11 Chapter 7
11 Chapter 7
11 Chapter 7
OXIDATION OF NAPHTHALENE
Abstract
Polycyclic aromatic hydrocarbons are carcinogenic substances to
which humans are exposed from the environment. The major exhausts of the
are emitted from diesel engines and can be much higher than those of Otto
engines. Naphthalene, a constituent of diesel and jet fuel is the most volatile
naphthalene burden, it is widely accepted that the major part comes from
has been demonstrated as one of the cost eective and eicient technologies to
destroy the troublesome volatile organic compounds.
Oxidation of Naphthalene
7.1 INTRODUCTION
concern because these are among the most toxic pollutants and can be
transported by small particles deep into human hngs. Therefore, it is desired
\ [O]
/ 1-Naphthol --in
[O]
Naphthalene OH \
2-Naphthol [O1 I
Oo
o ---
In the last decade certain success has been achieved in the resolution of
Chapter 7 g
production is by catalytic oxidation of 0-xylene or naphthalene using V205
operated at 340 to 385 C2. Of the current production of phthalic anhydride
produced quinine as the main product and naphthalene was oxidized to 1,4
Oxidation of Naphthalene
the tetrahedral vanadium sites inside the pore channels of MCM-4116. The
255
Chapter 7
so - 1- so
-"Naphthalene --A-Phthalicanhydridc 1
I
l
- f-20 ?
01 e re *i " 1 I ~e+0
Figure 7.1
The oxidation activity of" the catalyst obtained for a series of solvents
with different polarities is depicted in Figure 7.2.
256
Oxidation of Naphthalene
50
'
'
100
T
40- +80 l
'-I-Naphthalene A Phthalic anhydride
Ip AJBic -_
0
/-\
\-/
00-1
-4-I.
I Solvent/mm 01
I is
Figure 7.2
interface leading to the radical cation of the substrate and superoxide anion
while in the aqueous solution, the actual active species are assumed to be
hydroxyl radicals formed by oxidation of solvent2223. Acetonitrile is an aprotic
solvent. The activity of the catalysts is found to increase with the solvent
polarity and acetonitrile having more polar nature always enhances the activity.
In this solvent, the phase separation between the aromatic substrate and the
aqueous oxidant is greatly decreased thereby allows an easy transport of the
active oxygen species for the oxidation. According to Federica et a1.25 the
257
Chapter 7
l llll
Ti
** J fl ii: T T:
J J i if :anhydride
; i: f f T
A -I-Naphthalene
"0-Phthalic
M
I00-H
_ H-80
/R
so-U
l 7\
\ l F60 A l
y 2014
W
...ll
l iW
ll-20
I-4
1H
or ::F=-ii: = w>; Q-0
00-r:so
100 150 200
l Catalyst weight/mg J1
Figure 7.3
258
Oxidation of Naphthalene
IJi n
F
;I
L 80 " "' 80
I
T
'
L60
I W a __
-I-Naphthalene -9-Phihalic anhydridc
"20
0-|95~191
e - 286
J 381
e-0 1;
Volume/mmol
Figure 7.4
When the solvent was excess, the benzene or catalyst concentration at the
259
Chapter 7
r\
-|
14-so
5
O | 1%
T M If I-Naphthalene -Q-Phthalilclanl1ydn'dc
1l 3,"-4
-_2;.
Q
n-
kI
r\._
' \?
gir"
0.78---4
1.56 |
2.34 3 r12Q)
Volume/mmol
Figure 7.5
number of active centers for the reaction. Selectivity decline can be due to
r\ 1
T
Oxidation of Naphthalene
-0
60 ' 30
-I- Naphthalene Phthalic anhydride
1%
hi
Ll
\-ll
-0
1in
' 20+11| 44
a ~19
|r0
Volume/mmol
Figure 7.6
selectivity reaches a maximum and then decrease. This can arise from the
negative effect due to the production of H20 as a byproduct. The water and
261
Chapter 7
i\l50"
-.,
.|_
'
l
l
l
616
W F90I
90-
cl-I
1% l
3014 * 6
nn
\ Time/h 1
I23456736
while further increase in reaction time did not signicantly enhance the
conversion. Phthalic anhydride of about 88 % was obtained selectively in the
initial period of time. Further oxidation of this to acid can cause drop off in
selectivity with time. Similar observation was reported for benzene oxidation
and attributed to the poisoning of the surface sites by the reaction products
which in turn block the active sites with long time of reaction run3 1.
7.3 NAPHTHALENE OXIDATION OVER PREPARED CATALYSTS
262
Oxidation of Naphthalene
was carried out over all the prepared catalysts under the selected reaction
conditions as shown in Table 7.1.
Table 7.1
H202/mmol 44
Time/h 6
Catalyst Conversion
(
Selectivity (%)
wt. %) PAN
Ce
2VC
1.0
4VC
25.0
73.6
6VC
71.3
86.4
8VC
73.1
89.4
10VC
69.3
90.7
q_
100
2-Naphthol 1,4-Napqone
26.3
7.2 6.4
6.6 3.8
4.2 5.1
i#2&e' 7 _
Table 7.3 shows the results of naphthalene oxidation over VCRS series
of catalysts.
Table 7.3
Catalyst
RS
CRS
(wt.%)
PAN
ZVCRS l .2
4VCRS 25 .9
6VCRS 84.6
SVCRS 89.7
IOVCRS 76.9
1,4-Napqone
100
92.7
7.3
94.5
5.5
96.5
4.0
96.7
3.2
Silica and CRS support gave no oxidation products under the set
Oxidation of Naphthalene
Table 7.4
p
_
PRS
1.3
100
6VP
17.8
100
ZVPRS
6VPRS
vs
53.6
11.3
88.6
6vRs* 77.9 91.9 - 11.9
6vsG* 78.2 94.7 - 5.3
$-5min,#-4h
Praseodymia catalysts exhibit a very different behaviour during
265
Chapter 7
of active metal sites may occur during reactions and the enhanced catalytic
activity can arise from the presence of such homogeneous leached metal
species. The leaching of vanadium ions under reaction conditions from the
8vc
12.6
80.2
Filtiate 1 14.8 81.2
Oxidation of Naphthalene
recovered catalysts were reused for naphthalene oxidation under the same
reaction conditions. Table 7.6 displays the results obtained with regenerated
catalysts.
Table 7.6
8VCRS
1
26.2
82.3
2l 28.7
23.3 95.4
81.2
2 26.4 93.8
The activity of the reused catalyst was found to be lower than the fresh
catalyst as expected. It is attributed to the leaching of vanadium ions under the
supported vanadia catalysts are dependent on the catalyst, substrate and all
267
'.=P<"__--- _ _ _ _ . . . . _ _
other reaction parameters. The structural relationship of supported vanadia
catalysts and behaviour in benzene and ethylbenzene oxidation was already
inactive nature. Hence, the activity enhancement reveals that the nature of
vanadium species and its different site isolations/coordination environments
may be responsible for the differences in the conversion/selectivity behaviour.
Catalytic activity of VC and VCRS series of catalysts exhibits the same pattem
while phthalic anhydride selectivity was more with VCRS catalysts. Small
amount of 2naphthol was also produced with VC catalysts and selectivity to
formation of V-O-V species on the support surface. The EPR data of ceria
containing catalysts shows that the interaction of CeO2 with vanadia stabilizes
surface Ce sites, which inturn moderating the valence change ability of the
268
Oxidation of Naphthalene
The fonnation of silicate like SiO-Pr conguration was evidenced from 29Si
MAS NMR studies for VPRS catalysts.
of phthalic anhydride suggesting that ring rupture route was most probable
over these catalysts. This is possible with the highly dispersed tetrahedral
vanadia species on the supports. Formation of CeVO4 at higher vanadia loading
Chapter 7
shown that nature of solvent have an important role in oxidation reaction. The
aromatic ring. This low activity can be attributed to the difference in redox
property of praseodymia and ceria supported vanadia catalysts.
7.7 CONCLUSION
with H20; as oxidant._All the ceria supported vanadia catalyst prepared was
considerably active towards the oxidation, which produced phthalic anhydride
as the main product while praseodymia was less active and not produced
......................................................................................... ..
270
Oxidation of Naphthalene
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