Microporous and Mesoporous Materials 101 (2007) 176183 www.elsevier.

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Hydration of a-pinene over hydrophobic zeolites in 1,4-dioxane-water and in water

Takako Mochida a, Ryuichiro Ohnishi b, Naoto Horita a, Yuichi Kamiya a, Toshio Okuhara a,*
a

Graduate School of Environmental Science, Hokkaido University, Kita-ku, Sapporo 060-0810, Japan b Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi 332-0012, Japan Received 28 July 2006; received in revised form 10 October 2006; accepted 12 October 2006 Available online 27 November 2006

Abstract Acid catalyzed hydration of a-pinene in the presence of water was conducted over MFI, BEA, MOR and FAU type zeolites with various SiO2/Al2O3 molar ratios and over many other catalysts. Except for MFI, the catalytic activity of all zeolites increased and, then, fell down with increasing SiO2/Al2O3 ratio. Analysis of water adsorption isotherm and NH3-TPD revealed explicitly that, at high Al content, the crowded water molecules on an acid site inhibit the adsorption of a-pinene while, at low Al content, only a small number of water are competing with a-pinene to adsorb on an active site. The catalytic activity per acid site of all zeolites increased monotonously with increasing hydrophobicity. 2006 Elsevier Inc. All rights reserved.
Keywords: Hydration of a-pinene; Zeolites; Hydrophobicity; Water adsorption isotherm; Ammonia-TPD

1. Introduction Hydration of a-pinene is an important synthetic route to valuable terpenic alcohols, especially to a-tepineol and terpin, with many applications in perfumery and pharmaceutical industries [1]. The reaction was promoted on a variety of acidic catalysts [2], including mineral acids [3], heteropolyacids [4], cation exchange resins [5] and zeolites [69]. Within these, solid acids such as zeolites, cation exchange resins, immobilized heteropolyacids [10] and encapsulated zeolites [11,12] are desirable because of less waste, provided that they exhibit high catalytic performances in successive use. Only a few solid acids are acceptable in water-participating-reactions such as hydrolysis and esterication because of poor activities and stabilities. A diculty in the use of solid acids comes from severe poisoning of the acid sites
*

Corresponding author. Tel./fax: +81 11 706 4513. E-mail address: oku@ees.hokudai.ac.jp (T. Okuhara).

by water [13,14]. In this respect, the hydrophobic and acidic properties of solid surface should play the decisive roles for determining the catalytic activity. Various indexes have been proposed for hydrophobicity. Anderson and Klinowski dened hydrophobicity h as the ratio of weight loss at 423 to that at 673 K in thermogravimetric analysis [15]. Weitkamp et al. dened hydrophobicity HI as the weight ratio of hydrocarbon, e.g., toluene, to water adsorbed in a co-adsorption experiment [16,17]. Pires et al. [18] proposed another index E in the Dubinin and Astakhov equation (w = w0 exp[(A/E)n]) to t for water adsorption isotherm, where w, w0, A, n, E refer to the amount of adsorbed water at a relative pressure (P/P0), the amount of adsorbed water at limiting adsorption, RT ln (P0/P) and parameters, respectively. Olson et al. dened hydrophobicity as a fraction of the pore volume not lled by water at a relative water pressure between P/ P0 = 0.04 and 0.25 in water adsorption isotherm [19]. Since there is no widely accepted denition of hydrophobicity [19,20], we dene our hydrophobicity estimated from the amount of adsorbed water at zero of relative pressure.

1387-1811/$ - see front matter 2006 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2006.10.022

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Many reports were dealing with the relation between catalytic performances and hydrophobicities [2025]. These reports, however, compared activities of only a few catalysts and the comparative experiments have not been carried out systematically. In this paper, therefore, we are to use many catalysts including four kinds of zeolites with various SiO2/Al2O3 molar ratios and to show a correlation between catalytic activities of the acid catalyzed reaction of a-pinene in the presence of water, hydrophobicities and acidities of catalysts. 2. Experimental 2.1. Reaction Acid catalyzed hydration reaction of a-pinene was conducted using a batch reactor of 60 mL three-neck ask with a condenser, a sampler and a thermometer. In the ask, one layer homogeneous solution of a-pinene (3.3 mmol),
OH

1,4-dioxane (6 mL), water (24 mL) and 1,3,5-triisopropylbenzene (internal standard, 1.0 mmol) was charged in nitrogen atmosphere. After temperature of the reactor reached to 343 K, 0.08 or 0.3 g of catalyst was added under stirring with a magnetic stirrer. Weight of catalyst was adjusted so as to obtain pseudo 1st order rate constant with a reasonable accuracy. The reaction was also carried out in two layer solution of water and a-pinene. In this case, 0.66 mmol of a-pinene, 6 mL of water and 0.2 or 0.6 g of catalyst were charged in a glass ampoule of 10 mL in nitrogen atmosphere, which was, then, sealed o. The sealed ampoule was heated at 343 K while shaking. After a set reaction time, the ampoule was cracked to open and known amounts of 1,4-dioxane and 1,3,5-triisopropylbenzene were added to make a homogeneous solution. An aliquot of the reaction products was withdrawn from the ask or the ampoule, separated from catalyst and analyzed using a GC (Shimadzu, GC-14B) with a capillary column of 100% dimethylpolysiloxane (1.5 lm 0.25 mm 60 m). Reaction products were identied using such authentic samples as a-pinene, camphene, a-terpinene, limonene, c-terpinene, terpinolene, fenchol, borneol, a-terpineol (see Fig. 1) and a GC-Mass spectrometer (Shimadzu, GCMSQP5050). 2.2. Catalysts Table 1 shows suppliers, surface areas and pore sizes of MFI, BEA, MOR and FAU type zeolites with various SiO2/Al2O3 ratios and other catalysts used in the acid catalyzed reaction of a-pinene. In addition to these catalysts, solid acids such as SiO2Al2O3 (SAL-2, CCIC), NaonSiO2 (13% SiO2, Du Pont), MoO3/ZrO2 (MoO3/ ZrO2 = 0.1, home made), 9 and 23 atom%WO3/ZrO2
Table 1

OH -terpineol

OH terpin limonene terpinolene -terpinene MH: Monocyclic hydrocarbons

MA: Monocyclic Alcohols

-pinene camphene BH: Bicyclic hydrocarbon HO borneol OH fenchol

BA: Bicyclic Alcohols

Fig. 1. Reaction products of acid catalyzed reaction of a-pinene in the presence of water.

Suppliers and characteristics of zeolites and other catalysts Catalyst MFI SiO2/Al2O3/molar ratio 30 72 200 18 25 75 150 300 10 20 90 4.8 30 60 80 Type NH4 H NH4 NH4 NH4 H H H H H H H H H H Supplier ZEOLYST Tosoh Tosoh Tosoh ZEOLYST ZEOLYST Sud-chemie Nissan ZEOLYST CCIC CCIC ZEOLYST CCIC ZEOLYST ZEOLYST ZEOLYST Home made Organo Du Pont Surface area/m2 g1 400 654 385 650 680 650 773 620 500 360 500 740 780 720 780 143 45 <1 Pore size/nm 0.51 0.55, 0.53 0.56a

BEA

0.66 0.67, 0.56 0.56a

MOR

0.65 0.70, 0.26 0.57a

0.74 0.74a

Cs2.5H0.5PW12O40 Amberlyst15 Naon NR50

a b

0.450.60, 3.80b *25

Data were taken from the IZA web, http://topaz.ethz.ch/IZA-SC/StdAtlas.htm, on 02/10/2006. From Ar and N2 adsorption isotherm using Saito-Foley and Dollimor-Heal methods, respectively.

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Water adsorbed/ mmol g-1

15 a 10 b 5 c d

2.3. Other measurements Ammonia-temperature programmed desorption (NH3TPD) proles were obtained by a multi-task TPD system (BEL, Japan), equipped with a quadrupole mass spectrometer (ANELVA; M-QA100S). Sample of 0.1 g was treated at 473 K in case of Cs2.5H0.5PW12O40 or at 673 K in case of

0 0.0

0.1

0.2 0.3 Relative pressure, P/P0

0.4

0 0.5

Fig. 4. Water adsorption isotherms at 293 K and the estimation of the amount of water adsorption at zero of relative pressure on FAU zeolites with various SiO2/Al2O3 molar ratios of (a) 4.8, (b) 30, (c) 60 and (d) 80.

Q-mass signal at m/e = 16/ a.u.

c 100 40 Concentration of reaction products/ %

Concentration of -pinene/ %

80

30

60 b 40 c 20 d e 0 0 1 2 3 Time of reaction/ h 4 0 5 10 20

350

450

550

650 750 Temperature/K

850

950

Fig. 2. NH3-TPD spectra of (a) BEA (SiO2/Al2O3 = 75), (b) FAU (SiO2/ Al2O3 = 60), (c) MFI (SiO2/Al2O3 = 72), (d) MOR (SiO2/Al2O3 = 90) and (e) Cs2.5H0.5PW12O40.

50 a Selectivity of reaction products/ % 40

Q-mass signal at m/e = 16/ a.u.

30

20 c d e

10

c 350 450 550 650 750 Temperature/K 850 950

0 0 20 40 60 Conversion of -pinene/ % 80

Fig. 3. NH3-TPD spectra (thick line) of BEA (SiO2/Al2O3 = 25) and its peak-tted curves (ac). Acidity was calculated from sum of peak areas of (b) and (c).

Fig. 5. Time-course of reaction products (top) and plot of selectivity vs. conversion (bottom) in a-pinene hydration over 0.08 g of BEA (SiO2/ Al2O3 = 75) at 343 K in one layer solution. Lines of (a)(e) for monocyclic alcohols, monocyclic hydrocarbons, bicyclic alcohols, bicyclic hydrocarbons; and unidentied products, respectively.

Water adsorbed/ mmol g-1

(home made), a hydrothermally stable mesoporous aluminosilicate, MAS-7, (prepared according to reference [26]), 9 atom% Ta2O5/MgO (home made) and Nb2O5 nH2O (CBMM) were tested. Zeolites were calcined at 873 K for 5 h for ammonium forms and 773 K for 5 h for proton forms before use. Cs2.5H0.5PW12O40 was pretreated at 523 K, SiO2Al2O3, MoO3/ZrO2, WO3/ZrO2, MAS-7 were at 673773 K, Nb2O5 nH2O was at 343 K, and others were used as supplied.

20

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zeolites in vacuum for several hours, exposed to ammonia of 13 kPa for 20 min at 373 K and the excess ammonia was removed under a He ow for 0.5 h at 373 K. Temperature of the sample was raised at a rate of 10 K min1 to 973 K and desorbed gas was monitored using Q-mass at m/e = 16 and 18. Representative examples of NH3-TPD proles for MFI, FAU, MOR, BEA and a heteropoly acid were presented in Fig. 2. The proles of NH3-TPD were peak tted in Gaussian distribution using a program of Fityk, which was downloaded from http://www.unipress.waw.pl/tyk/. Number of acid sites (acidity) was calculated from a whole area of spectra excluding peak(s) at lower than 500 K, as exemplied in Fig. 3. Water adsorption isotherms were measured at 298 K using a BELSORP 18 apparatus (BEL, Japan). The amount of adsorbed water (in mmol g1) was obtained from extrapolation of the rst plateau region in water adsorption isotherm to zero of relative pressure, as shown in dotted lines of Fig. 4. The amount of adsorbed water at zero relative pressure was abbreviated to water0. An index of hydrophilicity, D, of the catalyst was dened from an equation of (water0) (Avogado number)/(surface area) and was expressed in a unit of H2O molecules per square nm. Hydrophobicity was dened to be a reciprocal of hydrophilicity, 1/D. The BET surface area was determined from a nitrogen adsorption isotherm at 77 K using a BELSORP 28SA apparatus (BEL, Japan).

Table 3 Catalytic performances on various catalysts of a-pinene hydration in one layer solutiona Catalyst Conversionb/ % 30 11 10 4 1 0 0 Selectivityd/% MA 27 30 0 49 0 BA 0 3 0 0 0 BH 18 16 32 20 0 MH 55 40 58 31 0 Others 0 11 9 0 100

Naon-SiO2 MoO3/ZrO2 Nb2O5 nH2Oc 9 atom% WO3/ZrO2 9 atom% Ta2O5/MgO 23 atom% WO3/ZrO2 MAS-7
a

Reaction condition: a-pinene 3.3 mmol, 1,4-dioxane 6 mL, water 24 mL and 1,3,5-triisopropylbenzene (internal standard) 1.0 mmol at 343 K over 0.3 g of catalyst. b Four hours of reaction time. c Pretreated with water at 343 K for 2 h. d MA, BA, BH, MH and others for monocyclic alcohols, bicyclic alcohols, bicyclic hydrocarbons, monocyclic hydrocarbons and unidentied products, respectively.

3. Results and discussion Alkenes having carbon number more than four are transformed not only to alcohols but also to isomerized alkenes when the alkenes are treated with water in the presence of acid catalyst. In the case of a-pinene, more complicated products are formed because of ring opening. They could be classied into four groups as monocyclic alcohols,

Table 2 Catalytic performances on zeolites and other catalysts of a-pinene hydration in one layer solutiona Catalyst SiO2/Al2O3/molar ratio 30 72 200 18 25 75 150 300 10 20 90 4.8 30 60 80 Conversionb/% Rate constantc/g1 h1 Selectivityd/% MA MFI 5 0 0 90 94 100 98 88 0 0 86 0 100 100 98 49 56 31 0 0 0 0 0.7 1.2 2.4 1.3 0.8 0 0 0.9 0 3.1 5.0 1.4 0.4 0.5 0.2 0 0 51 41 41 42 37 36 42 44 33 23b 27b 14b BA 0 18 15 16 15 14 20 13 13 13 4b 5b 8b BH 50 7 8 6 7 9 11 7 6 8 12b 16b 19b MH 50 23 32 33 33 37 27 34 33 42 57b 50b 55b Others 0 2 3 5 3 3 6 4 4 4 4b 2b 4b

BEA

MOR

FAU

Cs2.5H0.5PW12O40 Amberlyst15 Naon NR50 Blank

a

Reaction condition: a-pinene 3.3 mmol, 1,4-dioxane 6 mL, water 24 mL and 1,3,5-triisopropylbenzene (internal standard) 1.0 mmol at 343 K over 0.08 or 0.3 g of catalyst. Conversion was obtained using 0.3 g of catalyst. b Four hours of reaction time. c Pseudo 1st order rate constant. d MA, BA, BH, MH and others for monocyclic alcohols, bicyclic alcohols, bicyclic hydrocarbons, monocyclic hydrocarbons and unidentied products, respectively.

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Table 4 Catalytic performances on various catalysts in a-pinene hydration in two layer solutiona Catalyst SiO2/Al2O3/molar ratio 30 72 200 18 25 75 150 300 10 20 90 4.8 30 60 80 Conversion/% Rate constantb/g1 h1 Selectivitye/% MA MFI 1 14 1 46 46 62 46 50 3 0 41 0 96 92 77 75 39 6 2 0 0.3 0 1.0 1.0 1.6 1.0 1.3 0.1 0 1.0 0 5.3 5.5 1.7 1.4 0.9 0.2 0 0 5 0 22 22 17 18 23 0 0 21 0 13 13 13 45 32 17 0 BA 0 0 0 17 18 19 18 19 0 0 26 0 17 19 20 5 6 0 0 BH 0 15 0 14 15 13 14 16 75 0 12 0 19 17 17 6 14 17 0 MH 0 79 0 40 40 42 47 40 25 0 36 0 49 47 46 39 40 51 0 Others 0 0 0 6 6 9 4 2 0 0 5 0 2 4 4 6 9 14 0

BEA

MOR

FAU

Cs2.5H0.5PW12O40 Amberlyst15c Naon NR50d Blank

a

Reaction condition: a-pinene 0.66 mmol, water 6 mL and catalyst 0.2 or 0.6 g in an ampoule at 343 K for 4 h of reaction time. Conversion was obtained using 0.6 g of catalyst. b Pseudo 1st order rate constant. c Powdered. d Crashed. e MA, BA, BH, MH and others for monocyclic alcohols, bicyclic alcohols, bicyclic hydrocarbons, monocyclic hydrocarbons and unidentied products, respectively.

monocyclic hydrocarbons, bicyclic alcohols and bicyclic hydrocarbons, which are abbreviated to MA, MH, BA and BH, respectively (see Fig. 1). As described in Table 1
Table 5 Physical characteristics of various catalysts Catalyst MFI SiO2/Al2O3/molar ratio 30 72 200 18 25 75 150 300 10 20 90 4.8 30 60 80 Al contenta/mmol g1 1.05 0.45 0.17 1.69 1.25 0.43 0.22 0.11 2.85 1.53 0.36 5.12 1.05 0.54 0.41

and in experimental section, a wide variety of zeolites, metal oxides and cation exchange resins were tested as catalysts in the reaction. Fig. 5(top) shows time course of concentration

Acidityb/mmol g1 0.80 0.59 0.17 0.89 0.72 0.50 0.27 0.19 1.05 0.71 0.37 1.12 0.45 0.34 0.10 0.06e 4.70 0.80

Water0c/mmol g1 2.86 2.09 0.70 2.73 2.93 1.20 0.49 0.38 6.66 2.99 1.57 14.4 1.15 0.20 0.16 0.77

1/Dd nm2 H2O-molecules1 0.23 0.52 0.92 0.39 0.39 0.90 2.63 2.69 0.12 0.20 0.53 0.09 1.59 1.41 8.33 0.31

BEA

MOR

FAU

Cs2.5H0.5PW12O40 Amberlyst15 Naon NR50

a b c d e

From SiO2/Al2O3 molar ratio. From NH3-TPD. Amount of adsorbed water at zero of relative pressure obtained from water isotherm. Hydrophobicity. Nominal amount of proton.

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of reaction product groups and of a-pinene conversion over BEA (SiO2/Al2O3 = 75) zeolite in the one layer solution. Fig. 5(bottom) shows time course of formation selectivities of the reaction product groups. The selectivities to every product groups changed a little within the time course, suggesting that those are the initial products. Similar time courses were also observed over all zeolites. But, over Cs2.5H0.5PW12O40, Amberlyst15 and Naon NR50, the selectivities at 4 h of reaction time were used because that the selectivities became stable at 4 h. The selectivities, thus obtained, and the conversions at 4 h were compared, as shown in Tables 2 and 3. The molecular size of a-pinene was estimated to be 0.62 0.59 0.53 nm, which is larger than the micro-pore size (see Table 1) of MFI and smaller than those of BEA, MOR, and FAU zeolites. Thus, the reaction should not proceed over MFI but would go over other zeolites. In fact, this was the case. It should be also noted that the conversions of BEA and FAU increased and, then, decreased with increasing SiO2/Al2O3 molar ratio. Similar trends of activity with SiO2/Al2O3 ratio were reported by Finiels et al. [20] in hydration of phenylacetylene over MOR and Camblor et al. [22] in preparation of alkyl glucosides over BEA. Other catalysts, which are active in water-participating reactions, were much less active than zeolites in hydration of a-pinene except for Cs2.5H0.5PW12O40, Amberlyst 15, Naon NR50 and Nafion-SiO2, as shown in Tables 2 and 3. The reactions were also conducted in the two layer solution, as shown in Table 4. In fourth column of Tables 2 and 4, pseudo 1st order rate constants were presented, which were calculated from conversions and reaction times at low conversion level. On zeolites except for MFI, rate constants in the one layer solution were rather similar with those in the two layer, being 50% dierence at most. In contrast, rate constants on Cs2.5H0.5PW12O40 and Amberlyst15 in the two layer solution were 24 times higher than those in the one layer. The dierent behavior of zeolites from Cs2.5H0.5PW12O40 and Amberlyst15 was also observed for the formation selectivity of reaction products. In the one layer media, the selectivity of monocyclic alcohols (MA), mainly a-terpineol, were the main reaction products and amounted to 3550% on BEA, FAU and MOR zeolites while monocyclic hydrocarbons (MH) was the main on Cs2.5H0.5PW12O40, Amberlyst15, Naon NR50 and other oxide catalysts listed in Tables 2 and 3 except for low conversion catalysts. When the reaction media changed from one to two layer solution, the product distribution shifted to more MH and less MA on zeolites but to less MH and more MA on Cs2.5H0.5PW12O40 and Amberlyst15. We do not have rational reasons for these dierences between zeolites and other catalysts. Catalytic performances described above were compared with acidity and hydrophobicity, which were derived from ammonia-TPD and water adsorption isotherm, as listed in fourth, fth and sixth columns of Table 5. Although the acidity monotonously increased with Al content, slopes

Acid amount from NH3-TPD/ mmol g-1

1.2

slope = 1

0.8

0.4

0.0 0.0

0.5

1.0 1.5 2.0 Al content/ mmol g-1

2.5

3.0

Fig. 6. Comparison of Al content with acid amount measured by NH3TPD on FAU (j), BEA (n), MOR (d) and MFI ().

6 a Rate constant/ (g h)-1

b 2

c 0 0.0 0.2 0.4 0.6 0.8 Acidity/ mmole g-1 1.0 1.2

Fig. 7. Rate constant at 343 K in one layer solution vs. acidity on (a) FAU (j), (b) BEA (n), (c) MOR (d) and (d) Cs2.5H0.5PW12O40 ().

14 Number of water molecules adsorbed on one acid site 12 10 8 6 4 2 0 0 2 4 6 8 10 Hydrophobicity,1/D/ nm2 H2O molecule-1
Fig. 8. Number of water molecules adsorbed on one acid site vs. hydrophobicity (1/D) on FAU (j), BEA (n), MOR (d) and Cs2.5H0.5PW12O40 ().

progressively decreased, as shown in Fig. 6. This may suggest that some of Al did not expose to surface and were not accessible to ammonia at high Al content. Fig. 7 shows plots of 1st order rate constants in the one layer solution

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16 Rate constant per acidity/ (mmol h)-1 14 12 10 8 6 4 2 0 0 2 4 8 6 Hydrophobicity,1/D/ nm2 H2O molecule-1 10

Fig. 9. Rate constant per acidity vs. hydrophobicity (1/D) on FAU (j), BEA (n), MOR (d) and Cs2.5H0.5PW12O40 ().

against the acidities of various zeolites and Cs2.5H0.5PW12O40. The catalytic activities of three zeolites increased with the acidities at low acidity region, as was expected in the acid catalyzed reaction. Then, the activities fell down with the further increase. These trends have been explained by the increase of hydrophilicity with Al content [21,22]. However, a line of FAU was far apart from those of BEA and MOR. Fig. 8 shows a common feature of three zeolites, FAU, BEA and MOR, that number of water molecules adsorbed on one acid site changed a little and kept at about two on high hydrophobic surface while it sharply increased with decreasing hydrophobicity. a-Pinene should adsorb on acid site to promote the acid catalyzed reaction in the presence of water. However, Fig. 8 demonstrates that many water molecules was held on an acid site and will hinder the adsorption of a-pinene on low hydrophobic (or high hydrophilic) surface. As a result, the rate of the acid catalyzed reaction should go down. This was exactly happened, as shown in Fig. 9. The rate constant per one acid site was low at low hydrophobic surfaces where many water molecules are competing to adsorb on one acid site with a-pinene. In contrast, it was high at high hydrophobic surface where only a small number of water molecules are accessible to the acid site and a-pinene could easily adsorb on the active site. It is noteworthy that all points of FAU, BEA and MOR zeolites fell on one line except for two BEAs of SiO2/Al2O3 = 150 and 300, whose points moved to negative side. Another point for Cs2.5H0.5PW12O40 () was also away from the line but moved to positive side, i.e., low hydrophobicity but reasonable catalytic activity. One reason may come from higher acid strength of Cs2.5H0.5PW12O40 than those of zeolites, as shown in Fig. 2, where the highest peak temperature of NH3 desorption was observed on Cs2.5H0.5PW12O40. 4. Conclusion Acid catalyzed hydration reaction of a-pinene in the presence of water was carried out over MFI, BEA, MOR

and FAU type zeolites with various SiO2/Al2O3 molar ratios and many other catalysts including a heteropoly acid, cation exchange resins and metal oxides. The catalytic activities of all zeolites increased and, then, fell down with increasing SiO2/Al2O3 ratios, except for MFI. A little activity on MFI was attributed to smaller micro-pore size than the size of a-pinene molecule. Cs2.5H0.5PW12O40 and cation exchange resins promoted the reaction with moderate rate while other mono- and bi-metallic oxides showed poor catalytic performances. A hydrophobicity and amount of acid sites (acidity) were deduced from water adsorption isotherm and NH3TPD. The acidity was estimated from a whole area of spectra excluding peak(s) at lower than 500 K after peak deconvolution. The hydrophobicity was calculated from extrapolation of the rst plateau region in water adsorption isotherm to zero of relative pressure. The hydrophobicity increased with decreasing Al content in zeolites. Comparing catalytic performances with the hydrophobicities and acidities of various catalysts, it was concluded that the crowded water molecules on an acid site inhibit the adsorption of a-pinene at low hydrophobic zeolites while only a small number of water are competing with a-pinene to adsorb on an active site at high hydrophobic zeolites. Plots of catalytic activities per acid site and hydrophobicities of all zeolites fell on a common monotonous curve. Acknowledgment We appreciate the nancial support of Core Research for Evolutional Science and Technology (CREST) of Japan Science and Technology Agency (JST). References
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