Microporous and Mesoporous Materials 59 (2003) 133146 www.elsevier.

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Structural changes of Y zeolites during ion exchange treatment: eects of Si/Al ratio of the starting NaY
Koichi Sato *, Yoichi Nishimura, Nobuyuki Matsubayashi, Motoyasu Imamura, Hiromichi Shimada
National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan Received 13 June 2002; accepted 3 February 2003

Abstract The eects of Si/Al ratio of starting NaY zeolites on structural changes during ion exchange treatments were studied. Three zeolites of dierent Si/Al ratio were subjected to three cycles of ion exchange treatment using (NH4 )2 SO4 and subsequent calcinations, and analyzed after each cycle. In the rst ion exchange, the structural changes of the zeolites were almost independent of the Si/Al ratio of the starting NaY zeolites. For all three zeolites, about 60% of Na ions were exchanged, and the relative crystallinity decreased to about 80% of the starting NaY. In the second and third ion exchanges, the structural changes depended on the Si/Al ratio of the starting NaY zeolites. The zeolitic framework of Y zeolite with a low Si/Al ratio of 2.4 deteriorated, whereas Y zeolite with a medium Si/Al ratio of 2.8 and Y zeolite with a high Si/Al ratio of 4.1 retained their high crystallinity even after the third ion exchange. Furthermore, among the three zeolites, Y zeolite with a medium Si/Al ratio of 2.8 showed largest degrees of ion exchange, dealumination, and mesopore formation. 2003 Elsevier Science Inc. All rights reserved.
Keywords: Y zeolite; Ion exchange; Si/Al ratio; Mesopore; External surface

1. Introduction Y zeolite based catalysts are widely used in uid catalytic cracking (FCC) and hydrocracking processes due to their unique catalytic properties [1 4]. Before their use in these processes as solid acid catalysts, hydrothermally synthesized sodium-type

Corresponding author. Present address: National Institute of Advanced Industrial Science and Technology (AIST), Tohoku Center, 4-2-1, Nigatake, Miyagino-ku, Sendai, 9838551 Japan. Fax: +81-22-237-5226. E-mail address: koichi.sato@aist.go.jp (K. Sato).

Y zeolites (NaY) are transformed to proton-type Y zeolites (HY). The most common transformation method at present is the ion exchange treatment in a solution of ammonium salt followed by calcination that changes ammonium-type to proton-type. The ion exchange treatments at the same time cause extraction of Al from the zeolitic frameworks, thus yielding HY zeolites with favorable characteristics, namely, high Si/Al ratio and numerous mesopores larger than 2 nm in diameter. Many industrial processes, including FCC or hydrocracking processes, require HY zeolites that have high Si/Al ratios and large mesopore surface

1387-1811/03/$ - see front matter 2003 Elsevier Science Inc. All rights reserved. doi:10.1016/S1387-1811(03)00305-6

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areas, because such zeolites possess high hydrothermal stability and suitable acidic and porous properties for these catalytic reactions [5]. Numerous studies have been done on the eects of Si/ Al ratio of Y zeolites on catalytic performance during cracking reactions [6,7]. In previous studies, we clearly showed the superiority of HY zeolites with mesopores in the reaction of large molecules [8,9]. Another study [10] reported an advantage of the mesopores of HY zeolites as active catalytic sites for the synthesis of azo dyes. Certain ion exchange conditions, e.g., low pH, lead to signicant collapse of the zeolitic frameworks, because the framework structures of Y zeolites are more fragile than those of MFI or MOR zeolites. Furthermore, other dealumination treatments, such as steaming, SiCl4 treatment, and acid treatment, also cause the destruction of the structure of Y-type zeolites [1113]. Thus, ion exchange treatments cause changes in the properties and structure of Y zeolites and thereby aect the catalytic performance of the nal Y zeolite based catalyst. Despite the importance of such treatment-induced changes, past studies on ion exchange treatments of Y zeolites have focused mainly on ion exchange kinetics, equilibrium, and capacity for various cations [1419]. There have been only few academic articles that report the structural changes of Y zeolites during the ion exchange treatments. Furthermore, many studies assumed no changes in the zeolitic structure during both the ion exchange and subsequent catalyst preparation procedures. In this study, our goal was to clarify the structural changes of Y zeolites during ion exchange treatments to establish a method to prepare Y zeolite with a favorable Si/Al ratio and mesoporosity without a decrease in the crystallinity. To do this, we studied the eects of Si/Al ratio of the starting NaY zeolite on the structural changes of the Y zeolites. Because the Si/Al ratio of the starting NaY zeolite directly aects the ion exchange equilibrium [18], our premise was that the structures of HY zeolites strongly depend on the properties of starting NaY zeolites as well as on the ion exchange procedures. Until recently, the Si/Al ratio of NaY zeolites was limited to less than 3, because NaY zeolites

with high Si/Al ratios could not be hydrothermally synthesized. The methods to control the Si/Al ratios were limited to dealumination from thus prepared Y zeolites with low Si/Al ratios (<3.0). Since Delprato et al. developed a synthesis method of Y zeolites using 15-crown-5 as a template [20], NaY zeolites with high Si/Al ratios up to 5 have been synthesized. Taking advantage of this method, in this study we used three kinds of NaY zeolites with Si/Al ratios ranging from 2.4 to 4.1. The structural changes of each zeolite during the ion exchange treatments were evaluated by measuring the crystallinity, framework Si/Al ratio, and mesoporosity using X-ray diraction (XRD), nuclear magnetic resonance (NMR), N2 adsorption/desorption, and by determining the bulk and surface chemical composition. The morphological changes of each zeolite and its mesopores were evaluated by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Our results revealed the eects of Si/Al ratio on the chemical structure and morphologies such as mesoporosity.

2. Experimental 2.1. Ion exchange procedures Three kinds of NaY zeolites with dierent Si/Al ratios were used as the starting materials; NaY-A with a framework Si/Al ratio of 2.4 (Catalysts & Chemicals Industry Corporation, Japan), NaY-B with a framework Si/Al ratio of 2.8 (Tosoh Corporation, Japan), and NaY-C with a framework Si/Al ratio of 4.1 (prepared in our laboratory using 15-crown-5 as a template according to the procedure described in the literature [20]). The ion exchange and subsequent calcination procedures were repeated three times for each zeolite. Ion exchange was carried out at 368 K for 1 h using an aqueous solution of (NH4 )2 SO4 . The total amount of ammonium salt in the solution was 1.7 eq. for the rst ion exchange and 3.0 eq. for the second and third ion exchanges. The pH conditions were determined according to preliminary experiments described in Section 2.3. After each ion exchange in the solution, the sample was washed with pure water at 333 K, followed by

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drying in atmospheric air at 393 K for 12 h. The sample was then calcined in dry air. The temperature prole during the calcination was as follows: raising from 293 to 573 K with 3.3 K/min, maintaining 573 K for 1 h, raising to 873 K with 3.3 K/ min, maintaining 873 K for 3 h, and cooling to room temperature. The sample after each cycle of the ion exchange and subsequent calcination was respectively called IE1, IE2 or IE3. A commercially available USY zeolite (Tosoh Corporation) was used as the reference zeolite with a large volume of mesopores. The USY zeolite was treated in 0.1 mol/l HCl solution with stirring for 1 h at 298 K, then washed in deionized water at 333 K, and nally dried at 393 K for 12 h. Note that the USY zeolite before washing contained a large amount of extra-framework aluminum species. 2.2. Characterization of zeolites The relative crystallinity and unit cell parameters of zeolites were calculated from XRD patterns that were recorded with a MAC Science MXP-18 diractometer and CuKa radiation (0.1542 nm, 10 kV and 20 mA). The zeolite powder was packed in the cavity of a XRD sample holder made of glass. Then, the holder was kept in a closed vessel containing a saturated CaCl2 aqueous solution for 6 h to make the moisture in the sample at constant. The relative crystallinity was estimated by comparing the peak intensities of the ion exchanged sample with those of starting NaY. The total intensities of the six peaks assigned to (3 3 1), (5 1 1), (4 4 0), (5 3 3), (6 4 2), and (5 5 5) reections were used for the comparison according to ASTM D3906. Fig. 1 shows the comparison of the XRD patterns of HY-B (IE3) and NaY-B. Note that the relative crystallinity of HY-B (IE3) relative to NaY-B was 80%. The unit cell parameters were calculated from the (5 3 3) and (6 4 2) reection peak positions that were determined using the (1 0 1) reection peak of the anatase type of TiO2 (2h 25:3068) as an internal standard. The framework Si/Al ratio was obtained from the calculated unit cell parameters by using Brecks equation when the Si/Al ratio was smaller than 3 [21] and by using Engelhardts relation when it was larger than 3 [22]. The Si/Al ratio of the external

Fig. 1. XRD patterns of NaY-B and HY-B (IE3).

surface of the particles was measured by X-ray photoelectron spectroscopy (XPS) using a PHI5500 spectrometer with MgKa radiation (1253.6 eV, 300 W). The surface chemical composition was calculated using the peak areas and the atomic sensitivity factor given by the manufacturer [23]. The bulk Si/Al ratio was determined by inductively coupled plasma emission spectroscopy. The Na concentration was measured by atomic absorption analysis. The chemical state of Al was measured by 27 Al MAS-NMR using a Bruker AMX-500 NMR spectrometer. The rotor, lled with the hydrated zeolite, was spun at 4 kHz at the magic angle. The spectrum was recorded using a pulse of 1.0 ls and a repeat time of 5 s. The porosity of each sample was determined by measuring the N2 isotherm at 77 K with a Micromeritics ASAP 2010. The total surface area was calculated by using the BET method. The external surface area and micropore volume were calculated by using the t-plot method. Note that thus calculated external surface area contained both the mesopore surface area and the external surface area of the zeolite particles. The micropore surface area was calculated by subtracting the external surface area from the total surface area. The pore size distribution prole was calculated by using the BJH method with the N2 desorption isotherm [24]. The mesopore volume was calculated by integrating the dierential pore volume for a diameter range of 250 nm. The morphology of zeolite particles was evaluated by using SEM (Hitachi S-800 microscope). Before the observation, the sample was coated

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with Pt in vacuo to avoid surface charging. The morphology of the mesopores was evaluated by using TEM (Hitachi H-9000 microscope) with an acceleration voltage of 300 keV. Before the observation, the sample was suspended in chlorobenzene and dried on a microgrid. 2.3. Ion exchange conditions Table 1 summarizes the properties of the starting NaY and USY zeolites. The dierences in the initial Na concentrations among three NaY zeolites reect the dierent Si/Al ratios of the framework, because each Na cation compensates the negative charge arising from an Al atom in the framework. Because the ion exchange and subsequent calcination treatments reduce the crystallinity of Y zeolites, preliminary experiments using Y-B were at rst carried out to determine the ion exchange conditions that could minimize the reduction of the crystallinity during the ion exchange treatments. Table 2 shows the eect of pH during the rst ion exchange on the Na concentration and crystallinity of Y-B. The control of pH was carried out by the addition of an aqueous H2 SO4 solution (2.9 mol/l). The degree of ion exchange increased with decreasing pH, whereas the pH between 3.0 and
Table 1 Properties of starting NaY and USY zeolites Zeolite NaY-A NaY-B NaY-C USY
a

4.8 did not eect the crystallinity of the zeolite. This indicates that a low pH of 3.0 was the most favorable for the rst ion exchange. When the second ion exchange was conducted at a pH of 3.0, however, the crystallinity of the zeolite signicantly decreased, to less than 70%. The use of another ion exchange reagent, such as NH4 NO3 or CH3 COONH4 , instead of (NH4 )2 SO4 also caused a similar decrease in the crystallinity. Based on these preliminary results, in our experiments, we therefore used a pH of 3.0 for the rst ion exchange, and a pH of 4.5 for the second and third ion exchanges.

3. Results 3.1. Changes in morphology, structure, and chemical composition during ion exchange treatments Fig. 2 shows SEM photographs of NaY and HY (IE3) zeolites after the third ion exchange. The particle size of NaY-A was about 1 lm and that of NaY-C was 12 lm. Although the primary particle size of NaY-B was less than 1 lm, these primary particles aggregated and formed secondary particles about 13 lm in diameter. Comparison of the photographs of NaY and HY indicates that for all three zeolites the particle sizes and morphologies remained unchanged during the three cycles of ion exchange treatments. Table 3 summarizes the changes in Na concentration, crystallinity, and porosity of zeolites. For NaY-A, the Na concentration decreased by 56%, from 9.2% to 4.1%, during the rst ion exchange and nally reached 1.2% after the third ion exchange. For HY-B (IE1) and HY-C (IE1), the Na concentration decreased by 67%, to 2.6% and 2.3%, respectively, after the rst ion exchange. In the second and third ion exchanges, Na in Y-B was relatively easily exchanged as compared with Na in Y-A and Y-C. Thus, HY-B (IE3) exhibited the lowest Na concentration among the three zeolites after the three cycles of ion exchange. After the rst ion exchange, each zeolite maintained over 75% of crystallinity as compared to the respective starting NaY zeolite (Table 3). During the second and third ion exchanges, the decrease in

Na concentration (%) 9.2 7.1 6.1 0

Bulk Si/Al ratio 2.4 2.8 4.1 12.8

Relative crystallinitya (%) 109 100 124 94

Comparison with NaY-B.

Table 2 Eect of pH during the ion exchange on the relative crystallinity and Na concentration of Y-B zeolite Form Na form IE1 pH 3.0 4.0 4.8 Relative crystallinity (%) 100 86 82 86 Na concentration (wt.%) 7.09 2.66 2.74 2.87

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Fig. 2. SEM photographs of NaY and HY zeolites.

the crystallinity of Y-B and Y-C was relatively small, whereas that of Y-A was relatively linear during the second and third ion exchanges and nally reached 33%. Fig. 3 shows changes in Si/Al ratio of the zeolites measured by using chemical analysis, XRD, and XPS during the three ion exchanges. Before ion exchange treatment, for each zeolite, each method showed the same ratio, i.e., the Si/Al ratios

of the bulk (given by chemical analysis), framework (given by XRD), and surface (given by XPS) were similar for each zeolite. This indicates that the Si/Al atomic ratio was uniformly distributed throughout each zeolite particle and excluded the presence of extra-framework alumina species. The Si/Al ratios of Y-A were relatively constant between 2.4 and 2.9 during the three ion exchange cycles, independent of the analytical

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Table 3 Changes in the Na concentration and relative crystallinity of zeolites during the ion exchange Zeolite No. of ion exchange Na form IE1 IE2 IE3 Na form IE1 IE2 IE3 Na form IE1 IE2 IE3 Na concentration (%) 9.2 4.1 2.2 1.2 7.1 2.6 0.7 0.3 6.1 2.3 1.6 1.0 0 Relative crystallinity based on each Na form (%) 100 78 58 33 100 86 84 80 100 80 83 75 94a

Y-A

Y-B

Y-C

USY
a

Comparison with NaY-B.

method, thus indicating that the ion exchange treatments did not extract Al from the zeolitic framework of Y-A. In contrast to the Si/Al ratios of Y-A, those of Y-B diered according to the analytical method. The bulk Si/Al ratios measured by chemical anal-

ysis were relatively constant during the three ion exchange cycles, whereas the framework ratio measured by XRD increased during the second and third ion exchanges. The Si/Al ratio at the external surface measured by XPS also increased with increasing number of ion exchanges and nally reached 4.9 after the third ion exchange. These increases indicate that extraction of Al from the zeolitic framework occurred during the second and third ion exchanges and that the extracted Al was present inside the zeolite particles. The prole of the framework Si/Al ratio of Y-C was similar to that of Y-B; the ratio did not change during the rst ion exchange but increased during the second and third ion exchanges. Note that the change from 4.1 to 4.6 of Y-C was smaller than that from 2.8 to 5.0 of Y-B. Similar to bulk Si/Al ratio of Y-B, that of Y-C was constant during the three ion exchanges. In contrast, the surface Si/Al ratio of Y-C increased from 3.2 to 7.0 during the rst ion exchange and then decreased during the second and third ion exchanges. Fig. 4 shows the 27 Al MAS-NMR spectra of the zeolites. NaY-A and NaY-B exhibited a resonance peak at 60 ppm, and NaY-C at 55 ppm. These peaks correspond to tetrahedrally coordinated Al

(a) : Y-A
8
framework bulk surface

(b) : Y-B
8
framework bulk surface

(c) : Y-C
8

Si/Al

Si/Al

Si/Al

2
framework bulk surface

0 Na form 1

0 Na form 1

0 Na form 1

Cycle of ion exchange

Cycle of ion exchange

Cycle of ion exchange

Fig. 3. Changes in Si/Al ratio of (a) Y-A, (b) Y-B, and (c) Y-C.

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Fig. 4.

27

Al MAS-NMR spectra for (a) Y-A, (b) Y-B, and (c) Y-C.

species (AlIV ) in the zeolitic framework [25]. Small peaks at 30 and 85 ppm were attributed to the side spinning bands of the AlIV peak. All the spectra after the rst ion exchange exhibited a peak at 0 ppm that was assigned to octahedrally coordinated Al species (AlVI ). These observations indicate that none of the three NaY zeolites contained AlVI species but that ion exchange treatments yielded AlVI species in all the zeolites. In the spectra for Y-A, the intensity of the AlVI peak at 0 ppm was relatively constant during the second and third ion exchanges. The AlIV peak of Y-A at 60 ppm slightly shifted to 55 ppm and broadened after the rst ion exchange. In the spectra for Y-B, however, the intensity of the AlVI peak at 0 ppm increased after each ion exchange cycle, with the peak position of AlIV constant at 60 ppm. Broadening of the AlIV peak during the ion exchange for Y-B was less evident than that for YA. In the spectra for Y-C, the intensity of the AlVI peak at 0 ppm increased with increasing number of ion exchanges, similar to the observation for Y-B. However, the position of AlIV peak for Y-C was constant at 55 ppm, but the peak narrowed after the ion exchange treatments.

3.2. Changes in porosity during the ion exchange treatments In the N2 isotherm measurement, all three NaY zeolites showed typical type-I proles that are characteristic to microporous structures. After the ion exchange treatments, all three zeolites exhibited hysterisis in the isotherm proles for the P =P0 range between 0.05 and 0.9, which is a range that corresponds to the formation of mesopores. Table 4 summarizes the surface area and pore volume calculated from the isotherms. All three NaY zeolites showed similar micropore surface area of over 700 m2 /g and micropore volumes of about 0.33 cm3 /g, both of which are characteristic values for a Y-type zeolite framework. The surface area and volume of micropores decreased with increasing number of ion exchange cycles for all three zeolites, but the decreasing proles diered. The surface area and volume of micropores of Y-A did not change during the rst ion exchange, but signicantly decreased during the second and third ion exchanges. As a result, the micropore volume of HY-A (IE3) was about 40% of that of NaY-A. This decrease indicates the

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Table 4 Surface area and pore volume values of zeolites zeolite No. of ion exchange Na form IE1 IE2 IE3 Na form IE1 IE2 IE3 Na form IE1 IE2 IE3 Surface area (m2 /g) Micropore Y-A 720 714 637 299 707 651 649 644 717 588 644 648 691 External 45 57 85 68 46 73 99 122 38 41 43 58 130 Pore volume (ml/g) Micropore 0.327 0.324 0.285 0.133 0.330 0.302 0.301 0.299 0.334 0.274 0.303 0.302 0.321 Mesopore 0.034 0.039 0.045 0.040 0.068 0.077 0.093 0.114 0.015 0.016 0.018 0.025 0.186

Y-B

Y-C

USY

deterioration of the zeolitic framework structure and corresponds to the decreases in the crystallinity revealed by XRD. For both the Y-B and Y-C zeolites, the surface area and volume of micropores decreased during the rst ion exchange, but did not signicantly change during the second and third ion exchanges. The mesopore volume of Y-B increased with increasing number of ion exchanges, whereas that of Y-C did not. As a result, the mesopore volume of HY-B after the third ion exchange was almost four times larger than that of HY-C. The change in mesopore volume for the zeolites is reected in the pore size distribution proles in Fig. 5. For Y-A and Y-C, the prole did not change even after the third ion exchange, whereas for Y-B the mesopore volume for a diameter range of 310 nm increased with increasing number of ion exchanges. Note that the decreases in micropore volumes cannot be evidenced in the present pore size distribution proles showing the region of pore diameter larger than 2 nm. Fig. 5 shows the pore size distribution prole of the reference USY zeolite that had a large pore volume (Table 3). The prole (Fig. 5d) had two peaks, at about 4 and 15 nm, and the peak at 15 nm contributed to the large pore volume. Fig. 6 shows the TEM photographs of NaY-B, HY-B (IE3), and the reference USY. The photo-

graph of NaY-B (Fig. 6a) shows a well-crystallized lattice structure without deterioration. The photograph of HY-B (Fig. 6b) shows bright string-like regions, each about 5 nm wide, in addition to the lattice structure similar to NaY-B. These stringlike regions are presumably assigned to the mesopores revealed by the pore size distribution proles (Fig. 5b). This is conrmed by comparing the photograph of HY-B to that of USY (Fig. 6c) which had a large volume of mesopores about 5 15 nm in diameter. 4. Discussion For all three NaY before the ion exchange, the Si/Al ratios were independent of the analytical methods; i.e., the Si/Al ratios of the bulk, framework, and surface were similar for each zeolite (Fig. 3). This indicates that all the NaY zeolite particles had uniform zeolitic structure. The differences in the relative crystallinity among the three zeolites (Table 1) were likely due to dierences in their primary particles, such as average size of a primary particle or the direction of crystal growth, although the high crystallinity of NaY-C was partly due to the preparation method involving a template. Although the morphology of the particles did not change during the ion exchange treatments

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(a) : Y-A
0.2
Na form IE1 IE2 IE3

(b) : Y-B
0.2
Na form IE1 IE2 IE3

dV/dR (c m /g -nm)

0.1

dV/dR (c m3/g -nm) 50

0.15

0.15

0.1

0.05

0.05

0 1 5 10 Pore diameter (nm)

0 1 5 10 Pore diameter (nm) 50

(c) : Y-C
0.2
Na form IE1 IE2 IE3

(d) : USY
0.4 0.35 dV/dR (c m3/g -nm) 0.3 0.25 0.2 0.15 0.1

dV/dR (c m /g -nm )

0.15

0.1

0.05

0 1 5 10 Pore diameter (nm) 50

0.05 1 5 10 Pore diameter (nm) 50

Fig. 5. Pore size distribution for (a) Y-A, (b) Y-B, (c) Y-C, and (d) USY.

(Fig. 2), the structure changed. These structural changes depended on the Si/Al ratio of the starting NaY. During the rst ion exchange, however, the structural changes of the three zeolites had common features: (i) about 60% of Na was exchanged (Table 3), (ii) the relative crystallinity estimated by XRD decreased to about 80% (Table 3), (iii) the Si/ Al ratio of the framework was similar to that of the bulk (Fig. 3), and (iv) small amounts of AlVI species were formed (Fig. 4).

During the rst ion exchange, easily exchangeable Na ions were replaced by ammonium ions. The Na ions remaining after the rst ion exchange were probably located in the hexagonal prism [26,27] where ammonium cations could not approach by diusion [18]. The formation of AlVI indicates that some of the Al atoms in the framework were extracted and formed amorphous species. This corresponds to the observed decreases in crystallinity. However, the rst ion exchange did

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Fig. 6. TEM photographs of (a) NaY-B, (b) HY-B, and (c) USY (sliced sample).

not cause serious dealumination as indicated by the framework Si/Al ratio before and after the rst ion exchange remaining relatively unchanged. Higher Si/Al ratios at the external surface (measured by XPS) than in the bulk indicate that Al extraction primarily occurred at the external surface of the particles. This supports the former discussion that the ion exchange was controlled by the diusion of ammonium ions. The extracted Al was not deposited selectively on the external surface of the particles. In summary, during the rst ion exchange, some of the Na ions that were easily approachable from the outside were replaced by ammonium ions, and the extraction of Al and deterioration of the framework structure were not signicant. During the second and third ion exchanges, the three zeolites exhibited dierent behaviors. Firstly, the crystallinity of Y-A with a low Si/Al ratio of starting NaY decreased with increasing number of ion exchanges. At the same time, surface area and volume of micropores decreased. However, the relative amount of AlVI species did not increase and the changes in the framework Si/Al ratios were small. The dierences in the Si/Al ratios of the framework, bulk, and surface were relatively small. Secondly, the Na cations in Y-B with a medium Si/Al ratio were most easily exchanged.

Despite small decreases in the crystallinity, dealumination from the framework proceeded, resulting in a large mesopore volume. Lastly, the decreases in crystallinity and dealumination from the framework of Y-C with a high Si/Al ratio were relatively small, although a larger amount of AlVI species was formed than in Y-A. The ion exchange of NaY by ammonium ions during an ion exchange treatment is limited because ammonium ions cannot approach the inside of the hexagonal prisms. The calcination procedure after an ion exchange treatment likely causes the migration of Na to the outside of the hexagonal prisms. This migration of Na is accompanied by that of Al, because a Na ion compensates the negative charge arising from an Al atom in the framework. For Y-B, the migration of Na and Al relatively easily proceeded during the calcination. The migration of Al resulted in the formation of large amounts of mesopores, because mesopores are formed by the linkage of dealuminated sites that relieves the stress caused by structural defects [28,29]. Note that the dealumination from the framework and the formation of mesopores during the calcination treatment did not cause the destruction of the zeolitic framework, as reported in a previous study [8]. In contrast to Y-B, Y-C had a smaller degree of dealumination from the frame-

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work. This resulted in a smaller mesopore volume of Y-C after the second and third ion exchanges (Fig. 5), possibly causing the more reluctant ion exchange behavior of Y-C. Thus, the mesopore formation strongly depended on the amount of dealumination and geometry of dealuminated sites. Lunsford reported the classication of Al species in the framework according to the number of Al in the second nearest neighbor T sites [30]. When the number of Al in the unit cell increases, the expected number of Al in the second nearest neighbor T sites around a T site increases. For instance, a zeolite with a Si/Al ratio of 3.0 has 48 Al atoms in a unit cell. In this case, the average number of Al in the second nearest neighbor T sites is 0.67 with distribution of 16 for N0 -Al and 32 for N1 -Al according to his theory [30]. By using this theory, the distributions of the Al types in the present NaY zeolites were calculated as shown in Table 5. In NaY-C, more than two-thirds of Al species were N0 -Al and the rest were N1 -Al. This indicates that the dealuminated sites arising from the Al sites were most likely isolated and could survive without formation of mesopores during the calcination. In contrast, NaY-B contained 32 N1 -Al and 6 N2 -Al. The dealuminated sites of Y-B were easily interconnected with the nearest dealuminated sites and thus formed mesopores. The structural changes of Y-A with low Si/Al ratio diered from those of Y-B and Y-C with high Si/Al ratios. Although the observed decreases in the crystallinity, surface area, and micropore volume (Tables 3 and 4) indicate the deterioration of zeolitic framework during the second and third ion

exchanges, the SEM photographs (Fig. 2) revealed no serious changes. The framework Si/Al ratios during the ion exchange remained relatively constant, indicating little dealumination. Thus, the structural changes of Y-A were not accompanied by atomic rearrangement that would result in dealumination and formation of amorphous alumina. In general, the stability of the zeolitic framework during the ion exchange procedures decreased with increasing number of Al in the framework. The framework of Y-A with a low Si/ Al ratio was likely not stable under the present ion exchange conditions. Hence, the distortion and deterioration of the framework preceded the dealumination and migration of Al. The limited migration of Al also led to the reluctant exchange of Na ions by ammonium ions and to little formation of mesopores (Table 2, Fig. 5). The changes in the NMR spectra for Y-A (Fig. 4) agree well with these conclusions. The relatively constant AlVI ratios during the second and third ion exchanges correspond to little formation of amorphous alumina, whereas the peak broadening and shift of the AlIV peak to 55 ppm correspond to various AlIV environments with distorted symmetries [31]. Fig. 7 shows schematics of structural changes of the three zeolites during the second and third ion exchanges. In Y-A with a low Si/Al ratio, the ion exchange caused distortion and deterioration of the framework and did not result in dealumination that was likely not favored in the distorted framework. Prominent mesopore formation occurred only for Y-B with a medium Si/Al ratio. The increase in AlVI and constant Si/Al ratio of the bulk of Y-B

Table 5 Distribution of Al type in the zeolitic framework Zeolite Number of Ala in the framework (number/ unit cell) 56.5 50.5 37.6 Distribution of Al typeb N0 7 13 26 N1 32 32 12 N2 17 6 0

NaY-A NaY-B NaY-C

a b

Calculated from framework Si/Al ratios. Calculated using the theory by Lunsford [30]. N0 : 1 Al in the second neighbor T site; N1 : 2 Al in the second neighbor T site; N2 : 3 Al in the second neighbor T site.

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Fig. 7. Schematic of Si/Al ratio for the structural changes and formation of mesopores.

after the ion exchange indicated that the extracted Al formed amorphous alumina but was not removed from the particles. This amorphous alumina was probably located inside the particles, because the XPS result gave larger Si/Al ratios than did chemical analysis (Fig. 3). In Y-C with a high Si/Al ratio, although the ion exchange was accompanied by dealumination, the dealuminated vacancy did not make linkage due to the isolated location of the vacancy. The Al extracted during the ion exchanges formed amorphous alumina, similar to what occurred in Y-B. In the second and third exchanges, however, the Y-C particles could not accommodate the amorphous alumina inside because Y-C did not have an enough mesopore volume. As a result, part of the amorphous

alumina was deposited on the external surface of the particles, thus leading to decreasing the Si/Al ratio at the external surface of particles with increasing number of ion exchange (Fig. 3). Sasaki et al. studied mesopore formation mechanisms using a CCD-TEM technique [32]. They reported that mesopore formation occurred at the region of the twin crystal in the zeolite particles. This implies that mesopore formation is favored in small zeolite particles. The eect of relatively large particle size of Y-C should not be completely excluded in any discussion of mesopore formation. The features of the mesopores of Y-B diered from those of USY as evidenced by comparison of Fig. 5b with d and that of Fig. 6b with c. These observations are consistent with past studies on

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mesopores of Y-type zeolites [33,34]. The small and string-type mesopores in Y-B are probably the precursor of the large and bulky mesopores in USY; further dealumination treatments of Y-B would result in large mesopores.

References
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5. Conclusion The structural changes of Y-type zeolites during three cycles of ion exchange treatments were studied using three NaY zeolites with dierent Si/ Al ratios as the starting materials. The following conclusions were obtained. (1) In the rst ion exchange cycle, the structural changes were independent of the Si/Al ratio of the starting NaY zeolite, about 60% of Na ions were exchanged, and the relative crystallinity decreased to about 80% of the NaY. (2) In the second and third ion exchange cycles, the structural changes of the zeolites depended on the Si/Al ratio of the starting NaY zeolites. For YA with a low Si/Al ratio of 2.4, the zeolitic framework structure deteriorated as evidenced by decreases in the crystallinity and micropore surface area. However, these structural changes of Y-A were not accompanied by dealumination. Among the three zeolites, Y-B with a medium Si/Al ratio of 2.8 showed the most prominent dealumination and mesopore formation. For Y-C with a high Si/ Al ratio of 4.1, dealumination occurred but with little formation of mesopores. Y-B and Y-C retained their high crystallinity even after the third ion exchange cycle. The highest ion exchange ratio was achieved by Y-B. (3) The extracted Al during the ion exchange formed amorphous alumina, which was mainly deposited inside the zeolite particles. For Y-C with little formation of mesopores, however, part of the alumina was deposited on the external surface of the particles.

Acknowledgements This work was partly supported by Japan Science and Technology Corporation.

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