Materials Research Bulletin 41 (2006) 11051111

www.elsevier.com/locate/matresbu

Cobalt and nickel supported on HY zeolite: Synthesis,

characterization and catalytic properties
Anne M. Garrido Pedrosa a,*, Marcelo J.B. Souza b,
Dulce M.A. Melo a, Antonio S. Araujo a
a
Federal University of Rio Grande do Norte, Department of Chemistry, CP 1692, 59078-970 Natal-RN, Brazil
b
Federal University of Sergipe, Department of Chemical Engineering, 49100-000 Sao Cristovao-SE, Brazil
Received 25 May 2005; received in revised form 31 October 2005; accepted 14 November 2005
Available online 5 December 2005

Abstract
Bifunctional catalysts consisting of cobalt and nickel supported on HY zeolite were synthesized by solvent excess impregnation
and characterized by X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, atomic
absorption spectroscopy, thermogravimetric analysis and nitrogen adsorption. The profiles of metal reduction on zeolite were
obtained by temperature-programmed reduction. The catalytic properties of the bifunctional catalysts were verified by n-hexane
hydroconversion. X-ray diffraction and microstructural analyses showed the presence of crystalline phases in HY zeolite and in
samples after impregnation. A decrease in the micropore surface area was observed by nitrogen adsorption experiments and
attributed to a reduction in the accessibility to micropores. The catalysts showed catalytic activity in the hydroconversion of n-
hexane with selectivity to branched hydrocarbons. Such catalytic activity was related to the acid and metallic properties of the
bifunctional catalysts used.
# 2005 Elsevier Ltd. All rights reserved.

Keywords: Cobalt and nickel; HY zeolite; n-Hexane hydroconversion

1. Introduction

Hydroisomerization of n-paraffin is an important process in petroleum refinement because it results in an increase

in gasoline octanage. In this process, the molecules are reconstituted or reformed with the purpose of obtaining more
appropriate fractions for internal use in combustion engines. Such reactions require the use of solid acid catalysts,
especially bifunctional ones. Bifunctional catalysts with acidic function balanced by the metal function have shown
high efficiency in hydroisomerization of n-paraffin [14]. The activity of bifunctional catalysts with transition metals
supported on zeolites have been studied [1,58] and showed good activity and selectivity. However, these catalysts are
more active at high reaction temperatures, which can result in an increase in the cracking to isomerization ratio. It has
been shown that the metal sites and strength distribution acid sites are both important to determine the activity and
selectivity of these catalysts [911]. The metallic component is usually platinum as it is the most active transition
metal catalysts for several hydrocarbon reactions [12]. Pt-containing Y zeolite catalysts have been studied for this

* Corresponding author. Tel.: +55 84 32119241; fax: +55 84 32119241.

E-mail address: annemgp@yahoo.com (A.M. Garrido Pedrosa).

0025-5408/$ see front matter # 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2005.11.010
1106 A.M. Garrido Pedrosa et al. / Materials Research Bulletin 41 (2006) 11051111

process due to its large three-dimensional pore system [5,6,13]. However, data on cobalt or nickel supported on HY
zeolite are still scarce.
Y zeolite is a synthetic molecular sieve with three-dimensional 12-membered-ring pore system. This pore system
consists of spherical cages, referred to as super cages with a diameter of 1.3 nm connected of tetrahedral shape with
four neighboring cages through windows 0.74 nm in diameter [14,15]. This kind of pore system is interesting for
several applications due do its good stability and performance in many processes [16,17].
In the present study, bifunctional catalysts of cobalt and nickel supported on HY zeolite were synthesized. These
catalysts were characterized by different spectroscopic techniques and textural analysis. The catalytic properties of the
catalysts were also studied by n-hexane hydroconversion.

2. Experimental

NaY zeolite was supplied by Union Carbide Corporation. The material was highly crystalline and the atomic ratio of
Si/Al was 2.36. The acid form of this zeolite was obtained by ion exchange with 1 M NH4Cl solution at 70 8C for 2 h.
After that, the material was filtered, dried and calcined in air at 500 8C for 4 h resulting in the acid form (HY). The
supported metallic catalysts were prepared by solvent excess impregnation using 1 wt.% metal from M(NO3)2
6H2O
(M = Co or Ni) solution and subsequent calcination in air at 500 8C for 1 h. HY zeolite and bifunctional catalysts were
characterized by atomic absorption (Varian AA-175), X-ray diffraction (Shimadzu XRD-6000), Fourier-transformed
infrared spectroscopy (ABB Bomem MB104), scanning electron microscopy (Philips XL-30 ESEM), thermogravimetric
analysis (Perkin-Elmer TGA-7) and nitrogen adsorption (Quanta Chrome NOVA 2000). The bifunctional catalysts were
characterized by temperature-programmed reduction using H2Ar (1.55% H2) as reducing gas. The acidic properties
were investigated by n-butylamine desorption (Mettler TGA-851). Prior to the catalytic tests, bifunctional catalysts were
activated in situ under flowing H2 (30 ml min 1) at 450 8C for 5 h in order to reduce the metallic species.
Hydroisomerization of n-hexane was chosen as catalytic test reaction. The reaction was carried out in a fixed bed
continuous flow reactor [18] at atmospheric pressure. The catalytic bed was prepared using 200 mg of catalyst. The
reaction temperatures were varied between 300 and 380 8C. The reactant mixture (H2/n-hexane) was prepared by the
saturation of hydrogen with n-hexane in a bubbler. The reaction products were analyzed at 0.25 h from the beginning of
the experiment using a CG17A gas chromatographer coupled to a QP5000 mass spectrometer (Shimadzu).

3. Results and discussion

Chemical analyses carried out by atomic absorption showed that the catalysts depicted the following chemical
compositions: (a) Na57.2Al58.2Si133.8O384, (b) Na10.9H46.3Al54.8Si137.2O384, (c) Na9.9H45.7Al52.5Si138.5O384 and (d)
Na10.6H46.1Al54.5Si137.4O384, where (a) NaY, (b) HY, (c) Co*/HY and (d) Ni*/HY. The weight fractions of cobalt and
nickel on materials (c) and (d) were 1.4 and 1.1, respectively. XRD patterns for HY, Co*/HYand Ni*/HY catalysts (Co* or
Ni* = cobalt or nickel oxide) are shown in Fig. 1. All peaks observed could be assigned to the FAU structure characterized
by intense reflections at 2u equal to 6.398, 23.718 and 15.768 [17]. The presence of cobalt or nickel oxide along with the
HY phase could not be observed as a result of their small contents on zeolite. In the X-ray diffractograms of Co*/HYand
Ni*/HY it could also be observed that the number of diffract peaks did not change with respect to HY zeolite, indicating
that no crystalline transformation occurred during metal impregnation. Thus, the FAU structure still prevailed for Co*/HY
and Ni*/HY samples. Upon modification of HY by conventional salt impregnation, the relative intensity of the
characteristic peaks changed without any significant shift of the respective peak positions. This indicated that cobalt and
nickel species were present in the cavities and/or surface of HY (catalyst supported). IR spectra for HY, Co*/HYand Ni*/
HY catalysts (Co* or Ni* = cobalt or nickel oxide) are shown in Fig. 2. These spectra show absorption bands at 1150, 722
and 505455 cm 1 due to bonds of the structural internal tetrahedral and at 1020, 791, 573 and 380 cm 1 due to external
linkage of the zeolite structure. The spectra of Co*/HY and Ni*/HY catalysts are very similar to that of HY, which
indicated that the impregnation of cobalt and nickel oxides on HY zeolite did not affect the zeolite structure.
SEM analyses of the zeolite samples are shown in Fig. 3. The influence of the impregnation of cobalt and nickel on
the HY zeolite structure can also be confirmed from SEM images. The micrographs showed the presence of small
crystallites of ca. 1 mm uniformly distributed along some intergrowth. SEM demonstrated that the morphology and
particle size of Co*/HY and Ni*/HY catalysts did not change with respect to those of HY zeolite, indicating that no
crystalline transformations occurred during the impregnation of cobalt or nickel onto HY zeolite. Cobalt and nickel
 A.M. Garrido Pedrosa et al. / Materials Research Bulletin 41 (2006) 11051111 1107

Fig. 1. XRD patterns of Y zeolites.

oxide were finely dispersed as their presence did not result in significant contrast at magnifications up to 20 000. The
micropore area determined by DubininRadushkevich (DR) method showed that the impregnation of cobalt and nickel
on HY zeolite result in a small change on micropore structure. This can be verified by the decrease of the micropore
area and volume of all materials after impregnation. This effect may be attributed to the presence of metallic oxides
and extra framework aluminum species in the interior of the zeolite pores and channels. The decrease in micropore

Fig. 2. Infrared spectra of Y zeolites.

1108 A.M. Garrido Pedrosa et al. / Materials Research Bulletin 41 (2006) 11051111

Fig. 3. SEM images of zeolite samples: (a) NaY; (b) HY; (c) Co*/HY and Ni*/HY.

area was more pronounced for Co*/HY catalyst, probably due to the formation of larger particles inside the
micropores. The micropore area and volume determined by the DR method are both shown in Table 1.
Typical TG curves of the zeolite samples (not shown) showed basically two mass variation events. The first event in
the temperature range 30200 8C was attributed to the release of water molecules from the large cavities of the zeolite.
A second event of mass loss, broad and not well defined, took place in the temperature range 200800 8C and was
assigned to dehydroxylation. Quantitative information on the acid properties of the catalysts is shown in Table 2. The
acid site density per gram of zeolite was correlated with site strength (weak, medium or strong) which is generally
attributed in accordance with the temperature range of n-butylamine desorption [19]. In accordance with these results
it was observed that for M*/HY catalysts (M* = cobalt or nickel oxide), the experimental density of strong acid sites
was lower than that of HY zeolite. This drop in n-butylamine adsorption capacity was due to the partial blocking effect

Table 1
Micropore area, micropore volume and adsorption energy (E0) of zeolite samples
Zeolite Micropore area (m2 g 1) Vmp (cm3 g 1) E0 (kJ mol 1)
HY 426.9 0.12 10.83
Co*/HY 315.9 0.10 6.64
Ni*/HY 384.4 0.11 6.91

Table 2
Density of zeolite acid sites, where DT = temperature range and d = acidity
Zeolites Weak sites Medium + strong sites dtotal (mmol/gcat)
DT (8C) d (mmol/gcat) DT (8C) d (mmol/gcat)
HY 75262 1.230 262804 2.114 3.345
Ni*/HY 103302 1.423 302802 0.904 2.327
Co*/HY 105324 0.701 324805 0.945 1.646
 A.M. Garrido Pedrosa et al. / Materials Research Bulletin 41 (2006) 11051111 1109

Fig. 4. TPR profiles for (a) Ni*/HY and (b) Co*/HY.

of the HY pore system, as a result of the presence of cobalt and nickel oxide particles. Moreover, the partial blocked
pore system can be attributed to the de-aluminization process during calcination, which decreases the acid site density
or also can be attributed to partial exchange between nickel and cobalt ions with H+ of the acidic zeolite.
The reduction profile of nickel and cobalt species onto HY zeolite was evaluated by TPR (Fig. 4). Differences in the
reducibility of M*/HY based catalysts could be observed. The Ni*/HY catalyst showed two peaks related to nickel
reduction. Different reduction temperatures for Ni2+ corresponded to the location of cations in the zeolite. The first and
second peaks of nickel reduction, at 238 and 507 8C, are attributed to the reduction of Ni2+ species located in the
sodalite and hexagonal cavities, respectively. In addition, Co*/HY showed a peak related to cobalt reduction at 908 8C.
This peak could be assigned to the reduction of cobalt species which have a strong interaction with the support and
may be located within the hexagonal cavities. These species were formed during the synthesis of the bifunctional
catalysts.
The catalytic activity of the bifunctional catalysts was tested upon n-hexane hydroconversion. CGMS analyses
showed that the reaction products consisted of isomer products (C6-isomers) and cracking products, mainly ethane and
propane. These results are summarized in Table 3. The dependence of n-hexane hydroconversion on Co/HY and Ni/
HY catalysts with the reaction temperature is shown in Fig. 5a; Fig. 5b shows the selectivity to cracking and C6-
isomers products. It was noticed that the n-hexane total conversion increased with reaction temperature for both
catalysts. Ni/HY showed higher total conversion than Co/HY. On the other hand, the isomerization selectivity (Fig. 5b)
decreased with reaction temperature. The increase of the conversion with the reaction temperature for both catalysts is
an expected result due to higher activation of carbonium or carbenium ions at high temperatures. The decrease in
selectivity to isomerized products with increasing the reaction temperature could also be explained based on the
activation of carbonium or carbenium ions: the increase in temperature collaborated with the production of carbonium
or carbenium ions, thus decreasing the metalacid balance function which decreased the isomerization selectivity and
increased the cracking selectivity. Another possibility to the decrease of the metalacid balance function is that the
sintering of the metallic particles as the reaction temperature increased.

Table 3
Selective products for n-hexane hydroconversion on Co/HY and Ni/HY catalysts
Products Co/HY Ni/HY
300 8C 340 8C 380 8C 300 8C 340 8C 380 8C
Ethane (%) 5.11 6.42 2.14 4.96 3.38 3.26
Propane (%) 12.53 14.34 31.17 15.94 22.45 29.73
2-Metylpropane (%) 2.35 4.29 18.52 12.45 19.43 21.07
n-Butane (%) 0.32 4.84 11.22 8.67 8.82 10.70
2-Metylbutane 5.59 0.28 2.83 3.01 2.69 2.70
n-Pentane (%) 4.95 5.16 3.48 6.17 7.06 3.32
i-C6 (%) 69.15 64.67 30.64 48.80 36.17 29.23
Conversion (%) 24.65 25.47 50.57 37.36 43.17 52.80
i-C6 = 2-metylpentane; 3-metylpentane; 2,2-dimetylbutane and 2,3-dimetylbutane.
1110 A.M. Garrido Pedrosa et al. / Materials Research Bulletin 41 (2006) 11051111

Fig. 5. (a) n-Hexane total conversion on Co*/HY and Ni*/HY; (b) selectivity to n-hexane isomers (Si) and to cracking products (Sc) on Co*/HY (Co)
and Ni*/HY (Ni).

Catalytic tests for HY (results not shown) carried out at the same conditions established for the bifunctional
catalysts except for reduction step. At 300 8C predominantly indicated the formation of cracking products (ethane,
propane, n-butane, 2-metylbutane and n-pentane). C6-isomers were also formed, but in small amounts (<10%). This
suggested that n-hexane isomerization on Ni/HY and Co/HY catalysts occurred via the bifunctional mechanism, i.e.,
n-hexane was dehydrogenated on the metal phase and the n-hexene formed was protonated at Bronsted acid sites,
yielding a carbenium ion. After CC bond rearrangement, the isomeric carbenium ion desorbed as iso-hexene, which
was hydrogenated at metal phase, yielded C6-isomers. The results shown in Fig. 5b indicated that the Co/HY
bifunctional catalyst was more selective to paraffin isomerization than Ni/HY. These differences in the isomerization-
cracking activity and selectivity on Co/HY and Ni/HY could be correlated with differences in the acidity and
micropore area. Although the Ni/HY catalyst had smaller micropore area than Co/HY, the results of acidity (Table 2)
indicated that Ni-catalyst had higher density of acid sites than Co-catalyst. Such higher density collaborated to high
activity and selectivity to n-hexane cracking as well as to cracking of the branched products formed. From the results
shown in Fig. 5b, it could also be suggested that in Co/HY, the metallic sites were more dispersed on the support and
the ratio of metallic-to-acid sites was closer to ideal than in Ni/HY. The Ni/HY catalyst showed smaller selectivity to
isomerizated products at all reaction temperatures, suggesting that it has a low amount of metallic sites or low
dispersion of such sites which favors higher production of cracking products. Cracking of n-hexane on Bronsted acid
sites of zeolites has been studied, suggesting monomolecular [20,21], bimolecular [2224] and oligomeric [24,25]
 A.M. Garrido Pedrosa et al. / Materials Research Bulletin 41 (2006) 11051111 1111

reaction mechanisms. The monomolecular mechanism involves the direct protonation of an alkane to form a high-
energy transition state that resembles a strongly coordinated, non-classical penta-coordinated carbonium ion, which
subsequently cracks or dehydrogenates to yield an alkane and an alkene. The bimolecular cracking mechanism is the
classical chain process involving the transfer of a hydride between the reactant alkane and a smaller carbenium ion,
which was formed by the adsorption of an alkene on a Bronsted acid site, obtaining a smaller alkane product and a
reactant sized carbenium ion. Subsequent isomerization and b-scission of the reactant-sized carbenium ion produces
an alkene and another carbenium ion to complete the catalytic cycle. Oligomeric cracking involves the same essential
chemistry of the bimolecular cracking with the addition of alkylation reactions between an alkene adsorbed on a
Bronsted acid site and a second alkene molecule. The presence of metals, such as cobalt and nickel, favors activation
and hydrogen transfer reactions producing high paraffin/olefin ratios.

4. Conclusions

XRD and FTIR analyses showed the main peaks and bands characteristic of the Y structure in all samples. Both ion
exchange and impregnation decreased the micropore area and volume due to the reduction in the accessibility to
micropores. The impregnation of cobalt and nickel ions leads to a distribution of cobalt and nickel oxide inside the pore
system of HY zeolite. TPR profiles showed two peaks for nickel reduction in Ni*/HYand one peak for cobalt reduction in
Co*/HY. Higher density of acid sites was obtained on HY catalyst followed by Ni*/HYand Co*/HY. The incorporation of
cobalt and nickel in HY zeolite promoted the formation of materials with catalytic activity in the n-hexane
hydroconversion. The hydroconversion reactions occurred with the formation of normal and branched alkanes. The
selectivity to cracking products could be ranked as C3 > C5 > C2 > C4 and the selectivity to C6 isomers was 69% at
300 8C. An increase in the conversion degree with temperature was observed. On the other hand, the best C6 isomer
selectivity was observed at low temperatures due to the inhibition of catalytic cracking activity. The formation of olefins
was not observed, confirming the good hydrogenation performance of cobalt and nickel species on HY zeolite.

Acknowledgement

The authors acknowledge the Agencia Nacional do Petroleo (MCT/MME/PRH/ANP-30) for its financial support.

References

[1] A. Chica, A. Corma, P.J. Miguel, Catal. Today 65 (2001) 101.

[2] G. Onyestyak, G. Pal-Borbely, H.K. Beyer, Appl. Catal. A: Gen. 229 (2002) 65.
[3] G.D. Zakumbaeva, T.V. Van, A.I. Lyashenko, R.I. Egizbaeva, Catal. Today 65 (2001) 191.
[4] G. Boskovic, R. Micic, P. Pavlovic, P. Putanov, Catal. Today 65 (2001) 123.
[5] Z.B. Wang, T. Yashima, T. Komatsu, A. Kamo, T. Yoneda, Appl. Catal. A: Gen. 159 (1997) 119.
[6] V. Nieminen, N. Kumar, J. Datka, J. Paivarinta, M. Hotokka, E. Laine, T. Salmi, D.Yu. Murzin, Micropor. Mesopor. Mater. 60 (2003) 159.
[7] W. Zhang, P.G. Smirniotis, J. Catal. 182 (1999) 400.
[8] R.M. Jao, L.J. Leu, J.R. Chang, Appl. Catal. A: Gen. 135 (1996) 301.
[9] P. Canizares, F. Dorado, P. Sanchez-Herrera, Appl. Catal. A: Gen. 217 (2001) 69.
[10] H. Yasuda, T. Sato, Y. Yoshimura, Catal. Today 50 (1999) 63.
[11] G.C. Bond, Heterogeneous Catalysis: Principles and Applications, Oxford Science Publications, New York, 1987.
[12] J.A. Martens, P.A. Jacobs, J. Weitkamp, Appl. Catal. 20 (1986) 239.
[13] E.A. Havenga, Y. Huang, R.A. Secco, Mater. Res. Bull. 38 (2003) 381.
[14] J. Weitkamp, Solid State Ionics 131 (2000) 175.
[15] D. Klint, J.O. Bovin, Mater. Res. Bull. 34 (1999) 721.
[16] Q.Z. Zhai, T.S. Jiang, W.H. Hu, X. Guan, W. Wang, S. Qiu, Mater. Res. Bull. 37 (2002) 1837.
[17] W.M. Meier, D.H. Olson, C. Baerlocher, Atlas of Zeolite Structure Types, Elsevier, New York, 1996.
[18] A.M. Garrido Pedrosa, M.J.B. Souza, D.M.A. Melo, A.S. Araujo, L.B. Zinner, J.D.G. Fernandes, A.E. Martinelli, Solid State Sci. 5 (2003) 725.
[19] A.M. Garrido Pedrosa, M.J.B. Souza, D.M.A. Melo, A.G. Souza, A.S. Araujo, J. Therm. Anal. Cal. 75 (2004) 439.
[20] G. Puente, U.S. Sedran, J. Catal. 179 (1998) 36.
[21] B.W. Wojciechowski, Catal. Rev.-Sci. Eng. 40 (1998) 209.
[22] Y.V. Kissin, J. Catal. 163 (1996) 50.
[23] P.V. Shertukte, G. Marcelin, G.A. Sill, W.K. Hall, J. Catal. 136 (2) (1992) 446.
[24] Y.X. Zhao, G.R. Bamwenda, B.W. Wojciechowski, J. Catal. 142 (2) (1993) 465.
[25] J.S. Buchanan, J.G. Santiesteban, W.O. Haag, J. Catal. 158 (1) (1996) 279.