Applied Catalysis A: General 214 (2001) 213218

Production of camphene and limonene from pinene over acid di- and trioctahedral smectite clays
Cristina Volzone a, , Omar Masini b , Nora Alejandra Comelli b , Liliana Myriam Grzona b , Esther Natalia Ponzi c , Marta Isabel Ponzi b
a

CETMIC (Centro de Tecnolog a de Recursos Minerales y Cermica, CONICET-CIC-UNLP), C.C. 49, Camino Centenario y 506, 1897 M.B. Gonnet, Buenos Aires, Argentina b INTEQUI (CONICET-UNSL), 25 de Mayo 384, V. Mercedes, San Luis, Argentina c CINDECA (CONICET-UNLP), calle 47 no. 257, 1900 La Plata, Argentina

Received 29 August 2000; received in revised form 9 January 2001; accepted 12 January 2001

Abstract The conversion of alpha-pinene (-pinene) to camphene and limonene catalyzed by acid clays (dioctahedral and trioctahedral) was studied in a batch reactor. Conversions of about 50% were obtained after 1 h reaction at 373 K. Selectivities in camphene and limonene and their derivatives between 52.654.5% and 37.644.6%, respectively, were attained using smectites treated with acid as catalysts. The catalytic activity of smectites for the alpha pinene conversion was correlated with the structural and textural characteristics, and the total acidity of the clays. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Camphene; Limonene; -Pinene; Di- and trioctahedral smectite clays; Acid smectites

1. Introduction Clays and acid clays have been used in catalysis for many years. The catalytic properties of clays are determined by the dissociation of water molecule coordinated to the exchange cations and cations placed between clay layers, and to the isomorphic substitutions of the structure, etc. Smectites form 2:1 layer phyllosilicates. The layers that constitute the smectite structure are formed by an aluminum (or magnesium) oxide sheet in octahedral coordination between two silica sheets in tetrahedral coordination. The charge imbalance due to isomorphic substitutions in the structure layers is compensated by cations placed in
Corresponding author. Tel.: +54-221-4840267; fax: +54-221-4710075. E-mail address: volzcris@netverk.com.ar (C. Volzone).

interlamellar position. There exist two different series of smectites, the dioctahedral and the trioctahedral; according to the lling of the octahedral layers, the number of ions is 2.00 or 3.00 for each half cell unit. The camphene is commercially obtained from -pinene by isomerization over acidied titanium oxide. The isomerization of -pinene to camphene using the palygorskite mineral was obtained by Mortaland [1] many years ago. Recent studies about isomerization of -pinene were reported by Severino et al. [2], Findik and Gndz [3], Allahverdiev et al. [4], Lpez et al. [5], Masini et al. [6], and Ponzi et al. [7,8]. Rhodes and Brown [9], De Stefanis et al. [10], Moronta and Breen [11], and Breen [12] studied transformation reactions of terpenes using treated clays (acid clays, acid-treated polycation-exchanged clays and pillared clays). De Stefanis et al. [10] proposed that the isomerization of terpenes proceeds

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 4 9 4 - X

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Table 1 Cations of the structure 2:1 layer of the original smectites and acid smectites Samples S C SA15 CA15 F1 Si4+ (%) 21.68 28.91 34.23 28.52 24.29 Al3+ (%) 1.98 6.69 0.77 4.71 10.86 Fe2+ /Fe3+ (%) 0.62 1.02 0.17 0.30 1.00 Mg2+ (%) 14.83 1.88 2.65 0.80 2.41 Si4+ /(Al3+ + Fe2+ / Fe3+ + Mg2+ ) 1.24 3.02 9.53 4.91 1.70

via a mechanism involving carbo-cation generation. According to Rhodes and Brown [9], the principal factors that control the catalytic activity of acid clays are the accessible specic surface area, acid sites, and Al3+ in exchange position, taking into account the balance of these properties. Breen [12] mentioned that future works are necessary to understand which are the factors that control the catalytic activity of acid-treated polycation-exchanged clays. There exists little information about the inuence of these structural, textural, and acidic characteristics of different clays used as catalyst in the conversion and selectivity of terpenes. The aim of this work is to evaluate the inuence of the characteristics of the acid-smectitic clays on the catalytic transformation from -pinene to camphene and limonene.

2. Experimental 2.1. Materials and methods Clays used were: a montmorillonite (dioctahedral smectite) from Argentina called C and a saponite (trioctahedral smectite) from Ballarat, USA called S.
Table 2 Textural characteristics of original smectites and acid smectites Samples S C SA15 SA15 CA15 F1 Total surface area (m2 g1 ) 8 38 254 228 232 347 External surface area (m2 g1 ) 2 25 26 30 31 87

The smectites were characterized previously [13,14]. Tables 1 and 2 show data of these smectites. The acid treatment of smectites was carried out with a 6N solution of sulfuric acid at boiling temperature for 15 min. Afterwards, the solid was separated and washed with distilled water. The acid smectite was dried in air and then at 100 C before use. Such samples are called CA15 and SA15. On the other hand, the acid saponite was thermally treated up to 450 C (SA15). A commercial acid smectite (dioctahedral), F1, was used for comparison. The diffractograms of samples were obtained in an X-ray equipment XPERT systems using the PW3710 Electronic Control Unit with Philips 3020 Goniometer, Cu K radiation at 40 kV and 20 mA and Ni lter. The N2 adsorptiondesorption isotherms of samples were obtained at the liquid nitrogen temperature with a Micromeritics Accusorb instrument. The values of internal, external, and total surface area were achieved by the Gregg and Sing method [15]. The chemical compositions of the samples were attained by inductively coupled plasma-emission spectrometry (ICP). The total acidity was determined from the amount of adsorbed ammonia using a thermobalance (Shimadzu model TGA 50). The samples were dried in a He ow

Internal surface area (m2 g1 ) 6 13 228 198 201 260

Total volume adsorbed (cm3 g1 ) 0.024 0.070 0.218 0.202 0.241 0.330

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(150 ml min1 ) by heating from room temperature up to 373 K at 20 min1 and then cooled in He ow to 328 K. For ammonia adsorption, the catalyst was exposed to a NH3 He (3000 ppm) ow at 100 ml min1 , until a constant weight was obtained. FT-IR spectra of the catalyst samples with adsorbed ammonia were used to determine the presence of Brnsted acidity. The ammonia was adsorbed at room temperature by owing pure ammonia at a rate of 15 cm3 min1 for 30 min over the sample placed in a cell. The sample containing the adsorbed ammonia was mixed with potassium bromide, and the infrared spectrum was recorded using a Brucker IFS66 FT-IR equipment. The Brnsted acidity was evaluated by the presence of the adsorption band of 1400 cm1 assigned to NH4 + . 2.2. Reaction The reaction was carried out in a glass reactor with three openings. In one of them, a coolant was placed for the steam condensation. The second one was used for withdrawal of samples by a micropipette. A thermocouple was placed in the third opening to measure the reaction temperature. The reactor was submerged in a thermostatic glycerin bath. The reaction mixture was stirred by a magnetic stirrer at a rate of 500 rpm. In a typical run, 63 millimoles of -pinene (98.7% purity of a racemic mixture provided by Derivados de San Luis company) was heated up to 373 K, 100 mg of catalyst was added, and the mixture was heated for 1 h. Then, a 100 l sample was extracted for analysis. The reaction products were analyzed by gas chromatography (Shimadzu model GC-17A) with a FID detector, using a J&W DB-1 60 m 0.248 mm capillary column. N2 was used as the carrier gas and the temperature was programmed from 348 to 473 K at a rate of 3 K min1 . Identication of the products was made by comparing the standard terpene retention times (racemic mixtures) by means of the determination of Kovats indexes co-injecting an homologous series of hydrocarbons (C6 C18 ) and conrming the analysis by GCMS (Perkin-Elmer, Q-Mass 910 GC) using a capillary column Supelco SPB-1 30 m 0.32 mm for the separation using helium as carrier gas. The mass spectra obtained were compared with those reported in the literature [1618] and with those in the GCMS library.

3. Results and discussion 3.1. Characterization of acid clays 3.1.1. Chemical analysis Table 1 shows the chemical composition of ions that form the tetrahedral and octahedral sheets of the original clays and after the acid treatment. An important portion of the cations of the octahedral sheet (Al3+ , Mg2+ , and Fe2+ /Fe3+ ) was removed in both smectites after acid treatment. It is important to explain that the predominant cation in dioctahedral smectites is Al3+ , and Mg2+ is the predominant cation in the trioctahedral smectites, as it is observed in the composition of each clay, C and S, respectively. The removal of cations resulted in a structure with different surface area, porosity, and cation exchange in interlayer sites, etc. [13,19]. The molar ratio of Si with respect to the other cations (Table 1) that originally were 3.02 and 1.24 for C and S, became 4.91 for CA and 9.53 for SA after treatment. 3.1.2. X-ray diffraction Fig. 1 shows the spectra of natural clays before and after treatment. They showed that C was a dioctahedral smectite containing quartz and feldspar as impurity in low proportions. S was a trioctahedral smectite with amphibole magnesium as impurity. The acid treatment caused loss of crystallinity and decrease in the diffraction intensities. An important structural change was observed. The SA15 sample became amorphous. The commercial acid smectite F1, containing quartz as impurity, showed spectrum similar to that of CA15 sample. The d(0 0 1) spacing of C smectite increased to 15.58 after acid treatment, and this value was similar to that of F1 sample (15.78 ). This increase may be attributed to the Al3+ present between smectite layers that were extracted from the octahedral sheet of the structure [13]. On the other hand, the d(0 0 1) spacing of the S smectite decreased from 15.20 to 14.89 after acid treatment, and the X-ray diffraction intensities decreased. 3.1.3. Textural characteristics The N2 adsorptiondesorption isotherms of all samples were performed at 77 K on powder sample previously outgassed at 100 C for 12 h. The isotherms of the samples C and S [13,19] show a hysteresis

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Fig. 1. X-ray diffraction of the original smectites and after acid treatments: s: smectite; a: amphibole; q: quartz; f: feldspar.

loop of the H3 type from the Gregg and Sing [15] classication, suggesting slit-shaped pore form. The acid treatment affected the smectite textures, resulting in a hysteresis loop of a combination of H3 and H2 types. The H2 type is characteristic of the pores in ink-bottle form [15]. Fig. 2 shows only the adsorption isotherms of the acid smectites. At low pressure ratio, P/P0 (small pores), the curves were similar. The F1 sample showed higher adsorbed volume. In the intermediate zone of the isotherm (mesopore region) and at high pressure ratio, P/P0 , the slopes of the curves

were different. The F1 sample showed a continuous pore distribution. The acid smectites, CA15, and SA15 showed similar way of adsorption and lesser total adsorbed volume than F1. Table 2 shows the surface area values (total, external, and internal) of the original and treated samples obtained from the adsorption isotherms [15]. An important increase in the surface values was observed after acid treatment, mainly due to an increase of the internal surface of the material after removal of structural cations in the octahedral sheet (Al3+ , Mg2+ , Fe2+ /Fe3+ ). In the same table, the values of total adsorbed volume are shown, expressed as liquid volume; this also indicates an important increase after acid treatment.

3.2. Reaction study Through the reaction catalyzed by clays, a bicyclic compound, camphene, and monocyclic compounds as limonene, terpinolene, -terpinene, and -terpinene were obtained. The mechanism proposed by Wystrach et al. [20] to explain the transformation of -pinene is shown in Fig. 3. The ring is re-arranged producing bicyclic compounds or one of the rings is broken to produce monocyclic compounds. Products formed in the rst

Fig. 2. N2 adsorption isotherms of the acid smectites.

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Fig. 3. Products of -pinene conversion.

isomerization stage of -pinene are camphene, tricyclene limonene, and terpinolene. By subsequent transformation of limonene, - and -terpinene, - and -phellandrene and others are obtained. The isomerization reaction requires acid sites to proceed. Table 3 shows the conversion of -pinene, and selectivities of camphene, and the limonene and its derivative products at 373 K. The selectivities for the derivatives of the limonene as -terpinene, -terpinene, and terpinolene obtained using the more active CA15 were 0.4, 1.7, and 7.0%, respectively. The catalytic activity of acid smectites for the conversion of -pinene showed the following order: F1 > CA15 > SA15 > SA15 > C > S (68.5, 52.8, 41.7, 25.3, 12.3, and 10.1%, respectively). In our study, the performance of these solids improved with the acid treatment. This treatment caused crystallinity loss in smectites and increased their activities. Thus, the conversion values of -pinene passed from 10.112.3% of the original smectites (S and C) to 25.352.8% after activation.

There exists a certain correlation between the -pinene conversion and the surface area, particularly the internal surface area and the total surface area. Also, higher activity is observed with higher pore volume. The surface area depends on the acid treatment [13] and this effect can be used to optimize the catalytic activities, as was also mentioned by Rhodes and Brown [10]. All acid clays showed higher selectivity to camphene (52.654.5%) than to limonene and its derivatives (37.639.8%) (Table 3). Breen [12] also found high productions of camphene (42%) using acid-treated polycation-exchanged clays. A higher increase of selectivity in camphene is observed when a trioctahedral clay is treated with acid (from 32.7 to 52.6%) than a dioctahedral clay (from 42.2 to 54.5%). A similar behavior is observed with the production of limonene and its derivatives (Table 3). The commercial acid smectite showed higher conversion than that of the ones prepared in this work, but lower selectivity for camphene obtention. A lower selectivity in camphene (Table 3) is observed in those that present lower Si4+ /(Al3+ + Fe2+ /Fe3+ + Mg2+ ) ratio (Table 1). Fig. 4 presents results of total acidity as a function of conversion for the treated and untreated smectites, as well as for the F1 sample used for comparison. An increase in the catalytic activity is observed with an increase in the acidity. On the other hand, the Brnsted acidity of the trioctahedral samples are less acidic than the dioctahedral samples (Table 3), and the trioctahedral samples show lower conversions of -pinene. The selectivity in camphene was increased by the acid treatment, but this selectivity increase was more noticeable in limonene.

Table 3 Conversion of -pinene and selectivities of the products for different catalystsa Dioctahedral smectite F1 X: -pinene (%) S: camphene (%) S: limonene + derivatives (%) S: others (%) Brnsted acidity (a.u.)
a

Trioctahedral smectite CA15 52.8 54.5 39.8 5.7 0.235 S 10.1 32.7 9.9 57.4 SA15 41.7 53.7 44.6 1.7 0.096 SA15 25.3 52.6 37.6 9.8 0.098

C 12.3 42.2 14.5 43.3

68.5 48.3 45.3 6.4 0.196

X: conversion; S: selectivity.

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Acknowledgements We thank the CETMIC, CINDECA, CONICET, INTEQUI, and UNSL for nancial support. References
[1] L. Mortaland, US Patent No. 999,667 (1911). [2] A. Severino, A. Esculcas, J. Rocha, J. Vital, L.S. Lobo, Appl. Catal. A 142 (1996) 255. [3] S. Findik, G. Gndz, JAOCS 74 (1997) 1145. [4] A. Allahverdiev, G. Gndz, D. Murzin, Ind. Eng. Chem. Res. 37 (1998) 2373. [5] C. Lpez, K. Rodr guez, F. Machado, B. Mndez, P. Rodr guez, M. Hasegawa, Actas del XVI Simp. Iber. Catal. 2 (1998) 679. [6] O. Masini, L. Grzona, N. Comelli, R. Montenegro, A. Carrascull, M. Ponzi, Informacin Tecnolgica 8 (1997) 163. [7] E. Ponzi, O. Masini, N. Comelli, L. Grzona, A. Carrascull, M. Ponzi, Bol. Asoc. Chil. Quim. 44 (1999) 271. [8] M.I. Ponzi, N.A. Comelli, L.M. Grzona, E.N. Ponzi, Informacin Tecnolgica 10 (1999) 159. [9] C.N. Rhodes, D.R. Brown, Catal. Lett. 24 (1994) 285. [10] A. De Stefanis, G. Perez, O. Ursini, A.A.G. Tomlinson, Appl. Catal. A: Gen. 132 (1995) 353. [11] A. Moronta, C. Breen, Actas del XVI Simp. Iber. Catal. 2 (1998) 733. [12] C. Breen, Appl. Clay Sci. 15 (1999) 187219. [13] C. Volzone, J.M. Porto Lpez, E. Pereira, Rev. latinoam. ing. qu m. qu m. apl. 16 (1986) 205. [14] C. Volzone, S ntesis de esmectitas pilareadas con cromo (Cr-PILCs), Tesis, Facultad de Ingenier a, Universidad Nacional de La Plata (UNLP), Argentina, 1997. [15] J.S. Gregg, K.S.W. Sing, Adsorption Surface Area and Porosity, Academic Press, London, 1982, p. 303. [16] R. Adams, Identication of Essential Oil Components by Gas Chromatography/Mass Spectroscopy, Allured Publishing Corporation, IL, USA, 1995. [17] E. Stenhagen, S. Abrahamson, F. Mc Lafferty, Archives of Mass Spectral Data, Wiley, New York, 1970. [18] A. Swigar, R. Silverstein, Monoterpenes, Aldrich Chem Co, Wisconsin, WI, 1980. [19] C. Volzone, E. Pereira, Latin Am. Appl. Res. 22 (1992) 49. [20] V.P. Wystrach, L.H. Barnum, M. Garber, J. Am. Chem. Soc. 79 (1957) 5786.

Fig. 4. The -pinene conversion and total acidity of smectites.

The modication of the smectite structures by the acid treatment caused different acidity and textural changes in the system. This made them useful for their application in catalytic reactions of terpenes.

4. Conclusions The specic surface area and the pore volume increase and the total acidity in the clay by the acid treatment enhances the performance for its use in the conversion of -pinene. Conversions of -pinene of about 50% with selectivities in camphene between 52.654.5% were obtained with acid-treated dioctahedral and trioctahedral smectites after 1 h of reaction at 373 K. The selectivity in camphene was higher than the one of limonene and its derivatives in the treated clays. In the untreated clays, the selectivity in limonene and its derivatives is very low. In summary, the structural and textural characteristics of the acid smectites affect the conversion of -pinene as well as the acidity does.