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Role of Singlet Oxygen in The Oxidation of Toluene On Vanadium Molybdenum Catalytic Systems
Role of Singlet Oxygen in The Oxidation of Toluene On Vanadium Molybdenum Catalytic Systems
UDC 541.128
E-mail: mvvishnetskaya@mail.ru
2
Institute for Petroleum and Gas Problems, Siberian Branch of the Russian Academy of Sciences,
Ul. Oktyabrskaya 1, Yakutsk 677891 (Russia)
E-mail: istomsky@yandex.ru
Abstract
It was established that the catalysts based on van adium and molybdenum oxides exhibit activity in the
generation of the singlet form of molecular oxygen. The major reaction on mixed oxides having the composition
xV2O5 ⋅ yMoO3 is not the one-electron oxidation but the addition to the double bond, preferably in the meta
position. It was demonstrated that the oxidation of toluene on individual van adium and molybdenum oxides
follows independent routes: on V2O5, oxidation is realized mainly at the benzene ring, while on MoO3 it
occurs at the side chain.
van adate and metamolybdate taken in neces- addition to these products, we observed the
sary proportions, followed by thermal decom- formation of small amounts (less than 1 mass %)
position (similarly to the case of individual ox- of hydroquinone, anthraquinone etc. To estab-
ides). The specific surface of thus prepared sam- lish the contribution from hydroquinone as a ba-
ples was 56 m2/g. sic intermediate product forming MA, we pre-
The X-ray diffraction patterns were record- pared and studied reaction mixtures with the mass
ed with a DRON-3 instrument (ÑuKα radiation). concentration of hydroquinone 210 %. Accord-
Catalytic studies were carried out in a flow-type ing to the data of material balance with respect
reactor with steady-state catalyst layer within to carbon, the losses did not exceed 2 mass %.
temperature range 300500 °Ñ at atmospheric The amount of 1O2 was determined suing
pressure and the volume flow rate of raw ma- the jet method with the residual air pressure
terial input 0.51 h1. The samples of metal ox- approximately equal to 1 kPa, and linear flow
ides (0.250.5 g) were mixed with ground quartz rate of 260 cm/s [5]. The weighted portion of
(1.5 m2/g) and placed into the reactor. Toluene the catalyst was placed into a quartz reactor
was fed into the reactor in mixture with air at possessing low thermal inertia. Air was cooled
the molar ratio of toluene to oxygen equal to to room temperature at the reactor outlet and
1 : 10 and 1 : 6; the total rate of vapour-air mix- then it entered the cell in which active oxygen
ture flow into the reactor was 90 mL/min. selectively reacted with a chemiluminescent dye.
Liquid reaction products were an alyzed us- The intensity of chemiluminescence was record-
ing a Cambridge GC-95 chromatograph ed with a FEU-79 photomulti plier.
equi pped with a flame-ionization detector, cap-
illary column (50 m) with the FFAP phase. Gas- RESULTS AND DISCUSSION
eous products were analyzed with a Kristally-
uks-4000M chromatograph equi pped with a The data on toluene conversion, the yields of
katharometer, packed column (5 m) with acti- MA and BA depending on the composition of
vated carbon. Analysis of maleic anhydride and xV2O5 ⋅ yMoO3 at different temperatures, as well
benzoic acid was carried out dissolving the ob- as the data on the generation of singlet oxygen
tained products in water and titrating the 0.1 M are presented in Table 1. One can see that the
NaOH solution using an ATP-02 titrator. yield of MA for vanadium oxide is maximal at
Toluene oxidation with atmospheric oxygen 400 °Ñ, and then it decreases. The yield of ben-
on the catalysts under investigation proceeded zaldehyde for V2O5 is maximal at 300 °Ñ, but it
with the formation of benzaldehyde, maleic becomes equal to zero at 500 °Ñ. On molybdenum
anhydride (MA) and carbon oxides (COx). In oxide, the yield of benzaldehyde increases with
TABLE 1
Summary data on toluene oxidation on xV2O5 ⋅ yMoO3 with different x : y relations
an increase in temperature. The formation of MA benzaldehyde yield exactly coincides with that
did not occur on this catalyst. for individual MoO3 and is opposite to the be-
Thus, toluene oxidation on individual oxides haviour of the co-precipitated sample. The yield
proceeds via different routes: on V2O5 oxida- of MA (500 °Ñ) turned out to be identical for
tion proceeds mainly at the benzene ring, while the samples obtained through co-preci pitation
on MoO3 it proceeds at the side chain. and 4mechanical mixing. The largest difference
Inclusion of V2O5 into MoO3 in all the cases was observed for the comparison of COx yields:
causes an increase in toluene conversion degree. on the mechanical mixture, even at 500 °Ñ the
The samples with vanadium oxide content above reaction of complete oxidation proceeds only
50 mol. % in fact do not differ in conversion by 14 mol. %, while on the co-precipitated sam-
degree from the samples of pure V2O5. Accord- ple it proceeds by 54 mol. %. This is much higher
ing to the data shown in Table 1, even the in- than the calculated additive estimation which
clusion of 25 mol. % van adium oxide promotes is 22 mol. %. It should also be stressed that we
a substantial increase in the yield of benzalde- give the values of COx yield in the reaction of
hyde at low temperatures. The dependence of complete oxidation that is, taking into account
benzaldehyde yield on MoO3 content in mixed the oxide evolved during the formation of MA.
oxides is a function with extremum: the maxi- However, the data of X-ray phase an aly-
mal yield is observed at 300 and 400 °Ñ for the sis and EPR cannot explain the differences in
sample containing 50 % mol. MoO3, while at oxidation routes on oxide van adium-molybde-
500 °Ñ for the sample with the molar con- num catalysts. It is likely that different oxidiz-
centration of MoO3 equal to 100 %. ing agents take part in the formation of MA
The XPA data for xV2O5 ⋅ yMoO3 samples point and benzaldehyde.
to the formation of multiphase systems. For ex- The assumption concerning the partici pation
ample, for the sample with 25 mol. % V2O5 we of the singlet form of molecular oxygen in ox-
revealed three phases, with the predominance idation reactions on oxide catalysts was made
of MoO3 phase. After V2O5 content increased to for the first time by the authors of [6]. Later
40 mol. %, four phases were observed, with on [7], the ability of V2O5 and MoO3 to gener-
V2MoO3 as the dominating phase. In the case of ate 1O2 was discovered. However, quite differ-
the sample with V2O5 content equal to 50 mol. %, ent chemical n ature of these oxides did not
V2O5 phase starts to form; its contribution increas- allow one form an integrated opinion concern-
es with an increase in vanadium oxide content. ing the mechanisms of this generation.
The intensity of the lines corresponding to The data of chemiluminescence determina-
V2MoO8 phase decreases. For the sample with 75 tion of the amount of 1O2 generated into the
mol. % V2O5, the major phase is V2O5. gas phase from xV2O5 ⋅ yMoO3 are presented in
To determine the effect of the phase com- Table 1. The largest amount of 1O2 is generated
position, we prepared a sample of the mechan- on V2O5 ⋅ MoO3 and V2O5; no singlet oxygen was
ical mixture of individual van adium and mo- detected on MoO3. According to the EPR data
lybdenum oxides (75 mol. % MoO3). Toluene con- [8], with an increase in vanadium oxide con-
version degree on the mechanically mixed sam- tent, the fraction of paramagnetic centres V4+
ple at 400 °Ñ is 15 mol. %, while at 500 °Ñ it is increases. The VO2+ ions can be formed most
70 mol. %. These values are smaller than those probably through the reduction of V5+ by am-
obtained with co-preci pitated samples but ex- monia during thermal decomposition of ammo-
ceed (by 10 %) the value calculated using the nium metavanadate. On the other hand, vana-
additive scheme from the data for individual dium (V2O5) easily passes into the tetravalent
MoO3 and V2O5. In spite of the lower toluene state; singlet oxygen is evolved during this pro-
conversion degree on mechanical mixture, ben- cess. The transition from Mo6+ to Mo5+ was not
zaldehyde yield for this mixture is six times recorded in the EPR spectra; this corresponds
higher than that for the co-preci pitated sam- to the data of chemiluminescence an alysis on
ple and completely coincides with the results the generation of singlet oxygen with MoO3.
for individual MoO3. It should be noted that the For very low van adium oxide concentration
character of the temperature dependence of (2 mol. %), all V4+ ions are isolated, and these
324 M. V. VISHNETSKAYA a nd I. S. TOMSKIY
samples do not exhibit activity in the genera- Having compared these data with the re-
tion of singlet oxygen and in the formation of sults of catalytic transformations, we may con-
MA. Therefore, for MA to be formed during tol- clude that the formation of MA and benzalde-
uene oxidation, the associates of vanadium ox- hyde follows different independent routes: the
ide are necessary; they are formed when vana- formation of benzaldehyde is partici pated by
dium oxide concentration is above 40 mol. %. the tri plet form of oxygen, while the singlet
The data on the amount of carbon oxides form is necessary for the formation of MA.
COx formed in the reaction of complete oxida- It is usually presumed [13] that toluene at
tion (that is, taking into account the oxide first gets oxidized into benzaldehyde, and then
evolved during the formation of MA) show that into benzoic acid. Then benzene is formed in
the introduction of small amounts of molyb- decarboxylation reaction; through hydroquino-
denum oxide (up to 25 mol. %) enhances the ne it gives rise to MA and carbon oxides. It was
reactions of complete oxidation that are char- important for us to find out whether this mech-
acteristic of individual V2O5. It may be assumed anism, proposed previously for silver catalyst,
that an increase in the amount of COx, or com- is actual for the systems under consideration.
plete oxidation of MA, with an increase in va- First of all, the absence of even the traces of
nadium oxide content to 40 mol. % is connect- benzene in reaction products should be stressed.
ed with the transition of isolated centres into Second, hydroquinone was indeed detected in
associates. Subsequent decrease in the concen- trace amounts by means of potentiometric ti-
tration of COx can be due to the appearance tration. Therefore, one might expect that its
of V5+ centres and an increase in the concen- addition into the reaction mixture would cause
tration of these centres. One cannot exclude that an increase in MA yield but this did not hap-
it is this circumstance that explains an increase pen. It follows from these data that toluene ox-
in the amount of singlet oxygen generated from idation according to the mechanism proposed
the surface of mixed oxides in comparison with in literature does not occur in fact, and hydro-
pure vanadium oxide. quinone is not an intermediate product of tol-
Results obtained in the study un ambiguously uene oxidation but the fin al one.
point to the key role of the phase composition On the basis of the data obtained, we pro-
of catalysts in toluene oxidation. Judging from pose the scheme of toluene oxidation on van a-
the same yield of MA, the generation of sin- dium-containing oxide catalysts (Scheme 1).
glet oxygen is performed mainly by the phases The first two stages leading to the forma-
V2O5 and VO2, while the presence of V2MoO8 tion of benzaldehyde and benzoic acid proceed
phase promotes complete oxidation of sub- independently of the ability of the catalyst to
strates. Desorption of substrates from V2MoO8 generate 1O2. Then, in the case of relatively
may be hindered due to some reason, which low catalyst activity in the generation of the
leads to their complete oxidation. singlet form of oxygen, benzaldehyde and ben-
Scheme 1.
ROLE OF SINGLET OXYGEN IN THE OXIDATION OF TOLUENE 325