Applied Catalysis A: General 187 (1999) 225232

Alkylation of catechol with t-butyl alcohol over acidic zeolites

Jung Whan Yoo a , Chul Wee Lee a , Sang-Eon Park a, , Jaejung Ko b
a

Industrial Catalysis Research Lab., Korea Research Institute of Chemical Technology (KRICT), P.O. Box 107, Yusung, Taejon 305-606, South Korea b Department of Chemistry, Korea University, Chochiwon, Chungnam 339-700, South Korea Received 25 February 1999; received in revised form 31 May 1999; accepted 1 June 1999

Abstract The catalytic properties of H-ZSM-5 in catechol alkylation with t-butyl alcohol are compared to that of other solid acid catalysts, H-USY, H-beta, -alumina. H-ZSM-5 zeolite shows a selectivity higher than 84% and conversion higher than 90% for 4-tert-butylcatechol (4-TBC), while 3,5-di-tert-butylcatechol (DTBC) and 3-tert-butylcatechol (3-TBC) are produced as minor byproducts, which are identied by GC/MS and 1 H-NMR. When the Na cation-exchange level, Na/H, of NaH-ZSM-5 increases, the conversion and DTBC selectivity decrease rapidly and 3-tert-butylcatechol (3-TBC) selectivity grows. As the SiO2 /Al2 O3 ratio of H-ZSM-5 increases, the conversion and DTBC selectivity decrease. Selectivities for 4-TBC over NaH-ZSM-5 with three different Na cation-exchange levels and over ZSM-5 with three different SiO2 /Al2 O3 ratios are not changed signicantly. Surface modication of H-ZSM-5 via CVD with tetraethylorthosilicate (TEOS) or poisoning with tributylamine (TBA) leads to the reduction of DTBC selectivity, and simultaneously, to the improvement of 4-TBC selectivity. Variations of catalytic activity over ZSM-5 catalysts are compared and discussed in terms of the concentration and strength of the acid site determined by FT-IR spectroscopy. From this result, strong Brnsted acid sites seem to be responsible for the t-butylation of catechol. 1999 Elsevier Science B.V. All rights reserved.
Keywords: Alkylation; Catechol; t-Butyl alcohol; Zeolites; Acidity; Silylation; Pyridine adsorption; FT-IR

1. Introduction Catechol alkylation is an industrially important reaction since 4-tert-butylcatechol (4-TBC) and its derivatives are used as raw materials for the synthesis of several polymerization inhibitors, dye developers, pharmaceuticals, and agricultural chemicals. Commercial alkylation of aromatics is carried out via electrophilic substitution, where the metal halides AlCl3 , FeCl3 , and ZnCl2 are the most commonly used cata Corresponding author. Tel.: +82-42-860-7676; fax: +82-42860-7676 E-mail address: separk@pado.krict.re.kr (S.-E. Park)

lysts [1]. The use of these catalysts gives rise to many problems concerning handling, safety, corrosion, and waste disposal. Much effort has been put into developing alternative technology based on heterogeneous catalysts [2]. The use of zeolites in organic reactions has grown over the last several years because of the shape selectivity which the zeolites impose on a reaction, together with lower environmental pollution and higher purity of the product [34]. Hence, many reports on the alkylation of aromatics with alcohol or olen as the alkylating agent have been published [57], dealing with parameters which affect catalytic properties. For example, G. Bellussi et al. [5] reported benzene alkylation with

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

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Table 1 Characteristics of the zeolites used in catechol alkylation Catalysta H-ZSM-5 27% Na exchanged on H-ZSM-5 61% Na exchanged on H-ZSM-5 H-ZSM-5 H-ZSM-5 Silylated H-ZSM-5 with TEOS Poisoned H-ZSM-5 with TBA H-beta H-USY
a b

Notation HZ-3 27NaHZ-3 61NaHZ-3 HZ-5 HZ-8 S-HZ-3 P-HZ-3 HB H-USY

SiO2 /Al2 O3 30 30 30 50 80 30 30 25 30

SLangmuir (m2 g1 ) 425 425 425 425 425 720 780

Pore Size (nm)b 0.54 0.56 (straight) 0.55 0.51 (sinusoidal) 0.55 0.51 0.55 0.51 0.55 0.51 0.55 0.51 0.57 0.75 0.65 0.56 0.74 (sinusoidal) (sinusoidal) (sinusoidal) (sinusoidal)

(linear) (tortuous)

TEOS: tetraethylorthosilicate, TBA: tributylamine. S.-J. Chu et al., Appl. Catal. A: Gen. 123 (1995)51.

light olens catalyzed by beta zeolite; results showed that the catalytic activity and product selectivity are affected by the Al content and particle size of zeolite. In phenol alkylation with methanol using HY zeolite [6], the reaction is highly sensitive to the number and strength of the acid sites of the catalyst. B. Wichterlova et al. [7] used silylated H-ZSM-5 in toluene alkylation, where conversion and selectivity were improved. Generally, in the alkylation of aromatics using zeolites [510], catalytic activity was controlled by acidity (Al content in zeolite) and selectivity was controlled by pore structure and acid strength of zeolites. On the other hand, improvement of para-selectivity in the alkylation of aromatics is one of the most interesting spheres of work. It has been shown that a high para-selectivity in alkylation can be achieved via chemical modication of the zeolite crystal surfaces, using deposition of bulky silicon molecules that do not penetrate into the zeolite channels. This is ascribed to the blocking of active sites on the external surface and/or to decrease in the free diameter of the channel entrance [1113]. Although many articles about the alkylation of aromatics have been reported, only a few patents on the butylation of dihydroxy-substituted aromatics have been disclosed until now [1415]. In a Japanese patent [14], 4-TBC was prepared by catechol and t-butyl alcohol in the presence of FriedelCraft type catalysts, ZnCl2 , FeCl3 , and HCl, with low conversion and selectivity, and di-t-butylation of hydroquinone was achieved by isobutylene over acidic resin with low conversion and selectivity [15].

In this study, we try to understand the relationships between conversion/selectivity and the acidic nature of the catalyst for t-butylation of catechol with t-butyl alcohol over zeolites. Various zeolites, such as NaH-ZSM-5 with different ion-exchange levels and SiO2 /Al2 O3 ratios, modied H-ZSM-5 by silylation or poisoned by bulky amine, are also prepared and applied for the catalytic reaction. The concentration and strength of acid sites are determined by FT-IR spectroscopy.

2. Experimental 2.1. Catalyst preparation Commercially available zeolites such as H-ZSM-5, H-beta, and H-USY were provided by PQ company. The characteristics and notation of the zeolites studied in this work are summarized in Table 1. Two samples with different Na ion-exchange levels were prepared by using a 0.01 M NaNO3 solution at room temperature. Na-exchanged amounts were determined by ICP-AES (ICP-1000 III, Shimadzu I). Silylation was carried out as follows. HZ-3 zeolite was dehydrated at 450 C for 2 h under 105 Torr, followed by cooling down to room temperature. Then, tetraethylorthosilicate (TEOS) (Aldrich 99+%) vapor was exposed to the sample. It was kept at 200 C for 20 h, followed by pumping at the same temperature for 2 h. The sample was calcined at 550 C for 6 h in air. As for the poisoning of HZ-3 by amine, dehy-

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drated H-ZSM-5 zeolite was contacted with tributylamine (TBA) (Aldrich 99+%) and evacuated at 200 C for 2 h in order to remove the physisorbed amine. 2.2. Catalytic reaction The catalytic alkylation of catechol (Aldrich 99+%) with t-butyl alcohol (Aldrich 99+%) at 170 C was carried out at atmospheric pressure using a xed-bed vertical ow reactor. A mixture of catechol and t-butyl alcohol with a molar ratio of 1 : 3 was introduced into the reactor by means of a syringe pump with a WHSV of 4.85 h1 . The liquid products were collected every 1 h, and analyzed by gas chromatography using a ame ionization detector furnished with SE-30 30 m capillary column. Reaction products were identied by GC/MS (HP 5890 II GC-HP 5971 Mass Selective Detector) and 1 H-NMR (GEMINI-2000, 200 MHz). 2.3. Characterization of catalysts For FT-IR study, samples of 12 mg were pressed into self-supported wafers. These wafers were mounted in an infrared vacuum cell with calcium uoride windows. Then, the samples were degassed at 450 C for 2 h. 1 Torr of pyridine vapor was introduced into the cell at room temperature. The cell was elevated to 200 C and kept for 1 h; the samples were then evacuated at the same temperature for 1 h. In order to investigate the acid strength, desorption of pyridine was performed by evacuation at 200 C, 300 C, and 400 C, respectively. All the FT-IR spectra were measured at room temperature. The IR peak intensities were normalized with the 1882 cm1 band which is assigned to the SiO overtone of zeolite framework [16]. The FT-IR spectra were recorded by using a Nicolet Magna-IR 560 spectrometer over the range 10004000 cm1 with 2 cm1 resolution.

tion. Acidic zeolites can catalyze such a reaction due to the strong acidity of their protons. On account of the electrophilic nature of the alkylation over acidic catalysts, substitution at the para-position of catechol is favored. Four different reaction products can be produced in this reaction. As shown in Scheme 1, they are C-alkylated catechol derivatives such as 4-TBC (I), 3-TBC (II), and DTBC (III), and O-alkylated catechol isomer (IV). However, according to the result of GC/MS, only three different reaction products with different distributions were detected during the reaction with t-butyl alcohol over acidic catalysts. In order to identify the reaction products clearly, the reaction product mixture was separated and components were characterized by GC/MS and 1 H-NMR. They include 4-TBC (I) and DTBC (III), which were easily identied by comparing with commercially available products; the remaining reaction product is veried to be isomer II, 3-TBC, whose 1 H-NMR spectrum (CDCl3 , 200 MHz) shows 6.89 (multiplet, 1H, ArH), 6.70 (multiplet, 2H, ArH), 5.64 (broad singlet, 1H, OH), 4.90 (broad singlet, 1H, OH), 1.41 (singlet, 9H, t-Bu). The fragmentation pattern of isomer II is almost the same as that of isomer I, 4-TBC. No O-alkylated derivatives were observed. Among the various zeolites, H-ZSM-5 shows considerable conversion, the highest selectivity for 4-TBC and the lowest selectivity for DTBC. All the catalysts show poor catalytic activity below 100 C; this is so because of a diffusion limitation due to the constrained pores of the zeolite.

3.1. Effect of zeolite structure The catalytic activities for catechol alkylation with t-butyl alcohol over various zeolites such as HZ-3, HB, and H-USY are exhibited in Table 2. All catalysts show high conversion (at least 90%) and 4-TBC selectivity higher than 82%. These catalysts have also displayed high activity and selectivity in the previous studies related to the alkylation of aromatics [5,7,9]. On the other hand, poor catalytic activity was observed with less than 23% conversion over -alumina Al2 O3 . The catechol conversions over HZ-3 and H-USY zeolites are 90.8% and 93.8%, respectively, even

3. Results and discussion Since alcohols or olens can generally be used as alkylating agents in the alkylation of aromatic compounds, t-butylalcohol serves as the alkylating agent as well as solvent in this work. Acid-catalyzed alkylation is one type of a FriedelCraft substitution reac-

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Scheme 1. Table 2 Alkylation of catechol with t-butyl alcohol over various catalysts Catalysta Catechol conversion (%) Selectivity (%) 4-TBC HB H-USY HZ-3 27NAHZ-3 61NaHZ-3 HZ-5 HZ-8 S-HZ-3 P-HZ-3
a b

DTBC 15.0 13.9 12.7 7.3 2.2 9.0 8.1 10.9 10.5

3-TBC 2.5 2.5 2.5 5.4 11.3 3.3 3.4 2.7 2.4

P/Db 5.5 6.0 6.7 11.9 39.1 9.7 10.9 7.9 8.3

P/Oc 33.0 33.6 34.2 16.2 7.7 27.0 26.4 32.0 36.2

D/Od 6.0 5.6 5.1 1.4 0.2 2.8 2 .4 4.1 4 .3

93.0 93.8 90.8 57.2 24.2 82.3 80.2 89.4 90.5

82.5 83.6 84.8 87.3 86.5 87.7 88.5 86.4 87.1

See Table 1 for catalyst notation. P/D: 4-TBC/DTBC. c P/O: 4-TBC/3-TBC. d D/O: DTBC/3-TBC.

though they have the same SiO2 /Al2 O3 ratio. The lower conversion over HZ-3 than over H-USY might be attributed to the diffusion limitation for its smaller pore structure, which is shown in Table 1. However, HZ-3 exhibited the highest and lowest selectivities for 4-TBC (HZ-3 84.8%, HB 82.5%, H-USY 83.6%) and DTBC (HZ-3 12.7%, HB 15.0%, H-USY 13.9%), respectively, among three catalysts. The selectivity of the dialkylated by-product, DTBC, is increased in the order H-ZSM-5 < H-USY < H-beta. It seems that DTBC is formed on the external surface of zeolite because DTBC is too large to penetrate into the zeolite channels. The selectivity of 3-TBC is identical for three different zeolite catalysts, which suggests that the formation of 3-TBC is not related to the zeolite structure.

3.2. Effect of number of acid sites Although the conversion over HZ-3 is somewhat less than that over H-USY and HB, its high 4-TBC

selectivity can overcome this weak point. Since we thought that selectivity is a more important factor than the conversion on the catalyst for the production of ne chemicals, H-ZSM-5 is mainly investigated in this study. Table 2 demonstrates the relationship between the catalytic activity and Na ion-exchange level in catechol alkylation. Catalytic properties such as catechol conversion, selectivities of DTBC and 3-TBC are very sensitive to the number of acid sites; however, interestingly, 4-TBC selectivity is not. HZ-3, 27NaHZ-3, and 61NaHZ-3 zeolites give 90.8%, 57.2%, and 24.2% of catechol conversion and 12.7%, 7.3%, and 2.2% of DTBC selectivities, respectively; such results are closely related to the reduction of concentration of acid sites by Na ions. Hence catechol alkylation depends on the acidity of catalysts. The 4-TBC selectivities are not changed signicantly by Na content, indicating that 4-TBC formation is mainly controlled by zeolite pores. This trend is in good agreement with the results of catechol methylation over Mg-modied Al2 O3 catalysts reported by L. Kiwi-Minsker et al. [17]. L. Kiwi-Minsker reported that the activity and selectiv-

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ity of the aluminas used depend on the cation introduced. The catalytic activity of Mg-modied alumina decreases with increasing Mg content in the samples, and the selectivity too is strongly dependent on the Mg content. 61NaHZ-3 exhibits about ve times higher 3-TBC selectivity than HZ-3. 3-TBC selectivities are 2.5%, 5.4%, and 11.3% over HZ-3, 27NaHZ-3, and 61NaHZ-3 zeolites, respectively. 3-TBC formation is proportional to the Na content in zeolite, indicating that 3-TBC formation favors weak acid sites. 3.3. Effect of SiO2 /Al2 O3 ratios Catalytic properties of H-ZSM-5 with three different SiO2 /Al2 O3 ratios were compared. It is well known that the increment of aluminum content determines the increase in the acid site density [18]. As shown in Table 2, the catechol conversion and DTBC selectivities decrease slowly through decreases in the framework Al content. This slow decreasing trend is identical to the Brnsted acid site strength, which was determined by FT-IR study (see Section 3.5). Even though the reduction of Al content implies the reduction of acid site density, the acid site strength will be different. Changing rates, not only of conversion but also of product selectivity according to the SiO2 /Al2 O3 ratio, are not sensitive compared to those of Na-exchanged samples. HZ-3, HZ-5, and HZ-8 zeolites show 84.8%, 87.7%, and 88.5% 4-TBC selectivities, respectively. The phenomenon showing high 4-TBC selectivity in zeolite with a high SiO2 /Al2 O3 ratio is associated with the reduction of DTBC formation. This behavior is expected because the stronger acid sites of the external surface of HZ-3 zeolite can induce secondary catalytic reaction for producing DTBC from 4-TBC. DTBC will be formed over the zeolite having greater acidic property or high Al contents (DTBC selectivity: HZ-3 12.7%, HZ-5 9.0%, HZ-8 8.1%, respectively), which is proportional to the number and strength of acid sites on the external surface. DTBC formation shows the same trend as catechol conversion. 3.4. External surface modication by silylation or poisoning with base It was observed that DTBC can be produced on the external surfaces of zeolite; its formation is closely

related to the acid sites of the catalysts. In order to control the formation of DTBC, the silylated or poisoned HZ-3 zeolites are prepared and their catalytic selectivities are evaluated. The external surface of HZ-3 zeolite was modied in situ with TEOS and TBA according to the literature [19]. Catechol conversion over the modied HZ-3 is almost identical to that over HZ-3, which means that the modications do not change the concentration of acid sites located in the pores. And increment in 4-TBC selectivity (HZ-3 84.8%, S-HZ-3 86.4%, P-HZ-3 87.1%) and reduction in DTBC selectivity (HZ-3 12.7%, S-HZ-3 10.9%, P-HZ-3 10.5%) are obtained over external surface modied HZ-3 zeolites (see Table 2). Removal of external acid sites can be achieved by depositing the vapor of a bulky chemical whose molecular size is larger than the HZ-3 pore opening, while the internal structure of the zeolite remained unaffected. Since DTBC selectivity over modied catalysts was decreased by about 15%, it seems that the modication resulted in partial removal of acid sites on the external surface. Slightly improved 4-TBC formation with high activity can be achieved via silylation and poisoning of the zeolite external surfaces. 3-TBC selectivity is constant before and after surface modication, which implies that the formation of 3-TBC is not related to the external acid sites (see Table 2). Table 2 also summarizes product selectivity ratios over ZSM-5 catalysts with different Na contents, SiO2 /Al2 O3 ratios and external surface modication. Catalytic properties exhibit the same trends with Na content and increase in the SiO2 /Al2 O3 ratio, but the variation slope shows a big difference. As Na contents and SiO2 /Al2 O3 ratios increase, P/D ratios increase due to DTBC formation by external strong acid sites. Since 3-TBC seems to be formed on weaker acid sites, P/O ratios show the inverse trend.

3.5. Characterization by FT-IR 3.5.1. OH vibrational spectra FT-IR spectra of ZSM-5 with different Na amounts and SiO2 /Al2 O3 ratios in the region of the hydroxyl group are shown in Fig. 1. The spectrum of HZ-3 contains two main bands, at 3611 and 3744 cm1 . The band at 3611 cm1 is associated with the acidic

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Fig. 1. FT-IR spectra of the hydroxyl vibration region for (a) HZ-3, (b) 27NaHZ-3, (c) 61NaHZ-3, (d) HZ-5, and (e) HZ-8.

non-acidic silanol OH bands retained the same intensity. In the region 14001600 cm1 , four sharp bands due to CC stretching vibrations of pyridine are observed. The band at 1490 cm1 is due to the pyridine adsorbed on both Brnsted and Lewis acid sites, while the bands at 1546 and 1455 cm1 are due to the protonated pyridine molecule adsorbed on Brnsted acid sites and that adsorbed on Lewis acid sites, respectively. The alkalimetal cations in the zeolite also show a characteristic infrared band at 1443 cm1 after pyridine adsorption [25]. Decrease in both Brnsted and Lewis acid sites is observed as the SiO2 /Al2 O3 ratio and Na-exchange level of ZSM-5 zeolite increase. Generally, the acidity of a catalyst inuences product distribution as well as catalytic activity. In order to understand the relationship between catalytic activity and acidic properties of a catalyst, we calculated concentrations of Brnsted and Lewis acid sites in Table 3. Brnsted and Lewis acidities are determined on the basis of the integrated absorbances of the bands at 1546 and 1455 cm1 , respectively, using known molar absorption coefcients (1.3 106 cm mol1 for Brnsted acid bonded pyridine and 1.5 106 cm mol1 for Lewis acid bonded

OH groups (SiOHAl) and the 3744 cm1 band with the terminal, non-acidic OH groups bound to silicon framework atoms (SiOH) [2021]. Two weak bands, at 3663 and 3779 cm1 , are also detected; they are assigned to hydroxyls linked to aluminum atoms dislodged from the framework [2223]. When Na-exchanged capacity of HZ-3 increases, FT-IR intensity of the acidic OH group decreases drastically. In fact, catechol conversion is proportional to the IR intensity of the Brnsted acidic OH group at 3611 cm1 [24]. On the other hand, as the SiO2 /Al2 O3 ratio increases, the FT-IR intensities of acidic OH groups (Brnsted acid sites) decrease slowly (Fig. 1), which agrees well with catechol conversion (compare with Table 2). 3.6. Pyridine adsorption Fig. 2 shows the FT-IR spectra of pyridine adsorbed ZSM-5 with different Na-exchange levels and SiO2 /Al2 O3 ratios, respectively. For pyridine adsorbed samples, the acidic OH bands disappear; however, the

Fig. 2. FT-IR spectra of pyridine adsorbed (a) HZ-3, (b) 27NaHZ-3, (c) 61NaHZ-3, (d) HZ-5, and (e) HZ-8.

J.W. Yoo et al. / Applied Catalysis A: General 187 (1999) 225232 Table 3 Aciditya of Brnsted and Lewis acid sites for pyridine adsorbed ZSM-5s in terms of the evacuation temperature Catalyst 200 C B HZ-3 27NaHZ-3 61NaHZ-3 HZ-5 HZ-8
a

231

300 C L 242 51 56 157 77 B 231 60 15 113 93 L 151 48 51 104 57

400 C B 137 19 5 70 58 L 168 44 29 52 57

280 117 29 138 112

Finally, we can suggest a scheme for catechol alkylation based on Bellussis proposal [5]. Catechol alkylation with t-butyl alcohol is an electrophilic substitution on the aromatic ring. t-Butyl alcohol is dehydroxylated by the Brnsted acid sites to form the t-butyl cation species. They react with catechol, producing 4-TBC, which can bring about further alkylation over external Brnsted acid sites, producing DTBC.

mol g1 zeolite; B: Brnsted acid site; L: Lewis acid site.

4. Conclusions pyridine) [26]. Upon evacuation of pyridine adsorbed samples at 200 C, 300 C, and 400 C, as shown in Table 3, the decreasing rate of number of acid sites for ZSM-5 with higher Na ion-exchange levels is faster than that of H-ZSM-5 with higher SiO2 /Al2 O3 ratios. Similarly, as shown in Table 2, variations in catechol conversion and product selectivity in terms of the SiO2 /Al2 O3 ratio are not as sensitive as those of Na-exchanged samples. And catechol conversion is closely proportional to Brnsted sites rather than Lewis acid sites, i.e. catechol alkylation seems to be controlled mainly by Brnsted acid sites. But catechol conversion is not proportional to the concentration of Brnsted acid sites in any case; for example, upon evacuation at 200 C, the concentration of Brnsted acid sites for 27NaHZ-3 and HZ-8 is 117 and 112 mol g1 , respectively, which does not coincide with catechol conversion. However, upon evacuation at 400 C, the concentrations of Brnsted acid sites for 27NaHZ-3 and HZ-8 are 19 and 70 mol g1 , which shows the same trend as catechol conversion. From this experimental result, we expect that 27NaHZ-3 and HZ-8 will possess weaker and stronger Brnsted acid sites, respectively. This might be the reason why HZ-8 displays catechol conversion 20% higher than that of 27NaHZ-3. Hence, it can be proposed that t-butylation of catechol is associated with the stronger acid sites. This result is well supported by M. Trombetta et al. [27], who found that the Brnsted surface acidity scale correlates well with the catalytic activity in 1-butene conversion. And G. Bellussi et al. [5] illustrated that alkylation reactions catalyzed by acidic zeolites are commonly considered as proceeding via carbonium-ion-type mechanisms by referring to a report of P.B. Venuto et al. [28]. By performing the catalytic activity evaluation and FT-IR spectroscopy, we have investigated the inuences of various catalyst conditions such as zeolite types, Na contents, SiO2 /Al2 O3 ratios, external surface modication by silylation or poisoning by amine for the catalytic activity and product selectivity in catechol alkylation with t-butyl alcohol. From this reaction, 4-TBC is obtained as the major product, and DTBC and 3-TBC are obtained as minor by-products, which are veried by GC/MS and 1 H-NMR. The conclusions from the present results can be summarized as given below: 1. Among the catalysts studied in this work, H-ZSM-5 appears to be the most efcient catalyst for the selective formation of 4-TBC in catechol alkylation with t-butyl alcohol. 4-TBC selectivity is inuenced by the size of the zeolite pore aperture. 2. Catalytic activity is more closely related to Brnsted acid sites rather than Lewis acid sites, and catechol conversion depends on the number and strength of Brnsted acid sites. Higher concentration and stronger acid sites of catalyst produce higher catechol conversion. 4-TBC selectivity is independent of the acidity of the catalyst, but is controlled by the zeolite pore size and its structure. By-product 3-TBC formation is more likely to be favored on weakly acidic catalysts than on strongly acidic catalysts. On the other hand, DTBC is easily formed over the catalysts having stronger acidic sites on the external surface of the catalysts. 3. Selectivities of DTBC and 4-TBC can be improved by removing the external acidic sites through silylation and poisoning, using large

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J.W. Yoo et al. / Applied Catalysis A: General 187 (1999) 225232 [11] M. Niwa, Y. Murakami, J. Phys. Chem. Solid 50 (1989) 487. [12] B. Wichterlova, J. Cejka, Catal. Lett. 16 (1992) 421. [13] G. Mirth, J. Cejka, J. Krtil, J.A. Lercher, Stud. Surf. Sci. Catal. 88 (1994) 241. [14] J. Nagaoka, JP 49,109,325, 1974. [15] T.P. Malloy, D.J. Engel, US 4,323,714, 1982. [16] C.D. Chang, C.T.-W. Chu, J.N. Miale, R.F. Briger, R.B. Calvert, J. Am. Chem. Soc. 106 (1984) 8143. [17] L. Kiwi-Minsker, S. Porchet, P. Moeckli, R. Doepper, A. Renken, Stud. Surf. Sci. Catal. 101 (1996) 171. [18] S.G. Hedge, R. Kumar, R.N. Bhat, P. Ratnasamy, Zeolites 9 (1989) 231. [19] M. Huang, A. Adnot, S. Kaliaguine, J. Chem. Soc., Faraday Trans. 89 (1993) 4231. [20] P.A. Jacobs, R. von Ballmoos, J. Phys. Chem. 86 (1982) 3050. [21] C.T.W. Chu, C.D. Chang, J. Phys. Chem. 89 (1985) 1569. [22] V.L. Zholobenko, L.M. Kustov, V.Y. Borovkov, V.B. Kazasky, Zeolites 8 (1988) 150. [23] I. Kiricsi, C. Flego, G. Pazzuconi, W.O. Parker, R. Millini, C. Perego Jr., G. Bellussi, J. Phys. Chem. 98 (1994) 4627. [24] H.P. Boehm, H. Knozinger, in: J.R. Anderson, M. Boudart (Eds.), Catalysis, Science and Technology, Springer, Berlin, 1983, p. 39. [25] J.W. Ward, in: J.A. Rabo (Ed.), Zeolite Chemistry and Catalysis, ACS Monograph 171, American Chemical Society, Washington, DC, 1979, p. 118. [26] J. Take, T. Yamaguchi, K. Miyamoto, H. Ohyama, N. Misono, Stud. Surf. Sci. Catal. 28 (1986) 495. [27] M. Trombetta, G. Busca, S. Rossini, V. Piccoli, U. Cornaro, A. Guercio, R. Catani, R.J. Willey, J. Catal. 179 (1998) 581. [28] P.B. Venuto, L.A. Hamilton, P.S. Landis, J. Catal. 5 (1966) 484.

molecules that are bigger than the pore size of the zeolites. 4. The concentration of strong Brnsted acid sites determined by pyridine adsorption is in the following order: HZ-3 > HZ-5 > HZ-8 > 27NaHZ-3 > 61NaHZ-3. The same trend is also found for catechol conversion, indicating that this reaction is controlled by stronger Brnsted acid sites. References
[1] R.E. Burk, in: Twelfth Catalyst Report, National Research Council, Wiley, New York, 1940, p. 266. [2] A. Corma, A. Martinez, Catal. Rev. Sci. Eng. 35(4) (1993) 483. [3] J.W. Yoo, D.S. Kim, J.-S. Chang, S.-E. Park, Stud. Surf. Sci. Catal. 105 (1997) 2035. [4] H. van Bekkum, Stud. Surf. Sci. Catal. 41 (1988) 23. [5] G. Bellussi, G. Pazzuconi, C. Perego, G. Girotti, G. Terzoni, J. Catal. 157 (1995) 227. [6] S. Namba, T. Yashima, Y. Itaba, N. Hara, Stud. Surf. Sci. Catal. 5 (1980) 105. [7] J. Cejka, N. Zilkova, B. Wichterlova, G. Eder-Mirth, J.A. Lercher, Zeolites 17 (1996) 265. [8] J.L.G. Almeida, M. Dufaux, Y.B. Taarit, C. Naccache, Appl. Catal. A: Gen. 114 (1994) 141. [9] S.-J. Chu, Y.-W. Chen, Appl. Catal. A: Gen. 123 (1995) 51. [10] J. Medina-Valtierra, M.A. Sanchez, J.A. Montoya, J. Navarrete, J.A. de los Reyes, Appl. Catal. A: Gen. 158 (1997) L1.