J. Phys. Chem.

1996, 100, 14451-14456

14451

Physicochemical and Catalytic Properties of HZSM-5 Zeolites Dealuminated by the Treatment with Steam
J. Datka, S. Marschmeyer, T. Neubauer, J. Meusinger, H. Papp,* F.-W. Schu 1 tze, and I. Szpyt
Faculty of Chemistry and Mineralogy, Institute of Technical Chemistry, UniVersity of Leipzig, 04103 Leipzig, Linne strasse 3, Germany ReceiVed: March 6, 1996X

We studied the physicochemical properties (by 27Al MAS NMR, XPS, and IR spectroscopy) and catalytic activity (in n-heptane cracking) of a series of HZSM-5 zeolites treated at 770 K with water vapor at various partial pressures (0, 7, 13, 40, and 93 kPa). The treatment with steam removed Al from framework tetrahedral positions (as evidenced by 27Al MAS NMR studies) and yielded a decrease in the amount of acidic SiOH-Al groups. Quantitative IR studies of pyridine sorption showed that the amount of Si-OH-Al in parent and in dealuminated zeolites was very close to the amount of tetrahedral Al which remained in the framework. The Al atoms removed from the tetrahedral positions migrated (as given by XPS) to the surface. Only a small amount of these removed Al created Lewis acid sites. IR studies suggested that the vacancies created by removal of Al were filled with Si atoms migrating from other places in the zeolite. From IR studies of the desorption of ammonia it was concluded that mild dealumination (with 7 kPa of H2O) increased the acidic strength of Si-OH-Al groups. The experiments of chlorobenzene sorption suggested that this increase was in the first order due to removal (by steam treatment) of the less acidic hydroxyls. The more severe dealumination decreased the acidic strength of Si-OH-Al groups. The results of catalytic tests of n-heptane cracking agreed well with the IR results concerning acidity. The mild dealumination resulted in an increase in the catalytic activity which can be related to the increase in the acidic strength of Bro nsted sites which compensate the decrease in the number of sites. The further decrease in the cracking activity (for more severely dealuminated zeolites) may be explained by the decrease in both concentration and acidic strength of Bro nsted sites. The cracking activity of our HZSM-5 zeolites was higher when hydrogen was used (instead of nitrogen) as the carrier gas. This indicates that hydrogen transfer plays an important role in n-heptane cracking.

Introduction The physicochemical and catalytic properties of dealuminated zeolites are matter of growing scientific and commercial interest. This is due to the fact that dealumination results in the stabilization of the framework against mineral acids and temperature,1 and also, it can enhance the activity in acidcatalyzed reactions of the materials.2-6 It concerns especially the zeolites dealuminated under mild conditions. There are numerous publications dealing with these problems, and there are a few new characterization methods (like EPR, XPS) involved,7,8 helping to explain the observed catalytic phenomena. There exists, therefore, a growing base of results and additionally some models for interpretation of experimental results like the phenomena of very strong acid sites.24-29 Most of them (e.g., refs 3 and 9) focus on the point that the observed enhancement of catalytic activity is due to a synergistic interaction between Bro nsted acidic sites present in the zeolite (bridging Si-OH-Al groups related to framework aluminum) and any type of Lewis acidic sites connected with coordinatively unsaturated extraframework aluminum species. An increase in the acidic strength of bridging hydroxyls observed under mild dealumination conditions is an effect of an increase in polarization of O-H due to interaction with such Al sites. On the other
* To whom correspondence should be addressed. Faculty of Chemistry, Jagiellonian University, 30-060 Cracow, Ingardena 3, Poland. Research Centre Ju lich (KFA), Institute of Energy Process Engineering, P.O. Box 1913, 52425 Ju lich, Germany. X Abstract published in AdVance ACS Abstracts, July 1, 1996.

hand, Biaglow et al.,10 who studied by microcalorimetry a set of steamed HY zeolites, presented another point of view. They did not find superacidic hydroxyls and suggested that the enhanced catalytic activity of steamed zeolites was not due to high acidity. A similar interpretation was also proposed by Zholobenko et al.,11,12 who suggested the polarization of a paraffin molecule by a Lewis acid site created by steaming is the reason for the high catalytic activity of steamed zeolites. The aim of our study was to investigate the status of Al in HZSM-5 zeolite dealuminated by steaming. The acidic properties of steamed zeolites were compared with their catalytic activity in n-heptane cracking. We used 27Al MAS NMR spectroscopy, XPS, TPD, and IR spectroscopy to characterize our zeolite samples. 27Al MAS NMR gave information about the amount of tetrahedral and octahedral Al species, XPS (in combination with XRD) gave information about the localization of Al removed from the framework by steaming, and quantitative IR studies provided information on the concentration of Bro nsted and Lewis acidic sites, on the acidic strength of Bro nsted sites (bridging hydroxyls), and on the distribution of the acidic strength of acidic hydroxyls. The results of catalytic tests (cracking of n-heptane carried out in nitrogen and in hydrogen) were correlated with the data concerning acidity. We studied a series of HZSM-5 zeolites steamed at 770 K with various vapor pressures of water. Experimental Section Preparation. The starting material was a HZSM-5 zeolite (Si/Al ) 15) synthesized template free by Chemie AG Bitterfeld 1996 American Chemical Society

S0022-3654(96)00685-5 CCC: $12.00

14452 J. Phys. Chem., Vol. 100, No. 34, 1996

Datka et al.

Figure 1. 27Al MAS NMR spectra of HZSM-5 zeolites (parent, dealuminated with 7, 13, and 93 kPa H2O).

(Germany). Hydrothermal treatment was performed in a 2 mm deep bed under flowing nitrogen. Nitrogen with different partial pressures of water, 0, 7, 13, 40, and 93 kPa (0, 50, 100, 300, and 700 Torr), was flowing over the zeolite at 770 K for 2.5 h. NMR Studies. 27Al MAS NMR spectra were taken after dehydration at 673 K and subsequent 40 h rehydration (over saturated NH4Cl solution) of zeolite samples. The spectra were recorded with a BRUKER MSL 500 spectrometer with a spinning rate of 4.5 kHz. XRD Studies. Diffractograms of our ZSM-5 zeolites were recorded with a HZG 4 from Fa. SEIFERT FPM diffractometer with a graphite monochromator. XPS Studies. The measurements were made with a LHS 10 (MCD) system using Mg KR excitation. IR Studies. For IR studies, our zeolites were pressed into thin wafers (4-8 mg/cm2) and activated at 673 K in situ in the IR cell under vacuum (10-3 Torr) for 5 h. The spectra were recorded with BRUKER 66v and BRUKER 48 PC spectrometers equipped with MCT detectors. Catalytic Tests. The acidic cracking of n-heptane was carried out in a quartz glass tube reactor at 623 K and a total pressure of 2.5 MPa. The activation of the samples was performed in nitrogen 673 K for 3 h under normal pressure conditions. The partial pressure of n-heptane was fixed at 0.33 MPa. The weight of catalysts was constant for all experiments with 0.03 g. Cracking products were analyzed by on-line GC with a PLOT column. Results
27Al MAS NMR Studies. The 27Al MAS NMR spectra of four of our HZSM-5 zeolites (parent as well as dealuminated with 7, 13, and 93 kPa) are presented in Figure 1. There is a sharp line at 60 ppm due to tetrahedrally coordinated Al framework species. A broader line with much lower intensity is visible at 0 ppm. It is due to the octahedrally coordinated Al species. While the signal at 60 ppm decreases distinctly with dealumination, the signal at 0 ppm remains almost constant. The decrease in intensity of the 60 ppm signal indicates a decrease in the amount of tetrahedral Al. The constant intensity of the 0 ppm signal due to octahedral species should be interpreted in two ways. On one hand we can say that none (or a very low amount) of octahedral Al species are produced by the dealumination of the zeolite by water vapor. On the other hand, however, it cannot be excluded that extraframework Al creates bigger aggregates inside the channels or on the external surfaces. The concentrations of both tetrahedral and octahedral Al were calculated from the intensities of 60 and 0 ppm signals by using a procedure described in detail in ref 13.

Figure 2. XPS spectra of HZSM-5 zeolites (parent, dealuminated with 13 and 93 kPa H2O).

XPS Studies. XPS experiments were performed in order to study the migration of Al atoms in zeolite crystallites. Figure 2 shows the recorded spectra the Al 2p peak. The observed binding energies are practically constant. However, dealumination results in a strong increase in the intensity of the Al 2p peak of surface Al species. Figure 3 shows Si/Al values on the surface (obtained from XPS experiments) and in the bulk (calculated from XRD results). The Si/Al values of the surface were calculated from the intensities of Si 2p and Al 2p peaks by using appropriate sensitivity factors (taken from ref 15), and the Si/Al values concerning bulk from the XRD data (by using a correlation of the unit cell parameter and Si/Al; ref 16). According to the data presented in Figure 3, the steaming results in a distinct enrichment of Al in the crystallite surface. In the most dealuminated zeolite, the Si/Al ratio on the surface (about 8) is more than four times lower than in the bulk (about 35). It

Properties of HZSM-5 Zeolites

J. Phys. Chem., Vol. 100, No. 34, 1996 14453

Figure 3. Si/Al values on the surface and in the bulk for parent and dealuminated HZSM-5 zeolites.

Figure 5. Acidic strength of Bro nsted sites (A660/Ao) as function of the partial pressure of water.

TABLE 1: Characterization of Samples by NMR and IR Spectroscopy

27Al

MAS NMR

IR spectroscopy of pyridine adsorption

nsted acid Lewis acid vapor pressure tetrahedral octahedral Bro sites sites Al species Al species of H2O used (sites/u.c.) (sites/u.c.) (sites/u.c.)a (sites/u.c.) (kPa) 0 (parent) 7 13 40 93
a

6.0 3.2 3.2 2.0 1.4

0.6 0.4 0.4 0.7 0.8

4.8 3.1 3.1 1.9 0.8

0.2 0.2 0.3 0.4 0.6

Site/u.c. means site per unit cell of the zeolite.

Figure 4. IR spectra of OH groups in parent (a) and dealuminated HZSM-5 zeolites (b-e).

means that a great amount of Al removed from the framework migrated to the surface. IR Studies. Spectra of OH Groups. The spectra of OH groups in HZSM-5 parent zeolite and zeolites dealuminated with 7, 13, 40, and 93 kPa of water are presented in Figure 4. The treatment with steam results in a decrease in the Si-OH-Al band at 3610 cm-1 and in an increase in the Al-OH band at 3662 cm-1. The silanol group bands at 3725 and 3742 cm-1 are practically uninfluenced by this treatment. Concentration of Bro nsted and Lewis Acid Sites. The concentrations of both Bro nsted and Lewis acid sites were determined in quantitative studies of pyridine sorption. Small portions of pyridine were sorbed at 420 K until the intensities of the pyridinium ion (PyH+) band at 1545 cm-1 and the pyridine bonded to Lewis acid sites (PyL) at 1450 cm-1 became constant. The concentrations of Bro nsted and Lewis sites were calculated from these maximal intensities and extinction coefficients of PyH+ and PyL bands. The extinction coefficient of the PyH+ band (1545 cm-1) was determined in experiments in which measured portions of pyridine were sorbed in an activated parent HZSM-5 zeolite. The intensity of the 1545 cm-1 band increased linearly with the amount of pyridine sorbed, and the value of the extinction coefficient (0.079 cm2/mol) was calculated from the slope of this line. The extinction coefficient of the PyL band (1450 cm-1) was determined in experiments in which known portions of pyridine were sorbed in a dehydroxylated HY zeolite (activated at 1100 K). The intensity of the 1450 cm-1 band increased linearly with the amount of pyridine, reacting with Lewis sites (the amount of pyridine sorbed minus the amount of pyridine reacting with Bro nsted sitesscalculated from the intensity of PyH+ and the extinction coefficient of this band). The value of the extinction coefficient of the 1450 cm-1 PyL band was 0.269 cm2/mol. The values of the concentrations of both Bro nsted and Lewis acid sites are presented in Table 1. In all the zeolites, parent and dealuminated

ones, concentrations of Bro nsted sites are very close to the amounts of tetrahedral Al determined in 27Al MAS NMR studies. The concentration of Lewis sites increases upon the dealumination, but this increase is relatively low (from 0.2 to 0.8 site/unit cell). The amount of Lewis sites created upon dealumination is distinctly lower than the amount of Al removed from tetrahedral positions (4.0 Al/unit cell) in case of the most dealuminated zeolite (93 kPa H2O). Acidic Strength of Bro nsted Sites. The acidic strength of Bro nsted acid sites (Si-OH-Al groups) was studied in ammonia thermodesorption experiments followed by IR spectroscopy. An excess of ammonia was first sorbed at 320 K in activated zeolites, and the intensity of the band of ammonium ions at 1540 cm-1 (Ao) was measured. Ammonia was then desorbed at 660 K for 30 min, and the spectrum was recorded at 320 K. The intensity of the 1450 cm-1 band of ammonium ions which remained on the surface after desorption (A660) was measured, and the ratio A660/A0 (expressing the fraction of ammonium ions remaining at the surface after desorption) was taken as the measure of the acidic strength of Bro nsted sites. The A660/A0 values are presented in Figure 5. The maximal acidic strength of Bro nsted sites is observed in the mildly dealuminated (7 kPa H2O) zeolite. Distribution of the Acidic Strength of OH Groups. The information about the distribution of the acidic strength of SiOH-Al groups was obtained in experiments of chlorobenzene sorption. Two zeolites were studied: parent HZSM-5 and zeolite dealuminated with 7 kPa H2O (showing the highest acid strength and the highest catalytic activity, vide infra). Such a study was impossible for the more dealuminated zeolites (with 40 and 93 kPa H2O) because of a very low total amount of OH groups. The spectra of activated zeolites and zeolites with chlorobenzene sorbed and difference spectra are presented in Figure 6. Figure 6C shows expanded also the spectra of SiOH-Al groups interacting (by hydrogen bonding) with chlorobenzene. In the case of mildly dealuminated HZSM-5 zeolite (spectrum B), the band is narrower, thus suggesting a narrower distribution of the acidic strength. It should be noted that the

14454 J. Phys. Chem., Vol. 100, No. 34, 1996

Datka et al. from the rates of formation of hydrocarbons with one to six carbon atoms.14 The isomerization reactions were lower than 15% of the total conversion. A slight maximum of catalytic activity in n-heptane cracking can be observed (Figure 7) in the case of mildly dealuminated zeolite (7 kPa H2O). The reaction rate observed in case of the most dealuminated (93 kPa H2O) zeolite was even lower than in the non-dealuminated parent HZSM-5 zeolite. The same effects were observed when hydrogen was used as the carrier gas. The rate of n-heptane cracking was higher in hydrogen than in nitrogen. In both experiments, the main products of reaction were C3 and C4 hydrocarbons. Saturated hydrocarbons dominated over unsaturated products after cracking in hydrogen (Table 2). Discussion The treatment of HZSM-5 zeolite with steam resulted in removal of Al atoms from framework tetrahedral positions. This was demonstrated by 27Al MAS NMR studies (Table 1). The amount of framework Al decreased from 6 to 1.4 Al/u.c. upon the treatment with 93 kPa H2O. The loss of framework Al was accompanied by the loss of acidic Si-OH-Al groups as evidenced by IR spectroscopy. The OH band at 3610 cm-1 decreased (Figure 4), and the quantitative IR studies of pyridine sorption showed that the amount of acidic Si-OH-Al was practically equal to the amount of framework tetrahedral Al which remained in the framework after steaming (Table 1). While the treatment with steam removes Al atoms from tetrahedral framework positions, 27Al MAS NMR studies evidenced, however, that the amount of octahedral Al was practically constant in all the zeolites studied (Figure 1 and Table 1). It means that the removed Al atoms do not have octahedral coordination. It is also possible that some Al forms larger agglomerates in the channels or on the surface. The quantitative IR studies of sorbed pyridine showed (Table 1) that the concentration of Lewis acidic sites formed in steamed zeolites was much lower than the amount of Al which left tetrahedral positions. For the most dealuminated zeolite (93 kPa H2O), the amount of Lewis acid sites formed was 0.6 sites/unit cell and the amount of Al removed from tetrahedral positions was 4.0 Al /unit cell. Therefore only a small part of the removed Al creates Lewis acid sites. IR studies showed also that the intensity of the Al-OH band (3662 cm-1) increased upon dealumination (Figure 4), indicating that some Al atoms formed Al-OH species. The results of our XPS experiments (Figures 2 and 3) have shown that most of Al removed from the framework by the treatment with steam migrated to the external part of the crystals (this was evidenced by the distinct decrease in Si/Al ratio near the surface). The fact that the intensity of the Si-OH band (3742 cm-1) is practically uninfluenced by steaming (Figure 4) suggests that new silanol groups are not formed under our steaming conditions. A previous 29Si MAS NMR and IR study17 showed that in Y zeolite dealuminated by EDTA treatment, vacancies left by Al atoms removed, were not filled by Si atoms and many new Si-OH groups were formed. Cross-polarization 29Si MAS NMR experiments evidenced that these Si-OH groups were related to the vacancies. In the present study, of HZSM-5 dealuminated by the treatment with steam, no new silanol groups are formed (Figure 4), suggesting that the vacancies formed by Al-removing are filled by Si atoms migrating from other places in the zeolite. As mentioned, dealumination with EDTA leaves vacancies not filled with Si atoms. This difference can be explained by taking into account that, in our study, the dealumination (by treatment with steam) was done at a much higher temperature (770 K) than in the study with EDTA (370

Figure 6. Distribution of the acidic strength of OH groups in parent (A) and dealuminated with 7 kPa H2O (B) HZSM-5 zeolite: a, activated zeolite; b, zeolite with chlorobenzene sorbed; c, difference spectra. (C) Spectra of OH groups in parent (a) and in dealuminated (b) zeolite normalized to the same band area.

Figure 7. Catalytic activity (rate of n-heptane cracking) as a function of the partial pressure of water obtained with nitrogen and hydrogen as carrier gases.

submaxima of the highest frequencies (of the lowest ) are missing, suggesting that the less acidic hydroxyls are removed by dealumination. Catalytic Tests. The catalytic test reaction of n-heptane cracking was performed with nitrogen and hydrogen as carrier gases. The first point of measurement was after 2 min of time on stream (TOS). Figure 7 shows the initial cracking rate (TOS 2 min) as a function of the partial pressure of water during dealumination. Under the given reaction conditions, the conversion of n-heptane was lower than 5% and the rate was calculated

Properties of HZSM-5 Zeolites

J. Phys. Chem., Vol. 100, No. 34, 1996 14455

TABLE 2: Product Distribution and Molar Ratio of Paraffins to Olefins for Two Different Carrier Gases (H2 and N2) after Cracking of n-Heptane over Dealuminated Zeolites
zeolite/partial pressure of water (kPa) 0 hydrocarbons (%) C1 C2 C3 C4 C5 C6 iso-C7 P/Oa
a

7 N2 0 0.65 28.32 34.28 15.75 7.94 13.06 1.56 H2 1.77 1.30 26.67 33.37 18.13 11.00 7.75 5.66 N2 0.16 0.82 28.75 36.35 17.81 9.29 6.81 1.77 H2 2.11 1.37 27.14 32.08 17.02 10.33 9.96 4.67

13 N2 0 0.85 29.96 35.57 16.75 8.59 8.30 1.70 H2 1.91 1.38 27.20 34.12 18.37 9.89 7.12 4.20

40 N2 0 0.52 25.86 33.27 16.55 9.17 14.63 1.59 H2 2.02 1.35 24.50 33.09 18.13 10.96 9.96 4.47

93 N2 0 0.78 30.44 35.68 16.28 7.98 8.84 1.51

H2 2.41 1.28 26.18 32.01 17.13 10.52 10.47 5.30

Ratio of paraffins to olefins (mol/mol).

K). At this high temperature, the mobility of framework atoms is higher and it results in filling the vacancies left by Al. From the results of our IR studies of ammonia desorption, it can be concluded that the dealumination by steaming yields in a variation of acidic strength of Si-OH-Al groups. According to the data presented in Figure 5, the mild dealumination (7 kPa H2O) results in an increase in the acidic strength of SiOH-Al groups. Further dealumination dimishes the acidic strength. Two explanations of the increase in the acidic strength in mildly dealuminated zeolites can be considered. One of them assumes that this increase in acidity is due to the interaction of Si-OH-Al with an electron acceptor Al site created by dealumination (as considered by some authors, e.g., ref 9, in the case of faujasites dealuminated by steaming). Such an interpretation which was probably true for faujasites is less probable in the case of HZSM-5 zeolites in which the concentration of Al and Si-OH-Al groups is much lower than in faujasites; therefore, the distances are longer and the electrostatic interaction is much weaker. Our quantitative IR studies have shown that the concentration of Lewis acidic sites in our steamed zeolites is low (much lower than the concentration of Si-OH-Al groups) and that most of the Al migrates to the surface (XPS results). All these results suggest that the increase in the acidic strength of OH groups in mildly dealuminated HZSM-5 is probably not due to the interaction with electron acceptor Al species. Therefore, another interpretation can be taken into consideration. Our previous studies evidenced18-20 that Si-OH-Al groups in HZSM-5 zeolite were heterogeneous; five kinds of bridging hydroxyls of various acidic strength were found. We suppose that the heterogeneity of hydroxyl groups in HZSM-5 was due to the presence of SiOH-Al of various bridge geometries (XRD studies of Olson et al.21 found that the T-O-T bridge angle in the MFI structure varies from 143 to 175 and T-O bond distances from 0.152 to 0.167 nm). It may be assumed that the increase in the acidic strength of OH groups in mildly dealuminated HZSM-5 is the result of variation of the distribution of the OH acidic strength upon dealumination. The distribution of the acidic strength was therefore studied by following IR spectra of OH groups hydrogen-bonded to chlorobenzene molecules (Figure 6). It was found that in mildly dealuminated zeolite (7 kPa H2O) the distribution of the acidic strength of Si-OH-Al is narrower than in the parent zeolite. The band of hydrogen-bonded OH is narrowed from the site of high frequencies, indicating that the hydroxyls of the lowest acidic strength (of the lowest ) are missing. It may be suggested that the increase in the acidic strength of OH groups in mildly dealuminated zeolite (evidenced in ammonia thermodesorption experiments, Figure 5) is due to removal of the less acidic hydroxyls in the first order. It may be also suggested that the Al atoms which form the less acidic Si-OH-Al hydroxyls are these, which are initially removed

(by the treatment with steam) from the framework. The fact that the distribution of the acidic strength of Si-OH-Al in mildly dealuminated zeolite is narrower than in the parent one is another argument supporting a hypothesis that the increase in the acidic strength is not due to the interaction of Si-OHAl groups with electron acceptor Al species. If such an interaction would be the reason of the increase in the acidic strength of Si-OH-Al, the IR band of OH interacting with chlorobenzene should be only shifted to lower frequencies without visible variation of its half-width. The data presented in Figure 5 indicate also that the acidic strength of Si-OH-Al groups decreases in more strongly dealuminated zeolites. At the present moment no resonable interpretation of this decrease can be presented. It would be very interesting to study how stronger dealumination (at higher vapor pressures of water) influences the distribution of the acidic strength. Such a study is, however, not possible because the concentration of Si-OHAl hydroxyls is too low to obtain spectra of hydroxyls hydrogenbonded to chlorobenzene with reasonable signal-to-noise ratios. It should be noted that Auroux et al.,22 who studied acidity of HZSM-5 zeolites of various Al contents by microcalorimetry, reported a maximum of the acidic strength in zeolite with about 4.5 Al/unit cell, which is close to the value 3.2 Al/unit cell in our mildly steamed HZSM-5. According to Auroux, both the increase and decrease in Al content from the value 4.5 Al/unit cell result in a lowering of the acidic strength. Similar effects were also observed in our case (Figure 6). The catalytic properties of our zeolites were studied in the n-heptane cracking reaction. The data presented in Table 2 show that n-heptane cracking is a bimolecular reaction.14 The product distribution did not depend significantly on the acidity of zeolites. The results of our catalytic studies (Figure 7) agreed well with the data concerning zeolite acidity (Table 1 and Figure 7). The catalytic tests indicated that a maximum in catalytic activity is observed in mildly dealuminated zeolite (7 kPa H2O). The increase in the catalytic activity can be explained by considering the increase in the acidic strength of Si-OH-Al groups (as evidenced by IR spectroscopy, Figure 6). This increase in the acidic strength compensates the decrease in the number of acid sites (from 4.8 to 3.1 H+/unit cell). The further dealumination results in the decrease in the catalytic activity that can be explained by the decrease in both the concentration and acidic strength of Si-OH-Al. Similar effects were observed by Lukyanov,5 who reported also an increase in the catalytic activity of HZSM-5 in n-hexane cracking in mildly dealuminated zeolite and a decrease in activity for more severly dealuminated zeolites. Our results and also the results of Lukyanov5 suggest that there are defined conditions of zeolite dealumination which give zeolites of the optimum concentration and acidic strength of active sites.

14456 J. Phys. Chem., Vol. 100, No. 34, 1996 According to the data presented in Figure 7, higher cracking activity is observed if the reaction is carried out in hydrogen, instead of nitrogen. It suggests that hydrogen transfer plays an important role in the cracking reaction drawn in previous papers.14,23 Another piece of evidence on the role of hydrogen transfer in cracking is a considerably higher paraffins/olefins ratio in products (Table 2) when the reaction is carried out in hydrogen. Acknowledgment. This study was supported by a grant (0634/P3/94/07) of Komitet Badan Naukowych. The studies at Leipzig University were supported by Deutsche Forschungsgemeinschaft (DFG) within the Sonderforschungsbereich 294 Moleku le in Wechselwirkung mit Grenzfla chen at the University of Leipzig. F.W.S. was supported by a grant of the Hochschulerneuerungsprogramm (HEP) of the Sa chsisches Ministerium fu r Wissenschaft und Kultur. Additionally we thank D. Freude for measurement of the 27Al MAS NMR spectra and helpful discussion. References and Notes
(1) Scherzer, J. J. Am. Chem. Soc. Symp. Ser. 1984, 248, 157. (2) Brunner, E.; Ernst, H.; Freude, D.; Krause, C. B.; Prager, D.; Reschetilowski, W.; Schwieger, W.; Bergk, K.-H. Zeolites 1989, 9, 282. (3) Lago, R. M.; Haag, W. O.; Mikowsky, R. J.; Oslon, D. H.; Hellring, S. D.; Schmitt, K. D.; Kerr, G. T. In Proceedings of the 7th International Zeolite Conference; Murakami, Y., et al., Eds.; Kondansha: Tokyo, 1986; p 677. (4) Topsoe, N. Y.; Joensen, F.; Derouane, E. G. J. Catal. 1988, 110, 404. (5) Lukyanov, D. B. Zeolites 1991, 11, 325. (6) Lukyanov, D. B. Zeolites 1994, 14, 233. (7) Witzel, F.; Karge, H. G.; Gutche, A. In Proceedings of 9th International Zeolite Conference; von Balmoos, R., et al., Eds.; Butterworth-Heinemann: Boston, MA, 1993; p 283. (8) Arribas, J.; Corma, A.; Fornes, V.; Melo, F. J. Catal. 1987, 108, 135.

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(9) Makarova, M. A.; Garforth, A.; Zholobenko, V. I.; Dwyer, J.; Earl, G. J.; Ravlence, D. Proceedings of the 10th International Zeolite Conference; Weitkamp, J., et al., Eds.; Elsevier: Amsterdam, 1994; p 365. (10) Biaglow, A. I.; Gorte, R. J.; Kokotailo, G. T.; Parrillo, D. J. J. Catal. 1994, 148, 213. (11) Zholobenko, V. L.; Kustov, L. M.; Borovkov, V. Yu.; Kazansky, V. B. Kinet. Catal. 1987, 28, 965. (12) Zholobenko, V. L.; Kustov, L. M.; Kazansky, V. Y.; Loeffler, E.; Lohse, U.; Peuker, Ch.; Oehlmann, G. Zeolites 1990, 10, 304. (13) Freude, D.; Ernst, H.; Wolf, I. Solid State Nucl. Magn. Reson. 1994, 3, 271. (14) Meusinger, J.; Liers, J.; Moesch, A.; Reschetilowski, W. J. Catal. 1994, 148, 30. (15) Briggs, D.; Seah, M. P. Practical Surface Analysis; John Wiley and Sons: Chichester, U.K., 1983; p 511. (16) Kraak, P.; Scho del, R.; Goehl, I.; Brand, A.; Schwieger, W. Chem. Tech. 1992, 7, 8. (17) Datka, J.; Kolodziejski, W.; Klinowski, J.; Sulikowski, B. Catal. Lett. 1993, 19, 159. (18) Datka, J.; Boczar, M.; Rymarowicz, P. J. Catal. 1988, 114, 368. (19) Datka, J.; Boczar, M. Zeolites 1991, 11, 397. (20) Datka, J.; Boczar, M.; Gil, B. Langmuir 1993, 9, 2496. (21) Olson D. M.; Kokotailo, G. T.; Lawson, S. L. J. Phys. Chem. 1981, 85, 2238. (22) Auroux, A.; Gravelle, P. C.; Vedrine, J. C. Proceedings of 5th International Conference on Zeolites; Rees, L. V., et al., Eds.; Heyden: London, 1980; p 433. (23) Meusinger, J.; Corma, A. J. Catal. 1995, 152, 189. (24) Dwyer, J. In InnoVation in Zeolite Materials Science; Stud. Surf. Sci. Catal.; Grobet, P. J., et al., Eds.; Elsevier: Amsterdam, 1988; p 333. (25) Fritz, P. O.; Lunsfort, J. H. J. Catal. 1989, 118, 85. (26) Makarova, M. A.; Dwyer, J. J. Phys. Chem. 1993, 97, 6337. (27) Garallon, G.; Corma, A.; Formes, V. Zeolites 1989, 9, 84. (28) Chambellan, A.; Chevreau, T.; Khabtou, S.; Marzin, M.; Lavalley, J. C. Zeolites 1992, 12, 306. (29) Sauer, J.; Schirmer, W. In InnoVation in Zeolite Materials Science; Stud. Surf. Sci. Catal.; Grobet, P. J., et al., Eds.; Elsevier: Amsterdam, 1988; p 323.

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