Applied Catalysis A: General 240 (2003) 4151

Dealuminationaging pattern of REUSY zeolites contained in uid cracking catalysts

Francisco Hernndez-Beltrn a, , Juan Carlos Moreno-Mayorga a , Mar a de Lourdes Guzmn-Castillo a , Juan Navarrete-Bolaos a , Montserrat Gonzlez-Gonzlez b , Brent E. Handy b
b a Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas 152, 07730 Mexico City, DF, Mexico CIEP, Facultad de Ciencias Qu micas, Universidad Autnoma de San Luis Potos , Av. Dr. Manuel Nava 6, Zona Universitaria, 78210 San Luis Potosi, SLP, Mexico

Received 12 April 2002; received in revised form 15 July 2002; accepted 17 July 2002

Abstract The evolution of the properties of a REUSY zeolite contained in a uid cracking catalyst was investigated under laboratory steam deactivation procedures and in age fractions of the corresponding equilibrium catalyst (Ecat). The aging pattern, dened by the evolution of the zeolite surface area (ZSA) related to the decrease of the unit cell size (UCS), was similar between lab-steamed zeolites and Ecat fractions. A sharp drop in ZSA occurred at ca. 2.430 nm UCS. A study done by FT-IR spectroscopy suggested that zeolite dealumination initially took place more extensively on the sodalite cages and double six-member rings (D6R) of the structure and that the nal collapse of the zeolite framework occurred through destruction of the 12-member rings (12M). This can be explained by a crystal fracture and break down process and disassembling of the sodalite cages in the faujasite structure. NH3 microcalorimetry showed that strong acid sites in faujasites are destroyed by steam aging, but this effect does not lead to a reduction in the cracking activity of the Ecat form. The microactivity test (MAT) showed that the specic activity declined sharply at 2.430 nm UCS. Differences in product selectivity were related to the extent of damage of the zeolite, extra-framework alumina and mesoporosity. While further aging canceled the effect attributed to extra-framework alumina differences attributed to mesoporosity increased. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Zeolite; Faujasite; USY; Fluid cracking; Dealumination; Steam aging

1. Introduction Fluid cracking catalysts undergo deep modications due to deactivation and aging during their usage in commercial units. Important losses of pore volume and catalytic activity are observed mainly as a
Corresponding author. Tel.: +52-55-3003-8539; fax: +52-55-3003-8541. E-mail address: fjhernan@imp.mx (F. Hern andez-Beltr an).

consequence of the structure collapse of the zeolite active component [1]. A central theme in testing and assessment of uid cracking catalysts is to closely reproduce the effects of catalyst aging under industrial conditions at the microactivity and pilot plant level, and thus to improve our ability to rank catalysts and make predictions for commercial performance. Laboratory aging and deactivation protocols have been mostly developed by taking the average properties of equilibrium catalysts

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 3 3 - 7

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(Ecats) as a reference. However, various age fractions exist in Ecats as a consequence of the periodic addition of fresh catalyst and removal of existing catalyst into the main catalyst inventory in order to maintain conversion. The various age fractions of Ecat have widely diverse textural and chemical properties, representing a complex blend of catalyst particles at different stages of deactivation. Thus, the need for simulating the age prole of Ecats for supporting better testing methods has been recognized [1]. A very popular laboratory method used for accelerated catalyst aging involves steaming at high temperatures commonly ranging between 700 and 800 C. Steaming under controlled conditions is also frequently used to produce pre-stabilized dealuminated Y zeolites [25] commonly known as ultrastable Y (USY) that are incorporated into uid cracking catalysts. Several works have addressed the effects of steam aging on Y zeolites either pure or as catalyst components [37,8a,925]. Steaming produces the hydrolysis and break down of the zeolite AlOSi bonds and thus leads to its dealumination which typically destroys surface area, creates mesoporosity and leaves aluminum as extra-framework species, which may be located either within the existing micropores [17] or form deposits on the exterior surface of the zeolite crystallites [8a]. Migration of extra-framework alumina species from within the zeolite structure depends on the temperature and the steam partial pressure and thus it is accelerated under lab conditions, whereas commercial conditions being much less extreme lead to much slower migration rates [1]. Since the number and type of aluminum species present determine the acid character of the zeolite, they are typically identied as the origin of differences in catalytic behavior between Ecat and laboratory-steamed catalysts. Dealumination improves zeolite thermal and hydothermal stability and modies hydrogen transfer activity which widely governs product selectivity in cracking reactions. Basically, the lower content of framework aluminum in dealuminated zeolites is reected by a lower average unit cell size (UCS) of ca. 2.4502.455 nm compared to 2.4652.470 nm for non-dealuminated Y zeolites. Both non-dealuminated and USY zeolites undergo dealumination under commercial conditions. Typically, an equilibrated USY catalyst shows an average UCS of ca. 2.4202.430 nm. Rare earth exchange renders the zeolite more stable

to dealumination and thus it increases the UCS in equilibrated catalysts. Improving our knowledge on how the properties of the zeolite contained in the catalyst evolve under different conditions in regard to the age prole in Ecat is relevant for developing better catalyst aging and testing lab protocols. This will nally be useful for developing better catalysts. Therefore, one of the goals of this work was to study the evolution of structural and acidic properties of a USY zeolite contained in uid cracking catalysts that were laboratory steam deactivated for comparison with age fractions obtained by density grading of the corresponding Ecat obtained from a commercial unit. Another goal of this work was to gain insight on the mechanism of the zeolite structure collapse. 2. Experimental 2.1. Catalysts The catalyst under study contained a USY type zeolite (2.4551 nm UCS in fresh catalyst) partially exchanged with rare earth cations (1.5 wt.% as oxide in catalyst), supported in a silicaalumina matrix (33 wt.% Al2 O3 in catalysts). A sample of Ecat (2.4273 nm average UCS) was obtained from a commercial partial combustion unit and separated into seven density graded fractions according to a method already described [6]. The properties of Ecat and fractions are shown in Table 1. Samples coded from F1 to F7 corresponded to increasing age fractions of the catalyst in the unit, progressively showing lower surface areas, lower UCS and higher content of contaminant metals (Ni and V). The steam aging of the fresh catalyst was carried out in a uid bed reactor under 100% steam from 4 to 30 h, at T1 = 760 C, T2 = 788 C and T3 = 816 C over 100 g sample. The steamed samples (S) were coded after the temperature (T1 , T2 and T3 ) and time used for steaming (Table 2). 2.2. Characterization techniques The chemical analysis of the Ecat fractions and the fresh catalyst was determined by coupled plasma spectroscopy (CPS) and expressed as the wt.% of

F. Hern andez-Beltr an et al. / Applied Catalysis A: General 240 (2003) 4151 Table 1 Properties of Ecat fractions Code Specic surface (m2 /g) Total F1 F2 F3 F4 F5 F6 F7 184 169 170 167 160 154 92 Zeolite 152 133 135 131 122 115 66 Matrix 32 35 35 36 38 39 26 0.165 0.168 0.179 0.171 0.191 0.212 0.151 24.3233 24.3033 24.2933 24.2860 24.2834 24.2533 24.2250 Volume (cm3 /g) UCS () Metal (ppmw) Na 2172 2096 2286 2185 1967 1795 2187 Ni 357 396 424 436 522 604 627 V

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1410 1704 1873 1993 2411 2890 2472

oxides (dry basis). The fresh catalyst, the steamed samples and Ecat fractions were characterized by X-ray diffraction (Siemmens D-500) according to ASTM-D3942-90 leading to calculate the zeolite UCS. The total surface area and the zeolite surface area (ZSA) were calculated from nitrogen adsorption experiments (Micromeritics ASAP-2405) using the procedures outlined in ASTM-D3663 and ASTM-4222 (the t-plot method). Transmissionabsorption infrared spectroscopy studies was used to follow modications of zeolite structure upon dealumination. Experiments were conducted on pure catalyst powder compressed to form thin KBr-supported 2 cm wafers, using a Nicolet model 710 FT-IR collected at 4 cm1 resolution. Samples were evacuated in a Pyrex cell equipped with
Table 2 Properties of fresh catalyst and steamed samples Code Steaming condition T Fresh S-760-4 S-760-8 S-760-12 S-760-16 S-788-4 S-788-8 S-788-16 S-788-30 S-816-4 S-816-8 S-816-16 S-816-30 760 ( C) Time (h) 0 4 8 12 16 4 8 16 30 4 8 16 30

CaF2 windows at 673 K under vacuum (106 Torr). Spectra were analyzed in the 3001300 cm1 region. The acidity of catalysts was studied by NH3 titration microcalorimetry using a home-made apparatus similar to that described in [26]. Briey, small doses of high purity ammonia gas were admitted to a previously evacuated cell maintained at 473 K. Prior to dosing, all catalyst samples were heated under high vacuum (103 Pa) to 573 K, exposed to 33 kPa oxygen for 30 min and re-evacuated at this temperature to achieve a de-gas rate not greater than 0.1 Pa/min. 2.3. Chemical reaction The catalyst samples were tested in a uidized xed bed reactor ACETM unit (Kayser Technology) based on the principles of the ASTM-D3709 microactivity

Specic surface (m2 /g) Total 263 210 206 201 186 192 189 142 150 154 151 153 80 Zeolite 179 144 145 141 133 137 135 101 108 110 109 108 55 Matrix 84 65 61 60 53 56 54 41 42 44 42 45 25

Volume (cm3 /g)

UCS ()

0.187 0.195 0.194 0.200 0.188 0.196 0.185 0.177 0.183 0.190 0.174 0.180 0.139

24.5752 24.3533 24.3533 24.3333 24.3133 24.3433 24.3138 24.2734 24.2634 24.3433 24.2983 24.2734 24.2436

788

816

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test (MAT). Reaction conditions included catalyst to feed ratio (C/O, w/w) = 5, T = 793 K, WHSV = 16 h1 and 45 s for feed injection. The feed used was a mixture of atmospheric and vacuum gas oils having 23.35 API, 0.51% CCR, 11.9 K(UOP), 81 C aniline point, 2.0% S and 896 ppm basic nitrogen. The reaction products were analyzed by gas chromatography with two Hewlett-Packard 7960 instruments congured (Separation Systems Inc. Applications) for rening gas analysis and simulated distillation analysis, respectively. The feed conversion (wt.%) was calculated from the difference between the heavy fraction (>221 C) recovered from the reaction and that contained in the feed. Data used were for 98102% mass balance. The conversion data were expressed in terms of the SAK number [27] which gives the amount of catalyst surface area per unit conversion in terms of the second order rate constant (K = percent conversion/(100 percent conversion)). 3. Results and discussion 3.1. Dealuminationaging pattern Steam-aged samples showed higher values of matrix surface area compared to Ecat fractions (Tables 1 and 2). Ecat fractions showed only slight differences in the matrix surface area upon aging. On the contrary, the matrix surface area of steamed samples diminished extensively with steaming temperature and time but was consistently higher for steamed samples than for Ecat samples. The pore volume was somewhat higher for steamed samples. It varied according to age showing a maximum then fall associated with the loss of ZSA. Compared to matrix a different trend was shown by the zeolite. Fig. 1 shows the plot of the zeolite UCS as a function of the steaming time. After the rst 4 h steaming, the zeolite the UCS changed from 2.455 nm in the fresh catalyst to 2.430 nm showing that dealumination took place. For longer steaming periods, dealumination dramatically slowed. This behavior was already advanced by Beyerlein et al. [19] and is consistent with the known chemistry of Y zeolites showing that dealumination is rst order with respect to the content of framework aluminum. This implies that aluminum extraction from the zeolite framework

Fig. 1. Aluminum content per unit cell as a function of the steaming time: S-760 ( ); S-788 ( ); S-816 ( ).

becomes increasingly difcult as framework alumina decreases [10]. The plot of ZSA related to its corresponding UCS depicts the aging pattern of the zeolite in the catalyst [6]. The aging pattern showed two stages (Fig. 2) either with Ecat fractions or steamed samples. In a rst stage, a relative small decrease (2025%) in ZSA was accompanied by a relative large shrinkage of the UCS from 2.455 nm for the fresh catalyst to ca. 2.435 nm for the steamed samples. As aging proceeded, the decrease in ZSA became progressively larger with a fairly small decrease in UCS. Below 24.30 nm, the ZSA loss was dramatically faster than the UCS. About 70% of the fresh ZSA was lost. Similar patterns were obtained with steamed catalysts at 760 or 788 C. Steaming at 816 C initially showed higher ZSA loss associated to a much larger zeolite lattice destruction. However, this

Fig. 2. ZSA as a function of the aluminum content for samples of steamed catalyst and Ecat fractions: fresh catalyst (); S-760 ( ); S-788 ( ); S-816 ( ); Ecat fractions (); Ecat ().

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was followed by stabilization of the ZSA in between 2.440 and 2.430 nm UCS. Aging up to 30 h at 816 C caused the zeolite to collapse at a higher UCS than the corresponding Ecat fraction. It is worth to note that the data reported by Biaglow et al. [20], and Ino and Al-Khataff [21] for steamed USY zeolites show identical trends to those reported here, with a sharp decrease in ZSA occurring at ca. 2.430 nm. 3.2. Mechanism of zeolite lattice dealumination and collapse It is widely accepted that zeolite dealumination occurs by a complex chemical mechanism involving two steps: (i) hydrolysis of tetrahedral aluminum located in the zeolite framework by water at elevated temperatures; and (ii) silicon insertion [2,8a] on the vacancies left by aluminum. It has been stated that the silicon which is transported as Si(OH)4 under high temperature and steam atmosphere is probably produced by zeolite decomposition [2,8a]. It is possible that other components in the catalyst produce this silica as well. Silicon insertion and crystallinity decrease are consistent with unit cell shrinkage and ZSA loss, respectively. It is well known that rare earth cations improve also the hydrothermal stability of faujasites. The stabilization effect has been attributed to the location of rare earth cation inside the sodalite cage, the unit structure of faujasite. The higher dealumination rate initially exhibited by the fresh catalyst could involve aluminum sites that are not charge compensated by rare earth cations. The effect of dealumination and ZSA obtained after 4 h steaming reproduced the properties of the youngest Ecat fraction, i.e. the lowest density fraction. The nickel content in the catalyst is related to the average nickel content in the feed and the feed rate in the industrial unit. The Ni content of Ecat was thus used to estimate the average age of each fraction [6]. In the present case, the average residence time of F1 was estimated to ca. 30 days. The effect observed at the earliest stages of aging can be explained if one considers that a zeolite crystal fracture and break down process [7,8a,27] occurs. Aluminum ejection from the zeolite lattice would be much more affected than structure collapse or ZSA

loss. The crystal break down process would occur over preferential directions [7]. The pattern of ZSA loss either in Ecat fractions or steamed samples showed that below ca. 2.430 nm the stability of the zeolite lattice during the dealumination process was dramatically reduced. This effect could also be related to the crystal break down process since small crystals are less stable than larger crystals. However, another possibility exists. DRIFTS studies [16] showed that during steaming of pure USY zeolites and USY catalysts, acidic hydroxyls in supercages survived longer than those located in hexagonal prisms (six-membered double ring (D6R)). This would imply that different active sites in the faujasite lattice are affected differently by dealumination. Some insight about this question could be obtained by infrared spectroscopy. Fig. 3 presents the FT-IR

Fig. 3. FT-IR spectra in the 3001300 cm1 region for fresh catalyst and S-788 series.

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spectra of the fresh catalyst and steamed samples in the 3001200 cm1 region. The fresh catalyst showed bands at 347, 471, 542, 700, 756, 797, 916 and 1034 cm1 . Steam aging produced signicant changes in the FT-IR spectra. Bands at 700, 756 and 916 cm1 disappeared while bands at 615 and 861 cm1 appeared. Bands at 471 and 542 cm1 in the fresh catalysts shifted to lower frequencies in steamed samples. By contrast, bands at 347 and 1034 cm1 shifted to higher frequencies. The complexity of the IR spectrum in the fresh catalyst could be attributed to the various silica-based components found in it. The FT-IR signals arising from those components simplied upon steaming showing that such functional groups are unstable. By contrast, bands attributed to the faujasite zeolite [2] appeared. These signals are assigned to the asymmetric (1081 cm1 ) and the symmetric stretching (835 and 802 cm1 ) of TO bonds. Absorption bands at ca. 390 and 615 cm1 corresponded, respectively, to vibrations of the 12-membered rings (12M) that comprise the entrance to the large cavity and the D6R which make up the sodalite cages in the faujasite structure. Longer steaming periods decreased the intensity of such bands and produced shifting to higher frequencies, which is consistent with lattice destruction and lower aluminum content per unit cell. The integrated values (absorbance mode) of the 390 and 615 cm1 bands were calculated and compared in order to collect information about the variation in their relative population upon steaming. Overlapping of the band corresponding to D6R in the fresh catalyst was found. Deconvolution of the signal between 540 and 620 cm1 showed three bands at 562, 589 and 606 cm1 . This was interpreted as being produced by D6R with different Al contents. Fig. 4 shows the results of the ratio of those bands for S-788 series, the fresh catalyst, sample S-815-30 and fractions F7 and F4. According to our results the integrated signal of the D6R decreased faster than that for the 12M between the fresh zeolite and that with 2.430 nm UCS. For lower UCS, the band related to the 12M decreased proportionally more. Coincidentally, the ratio of 12M/D6R showed a maximum at approximately 2.430 nm. It is well known that during steam dealumination zeolite crystallinity is lost and mesopososity is created. These features are produced as a consequence of

Fig. 4. Ratio of the integrated values of the 390 cm1 (12M) to 615 cm1 (D6R) FT-IR bands (absorbance mode) of steamed samples ( ), Ecat fractions (), CBV series () and fresh catalyst ().

a crystal fracture and break down process [7,8a,19]. High resolution TEM studies suggested that the mesopores are formed by dissociation of the TOT bonds in the D6R [7] while sorption studies indicate that entire sodalite units are destroyed during hydrothermal dealumination [8b,8c]. Our FT-IR results could be rationalized on this basis. The crystal break down process would involve the sodalite cages thus implying extensive D6R destruction. Therefore, the relative population of 12M over D6R increases thus corresponding to the increase in the 12M/D6R ratio. The fact that during steaming acidic hydroxyls in supercages survived longer than those in hexagonal prism [16] would be consistent with the this result. As the crystal break down proceeds it is possible that sodalite cages unassemble, thereby destroying the supercage and the associated 12M. This would correspond to a signicant ZSA loss observed below ca. 2.430 nm and the decrease in the 12M/D6R ratio. The rare earth cations are typically located in the sodalite cage and in the D6R. Thus, it is possible that the these building blocks remain associated one to each other. Fig. 4 shows also data points calculated for a series of commercial Y dealuminated zeolites (CBV series, PQ Corp.). The properties of these zeolites have been reported in literature [2831]. These zeolites are dealuminated to very low Al contents but exhibit high crystallinity and thus high surface area. Compared to steamed or Ecat fractions, CBV zeolites showed only a slight change in the 12M/D6R ratio thus conrming that their structure remained undamaged.

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Fig. 5. NH3 microcalorimetry: Differential heat of adsorption as a function of coverage: fresh catalyst (); S-788-4 ( ); S-788-12 ( ); S-788-30 ( ); F1 (); F6 ().

3.3. Characterization of acidity Ammonia microcalorimetry showed that the effect of steam aging was to reduce the site density of important acid sites (Fig. 5). This was evidenced by the reduction in the initial heat value as well as for sites corresponding to Qads > 100 kJ/mol. The fresh catalyst had a site density of ca. 290 mol/g. After 4 h steaming at 788 C, the acid site density diminished to one-fourth the initial value, and for 30 h, the density was less than 10 mol/g. The initial adsorption heat on the fresh catalyst was 150 kJ/mol and this diminished to 125 kJ/mol in steamed samples. In each sample, the ammonia site density was considerably lower than the framework Al3+ density, although both values decreased rapidly with steaming time. The titrated acid sites may be Lewis or Brnsted type, and although some studies [32,33] have suggested that a small number of stronger Lewis sites may form during steaming, this was not observed here. Microcalorimetric data obtained with Ecat samples are shown in Fig. 5. The site density of the youngest and an intermediate age fraction (F1 and F6, respectively) was higher than the density recorded with the fresh catalyst laboratory steamed at 788 C for 30 h (S-788-30). Despite considerable differences between these fractions in terms of textural properties and metals (V and Ni) content, their acid site (Qads = 80160 kJ/mol) densities were comparable at 4050 mol/g catalyst basis. The zeolite framework Al3+ content in Ecat and its fractions was very low and cannot be determined with precision from UCS measurements, but it could be easily at

or below the acid site density levels mentioned. To explore the reducibility of the Ecat samples and possible inuence of residual coke contained in these samples, calorimetric runs were performed in which the samples were pre-oxidized (250 Torr O2 , 600 C) or pre-reduced (250 Torr NH3 , 300 C). All samples were initially gray and became white with the pre-oxidation treatment. The data show that this led to a modest decrease in the acid site density, perhaps implying that coke deposits removed by this treatment were responsible for some of the acidity measured in untreated Ecat. Results from pre-reduced Ecats do not show signicant changes in acid density, indicating a lack of activity from reducible metal contaminants. In general, the microcalorimetry results presented here showed that strong acid sites in faujasites are destroyed by steam aging, but importantly, this effect does not lead to a reduction in the cracking activity of the Ecat form. Mechanistically, cracking reactions may only need a small number of strong acid sites as initiators to form carbenium ion intermediates. Also, it has been shown recently that the cracking activity in dealuminated faujasites is better associated to newly formed, but weaker SiOAl Brnsted sites created from extra-framework Al3+ and silica [16]. Moreover, Lewis sites predominate in both steam dealuminated and in Ecat catalysts [15]. 3.4. Catalytic properties The FFB catalytic test showed that the SAK number varied mostly between 60 and 100 (Fig. 6). Higher SAK numbers for lower UCS were observed thus indicating that the catalytic activity per surface area (or the specic activity) diminished with catalyst aging. SAK increased by about 20 units when UCS shirked from 2.435 to 2.430 nm with a small loss in ZSA. A signicant increase up to 140 in the SAK number was observed for samples below 2.425 nm UCS. It is worth to notice that the SAK values for steam-aged samples and Ecat fractions at same UCS was very similar except for the most aged samples F7 (UCS = 24.225) and S-816-30. The latter had a similar SAK number but much higher UCS. This would imply that for this advanced aging the catalytic activity is mainly dictated by the available zeolite internal volume rather than by the acid sites density.

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Fig. 6. SAK number as a function of the aluminum content in zeolites for samples of steamed catalysts and Ecat fractions: S-760 ( ); S-788 ( ); S-816 ( ); Ecat fractions (); Ecat ().

Fig. 7af show plots for product yield and product ratios as a function of the second order rate constant K. The dry gas (H2 , C1 C2 ) yield increased at higher K and varied from 1 to ca. 3 wt.%. While the H2 /CH4 ratio in Ecat fractions was higher than that observed for steamed samples (Fig. 7a) no difference in total dry gas yield was observed. This could be associated to a compensation effect between dehydrogenation reactions and thermal cracking. While the higher H2 selectivity in Ecat fractions could be produced by the contaminant metals that increased progressively from F1 to F7, the higher matrix surface area in steamed samples would account for higher yields of CH4 produced by thermal cracking. The coke yield varied from 2 to ca. 8 wt.% (Fig. 7b). Differences were observed between some steamed samples and Ecat fractions. The trend exhibited by Ecat fractions and samples S-760 seemed to match one with each other, while the coke yield increased when the catalyst was steamed for 48 h at higher temperatures than 760 C. While the coke yield varied in only a relatively small amount (15%) for the most aged samples, in general the Ecat fractions showed low or similar coke yields compared to steamed samples. It was concluded that the effect of metals in Ecat fractions was rather negligible. In general, the gasoline yield varied between 45 and 50 wt.% (Fig. 7c) and fell to 2530 wt.% due to the lower conversion for samples S-816-30 and F7. Samples S-760-4, S-760-8 and S-816-4 produced 12% lower gasoline yield compared to other steamed

samples. The LPG yield (Fig. 7d) varied between 5 and 18 wt.%. In general, compared to steamed samples, the Ecat fractions produced somewhat lower gasoline yields with a concomitant increase in the LPG yield except for samples S-760-4 and S-760-8 that produced higher amounts of coke. Differences in gasoline and LPG yields for Ecat fractions and steamed samples were 0.51 wt.%. Samples F7, S-816-30 and S-816-4 exhibited larger differences. Variations due to relative error for gasoline and LPG yields were 0.35 and 0.2%, respectively. Therefore, the observed differences in yields were actually produced by catalysts. The iC4=/iC4 (iso-butene/iso-butane) ratio (Fig. 7e) and the iC4/nC4 (iso-butane/normal butane) ratio (Fig. 7f) were also used to obtain insight on the effects of aging conditions over the zeolite properties. The iC4=/iC4 ratio varied in a wide range from 0.2 to 2 and increased exponentially at lower K. Similar trends and values were observed when Ecat fractions and steamed samples were compared at constant K except for F7 that showed a higher value compared to S-816-30. Differences were more evident with the iC4/nC4 ratio (Fig. 7f). While the ratio varied between 3 and 4.5 a maximum at ca. K = 2 was observed. Comparison between steamed and Ecat fractions showed that the iC4/nC4 ratio at constant K was slightly higher for samples steamed at 760 C and quite different with samples F7, S-816-30 and S-816-4. While the higher coking tendency in steamed samples could be related to a higher matrix surface area, interesting effects on catalytic properties were produced when the steaming temperature was varied. Samples steamed at 760 C produced lower coke yields and higher values of the iC4/nC4 ratio compared to samples steamed at higher temperatures. Steaming at 816 C for 4h destroyed more zeolite at a given UCS. The gasoline yield was lower whereas the LPG and coke yields were higher. With some exceptions, the gasoline yields were higher with steamed catalysts than with Ecat fractions. Our results could be explained considering the extent of modication of the external surface of the zeolite crystals during dealumination. This would depend on the aging conditions used. It is well known that the collapse of the zeolite framework produces mesoporosity and extra-framework alumina that might be active in non-selective cracking reactions. Moreover,

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Fig. 7. Distribution of products in the cracking of a vacuum gas oil for steam-aged samples compared to Ecat fractions: (a) coke yield; (b) hydrogen/methane ratio; (c) gasoline yield; (d) LPG yield; (e) iso-butene/iso-butane ratio; (f) iso-butane/normal butane ratio. Series S-760 ( ); S-788 ( ); S-816 ( ); Ecat fractions (); Ecat ().

under industrial conditions zeolite aging occurs at a much slower rate than under lab-steaming conditions. Therefore, it is reasonable to picture that mesoporosity and extra-framework alumina produced on steamed samples had a much larger effect than in Ecat fractions and specially for samples steamed at higher temperature and for short time periods as shown by sample S-816-4. Ecat fractions would impose somewhat larger diffusion constraints to the gasoline components thus reducing the liquid yield with the concomitant increase in gases. While extra-framework

species readily evolved to less active species differences in diffusion constraints seemed to increase with aging as it was shown by comparing results obtained with the most aged samples S-816-30 and F7. Moreover, according to the crystal break down mechanism it could be assumed that the average size of crystals produced in S-816-30 was smaller thus explaining that the zeolite lattice had collapsed at higher UCS. From our results it was somehow evident that aging either in a commercial unit or in a laboratory steamer reduced the number and strength of acid sites

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contained in the cracking catalyst. We expected a much higher decrease in the catalytic activity (i.e. much higher SAK number) than it was actually observed. No evidence for superacid sites was found with NH3 microcalorimetry thus a compensation effect due to stronger acid centers was ruled out. These results agree with the known fact that the strong acid sites present in Y type zeolites are readily destroyed upon steaming and that the acid properties solely cannot account for the cracking activity. There has been a lot of debate concerning the origin of the cracking activity in steamed and equilibrated catalysts. A number of studies [18,2124] point out that the cracking activity is related to isolated acid sites while the product selectivity (i.e. olens, coke, etc.) largely dictated by hydrogen transfer reactions is attributed to paired sites, the breakpoint being at 2.430 [22,23] or 2.436 nm UCS [21,24]. From TPDTGA experiments using 2-propanamine Biaglow et al. [20] showed that the MAT activity in steamed cracking catalysts correlated with strong acid sites while recognizing that mass transfer existed and that only approximately half of sites associated to framework aluminum was active. Similarly, Maesen and Hertzenber [25] showed that strong acid sites are located in the supercage of the faujasite structure. DRIFTS studies showed recently [16] that the acid properties of steamed and equilibrated cracking catalysts evolve very fast with new SiOAl Brnsted acid sites of lower strength, created from extra-framework alumina and silica, that eventually dominate the cracking activity. One other group [15] suggested that only Lewis acid sites were present in steamed and equilibrated cracking catalysts and thus only these type of site could be associated to the catalytic activity. In spite of the controversy it is clear enough so far that steam dealumination entrains deep modications on the acidity properties of the zeolite as well as in the diffusion pattern and adsorption constants of hydrocarbon molecules within the zeolite micropore volume. All these factors have a strong impact on the cracking mechanism and kinetics [3,4,11]. In the present case, the zeolite dealumination going from 2.435 to 2.430 nm UCS showed a consistent decrease in the specic activity of the catalyst. Is not only the loss of strong acid sites due to dealumination but to

neutralization by extra-framework aluminum species [17,25], thus producing the SAK number to increase progressively. This effect could be compensated by increasing the rates of bimolecular and oligomeric cracking as suggested by Williams et al. [11]. Comparatively, a very high impact on the SAK number occurred under 2.430 nm UCS. Here, the zeolite framework collapse was much more important. The deep change in the SAK number below 2.425 UCS is clearly related to the 12M destruction in the zeolite structure where probably the catalytically active acid sites are found.

4. Conclusions The dealuminationaging pattern showed by steamed samples was very similar to that found for Ecat fractions. In a rst stage the aging pattern showed a relative small decrease in ZSA with a large shrinkage of the UCS. Below 24.30 nm UCS the ZSA loss was dramatically faster than UCS reduction. FT-IR studies suggested that the collapse of the zeolite framework occurred by disassembling sodalite cages that destroy the supercages and the associated 12M. NH3 microcalorimetry showed that strong acid sites in faujasites are destroyed by steam aging, but importantly, this effect does not lead to a reduction in the cracking activity of the Ecat form. However, some differences in product selectivity were evidenced. These were related to the extent of damage of the zeolite. Extra-framework alumina and mesoporosity are probably the source of such differences. While further aging canceled the effect attributed to extra-framework alumina differences attributed to mesoporosity increased. Research work is still necessary in order to understand the effect of other catalyst variables, i.e. rare earth content, zeolite crystal size, mode of synthesis, etc. upon the dealumination pattern of ultrastable zeolites contained in uid cracking catalysts.

Acknowledgements This work was nancially supported by IMP Maya Crude Oil Research Program through projects D.01024 and D.00290. The authors wish to thank

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Professor F. Figueras for reviewing this manuscript, Dr. H. Armendriz for fruitful discussions and Ms. A. Rodr guez for technical assistance. References
[1] P. OConnor, E. Brevoord, A.C. Pouwels, H.N.J. Wijngaards, in: P. OConnor, T. Takatsuka, G.L. Woolery (Eds.), Deactivation and Testing of Hydrocarbon-Processing Catalysts, ACS Symposium Series 634, American Chemical Society, Washington, DC, 1996, p. 146. [2] D.W. Breck, Zeolite Molecular Sieves: Structural Chemistry and Use, Wiley, New York, 1974 (Chapter 6). [3] A. Corma, V. Forns, A. Mart nez, A.V. Orchills, in: W.H. Flank, E. Whyte Jr. (Eds.), Perspectives in Molecular Sieve Science, vol. 368, Proceedings of the 195th National Meeting of American Chemical Society, Toronto, Canada, American Chemical Society, Washington, DC, 1988, p. 542. [4] A. Corma, M. Grande, V. Forns, S. Cartlidge, M.P. Shatlock, Appl. Catal. 66 (1990) 45. [5] C.S. Triantallidis, A.G. Vlessidis, N.P. Evmiridis, Ind. Eng. Chem. Res. 39 (2000) 307. [6] F. Hernndez-Beltrn, R. Garc a de Len, E. Mogica, J.C. Moreno-Mayorga, R. Gonzlez, in: P. OConnor, M. Occelli (Eds.), Fluid Catalytic Cracking V: Materials and Technological Innovations. Studies in Surface Science and Catalysis, vol. 134, Elsevier, Amsterdam, 2001, p. 87. [7] Y. Sasaki, T. Suzuki, Y. Takamura, A. Saji, H. Saka, J. Catal. 178 (1998) 94. [8] (a) R.A. Beyerlein, C. Choi-Feng, J.B. Hall, B.J. Huggings, G.J. Ray, Top. Catal. 4 (1997) 27; (b) U. Lohse, H. Stach, H. Thamm, W. Schirmer, A.A. Isirikjan, N.I. Regent, M.M. Dubinin, Z. Anorg. Allg. Chem. 460 (1980) 179; (c) H. Stach, U. Lohse, H. Thamm, W. Schirmer, Zeolites 6 (1986) 74. [9] P. Hudec, V. Jorik, A. Smieskova, Z. Zidek, React. Kinet. Catal. Lett. 60 (1) (1997) 15. [10] M. Gusinet, Q.L. Wang, G. Giannetto, Catal. Lett. 4 (1990) 299. [11] B.A. Williams, S.M. Babitz, J.T. Miller, R.Q. Snurr, H.H. Kung, Appl. Catal. A 177 (1999) 161. [12] B.A. Williams, J.T. Miller, R.Q. Snurr, H.H. Kung, Micropor. Mesopor. Mater. 35/36 (2000) 61.

[13] G. de la Puente, U.A. Sedrn, Micropor. Mater. 12 (1997) 251. [14] I. Halasz, J. Horvath, T. Mandy, L. Schmidt, E. Tasnadi, in: B. Drzaj, S. Hocevar, S. Pejovnik (Eds.), Zeolites: Synthesis, Structure, Technology and Application. Studies in Surface Science and Catalysis, vol. 124, Elsevier, Amsterdam, 1985, p. 393. [15] M.L. Occelli, M. Kalwei, A. Wlker, H. Eckert, A. Auroux, A.C. Gould, J. Catal. 196 (2000) 134. [16] X. Liu, R.E. Truitt, G.D. Hodge, J. Catal. 176 (1998) 52. [17] A. Gola, B. Rebours, E. Milazzo, J. Lynch, E. Benazzi, S. Lacombe, L. Delevoye, F. Fernandez, Micropor. Mesopor. Mater. 40 (2000) 73. [18] L.A. Pine, P.J. Maher, W.A. Wachter, J. Catal. 85 (1984) 466. [19] R.A. Beyerlein, G.A. Tamborski, C.I. Marshall, B.L. Meyers, J.B. Hall, R.J. Huggins, in: Fluid Catalytic Cracking II: Concepts in Catalyst Design, ACS Symposium Series 452, American Chemical Society, Washington, DC, 1991, Chapter 8, p. 109. [20] A.I. Biaglow, C. Gittleman, R.J. Gorte, R.J. Madon, J. Catal. 129 (1991) 8893. [21] T. Ino, S. Al-Khataff, Appl. Catal. A 142 (1996) 5. [22] G. de la Puente, E. Falabella Souza-Aguilar, F.M. Zanon Zotin, V.L. Doria Camorim, U. Sedran, Appl. Catal. A 197 (2000) 41. [23] G. de la Puente, U. Sedran, Chem. Eng. Sci. 55 (2000) 759. [24] S. Al-Khattaf, Appl. Catal. A 231 (2002) 293. [25] T.L.M. Maesen, E.P. Hertzenberg, J. Catal. 182 (1999) 270. [26] B.E. Handy, S.B. Sharma, B.E. Spiewak, J.A. Dumesic, Measure. Sci. Technol. 4 (1993) 1350. [27] R.W. Mott, in: Proceedings of the NPRA Annual Meeting, AM-91-43, 1719 March 1991. [28] M.J. Remy, D. Stanica, G. Poncelet, E.J.P. Feijen, P.J. Grobet, J.A. Martens, P.A. Jacobs, J. Phys. Chem. 100 (1996) 12440. [29] S. Morin, P. Ayrault, N.S. Gnep, M. Guisnet, Appl. Catal. A 166 (1998) 281. [30] G. Catana, D. Baetens, T. Mommaerts, R.A. Schoonheydt, B.M. Weckhuysen, J. Phys. Chem. B 105 (2001) 4904. [31] B.E. Handy, A. Jacobo, Ma. Guadalupe Cardenas Galindo, M. Gonzlez-Gonzlez, Ma. Elena Llanos, Ma. de Lourdes Guzmn-Castillo, F. Hernndez-Beltrn, Top. Catal. 19 (3/4) (2002) 249. [32] N. Cardona-Mart nez, J.A. Dumesic, Adv. Catal. 38 (1992) 149. [33] D.J. Parrillo, C. Lee, R.J. Gorte, Appl. Catal. A 110 (1994) 67.