Applied Catalysis A: General 185 (1999) 259268

Coking and deactivation during n-hexane cracking in ultrastable zeolite Y

Boontham Paweewan, Patrick J. Barrie , Lynn F. Gladden
Department of Chemical Engineering, University of Cambridge, Pembroke Street, Cambridge CB2 3RA, UK Received 25 February 1999; received in revised form 5 May 1999; accepted 6 May 1999

Abstract A multi-technique approach has been used to investigate coke formation and the effects of coke formation during n-hexane cracking on ultrastable zeolite Y. The product analysis reveals that propane and propene are the major products, and this suggests that the reaction initiation step may be direct protonation at very strong Brnsted acid sites. The coke formed does not change in composition signicantly over the course of the reaction. Infrared spectroscopy reveals that the vast majority of Brnsted and Lewis acid sites are still present in the catalyst, even when the catalyst activity has become low. Diffusion measurements using pulsed eld gradient (PFG) NMR show that the mobility of adsorbed n-butane or n-hexane is not affected by the presence of the coke, and so shows that pore blockage is not a signicant factor. Based on the experimental results, it is argued that selective site poisoning of a few very strong acid sites is the main deactivation mechanism for this reaction under the conditions employed. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Coking; Deactivation; Cracking; Zeolite Y; Poisoning, selective site

1. Introduction Catalytic cracking over zeolite-based catalysts is an important reaction in the petrochemical industry. It is generally accepted that the initial cracking activity is principally due to the Brnsted acidity of the zeolite, and the reaction mechanism has been investigated extensively [14]. However, the reaction is a complex one and results from one zeolite-reactant system are not necessarily directly applicable to another. The catalyst may have a range of different Brnsted acid sites present with varying degrees of acidity, and the Lewis acid sites present may also have an inuence. Characterisation of acid sites in zeolites has thus been

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studied using a wide variety of different techniques [510]. The combined inuence of the range of different strength acid sites and pore diffusion has also been considered [11]. The situation is complicated by the fact that catalyst deactivation takes place during the cracking reaction. The major cause of deactivation under laboratory conditions is the formation of carbonaceous residues known as coke within the catalyst. A wide variety of analytical techniques have been used to study both the formation of coke and its inuence on deactivation [1217]. Despite previous work, there is still no generally accepted model for coke formation and, more importantly, for predicting the effects of the coke on catalyst activity and selectivity [18]. Thus, an important research topic is the identication of the mechanism as to how coke causes deactiva-

0926-860X/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 1 4 3 - X

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tion during a particular cracking reaction on a specic zeolite. While n-hexane and n-heptane cracking on zeolite Y have previously been studied by several groups of workers [13,17,1927], there remain differences in interpretation of the coke formation and deactivation mechanism for this reaction. Coke can affect the catalytic activity of zeolites through both site poisoning and pore blocking mechanisms, and it is important to be able to distinguish between the two. Further, the coke formed may not necessarily be distributed homogeneously throughout the zeolite particles. For instance, a recent paper found that a large decrease in activity occurred even though only few acid sites were poisoned, and it was proposed that the reaction was diffusion limited [25]. For a diffusionlimited reaction, n-hexane cracking and coke deposition will occur primarily near the external surface of the zeolite crystallites, with little reaction at the particle interior. Other workers have suggested that the initial deactivation for this reaction is based on site poisoning [20,21], while others have found that the coke limits access of the reactant to the active sites [13,17,23]. In a previous paper, we adopted a multi-technique approach to investigate coke formation and the deactivation mechanism during the conversion of ethene on ultrastable zeolite Y at 773 K [28]. It was found that both site poisoning and pore blockage played signicant roles. In this paper, we report results on n-hexane cracking in ultrastable zeolite Y using the same range of techniques. The products were analysed using gas chromatography, and the chemical nature of the coke formed, and its inuence on the number of acid sites and molecular transport, were studied using infrared and NMR spectroscopic methods. The results shed new light on the deactivation mechanism for this particular reaction, and resolve some of the contradictions in the literature.

2. Experimental The sample of steamed zeolite Y, denoted HUSY, used in this work came from the same batch as that used in our study on coke formation during ethene conversion on ultrastable zeolite Y [28]. The sample

has been well characterised previously [29] and has a framework Si/Al ratio of 4.15 (based on unit cell parameter) and a bulk Si/Al ratio of 2.65 from Xray uorescence measurements. Coke was generated by passing nitrogen at 50 ml/min through a saturator containing n-hexane at 303 K, and then on to a xed bed reactor containing 500 mg of calcined catalyst at 773 K. The products from the reaction were analysed using a Phillips Pye 4500 gas chromatograph (GC) equipped with a ame ionisation detector and a Porapak Q column. After a specied time on stream, the saturator was bypassed, and the reactor cooled down to room temperature under the nitrogen atmosphere. Coked samples were obtained in this way after 5, 10, 15, 25, 65, 125, 185 and 245 min of time on stream. The integrity of the coked samples was checked by powder X-ray diffraction, and the samples were then examined by a variety of techniques. One portion of the coked sample after 125 min on stream was checked for catalytic activity for ndodecane cracking. In this experiment, n-dodecane was fed at a rate of 0.1 ml/min using a peristaltic pump in a ow of nitrogen at 50 ml/min to the reactor at 773 K, and the light products were analysed using a gas chromatograph as above. Negligible thermal cracking was observed when the catalyst was absent. The BET surface area was obtained by analysing nitrogen adsorption at 77 K in a conventional volumetric apparatus (Micromeritics ASAP 2000). Each coked sample was pre-treated by heating to 673 K at 105 Torr for 12 h in order to remove all water prior to starting the BET adsorption isotherm experiment. The weight percent of coke present in the samples was estimated by thermogravimetric analysis (TGA). The sample was heated to 973 K at a rate of 10 K/min in an inert gas to remove water, and the weight loss at that temperature when the gas was switched to air was measured. Infrared spectra were obtained on a Nicolet Magna 750 FT-IR spectrometer equipped with a Spectra Tech 0030-102 diffuse reectance assembly. Each coked sample was heated in a helium gas ow to 673 K to remove water present in the pore space before recording the spectrum at elevated temperature. Infrared spectra were also obtained on pyridine adsorbed within

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the catalyst. For these measurements, the sample were exposed to pyridine vapour at 573 K for 10 min, and then left in a ow of helium gas at that temperature for 5 min, before recording the spectrum at room temperature. The spectra are plotted assuming the model of Kubelka and Munk for diffuse reectance [30], with the KubelkaMunk function being analogous to absorbance [31]. 13 C solid state NMR spectra were obtained at 50.32 MHz on the coked samples using crosspolarisation (CP), magic-angle spinning (MAS) and high-power proton decoupling on a Bruker MSL200 spectrometer. Spectra were acquired overnight using a contact time of 1 ms and a recycle delay between scans of 1 s. The sample spinning rate was 4 kHz, and spinning sidebands were suppressed using the ve -pulse TOSS method [32]. Chemical shifts are quoted relative to external tetramethylsilane (TMS). Diffusion measurements on n-butane and n-hexane adsorbed within the fresh zeolite and the coked samples were made using pulsed eld gradient (PFG) NMR spectroscopy [3335]. For the diffusion measurements, either n-butane or n-hexane were adsorbed into each sample at a loading of approximately 10 molecules per unit cell. The 1 H NMR spectra were acquired at 200.13 MHz. After measuring the T1 and T2 nuclear relaxation times to aid choice of the acquisition parameters, diffusivities were measured using the PFGLED pulse sequence. This uses a stimulated echo and minimises any errors due to eddy current effects [36]. For single-component diffusion, the signal intensity is expected to follow the form ln(I/I0 ) = 2 g2 2 D( /3) where I is the observed intensity, I0 the intensity in the absence of gradient pulses, the gyromagnetic ratio of 1 H, g is the applied eld gradient amplitude, is the length of the gradient pulse, the interval between the gradient pulses, and D the diffusion coefcient [3436]. For measurements on adsorbed n-butane, was varied while maintaining g at 1 T/m and at 10 ms. For measurements on adsorbed n-hexane, was again varied, with g and xed at values of 2 T/m and 160 ms, respectively. Due to the presence of both intercrystalline and intracrystalline diffusion, it was necessary to analyse the experimental data assuming the presence of two distinct diffusion components using a least-squares tting routine.

Fig. 1. Plot of n-hexane conversion (circles, left axis) and coke content (squares, right axis) as a function of time on stream.

3. Results and discussion 3.1. The reaction A typical plot of n-hexane conversion against time on stream, together with the coke loading, is shown in Fig. 1. It is known that signicant deactivation occurs during the rst minute of time on stream [22]. It can be seen that the activity continues to drop rapidly during the rst 60 min or so of the reaction, and the conversion becomes close to zero after 180 min. The line shown in Fig. 1 for the conversion uses the exponential decay equation X = X0 exp(kd t), where X is the conversion at time t, X0 conversion at zero time, kd the deactivation rate constant and t the time on stream. The product selectivities during the reaction are shown in Fig. 2. The major products are the C3 hydrocarbons propene and propane (not resolved by the gas chromatograph column used), with the other products being in the C1C4 range. During the rst 60 minutes, an increasing proportion of the products are C1 and C3 species, while the relative amount of C4 species decreases. The proportion of C2 species remains roughly constant. The generally accepted theory of the cracking of alkanes on a solid with acid sites is that cracking proceeds via formation of a tricoordinated carbenium ion as an intermediate, which then undergoes -scission to form an alkene fragment and a carbenium ion fragment [37,38]. However, it has been suggested that for-

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Fig. 2. Plot showing product selectivity as a function of time on stream.

mation of primary carbenium ions is unlikely to occur, and that the intermediate may in fact be a protonated cyclopropane species [39,40]. Direct protonation of hydrocarbons to form pentacoordinated carbonium ions provides an alternative cracking mechanism and this has been suggested to occur when very strong Brnsted acid sites are present at high temperatures; this route is expected to be signicant when the reactant is difcult to crack [39,41]. A combination of the mechanisms has been proposed: initial formation of a pentacoordinated ion will be followed by protolytic ssion to give an alkene and an adsorbed carbenium ion that will then react further [3,42]. Bimolecular reactions, involving hydrogen transfer between the reactant and adsorbed carbenium ions, may also then occur in a chain mechanism to produce a range of products [3]. Coke may be formed within the catalyst from bimolecular interactions between adsorbed species [3]. The main area of uncertainty in the proposed reaction mechanisms is the initiation step in which the rst reactive ion is formed. Reaction at Lewis acid sites has

been proposed as an alternative initiation step for the cracking mechanisms [4345], but other groups have found that Lewis acid sites do not play a signicant role during the cracking of light hydrocarbons [46]. Thermal cracking has been suggested as a possible initiation step during the cracking of heavy hydrocarbons [47]. The product distribution is shown in Fig. 2 and is similar to that obtained recently in the literature under conditions favouring monomolecular cracking [27]. It is worth observing that -scission of the most stable C6 carbenium ions that can be formed (in principle at Lewis acid sites or by bimolecular hydrogen transfer reactions) would give C2 and C4 species, and that these are only observed in relatively small quantities in the reaction under investigation. The observation of C3 species as dominant products in Fig. 2 thus suggests that the major mechanism occurring in this catalyst is in fact direct protonation of one of the middle carbons of the n-hexane molecule at very strong Brnsted acid sites to form a non-classical pentacoordinate carbonium ion. The protonation would then be followed by ssion into propane and a C3 carbenium ion. The carbenium ion may react further, or lose a proton to form propene. Direct protonation followed by ssion is also a source of the C2 and C4 products, as is the carbenium ion mechanism. It is, of course, possible that C4 species can react further in the catalyst (e.g. to give C1 and C3 species). Thus, the increasing selectivity towards methane as the reaction proceeds is due to transformation of products rather than direct protolytic cracking. These results are consistent with some recent studies on n-hexane cracking in dealuminated zeolite Y [24] and for n-hexane cracking in ZSM-5 zeolite [4850]. The possibility that initiation of the reaction may occur only at a few very strong active sites, which is suggested by the observed product distribution, is discussed further below when the deactivation mechanism is considered.

3.2. The chemical nature of the coke formed The total amount of coke formed was determined by thermogravimetric analysis and is shown in Fig. 1. It can be seen that it only takes a small amount of coke to have a large effect on catalytic activity. It can also be

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Fig. 3.

13 C

MAS NMR spectra of coked samples after a time on stream of: (top) 25 min; (middle) 125 min; (bottom) 185 min.

seen that coke continues to form even after 120 min reaction time when the catalyst activity is low. However, the amount of coke formed during n-hexane cracking is signicantly less than that formed during ethene oligomerisation on the same catalyst under identical conditions [28]. In order to probe the chemical identity of the coke formed, both 13 C solid state NMR spectroscopy and infrared spectroscopy were used. 13 C solid state NMR spectroscopy has been used previously to characterise coke formed in zeolite cata-

lysts [28,5155]. In this work, we achieved high quality 13 C spectra using the cross-polarisation (CP) technique at natural abundance without any chemical treatment. Spectra are shown in Fig. 3. Two major spectral regions can be identied: the asymmetric peak at 130 ppm is associated with aromatic carbon environments (though polyalkenes also resonate in this region), while the peaks at 1050 ppm are associated with saturated aliphatic carbon species. One frequently used parameter in coal chemistry is the aromaticity,

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Fig. 4. FTIR spectra (CH stretching region) of dehydrated HUSY after a time on stream of: (a) 10 min; (b) 65 min; (c) 185 min.

Fig. 5. FTIR spectra (OH stretching region) of dehydrated HUSY after a time on stream of: (a) 0 min (fresh catalyst); (b) 65 min; (c) 245 min.

dened as the fraction of carbon present in the sample that is in aromatic environments [56]. From the spectra we obtain aromaticities (2%) of 71% for the sample after 15 min on stream, 75% after 25 min on stream, 80% after 125 min on stream and 78% after 185 min on stream. Thus, there may be a small increase in the aromaticity of the coke in the early stages of the reaction, but it does not change signicantly after reaching a limit of 7880% for this reaction. This may be contrasted to the case for ethene conversion in ultrastable zeolite Y under the same conditions, in which the coke becomes fully polyaromatic [28]. Infrared spectroscopy has also commonly been used to study the chemical nature of coke within zeolites. The so-called coke band indicating polyalkenes or polyaromatic species at around 1600 cm1 is a good indicator of the presence of coke [57]. Infrared spectra recorded using diffuse reectance show a peak at 1590 cm1 that increases in intensity with longer times on stream; this indicates the presence of aromatic species in agreement with the 13 C NMR results. There are no other peaks in the region 14001800 cm1 . The spectra of the CH stretching regions are shown in Fig. 4. A broad band is observed centred at about 3070 cm1 , indicating CH stretches associated with aromatic or polyalkene carbon environments. The bands at 2960 and 2930 cm1 are due to CH3 and CH2 asymmetric stretching modes, and these indicate the presence of aliphatic carbon in the coke. The intensities of all the bands in the CH stretching region increase with time on stream reect-

ing the larger amounts of coke present. The fact that the relative peak intensities remain approximately constant after 1025 min time on stream indicates that the aromaticity of the coke does not change signicantly after this stage under the conditions employed; this is in agreement with the 13 C NMR results. This may be contrasted to the case for ethene conversion in ultrastable zeolite Y under the same conditions, in which the CH bands became too weak to detect by IR spectroscopy as the coke became exclusively polyaromatic [28]. 3.3. The effect of coke formation Coke may affect catalyst activity and selectivity through site poisoning (consumption of active acid sites) or pore blocking, which will affect the available surface area and the molecular mobility of reactant and products. The distribution of coke within the catalyst is also an important consideration. Direct measurements of this have been difcult to obtain, but there has been some success using the 129 Xe NMR technique [53,5861]. The acid sites present in the coked samples were characterised by FTIR spectroscopy, including pyridine adsorption measurements. Fig. 5 shows the spectra of the dehydrated catalyst in the OH stretching region. In the fresh HUSY catalyst, there are three OH stretching bands at 3736, 3660 and 3585 cm1 and these are attributed to terminal silanol groups, to Brnsted acid sites in the supercages, and to Brnsted

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Fig. 6. FTIR measurements of adsorbed pyridine on HUSY after a time on stream of: (a) 0 min (fresh catalyst); (b) 65 min; (c) 245 min.

acid sites in the smaller sodalite cages, respectively [62,63]. There may also be a contribution from extraframework AlOH groups in this region. It can be seen that there is no reduction in the number of acid groups detected with increasing time on stream, even after four hours reaction time. This indicates that the majority of active centres are not removed during deactivation by coking under the reaction conditions employed. Some workers have reported the presence of an OH stretching band at 3600 cm1 in zeolite Y after chemical dealumination, or after steam dealumination followed by acid leaching, and this band has been assigned to particularly strong Brnsted acid sites [6469]. The intensity of this band has been found to decrease during n-hexane cracking, and so it may well be these sites that are removed during the coking reaction [68,69]. However, this band is only rarely observed for steam dealuminated zeolite Y samples (unless acid leaching is also performed), and it is not resolved in the spectra shown in Fig. 5. No rm conclusion can therefore be drawn from our FTIR spectra alone about whether any particularly strong acid sites are affected by coking. One method to quantify Brnsted and Lewis acid sites is by using pyridine adsorption in conjunction with infrared spectroscopy. FTIR spectra on pyridine within the fresh and coked catalysts are shown in Fig. 6. The band at 1546 cm1 is characteristic of pyridine bonded to a Brnsted acid site, while that at 1453 cm1

is characteristic of pyridine bonded to a Lewis acid site [5]. Other bands in this spectral region are due to other vibrational modes for pyridine which overlap and so do not easily distinguish between the different acid sites present. For the coked sample after 65 min reaction time, there is no signicant reduction in signal intensity of either of the two characteristic bands, and adsorbed pyridine can still easily be observed in the FTIR spectra of the sample that had 245 min time on stream. The BET surface area of the coked samples was found to remain high, being 610 m2 /g for the fresh catalyst, and 518 m2 /g after 125 min on stream. However, the small size of the nitrogen molecule means that the BET surface area is not necessarily a good indicator of pore blockage or restricted diffusion for larger molecules. In order to shed more light on the deactivation mechanism, self-diffusion measurements on adsorbates within the coked catalyst were performed using PFG NMR to see whether the coke is inuencing molecular transport within the zeolite pore space. n-Butane was used as a probe molecule, as was also the case in our previous work [28], due to its diffusivity and favourable NMR relaxation characteristics making the PFG NMR experiment straightforward. Results are shown in Fig. 7. For single-component diffusion, the plot of ln(I/I0 ) against 2 g2 2 ( /3) is expected to be linear with a gradient of D, where D is the diffusion coefcient [3335]. However, the log attenuation plots in Fig. 7 show a curve. This

Fig. 7. PFG NMR intensity results for n-butane adsorbed in zeolite HUSY after a time on stream of: (a) 0 min (fresh catalyst); (b) 65 min; (c) 185 min.

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is because the length-scale being probed by the PFG NMR measurement, which is of the order of 6D , is greater than the particle size (0.5 1 m for the sample used) [34,35]. Hence both interparticle and intraparticle effects are being observed. The initial slope depends on the interparticle diffusivity and the relative weighting of how long the adsorbed molecule spends in each region, while the nal slope gives the intraparticle diffusivity only [35]. Thus, the curves may be tted using a least-squares tting routine in order to obtain the intraparticle diffusivity. The slower diffusion components, corresponding to intraparticle diffusivity, for the fresh sample and those after 65 min and 185 min of reaction time were found to be 2.6 109 , 2.2 109 and 1.6 109 m2 /s (all 0.2 109 m2 /s), respectively. This is about the same value, 2 109 m2 /s, found by PFG NMR for n-butane in zeolite NaX [70]. Thus, there is little change in the diffusivity of n-butane, even after 4 h on stream. This may be contrasted with our previous work on ethene oligomerisation which showed a signicant drop in n-butane intracrystalline diffusivity with increasing time on stream [28]. It was also possible to measure the diffusion constant of the reactant itself by performing PFG NMR experiments on n-hexane adsorbed within the coked zeolite. However, the NMR relaxation times of adsorbed n-hexane are smaller than those for n-butane, and this results in slightly more experimental scatter in the data points. As was the case with the measurements on n-butane, a two-component t is necessary to t the experimental data as shown in Fig. 8. It can be seen that the signal attenuation does not depend on the time on stream and tting a single line to the data gives the average intraparticle diffusivity of n-hexane within ultrastable zeolite Y to be 4.5 (0.5) 1012 m2 /s. 3.4. Discussion of the deactivation mechanism The infrared spectroscopic results clearly show that removal of Brnsted and Lewis acid sites does not occur to a signicant extent, and thus that uniform site poisoning is not responsible for the deactivation of ultrastable zeolite Y during n-hexane cracking. Further, it is clear that the deactivation is not due to the pore blockage mechanism, as the diffusion rate of the reactant through the bulk particle is unaffected by the

Fig. 8. PFG NMR intensity results for n-hexane adsorbed in zeolite HUSY after a time on stream of 0 min (circles), 65 min (squares), and 125 min (diamonds).

presence of coke. It should be noted that these observations are consistent with those of some other workers [25]. It is also clear that the deactivation mechanism during n-hexane cracking on ultrastable zeolite Y is very different to the one that takes places during ethene conversion, in which both uniform site poisoning and pore blockage effects were observed [28]. The analysis of the product distribution discussed above indicates that the initiation step in the n-hexane cracking reaction is direct protonation of the reactant by a very strong Brnsted acid site. It is possible that only a relatively small number of such active sites are present in ultrastable zeolite Y. For instance, they may only be present at defects, or at Brnsted sites where an adsorbed molecule can simultaneously interact with a Lewis acid site. This leads to the possibility that selective site poisoning is the main deactivation mechanism: the few highly active sites would be removed, resulting in considerable loss of activity, but the majority of the acid sites would be unaffected and diffusion within the pore space would also be unaffected. Another possible explanation, as proposed by Hopkins et al. [25], is that the reaction is diffusion limited with pore mouth poisoning as the main deactivation mechanism. In this case, virtually all the reaction would take place near the external surface of the crystallites, and only this region would become coked. Again transport and the number of active sites present in the bulk solid would be barely affected.

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In order to distinguish between the selective site poisoning and the pore mouth poisoning models, a sample of coked zeolite Y (deactivated by 125 min on stream for the n-hexane cracking reaction) was tested for catalytic activity in the cracking of n-dodecane. If pore mouth poisoning had been responsible for the deactivation, it would be expected that n-dodecane conversion would be very low (other than a small amount of thermal cracking) as the reaction would be more diffusion limited than the n-hexane cracking case. On the other hand, if selective site poisoning was responsible, it would be expected that the coked catalyst would be highly active, as n-dodecane would be cracked on relatively low strength acid sites compared to nhexane. It was found that the coked sample was highly active, giving a conversion to light products comparable to a fresh catalyst sample. This observation conrms that the selective site poisoning mechanism must be the one responsible for deactivation during n-hexane cracking.

Acknowledgements We thank the Cambridge Overseas Trust and the Cambridge Thai Foundation for funding Boontham Paweewans studentship. We are grateful to Dr. Mick Mantle and Dr. Sunil Ashtekar for their experimental help with the NMR and the infrared measurements. References
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4. Conclusions Coking and deactivation during n-hexane cracking on ultrastable zeolite Y has been studied using a variety of techniques. The product distribution suggests that the initiation step is direct protonation at very strong Brnsted acid sites, and it may be the removal of these that is the principal cause of deactivation for this reaction. The coke formed has an aromaticity of about 7880%, and does not become highly polyaromatic even after four hours on stream under the conditions employed. It is found that the bulk of the acid sites present in the catalyst are not removed, even though the catalyst activity drops signicantly, while diffusion measurements show that pore blockage is not a factor. A selective site poisoning model for deactivation under these conditions is thus proposed. It should be noted that the deactivation mechanism is very different to that observed during ethene conversion on the same catalyst. This work highlights the need for a multitechnique approach to the study of coking and deactivation in zeolite catalysts. Caution is needed when drawing conclusions on the deactivation mechanism from one reaction to another, and from one zeolite to another, as the initiation step may be different.

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