T.D. Conesa et al. / Journal of Catalysis 252 (2007) 1–10
9
Table 8
Total conversion (X ) and product distribution (S ) in the microwave-assisted
under microwave heating exhibited a significant decrease in se-
lectivity to ε-caprolactam.
a
T
i
◦
Beckmann rearrangement of Cdox at 180 C using various micro-mesoporous
Quantitative oxime conversion was obtained for all ma-
terials in the gas-phase reaction. However, the selectivity to
ω-laurolactam was lower than that of ε-caprolactam. Liquid-
phase results of the Beckmann rearrangement of cyclodode-
canone oxime on SiAlP-X catalysts using conventional heat-
ing showed lower conversion and selectivity to ω-laurolactam
compared with microporous Beta25 zeolite. Interestingly, under
microwave heating, the catalytic activity of the SiAlP-X mate-
rials was found to be close to that of zeolite Beta25. Overall,
ε-caprolactam and ω-laurolactam were obtained on SiAlP-X
catalysts in both the gas and liquid phases.
b
materials
Catalyst
X
S
ω-l
S
Cdone
T
(mol%)
(mol%)
(mol%)
c
Blank
Beta25
SiAlP-6
SiAlP-4.5
SiAlP-3
SiAlP-2
–
–
>99
98
98
>99
>99
–
–
2
2
–
–
76
42
65
66
60
d
Beta25
100
79
>99
96
–
4
d
SiAlP-4.5
a
Dodecanenitrile and 11-dodecenenitrile (CN) were not detected.
20 mg Cdox, 3 mL chlorobenzene, 20 mg catalyst, 275 W, 15 min.
No reaction.
b
c
d
Acknowledgments
20 mg Cdox, 3 mL chlorobenzene, 40 mg catalyst, 275 W, 5 min.
This research was subsidized by grants from the Direc-
ción General de Investigación (projects CTQ2005-04080 and
CTQ2007-65754/PPQ), Ministerio de Ciencia y Tecnología,
FEDER funds, and the Consejería de Innovación, Ciencia y
Empresa (Junta de Andalucía, project FQM-191).
3.3.2. Microwave heating
The data obtained from catalytic tests performed under mi-
crowave heating, with chlorobenzene as solvent, are summa-
rized in Table 8. In general, the experiments provided very
good catalytic activities for SiAlP-X materials. This indicates
that the activity of the SiAlP-X materials is close to that of
Beta25 and greater than that of zeolite ZSM-5(30). Dodeca-
nenitrile and 11-dodecenenitrile were not detected in the re-
action products, and only traces of cyclododecanone were de-
tected. ω-Laurolactam was obtained in high yields and selectiv-
ities (>96%). The activity observed under microwave heating
differed from conventional heating where, although relatively
high conversion and selectivity values were observed at rela-
tively short reaction times (typically under 5 h), the activities
were much lower than those of the zeolites [ZSM-5(30) and
Beta25].
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