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Catalysis Science & Technology
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min, respectively. The final product consisted of 98% of 2-PEA and
only 2% of oligomers. No styrene and EB formation is observed. This
approach ensure a selective production of 2-PEA from SO. This
result is as good as the representative performances previously
reported for the direct hydrogenation of SO to 2-PEA, with different
catalysts, under various conditions (Table 1). It is important to note
that the best previous results were obtained either over noble
metals (sometimes in an alkaline medium) or with Ni-based
catalysts at a high catalyst/SO ratio.
this is significantly more selective to 2-PEA than Ni-based catalyst.
DOI: 10.1039/C5CY00779H
On the basis of these results, a new and efficient strategy to
produce selective 2-PEA from SO was proposed on the basis of
catalytic cascade reactions (i.e., isomerization of SO over acidic Al-
SBA-15 catalyst, followed by hydrogenation over metallic cobalt
containing active material). From this approach, an extend strategy
of selective synthesis of 2-PEA by three-step catalytic process could
be suggested, including also the epoxidation of ST to SO over
titanium containing zeolites.
As it is known, SO can also be easily prepared by epoxidation of ST
over titanium containing microporous and mesoporous materials.46
A feasible process to obtain 2-PEA with high selectivity from styrene
can be also proposed. The integrated system includes 3 consecutive
selective reactions, catalyzed by three different materials, as
follows: (i) the conversion of styrene to SO by clean oxidation with
H2O2 catalyzed by a microporous titanosilicalite, TS-1,46 followed by
(ii) the isomerization of SO into PAA over Al-SBA-15, and finally, (iii)
the hydrogenation of PAA to 2-PEA over Co-MO(RT) (Scheme 3).
Acknowledgements
This work was partially supported by a grant of the Romanian
National Authority for scientific Research, CNCS – UEFISCDI,
project number PN-II-RU-TE-2012-3-0403.
References
1
C.Jr. Huang, S.L. Lee and C.C. Chou, J Biosci Bioeng, 2000, 90,
142;
2
M.M.W. Etschmann, W. Bluemke, D. Sell and J. Schrader,
Appl Microbiol Biotechnol, 2002, 59, 1;
3
4
D. Hua and P. Xu, Biotechnol Adv, 2011, 29, 654.
A. Karami, A. Niazi, G. Kavoosi, M. Khosh-Khui and H. Salehi,
Physiol Mol Biol Plants, 2015, 21, 43.
5
6
R.V. Chaudhari, M.M. Telka and C.V. Zaccheria, 2000, US
Patent 6166269.
C. Shell, Ingredients for the Modern Perfumery Industry, in:
The Chemistry of Fragrances, (Eds.: D. Pybus, C. Shell), RSC
Publishing, Cambridge, UK, 2006, pp. 101-102.
S.C. Laha and R. Kumar, J Catal, 2001, 204, 64.
J. Song, Z. Zhang, T. Jiang, S. Hu, W. Li, Y. Xie and B. Han, J
Mol Catal A: Chem, 2008, 279, 235.
7
8
9
S. Mitsui, S. Imaizumi, M. Hisashige and Y. Sugi, Tetrahedron,
1973, 29, 4093.
10 V.G. Yadav and S.B. Chandalia, Org Proc Res Develop, 1998,
2
, 294.
Scheme 3. Three-step cascade reactions for the selective preparation of 2-PEA, starting
from ST precursor.
11 I. Vicente, P. Salagre and Y. Cesteros, Appl Clay Sci, 2011, 53
,
212.
12 I. Vicente, P. Salagre and Y. Cesteros, Appl Catal A : Gen,
2011, 408, 31.
13 C.V. Rode, M.M. Telkar and R.V. Chaudhari, Stud Surf Sci
Catal, 2000, 130, 533.
14 O. Bergada, P. Salagre, Y. Cesteros, F. Medina and J.E.
Sueiras, Appl Catal A-Gen, 2007, 331, 19.
The proposed approach, in three cascade reaction, is a very
promising way to selectively transform ST to 2-PEA using green
efficient process involving the use of heterogeneous catalysts.
15 O. Bergada, P. Salagre, Y. Cesteros, F. Medina and J.E.
Sueiras, Catal Lett, 2008, 122, 259.
Conclusions
16 O. Bergada, P. Salagre, Y. Cesteros, F. Medina and J.E.
Sueiras, Appl Catal A-Gen, 2004, 227, 125.
17 I. Kirm, F. Medina, X. Rodriguez, Y. Cesteros, P. Salagre and
J.E. Sueiras, J Mol Catal A: Chem, 2005, 239, 215.
18 C.V. Rode, M.M. Telkar, R. Jaganathan and R.V. Chaudhari, J
Mol Catal A: Chem, 2003, 200, 279.
Selective production of 2-PEA were investigated by using Co- and
Ni-based catalysts, supported on MgO-Al2O3 homogeneous mixed
oxides. Active catalysts were obtained by calcination of
corresponding LDH precursors, and then reduced under H2. SO and
PAA were both used as starting molecules for the synthesis of 2-
PEA.
When SO was used as starting molecule and metallic nickel as active
phase, low reaction temperatures were favorable to the
hydrogenation of SO to 2-PEA. Using metallic cobalt as active phase,
deoxygenation of SO to ST occurred.
19 A.A. Dabbawala, N. Sudheesh and H.C. Bajaj, Dalton Trans,
2012, 41, 2910.
20 G.D. Yadav and Y.S. Lawate, J Supercrit Fluids, 2011, 59, 78.
21 G.D. Yadav and Y.S. Lawate, Ind Eng Chem Res, 2013, 52
,
4027.
22 I. Kirm, F. Medina, J.E. Sueiras, P. Salagre and Y. Cesteros, J.
Mol Catal A: Chem, 2007, 261, 98.
23 M.M. Telkar, C.V. Rode, R.V. Chaudhari, S.S. Joshi, and A.M.
Nalawade, Appl Catal A-Gen, 2004, 273, 11.
When PAA was used as starting molecule, the selectivity to 2-PEA
was controlled by both reduction and reaction temperatures, over
metallic nickel containing material. Instead, when metallic cobalt
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