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8980 Ind. Eng. Chem. Res.

2007, 46, 8980-8992

Semicontinuous Studies on the Reaction Mechanism and Kinetics for the


Liquid-Phase Oxidation of p-Xylene to Terephthalic Acid†
Qinbo Wang,* Youwei Cheng, Lijun Wang, and Xi Li
Department of Chemical Engineering, Zhejiang UniVersity, Hangzhou,
310027 Zhejiang, People’s Republic of China

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

of the solvent vaporized during sampling. These all directly


affected the accuracy and credence of these experimental results.
Furthermore, a first-order kinetic model, which is empirical but
not derived from the reaction mechanism, was used to correlate
the experimental results.
From the above brief review, it can be said that, although
many public reports dealt with the subject on the oxidation
Figure 1. Lumped kinetic scheme for the oxidation of p-xylene to
terephthalic acid.
mechanism and kinetics of PX to TA, the available literature is
still not complete when one looks for a detailed and complete
This is mainly because the estimation of the kinetics parameters mechanism and industrially applicable kinetics.5-7 There exists
of the radical chain reactions by fitting of the experimental data a scope and a need to further study the mechanism and kinetics
cannot be performed when the concentrations of the participating of this reaction.
components (that is, the radical species in the liquid phase) In recent years, the workgroup of Li carried out some batch
cannot be measured. In order to lower the computing efforts, experiments on the oxidation of PX to TA under the industrial
the most common approach is to lump the detailed mechanism oxidation conditions. The experimental results showed that the
into a set of global reactions that involve only molecular species, reaction rate varied insignificantly with the concentration of
whose concentration can be, in principle, easily monitored as a liquid reactants, and the apparent reaction order was ,1, which
function of time.35-38 Without involving formal procedure of was apparently inconsistent with the widely accepted first-order
general validity but simply including the minimum number of assumption.2-4,8-17,43-46 When the catalyst cycle and interaction
reactions to describe the behavior of all the species of interest, of radicals were considered, the following 28-parameter kinetic
various lumped kinetic schemes for the liquid-phase catalytic model was proposed by Wang and Cheng based on a compli-
oxidation process of PX to TA have been developed in the cated radical chain-reaction mechanism3,4,45
literature.2-16,35-40 By accounting for the most important
intermediates and final products of the process, i.e., p-tolual- kjcj
dehyde (TALD), p-toluic acid (PT), 4-carboxybenzaldehyde (4- rj ) j ) 1-4 (1)
CBA), and TA, Wang and co-workers recently proposed a (d1jc1 + d2jc2 + d3jc3 + d4jc4 + j)βj
lumped kinetic scheme shown in Figure 1 for the liquid-phase
oxidation of PX catalyzed by cobalt acetate and manganese where kj is the reaction rate constant and is affected by
acetate, promoted by hydrogen bromide, which may have temperature, catalyst concentration and ratio, etc. The model
important practical applications in the production of TA,2,12,13,15,16 parameter j represents a modification of the kinetics considering
where the reactions of PX to TALD and PT to 4-CBA involve the effects of other side reactions and chain-termination reac-
the addition of 1O2 and the removal of 1H2O, and the reactions tions. When the kinetics model (eq 1) was used to simulate the
of TALD to PT and 4-CBA to TA involve the addition of 1/2O2. industrial PX oxidation reactors at high temperature, the
By PX batch added into the oxidation system, the workgroup simulated results agreed well with the plant field data. However,
of Cao35-38 studied the air oxidation of PX in methyl benzoate the literature-reported first-order reaction kinetics completely
in the temperature range from 80 to 130 °C, catalyzed by cobalt failed to predict the special features of high conversion
naphthenate, and promoted by TALD. On the basis of the (>99.5%) and high yield (>97%) in an industrial continuous
assumption that all the reactions are zeroth order with respect stirred tank reactor.2-4,45,47
to gaseous reactant and first order with respect to liquid By using a specially designed experimental technique, the
reactants, a lumped kinetic model for the liquid-phase oxidation oxidation of PX to TA was completely studied, and a great deal
of PX to TA was presented. However, the experimental of experimental data was obtained.2-4,8-17,43-46 These batch
conditions differed from the currently adopted industrial opera- studies disclosed the reaction mechanism and quantitatively
tion condition greatly; furthermore, the kinetic models are determined the effects of various reaction conditions on the
completely empirical but not derived from the oxidation reaction rate, which was practically and theoretically valuable.
mechanism. From different simplified radical chain-reaction Recently, a new semicontinuous oxidation apparatus was set
mechanisms, different kinetic models were derived by Scott,39 up by Wang, and some oxidation experiments were performed.2
Kamiya,18 Hronec,23,24 Suresh,6 Jones20-22, Partenheimer,25-27,40 Comparison of the semicontinuous experimental results and the
etc. However, the same as that of the workgroup of Cao,35-38 predicted results by eq 1 with the model parameters determined
most of these studies were studied at conditions far away from from batch experimental results is shown in Figure 2, in which
the industrial operation condition. These defects made these apparent disagreement appears.2 It shows that the overly
experimental results unable to be used for practical use. complex model eq 1 still fails to describe the semicontinuous
Zhou41 and Wen42 studied the PX oxidation process at high system that it has not already been “fit” to, e.g., it appears to
temperatures. The experimental conditions covered the range have no predictive powers at all. There might be two reasons.
that might be adopted in the high-temperature oxidation process. First, the model parameters in eq 1 were regressed from the
Also, based on the assumption that all the reactions are zeroth batch experimental results. However, in batch experiments, the
order with respect to gaseous reactant and first order with respect concentrations of liquid reactants were much higher than those
to liquid reactants, a lumped kinetic model for the liquid-phase in semicontinuous experiments. When the cumbersome kinetic
oxidation of PX to TA was presented and the effects of model eq 1 determined at higher concentration was extrapolated
temperature, catalyst concentration and ratio, and oxygen to predict the semicontinuous experimental results, some
pressure on the reaction rate were determined. However, the uncertainty existed and discrepancy might occur. Second, the
established experimental technique for temperature controlling, model parameters in eq 1 are too many to be uniquely
sampling, and concentration determination for liquid-phase determined by common data-regressing method, which resulted
compounds was insufficient. As reported by Zhou41 and Wen,42 in a nonuniqueness in model-parameters determination.2 Because
the experimental temperature fluctuated with the amplitude of of this uncertainty and nonuniqueness, when eq 1 was used to
(20 K, and some of the liquid reactant crystallized and some simulate the industrial oxidation reactor in our previous
8982 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007

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)

Different from the oxidation of the methyl group, no reactive


C-H bond exists in the aldehyde group, which makes the direct k25
HOOC-Ph-CO3• + Co(II) + H+ 98
reduction of peroxide radical CH3-Ph-CO3• by metal ions to
the corresponding aromatic acid impossible. It indicates that HOOC-Ph-COOOH + Co(III) (32)
similar reactions such as 6 and 7 will not occur in the oxidation
of the aldehyde group. However, the reducibility of the aldehyde k26
group is strong and the following self-catalyzed reaction between HOOC-Ph-CO3• + Mn(II) + H+ 98
aldehyde group and aromatic peracid may occur to generate HOOC-Ph-COOOH + Mn(III) (33)
aromatic acid:32,48
k14 k27
CH3-Ph-COOOH + CH3-Ph-CHO 98 HOOC-Ph-COOOH + HOOC-Ph-CHO 98
2CH3-Ph-COOH (21) 2HOOC-Ph-COOH (34)

The oxidation of TALD to PT can be expressed by the radical k28


chain reactions 17-21, and the major radicals and peracid in Br• + HOOC-Ph-CO• 98HOOC-Ph-COBr (35)
the oxidation of TALD to PT are Br•, CH3-Ph-RCO•, CH3-
Ph-CO3•, and CH3-Ph-COOOH. Here also, only the follow- k29
ing reactions between Br• radical and other radicals are Br• + HOOC-Ph-CO3• 98HOOC-Ph-CO3Br (36)
considered as the chain-termination reactions:
There must be many other chain reactions that are not considered
k15
• • in the above mechanism, but the radical chain reactions 2-36
Br + CH3-Ph-CO 98 CH3-Ph-COBr (22)
might be expected to approximately represent the reaction
k16 mechanism for the oxidation of PX to TA.
Br• + CH3-Ph-CO3• 98 CH3-Ph-CO3Br (23) Kinetic Model. The oxidation of PX to TA is a typical
consecutive reaction; coupling effects exist among reactants,
Oxidation of PT to 4-CBA. Similar to the oxidation of PX radicals, and catalyst. Rounded consideration of these interac-
to TALD, the oxidation of PT to 4-CBA also belongs to the tions is necessary for the mechanistic kinetic model establish-
oxidation of methyl group to aldehyde group, and the following ment. According to the mechanism illustrated by reactions 2-36,
radical chain reactions can be determined according to that of the reaction rates for the major reactants PX, TALD, PT, and
reactions 2-8, 15, and 16: 4-CBA may be determined as
8984 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007

d[PX] negligible. By this assumption, the items representing termina-


) -r1 ) -k4[PX][Br•] tion reactions in eq 38 can be neglected.
dt
By using these two assumptions, eq 38 becomes
d[TALD]
) r1 - r2 ) r1 - [TALD](k10[Br•] +
dt k4[PX][Br•]
k14[CH3-Ph-COOOH]) [CH3-Ph-CH2•] )
k5[O2]
d[PT] k4[PX][Br•]
) r2 - r3 ) r2 - k17[PT][Br•] [CH3-Ph-CH2O2•] )
dt
k6[Co2+][H+] + k7[Mn2+][H+]
d[4-CBA]
) r3 - r4 ) r3 - [4-CBA](k23[Br•] + k10[TALD][Br•]
dt [CH3-Ph-CO ] ) •
k27[HOOC-Ph-COOOH]) (37) k11[O2]
k10[TALD][Br•]
When the steady-state approximation is used for radicals and [CH3-Ph-CO3•] )
aromatic peracids produced in the radical chain reactions, the k12[Co2+][H+] + k13[Mn2+][H+]
concentrations for these radicals and peracids from the mech-
k17[PT][Br•]
anism presented above lead to the expressions [HOOC-Ph-CH2•] )
k18[O2]
(k2[Co3+] + k3[Mn3+])[Br-] ) (k4[PX] + k10[TALD] + •
k17[PT][Br•]
[HOOC-Ph-CH2O2 ] )
k17[PT] + k23[4-CBA] + [I•])[Br•] k19[Co2+][H+] + k20[Mn2+][H+]
k4[PX][Br•] ) (k5[O2] + k8[Br•])[CH3-Ph-CH2•] k23[4-CBA][Br•]
[HOOC-Ph-CO•] )
k5[O2][CH3-Ph-CH2•] ) (k6[Co2+][H+] + k24[O2]
+ •
k7[Mn ][H ] + k9[Br ])[CH3-Ph-CH2O2 ]
2+ • k23[4-CBA][Br•]
[HOOC-Ph-CO3•] )
k25[Co2+][H+] + k26[Mn2+][H+]
k10[TALD][Br•] ) (k11[O2] + k15[Br•])[CH3-Ph-CO•]
k10[Br•]
k11[O2][CH3-Ph-CO•] ) (k12[Co2+][H+] + [CH3-Ph-CO3H] )
k14
k13[Mn2+][H+] + k16[Br•])[CH3-Ph-CO3•]
k23[Br•]
+ +
(k12[Co ][H ] + k13[Mn ][H ])[CH3-Ph-CO3 ] )
2+ 2+ • [HOOC-Ph-CO3H] ) (39)
k27
k14[CH3-Ph-CO3H][TALD]
It is shown in eq 39 that the concentrations of all the radicals
k17[PT][Br•] ) (k18[O2] + k21[Br•])[HOOC-Ph-CH2•] and peracids are linearly related to the concentration of Br•
radical, and the total concentration of radicals can be expressed
k18[O2][HOOC-Ph-CH2•] ) (k19[Co2+][H+] + as
k20[Mn2+][H+] + k22[Br•])[HOOC-Ph-CH2O2•] 4
• •
k23[4-CBA][Br ] ) (k24[O2] + k28[Br ])[HOOC-Ph-CO ] • [I•] ) ∑ ki[Ii•] ) ∑
j)1
fjcj[Br•] (40)

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

42 is a radical competition model and reveals the following three


aspects of mechanism. Co(III) + CH3-Ph-CHO f
(1) Radical Br• is a key factor to initiate the oxidation process, Co(II) + CH3-Ph-CO• + H+
and its concentration determines the reaction rate directly. When
the concentration of reactants increases, from eq 41 we can see Co(III) + HOOC-Ph-CHO f
that the concentration of radical Br• decreases, which restricts Co(II) + HOOC-Ph-CO• + H+
the acceleration of the reaction rate. When the concentration of
reactants decreases, from eq 41 we can see that the concentration Mn(III) + CH3-Ph-CHO f
of radical Br• increases, which restricts the deceleration of the Mn(II) + CH3-Ph-CO• + H+
reaction rate. Because of the restriction effect of radical Br•,
the change of apparent reaction rate is not sensitive with the Mn(III) + HOOC-Ph-CHO f
change of reactants concentration. This unique characteristic is Mn(II) + HOOC-Ph-CO• + H+ (43)
consistent with the large quantity of experimental data in our
group.2-4,8-17,43-46 Further, based on model eq 42 and the
In our previously proposed mechanism, besides mechanism
determined model parameters, the simulation results for an
II (represented by eqs 5, 17, 24, and 30), mechanism I
industrial oxidation reactor agree well with the plant field
data.2 (represented by eq 43) was also considered.8,45 In this work, eq
43 was omitted, which made the reaction mechanism simpler
(2) The oxidation rate is approximately independent with the
and more reasonable.
oxygen concentration in the liquid, and the reaction is zeroth
order with respect to the gaseous reactant. Only when the oxygen (2) Generation and Decomposition of Peroxide. The
concentration in the liquid phase is low enough to influence peroxide CH3-Ph-RCH2OOH generated by eqs 9-12 is
the assumption of [O2] . [Br•] will the oxidation rate be affected unstable and may be decomposed in two ways. One is the
by the oxygen concentration. This is consistent with most of decomposition by Co(II) and Mn(II) through eqs 13 and 14,
the reported experimental results.14,35-38,49 the other is the self-decomposition through the following
(3) When the reactants concentration is low enough to be reaction
negligible compared with the model parameter  in eq 42, the
kinetic model will be reduced to a first-order kinetic model,
CH3-Ph-CH2OOH f CH3-Ph-CH2O• + •OH (44)
which is widely assumed in most of the research.35-38,41,42
Comparison of the Present Oxidation Mechanism and
Kinetics with our Previous One. Our previous reaction
mechanism reveals our previous comprehension and understand-
ing on the PX oxidation process. Through several years of In our previously proposed mechanism, the two decomposi-
further study on this process, in this work, our previously tion ways have been considered. Furthermore, the formation
proposed mechanism was complemented and perfected in the and decomposition of HOOC-Ph-CH2OOH are also consid-
following aspects. ered. Partenheimer7,25-27 and Sheldon and Kochi32 reported that
the generating rates of CH3-Ph-CH2OOH and HOOC-
(1) Effect of Metal Catalyst on the Initiation of the
Ph-CH2OOH were much faster than their decomposition
Oxidation. Initiation of the oxidation of alkyl aromatic hydro-
rates, which resulted in most of the methyl group being oxidized
carbons can be explained in terms of two mechanisms: (i) the
electron-transfer mechanism in which electron transfer occurs into aldehyde group directly, and the decomposition re-
from arene to a metal catalyst complex, producing an arene actions for CH3-Ph-CH2OOH and HOOC-Ph-CH2OOH
radical cation that in turn forms a benzyl radical by proton loss, could be neglected when only the main reactions were consid-
and (ii) abstraction mechanism in which benzylic hydrogen is ered. In this sense, the oxidation of methyl group to aldehyde
abstracted by bromine atoms, RO• radicals, or ROO• radicals. group can be substantially simplified, and also the number of
Mechanism I is more applicable to the oxidation process with radical species can be reduced. This simplification is also
no presence of promoter Br, and mechanism II is important in reasonable.
the Co/Mn/Br catalytic oxidation of PX.5 In the oxidation of (3) Radical Chain Termination. The major chain-termina-
PX to TA, mechanism I can be represented by the following tion reactions are those between two radicals.19,24 In our
reactions: previously proposed mechanism, all the reactions between any
two radicals are considered, which results in all kinds of
Co(III) + CH3-Ph-CH3 f byproducts. In this wok, the main reactions are concerned.
Co(II) + CH3-Ph-CH2• + H+ Because Br• radical acts the most important role in chain
initiation and propagation, here only the following reactions
Co(III) + HOOC-Ph-CH3 f between Br• radical and other radicals are considered as the
Co(II) + HOOC-Ph-CH2• + H+ chain-termination reactions. This simplification also seems
reasonable.
Mn(III) + CH3-Ph-CH3 f
Additionally, considering reaction 43, the above generation
Mn(II) + CH3-Ph-CH2• + H+ and decomposition reactions of peroxide, and the radical chain
termination due to the reactions between any two radicals, we
Mn(III) + HOOC-Ph-CH3 f
previously obtained the following kinetic model for the oxidation
Mn(II) + HOOC-Ph-CH2• + H+ of methyl group and aldehyde group separately:
8986 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007

4 incorporation rate of the jth component and will be discussed


∑ bici in detail in a following paper. The meaning of other symbols is
i)1 reported in the notation. The oxygen mass balance and the
rm ) km cm m ) 1, 3 energy balance are not considered here since the reactor has
4 4

∑ ∑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 5. Concentration of reactants vs time in semicontinuous oxidation


experiment.
Figure 8. Concentration of PT vs time at different stirring rates in
semicontinuous oxidation experiment.

Figure 6. Concentration of PX vs time at different stirring rates in


semicontinuous oxidation experiment.
Figure 9. Concentration of 4-CBA vs time at different stirring rates in
value and then decreases. The concentration of reactant PX semicontinuous oxidation experiment.
decreases monotonically, and the total concentration of product
TA in liquid and solid increases monotonically. These are the monotonically with time, and the reactants detected in semi-
typical characteristic of consecutive reactions. From the se- continuous experiments are the same as those detected in batch
quence each reactant generates and shrinks, we can make a experiments, which all confirms that the reaction scheme of PX
conclusion that the methyl of PX is first oxidized to aldehyde liquid-phase catalytic oxidation to TA can be determined as that
(TALD) and acid (PT). At the two-fifths time of the total batch shown in Figure 1.
reaction time, the first methyl is almost completely oxidized. Effect of Stirring Rate. Experimental runs 1-2 and 4 were
The concentration of PT reaches a maximum value, and the carried out to determine the effect of stirring rate on the
second methyl is followed to be oxidized, which is a relatively oxidation process. The experimentally determined evolutions
slower process. During this course, the second methyl is oxidized of PX, TALD, PT, and 4-CBA concentrations in solution with
to aldehyde (4-CBA) and then 4-CBA is oxidized to acid (TA). time are scattered in Figures 6-9, respectively. It clearly shows
Cao, Cincotti, and co-workers detected microcontents of p- that the effect of stirring rate on the component concentration
toluoalcohol and 4-carboxybenzylalcohol in the oxidation of PX in solution is insignificant under the conditions of this study,
at low temperature,35-38 but they are not detected here. It is and the PX oxidation process is controlled by chemical reactions.
mainly because the reaction rate at high temperature is much The influences of mass transfer and gas-liquid mixing on the
faster and the concentrations of p-toluoalcohol and 4-carboxy- oxidation process are negligible under the studied experimental
benzylalcohol are not high enough to be detected. The results conditions. In the section Lab Reactor Model, the assumption
from semicontinuous experiments shown in Figure 5 confirm that the description of the diffusion and reaction processes at
the above analysis. The reactants’ concentrations increase the gas-liquid interface is negligible because of the elimination
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8989

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.

Figure 12. Concentration of PT vs time at different PX feed rates in


semicontinuous oxidation experiment.
Figure 15. Concentration of TALD vs time at different initial PX
concentrations in batch oxidation experiment: scatter, experimental results;
of mass transfer influence is reasonable. The experimental runs line, model simulated results.
to study the kinetics of PX oxidation to TA can be chosen to
be 750 rpm. By minimizing the difference between the calculated reactant
Model Parameters Determination. The time evolutions of concentrations and the experimental determined reactant con-
experimentally determined concentration for major reactants PX, centrations, the model parameters for PX oxidation to TA are
TALD, PT, and 4-CBA at different PX feed rates in semicon- determined and given in Table 2.
tinuous oxidation experiments are scattered in Figures 10-13, For comparison, the time evolutions of model-calculated
respectively. The experimental results show that the determined concentrations for PX, TALD, PT, and 4-CBA in both semi-
concentrations of liquid-phase reactants increase approximately continuous experiments and batch experiments are also lined
linearly with time, which indicates that the reaction rates for in Figures 10-17, where it can be seen that the obtained
the liquid-phase reactants are approximately independent from agreement is, in general, satisfactory. The average relative
their concentration. The batch experiment results performed at deviation of the simulated value and the experimental data is
the same temperature are also scattered in Figures 14-17, <7%. Although the fitting accuracy by eq 42 is not as good as
respectively.2,3,44 To ensure the kinetic model eq 42 is applicable that by eq 1, the number of model parameters is greatly
not only for semicontinuous experiments but also for batch decreased, which makes the model eq 42 more predictable and
experiments, we put the semicontinuous experimental data and applicable.
the obtained batch experimental results2,3,44 shown in Figures Comparing eq 1 with eq 42, we find that the mode structure
14-17 together to determine the model parameters in eq 42. is similar, but the model parameters for eq 42 are greatly
8990 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007

Figure 19. Concentration of TALD vs time at different reaction temper-


atures in semicontinuous oxidation experiment.
Figure 16. Concentration of PT vs time at different initial PX concentra-
tions in batch oxidation experiment: scatter, experimental results; line, model
simulated results.

Figure 20. Concentration of PT vs time at different reaction temperatures


in semicontinuous oxidation experiment.

Figure 17. Concentration of 4-CBA vs time at different initial PX


concentrations in batch oxidation experiment: scatter, experimental results;
line, model simulated results.

Figure 21. Concentration of 4-CBA vs time at different reaction temper-


atures in semicontinuous oxidation experiment.

respectively. When eq 42 and the experimental data are used


to determine the model parameters, we find the following
Figure 18. Concentration of PX vs time at different reaction temperatures Arrehenius equation can represent the effect of temperature on
in semicontinuous oxidation experiment.
the reaction well
Table 2. Model Parameters in Equation 42
ki ) ki0 exp(-Ea/RT) (48)
i)1 i)2 i)3 i)4
10-10ki0/(1/min) 8.148 13.97 1.164 4.656 Semicontinuous experimental data shown in Figures 18-21
λi/(kgHAc/mol) 3.97 2.19 1.00 1.98
 0.30 and the previously obtained batch experimental results2,3,44 are
Ea/(kJ/mol) 84.2 put together to determine the model parameters in eq 48. The
determined model parameters in eq 48 are also shown in Table
different from those for eq 1 reported earlier by Wang et 2. The average relative deviation of the calculated and experi-
al.3,4,8,15,44 When the two models are used to simulate a specific mental data is <10%.
industrial operation condition, the simulated results are similar.2 From Table 2, two interesting and consistent results can be
However, the kinetics model determined in this work is better obtained. (i) The reaction of PT to 4-CBA is the slowest step,
than the previous one because not only the batch data but also and it is the control step of the oxidation process. This result is
the semicontinuous experimental data are considered.2 consistent with most of the research results on PX oxidation to
Effect of Temperature. The time evolutions of experimen- TA. (ii) The rate ratio of the oxidation of the first methyl group
tally determined concentration for major reactants at different to the second methyl group of PX is ∼7:1, which is consistent
experimental temperatures are scattered in Figures 18-21, with the predicted rate ratio by the Hammett function recom-
Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8991

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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