Pergamon ('hemwal En~li,leerin9 5cWnce. Vol 52, Nos 21 22. pp 4205-4213.

1997
1997 Elsevier Science Lid All rights reserved
Prmted in Great Britain
Pi l : S0009-2509(97)00263-7 o0o9 2509 97 $17.00 + 0.00
Effect of cat al yst concentrati on and
si mul at i on of precipitation processes on
liquid-phase cat al yt i c oxi dat i on of p - x y l e ne
to terephthalic acid
A. Cincotti, R. Orrfi, A. Broi and G. Cao*
Dipartimento di Ingegneria Chimica e Materiali, Universita'degli Studi di Cagliari.
Piazza d' Armi, 09123 Cagliari, Italy
(Accepted 7 July 1997)
Abstract---The influence of catalyst concentration, i.e. cobalt naphthenate, on product distribu-
tion and kinetic constants of the lumped kinetic scheme of liquid-phase p-xylene oxidation
proposed in previous works (cf. Cao e t al . , 1994a, b) is investigated. The experiments involving
various levels of catalyst concentrations (from 1.67 to 33.3 10-4 mol/kgi) are conducted in an
isothermal semi-batch oxidation reactor where both the gas and the liquid phase are well
mixed. The dependence of the kinetic constants of the lumped kinetic scheme on the catalyst
concentration is examined. In addition, the interaction between the chemical reactions of the
lumped kinetic scheme for p-xylene oxidation to terephthalic acid and the precipitation kinetics
of both 4-carboxybenzaldehyde and terephthalic acid is analyzed theoretically. A semi-batch
gas-liquid reactor model which incorporates the description of the above phenomena allows us
to identify their interplay..(" 1997 Elsevier Science Ltd
K e y w o r d s : p-xylene; oxidation; terephthalic acid; catalyst: precipitation.
I NT RODUC T I ON
In the chemical industry, liquid-phase catalytic oxida-
tion of organic compounds, which can be either
homolytic or heterolytic depending upon the mecha-
nism of oxygen activation (cf. Emanuel and Gal,
1986), constitutes a wide class of important processes.
In particular, when addressing the study of homolytic
oxidation processes, e.g. cyclohexanol from cyclo-
hexane, terephthalic acid from p-xylene, isophthalic
acid from m-xylene, emphasis was placed on the in-
vestigation of the catalytic system, i.e. catalyst and
promoter concentration, nature of solvent, reaction
temperature, etc., and its influence on the oxidation
rate (Sheldon and Kochi, 1981; Raghavendrachar and
Ramachandran, 1992). This type of approach typi-
cally accounts for the complex nature of the catalyst
within the already complex chain elementary reaction
schemes, which involve a very large number of rad-
icals as well as molecular species (cf. Carr~ and San-
tacesaria, 1980). However, when simulating the
gas-liquid reactors, the formulation of detailed kinetic
models of oxidation processes requires a large compu-
tation effort for solving the diffusion-reaction equa-
*Corresponding author. Tel.: 39/70/675-5058: fax:
39.'70/675-5067: e-mail: cao@visnu.dicm.unica.it.
tions in the film at the gas-liquid interface, coupled
with the continuity equations for both gaseous and
liquid bulk phases. This is due to the intrinsic differ-
ence between the space scale typical of molecular and
radical species. In addition, the estimation of kinetic
parameters of chain elementary reaction kinetic
schemes may not be reliable due to the difficulty of
monitoring all participating species, including highly
reactive radicals, as a function of time in semi-batch
reactors where specific experimental studies are typi-
cally conducted.
The most common approach is to lump the detailed
mechanism into a set of g l o b a l r e a c t i o n s which in-
volves only molecular species, whose concentration
can be, in principle, easily monitored as a function of
time. Without involving formal procedure of general
validity but simply including the minimum number of
reactions to describe the behavior of all the species of
interest, various lumped kinetic schemes for homolytic
oxidation processes have been developed in the litera-
ture, by Cavalieri d' Oro e t al . (1980) for p-xylene
oxidation, Chen e t al . (1985) for o-xylene oxidation,
Morbidelli e t al . (1986) for ethyl-benzene autoxidation
and Krzysztoforski e t al . (1986) for cyclohexane oxi-
dation.
By accounting for the most important inter-
mediates and final products of the process, i.e.
p-tolualdehyde, p-tolualcohol, p-toluic acid,
4205
4206 A. Cincotti e t al .
4-carboxybenzylalcohol, 4-carboxybenzaldehyde, both reactants and products. It was also shown that
terephthalic aldehyde and terephthalic acid, Cao e t a l . the model was able to describe the reactor behavior in
(1994a, bl have recently proposed the following lum- any of the regimes which may prevail depending upon
ped kinetic model for the liquid-phase oxidation of the operating conditions and the depletion of liquid
p-xylcne catalyzed by cobalt naphthenate: reactants in time.
terephthalic aldehyde
CHO
+
/ CHO " ~
p-xylene p-tolualdehyde p-toluic acid
CH~ CHO COOH
CH.~ CH, CH 3
CH~
p-toluic alcohol
4-carboxybenzaldehyde
COOl I
k5 ,. +
CHO
COOH /k~
CH,OH
4-carboxybenzylalcohol
terephthalic acid
COOH
k~, ,,- +
COOH ( I )
which may have important practical implications in
the production of terephthalic acid. All the lumped
reactions were assumed to be zeroth and first order
with respect to the gaseous and the liquid reactant,
respectively. The reliability of the proposed kinetic
model was illustrated by comparison with suitable
experimental data obtained in a semi-batch oxidation
reactor where both the gas and the liquid phase are
well mixed. The experiments included different values
of the initial concentrations of the liquid reactants,
two gaseous reactants (i.e. pure oxygen and air), tem-
perature values in the range 80-130~C and were con-
ducted at a unique value of the catalyst concentration
(i.e. 1 I 0- 3 mol/kg~). However, catalyst concentra-
tion plays a fundamental rote upon the global rate of
a wide variety of oxidation reactions such as the
cobalt-catalyzed oxidation of toluene in acetic acid (cf.
Scott and Chester, 1972; Kamiya and Kashima, 1972),
the oxidation of alkyl-benzenes in acetic acid
catalyzed by cobalt acetate and sodium bromine {cf.
Kamiya, 1974), the durene oxidation in acetic acid
catalyzed by cobalt salts (cf. Hanotier and Hanotier-
Bridoux, 1981), the catalytic oxidation of p-xylene (cf.
Zaidi, 1986; Raghavendrachar and Ramachandran,
1992).
The proposed lumped kinetic scheme was also in-
corporated (cf. Cao e t a l . , 1994a) into semi-batch
gas-liquid reactor model that properly accounts for
inter- and intraphase mass transport processes of
The formulation of detailed kinetic models is even
less desirable when the interaction among mass trans-
fer resistances, chemical reactions and precipitation
phenomena plays a fundamental role. This is parti-
cularly the case of liquid-phase p-xylene oxidation,
where the formation of 4-carboxybenzaldehyde and
terephthalic acid occurs through a reaction precipita-
tion process, i.e. the latter compounds are formed by
chemical reactions in concentration exceeding their
solubility. Note that 4-carboxybenzaldehyde is prob-
ably one of the most deleterious contaminant of
terephthalic acid, since its aldehyde group is unable to
undergo condensation reactions with ethylene glycol
during PET polymerization (cf. McElroy Brown and
Myerson, 1989). Only few studies concerning reactive
precipitation have been reported in the literature (cf.
Garside and Shah, 1980; Aslund and Rasmunson,
1992 and references therein). This is particularly true
when considering the simultaneous presence of
gas-liquid mass transfer, chemical reaction and pre-
cipitation, which remain unexplored until recently
(Wachi and Jones, 1990; Wachi and Jones, 1991).
The present work consists in two parts. In the first
one, the effect of cobalt naphthenate concentration on
product distribution and kinetic constants of the lum-
ped kinetic scheme (1) is established. In particular, the
reactions leading to the formation of p-toluic acid are
considered by operating at low values of p-xylene
conversion. Various values of catalyst concentration
Catalytic oxidation of p-xylene
are investigated by running the experimental reactor
used in previous works (cf. Cao e t a l . , 1994a, b) under
the kinetic regime. Run
In the second part, the interaction between chem-
ical reactions of the lumped kinetic scheme (1) and the
precipitation kinetics of both 4-carboxybenzaldehyde
and terephthalic acid is analyzed theoretically. The
latter phenomena are described by appropriate popu-
lation balance equations incorporated in a semi-batch
reactor model.
E X P E R I M E N T A L
The experimental set-up and procedure are de-
scribed in detail by Cao e t a l . (1994at. As sum-
marized in Table 1, the experimental runs performed
were carried out at three temperatures (80, 110 and
120~'C) and six levels of cobalt naphthenate concen-
tration, while maintaining fixed initial p-xylene
(4 mol/kgt) and p-tolualdehyde (0.11 mol,,"kg,) concen-
trations.
The experiments were run in a semi-batch reactor
continuously fed with pure oxygen where, after the
temperature reached the desired value, suitablc
amounts of catalyst (0.05 1 cm 3) and p-tolualdehyde
(6 cm 3) as promoter were added. Methyl benzoate was
used as solvent. All the experimental runs were per-
formed at a stirring speed of 800 rpm, where the
influence of this variable on the product distribution
becomes negligible (cf. Cao e t a l . , 1994a). Each run
was carried out up to conversion values of p-xylene of
about 14%. Thc reproducibility of the experimental
runs was verified by repeating each of them at least
twice.
The reaction products were analyzed by HPLC
using the technique described by Cao e t a l . (1994a, b)
and Viola and Cao (19961.
THE MODEL EQUATIONS
At the p-xylene conversion levels considered in this
work the lumped kinetic scheme( l ) becomes (cf. Cao
e t a l . , 1994a):
p-xylene p-tolualdehydc
CH~ CHO
CH~ CH~
k ~ CH: OH/ k,
CH,
p-toluie alcohol
p-toluic acid
C(X)H
IlL
CH~
( 2 )
4207
lable 1. Operating conditions for the experimental runs
T [ ('~ ('~,, {mol.kgh 104
I 80 5.o
2 110 5.0
3 120 5.o
4 120 1.67
5 120 2.67
6 120 10.0
7 120 15.0
g 12(1 33.3
where each reaction involves the addition of I..2 0 2
and the corresponding kinetics are assumed to be
zeroth and first order with respect to oxygen and the
liquid reactant, respectively. The above scheme has
been inserted in the model of a semi-batch gas-liquid
reactor to simulate the experimental data. Since all
experiments were run under the kinetic regime, the
following mass balances are used:
dCi ~~
d t - ~ " v j ' i r j i = 1, N c (3)
along with the initial conditions:
Ci = (' ~ at t =0. i = l . Nc (4)
where C~ is the concentration of the ith component
and the meaning of other symbols is reported in the
Notation. The oxygen mass balance and the energy
balance are not considered since all reactions are of
zeroth order with respect to oxygen and the reactor
has been operated under isothermal conditions.
In order to simulate the precipitation phenomena
of 4-carboxybenzaldehyde and terephthalic acid,
a mathematical model of a semi-batch gas liquid re-
actor where the reactions of the lumped kinetic
scheme (1) occur, is developed under the following
assumptions:
-- isothermal conditions:
kinetic regime:
---negl i bi bl c agglomeration and disruption {cf.
Wachi and Jones, 19911;
precipitation due to supersaturation of 4-car-
boxybenzaldehyde and terephthalic acid;
spherical crystals;
growth rate independent of linear crystal di-
mension (cf. Garsidc and Shah, 1980).
The mass balances for the non-precipitating species
are identical to those reported in eq. (3), while those
for precipitating species are as follows:
dC~
- k s ( " . ~ + k - ( ' - 4 k i o ( ' ~ - k , , ( " ~ - B ~ - . . G ~ { 5 )
dt
dC,,
- - - = k ~ ( ' : - B g - G~, (6)
d t
where BI and G I , i = 5 and 6 are the mass-based
nucleation and growth rate, respectively.
4208
The population balances of the precipitated par-
ticles are
~Ni G. ~Ni
?~-+ ' dL =0, i = 5, 6 (7)
where N~ is the population density of particles, G~
represents the linear growth rate, t is the time and L is
the coordinate of particle dimension. Equations (3)
and (5)--(7) are subjected to the following initial and
boundary conditions:
C~ = C o at t = O, i = l , N c ( 8)
N ~ = 0 at t = 0 , VL , i = 5 , 6 ( 9)
J i
Ni = ~ a t L= Lo. i , Vt, i = 5, 6 (10)
where J~ is the number nucleation rate and Lo.~ is the
effective nucleic dimension. Note that the boundary
condition (I0) is used by several authors (cf. Garside,
1985; Dirksen and Ring, 1991; Jones e t al . , 1992) and
may become the dominant factor of crystal distribu-
tion.
The mass-based nucleation and growth rate equa-
tions are as follows:
n ~) ~. i j i L3. i , i = 5, 6 (I I)
B~ = g
G ~ = 7zGi~s. i L 2 N i ( L ) d L , i = 5, 6 (12)
where n/6 and ~r are related to the spherical crystals,
t~.~ is the crystal density, and the corresponding num-
ber rate of nucleation and linear crystal growth rate
are expressed through the following equations (cf.
Wachi and Jones, 1991):
J i = k , . i ( Ci - C~')"', i = 5, 6 (13)
Gi = kg. i ( Ci - C * ) g', i = 5, 6 (14)
where k,.~ and k~.~ are the nucleation and growth rate
constant, respectively, ni and 9i are the orders of
nucleation and growth, respectively, and C* is the
equilibrium saturation concentration.
The governing balance equations are in the form of
a system of ordinary and partial differential equa-
tions. A backward finite-difference scheme was ad-
opted for the spatial derivative appearing in the popu-
lation balances (7) in order to obtain a set of ordinary
differential equations which are solved as an initial
value problem using standard routines. During the
computations, the value of the finite-difference points
was generally kept as 600 and the integral appearing
in eq. (12) was solved numerically using standard
routines.
RESULTS AND DISCUSSION
The first goal of this work is to establish the behav-
ior of the liquid-phase p-xylene oxidation as a func-
tion of catalyst concentration. For this we consider
the overall oxygen uptake, Uo~, defined as follows
A. Cincotti et al.
with respect to the lumped kinetic scheme (2):
Uo2 = [ C2 - C + 2 C3 + C , ] (15)
where Ci represents the experimentally measured con-
centration of the reaction products.
A plot of the quantity Uo: as a function of time for
the experimental runs 4- 6 in Table 1, where different
values of catalyst concentration have been considered,
while maintaining constant the initial p-xylene and
the p-tolualdehyde concentration, is shown in Fig. 1.
From the slopes of these curves evaluated at t = 0, the
initial value of the oxygen uptake, R~2, was computed
and plotted in Fig. 2 as a function of catalyst concen-
tration. In the same figure the p-xylene conversion
values reached in the corresponding experimental
runs at t = 60 min are also reported. It is seen that as
the catalyst concentration increases both quantities
first increase and then reach a plateau. Note that this
behavior is consistent with that reported in the litera-
ture for p-xylene oxidation to p-toluic acid catalyzed
by cobalt acetate and sodium bromine in acetic acid
as solvent (cf. Zaidi, 1986). In order to demonstrate
that all experiments were conducted under the kinetic
regime, we have performed the experimental runs 1 - 3,
where only the temperature values have been changed
with respect to run 3. The corresponding initial values
of oxygen uptake are shown in Fig. 3 as a function of
temperature. From the linear behavior of the Ar-
rhenius-like plot shown in Fig. 3, it may be concluded
that the reactor operates in the chemically controlled
regime for the specific catalyst concentration used for
runs 1-3, and, consequently, for all catalyst concen-
tration levels considered in this work, at which equal
or lower oxidation rates are found (cf. Fig. 2). The
apparent activation energy is equal to about
18 kcal/ mol, i.e. a typical value of oxidation reactions,
which compares fairly well with those reported in the
literature for p-xylene oxidation in the presence of
water (cf. Hronec and Ilavsky, 1982; Hronec et al.,
1985; Hronec and Hrabe, 1986). As expected, the
apparent activation energy is also very similar to the
one obtained by Cao et al. (1994a) under the operat-
ing conditions corresponding to run 6 of the present
work using the same experimental set-up and proced-
ure. The values of the kinetic constants appearing in
the lumped kinetic scheme (2) are then estimated by
fitting the time evolution of the experimental product
composition of run 1-8 in Table 1 through a non-
linear least-squares procedure using the model given
by eqs (3) and (4). The comparison between model
results and experimental data is shown in Figs
4(a)-(h), where it may be seen that the obtained agree-
ment is generally satisfactory. This allows us to con-
clude that the lumped kinetic scheme proposed by
Cao e t al. (1994a) retains a level of process description
detailed enough to characterize the distribution of the
most important products not only for a specific value
of the catalyst concentration, as demonstrated by Cao
e t al . (1994a, b) by varying reaction temperature and
initial concentration of liquid reactants, but also
when changing catalyst concentration levels within a
05
- - 0 2
0 {I "
I I
i
I
0
0
Catalytic oxidation of p-xylene
Run4
0 Run 5
Run 6
40 6 0 8( I ID0 [ 20 140
Tmae [rn~]
Fig. 1. Overall oxygen uptake, Uo2, as a function of time for
different temperature values: runs 4-6 in Table 1.
O0
0

0 0 0
0
R o :
O p- x y l m~ c t mve r ~ on
i r , i . t . i . i i 0 t l ~
05 i c 15 20 25 ~ o a ~
Cc. , t [ r r l ol / k l ~ / ] x 1( ) ]
0 o5
=
5
Fig 2. Initial uptake rate of oxygen, R2, and p-xylene
conversion at t = 60 min as a function of catalyst concentra-
tion: runs 3-8 in Table I.
D" [ " , ' , ' , " ,
i,
i t . .
\
L . i . l . i . , . , . i
2 .~o 2~5 2.6o 26s 2.70 2 7~ 2,~o 2s~
i / r [ KI [ x 10 3
Fig. 3. Initial uptake rate of oxygen, Rg:. as a function of
temperature: runs 1-3 in Table 1.
relatively wide range. This variable was, in fact, as-
sumed to be included in the apparent rate constants of
the lumped reactions. Moreover, from the Arrhenius
plot of the absolute value of the rate constant k~
shown in Fig. 5(a) a straight line is obtained, whose
slope provides an apparent activation energy value of
42 09
17.2 kcal/mol which is in good agreement wi th those
reported in the literature ( cf. Bang and Chandalia,
1974 for methyl-p-toluate oxidation; Chen et al . , 1985
for o-xylene oxidation). Similar plots are obt ai ned for
the reactivity ratios pj = k f i k l , j = 2-4, as shown in
Fig. 51b). As expected, the results reported in Figs 5(a)
and ( b/ are also similar to those obt ai ned by Cao et al.
(1994a) for the same system at a catalyst concent ra-
tion equal to 1 I 0 3 mol/ kgl. Thc estimated values
of k~ and the reactivity ratios pj, j = 2 4 at each
t emperat ure and cobalt napht henat e concent rat i on
value are summari zed in Tables 2 and 3, respectively,
together with the average percentage error, r/, arising
from the fitting procedure. The paramet er values cor-
responding to C~a, = 1 x 10 3 mol:kgt compare very
well with those obtained by Cao et al. 11994aL
From the values of the kinetic constants k a, k2 and
k4 rcported in Table 3, it may be seen that a similar
behavior to that reported in Fi g 2 for the case of
initial oxygen uptakc is found. This is also true for the
kinetic constant k 3 only for a certain range of catalyst
concentration. Thus, the kinetic of reaction of the
lumped kinetic scheme 121 may be assumed to be not
only zeroth and first order with respect to oxygen and
the liquid reactant, respectively, as previously demon-
strated {cf. C a o et al., 1994a, b), but also as dependent
upon catalyst concent rat i on t hrough a f unction to be
evaluated, i.e. rj = k J ) [ t C~ , J C, e x p { - E / R T I , where
C~ is the concent rat i on of the ith component in the ith
reaction. Al t hough at this stage an empirical function.
f ( C~ , , L can be obtained, it should be noted that the
assumed expression of the reaction rate is in good
agreement with the correspondi ng expressions avail-
able in the literature for the consumpt i on rate of
substrate and oxygen during cobalt catalyzed oxida-
tion of toluene in acetic acid ( of . Hanot i er and
Hanot i er-Bri doux. 1981), wherc the complex radical
chain mechanism, typical of homol yt i c oxidations, has
been account ed for. Not e that the f unction f(C,,,I has
been also assumed, in the literature, to cont ai n cobal-
tic and the cobal t ous ion concentration, accordi ng to
the presence of a monomer - di mer equilibrium of co-
baltic acetate. However, since detailed radical chain
mechanisms cannot be used for simulating gas liquid
reactors, as discussed in the introduction, the estab-
lished dependence of the rate of each reaction of the
lumped kinetic scheme (2J on catalyst concent rat i on
may have a clear practical value.
Let us now consider the behavi or of a semi-batch
gas-l i qui d reactor where the p-xylene oxi dat i on to
terephthalic acid occurs together with co-precipita-
tion of the latter one and the 4-carboxybenzaldehyde.
The model equat i ons (3)-I 14) contain a large number
of physico-chemical parameters, which, unf ortunate-
ly, are not available in the literature for our reacting
system with the exception of the kinetic constants of
the lumped kinetic scheme I1) which are taken from
Cao et al. (1994bt and correspond to a t emperat ure
of 120C and a catalyst concent rat i on equal to
1 10 3 mol/kg~. To overcome this difficulty and
with the aim of theoretically demonst rat i ng that the
4210 A. Ci ncot t i et al.
020
O~
O~
~~
~ D I
O 08
0.04
0 02,
0 00~
' ' " ' ' ' " ( "a) " '
o p-xylene conversion
[ ] p-ml ml dehyde
O p4o~ c
A p401~
moddfit
n ~ r~ ~ ~ n ~ []

l . I , I , I , i
~0 DO ~ 200 2 ~ ~
Tune {mini
1
os [- O p-x' yla~conv~Aon (b)
| o /
I 0 p-toluicackl ^ /
~~
Ol ^
0 . 0 4 ( I bO gO ~ [20 J40
TLme [ram]
05
0.4
~ 0 2
0
040
O35
{ ) 3 0
025
~
020
" o~
~
o ~ r
005
05
04
" i 0. 2
0c ~
, | ! , i
0 p -xy k ne convm~ion (c)
o p-totualdd~ yde / A
0 p-tOhaic acid
A p-tOhfic ~ / . ~
2 0 30 4 0 5O 6O
Time [mini
i , w , 1 , i i
O p-xyl ene oonversi(m (e)
o pqo~kid~yd~ /
0 p-tOl~C~td
I0 2 0 30 40 ~ ) 6 0
Tune [rain]
i i i i
0 p-xyl ene o~ v ers i on (g)
0 p - t o h ~ d e
0 p-toluic acid ~
/X p-tOhfic aloohol
modd fit
I ) 2 0 30 4 0 50 60
T m - , e l m i n l
0 5
04
i 02
Ol
o o:
i . i - i , i , ,
o p-xyl ene conv ~ si on ( d) -
o p- t o~ ak l ehyde /
0 pltOluic acid
20 4 0 6 0 80 1OO RO 0
Time [mini
,
"~ 02
o~
0 p-X ylene oonv~ rsion ( f)
n p4 oluddehyde
0 p -toluic acid O/ / /
A pqolt~ak~ho4
I O 2 0 3 0 40 N) 6U
" r um [nunl
LO i , , , ' , '
' 0 p -x-y k n e cmvo'sion (h)
o s ~- D p-tolualddlyde J
I o p - t a , ~
~ [ ~ p - t a ~ a o a ~ /
6
o 2 0 4 0 6 0 80 IOO 120
T une [mini
Fig. 4. Cauatedvsexperimentavauesfprductcncentratinandp-xylenecnversinasafunctinf
t i me f or var i ous t emper at u r es and cat al yst concent r at i ons: r u ns I(a)--8(h) in Tabl e 1.
Catalytic oxidation of p-xylene 4211
Table 4. Parameter values for the model given by eqs
13)-(14)
n
(a~
- ' ~ Parameter Value
(' ~ 6 x 1(1-6 mol..'kg~ )
~ C* 6 x 10 -~' mol:'kg~*
_E ~ C'? 4.0 mol.'kg~
- " C 0 . 1 1 mol kg[
~ , qs 2.0*
~ ~ ~-h, 1.0"
k~ 2.118x10 . s ~ '
k: 8.56x 10-4. s '
I I I I t I i I , I
250 2 55 26 0 26 5 270 2.75 28 0 2.85 k 3 4. 94 10 -4 s '
I/TIK.I] x 103 k 4 1.6x 10 5. ' s'
ks 7.5 x 10-%s'
k~, 1.83 x 10-4.s *
' k , 6.68 x 10 ' a s'
no~ (b) k~ 1.8 x 10 ""s'
k,~ 4.83 x 10 -~' s'
11- - - - - 41.
O----------& ..... kto 1.65 x 10-' L' s '
=.~ O kq.s 8.0 x 10 " ~*
" kq.~, 8,0 x 10 ~o.
P : k,.5 6.0 x 10 '~*
.~ 0 p~ k,,.6 5.0 x 104.
,~ p.~ Lt).5 1.0x 10-:m~*
" Lo.~> 1.0 10 "" m,*
........ ~ fi~. s 9360 mol.'m 3:
fi~.. 9350 mol..m~
I I I I , I I I
50 2 55 26 0 265 270 2.75 2 8O : . 85 *See text for c omme nt s .
l[ rlK-q x 103 ' Fr om Cao e t al . 11994b).
: From Lange 11973).
Fig. 5. Arrhenius plots for the reaction rate constant k~ (a) ' From Perry and Green 11984).
and reactivity ratios Ps, P3 and P4 (b) of the lumped kinetic
scheme (2) at C,~, = 5.0 x 10" mo ..'kg~. model devel oped pr oper l y accou nt s f or t he i nt er ac-
t i on b et ween chemi cal r eact i on and pr eci pi t at i on phe-
nomena, we cons i der t he model par amet er s su m-
Table 2. Numerical values of the Arrhenius parameters of mar i z ed in Tab l e 4. Not e t hat s ome of t hem, i.e.
* and Lo 6, are t ak en f r om t he l i t er at ur e
the reactivity ratios for the reactions of the lumped kinetic C5, Co, Lo.5
scheme (1) at C:,, = 5 x 10 4 mol/ kgl, pj = k j , . ' k l , where (cf. Wachi and J ones, 1991) even if t hey do not ref er
k t = .4~ e x p( - E ~ . R T )* specifically t o ou r system. F or t he par amet er s r el at ed
to t he l i near gr owt h and nu mb e r nu cl eat i on rat es, we
Reaction pj (110 Ct t AEj = Ej - E~ select t he val ues r epor t ed in Tab l e 4 so t hat t he
{kcal/mol) q u ant i t i es ab ove fall wi t hi n t he qui t e l arge r ange re-
2 46.27 0.83 por t ed in t he l i t er at ur e f or r eact i on pr eci pi t at i on sys-
t ems (cf. Gar si de, 1980).
3 34.46 4.67
4 ('1.871 6.21 The t i me b ehavi or of t he speci es p-xyl ene, p- t ol ui c
al cohol , p- t ol u al dehy de, t er epht hal i c al dehy de, p-t ol -
At = 3,620.000/min; E~ = 17.2 kcal/mol, uic aci d and 4- car b ox y b enz y l al cohol , is not r epor t ed
" p f l T ) = p~ 1110 C) exp[ - AEi(1.' T - 1/383); R]. si nce t hey do not u nder go pr eci pi t at i on phe nome na
Table 3. Estimated values of the kinetic parameters of the lumped kinetic scheme (21 as
a function of catalyst concentration
C,~, (mol/kg~) x 104 kl (per min) x 10'* P: Ps P4 ~1(%1
1.67 4.38 71.2 59.8 1.6 6.5
2.67 7.04 69.2 71.4 1.8 4.2
5.0 11.3 45.7 35.0 1.1 1.1
10 12.7 39.2 27.4 0.9 2.7
15 l l . l 41.8 41.6 1.1 2.2
33.3 11.0 44.7 45.0 1.1 4.6
4212
" L
o_ =
8
f:.
, , " ~ . . . . - -
,.' .
;, , L ,
2
A. Cincotti et al .
010 ~"
O05
i
o~ ~
Fig. 6. Comparison between theoretical 4-carboxybenz-
aldehyde and terephthalic acid concentration time profiles
with (solid line) or without (dashed line) precipitation.
and depend only upon chemical reaction on the basis
of the kinetic scheme (1). As expected, all these species,
except for p-xylene, which is continuously consumed,
go through a maximum and eventually disappear
from the solution. On the other hand, the effect of
precipitation phenomena involving 4-carboxybenz-
aldehyde and terephthalic acid may be clearly seen in
Fig. 6 which shows the time profiles of these two
species if their precipitation is neglected, i.e.
B' I = G~ =0 in eqs (5) and (6), respectively, or taken
into account. In general, it may be noted that the time
profile of the two species when precipitation is ac-
counted for by the model lies below those correspond-
ing to the case when precipitation is not considered. B~
In particular, 4-carboxybenzaldehye displays the
same qualitative behavior in both cases. This is be- (?'c~t
cause it behaves as an intermediate species and thus it C,
is expected to first increase up to a maximum value
and then decrease when consumption rate prevails. C *
The latter one is clearly enhanced when precipitation
also occurs. When considering the terephthalic acid Ej
behavior, it is seen that its concentration increases,
eventually reaching a plateau if precipitation phe- 9~
nomena are not accounted for, since it is the only
non-reacting species according to the kinetic scheme G~
(1). On the other hand, by taking precipitation into
account in our model, terephthalic acid is not only G~
formed by chemical reaction but also precipitates
simultaneously, when its solution concentration ex- ko.i
ceeds the corresponding saturation value, so that the
concentration profile shows a maximum in time. kj
Although the proposed model is able to properly k,.~
simulate the time course of the crystal size distribution
of 4-carboxybenzaldehyde and terephthalic acid, we do j~
not report the corr~pondi ng results in this work for
lack of knowledge of the appropriate model para- L
meters rclated to the precipitation phenomena in- Lo.~
volved in our system. Suitable experimental studies are
certainly needed in order to evaluate these parameters. ~,~
N~
NR
C ONC LUDI NG REMARKS
In this paper, we present both experimental and
theoretical work related to the catalytic liquid-phase
oxidation of p-xylene.
In the experimental part, the effect of catalyst con-
centration on product distribution and kinetic con-
stants of the lumped kinetic scheme proposed by Cao
e t a / . (1994a) is investigated. It is concluded that this
lumped kinetic scheme retains a level of process de-
scription detailed enough to characterize the distribu-
tion of the most important products when changing
catalyst concentration levels within a relatively wide
range. Experimental reaction studies to demonstrate
the effect of varying the catalyst to promoter, i.e. p-
tolualdehyde, ratio are currently in progress.
In the theoretical part, a semi-batch reactor model,
which accounts for the presence of the reactions of the
lumped kinetic scheme proposed by Cao e t a l . (1994b)
and precipitation phenomena of 4-carboxybenzal-
dehyde and terephthalic acid, is developed, it is shown
that the time profiles of these species display a max-
imum whose value depends upon the relative magni-
tude of the rates of reactions where these species are
involved and the precipitation parameters. The model
may provide a useful tool for the simulation of
gas-liquid oxidation reactors of p-xylene to tereph-
thalic acid. The problem of accounting for intra- and
interphase mass transfer resistances when simulating
precipitation phenomena occurring in complex reac-
tion systems of the type considered in this work is
currently being investigated.
NOT AT I ON
mass-based nucleation rate of the ith pre-
cipitating component, mol kg i ~ s- 1
catalyst concentration, mol kg i
concentration of the ith component,
mol kgf t
equilibrium solubility of the ith precipitating
component, mol kg7 t
activation energy of the j t h reaction,
cal mol - t
order of growth of the ith precipitating com-
ponent
linear growth rate of the ith precipitating
component, m, s- 1
mass-based growth rate of the ith precipita-
ting component, mol kg/ ~ s-
growth rate constant of the ith precipitating
component
rate constant for the j th reaction, mi n- t
nucleation rate constant of the ith precipita-
ting component
number nucleation rate of the ith precipita-
ting component, kg~- t s
coordinate of particle dimension, ms
effective nucleic dimension of the ith precipi-
tating component, m,
order of nucleation of the ith precipitating
component
number of components in the system
population density of particles of the ith
precipitating component, kg~- 1 m~- t
number of reactions in the system
Catalytic oxidation of p-xylenc
pj reactivity ratio, k~,.'k~
r~ rate of the j th reaction, mol kg{ ~ min
R{)): overall initial oxidation rate, mol kgi j
rain
t time, s
T temperature, K
Uo: overall oxygen uptake, tool kg[
Greek letters
AEj E~ - Et , cal mol-
~1 average percentage error
rj., stoichiometric coefficient of the ith compon-
ent in the j th reaction
t~.~ crystal density of the ith precipitating com-
ponent, mol m~ ~
r dimensionless time, t k~
Subscripts
i component index
j reaction index
I liquid phase
s solid
Superscript
0 initial conditions
REFEREN CES
Aslund, B. L. and Rasmuson, A. C. (1992) Semibatch
reaction crystallization of benzoic acid, A.I.Ch.E.J.,
38, 328.
Bang, S. R. and Chandalia, S. B. (1974) Liquid phase
oxidation of methyl-p-toluate to monomethyl
terephtalate. Ind. Chem. Enyn9, 16, T92.
Cao, G., Servida, A., Pisu, M. and Morbidelli, M.
(1994a) Kinetics of p-xylene liquid-phase catalytic
oxidation. A. I. Ch. E. J. 40, 1156.
Cao, G., Pisu, M. and Morbidelli, M. (1994b) A lum-
ped kinetic model for liquid-phase catalytic oxida-
tion of p-xylene to terephthalic acid. Chem. Engng
Sci., 49, 5775.
Carr'a, S. and Santacesaria, E., (1980) Engineering
aspect of gas--liquid catalytic reactions. Catal. Ret'.-
Sci. Enyng, 22, 75.
Cavalieri d' Oro, P., Danoczy, E. and Roflia, P. (1980)
On the low temperature oxidation of p-xylene. Oxi-
dation Commun., 1, 153.
(' hen, Z., I,i, G., Li, W., Dai, L., Niu, Y,, Hu, J., Gu, J.,
Mao, X. and Li, M. (1985) The kinetics of the
oxidation of o-xylene. Int. Chem. Engng, 2:5, 738.
Dirksen, J. A. and Ring, T. A. (1991) Fundamentals of
crystallization: kinetic effects on particle size distri-
butions and morphology. Chem. Engng Sci., 46,
2389.
Emanuel, N. M. and Gal, D. (1986) Modelling of
Oxidation Processes. Akademiai Kiado, Budapest
Garside, J. and Shah, M. B. (1980) Crystallization
kinetics from MSMPR crystallizers. Ind. Engng
Chem. Process Des. Dev., 19, 509.
Garside, J. (1985) Industrial crystallization from solu-
tion. ('hen1. Engng Sc/. 40, 3.
4213
Hanotier. J. and Hanotier-Bridoux, M. (19811 Mecha-
nism of the liquid phase homogeneous oxidation of
alkylaromatic hydrocarbons by cobalt salts. J. Mol.
Catal. 12, 133.
Hronec, M. and llavsky, J. (1982) Oxidation of poly-
alkylaromatic hydrocarbons. 12. Technological as-
pects of p-xylene oxidation to terephthalic acid in
water. Ind. Engng Chem. Prod. Res. Dev.. 21. 455.
Hronec, M.. Cvengrosova, Z. and llavsky, J. (1985)
Kinetics and mechanism of cobalt-catalyzed oxida-
tion of p-xylene in the presence of water, hld. Engng
Chenl. Proc. Des. Det'., 24. 787.
Hronec, M. and Hrabe, Z. (1986) Liquid-phase oxida-
tion of p-xylene catalyzed by metal oxides. Ind.
Engng Chent. Prod. Res. Dev., 25, 257.
Jones, A. G.. Hostomsky, J. and Li, Z. (1992) On the
effect of liquid mixing rate on primary crystal size
during the gas liquid precipitation of calcium car-
bonate. Chem. Engng Sci., 47, 3817.
Kamiya, Y. and Kashima, M. (1972) The autoxidation
of aromatic hydrocarbons catalyzed with cobaltic
acetate in acetic acid solution, d. Catal. 25, 326.
Kamiya, Y. (1974) Catalysis by cobalt and bromine
ions in the autoxidation of alkylbenzenes in acetic
acid. d. Catul. 33. 480.
Krzysztoforski. A., Wojcik, Z., Pohorecki, R. and Bal-
dyga, J. (1986) Industrial contribution to the reac-
tion engineering of cyclohexane oxidation. Ind.
Engng Chem. Process Des. Dev., 2:5, 894.
Lange, N. A. 11973) Lange's Handbook of ('hemistry,
ed. J. A. Dean. McGraw-Hill, New York. U.S.A.
McElroy Brown, P. and Myerson, A. S. (1989) The
growth, dissolution and aging of terephthalic acid
crystals. A.I.Ch.E.J., 35, 1749.
Morbidelli, M., Paludetto, R. and Carra. S. (1986)
Gas liquid autoxidation reactors. Chem. Engng
Sci.. 41, 2299.
Perry. R. H. and Green, D. {1984) Perry's Chemical
Engineers" ltandhm)k. McGraw-Hill, New York,
U.S.A.
Raghavendrachar, P. and Ramachandran, S. (1992)
Liquid-phase oxidation of p-xylene. Ind. Engng
Chem. Res. 31,453.
Scott, E. J. Y. and Chester, A. W. (1972) Kinetics of the
cobalt-catalyzed autoxidation of toluene in acetic
acid. The role of cobalt. J. Phys. Chem., 76, 1520.
Sheldon. R. A. and Kochi. J. K. (1981) Metal
Catalyzed Oxidation of Organic Compounds. Aca-
demic Press. New York, U.S.A.
Viola. A. and Cao, G. (1996) A rapid direct analysis of
p-xylene oxidation products by reverse phase
HPLC. J. Chromatogr. Sci., 34, 27.
Wachi, S. and Jones, A. G. (1990) Model calculations
of precipitation with gas-liquid rapid chemical re-
action. Industrial Crystallization 90, ed. A. Mers-
mann, pp. 229 235. GVC-VDI, Dfisseldorf.
Wachi, S. and Jones, A. G. {1991) Mass transfer with
chemical reaction and precipitation. Chem. Enqng
Sci., 46, 1027.
Zaidi, S. A. H. (1986) Liquid phase oxidation of p-
xylene to p-toluic acid. Appl. Catal.. 27, 99.