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The reaction mechanism and kinetics for the liquid-phase catalytic oxidation of p-xylene to terephthalic
acid are briefly reviewed, which indicates that the available literature is not complete when one looks
for the industrially applicable mechanism and kinetics. In this work, a detailed radical chain reaction mech-
anism for the liquid-phase catalytic oxidation of p-xylene to terephthalic acid is proposed. Using several
assumptions, a simple fractional-like kinetic model is derived from the assumed reaction mechanism. Several
semicontinuous oxidation experiments are carried out at different reactant feed rates and temperatures. The
experimental results show that the measured concentrations of liquid-phase reactants increase approx-
imately linearly with time, which indicates that the reaction rate for the liquid-phase reactants is approx-
imately independent from its concentration. The derived kinetic model can explain and correlate these
experimental results satisfactorily. By combining the results determined in batch oxidation experiments
with the semicontinuous experimental results, the kinetic model parameters are determined by data fitting.
The correlated results generally agree with both the semicontinuous and the batch experimental results
satisfactorily.
Introduction the following general free radical chain reactions involving the
initiation, propagation, and termination steps are commonly
As one of the most important aromatic compounds, tereph-
accepted2-34
thalic acid (TA) is widely used in organic synthesis, particularly
in the polyester industry. Worldwide production of TA has
M3+ + Br- f M2+ + Br•
increased at an annual rate of >10% for the last 5 years, and
the demands of TA have exceeded 30 million ton in the last
Br• + RCH3 f RCH2• + H+ + Br-
year.1 Commercially, the majority of TA is produced by the air
oxidation of p-xylene (PX) in acetic acid in the temperature
RCH2• + O2 f RCH2O2•
range from 150 to 210 °C, catalyzed by cobalt and manganese
salts and promoted by bromine.2-4 To gain a better insight into
RCH2O2• + M2+ f RCHO + M3+ + OH-
the reaction mechanism and identify the effects of different
parameters on the progress of the oxidation process, it is essen-
RCHO + M3+ f RCO• + M2+ + H+
tial to study the reaction kinetics. Further, the rational design,
optimization, control, and analysis of the oxidation of PX to RCHO + Br• f RCO• + Br- + H+
TA process also require the knowledge of the reaction
kinetics.2-4 RCO• + O2 f RCO3•
The liquid-phase catalytic oxidation of PX to TA be-
longs to the kind of classical free radical chain reaction. Re- RCO3• + RH f RCO3H + R•
searchers such as Kamiya,18 Hendriks,19 Jones,20-22
Hronec,23,24 Partenheimer,7,25-27 Suresh,6,28 Harustiak,29-31 RCO3H + RCHO f 2RCOOH
Wang,4,8 Cheng,10,11,13 etc. had studied the mechanism
of PX to TA for many years. In the oxidation of PX to RCO3H + M2+ f RCO2• + M3+ + OH-
TA, a mixture of cobaltic, manganic, and bromide salts are
used as catalyst species. Until now it is commonly accepted RCO2• + RH f RCOOH + R•
that, under the reaction conditions employed, Mn(III) and Co-
(III) are not powerful enough to initiate the free radical re- Ii• + Ii• f IiIj
action by electron-transfer mechanism. The combined effect of
Co and Mn ions is only to decompose hydroperoxides to yield where M denotes metal catalyst such as Co or Mn, R denotes
free radicals. The initiation mechanism is predominantly aromatic reactants, and I denotes radicals produced. Here, the
hydrogen abstraction from methyl groups by bromine atoms. initial step is thought to be the generation of Br• radical and
The Mn and Co ions oxidize the bromine ions formed to the hydrogen abstraction illustrated in the first two reactions.
bromine atoms, thus ensuring the availability of bromine atoms The propagation step consists of oxidation of the substrates by
for initiation.5 Although different in some specific chain reaction, molecular oxygen, metal ion, and Br• radical, and reduction of
radicals and hydroperoxides by metal ion. The termination step
* Address correspondence to Dr. Wang. Phone: +86-571-87952210.
consists of reactions between two radicals.
Fax: +86-571-87951227. E-mail: wang_qinbo@zju.edu.cn. The formulation of detailed kinetic models of the complex
†
This paper is partly abbreviated from the Ph.D. dissertation of process that describes all the involved radical chain reactions
Qinbo Wang. and all the intermediate products is not desirable in practice.
10.1021/ie0615584 CCC: $37.00 © 2007 American Chemical Society
Published on Web 11/13/2007
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8981
k3
Mn(III) + Br- 98 Mn(II) + Br• (4)
Br• radical is the reaction initiator, and the chain propagation
and termination reactions from PX to TA can be illustrated by
the following reactions. To simplify the treatment, some
assumptions are necessary:23 (a) there is no inclusion of RCH2O•
and •OH radicals in the propagation and termination steps; (b)
chain termination takes places by reactions of Br• radical and
other active radicals, and others radicals are not allowed to
undergo termination reactions.
Oxidation of PX to TALD. Br• radical initiates the oxidation
of PX by hydrogen abstraction from PX, which can be shown
Figure 2. Comparison of the predicted results by eq 1 and the semicon- as3,4,7,45
tinuous experimental results: scatter, semicontinuous experimental results;
k4
line, predicted results by eq 1 with with model parameters determined from
batch experimental results.
Br• + CH3-Ph-CH3 98 CH3-Ph-CH2• + H+ + Br- (5)
works, some minor modifications were made for different where Ph denotes the benzene ring. The generated CH3-Ph-
oxidation processes.2 A more simple and practical kinetic model CH2• radical has high reactivity and can be combined with
is required to be derived from the radical chain-reaction molecular oxygen quickly to generate CH3-Ph-CH2O2• radical
mechanism, and the model parameters also needed to be by the reaction
uniquely redetermined by using both the batch and semicon- k5
tinuous experimental results. This is just the aim of the present CH3-Ph-CH2• + O2 98 CH3-Ph-CH2O2• (6)
work.
As an extension of our kinetic studies on the oxidation of and then the following six parallel radical reactions may occur:
PX to TA in the aqueous acetic acid system, the present work
k6
consists of two parts. In the first part, a radical chain-reaction
CH3-Ph-CH2O2• + Co(II) + H+ 98 CH3-Ph-CHO +
mechanism will be proposed and compared with the previously
proposed oxidation mechanism in detail. On the basis of the Co(III) + H2O (7)
proposed mechanism, a simpler kinetics model than eq 1 will
k7
be derived. In the second part, semicontinuous studies on the CH3-Ph-CH2O2• + Mn(II) + H+ 98 CH3-Ph-CHO +
oxidation process will be discussed. On the basis of the presently
obtained semicontinuous experimental results and the previously Mn(III) + H2O (8)
obtained batch experimental results, the model parameters in
the proposed kinetics will be determined by data fitting. CH3-Ph-CH2O2• + Co(II) + H+ f
CH3-Ph-CH2OOH + Co(III) (9)
Reaction Mechanism and Kinetic Model
Reaction Mechanism. Elucidation of the reaction mechanism CH3-Ph-CH2O2• + Mn(II) + H+ f
helps in selecting more efficient catalysts, optimizing the CH3-Ph-CH2OOH + Mn(III) (10)
reaction intermediates, selecting reaction conditions, and design-
ing a commercial reactor. This process also generates ideas for CH3-Ph-CH2O2• + RCH3 f
further research and development.5 The oxidation of hydrocar-
bons is usually explained in terms of the classical free radical CH3-Ph-CH2OOH + RCH2• (11)
chain mechanism involving the initiation, propagation, and
termination steps.5 CH3-Ph-CH2O2• + HAC f
Catalyzed oxidation of PX by cobalt salts is characterized CH3-Ph-CH2OOH + (AC)• (12)
by an induction period in which cobalt(II) ions are oxidized to
Co(III). Monomeric Co(III) ion is a powerful oxidizing agent The hydroperoxide CH3-Ph-RCH2OOH generated by reac-
when it is surrounded by O-donor ligands such as water, OH- tions 9-12 is unstable and may be decomposed by Co(II) or
ions, or RCOO- ions.5 When Mn and Br are added to the Mn(II) through the following two reactions
catalytic system, Mn(III) and Co(III) are not powerful enough
to initiate the free radical reaction by electron-transfer mech- CH3-Ph-CH2OOH + Co(II) + H+ f
anism. The combined effect of Co and Mn ions is only to
decompose hydroperoxides to yield free radicals. The initiation CH3-Ph-CH2O• + Co(III) + H2O (13)
mechanism is predominantly hydrogen abstract from methyl
groups by Br• radical. The Mn and Co ions oxidize the bromine CH3-Ph-CH2OOH + Mn(II) + H+ f
ions formed to Br• radical, thus ensuring the availability of CH3-Ph-CH2O• + Mn(III) + H2O (14)
bromine atoms for initiation.5 These reactions can be illustrated
by the following:3,4,7,45 Partenheimer reported that the rates of reactions 7 and 8 were
k1 much faster than those of reactions 9-12, which resulted in
Co(III) + Mn(II) 98 Co(II) + Mn(III) (2) most of the methyl group being oxidized into aldehyde group
directly, and the radical reactions 9-14 could be neglected7,25-27
k2 when only the main reactions were considered. In this sense,
Co(III) + Br- 98 Co(II) + Br• (3) the oxidation of PX to TALD can be expressed by the radical
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8983
chain reactions 2-8 and the major radicals are Br•, CH3-Ph- k17
RCH2•, and CH3-Ph-RCH2O2•. Br• + HOOC-Ph-CH3 98
The major chain-termination reactions are those between two HOOC-Ph-CH2• + H+ + Br- (24)
radicals.19,24 Because Br• radical acts the most important role
in chain initiation and propagation, here only the following k18
reactions between Br• radical and other radicals are considered HOOC-Ph-CH2• + O2 98 HOOC-Ph-CH2O2• (25)
as the chain-termination reactions: k19
HOOC-Ph-CH2O2• + Co(II) + H+ 98
k8
Br• + CH3-Ph-CH2• 98 CH3-Ph-CH2Br (15) HOOC-Ph-CHO + Co(III) + H2O (26)
k9 k20
Br• + CH3-Ph-CH2O2• 98 CH3-Ph-CH2O2Br (16) HOOC-Ph-CH2O2• + Mn(II) + H+ 98
HOOC-Ph-CHO + Mn(III) + H2O (27)
Oxidation of TALD to PT. The aromatic aldehyde group
also can be oxidized to the corresponding peroxide radical k21
RCO3• in the same manner as that of the methyl group, and it Br• + HOOC-Ph-CH2• 98HOOC-Ph-CH2Br
(28)
then reacts with divalent metal ion to generate aromatic peracid
RCOOOH.3,4,45 The specific reactions may be as follows: k22
Br• + HOOC-Ph-CH2O2• 98
k10
HOOC-Ph-CH2O2Br (29)
Br• + CH3-Ph-CHO 98
CH3-Ph-CO• + H+ + Br- (17) Oxidation of 4-CBA to TA. Similar to the oxidation of
TALD to PT, the oxidation of 4-CBA to TA also belongs to
k11
CH3-Ph-CO• + O2 98 CH3-Ph-CO3• (18) the oxidation of aldehyde group to carboxy group, and the
following radical chain reactions can be determined according
k12
to that of reactions 17-23
CH3-Ph-CO3• + Co(II) + H+ 98
k23
CH3-Ph-COOOH +Co(III) (19) Br• + HOOC-Ph-CHO 98
k13
HOOC-Ph-CO• + H+ + Br- (30)
CH3-Ph-O3• + Mn(II) + H+ 98
k24
CH3-Ph-COOOH + Mn(III) (20) HOOC-Ph-CO• + O2 98HOOC-Ph-CO3• (31)
k24[O2][HOOC-Ph-CO•] ) (k25[Co2+][H+] + By inserting eq 40 into the first equation in eq 38, the expression
k26[Mn2+][H+] + k29[Br•])[HOOC-Ph-CO3•] for the concentration of Br• radical can be obtained in the
following form,
(k25[Co2+][H+] + k26[Mn2+][H+])[HOOC-Ph-CO3•] )
1
k27[HOOC-Ph-CO3H][4-CBA] (38) [Br•] ) (41)
λ1c1 + λ2c2 + λ3c3 + λ4c4 +
where [I•] ) ∑ ki[Ii•] represents the linear assembled total
where is an approximate modification of [Br•]. By inserting
concentration of all the reactive radicals that are generated in
eq 41 into eq 37, the simplified kinetic model for PX liquid-
the oxidation process. Theoretically, by coupling eq 38 with eq
phase catalytic oxidation to TA can be
37, the detailed mechanistic kinetic models can be obtained.
However, the kinetic models obtained in this manner are too kici
complex and difficult to be used practically. Some simplifica- ri ) kici[Br•] ) (42)
λ1c1 + λ2c2 + λ3c3 + λ4c4 +
tions are necessary, and the following assumptions are made:
(a) Since oxidation operates at high oxygen pressure, the where ki is the reaction rate constant, and factors affecting ki
concentration of oxygen in the liquid may be much higher than are temperature, water content, and catalyst concentration and
that for Br• radical, i.e., [O2] . [Br•]. ratio. Comparing model eq 42 with the previously obtained
(b) The products of chain-termination reactions 14-15, 21- model eq 1, we find that the number of model parameters needed
22, 27-28, and 34-35 are side products or byproducts, which to be regressed are greatly decreased from 28 to 9 at a certain
are microcontent compounds referring to the main reaction operation condition, and the nine model parameters can easily
products. The concentrations of byproducts are assumed to be be uniquely determined by data fitting.2 Mechanistic model eq
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8985
∑ ∑ai,jcicj
i)1 j)1
been operated under isothermal conditions and all reactions are
of zero order with respect to oxygen, because at the experimental
(45) oxygen partial pressure, no obvious effect of oxygen partial
4 4 4
pressure on the reaction was found.
∑
i)1
bici + ∑∑ci,jcicj
i)1 j)1
The kinetic parameters are determined in a nonlinear opti-
r a ) ka ca a ) 2, 4 mization, minimizing the difference between the simulated and
4 4 the experimental time evolution of the product composition of
∑ ∑ai,jcicj
i)1 j)1
experimental runs 3-8 and that of previously obtained results
in batch experiments. The fourth-order Runge-Kutta method
is used to solve eq 46, and the simplex method is used in the
The kinetic model eq 45 is cumbersome to be used directly. nonlinear optimizations. The method is implemented in the
Furthermore, the parameters in the model are too many to be Matlab Optimization Toolbox (The Mathworks). The simulation
uniquely determined by data fitting. In our previous work, we is written in Matlab to use its optimization routine.
simplified eq 45 into eq 1, in which there are still as many as
28 model parameters that need to be determined. In this project, Experimental Setup and Procedure
the reaction mechanism is further simplified, which directly
results in the simpler kinetic model eq 42, in which only 9 model Apparatus and Procedure. The industrial reactor is a
parameters need to be determined. continuous reactor, into which the solvent, reactants of PX, and
The liquid-phase catalytic oxidation of PX to TA involves air are continuously fed and the reaction slurry, including TA
many complex radical chain reactions, and many uncertainties product, is continuously discharged out. The operation of
exist when dealing with these reactions. It is impossible to continuous reactor is steady state, and the concentrations of
consider all the radical chain reactions that occurred in the reactant PX, intermediates TALD, PT, and 4-CBA and the
oxidation process, and only the most important reactions are product TA in solution are very low. In our previous works,
considered in the presently proposed mechanism. Although we studied the PX oxidation in a batch reactor, in which the
many assumptions are made during the derivation of the kinetic liquid reactant PX was batch-added into the reactor, while the
model eq 42, we find most of the experimental results can be gaseous reactant air was continuously fed through the reactor.
well-explained by the model eq 42,2-4,8-17,43-46 which will be In this work, we further studied the PX oxidation in a
discussed in detail in the following sections. semicontinuous reactor, in which the liquid reactant PX and
the gaseous reactant air were all continuously fed into the
Lab Reactor Model reactor. However, in the batch and semicontinuous experiments,
no slurry was discharged. The apparatus employed in this work
In the reactor for the manufacturing of TA, PX is oxidized appears in Figure 3.
to TA in the liquid phase. Owing to the low solubility of TA in The 2.0 L reactor was constructed from titanium to resist
aqueous acetic acid, most of it precipitates as it forms. When corrosion and was designed for temperatures up to 533 K and
TA is crystallized, the impurity 4-CBA will also incorporate pressures up to 60 atm. A paddle-type agitator with a turbine
into TA crystals. In this sense, the reactor for the manufacturing impeller is used for agitation. The system was equipped with
of TA has two functions: reaction and crystallization. In the three condensers in order to ensure complete condensation and
present manuscript, we are just concerned with the reaction, recycle of the evaporated compounds. The pressure was
and in a following manuscript, we will be concerned with the controlled by a back-pressure valve to be 18 atm. A Pt100
crystallization. The crystallization of TA has no effect on the thermal resistance thermometer was inserted into the vessel for
reaction process; however, the incorporation of 4-CBA will the measurement of temperature, and the thermometers had an
affect the concentration of 4-CBA in solution, which will uncertainty of (0.1 K. In each experiment, TA seeds, solvents
directly influence the reaction process. By taking into account acetic acid and water, and catalysts Co/Mn/Br were batch-
only the formation of the molecular species that represents the deposited in the reactor at room temperature. The slurry in the
most important intermediate and final product, the lumped vessel was heated at 10 K/min to the experimental temperature.
kinetic scheme as shown in Figure 1 and the kinetic model of The temperature was maintained within (0.5 K of the desired
eq 42 is used. The description of the diffusion and reaction temperature by a proportional-integral-derivative (PID) con-
processes at the gas-liquid interface is neglected because of trolling system shown in Figure 3. When the temperature was
the elimination of mass transfer influence. Since all experiments higher than the desired point, the computer program would start
are performed under the kinetic regime, the following mass the peristaltic pump, and cooling oil would flow through the
balances are used, spiral cooling coil in the vessel to cool the content in the reactor.
When the temperature was lower than the desired point, the
dcj 4
dt
) ∑
i)1
νi,jrj + Fj/Mj - NLS,j j)1∼4 (46) computer program would start the heating controlling circuit,
and the reactor wall would be electrically heated. When the
slurry temperature was heated to the experimental point, the
along with the initial conditions liquid reactant PX and the gaseous reactant air were continuously
fed into the reactor, and the oxidation began. The reaction slurry
cj ) cj,0 j ) 1-4 (47) was sampled every 10 min. Each oxidation experiment lasted
90 min. To simultaneously determine the components content
where cj and Fj are the concentration and feed rate of the jth in the solution and solid, we separated the solution from the
component, and for batch operation, Fj ) 0. NLS,j is the slurry at the experimental temperature by using the specially
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8987
Figure 3. Experimental apparatus for the liquid-phase catalytic oxidation of p-xylene to terephthalic acid: 1, nitrogen cylinder; 2, air cylinder; 3, mass
flowmeter; 4, nitrogen/air switch valve 1; 5, air buffer vessel; 6, thermal resistance thermometer; 7, aging vessel; 8, vessel wall heating control circuit; 9,
cooling coil; 10, cooling oil tank; 11, peristaltic pump; 12, agitator; 13, condenser; 14, back-pressure valve; 15, gas-liquid separator; 16, flowrator; 17, vent
washing tank; 18, dewatering cotton; 19, nitrogen sweeping valve; 20, sampling valve; 21, atmospheric valve; 22, solid-phase sample collector; 23, sintered
metallic filter; 24, liquid-phase sample collector; 25, plunger-type pump; 26, reactant tank.
Table 1. Operating Conditions for the Experimental Runs HPLC analyses. The mass ratio of liquid component to the
run T /°C N/rpm FPX/(g/min) run T /°C N/rpm FPX/(g/min) internal standard substances in the liquid was determined by
1 160 600 3.76 5 160 750 3.36
HPLC. Gradient elution was used for complete separation of
2 160 900 3.76 6 160 750 2.77 the analytes at room temperature. The mobile phase consisted
3 160 750 4.24 7 156 750 3.76 of three eluents (i.e., water + acetonitrile + methanol), and the
4 160 750 3.76 8 164 750 3.76 following three-component gradient evolution program was
designed sampling system shown in Figure 3. When the adopted: at 0 min, 5 mass % acetonitrile and 95% water; from
sampling valve (valve 20) was open, the slurry was transferred 0 to 5 min, the mixture composition changed linearly with time
from the reactor into a titanium pipe between the atmospheric to become 85 mass % water, 5 mass % methanol, and 10 mass
valve (valve 21) and nitrogen sweeping valve (valve 19). The % acetonitrile; from 5 to 8 min, the mixture composition
titanium pipe was electric heated around the wall, and the wall changed linearly with time to become 55 mass % water, 10
temperature was controlled to be equal to the slurry temperature. mass % methanol, and 35 mass % acetonitrile; from 8 to 12
After this was done, the sampling valve was closed, and the min, the mixture composition changed linearly with time to
atmospheric valve and the nitrogen sweeping valve were opened. become 15 mass % water, 10 mass % methanol, and 75 mass
The slurry was then pressed toward a porous sintered metallic % acetonitrile; from 12 to 14 min, the mixture composition
filter with an internal aperture size of 1 µm. The filtered solution changed linearly with time to become pure acetonitrile; and from
was then collected and cooled in a liquid sample collector, and 14 min on, it became 100 mass % acetonitrile. Each analysis
the components’ concentrations in the solution were determined took ∼20 min.
by the chromatograph method. The filtered crystals in the solid- The mass ratio of solvent HAc to the internal standard
phase sample collector were taken out. The concentration of substances in the solution was determined by a Shimadzu GC-
4-CBA in the solid was determined by the chromatograph 9A GC with a hydrogen flame ionization detector. The SE-54
method, and the size distribution of TA crystals was measured (30 m) capillary chromatographic column was used. To verify
by Malvern 2000S laser particle size analyzer. About 10 mL of the uncertainty of the concentration measurement, two TA +
saturated solution was sampled each time. The experimental 4-CBA + PT + TALD + PX + toluene + HAc solutions of
runs’ reproducibility was verified by repeating each of them at known concentration were analyzed. Compared with the known
least twice.2,17 The experimental conditions were listed in Table concentration, the uncertainty of concentration was <3.0% of
1, while fixing the reaction pressure at 1.8 MPa, the oxygen the known concentration. To check the reproducibility, the two
volume fraction in the vent at 4%, the initial mass percent of solutions were measured at least five times, and the reproduc-
water at 3%, the catalyst mass fraction at w(Co) ) 1.9 × 10-3, ibility was evaluated with a mean relative deviation of <3.0%.
the catalyst ratio (molar) at Co/Mn/Br ) 26/1/18, and the mass
of crude TA seeds at 50 g, in which the mass content of 4-CBA Results and Discussion
is 4500 ppm and the mass content of PT is 7000 ppm.
Analytical Techniques. The liquid reactant PX, liquid Confirmation of the Reaction Scheme. First, a batch
intermediates TALD, PT, and 4-CBA, and product TA in the experiment and a semicontinuous experiment at the reference
solution were analyzed by high-performance liquid chromatog- experimental condition were carried out to confirm the reaction
raphy (HPLC), and the solvent of acetic acid was analyzed by scheme. The batch experimental results2,3,44 are scattered in
gas chromatography (GC). The internal standard method was Figure 4, and the semicontinuous experimental results are
used in the analysis, and toluene was used as the internal scattered in Figure 5. The results given in Figure 4 show the
standard substance to correlate the data obtained from GC and concentration of each intermediate first increases to a maximum
8988 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007
Figure 4. Concentration of reactants vs time in batch oxidation experiment. Figure 7. Concentration of TALD vs time at different stirring rates in
semicontinuous oxidation experiment.
Figure 10. Concentration of PX vs time at different PX feed rates in Figure 13. Concentration of 4-CBA vs time at different PX feed rates in
semicontinuous oxidation experiment. semicontinuous oxidation experiment.
Figure 11. Concentration of TALD vs time at different PX feed rates in Figure 14. Concentration of PX vs time at different initial PX concentra-
semicontinuous oxidation experiment. tions in batch oxidation experiment: scatter, experimental results; line, model
simulated results.
mended by Partenheimer7 and Suresh et al.6 This result also β ) model parameters in eq 1
directly proves the validation and predictability of the mecha- ) model parameters in eq 1 and eq 42
nistic kinetic model eq 42. νij ) stoichiometric coefficient of the jth component in the ith
reaction
Conclusions
AbbreWiations
In some previous papers, a lumped kinetic scheme and a 4-CBA ) 4-carboxybenzaldehyde
fractional-like kinetic model for the liquid-phase oxidation of
PT ) p-toluic acid
p-xylene to terephthalic acid catalyzed by cobalt acetate and
PX ) p-xylene
manganese acetate and promoted by hydrogen bromide was
TA ) terephthalic acid
proposed and tested based on the batch experimental results.8-16
Recently, the workgroup led by Xi carried out some semicon- TALD ) p-tolualdehyde
tinuous studies, which provided a further insight into the reaction
mechanism and kinetics.2,17 Literature Cited
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