Applied Catalysis A: General 340 (2008) 271277

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

CoBr2-MnBr2 containing catalysts for catalytic oxidation of p-xylene to

terephthalic acid
Kuo-Tseng Li *, Shih-Wei Li
Department of Chemical Engineering, Tunghai University, Taichung, Taiwan, ROC

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 20 October 2007
Received in revised form 14 February 2008
Accepted 18 February 2008
Available online 10 March 2008

Catalytic oxidation of p-xylene (PX) to terephthalic acid (TA) was studied with catalysts containing cobalt
acetate, manganese acetate, CoBr2 and MnBr2. The catalysts contain neither highly corrosive hydrogen
bromide nor other metal ions, and have the advantage of easy catalyst recovery. The effects of Br/Co
atomic ratio, reaction time and temperature, PX concentration, oxygen pressure, and catalyst
concentration on PX conversion and product/intermediate yields were investigated. The catalyst system
had a suitable reaction temperature of 100 8C, which was much lower than the commercial process
temperature (175225 8C). The maximum product (TA) yield was 93.5%, obtained at a Br/Co atomic ratio
of three. Higher Br concentration resulted in the lower TA yield, which was ascribed to the benzylic
bromide formation. The synthesis of TA could be adequately described as four reaction steps in series
(PX ! p-tolualdehyde ! p-toluic acid ! 4-carboxybenzaldehyde ! TA), with a pseudo-rst-order rate
equation for each step, and the third step was rate-limiting. The rate constant ratios (kj/k3, j = 1 ! 4)
obtained at 100 8C were similar to the kj/k3 values reported earlier for cobalt acetate/manganese acetate/
HBr catalysts in a range of 185191 8C.
2008 Elsevier B.V. All rights reserved.

Keywords:
Oxidation catalysts
Cobalt bromide
Manganese bromide
p-Xylene
Terephthalic acid

1. Introduction
Transition metal-catalyzed autoxidation of p-xylene (PX) to
terephthalic acid (TA) is one of the largest industrial-scale
applications of homogeneous catalysis [1]. Puried terephthalic
acid (PTA) is the ninth largest industrial chemical [2], which is used
as raw material for the production of saturated polyestermainly
polyethylene terephthalate (abbreviated as PET) [3].
Most of PTA used worldwide is manufactured by the Amoco
Mid-Century (MC) method, which uses a catalyst consisting of
cobalt acetate Co(OAc)2, manganese acetate Mn(OAc)2 and
hydrobromic acid (HBr) [2,4,5]. The Amoco process is operated
at high temperature (175225 8C) and pressure (1530 atm) of air
in an acetic acid medium [6]. Solutions of HBr are highly corrosive,
are very dangerous to handle and are highly harmful to the
environment. It is highly desired to eliminate HBr in the TA
production process. CoBr2 and MnBr2 have lower corrosion
characteristics than HBr [7]. However, no scientic literature
has reported the catalytic performances of CoBr2-MnBr2 contain-

* Corresponding author. Tel.: +886 4 23590262; fax: +886 4 23590009.

E-mail address: ktli@thu.edu.tw (K.-T. Li).
0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.02.025

ing catalysts for PX oxidation to TA. Kamiya et al. [8] briey

compared the performances of CoBr2 alone (without the addition
of MnBr2) and NaBr-cobalt decanoate for p-xylene oxidation in a
glass reactor (operated at low reaction pressure), and found that
CoBr2 alone showed a very pronounced induction period at high
catalyst concentration. The data presented by Kamiya et al. were
mainly obtained with NaBr-cobalt decanoate system.
This paper deals with the use of CoBr2 and MnBr2 as the
bromine sources for p-xylene oxidation to terephthalic acid. As
mentioned above [7], CoBr2-MnBr2 containing catalyst is less
corrosive than HBr-containing catalyst. In addition, the catalyst
system studied here is easier to be recovered than Co/Mn/Br
catalysts containing NaBr [8,9] or other metal compounds [4]
because the former contains no other metal ions.
We found that CoBr2-MnBr2 containing catalyst was capable of
catalyzing p-xylene oxidation effectively at 100 8C, which was
much lower than the reaction temperature used in the commercial
process. The milder oxidation temperature has the following
advantageous points: the lower combustion rates of reactant (PX)
and solvent (which produce unwanted CO and CO2) [10], the lower
equipment corrosion rate, the lower energy cost, and the lower
catalyst deactivation rate (due to the lower terephthalic acid
solubility in acetic acid [3,9]).

K.-T. Li, S.-W. Li / Applied Catalysis A: General 340 (2008) 271277

272

2. Experimental
The oxidation experiments were carried out with a 300 ml
stirred reactor made of titanium (supplied by Parr Instruments
Co.). The high-pressure autoclave was equipped with a temperature control unit, a pressure gage, a gas inlet valve, a gas sparger, an
agitator, a liquid sampling valve, and a gas release valve.
In a typical run, a specic amount of p-xylene (TEDIA, Faireld,
OH, USA), a specic amount of catalyst containing CoBr2, MnBr2,
cobalt acetate (Co(OAc)2) and manganese acetate (Mn(OAc)2) (all
from Aldrich, St. Louis, MO, USA), and 60 ml of glacial acetic acid
(HOAc) (Scharlau Chemie, Barcelona, Spain) were mixed together
and charged into the reactor. After reaching the desired
temperature, pure oxygen was introduced into the reactor at a
desired pressure (2 atm or 10 atm) and the agitator speed was set
at 300 rpm. At the end of the reaction, solid and liquid products
were separated. The recovered solid product was dried and
weighed. Dimethyl sulfoxide was used to dissolve the components
in solid and liquid products and the component compositions were
determined with a Shimadzu (Kyoto, Japan) high performance
liquid chromatography (model: LC-10A) equipped with a 250 mm
long C-18 column and a UV detector (wavelength was set at
254 nm). The p-xylene conversion was dened as (moles of pxylene reacted)/(moles of p-xylene fed to the reactor)  100%. The
yields of product (terephthalic acid) and intermediates ( ptolualdehyde, p-toluic acid (PT), 4-carboxybenzaldehyde, terephthaldicarboxaldehyde) were dened as (moles of the product
or intermediate produced)/(moles of p-xylene fed to the
reactor)  100%. The selectivity of product and intermediate were
dened as (moles of the product or intermediate produced)/(moles
of p-xylene reacted)  100%.
3. Results and discussion
The oxidation of p-xylene was carried out at seven Br/Co atomic
ratios (catalyst compositions are listed in #1 ! #7 of Table 1), two
catalyst concentrations (#4 and #8 of Table 1), three reaction
temperatures (100 8C, 110 8C, 120 8C), three PX concentrations (PX/
solvent weight ratio = 0.08, 0.16, and 0.32), and two oxygen
pressures (2 atm and 10 atm). The effects of these variables on PX
conversion and product/intermediate yields were investigated. In
addition, rate equations were obtained from the concentration
proles of reactant, intermediates and product.
3.1. Effect of Br/Co atomic ratio
CoBr2/Co(OAc)2/MnBr2/Mn(OAc)2 catalysts with seven Br/Co
atomic ratios (ratio = 1, 1.5, 2, 3, 4, 5, 6) were used for the oxidation
of p-xylene at 100 8C. The amounts of CoBr2/Co(OAc)2/MnBr2/
Mn(OAc)2 added for varying Br/Co atomic ratio are shown in
#1 ! #7 of Table 1. Fig. 1 shows TA yield as a function of Br/Co
atomic ratio under the following condition: PX/HOAc weight
ratio = 0.08, reaction time = 1 h, Mn/Co atomic ratio = 2, and
oxygen pressure = 10 atm. When Br/Co atomic ratio is less than

Fig. 1. Variation of TA yield as a function of Br/Co atomic ratio (PX/HOAc weight

ratio = 0.08, reaction time = 1 h, oxygen pressure = 10 atm, Mn/Co atomic ratio = 2,
reaction temperature = 100 8C).

3, TA yield increases rapidly with the increase of Br/Co atomic

ratio, which should be due to the increase of catalyst activity with
increasing Br/Co atomic ratio. For p-xylene oxidation with NaBr/
cobalt decanoate catalyst in a glass reactor, Kamiya et al. [8] found
that the oxidation rate (expressed in terms of measured oxygen
consumption rate) increased with increasing sodium bromide/
cobalt ratio, and reached a limiting value at a sodium bromide/
cobalt ratio of eight.
Fig. 1 also shows that TA yield levels off when Br/Co atomic ratio
is in the range of 34, which suggests that the oxidation rate
reaches a limiting value and Br concentration does not signicantly
affect TA yield in this situation. TA yield reaches a maximum value
of 92.6% at a Br/Co atomic ratio of 4, and decreases slightly at the
higher Br/Co atomic ratio (TA yields are 90.8% and 89.7% when Br/
Co atomic ratios are 5 and 6, respectively). That is, a large excess of
Br concentration is detrimental to TA yield. It was proposed that
excess dibromide radicals might be formed during the chain
reaction, which reacted with ArCH2 to produce undesired benzylic
bromide (ArCH2Br) [4,11]. Therefore, a high bromide concentration
might result in the formation of an excess of benzylic bromide,
which decreases TA yield when Br/Co atomic ratio is greater than 4,
as shown in Fig. 1.
Fig. 2 shows TA yield as a function of reaction time for Br/Co
atomic ratios = 3, 4, and 6 (catalyst compositions are listed in #4,
#5, and #7 of Table 1). The amount of PX (PX/HOAc weight
ratio = 0.16) used for Fig. 2 is two times that used for Fig. 1 (PX/
HOAc weight ratio = 0.08). Fig. 2 indicates that TA yield increases
with increasing Br concentration at the earlier stage of reaction (at
1 h reaction time, TA yields are 17.7%, 24.1% and 26.1% when Br/Co
atomic ratios are 3, 4, and 6, respectively), but TA yield decreases
with increasing Br at the latter stage of reaction (at 3 h reaction
time, TA yields are 93.5%, 92.7% and 91.1% when Br/Co atomic
ratios are 3, 4, and 6, respectively).

Table 1
Catalyst compositions used for studying the effects of Br/Co atomic ratio and catalyst concentration
#

Br/Co ratio

CoBr2 (mmol)

1
2
3
4
5
6
7
8

1
1.5
2
3
4
5
6
3

0.075
0.1125
0.075
0.075
0.075
0.15
0.225

MnBr2 (mmol)

0.075
0.15
0.3
0.3
0.3
0.45

Co(OAc)2 (mmol)

Mn(OAc)2 (mmol)

0.075
0.038
0.075
0.075
0.15
0.075

0.3
0.3
0.225
0.15

0.225

0.45

K.-T. Li, S.-W. Li / Applied Catalysis A: General 340 (2008) 271277

273

Fig. 2. TA yield as a function of reaction time for catalysts with Br/Co atomic
ratios = 3, 4, and 6 (PX/HOAc weight ratio = 0.16, oxygen pressure = 10 atm, Mn/Co
atomic ratio = 2, reaction temperature = 100 8C).

Fig. 3. TA yield as a function of reaction time for catalysts with Br/Co atomic
ratios = 3 and 6 (PX/HOAc weight ratio = 0.32, oxygen pressure = 10 atm, Mn/Co
atomic ratio = 2, reaction temperature = 100 8C).

Fig. 3 shows TA yield as a function of reaction time for Br/Co

atomic ratio = 3 and 6 (catalyst compositions are listed in #4 and
#7 of Table 1) for PX/HOAc weight ratio = 0.32. The amount of PX
used for Fig. 3 is four times that used for Fig. 1 (PX/HOAc weight
ratio = 0.08) and is two times that used for Fig. 2 (PX/HOAc weight
ratio = 0.16). In Fig. 3, the catalyst with Br/Co atomic ratio = 6 has
higher TA yield at the earlier stage of reaction (when t 2 6 h), but
the catalyst with Br/Co atomic ratio = 3 has higher TA yield at the
latter stage of reaction (when t 3 9 h). That is, the effect of Br/Co
atomic ratio on TA yield shown in Fig. 3 is similar to that shown in
Fig. 2.
All of Figs. 13 indicate that high Br concentration is detrimental
to the nal TA yield. As mentioned above, high bromide concentration might result in the formation of larger amount of benzylic
bromide [4,11], and lower the nal TA yield at the higher Br/Co
atomic ratio. At the earlier stage of reaction, higher TA yield observed
for the catalysts with the higher Br concentration (shown in Figs. 2
and 3), which should be due to the increase of catalyst activity with
increasing Br concentration.
Comparisons of Figs. 13 indicate that reaction time needed to
reach the same TA yield increases more rapidly than the increase of
reactant concentration (i.e., PX/HOAc ratio) when catalyst amount

is maintained constant. It takes approximately 1 h, 3 h, and over

12 h to reach 90% TA yield for PX/HOAc weight ratio of 0.08 (shown
in Fig. 1), 0.16 (shown in Fig. 2), and 0.32 (shown in Fig. 3),
respectively. That is, the higher the PX concentration the lower the
TA turnover frequency (TOF = TA molecules produces/(Co molecules reaction time)). At Br/Co atomic ratio = 3 (catalyst compositions is listed in #4 of Table 1), turnover frequencies are 512 h1,
363 h1, and 167 h1 when PX/HOAc weight ratios are 0.08, 0.16,
and 0.32, respectively.
For the synthesis of terephthalic acid from p-xylene, it was
proposed that the oxidation reactions occurred according to the
stoichiometry shown in Fig. 4 [4]. p-Tolualdehyde (TALD), p-toluic
acid, 4-carboxybenzaldehyde (4-CBA), and terephthaldicarboxaldehyde (TDAD) are the intermediate species formed during the
oxidation of p-xylene. Water is one of the products of p-xylene
oxidation, therefore, its concentration varied with PX/HOAC
weight ratio and reactant time. For PX/HOAc weight ratio = 0.32,
the nal water content was around 7.5 wt%.
Fig. 5 presents species (including PX, TALD, PT, 4-CBA, TA and
TDAD) dimensionless concentrations (normalized with the initial
concentration of PX) as a function of reaction time under the
following conditions: catalyst composition is listed in #4 of

Fig. 4. Reaction scheme for TA synthesis from PX oxidation.

274

K.-T. Li, S.-W. Li / Applied Catalysis A: General 340 (2008) 271277

Fig. 5. Species dimensionless concentrations (normalized with PX initial

concentration) vs. reaction time for catalyst with Br/Co atomic ratio = 3.
Reaction conditions: PX/HOAc weight ratio = 0.32, oxygen pressure = 10 atm,
reaction temperature = 100 8C, catalyst composition is listed in #4 of Table 1.

Table 1, T = 100 8C, P O2 10 atm, PX/HOAc weight ratio = 0.32.

Fig. 5 indicates that PT and 4-CBA are the major intermediates,
TALD and TDAD are the minor intermediates. Similar results were
obtained for the catalysts with Br/Co atomic ratio = 4 and 6
(catalyst compositions are listed in the entries #5 and #7 of
Table 1).
In Fig. 5, PT concentration (with a maximum CPT/Cxylene,0 = 0.72
at t = 3 h) is much larger than TDAD concentration (CTDAD/
Cxylene,0 < 0.03), which suggests that most of TA is formed via
the route PX ! TALD ! PT ! 4-CBA ! TA. PT concentration is also
much larger than TALD concentration (CTALD/Cxylene,0  0.05),
which indicates that the second step reaction (TALD ! PT) is
much faster than the third step reaction (PT ! 4-CBA). At t 3 9 h,
PT concentration is greater than 4-CBA concentration (C4-CBA/
Cxylene,0 < 0.12), which indicates that the forth step reaction (4CBA ! TA) is faster than the third step reaction (PT ! 4-CBA).
Therefore, the rate-limiting step (i.e., the slowest step) for TA
synthesis should be the step for the oxidation of p-toluic acid to 4carboxybenzaldehyde (PT ! 4-CBA).

Fig. 6. Species dimensionless concentrations vs. reaction time for catalyst with Br/
Co atomic ratio = 3 and three times catalyst concentration. Reaction conditions:PX/
HOAc weight ratio = 0.32, oxygen pressure = 10 atm, reaction temperature = 100 8C,
catalyst composition is listed in #8 of Table 1.

yield obtained at 10 atm is 91.2% (at t = 9 h, shown in Fig. 6), but the
maximum TA yield obtained at 2 atm is only 14.4% (at t = 12 h,
shown in Fig. 7). At 2 atm (Fig. 7), PX concentration is still
signicant (conversion = 85%) at t = 9 h, therefore, the PX concentration prole can be used to determine the kinetics of the rst
step reaction (PX ! TALD). At 10 atm (Fig. 6), PX disappears
completely at t = 1.5 h.
In Figs. 57, the sum of the nal product (TA) and intermediate
(TALD, PT, 4-CBA, and TDAD) concentrations is approximately
equal to the initial reactant (PX) concentration. The mole balance
on aromatic compounds indicates that the combustion of aromatic
species to COx (CO and CO2) was negligible under the experimental
conditions.
3.4. Effect of temperature
Table 2 shows the effect of reaction temperature on PX
conversion and product/intermediate yield in the range of 100
120 8C. It is surprising to nd that PX conversion decreases with
increasing reaction temperature in the temperature range. Therefore, the suitable reaction temperature for the CoBr2/cobalt
acetate/MnBr2/manganese acetate catalyst system is 100 8C.

3.2. Effect of catalyst concentration

In Fig. 5, the nal TA yield is only 86% at t = 12 h, which indicates
that catalyst amount used (listed in #4 of Table 1) was not enough
to catalyze the amount of reactant used (PX/HOAc weight
ratio = 0.32). Therefore, catalyst amount was increased three
times (catalyst composition is listed in #8 of Table 1, which is
three times that listed in #4 of Table 1) and the oxidation results
are shown in Fig. 6. TA yield reaches 86.52% at 3 h, which is about
the same as the TA yield (= 86.03%) obtained at 12 h in Fig. 5.
Therefore, the increase of catalyst concentration results in a
dramatic decrease of the reaction time. In Fig. 6, the nal (at t = 9 h)
TA yield is 91.2%.
3.3. Effect of pressure
In order to study the kinetics of p-xylene oxidation, oxygen
pressure was reduced to 2 atm (other reaction conditions were the
same as those used for Fig. 6) and the results are presented in Fig. 7.
Comparisons of Figs. 6 and 7 indicate that oxygen pressure has a
dramatic effect on TA yield and PX conversion. The maximum TA

Fig. 7. Species dimensionless concentrations vs. reaction time for oxygen

pressure = 2 atm. Reaction conditions: PX/HOAC weight ratio = 0.32, reaction
temperature = 100 8C, catalyst composition is listed in #8 of Table 1.

K.-T. Li, S.-W. Li / Applied Catalysis A: General 340 (2008) 271277

Table 2
Effect of reaction temperature on PX conversion and TA/intermediate yields

Table 3
Rate constants at P O2 2 atm and Br/Co atomic ratio = 3

Temperature

PX conversion (%)
TA yield (%)
TALD yield (%)
PT yield (%)
4-CBA yield (%)
TDAD yield (%)

100 8C

110 8C

120 8C

94.2
11.2
5.0
71.6
5.7
0.7

87.6
18.1
2.3
57.9
8.8
0.5

62.9
0.5
15.9
44.1
1.8
0.6

Reaction conditions: PX/HOAC weight ratio = 0.32, oxygen pressure = 10 atm,

catalyst composition: listed in #4 of Table 1, reaction time = 3 h.

It is known that the conversion of bromide to benzylic bromide

decreases Co/Mn/Br catalyst activity and PX oxidation rate [12,13].
When all of the active ionic bromide is converted to benzylic
bromide, the resultant Co/Mn catalyst is much less active, and
imparts a deep coloration (brown color) to the system [13].
Therefore, the formation of benzylic bromide can be detected from
the color of the solution after the oxidation reaction.
At 100 8C, the reaction solution color was golden yellow, which
indicated that the formation of benzylic bromide was negligible at
low temperature. At 110 8C and 120 8C, the solution color was
brown, which indicated that the formation of benzyl bromide was
signicant. This resulted in the lower active ionic bromide
concentration and the lower PX conversion at the higher reaction
temperatures (110 8C and 120 8C), as shown in Table 2.
3.5. Kinetics
Figs. 57 indicate that TDAD formation is negligible, therefore,
PX oxidation to TA should mainly occur according to the following
four reaction steps in series:
k1

k2

k3

k4

A!B!C!D!E

(1)

The nomenclature in Eq. (1) is used to denote the various species in

PX oxidation: A = PX, B = TALD, C = PT, D = 4-CBA, and E = TA. To
determine the reaction rate parameters from the measured species
concentration proles (e.g., Figs. 57), the following differential
equations were established to describe the reaction system in a
batch reactor by assuming a pseudo-rst-order equation for each
step of PX oxidation:
dC A
k1 C A
dt

(2)

dC B
k1 C A  k2 C B
dt

(3)

dC C
k2 C B  k3 C C
dt

(4)

dC D
k3 C C  k4 C D
dt

(5)

CA
ek1 t
C A0

(6)

CB
k1

ek1 t  ek2 t
C A0 k2  k1

(7)

k1 k2 e
k3  k2 k3  k1

Catalyst composition
is listed in #4 of Table 1

Catalyst composition
is listed in #8 of Table 1

k1
k2
k3
k4

0.0466 (= 3.11k3)
0.26 (= 17.33k3)
0.015
0.15 (= 10k3)

0.1794 (= 3.98k3)
0.5 (= 11.1k3)
0.045
0.46 (= 10.22k3)

CD
k1 k2 k3 ek1 t  ek4 t
k1 k2 k3 ek2 t  ek4 t


C A0 k3  k1 k2  k1 k4  k1 k3  k2 k2  k1 k4  k2

k1 k2 k3 ek3 t  ek4 t
k3  k2 k3  k1 k4  k3

(8)

(9)

The product (TA) concentration was determined from the

following material balance equation:
C E C A0  C A  C B  C C  C D

(10)

Suitable rate constants (k1 ! k4) were substituted into Eqs. (6)(9)
for calculating the dimensionless species concentrations (Cj/CA0,
j = A, B, C, D, E) as a function of reaction time (t), and the calculated
values were compared with the experimental data. Comparisons of
the calculated values and the experimental data are shown in
Fig. 8(A)(D). Fig. 8(A) and (B) are the comparisons for P O2 2 atm
with two different catalyst concentrations (#4 and #8 in Table 1,
respectively), Fig. 8(C) and (D) are the comparisons for P O2
10 atm with two different catalyst concentrations (#4 and #8 in
Table 1, respectively). Fig. 8(A)(D) indicates that pseudo-rstorder kinetics is able to t the experimental data satisfactorily. The
reaction rate constants (k1 ! k4) used to t the experimental data
are listed in Table 3 (for P O2 2 atm) and in Table 4 (for
PO2 10 atm), which mostly indicate that k2 > k4 > k1 > k3 (except
for P O2 10 atm, k1  k4). That is, the third-step reaction (PT ! 4CBA) is the slowest and controls the overall rate of PX oxidation to
TA. In Tables 3 and 4, the values of k1, k3, k4 increase approximately
linear with increasing catalyst amount, which suggests that steps
1, 3, and 4 were operated under chemical control condition. The
increase of k2 is less than the increase of catalyst amount (k2 is
approximately doubled when catalyst amount is tripled), which
indicates that the second step (the fastest step) might be affected
by mass transfer.
In Fig. 8(A)(D), rate constants (k1 ! k4) do not vary with the
reaction time, which indicates that catalyst deactivation was not
signicant under the experimental conditions.
For Co(OAc)2/Mn(OAc)2/HBr catalyzed PX oxidation in HOAc
and in the temperature range of 184197 8C, Wang et al. [15]
proposed the following kinetic model for the reaction scheme
shown in Eq. (1):
r j k j P4

Cj

(11)

bj

di C i u

where rj and kj are the rate and the rate constant of jth step reaction,
respectively, Cj is the concentration of the jth component, d, u and b
are kinetic parameters. They also found that k2 > k4 > k1 > k3, and
Table 4
Rate constants at P O2 10 atm and Br/Co atomic ratio = 3
Rate constants (h1)

Catalyst composition
is listed in #4 of Table 1

Catalyst composition
is listed in #8 of Table 1

k1
k2
k3
k4

0.699 (= 3.58k3)
3.9 (= 20k3)
0.195
0.75 (= 3.85k3)

2.69 (= 4.6k3)
7.5 (= 12.82k3)
0.585
2.3(= 3.93k3)

k2 t

CC
k1 k2 e
k1 k2 e


C A0 k3  k1 k2  k1 k3  k2 k2  k1
k3 t

Rate constants (h1)

i1

Integrations of Eqs. (2)(5) with the initial conditions (at t = 0,

CA = CA0, CB = CC = CD = 0) yield [14]

k1 t

275

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K.-T. Li, S.-W. Li / Applied Catalysis A: General 340 (2008) 271277
Fig. 8. (a) Test of pseudo-rst-order kinetic model for PX oxidation to TA. Reaction conditions: oxygen pressure = 2 atm, PX/HOAc weight ratio = 0.32, reaction temperature = 100 8C, catalyst composition is listed in #4 of Table 1. The
right coordinate is for PX concentration, the left coordinate is for other species concentrations. (b) Test of pseudo-rst-order kinetic model for PX oxidation to TA (reaction conditions are the same as those used for Fig. 7). (c) Test of
pseudo-rst-order kinetic model for PX oxidation to TA (reaction conditions are the same as those used for Fig. 5). (d) Test of pseudo-rst-order kinetic model for PX oxidation to TA (reaction conditions are the same as those used for
Fig. 6).

K.-T. Li, S.-W. Li / Applied Catalysis A: General 340 (2008) 271277

the rate constant ratios they obtained were in the following ranges:
k1/k3 = 3.8 ! 5.43; k2/k3 = 14 ! 21.9; k4/k3 = 9.1 ! 10.12. The rate
constants obtained by Wang et al. are unexpectedly similar to the
rate constant ratios we obtained here (k1/k3 = 3.11 ! 4.6; k2/
k3 = 11.1 ! 20; k4/k3 = 10 ! 10.22 (at P O2 2 atm); as shown in
Tables 3 and 4). The similarity of rate constant ratios suggests that
the reaction mechanism of PX oxidation with CoBr2/cobalt acetate/
MnBr2/manganese acetate catalyst system might be similar to the
reaction mechanism of PX oxidation with Co(OAc)2/Mn(OAc)2/HBr
catalyst system. In addition, the active species of the two catalyst
systems might be similar to each other. It has been proposed that the
Co(OAc)2/Mn(OAc)2/HBr catalyst is not just a single catalyst, but is
composed of a large number of different active catalyst species, i.e.,
different coordination compounds [16]. Partenheimer [16] suggested that at least ve different metal oxidants ([Co(III)], [Co(III)Co(II)], [Co(III)-Mn(II)], [Co(III)-CO(III)], [Co(III)-Mn(III)]), each with
varying amounts of aqua ligands, can be formed from the
homogeneous Co/Mn/Br catalyst during the p-xylene oxidation in
acetic acid.
4. Conclusions
The oxidation of p-xylene (PX) to terephthalic acid was carried
out in acetic acid (HOAc) with the presence of CoBr2-MnBr2
containing catalysts. Br/Co atomic ratio, reactant concentration,
reaction temperature, and oxygen pressure affected catalyst
performances strongly. With the increase of Br/Co atomic ratio,
catalyst activity increased but TA selectivity decreased, therefore,
the optimum Br/Co atomic ratio was around 3. Higher Br
concentration was detrimental to TA yield, which might be due
to the formation of benzylic bromide. The suitable reaction
temperature was 100 8C. Further increase in reaction temperature
resulted in the decrease of catalyst activity, which was also
ascribed to the formation of benzylic bromide. The maximum TA
yield obtained was 93.5%, which occurred at 100 8C, Br/Co atomic
ratio = 3 and PX/HOAc weight ratio = 0.16. The major route for PX

277

oxidation to TA was a four-step series reaction with three

intermediates ( p-tolualdehyde (TALD), p-toluic acid, 4-carboxybenzaldehyde (4-CBA)). The rate of each reaction step could be
represented by a pseudo-rst-order kinetics and the rate constants
decreased in the following order: k2 (TALD ! PT) > k4 (4CBA ! TA) > k1 (PX ! TALD) > k3 (PT ! 4-CBA). The rate constant
ratios of CoBr2-MnBr2 containing catalysts (at 100 8C) were
unexpectedly similar to the rate constant ratios of HBr containing
catalyst (at 184197 8C), which suggested that the two catalyst
systems had similar reaction mechanism and similar active
species.
Acknowledgement
The authors are grateful to National Science Council of ROC for
nancial support (NSC-94-2214-E029-002).

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