R. Rachwalik et al. / Applied Catalysis A: General 427–428 (2012) 98–105
105
the other sample at the same temperatures, although visible, is
much less pronounced. These observations confirm that limonene
is more reactive than camphene and, therefore, can be probably
further transformed, via a carbocation intermediate, into different
products of limonene group, such as terpinenes, terpinolenes and
p-cymene (cf. Scheme 2).
acid strength. Different characteristics of the acid sites in the zeolite
materials under study with the same architecture is thus respon-
sible for their particular catalytic behaviour in the transformations
of pure ␣-pinene and pure limonene.
Acknowledgements
In order to verify experimentally this assumption, pure
limonene was used as a feed and the results of its transformation
over the ferrierite catalysts in the temperature range of 313–348 K
are depicted in Fig. 9. (At 363 K, the selectivity to limonene is nearly
steady during the reaction time studied.) As seen, the conversion
of limonene on the two ferrierite catalysts is strikingly different,
i.e. significantly higher over the zeolite from Tosoh (38%). At the
same temperature conversion over H-FER (Z) hardly exceeds 5%.
Limonene is, therefore, easily transformed into different products
on H-FER (T). On the other hand, the H-FER (Z) catalyst, exhibit-
ing Brønsted acid sites of the higher strength and containing more
faults as well as more extraframework aluminium, tends to produce
more oligomeric species during the transformation of ␣-pinene.
The presence of such species inhibits efficiently formation of by-
products and directs the isomerization of ␣-pinene to the main
primary products, camphene and limonene.
We are grateful to Professor J. Datka and Dr. K. Góra-Marek of
the Jagiellonian University, Kraków, for the IR measurements. B.S.
is indebted to the Ministry of Science and Higher Education for the
NMR 500 MHz spectrometer equipment grant (project No. 75/E-
68/S/2008-2). The ferrierite samples were kindly supplied by Tosoh
Corporation (Japan) and Zeolyst International (US).
References
[
1] C.S. Sell, The Chemistry of Fragrances From Perfumer to Consumer, 2nd ed., The
Royal Society of Chemistry, Cambridge, 2006.
[2] C.S. Sell, A Fragrant Introduction to Terpenoid Chemistry, The Royal Society of
Chemistry, Cambridge, 2003.
[
[
3] E. Breitmaier, Terpenes, Wiley-VCH, Weinheim, 2006.
4] V.P. Wystrach, L.H. Barnum, M. Garber, J. Am. Chem. Soc. 79 (1957) 5786–5790.
[5] A. Severino, A. Esculcas, J. Rocha, J. Vital, L.S. Lobo, Appl. Catal. A: Gen. 142
1996) 255–278.
(
[
6] R.G. Berger, Flavours and Fragrances, Chemistry, Bioprocessing and Sustain-
ability, Springer-Verlag, Heidelberg, 2007.
Due to lower formation of oligomeric products, isomerization
of pure limonene proceeds more easily over zeolite H-FER (T) at
[7] K. Bauer, D. Garbe, H. Surburg, Common Fragrance and Flavor Materials, 4th
ed., Wiley-VCh, Weinheim, 2001.
3
48 and 338 K. On this catalyst, limonene undergoes facile transfor-
mations to other hydrocarbons of the limonene group, like ␣- and
-terpinene, terpinolenes and p-cymene (Scheme 1 and Fig. 9). At
about 313 K, the isomerization of limonene is essentially stopped
Fig. 9b). Therefore, in the transformation of pure ␣-pinene, the
[
8] M. Gscheidmeier, R. Gutmann, J. Wiesmüller, A. Riedel, US Patent 5,559,127
1997).
(
␥
[9] M. Gscheidmeier, H. Häberlein, H.H. Häberlein, J.T. Häberlein, M.C. Häberlein,
US Patent 5,826,202 (1998).
[
[
10] C.M. Lopez, F.J. Machado, K. Rodriguez, B. Mendez, M. Hasegawa, S. Pekerar,
Appl. Catal. A: Gen. 173 (1998) 75–85.
11] A.I. Allahverdiev, G. Gündüz, D.Y. Murzin, Ind. Eng. Chem. Res. 37 (1998)
2373–2377.
(
selectivity to limonene vs. the reaction time remains practically
constant at this temperature, while it is decreasing by ca. 10% at
[
[
12] A.I. Allahverdiev, S. Irandoust, D.Y. Murzin, J. Catal. 185 (1999) 352–362.
13] C. Lopez, F. Machado, K. Rodríguez, D. Arias, B. Méndez, M. Hasegawa, Catal.
Lett. 62 (1999) 221–226.
3
38 and 348 K (Fig. 8b).
[
14] R. Rachwalik, Z. Olejniczak, J. Jiao, J. Huang, M. Hunger, B. Sulikowski, J. Catal.
4
. Conclusions
252 (2007) 161–170.
[
15] Ł. Mokrzycki, B. Sulikowski, Z. Olejniczak, Catal. Lett. 127 (2009) 296–303.
We have shown that ␣-pinene can be transformed effectively
[16] B. Gil, Ł. Mokrzycki, B. Sulikowski, Z. Olejniczak, S. Walas, Catal. Today 52 (2010)
4–32.
17] L. Grzona, N. Comelli, O. Masini, E. Ponzi, M. Ponzi, React. Kinet. Catal. Lett. 71
2000) 27–32.
[18] M.A. Ecormier, A.F. Lee, K. Wilson, Micropor. Mesopor. Mater. 80 (2005)
01–310.
2
over the hydrogen forms of ferrierite of different origin. The ini-
tial reaction rates of ␣-pinene are high, and in general exceed
those found for other classes of catalysts, heteropolyacids and
sulphonated zirconium oxide. The characteristic behaviour of ␣-
pinene conversion vs. the reaction temperature can be related to
the formation of oligomeric products and the ability of a catalyst
to isomerize further the limonene formed. Formation of oligomeric
products is more pronounced on the ferrierite containing Brønsted
sites of higher acid strength. The H-FER (T) sample exhibits, at 363 K,
a higher selectivity towards camphene and a lower one to limonene
than the H-FER (Z) material does. Deposition of the HRTP products,
observed for both catalysts at 363 K, prevents efficiently consecu-
tive reactions and, therefore, favours the formation of camphene
and limonene from ␣-pinene. Limonene can be further isomerized
over the ferrierite from Tosoh at 348 and 338 K giving terpinenes,
terpinolenes and finally p-cymene. These consecutive transforma-
tions of limonene, one of the two primary products formed over
ferrierite catalysts from ␣-pinene, are essentially not observed for
the H-FER (Z) ferrierite sample containing Brønsted sites of higher
[
(
3
[
[
19] N.A. Comelli, E.N. Ponzi, M.I. Ponzi, J. Am. Oil Chem. Soc. 82 (2005) 531–535.
20] D.R. Brown, C.N. Rhodes, Catal. Lett. 45 (1997) 35–40.
[21] C. Breen, R. Watson, J. Madejova, P. Komadel, Z. Klapyta, Langmuir 13 (1997)
473–6479.
22] O. Masini, L. Grzona, N. Comelli, E. Ponzi, M. Ponzi, J. Chil. Chem. Soc. 48 (2003)
01–104.
[23] N.A. Comelli, L.M. Grzona, O. Masini, E.N. Ponzi, M.I. Ponzi, J. Chil. Chem. Soc.
9 (2004) 245–250.
6
[
1
4
[
[
24] A.D. Newman, A.F. Lee, K. Wilson, N.A. Young, Catal. Lett. 102 (2005) 45–50.
25] D. Freude, M. Hunger, H. Pfeifer, G. Scheler, J. Hoffmann, W. Schmitz, Chem.
Phys. Lett. 105 (1984) 427–430.
[26] Y. Jiang, J. Huang, W. Dai, M. Hunger, Solid State Nucl. Magn. Reson. 39 (2011)
16–141.
27] C. Doremieux-Morin, P. Batamack, J.M. Bregeult, J. Fraissard, Catal. Lett. 9 (1991)
03–409.
1
[
4
[28] J. Datka, M. Kawałek, K. Góra-Marek, Appl. Catal. A: Gen. 243 (2003) 293–299.
[
[
[
29] B. Gil, G. Ko sˇ ová, J. Cˇ ejka, Micropor. Mesopor. Mater. 129 (2010) 256–266.
30] E.A. Paukstis, E.N. Yurchenko, Usp. Khim. 52 (1983) 426–454.
31] B.G. Harvey, M.E. Wright, R.L. Quintana, Energy Fuels 24 (2010) 267–273.
[32] J. Datka, B. Gil, J. W e˛ glarski, Micropor. Mesopor. Mater. 21 (1998) 75–79.