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.05.011
98
2. Experimental
2.1. Catalysts preparation
70 wt.% ZrO215 wt.% Al2O315 wt.% WO3 (ZrAlW)
ternary oxides were prepared by the solgel method from
organic precursors with the hydrolysis process assisted by
the addition of the aqueous ammonia metatungstate solution
as follows: required volumes of zirconium(IV) propoxide,
Zr(O-Prop)4 (Aldrich), and aluminum-tri-sec-butoxide,
Al(O-sec-Bu)3 (Aldrich), were dissolved in a glass flask
containing 1-propanol (Fermont), and hexylene glycol, 2methyl-2,4-pentanediol (Aldrich), as a complexing agent
[18]. The solution was heated with continuous stirring to
70 8C and kept there for 1 h. Then, the required volume of
the aqueous ammonia metatungstate (AMT) solution
(NH4)6H2W12O40nH2O (Aldrich) was added to the homogeneous alkoxide solution in the glass flask to perform the
hydrolysis. The gels obtained were aged in the glass flask
with the remaining AMT solution at 40 8C for 2 h and then at
room temperature for 12 h. After that, the gels were dried in
an oven at 100 8C for 12 h followed by calcination at 800 8C
for 4 h. 85 wt.% ZrO215 wt.% WO3 (ZrW) binary oxides
were prepared by the same method except for the addition of
the alumina precursor.
The ZrW and ZrAlW oxides calcined at 800 8C were
impregnated with solutions of varying concentrations of
PdCl2 (Aldrich) to give catalysts with 0.3, 0.6, and 1.0 wt.%
of Pd. Some samples were coimpregnated with a
H2PtCl6xH2O solution (Aldrich) to give bimetallic catalysts
with Pd (0.6 wt.%)Pt (0.3 wt.%), and Pd (1.0 wt.%)Pt
(0.3 wt.%). In order to study the effect of Pt, the ZrAlW
oxide was also impregnated with H2PtCl6xH2O to give
catalysts with 0.3 and 0.9 wt.% Pt. After impregnation, the
excitation line of the laser was 532 nm and the laser power
was of 25 mW.
27
Al NMRMAS spectra of the catalysts calcined at
600 8C for 3 h were recorded at 23 kHz with a Bruker 400
spectrometer and using AlCl3 0.1 M solution as the standard
reference. Scan conditions were 0.35 ms pulse with a delay
time of 1.0 s. The unresolved 27Al NMR spectra were
deconvoluted in three peaks by using a standard Lorentzian
function.
FT-IR of adsorbed pyridine experiments were performed
in order to determine the type and amount of surface acid
sites of the ZrW mixed oxide and catalysts with 1.0 wt.% of
palladium. They were carried out by using a Fourier
transform infrared (FT-IR) Perkin-Elmer spectrometer
Model 170-SX. Pretreatment of the samples prior to the
adsorption of pyridine consisted in outgassing followed by
heating to 500 8C at 20 8C min 1 and cooling to room
temperature. After the pretreatment, the samples were
exposed to saturated pyridine vapor for 20 min. IR spectra
were recorded after desorption at 50, 100, 200, 300, and
400 8C.
2.3. Catalytic activity test
Hydroisomerization of n-hexane (n-C6H14) over the Pd,
Pt and PdPt catalysts calcined at 600 8C for 3 h was
performed in a Multi-Channel Fixed Bed Reactor (Symyx).
This equipment is appropriate to evaluate the activity and
selectivity of 48 samples in parallel by applying highthroughput testing techniques with a matrix arrangement of
6 columns 8 rows. Briefly, this system consists of six
reactor heads each one containing eight wells for steel
micro-reactors of approximately 4 mm inner diameter and
47 mm length. The six reactor heads are connected
independently to six chromatographs (Agilent, 6850 Series)
equipped with a SPB-1 capillary column (Supelco) and a
flame ionization detector (FID) to do the reaction product
analysis. For the catalytic evaluation 100 mg of catalyst was
diluted with 200 mg of inert silicon carbide by mixing them
and then packed within the micro-reactors and fixed into the
well reactor heads. Pretreatment of the catalysts was carried
out in situ prior to the activity test, and consisted in a dryingreduction program; drying the samples at 260 8C for 2 h in
helium (200 cm3 min 1) followed by reduction in hydrogen
flow (200 cm3 min 1) at 350 8C for 3 h.
99
3. Results
3.1. BET surface area
The BET surface area (SBET) of the Pd, Pt, and bimetallic
PdPt catalysts supported on ZrW and ZrAlW prepared by
solgel via the hydrolysis assisted by the AMT solution is
shown in Table 1. Their SBET were in the range 67
89 m2 g 1 with the lowest values observed in the catalysts
supported on ZrW (alumina free). The addition of 15 wt.%
of alumina increased the SBET of the catalysts for about 15%.
3.2. X-ray diffraction
The XRD patterns of the Pd and bimetallic PdPt
catalysts supported on ZrAlW after calcination at 600 8C are
shown in Fig. 1. Pd, Pt or PdPt phases were not observed.
For the catalysts supported on ZrW (0 wt.% of Al2O3),
Table 1
Specific surface area and H2 uptake from the TPR profiles of mono- and bimetallic PdPt/ZrO2Al2O3WOx catalysts calcined at 600 8C/3 h; previous
calcination of the supports at 800 8C/4 h
Catalysts
SBET (m2 g 1)
Pd (0.6 wt.%)/ZrW
Pd (0.6 wt.%)/ZrAlW
Pd (0.6 wt.%)Pt (0.3 wt.%)/ZrAlW
Pt (0.3 wt.%)/ZrAlW
Pd (1.0 wt.%)/ZrW
Pd (1.0 wt.%)/ZrAlW
Pd (1.0 wt.%)Pt (0.3 wt.%)/ZrAlW
69
89
80
85
67
78
87
11.28
31.17
35.97
69.00
38.60
27.60
100
Fig. 2. TPR profiles of the ZrW support and the mono- and bimetallic Pd
(0.6 wt.%)Pt (0.3 wt.%)/ZrO2Al2O3WOx catalysts. The catalysts were
calcined at 600 8C/3 h; previous calcination of the supports at 800 8C/4 h.
101
27
Al NMRMAS spectra
Table 2
Binding energies (eV) of W 4f7/2 transition, atomic W/(Zr + Al) ratio, and surface density of W atoms of the mono- and bimetallic PdPt catalysts calcined at
600 8C/3 h; previous calcination of the mixed oxide supports at 800 8C/4 h
Catalyst
Pd (0.6 wt.%)/ZrAlW
Pd (0.6 wt.%)Pt (0.3 wt.%)/ZrAlW
Pd (1.0 wt.%)/ZrW
Pd (1.0 wt.%)Pt (0.3 wt.%)/ZrAlW
Pt (0.3 wt.%)/ZrAlW
33.00
31.97
34.18
33.59
33.42
36.03
36.44
35.69
35.12
34.93
38.43
37.51
39.08
38.27
38.68
Surface density of
W atoms (W/nm2)
0.115
0.199
0.191a
0.173
0.171
4.4
4.9
5.8
4.5
4.6
102
Fig. 6. Raman spectra of ZrAlW mixed oxide calcined at 800 8C/4 h and
catalysts with 1.0 wt.% of palladium calcined at 600 8C/3 h; previous
calcination of the supports at 800 8C/4 h: (a) ZrAlW; (b) Pd (1.0 wt.%)/
ZrAlW; (c) Pd (1.0 wt.%)Pt (0.3 wt.%)/ZrAlW; (d) Pd (1.0 wt.%)/ZrW.
103
Fig. 8. FT-IR spectra of adsorbed pyridine of the ZrW mixed oxide calcined at 800 8C/4 h and the catalysts with 1.0 wt.% of palladium calcined at 600 8C/3 h;
previous calcination of the supports at 800 8C/4 h.
4. Discussion
The enhancement of SBET of Pd/ZrAlW catalysts after
calcination at 600 8C for 3 h with respect to that of Pd/ZrW
catalysts indicates that Al2O3 acts as a textural promoter of
the ZrW oxide. Besides, the high SBET of the catalysts
prepared by solgel via the hydrolysis assisted by the
aqueous AMT solution is due to the high homogenization of
the components in the material. This is supported by the fact
that there are no diffraction lines of alumina in the patterns
indicating that alumina was homogenously mixed with
zirconia and WOx. The fact that Pd, Pt or PdPt phases were
no detected by XRD (Fig. 1) suggests that oxidized particles
were either non-crystalline or very small. The detection of a
slight amount of the monoclinic WO3 phase in the catalysts
supported on ZrW suggests that zirconia facilitates the
formation of some WO3 microcrystallites. For the catalysts
supported on ZrAlW, only diffraction lines belonging to the
tetragonal zirconia phase were detected indicating that WOx
is highly dispersed both on the surface as within the bulk of
the oxide support either as amorphous or microcrystalline
104
Fig. 9. Total acidity and amounts of Bro nsted acid and Lewis acid of the ZrW mixed oxide calcined at 800 8C/4 h and the catalysts with 1.0 wt.% of palladium
calcined at 600 8C/3 h; previous calcination of the supports at 800 8C/4 h.
105
106
Table 3
27
Al NMRMAS spectra of mono- and bimetallic PdPt catalysts calcined at 600 8C/3 h: population % of each deconvoluted spectral component
Catalysts
Pd (0.6 wt.%)/ZrW
Pd (0.6 wt.%)/ZrAlW
Pd (0.6 wt.%)Pt (0.3 wt.%)/ZrAlW
Pt (0.3 wt.%)/ZrAlW
Pd (1.0 wt.%)/ZrW
Pd (l.0 wt.%)/ZrAlW
Pd (1.0 wt.%)Pt (0.3 wt.%)/ZrAlW
Population %
P1, octahedral ( 2.32 to 1.51 ppm)
90.47
86.71
88.28
64.10
70.39
1.28
5.18
4.22
9.84
9.17
8.23
8.18
7.49
26.00
20.40
107
108
(4)
(5)
(6)
(7)
(8)
Acknowledgements
The authors gratefully acknowledge the technical
assistance of Mr. Carlos Franco in the development of the
RMN experiments. A. Barrera thanks to the Instituto
Mexicano del Petro leo for the scholarship granted during his
post-doctoral stay.
5. Conclusions
References
(1) Addition of Al2O3 to the ZrW mixed oxides prepared by
solgel via the hydrolysis assisted by the aqueous
ammonia metatungstate solution generates solids with
higher specific surface area.
(2) Zirconia in the tetragonal phase predominates in the
mixed oxides and mono- and bimetallic PdPt catalysts,
whereas the addition of Al2O3 to ZrW modifies its
crystallinity and avoids the formation of WO3 bulk
nanocrystals. In these materials, the WOx species are
found highly dispersed.
(3) There is a coexistence of various oxidation states of
tungsten on the surface of the mono- and bimetallic Pd
Pt catalysts after calcination. The presence of reducedstate WOx species could be ascribed to either an
electronic transfer from the noble metal to the surface
109
[30] P.G. Gassman, D.W. Maomber, S.M. Willging, J. Am. Chem. Soc. 107
(1985) 2380.
[31] V.M. Benitez, C.A. Querini, N.S. Fgoli, Appl. Catal. A: Gen. 252
(2003) 427.
[32] I. Wachs, C. Chersich, J. Hardengerg, Appl. Catal. 13 (1985) 335.
[33] V. Benitez, N.S. Fgoli, Catal. Commun. 3 (2002) 487.
[34] J. Horsley, I. Wachs, J. Brown, G. Via, F. Hardcastle, J. Phys. Chem. 91
(1987) 4014.
[35] K. Fuimoto, F.H. Ribeiro, M. Avalos-Borja, E. Iglesia, J. Catal. 179
(1998) 431.
[36] X.L. Seoane, N.S. Fgoli, P.C. LArgentiere, J.A. Gonza lez, A. Arcoya,
Catal. Lett. 47 (1997) 213.
[37] C. Bigey, L. Hilaire, G. Maire, J. Catal. 184 (1999) 406.
[38] M. Sun, T. Bu rgi, R. Cattaneo, R. Prins, J. Catal. 197 (2001) 172.
[39] R.J. Colton, A.M. Guman, J.W. Rabalais, J. Appl. Phys. 49 (1)
(1978).
[40] P.C. LArgentiere, N.S. Fgoli, React. Kinet. Catal. Lett. 64 (2) (1998)
221.
[41] E. Iglesia, Structure and catalytic function of oxide nanostructures, in:
Proceedings of the XIX Simposio Iberoamericano de Cata lisis, Me rida, Yucata n, Me xico, September 511, 2004.
[42] D.G. Barton, M. Shtein, R.D. Wilson, S.L. Soled, E. Iglesia, J. Phys.
Chem. B 103 (1999) 630.
[43] S. Kuba, P. Lukinskas, R.K. Grasselli, B.C. Gates, H. Kno zinger, J.
Catal. 216 (2003) 253.
[44] M.L. Occelli, S. Biz, A. Auroux, P.S. Iyer, Appl. Catal. A: Gen. 179
(1999) 117.
[45] J.A. Wang, X. Bokhimi, A. Morales, O. Novaro, T. Lo pez, R. Go mez,
J. Phys. Chem. B 103 (2) (1999) 299.
[46] E. Zhao, S.E. Hardcastle, G. Pacheco, A. Garcia, A.L. Blumenfeld, J.J.
Friapiat, Micropor. Mesopor. Mater. 31 (1999) 9.
[47] C. Bigey, G. Maire, J. Catal. 196 (2000) 224.
[48] H. Kno zinger, P. Ratnasamy, Catal. Rev. 17 (1978) 31.
[49] J.C. Summers, D.R. Monroe, Ind. Eng. Chem. Prod. Res. Dev. 20
(1981) 23.