Transactions of Tianjin University

https://doi.org/10.1007/s12209-018-0146-6

RESEARCH ARTICLE

Kinetics and Mechanism Modeling of Liquid‑Phase Toluene Oxidation

to Benzaldehyde Catalyzed by Mn–Mo Oxide
Wang Li1 · Qingjun Zhang1 · Aiwu Zeng1

Received: 12 December 2017 / Revised: 5 March 2018 / Accepted: 21 March 2018

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
In this study, liquid-phase aerobic oxidation of toluene catalyzed by Mn–Mo oxide was conducted in a 1.0 L batch reac-
tor. The macroscopic kinetics of toluene consumption and benzaldehyde generation at 413–443 K were obtained from a
combination of experimental observation and hypothetical models. The results clearly showed that both the oxidation rate
of toluene and generation rate of the aromatic product were proportional to the concentration of the substrate, the partial
pressure of oxygen and the surface area of the catalyst. The energy barrier of toluene oxidation to benzyl alcohol was the
highest (≈ 81 kJ mol−1), while that of benzyl alcohol oxidation to benzaldehyde was the lowest (≈ 57 kJ mol−1). Moreover,
the activation energy of further oxidation of benzaldehyde in an acetic acid solvent was only slightly lower (≈ 1.9 kJ mol−1)
than that of toluene oxidation. Significantly, the transformation of benzyl alcohol indeed contributed to the generation of ben-
zaldehyde and this step conformed to a first-order parallel-consecutive model. Increased reaction temperature and residence
time favored the transformation of benzyl alcohol to benzaldehyde. In addition, doping with molybdenum at Mn/Mo = 3/1
enhanced the catalytic performance of the heterogeneous catalyst and was attributed to the presence of a synergetic effect
between different metal cations. Regarding the microscopic kinetics, the LH-OS-ND mechanism (Langmuir–Hinshelwood
adsorption of reagents on the same type of active sites and non-dissociative adsorption of oxygen) was verified as responsible
for the heterogeneous oxidation of toluene. Oxygen and benzaldehyde were weakly adsorbed (ΔHads,Oxy ≈ − 15 kJ mol−1,
ΔHads,Bald ≈ − 30 kJ mol−1), but showed strong mobility (ΔSads,Oxy ≈ − 22 J mol−1 K−1), ΔSads,Bald ≈ − 39 J mol−1 K−1). The
fundamental intrinsic rates were deduced based on the LH-OS-ND mechanism and showed great consistency with the
macroscopic results.

Keywords  Liquid phase · Oxidation of toluene · Heterogeneous catalyst · Benzaldehyde · Kinetics · LH-OS-ND mechanism

Introduction temperature and pressure [1, 2]. Furthermore, heterogeneous

Recently, the aerobic liquid-phase oxidation of toluene to
benzaldehyde using heterogeneous catalysts has attracted
much research attention. This is due to its moderate reaction
conditions and excellent catalytic performance compared
with gas-phase oxidation, which inevitably propels tolu-
ene toward deep oxidization into CO and ­CO2 under higher
Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1220​9-018-0146-6) contains
supplementary material, which is available to authorized users.
* Aiwu Zeng
awzeng@tju.edu.cn
1
School of Chemical Engineering and Technology, Tianjin
University, Tianjin 300350, China
catalysis could become resource-saving and environmental
friendly by making the catalysts recyclable and avoiding
the pollution processes that originate from the separation
process involved in the catalytic oxidation of toluene with
homogeneous catalysts [3, 4]. Thus far, researchers have
discovered several efficient heterogeneous catalysts with
persistent reactivity and high selectivity for the oxidation
of toluene toward benzaldehyde. Lv et al. [5] synthesized
ceria nanocube particles in aqueous solution under hydro-
thermal conditions at 453 K with oleic acid as the surface
adsorbent and observed that the catalyst exhibited consider-
able high selectivity toward benzaldehyde when toluene was
oxidized by oxygen in acetic acid solution. Acharyya et al.
[6] prepared a ­CuCr2O4 spinel nanoparticle catalyst with
size between 30 and 60 nm using a hydrothermal synthesis
method in the presence of cetyltrimethylammonium bromide

13
Vol.:(0123456789)

as a surfactant. They achieved 57.5% toluene conversion and
84.4% selectivity toward benzaldehyde with ­H2O2 as the
principal oxidant donor at 348 K in the liquid phase.
Of the alkyl aromatic hydrocarbons, toluene is one of the
most difficult to oxidize, as the initiation step of inert tolu-
ene to active benzyl radical demands high activation energy.
The dissociation energy of carbon hydrogen bonds on tolu-
ene methyl is up to 356 kJ mol−1 without the presence of a
catalyst [7]. Therefore, harsh reaction conditions (high tem-
perature and/or pressure) are usually required. To improve
this situation, catalysts are often used in the liquid-phase
oxidation of toluene. The more efficient the catalyst, the
easier is it to trigger the initial radical reaction. Manganese
oxides alone or doped are considered active catalysts for the
oxidation of aromatic hydrocarbons. Their catalytic proper-
ties are related to mixed valence manganese in the frame-
work of the catalyst and to the high mobility of the oxygen
species on the surface of solid catalysts [8, 9]. Cobalt salts
plus bromide have been widely applied as catalysts in liquid-
phase toluene oxidation in large-scale industries. Thus, pre-
vious kinetic research reported in the literature has mainly
focused on homogeneous catalysis [10–12]. The effect of
substrate concentration and/or oxygen partial pressure on
the oxidation rate of toluene has been discussed and it was
generally believed that the consumption rate of toluene was
proportional to its concentration, namely, the reaction rate
was first order to toluene [11, 12]. However, with respect to
the contribution of oxygen partial pressure, many different
and conflicting conclusions have been presented. Morimoto
and Ogata [12] argued that the oxidation rate of toluene was
independent of oxygen percentage above 42% and propor-
tional to it below 42%. Nevertheless, the oxidation reaction
of toluene has been reported as zero order, half order, and
first order to oxygen partial pressure by different researchers
(Helfferich [13], Bhattacharya et al. [14], and Hoorn et al.
[15]), but no reasonable explanations have been offered.
Moreover, different from homogeneous catalysis, in hetero-
geneous catalysis the reactants used have to overcome the
mass transfer resistance of the solid–liquid phase interface
and are then adsorbed onto the surface of the solid catalyst
to incur oxidation [15]. The complex surface properties of
solid catalysts, such as surface area, surface polarity, and
surface oxygen species do influence the adsorption-reaction
steps [16]. Therefore, the kinetics of heterogeneous catalysis
in toluene oxidation is still a problem to be solved.
It is a pity that few reports exist in the literature on het-
erogeneous catalyzed oxidation of toluene to benzaldehyde
in acetic acid, although the present researchers found a mul-
titude of high-efficiency heterogeneous catalysts. Moreover,
as is well known that benzyl alcohol can possibly be further
oxidized to benzaldehyde during the oxidation process, this
has been ignored by most previous research [17]. Therefore,
we propose, as a matter of urgency, an integrated kinetic
13
W. Li et al.
model and complementary oxidation mechanism, in which
the surface effects of the heterogeneous catalyst and the
mutual transformation of the oxidation products are ade-
quately addressed.
In this work, an improved network was structured and
this revealed the indispensable step of benzyl alcohol trans-
formation to benzaldehyde. Based on this reaction network,
the macroscopic kinetic rates of toluene consumption and
benzaldehyde generation were calculated. The generation
of benzaldehyde can be regarded as a parallel-consecutive
reaction consisting of direct oxidation from toluene and
indirect transformation from benzyl alcohol. It was also
found that the Mn/Mo ratio influences the kinetics due to the
synergetic effect of bimetallic oxides. The Langmuir–Hin-
shelwood (L–H) competitive non-dissociative mechanism
was proposed to clarify the detailed steps of heterogene-
ous catalyzed toluene oxidation in nature. The mechanism
considers the reactant to be adsorbed on the same type of
surface-active sites on the Mn–Mo oxide, and it is then
oxidized with non-dissociative adsorbed dioxygen under
catalysis by the fluctuant manganese ions. Presumably, the
surface polarity of the catalyst affects the oxidation of tolu-
ene. A low-polarity surface on the Mn–Mo oxide is favorable
to both adsorption of nonpolar toluene and desorption of
polar benzaldehyde; thus, it improves the high selectivity of
toluene conversion to benzaldehyde. The microscopic rates
determined for the fundamental oxidation steps lie within
the proposed L–H mechanism. These derivations are in line
with the experimental kinetics.
Experimental
Materials
Mn(CH3COO)2·4H2O, ­(NH4)6Mo7O28·4H2O, citric acid,
nitric acid (65–68%), and deionized water (HPLC grade)
were purchased from Aladdin Technology, China. The tol-
uene, acetic acid, and sodium bromide were of analytical
grade. All chemicals were used without further purification.
Preparation of Catalyst
Mn–Mo bimetallic oxides were prepared from the man-
ganese salt and molybdate using the sol–gel method. An
aqueous solution of 5.04 g (­ NH4)6Mo7O28·4H2O dissolved
in 50 mL deionized water was prepared in advance. Then,
21 g Mn(CH3COO) 2·4H2O in 100 mL deionized water was
added into the aqueous solution with vigorous stirring. The
pH of the precursor solution was adjusted to the range of
1–2 by adding dropwise concentrated nitric acid. Then, the
obtained homogeneous solution was heated at 358 K for 24 h
in an oil bath to synthesize the sol particles. Excess water
Kinetics and Mechanism Modeling of Liquid-Phase Toluene Oxidation to Benzaldehyde Catalyzed…
was evaporated at 393 K for 12 h in a vacuum oven. The
dried gel was calcined at 773 K for 3 h in air. After grinding
with a mortar and pestle, the resulting powders were sieved
through a 320-mesh screen. Powder X-ray diffraction pat-
terns were collected using a RIGAKU D/Max-2500 X-ray
diffractometer with a Cu Kα radiation source. Diffraction
patterns in the range of 10°–70° were recorded at a rate of
4° min−1. The BET surface area was measured using ­N2
adsorption–desorption isotherms at a liquid ­N2 temperature
of 77 K using a Quantachrome Autosorb-iQ2-MP analyzer.
Prior to these measurements, the sample was pre-treated
at 573 K for 3 h under vacuum. X-ray photoelectron spec-
tra (XPS) were recorded on a Thermo Scientific Al Kα
X-Ray photoelectron spectrometer and the binding energies
(± 0.1 eV) were determined with respect to the position of
the C 1 s peak at 284.8 eV.
In Fig. S1a, the prepared catalyst shows high-crystal-
linity manganese molybdenum oxide at 2θ = 25.72°. The
other diffraction angles also match the standard PDF card
(JCPDS#72-0285). Figure S1b reveals the coexistence of
divalent and trivalent manganese cations on the surface of
the catalyst. The characteristic peak with binding energy
located at 640.8 eV is ascribed to M ­ nMoO4 and the sec-
ond peak at 642.1 eV is ascribed to ­Mn2O3 [18]. The molar
­ n2+ to M
ratio of M ­ n3+ was maintained at 0.72 throughout
the Gaussian functional peak-fitting processes, as shown in
Table S1. Fluctuating-valence manganese cations enable the
­ n3+
redox activity of the solid catalyst and relatively more M
is preferable for toluene oxidation [19]. Figure S1c reveals
that the oxygen species combine in two different forms on
the catalyst surface. The XPS peak with a binding energy at
531.2 eV is attributed to surface-adsorbed oxygen, while the
lower peak at 530.2 eV is ascribed to surface lattice oxygen
[20]. Gaussian simulation shows that the molar ratio of O ­ ads/
Olat on the catalyst surface is maintained at 0.84, as listed
in Table S1. The presence of adsorbed oxygen species indi-
cates an abundance of oxygen vacancies, which reciprocate
transformation between the empty active sites and adsorbed
oxygen on the solid catalyst surface. Figure S1d shows that
the surface of the solid catalyst is more porous so that the
substrate compounds are adsorbed onto it. The BET meas-
urement showed the mean pore diameter to be about 19 nm,
and hence the pores were classified as mesopores.
Oxidation of Toluene
The heterogeneous catalyzed oxidation of toluene was stud-
ied experimentally in a 1.0 L stainless steel batch reactor.
The same starting materials were applied in all the oxidation
tests: 2.0 g catalyst, 2.0 g sodium bromide, 100 mL toluene,
and 300 mL acetic acid were taken in a bubble reactor. The
reactor was then purged with nitrogen to 0.8 MPa and that
there was no leakage ensured. Subsequently, the pressure
was adjusted to 0.6–1.2 MPa and the temperature of heated
feed liquid to 413–448 K. Finally, air was introduced at
the bottom of the device at a flow rate of 1100 mL min−1.
Products were sampled every half hour and the samples
were quantitatively analyzed using an Agilent GC-7890A
equipped with a DB-FFAP capillary column and a flame
ionization detector. The conversion of toluene and selectivity
of the oxidation products were calculated and normalized
with respect to the GC response factors. A GC–MS equipped
with an HP-5 capillary column (25 m length, 0.28 mm id,
0.25 μm film thickness) was used to identify the composition
of the products [21].
Results and Discussion
Macroscopic Consumption of Toluene
Relevant literature has generally reported the oxidation
rate of toluene to be first order to its concentration [12, 13].
Therefore, the consumption of toluene can be expressed by
Eq. (1):
( )
1
ln = kt, (1)
1−X
where X is the conversion rate of toluene, %; t is residence
time, h; k is the rate constant, ­h−1.
Figure 1 shows that the natural logarithms of the meas-
ured conversion rate of toluene have a linear relationship
with residence time over the interval of 413–443 K. This
shows that the oxidation rate of toluene obeys first-order
principles within the scope of these experimental conditions.
The kinetic parameters are enumerated in the first two col-
umns in Table 1 and the macroscopic oxidation of toluene
can be embodied into Eq. (2):
3
413 K
423 K
433 K
2 443 K
−ln(1−X )
1
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Time(h)
Fig. 1  Conversion of toluene versus residence time in the range
of 413–443  K at fixed 1.0  MPa and with catalyst surface area of
28.32 m2 g−1 (Mn/Mo = 3/1)
13
 W. Li et al.

Table 1  Macroscopic kinetic parameters of toluene consumption

0.6 MPa
(SCata = 56.64 m2 g−1, (T = 433 K, (T = 433 K, 2 0.8 MPa
PSys = 1.0 MPa) SCata = 56.64 m2 g−1) PSys = 1.0 MPa) 1.0 MPa
1.2 MPa
T (K) k ­(h−1) PSys (MPa) k′ ­(h−1) SCata ­(m2 g−1) k′ ­(h−1)

−ln(1− X )
413 0.1423 0.6 0.2364 14.16 0.0863
1
423 0.2445 0.8 0.3140 28.32 0.1964
433 0.3931 1.0 0.3931 42.48 0.3347
443 0.6097 1.2 0.4720 56.64 0.3931
19.528 −1
A = e ­(h ), k′=0.007 PSys SCata ­(h−1)
Ea= 73.696 kJ mol−1 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Time(h)

Fig. 2  Conversion of toluene versus residence time in the range

dc 73696
of 0.6–1.2  MPa at fixed 433  K and with catalyst surface area of
− Tol = 3.026 × 108 e− RT cTol , (2) 28.32 m2 g−1 (Mn/Mo = 3/1)
dt
where cTol is the concentration of toluene (Tol), mol L−1; T
is the reaction temperature, K. consumption rate is proportional to system pressure and cat-
However, the concentration of dissolved oxygen plays a alyst surface area separately. Thus, the two reaction orders
significant role in the oxidation of toluene [22]. Further- were determined to be n1 = 1.0, n2 = 1.0. In addition, the
more, the amount of surface area possibly affects the kinetics slopes of the straight lines show a positive trend related to
as toluene oxidation occurs at the surface of the catalyst. an incremental independent variate, as listed in the third to
Thus, a trade-off consideration of the two factors is impera- sixth columns in Table 1. An experiential function formula
tive for toluene consumption rate and is expressed in Eq. (3): is given as k′= 0.007 PSys SCata, in which the overall rate con-
stant k′ remains proportional to the system pressure PSys and
dcTol
−
n1
= k cTol cOxy
n2
SCata . (3) catalyst surface area SCata, although the case can show a huge
dt bias when the amount of catalyst exceeds 1.5 g. As men-
The BET measurement is easily obtained and the surface tioned, the effect of dissolved oxygen concentration on the
area of the prepared catalyst was 28.32 m2 g−1. However, kinetics is indirectly reflected in the system pressure; thus,
the oxygen concentration dissolved in the liquid phase is the toluene consumption rate can be similarly regarded as
difficult to measure accurately under these present reaction first order to the oxygen concentration. Finally, liquid-phase
conditions of high temperature and pressure. Fortunately, aerobic oxidation of toluene is determined to be first order
Tang and Liang [23] pointed out that the system pressure to toluene concentration, oxygen concentration, and catalyst
can indirectly illustrate the effect of oxygen concentration on surface area. The macroscopic consumption of toluene can
kinetics, instead of using the specific concentration of dis- be determined as:
solved oxygen. Fresh air was continuously bubbled through 73696
(5)
6 − RT
the liquid phase and the oxygen concentration remained con- cTol = cTol,0 e−5.44×10 e PSys SCata t
,
stant under a specific system pressure. Hence, Eq. (3) can be
adjusted to Eq. (4) by introducing Henry’s law.
1.6 14.16 m2/g
dcTol 28.32 m2/g
n1 n2 − 73696 n n
− = k� cTol = kapp PSys SCata cTol = Aapp e RT 1
PSys 2
SCata cTol , 42.48 m2/g
dt 1.2 56.64 m2/g
(4)
−ln(1−X )

−1
where k′ is the overall rate constant, ­h ; kapp is the apparent 0.8
rate constant, ­h−1; Aapp is the apparent pre-exponential factor,
­h−1; PSys is the system total pressure, MPa; SCata is the cata-
0.4
lyst surface area, ­m2 g−1; n1 and n2 are reaction orders with
respect to the system total pressure and catalyst surface area.
0.0
Regarding the effects of oxygen concentration and sur- 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
face area, two plots of respective conversions of toluene Time(h)
versus residence time are depicted in Figs. 2 and 3. Each
fitting curve in these diagrams shows a good linear rela- Fig. 3  Conversion of toluene versus residence time with catalyst sur-
face area of 14.16–56.64  m2  g−1 (Mn/Mo = 3/1) at fixed 433  K and
tionship with residence time and demonstrates that toluene
1.0 MPa

13
Kinetics and Mechanism Modeling of Liquid-Phase Toluene Oxidation to Benzaldehyde Catalyzed…

1.2
2
CH2OH
Concentration of toluene(mol/L)
428 K, 0.8 MPa, 21.24m /g
2
428 K, 1.0 MPa, 35.40m /g
1.0 2
438 K, 0.8 MPa, 21.24m /g
2
438 K, 1.0 MPa, 35.40m /g
2
0.8 448 K, 0.8 MPa, 21.24m /g

[O] k3
0.6
[O]
k2
0.4
CH3 CHO COOH
[O] [O]
0.2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 k1 k4
Time(h)

Fig. 4  Calculated prediction (curve) versus experimental measure- Scheme 1  Parallel-consecutive model for generation of benzaldehyde
ment (symbol) for toluene concentration from toluene

where cTol,0 is the initial concentration of toluene, mol L−1.
Equation (5) was used to calculate the predicted concen-
tration of toluene under arbitrary reaction conditions. Then
this calculated value was compared with the experimental
measurements, as shown in Fig. 4. This reveals that the pre-
dicted toluene concentration is an excellent match with the
experimental measurement. Therefore, the finally obtained
formula, Eq. (5), is feasible for describing the macroscopic
oxidation of toluene.
Macroscopic Generation of Benzaldehyde
The oxidation of benzaldehyde was much faster than that of
toluene, as previously reported [24], thereby the selectivity
toward benzaldehyde significantly decreased as residence
time increased. In addition, the reaction temperature remark-
ably influenced the benzaldehyde oxidation process [25].
Although some researchers [26–28] have reported that the
oxidation of benzaldehyde to benzoic acid is a first-order
reaction, the kinetics of benzaldehyde generation during the
process of toluene oxidation is still a controversial theme.
In this work, we put forward a parallel-consecutive reaction
model, considering the step where benzyl alcohol is further
oxidized to benzaldehyde during the generation of benzal-
dehyde from toluene. Benzyl acetate, benzoate, and other
reaction products were not taken into account in the kinetic
studies because the competing esterification of benzyl alco-
hol in acetic acid is an order of magnitude slower than that
of continual oxidation to benzaldehyde [29]. On the other
hand, the initial concentration of benzyl alcohol, as appears
in the kinetic formula, is the amount of free benzyl alcohol
and combined acetate. Thereby, the reaction model can be
simplified as Scheme 1.
Several other reports [30–33] showed that the oxidation
of benzyl alcohol to benzaldehyde was proportional to the
benzyl alcohol concentration, oxidant, and quantity of cata-
lyst, respectively. In our work, it was discovered that the
concentration ratio of intermediate benzyl alcohol to ben-
zaldehyde remained constant during the initial oxidation
stage of 0.5–1.5 h (0.47–0.49 at 413 K, 0.50–0.52 at 423 K,
0.54–0.57 at 423 K, and 0.59–0.61 at 443 K. See Table S2).
This phenomenon demonstrates that the oxidation of tolu-
ene is possibly a parallel reaction due to the constant ratio
of the two different oxidation products [34]. Therefore, we
first assumed that the initial generation rates of benzyl alco-
hol and benzaldehyde are both first order to toluene. The
consideration of oxygen partial pressure and surface area of
catalyst was suspended due to the fixed 1.0 MPa and 2.0 g
catalyst. Finally, based on the first-order parallel-consecutive
law, the generation of benzaldehyde is given by Eq. (6):
⎧ dcTol � �
⎪ − dt = k1 + k2 cTol
⎪
⎪ dcBalc � �
= k2 cTol − k3 cBalc
⎪ dt
⎨ dc � � (6)
⎪ Bald
= k1 cTol + k3 cBalc − k4 cBald
⎪ dt
⎪ dcBac
⎪ = k4 cBald ,
⎩ dt
where cBalc, cBald, and cBac are the concentrations of benzyl
alcohol (Balc), benzaldehyde (Bald), and benzoic acid (Bac),
respectively; k1 and k2 are the rate constants of the parallel
oxidation of toluene to benzaldehyde and benzyl alcohol,
respectively; k3 and k4 are the rate constants of the oxidation
of benzyl alcohol and benzaldehyde separately.
The four undetermined rate constants in the parallel-
consecutive model can be obtained using the Runge–Kutta
iteration in MATLAB routine (ODE45) and specific values
are given in Table 2. The apparent pre-exponential factor
and activation energy for each reaction step were calculated
using Arrhenius’ law. Comparison of the four energy barriers

13
 W. Li et al.

Table 2  Macroscopic kinetic parameters of benzaldehyde generation from toluene

T (K) k1 ­(h−1) k2 ­(h−1) k3 ­(h−1) k4 ­(h−1)

413 0.0961 0.0462 0.3022 0.3239

423 0.1630 0.0815 0.4474 0.5441
433 0.2520 0.1411 0.6505 0.8923
443 0.3809 0.2288 0.9299 1.3125
km= Am exp(−Ea,m/RT) (m = 1, 2, 3, 4)
Am ­(h−1) e17.928 e20.634 e15.400 e19.698

Ea,m (kJ mol−1) 69.530 81.389 56.987 71.442

0.3 contended in the previous work [35]. This is likely attribut-

Concentration of Balc or Bald(mol/L)

Concentration of Tol or Bac(mol/L)

1.0 Toluene able to the stronger inhibition from hydrogen bonding to

Benzoic acid
Benzyl alcohol
0.8 Benzaldehyde
0.6
0.4
0.2
remove k1
0.0
0 1 2 3 4 5
Time(h)
Fig. 5  Validation of necessary direct toluene oxidation pathway in
parallel-consecutive model at 443 K
shows that the oxidation of toluene to benzaldehyde is easier
than to benzyl alcohol, while benzyl alcohol is quicker to
undergo further oxidation to benzaldehyde. Meanwhile, the
activation energy of benzaldehyde oxidation in acetic acid
is only slightly lower than that of toluene. These results are
almost consistent with the reports of Tan et al. [35], in which
the authors indicate that toluene oxidation to benzyl alcohol
is a rather slow reaction, while intermediate benzyl alco-
hol is quickly converted into benzaldehyde. However, a few
differences still exist due to the different catalyst systems.
In our research, the transformation of benzyl alcohol was
easier than further oxidation of benzaldehyde because of the
lower activation energy, while the opposite conclusion was
a carbonyl α-substituent of benzaldehyde on the porous
surface of the catalyst in an acetic acid solvent, which, in
0.2
essence, stabilized the benzaldehyde [29]. Therefore, benza-
ldehyde, an oxidation intermediate of toluene, is more likely
to give a high yield under the present operating conditions.
0.1 When applying Eq.  (6), it can be seen that the fitted
curves show a good match with the experimental points
in Fig. 5. Therefore, generation of benzaldehyde from the
0.0 liquid-phase oxidation of toluene can presumably be con-
6 7 8
sidered a first-order parallel-consecutive reaction. The k2
pathway is necessary as benzyl alcohol was detected in the
oxidation products, but the k1 pathway is not dispensable in
the generation of benzaldehyde. The model fails if the direct
oxidation pathway to benzaldehyde is removed and huge bias
results between the experimental points and the fitting curve
of benzaldehyde if the k1 pathway is removed. Therefore,
the k1 pathway is necessary. In other words, benzaldehyde
generation not only results from the transformation of benzyl
alcohol, but also the direct oxidation of toluene. Analogous
to toluene, the oxidation of benzyl alcohol and benzaldehyde
is proved to be a first order to both system pressure PSys and
catalyst surface area SCata, as shown in Table 3. Taking these
two factors into account, the concentration of the fundamen-
tal oxidation products is integrated as:
k2 cTol,0 ( −k t )
cBalc = e 2 − e−k3 t PSys SCata , (7)
k3 − k2

Table 3  Oxidation rates PSys (MPa) (SCata = 56.64 m2 g−1) (PSys = 1.0 MPa)

of benzyl alcohol and
benzaldehyde related to system dcBac/dt dcBalc/dt SCata ­(m2 g−1) dcBac/dt dcBalc/dt
pressure and catalyst surface (mol L−1 h−1) (mol L−1 h−1) (mol L−1 h−1) (mol L−1 h−1)
area at 443 K
0.6 0.7854 0.5572 14.16 0.3268 0.2331
0.8 1.0476 0.7431 28.32 0.6562 0.4720
1.0 1.3125 0.9299 42.48 0.9851 0.6952
1.2 1.5743 1.1142 56.64 1.3125 0.9299

13
Kinetics and Mechanism Modeling of Liquid-Phase Toluene Oxidation to Benzaldehyde Catalyzed…

� � benzyl alcohol to benzaldehyde. Table 4 distinctly indicates

⎛ k1 e−k1 t − e−k4 t
⎜ k4 −k �
cBald = cTol,0
⎜ +k2 k3 ( 3 2 )
−k4 t + k −k e−k2 t − k −k e−k3 t
k −k e
⎝ (k4 −k3 )(k4 −k2 )(k3 −k2 )
cBac = cTol,0 − cTol − cBalc − cBald .
Equations (7)–(9) were then applied to calculate the pre-
dicted concentrations of benzyl alcohol, benzaldehyde, and
benzoic acid under different operating conditions. Then,
these calculated concentrations were compared with the
experimental measurements, as shown in Fig. 6. The com-
parison illustrates that the predicted concentrations are pre-
cisely consistent with the experimental observations. There-
fore, the above-deduced concentration formulas are feasible
for the description of the generation of the three fundamental
oxidation products of toluene.
Obviously, Eq. (8) consists of two terms: the former term
represents a simple prediction based on the first-order con-
secutive model, in which benzaldehyde is only generated
from the direct oxidation of toluene and is completely oxi-
dized to benzoic acid; the latter term originates from the
proposed parallel-consecutive model that supplements the
generation pathway of benzaldehyde from further transfor-
mation of benzyl alcohol. Therefore, the ratio of these two
terms represents the contribution of the transformation of
⎞
� ⎟P S ,
that this transformation pathway is significant in the genera-
( 4 3) ( 4 2)
⎟ Sys Cata
⎠ tion of benzaldehyde. In the first 2 h, the direct formation
of benzaldehyde from toluene was the fundamental mecha-
(8)
nism, as the consumption rate of toluene was predominant
(9) at the high toluene concentration. When extending the resi-
dence time beyond 3 h, the ratio of transformation to direct
oxidation was over 1.337 due to the diminishing toluene
concentration and the increasing benzyl alcohol concentra-
tion. In fact, this was the most dominant status at the final
reaction stage within 5–6 h and illustrates that the transfor-
mation of benzyl alcohol is indispensable due to the con-
siderable contribution to the yield of benzaldehyde during
deepening oxidation. Because of its lowest energy barrier,
benzyl alcohol oxidation easily occurs and contributes a lot
to benzaldehyde generation. Of course, reaction temperature
has a significant influence on the transformation pathway. If
the temperature is incremental, the related ratio to benzyl
alcohol transformation doubles approximately. This favors
the parallel oxidation of toluene to benzyl alcohol rather than
benzaldehyde due to the higher activation energy (exceeding
11.86 kJ mol−1). This is sensitive to incremental tempera-
tures and results in relatively high concentrations of benzyl
alcohol at elevated reaction temperatures. The concentrated
benzyl alcohol accelerates the transformation. Therefore, the
contribution of benzyl alcohol oxidation to benzaldehyde
enhances with the rising temperature.

Influence of Mn/Mo Ratio

Concentration of Balc or Bald(mol/L)

0.30 1.2
Benzyl alcohol Benzaldehyde
Concentration of Bac(mol/L)

0.25
Benzoic acid (428K, 0.8MPa, 21.24m2/g) Generally, binary transition metal oxides exhibit better cata-
Benzyl alcohol Benzaldehyde
Benzoic acid (438K, 1.0MPa, 35.40m2/g) 0.9 lytic properties than mono oxides due to the synergetic effect
0.20 between the discrepant valence states of various metal cati-
0.15 0.6 ons [36]. Indeed, the Mn–Mo composite oxide shows fine
catalytic performance for toluene oxidation to benzaldehyde,
0.10 compared with either the negligible conversion with individ-
0.3
0.05
ual ­MoO3 or the low selectivity toward benzaldehyde with
single ­Mn2O3. However, the optimum ratio of Mn/Mo in pre-
0.00
0 1 2 3 4 5 6 7 8
0.0 pared catalysts needs to be investigated in the kinetic studies.
Time(h) The catalytic performance profiles for toluene oxidation over
Mn–Mo oxides are shown in Fig. 7. For all four catalysts, we
Fig. 6  Calculated prediction (curves) versus experimental measure- considered the conversion of toluene as the criteria of activ-
ment (symbols) for concentration of fundamental oxidation products ity and the generation of benzaldehyde as the selectivity. The

Table 4  Contribution of the T (K) nTrans/naDirect

transformation of benzyl
alcohol to benzaldehyde t = 1 h t = 2 h t = 3 h t = 4 h t = 5 h t = 6 h

413 0.0733 0.1484 0.2253 0.3046 0.3870 0.4725

423 0.1162 0.2421 0.3795 0.5307 0.6989 0.8875
433 0.1980 0.4327 0.7135 1.0528 1.4716 1.9895
443 0.3221 0.7519 1.3370 2.1506 3.3011 4.9524
a
 nTrans/nDirect represents the molar ratio of transformation part to direct one for benzaldehyde generation

13
 W. Li et al.

results show that the catalytic activity was in the order of the catalytic experiments were investigated in terms of rate
Mn/Mo = 3/1 > Mn/Mo = 3/0 > Mn/Mo = 1/1 > Mn/Mo = 1/3, constants and activation energies to further analyze the root
while the selectivity was in the order of Mn/Mo = 1/3 > Mn/ cause of the different performances exhibited by the four
Mo = 1/1 > Mn/Mo = 3/1 > Mn/Mo = 3/0. Evidently, the rich catalysts. These kinetic parameters were obtained using
manganese cations favored the activity of the catalysts, but Arrhenius’ law and are listed in Table 5. Some increase in
doping with molybdenum cations enhanced the exclusive rate constant with the addition of molybdenum was observed
oxidation of toluene to high-yield benzaldehyde. In the in the Mn/Mo = 3/1 catalyst. This is consistent with the
­ n3+/
partial oxidation of toluene, the high redox potential M results of Tarjomannejad et al. [39], in which the Eapp value
Mn2+ pairs were prominent active sites for oxidation due showed no significant change, but the pre-exponential factors
to their strong oxidizability [37]. The abundance of mixed increased with a slight replacement of less active metal cati-
valent Mn provided many active sites for the oxidation of ons. At low Mo doping, the redox performance of the cata-
toluene and its intermediate, causing high conversion of lyst was enhanced as the synergetic effect between different
toluene but low selectivity to benzaldehyde. Suitable dop- metals caused the augmentation of both toluene conversion
ing with molybdenum caused a significant improvement in and benzaldehyde selectivity. However, adverse conditions
the selectivity of benzaldehyde and this is attributed to the appeared with continuous molybdenum addition. Excessive
synergetic effect of bimetallic oxides. Enhanced electron molybdenum suppressed the catalytic performance due to
transfer occurs between transition metals and gaseous oxy- the low redox activity, leading to a slow oxidation rate and
gen [38], resulting in strengthened redox behavior in both high activation energy. Therefore, optimum doping with Mo
­Mn3+/Mn2+ and ­Mo6+/Mo4+ pairs, as described in Eqs. (10) for the heterogeneous catalyzed oxidation of toluene was
and (11): equal to Mn/Mo = 3/1.

2Mn2+ + Mo6+ → 2Mn3+ + Mo4+ , (10) Langmuir–Hinshelwood Mechanism

(11)
4+
O2 + Mo → O2− + Mo .6+
Heterogeneous catalysis generally follows one of the two
2

mechanisms [40–43]: (1) the Langmuir–Hinshelwood

Therefore, the most efficient catalyst for the selective oxi- (L–H) mechanism or (2) the Mars–van Krevelen (M–K)
dation of toluene has a ratio of Mn/Mo = 3/1. In addition, mechanism.
In the L–H model, reaction steps on the surface are con-
sidered to be a combination of adsorption of reactants, sur-
face reaction, and desorption of the product. The Langmuir
selectivity of benzaldehyde SBald(%)
Conversion of Toluene X Tol (%) or

140 X Tol at Mn/Mo=3/0 XTol at Mn/Mo=3/1

X Tol at Mn/Mo=1/1 XTol at Mn/Mo=1/3 adsorption isotherm can be either non-competitive or com-
120 S Bald at Mn/Mo=3/0 SBald at Mn/Mo=3/1
S Bald at Mn/Mo=1/1
petitive. For non-competitive adsorption in toluene oxida-
SBald at Mn/Mo=1/3
100 tion, the existence of two types of active site on the surface
80 of the solid catalyst is assumed. One is covered by oxygen
60 only, and the other adsorbs toluene and its oxidation interme-
diate. This assumption was used by Smeds et al. [44] when
40
studying the kinetics of ethylbenzene hydrogenation on Ni/
20 Al2O3 and validated as proper. For competitive adsorption in
0 toluene oxidation, reactant adsorption was assumed to take
0 1 2 3 4 5
Time(h)
place at the same type of sites. All adsorption steps were
assumed to be in pseudo-equilibrium and desorption of ben-
zoic acid can be fast and irreversible. Surface reaction was
Fig. 7  The influence of Mn/Mo ratio on conversion of toluene (solid
symbols) or selectivity to benzaldehyde (hollow symbols) at 443  K, the rate-determining step. Thereby, Eqs. (12)–(15) are given
1.0 MPa, and 2.0 g catalyst

Table 5  Effect of Mn/Mo ratio on macroscopic kinetic parameters of benzaldehyde generation from toluene

Mn/Mo ratio k1 ­(h−1) k2 ­(h−1) k3 ­(h−1) k4 ­(h−1) E1 (kJ mol−1) E2 (kJ mol−1) E3 (kJ mol−1) E4 (kJ mol−1)

3/0 0.3610 0.1925 0.9054 1.3421 69.786 81.638 57.512 69.884

3/1 0.3809 0.2288 0.9299 1.3125 69.530 81.389 56.987 71.442
1/1 0.2148 0.1425 0.6542 0.8847 72.012 83.734 58.263 74.365
1/3 0.0865 0.0589 0.2862 0.3356 76.530 85.462 59.524 77.737

13
Kinetics and Mechanism Modeling of Liquid-Phase Toluene Oxidation to Benzaldehyde Catalyzed…

based on two different types of adsorption [see detailed reac- Stead-state balance for non-competitive type:
tion steps in Supplementary Information]. �
Adsorption–desorption balance of non-competitive type: ⎧ � γI γI γI v
⎪ k1 + 2k3 cTol 𝜃 = ko1 cOxy 𝜃1
⎪ γI I
⎧ 𝜃j = K c 𝜃j ⎪ k5 cBalc 𝜃 = koγ cvOxy 𝜃2
⎪ Oxy Oxy Oxy 1v ⎨ I 2
(16)
⎪𝜃 = K c 𝜃 ⎪ kγ cBald 𝜃 = kγI cv 𝜃3
⎪ Tol Tol Tol 2v ⎪ 7 o3 Oxy
⎪ 𝜃Balc = KBalc cBalc 𝜃2v ⎪ 𝜃 + 𝜃1 + 𝜃2 + 𝜃3 = 1.
⎨ (12) ⎩
⎪ 𝜃Bald = KBald cBald 𝜃2v
⎪𝜃 + 𝜃 = 1
⎪ Oxy 1v
Mass balance at active sites:
⎪𝜃 + 𝜃
⎩ Tol Balc + 𝜃Bald + 𝜃2v = 1.
𝜎Cata = 𝜎 + OLat 𝜎 + 𝜎1 + ⋅ ⋅ ⋅ + 𝜎2 + ⋅ ⋅ ⋅ + 𝜎3 + ⋅ ⋅ ⋅ (17)
For competitive adsorption, it can be written as:
Mass balance at active sites: ( )
γII γII γII γII II
k1 + 2k3 cTol 𝜃+k5 cBalc 𝜃+k7 cBald θ = koγ cvOxy (1 − 𝜃).
𝜎Cata = 𝜎1 + jO2∕j 𝜎1 + ⋯ + 𝜎2 + PhCH3 𝜎2 + ⋯ (13)
1

(18)
For competitive adsorption, it can be written as: Mass balance at active sites:
⎧ 𝜃j = K c 𝜃j 𝜎Cata = OLat 𝜎 + 𝜎 + ⋅ ⋅ ⋅ (19)
⎪ Oxy Oxy Oxy v
⎪ 𝜃Tol = KTol cTol 𝜃v For weakly adsorbed species in a multi-component
⎪ mixture:
⎨ 𝜃Balc = KBalc cBalc 𝜃v (14)
⎪
⎪ 𝜃Bald = KBald cBald 𝜃v bc
θi = ∑ �i i � , (20)
⎪𝜃 + 𝜃 + 𝜃 bi ci
⎩ Oxy Tol Balc + 𝜃Bald + 𝜃v = 1.

where θi, bi and ci are surface coverage, adsorption coef-

Mass balance at active sites: ficient, and concentration of the ith hydrocarbon (toluene,
benzyl alcohol, and benzaldehyde), respectively.
𝜎Cata = 𝜎 + jO2∕j 𝜎 + PhCH3 𝜎 + PhCH2 OH𝜎 + PhCHO𝜎+ ⋅ ⋅⋅
The aforementioned Eqs. (12)–(20) are thereby solved
(15) and finally the simplified Eqs.  (21)–(24) obtained [see
The M–K mechanism also consists of two steps. In the details in Supplementary Information].
first step, the lattice oxygen of the catalyst oxidizes the sub- For L–H non-competitive mechanism:
strate and produces a partially reduced catalyst. It is consid-
( )1∕j
ered that each hydrocarbon reduces the catalytic species to ci POxy SCata ( )
1 b c d
a different oxidation state. In the second step, the reduced =
+ cTol + cBalc + cBald ,
ri a a a a
catalyst is re-oxidized by molecular oxygen. For non-com-
𝛽I ( )1∕j
petitive adsorption, four types of active sites are assumed to a = ki Ki KOxy ∕kc,Oxy ,
(21)
exist on the surface of the heterogeneous catalyst. σ, σ1, σ2, b = KTol ,
and σ3 represent active sites for an empty surface, toluene,
c = KBalc ,
benzaldehyde, and benzyl alcohol, respectively. A similar
assumption was used by Antonello and Barresi [45] for deep d = KBald ,
catalytic oxidation of aromatic hydrocarbon mixtures and
validated as proper. For competitive adsorption, surface
adsorption and reactant reactions are assumed to occur at where POxy is the oxygen partial pressure; ri is the oxidation
the same active sites. The steady-state approximation for rate of the ith hydrocarbon; KOxy is the adsorption balance
the two different types of adsorption is in conjunction with constant for oxygen; Ki is the adsorption balance constant
the overall active sites, which fluctuate between being par- for the ith hydrocarbon; kc,Oxy is Henry’s constant for oxy-
tially reduced and re-oxidized. It is also stated that different gen; kβI
i is the overall rate constant of oxidation of the ith
reduced catalysts can be oxidized to the same fresh active hydrocarbon; and j is the dissociation adsorption exponent
sites. Thereby, Eqs. (16)–(19) are given [see detailed reac- of oxygen (1 for non-dissociative adsorption, 2 for dissocia-
tion steps in Supplementary Information]. tive adsorption).

13
 W. Li et al.

For L–H competitive mechanism: the re-oxidation rate constants of different active sites; kγI
i
� is the overall oxidation rate constant of the ith hydrocar-
� �
� c P �1∕j S bon; v is the stoichiometric coefficient of reduced catalyst
� i Oxy Cata
re-oxidation.
ri
� � For M–K competitive mechanism:
1 b 1∕j c d e ( )v
= √ + √ POxy + √ cTol + √ cBalc + √ cBald , ci POxy SCata ( b c d
)
a a a a a = cTol + cBalc + cBald ,
√ � ri a a a
II � �1∕j (22) γII ( )v
a = ki𝛽 Ki KOxy ∕kc,Oxy , a = ki Ki KOxy ∕kc,Oxy ,
� �1∕j ( II ( )v ( II ))
γ γII
b = KOxy ∕kc,Oxy , b = bTol koγ POxy ∕kc,Oxy + 0.5 k1 + 2k3 ,
c = KTol , ( II ( ) )
v γII
c = bBalc koγ POxy ∕kc,Oxy + 0.5k5 ,
d = KBalc , ( II ( )v )
γII
e = KBald . d = bBald koγ POxy ∕kc,Oxy + 0.5k7 .
For M–K non-competitive mechanism: (24)
( )v
ci POxy SCata ( b c )
=
d e
+ cTol + cBalc + cBald , The initial conversion of toluene is much reduced at a low
ri a a a a reaction temperature (413 K) with 2.0 g of catalyst, thus the
γI ( )v
concentrations of alcohol and aldehyde are considered trace
a = ki Ki KOxy ∕kc,Oxy ,
γI ( )v amounts. Therefore, the terms cBalc and cBald could be omit-
b = ko1 POxy ∕kc,Oxy , ted in Eqs. (21)–(24). The left side of these equations should
( I ) (23)
γ γI
c = 0.5 k1 + 2k3 , then be linear with toluene concentration. However, only the
( I/ I) I L–H competitive mechanism lacking the oxygen dissociation
γ γ
d = 0.5 ko1 ko2 k5 ,
γ
step seems to be rational. The others are not applicable as
( I/ I) I the intercepts of the fitting lines of the models are negative,
γ γ γ
e = 0.5 ko1 ko3 k7 , as shown in Table 6. Details of the L–H competitive non-
dissociative mechanism are depicted in Scheme 2, which was
illuminated by Savara et al. [46]. Undetermined parameters in
where k1γI and kγI the L–H model are calculated by applying the nonlinear least-
3 are the oxidation rate constants for tolu-
ene; k5γI and kγI squares method. In addition, the thermodynamic changes in
7 are the oxidation rate constants for benzyl
alcohol and benzaldehyde, respectively; kγI γI γI adsorption–desorption and the kinetic activation energies of
o1, ko2 and ko3 are

Table 6  Applicability evaluation of four types of L–H and M–K models

T (K) POxy (MPa) cTol (mol L−1) rTol (mol L−1 h−1) cTol (POxy)j or vSCata/rTol = acTol + b (L–H [cTol (POxy)jSCata/rTol]0.5 = acTol + b (L–H
non-competitive mechanism, M–K non- competitive mechanism)
competitive or competitive mechanism)

413 1.2 0.695 0.155 Non-dissociative Dissociative Non-dissociative Dissociative

413 1.0 0.730 0.125
413 0.8 0.763 0.097 y  = 3.0479x–0.9978 y  = 15.479x–8.7183 y  = 1.313x + 0.1457 y  = 4.2958x
413 0.6 0.817 0.069 –1.5302
418 1.2 0.745 0.149 R2 = 0.9993 R2 = 0.9786 R2 = 0.9938 R2 = 0.9618
418 1.0 0.780 0.119
418 0.8 0.793 0.094 Abandoned Abandoned Accepted Abandoned
418 0.6 0.842 0.067

13
Kinetics and Mechanism Modeling of Liquid-Phase Toluene Oxidation to Benzaldehyde Catalyzed…

Active site
Mn-Mo O O
O2 CH2 O OH
k1
CH 3
CH 2 k3 Mn-Mo
Mn-Mo k4
H
k2
Mn-Mo
k6 Active site
k7 k5
CH 2 CH 2 CH 2 +
CH2 OH Mn-Mo
OH OH
OH O
Mn-Mo
Mn-Mo k13
Mn-Mo

k8 CH OH CH OH
CH OH
Active site O OH
OH O O H
+ H2 O + CHO +
Mn-Mo k16 Mn-Mo Mn-Mo
k15 Mn-Mo k14
k9

C=O
C=O C=O

O O OH
H k10 k11 k12 C=O +
+ Mn-Mo
Mn-Mo Mn-Mo Mn-Mo
OH

Scheme 2  LH-OS-ND mechanism for liquid-phase oxidation of toluene

the surface reactions are given in Eqs. (25)–(26). The dis- The K value of toluene is generally the highest, illustrat-
tribution of the residual is uniform, and the residual sum of ing that this weakly polar hydrocarbon has an advantage
squares for the oxidation rate of toluene is below 1.50 × 10−3 when being adsorbed onto the surface of a catalyst com-
in the range of 413–443 K, as shown in Fig. S2. All evalua- pared with the strongly polar components (benzyl alcohol,
tions of the proposed L–H mechanism are listed in Table 7. benzaldehyde, and benzoic acid). This seems to show that
( ) the surface polarity of Mn–Mo oxides, like most minerals,
Ea,i
ki = Ai exp − , (25) is prone to nonpolarity [47]. It is stated that oxygen and ben-
RT
zaldehyde have weak adsorption (ΔHads,Oxy ≈ − 15 kJ mol−1,
( ) ΔH ads,Bald  ≈ − 30  kJ  mol −1 ), but strongly mobile
ΔSads,i ΔHads,i
Ki = exp − , (26) adsorption species (ΔS ads,Oxy  ≈ − 22  J  mol −1   K −1 ,
R RT ΔSads,Bald ≈ − 39 J mol−1 K−1). This indicates that the oxida-
tion of toluene takes place via the adsorbed oxygen species,
where Ai and Ea,i are the pre-exponential factor and acti-
but the deep oxidation of benzaldehyde is considered as it
vation energy of surface reaction, respectively; ΔSads,i and
can easily escape from the surface of the catalyst [44]. On
ΔHads,i are the entropy and enthalpy of adsorption of the ith
the other hand, the calculated energy barrier of the intrinsic
hydrocarbon, respectively.
oxidation of toluene is slightly higher at 3.7 kJ mol−1 than

Table 7  Thermodynamic and kinetic parameters in LH-OS-ND models

T (K) KOxy KTol KBalc KBald kTol ­(h−1) kBalc ­(h−1) kBald ­(h−1) RRS

413 6.768 70.021 60.004 54.010 0.130 0.299 0.315 7.41 × 10−4

423 5.895 48.756 47.700 45.100 0.222 0.441 0.537 9.56 × 10−4
433 5.561 35.321 35.750 36.355 0.382 0.648 0.888 1.12 × 10−3
443 4.920 23.426 29.980 30.231 0.589 0.922 1.286 1.33 × 10−3
ΔSads,i (J mol−1 K−1) − 21.557 − 97.290 − 53.295 − 38.767 Ea (kJ mol−1)
ΔHads,i (kJ mol−1) − 15.439 − 54.818 − 36.073 − 29.738 77.367 57.243 71.861

13
 W. Li et al.

that of the macroscopic observation. It is possible that the catalyst affected the kinetics of toluene oxidation. Doping
resistance of the surface adsorption increases the difficultly with molybdenum at Mn/Mo = 3/1 resulted in enhanced cat-
of oxidation. Equations (27)–(30), deduced from the LH- alytic performance because of the synergetic effect in binary
OS-ND mechanism, are the final rate equations for the het- metal oxides. Four types of mechanisms are proposed and
erogeneous liquid-phase oxidation of toluene. discussed, but only the LH-OS-ND mechanism is verified as
( )
−7110
4.94 × e 102
cTol POxy SCata RT

−rTol = ( (
−21.557 15.439
) (
−97.290 54818
) (
−53.295 36073
) (
−38.767 29738
) )2 , (27)
+ + + +
1+e R RT cOxy + e R RT cTol + e R RT cBalc + e R RT cBald

(( (
−7110
)/ ( ( ) )) (
−5731
) )
2.706− 11859
4.94 × 102 e RT 1+e RT cTol − 6.22 × 102 e RT cBalc POxy SCata
rBalc = ( ( ) ( ) ( ) ( ) )2 , (28)
−21.557 15.439 −97.290 54818 −53.295 36073 −38.767 29738
+ RT + RT + RT + RT
1+e R cOxy + e R cTol + e R cBalc + e R cBald

(( (
−7110
)/ ( ( ) )) (
−5731
) (
−26684
) )
2.706− 11859
4.94 × 102 e RT 1+e RT cTol + 6.22 × 102 e RT cBalc − 2.79 × 105 e RT cBald POxy SCata
rBald = ( ( ) ( ) ( ) ( ) )2 ,
−21.557 15.439 −97.290 54818 −53.295 36073 −38.767 29738
+ RT + RT + RT + RT
1+e R cOxy + e R cTol + e R cBalc + e R cBald
(29)
( )
−26684
2.79 × 105 ecBald POxy σCata RT

rBac = ( (
−21.557 15.439
) (
−97.290 54818
) (
−53.295 36073
) (
−38.767 29738
) )2 . (30)
+ + + +
1+e R RT cOxy + e R RT cTol + e R RT cBalc + e R RT cBald

Conclusions applicable to the heterogeneous oxidation of toluene. Oxy-

An improved reaction network, which demonstrates that
the transformation of benzyl alcohol is indispensable to the
generation of benzaldehyde in the heterogeneous liquid-
phase oxidation of toluene, is proposed in this paper. In
the macroscopic experiments, the consumption of toluene
was found to be first order to the concentration of toluene,
oxygen partial pressure, and surface area of the catalyst.
Benzaldehyde generation was verified and obeyed a first-
order parallel-consecutive mode; it comprised not only the
direct oxidation of toluene, but also the transformation of
benzyl alcohol. Reaction temperature and residence time
significantly influenced the contribution of benzyl alcohol
to the benzaldehyde yield. Enhanced temperature and pro-
longed residence time prompted the transformation path-
way. A comparison of activation energies showed that the
step where benzaldehyde oxidizes into benzoic acid was of
the same level of difficulty as that of toluene oxidation to
benzaldehyde, while the benzyl alcohol transformation to
benzaldehyde was easier. In addition, the Mn/Mo ratio of the
gen species are added pairwise in the form of molecules onto
the surface of the catalyst and exhibit weak adsorption but
strong mobility. Moreover, benzaldehyde easily moves away
from the nonpolar surface of the catalyst due to its weak
adsorption, avoiding further oxidation to benzoic acid. As
a result, considerable benzaldehyde yields can be obtained
from the heterogeneous catalyzed oxidation of toluene using
the Mn–Mo oxide.
Acknowledgements  This study was supported by the National Natural
Science Foundation of China (No. 21376163).
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