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Role of Structure and Acidic Nature on Catalytic Behavior of Nickel Supported H-mordenite, H-ZSM-5, and alumina Catalysts
M. S. Ghattas , H. M. Gobara , S. A. Henin , S. A. Hassan & F. H. Khalil
a b a a a b a

Catalysis Department, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt Chemistry Department, Faculty of Science, Ain Shams University, Abbasia, Cairo, Egypt

Available online: 24 Oct 2007

To cite this article: M. S. Ghattas, H. M. Gobara, S. A. Henin, S. A. Hassan & F. H. Khalil (2007): Role of Structure and Acidic Nature on Catalytic Behavior of Nickel Supported H-mordenite, H-ZSM-5, and alumina Catalysts, Petroleum Science and Technology, 25:10, 1279-1291 To link to this article: http://dx.doi.org/10.1080/10916460600803645

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Petroleum Science and Technology, 25:12791291, 2007 Copyright Taylor & Francis Group, LLC ISSN: 1091-6466 print/1532-2459 online DOI: 10.1080/10916460600803645

Role of Structure and Acidic Nature on Catalytic Behavior of Nickel Supported H-mordenite, H-ZSM-5, and alumina Catalysts
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M. S. Ghattas, H. M. Gobara, and S. A. Henin
Catalysis Department, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt

S. A. Hassan
Chemistry Department, Faculty of Science, Ain Shams University, Abbasia, Cairo, Egypt

F. H. Khalil
Catalysis Department, Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt

Abstract: Nickel metal was loaded in different percentages (7, 10, and 13% w/w) on different supports (H-mordenite, H-ZSM-5, and alumina). The prepared catalyst samples were tested in cyclohexane conversion using microreactor pulse technique. Structure was followed up by XRD analysis. Chemisorption of tert-butylamine (TBA) was adopted for estimating the number of surface acid sites. It was found that all prepared samples displayed cracking activity, being mostly related to the fraction of acid sites remaining on the surface after coverage with supported Ni atoms. Hmordenite-supported samples exhibited mainly isomerization functionality by showing a larger portion of surface acid sites. H-ZSM-5-supported samples showed higher dehydrogenation activity. Agglomeration seemed to be responsible for lower activity of the sample of higher Ni content. The formed NiOOH phase was suggested to be responsible for increased dehydrogenation activity on H-ZSM-5 samples and increased cracking activity on alumina-supported samples of higher Ni content. Keywords: alumina, acidity, cyclohexane conversion, H-mordenite, H-ZSM-5, metal-support interaction

Address correspondence to Maged Samir Ghattas, Petroleum Rening Division, Egyptian Petroleum Research Institute, Nasr City, Cairo 11727, Egypt. E-mail: msg_ epri@yahoo.com 1279

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INTRODUCTION Bifunctional catalysts with metallic and acidic functionality are used in numerous industrial processes in petroleum rening and in petrochemical industries. Transition metal can catalyze reactions such as isomerization, (de)hydrogenation, and hydrogenolysis of hydrocarbons. Catalytic hydrocracking is an essential process in a modern renery for the conversion of middle and heavy distillates and residuals into more valuable products (Arroyo et al., 2000). Zeolites play an important role in the catalysts used in hydrocarbon conversion because they improve catalytic activity, selectivity, or stability by imparting shape selectivity (Blauwhoff et al., 1999; Jensen et al., 2002; Habib and Dahlberg, 2002; Van Veen et al., 2002; Corma et al., 2002; Kramer et al., 2001; Daage et al., 2002). It is well known that zeolites such as ZSM-5 (Gervasini, 1999; Iwamoto et al., 1988) and mordenite (Haag and Lago, 1983; Lzaro et al., 1991; Caizares et al., 1998) can be modied by incorporating metals such as Cu, Co, Ni, Mn, Ga, etc., in order to obtain catalysts for these industrial processes. Nickel catalysts are considered cheap economic substitutes for platinum catalysts toward conversion of hydrocarbons. They play different roles such as cracking, isomerization, and (de)hydrogenation catalysts according to their support and nickel percent loading. The state of nickel on some supports, such as alumina and HY zeolite, can be strongly modied causing surprising changes of the catalytic properties. For example, the well-known hydrogenolysis activity of nickel could be suppressed, whereas its dehydrogenating property increased and became predominant in some cases (Lanh et al., 1991; Hoang et al., 1994). The acid-site, metal-site densities, and acid-strength distribution are important parameters where their proper balance is critical in determining the activity of these catalysts (Taylor and Petty, 1994; Walters et al., 1995). The presence of a metal on zeolite surfaces may modify the Brnsted centers (Minchev et al., 1994) and the metal state may be modied by the inuence of the support (Lanh et al., 1991). This work was undertaken to study the effect of nickel-support interaction in different samples composed of nickel with different percentage loadings (namely, 7, 10, and 13%) on the catalytic activity of the catalysts under investigationthe support chosen being H-mordenite, H-ZSM-5, and alumina.

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EXPERIMENTAL Catalyst Preparation H-Mordenite, H-ZSM-5, and Al2 O3 were treated as follows:

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(1) H-Mordenite (Si/Al ratio 10.8) was obtained by treatment of Namordenite (School of Chemical Engineering, Seoul Natl University, Seoul) with 0.2 N NH4 Cl solution with stirring for 72 hr at room temperature, then washed with distilled water til free from chloride ions. The slurry was dried at 120C and calcined at 400 C in a stream of air for 4 hr. (2) H-ZSM-5 was obtained by a treatment of Na-ZSM-5 (of high Si/Al ratio D 80 supplied by the Institute of Organic Chemistry, Academy of Science, Moscow), rst by heating in a stream of air at 550C to exclude organic matters, then applying the same procedure as described for Namordenite. (3) Al2 O3 (specic surface area D 230 m2 g 1 , pore volume D 0.72 c.c. g 1 , and containing Na2 O3 and Fe2 O3 < 0.02 wt%) supplied by the Institute of Catalysis (Novisipersk, Russia) and was calcined at 450C in a stream of air for 6 hr. The supported samples were prepared by impregnating the required amount of the support with nickel nitrate hexahydrate solution of the proper concentration. The obtained slurry was stirred vigorously for 15 min and dried at 110C for 16 hr, then calcined at 200 C for 4 hr in a stream of air. To effect homogenity, the produced oxide was reduced using in a ow of H2 at 350C for 4 hr.

Catalyst Characterization X-ray Diffraction (XRD) Analysis The x-ray diffraction (XRD) analysis for all metal oxide catalyst samples was carried out using x-ray diffraction equipment model PW/1710 (Philips Company, the Netherlands) using an Ni lter and Cu k-radiation ( D 1:542 ) at 40 kV and 30 mA. Acidity Determination The chemisorption of t-butyl amine (TBA) was applied in order to estimate the surface acidity (Andrs et al., 1990) of all catalyst samples at the appropriate temperature, i.e., far from its physical adsorption and before its catalytic decomposion of TBA. A microreactor pulse technique was applied. 0.5 g of dry sample was preheated at 450 C for 2 hr in a stream of hydrogen. The adsorption of TBA was carried out under atmospheric pressure using a ow rate of 30 ml/min. T-butyl amine was injected in doses of 2 L to the sample cell in a stream of hydrogen as a carrier gas. The desorbsion peaks of TBA after complete neutralization of all surface acid sites were detected using computerized data acquisition.

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Catalytic Activity The catalytic activities of the prepared catalysts were tested by cyclohexane dehydrogenation as a model reaction using a microcatalytic pulse technique. The microreactor was lled with 0.25 g of the tested catalysts. The products were then directly passed through a chromatographic column, 200 cm in length and 0.6 cm in internal diameter packed with acid washed PW and (6080 mesh size) loaded with 15% by weight squalane adjusted and controlled at 40 C. A am ionization detector (FID) was used. The reactions were carried out under atmospheric pressure in the temperature range 180C 450 C. Hydrogen ow rate and cyclohexane doses were kept constant at 50 ml/min and 2 L, respectively. A computerized data acquisition was used for integration and recording the efuents yield.

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RESULTS AND DISCUSSION X-ray Diffraction Analysis Ni/Hmordenite (Ni/H-M) Catalysts The XRD pattern of H-mordenite support is shown to be diminished upon loading with nickel in different percentages (Figure 1), retaining the characteristic lines of the different faces, although with less intensity. No characteristic lines of different Ni species could be detected. Ni/H-ZSM-5 Catalysts Figure 2 indicated that XRD patterns of the supported nickel samples differ from the traditional one of H-ZSM-5, only in that a new peak at d D 6:9 characterizing most probably NiOOH (ASTM card No. 6-75). This phase seems to be formed due to the interaction between NiO with the free OH present in the framework of the support. The intensity of this phase increases by increasing Ni content especially in highly loaded samples (10 and 13% w/w Ni). No characteristic peaks of NiO phase could thus be detected. One may suggest that a fraction of the formed nickel species can be imbedded in the channels or the cages of the support, being more pronounced in the sample containing 7% Ni. This may conrm the possibility of interaction of this phase with OH of the support and formation of NiOOH in the samples of higher Ni content. Ni/ alumina Catalysts The obtained XRD pattern of the used alumina support (Figure 3) is characteristic for the alumina (ASTM card No. 10-425) with the indicated dspacing. No sign of a presence of an NiO phase in the case of the supported

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Figure 1. XRD of nickel/H-M catalysts.

sample. One cannot exclude the possibility of formation of the strong interaction phase of nickel aluminate (NiAl2 O4 ), d-spacing of which (2.43, 2.01, 1.54, and 1.42 ) seem to overlap with these characteristic peaks of alumina shown. Moreover, for the catalyst of the higher nickel loading (viz., 13% w/w), a small peak is observed with d-spacing D 6.7 , which may be referred to the NiOOH phase starting to be formed at this high content. Acidities of the Catalysts Under Investigation The acidities expressed in mole TBA adsorbed per g catalyst, for different supports, and supported Ni samples are summarized in Table 1. These values

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Figure 2. XRD patterns of Ni/H-ZSM-5 catalysts.

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Figure 3. XRD of nickel/ alumina catalysts.

were converted into the number of acid sites on the surface of 1-g catalyst samples. It is clearly evident that the acidity of the pure support run in order, H-mordenite > H-ZSM-5 > alumina. Mordenite has the highest acidity most probably due to textural structure where Si/Al ratio 10.8, whereas it is 80 in case of high silica H-ZSM-5, which consequently have less OH groups. In all supported samples, acidity decreases gradually with the increase in Ni wt%. Acidity suffers a greater decrease compared to the original support in the sample of 7% wt after which the decrease becomes monotonous. Considering the percentage of the total acid sites existing on each support that being covered by the supported Ni species, it appears that the highest coverage with Ni species takes place in the order H-ZSM-5 > H-mordenite >

1286 Table 1. Acidity function of the investigated catalysts Catalysts H-Mordenite (supp.) 7% Ni/H-Mordenite 10% Ni/H-Mordenite 13% Ni/H-Mordenite H-ZSM-5 (supp.) 7% Ni/H-ZSM-5 10% Ni/H-ZSM-5 13% Ni/H-ZSM-5 -Al2 O3 (supp.) 7% Ni/ -Al2 O3 10% Ni/ -Al2 O3 13% Ni/ -Al2 O3
a TBA b TBA

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mole/g catal. 536a 263a 236a 177a 214b 114b 108b 93b 107c 93c 79c 63c

No. acid sites/g catal. 2:14 1:58 1:42 1:07 1:29 6:84 6:94 5:58 6:41 5:6 4:76 3:78 1020 1020 1020 1020 1020 1019 1019 1019 1019 1019 1019 1019

% acid sites covered by Ni 26.2 33.6 50.0 47.0 46.0 56.7 12.6 25.7 41.0

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adsorption at 200C. adsorption at 250C. c TBA adsorption at 160 C.

alumina. This means that the remaining exposed acid sites are greater in H-mordenite-supported surface than on H-ZSM-5, which should reect on the isomerization activity. Moreover, the Brnsted acids are known to be converted to Lewis acids at a higher temperature >350 C (Ghattas, 1995) leading to higher cracking products with the original Lewis acid formed in mordenite support. The fraction of nickel interacted with the support surface is larger on H-ZSM-5 than on H-mordenite and alumina (as evidenced from XRD analysis). It should take into consideration that the pore structure of the support plays a role in the evolution of the acidity. Blocking of micropores by Ni atoms may take place in H-mordenite and H-ZSM-5, whereas alumina have wider pores that permit penetration of Ni atoms inside. Catalytic Activity of the Catalysts Under Investigation Cyclohexane Conversion over Ni/H-mordenite Figure 4 represents the catalytic conversion of cyclohexane over Ni/H-mordenite catalysts (7, 10, and 13 w/w Ni). Over these catalysts, cyclohexane isomerization is more pronounced than its dehydrogenation, which seems to be due to the presence of strong Brnsted acid sites being increased by increasing both nickel-loading and reaction temperature up to 270C. At a temperature

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Figure 4. Catalytic conversion of cyclohexane over Ni/H-mordenite catalysts: (a) 7% Ni, (b) 10% Ni, and (c) 13% Ni.

more than 270C, the formation of other products probably, propane may be favored according to thermodynamic feasibility. Cracking yield in mole percentage and selectivity increase with the increase in reaction temperature and nickel-loading. It achieves 100% at 360C on the catalyst sample containing 13% w/w Ni. Isomerization reaction occurs at low temperatures (viz., 210C360C), while cracking is more favored at a higher temperature (viz., 360C480C).

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Figure 5. Catalytic conversion of cyclohexane over Ni/H-ZSM-5 catalysts: (a) 7% Ni, (b) 10% Ni, and (c) 13% Ni.

The two reactions seem to take place at different acid sitesBrnsted for isomerization and Lewis acid sites for cracking. The result in general run in harmony with those of acidity data. Cyclohexane Conversion over Ni/H-ZSM-5 The results illustrated in Figure 5 indicated that both cracking and dehydrogenation of cyclohexane take place with no isomerization products. Referring

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to results of acidity, the cracking activity can be referred to the remaining exposed acid sites (after covering with nickel), being less than those existing in H-mordenite supported samples. The dehydrogenation activity appears to decrease with the increase in nickel percentage loading. This can be understood in view of the narrower pore system of H-ZSM-5, where more fractions of nickel atoms will exist on the surface in larger aggregates of lower dehydrogenation activity, becoming more pronounced on the catalyst sample of 13% Ni by weight. The absence of isomerization products can also be interpreted in view of the observation that the major fraction of surface nickel and probably NiOOH species formed (cf. XRD results) is site-interacted with the support acid sites remaining only acid site exposed for the isomerization reaction. Cyclohexane Conversion over Ni/ alumina Low yield of cyclohexane dehydrogenation to benzene was observed over Ni/ alumina catalysts as shown in Figure 6. It exhibits higher cracking activity, which increases by elevating the nickel-loading and reaction temperature. The much-less dehydrogenation activity may be referred to the lessexposed nickel species as a result of the formation of a strong interaction phase, namely, NiAl2 O4 with the defective tetrahedral sittings of alumina. The cracking activity seems to result from some remaining acid sites of the alumina surface after being covered by nickel atoms. Moreover, the produced NiOOH species, especially in the sample of high nickel content (viz., 13% w/w) may also be responsible for this cracking activity (refer to XRD results).

CONCLUSIONS The following conclusions may be drawn. The three types of investigated catalysts, Ni/H-mordenite, Ni/H-ZSM-5, and Ni/ Al2O3 , were found to display cracking especially in the high temperature range, 360 C480C. Most of the fraction of acid sites remained on H-mordenite > H-ZSM-5 after being covered with supported nickel atoms. NiOOH phase formed in Al2 O3 -supported samples (especially of 13% Ni w/w) played an additional role in cracking activity. H-mordenite-supported samples were considered as isomerization catalysts. The remaining acid site on the support surface after being covered with Ni atoms appear operating factor in this reaction (especially the sample of 13% Ni w/w). H-ZSM-5-supported samples were considered as dehydrogenation catalysts. The fraction of exposed Ni atoms existing, mainly covering the extent of its acid sites, appear as operating factors which associate in less active larger particles in the sample of higher Ni content.

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Figure 6. Catalytic conversion of cyclohexane over Ni/ alumina catalysts: (a) 7% Ni, (b) 10% Ni, and (c) 13% Ni.

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