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Catalytic Liquid Phase Oxidation of Toluene to Benzoic Acid Ad

Article (PDF Available) in Chemical Engineering & Technology 31(3) · March 2008 with 924 Reads
DOI: 10.1002/ceat.200700140

Cite this publication

Ali Gizli
Guelin Aytimur
3.03 · Ege University

Erden Alpay Süheyda Atalay

16.87 · Ege University 26.16 · Ege University

Abstract

The production of benzoic acid from toluene in the liquid phase with pure oxygen was studied. Investigations have been carried out with a
view to determining the most suitable reaction conditions with respect to operating variables including oxygen flow rate, reaction
temperature, batch time and catalyst loading. In a series of batch experiments carried out at 4 atm, the optimum values of mole ratio of
oxygen to toluene, temperature, reaction time, and catalyst loading were found to be 2, 157 °C, 2 h and 0.57 g/L, respectively. In addition,
a kinetic study was carried out by taking into consideration the optimum reaction conditions. The model dependent on the formation of
benzyl radical was found to be feasible for describing the catalytic oxidation of toluene to benzoic acid in the liquid phase. The activation
energy was determined as 40 kJ/mol.

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Figures - uploaded by Erden Alpay Author content

+1

Experimental Set-up. . Experimental conditions. The dimensions of the sparger . Results of experiments.
and bubble reactor.

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Chem. Eng. Technol. 2008, 31, No. 3, 409–416 409

Ali Gizli1 Research Article

2
Gülin Aytimur
Erden Alpay 2
2
Catalytic Liquid-Phase Oxidation of Toluene
Süheyda Atalay
to Benzoic Acid
1
Akzo Nobel Kemipol,
Kemalpasa, Izmir, Turkey.
The production of benzoic acid from toluene in the liquid phase with pure oxy-
2
Ege University, Chemical gen was studied. Investigations have been carried out with a view to determining
Engineering Department, the most suitable reaction conditions with respect to operating variables includ-
Izmir, Turkey. ing oxygen flow rate, reaction temperature, batch time and catalyst loading. In a
series of batch experiments carried out at 4 atm, the optimum values of mole ra-
tio of oxygen to toluene, temperature, reaction time, and catalyst loading were
found to be 2, 157 °C, 2 h and 0.57 g/L, respectively. In addition, a kinetic study
was carried out by taking into consideration the optimum reaction conditions.
The model dependent on the formation of benzyl radical was found to be feasible
for describing the catalytic oxidation of toluene to benzoic acid in the liquid
phase. The activation energy was determined as 40 kJ/mol.

Keywords: Benzoic acid, Catalysis, Liquid phase, Liquid-Phase Oxidation, Oxidation

Received: April 16, 2007; accepted: December 17, 2007
DOI: 10.1002/ceat.200700140

1 Introduction process. In these studies, the diversity of reaction products

such as benzoic acid, benzaldehyde and benzylalcohol can be
Benzoic acid and its salts and esters are used in medicines, ve- seen to depend on the operating conditions and the catalysts
terinary medicines, industrial raw materials, preservatives for used [9–11].
food, cosmetics, resin preparations, plasticizers, dyestuffs, syn- One of the oldest studies is based on the research performed
thetic fibers, and intermediates [1–4]. Benzoic acid can be pro- by Bhattacharya et al., in which research has been carried out
duced by the catalytic oxidation of toluene in both vapor and on the process for the production of benzoic acid from the air
liquid phases. The vapor-phase oxidation of toluene by air or oxidation of toluene in a semi-continuous reactor, on a heavy
oxygen has been studied by many researchers with the aim of metal ion based catalyst such as cobalt or manganese, at a tem-
finding conditions and catalysts for the selective oxidation to perature in the range of 120–150°C and at 10 atm [12].
benzaldehyde or benzoic acid [1, 5, 6]. Borgaonkar et al. studied the liquid-phase oxidation of tolu-
Kaszonyi studied the oxidation of toluene by air with the ene to benzaldehyde by air and searched for the effects of var-
aim of increasing the selectivity of toluene oxidation by chang- ious process parameters, e.g., temperature, period of reaction,
ing the concentration and the ratio of active sites on vanadium pressure and concentrations of the species, catalyst, and pro-
based catalysts [7]. Antol investigated the reaction parameters, moter, on the overall conversion and yield of benzaldeyde
additives and co-oxidants on the selectivity of toluene oxida- [13]. In another study, the simultaneous production of ben-
tion to benzoic acid in the vapor phase [8]. zoic acid and benzaldeyde by liquid-phase oxidation of toluene
The liquid-phase oxidation of toluene with air in the pres- in the presence of cobalt acetate catalyst was investigated [14].
ence of a homogenous or emulsified cobalt catalyst is the pro- In the studies performed recently, the types of the catalysts
cess used for the commercial production of benzoic acid. Man- used for the liquid-phase oxidation of toluene have shown
ganese catalysts are also effective, but less so than cobalt salts. more diversity compared to previous studies. Chromium sili-
These may be water soluble, e.g., cobalt acetate or oil soluble, calite, vanadium silicalite, iron on c-alumina, mesoporous nio-
e.g., naphthenate, stearate, hexanoate, etc. [1]. Various studies bium-silica and niobium-cobalt silica, bismuth oxide impreg-
on the liquid-phase oxidation of toluene with air have been nated on ZSM-5, Mg-Mn-Al ternary hydrotalcite-like layered
performed to optimize the operating conditions affecting the hydroxides, uranium containing silica mesoporous molecular
sieves have all been used recently as catalysts for the process
[10, 11, 15–18]. In addition, in some of these studies, it was
– observed that the replacement of oxygen by hydrogen peroxide
Correspondence: G. Aytimur (gulin.aytimur@ege.edu.tr), Ege Univer-
as the oxidizing agent was useful [10, 15, 16]. However, it is
sity, Faculty of Engineering, Chemical Enginnering Department, 35100 known that pure oxygen is preferred as the oxidizing agent
Bornova, Izmir, Turkey. since it results in higher conversion, lower operating pressure

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

410 A. Gizli et al. Chem. Eng. Technol. 2008, 31, No. 3, 409–416

and initial costs, and a higher energy saving. Therefore, the de- vated pressures are required and the benzoic acid produced is
velopment of a process for toluene oxidation to benzoic acid a corrosive material, the reactor is a stainless steel cylindrical
with pure oxygen is very important. vessel having an available volume of 7 L. The dimensions of
It was also reported in the literature that the oxidation reac- the reactor are 108 mm inside diameter and 760 mm in height
tion of toluene proceeded by a free radical mechanism and was with a 10 mm jacket surrounding the reactor. The related di-
characterized by an induction period, probably representing mensions considering both the reactor and the sparger are il-
the time required to form a benzyl radical [1, 19]. The reaction lustrated in Fig. 2. The pure oxygen enters the reactor through
is a complex system in which chemistry, kinetics, thermody- the sparger, which is a disc and deepened 724 mm into the re-
namics, transport processes and hydrodynamics all play an im- actor. There are many holes of 2 mm diameter in the disc
portant role [19]. through which pure oxygen bubbles out at high speed, which
The main objective of this study was to investigate the liquid ensures proper agitation. The thermocouple well is a straight
phase oxidation of toluene to benzoic acid by using pure oxy- stainless steel tube with a sealed bottom, and it extends to the
gen with a cobalt stearate catalyst. This aim, with the inclusion bottom of the reactor. It is used to measure the temperature of
of experimental data on toluene oxidation, was achieved by de- the reaction mixture. The temperature in the reactor was con-
termining the optimum process parameters such as tempera- trolled by cold water and hot oil, both circulating in the jacket
ture, pressure, oxygen flow rate, loading of catalyst and time of in different channels. The flows of both liquids were controlled
reaction. In addition, the kinetics of the reaction was investi- by the gate valves, i.e., V 4 and V5 for the cold water and V8
gated by using the data obtained for a series of experiments at and V9 for the hot oil, see Fig. 1.
different temperatures. The mechanism and the rate constant The ball valve, V3, is used to charge toluene and catalyst dis-
of the reaction were also determined. solved in toluene, to the reactor. The product was taken from
V7 on the bottom of the reactor. The flow rate of pure oxygen
supplied from the cylinder is adjusted by V10, which is a needle
2 Experimental valve and there is a rotameter to measure the flow rate of gas
positioned just following it. The effluent from the reactor en-
2.1 Experimental Setup ters the stainless steel condenser, which is cooled by cold water.
The flow rate of cooling water is adjusted by the gate valve V11.
The flow diagram of the experimental setup is shown in Fig. 1. This condenser is fixed with a slope so that the condensate
The setup can be considered as consisting of mainly reactor could easily flow to the decanter without any accumulation.
and cooling sections. Compressed pure oxygen from a cylinder The vapor phase leaving the first condenser flows to the second
with a pressure control adaptor flows to the reactor. Since ele- one, which is cooled by a chilled alcohol solution circulating

Figure 1. Experimental Set-up.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

Chem. Eng. Technol. 2008, 31, No. 3, 409–416 411

ture. Hot oil was used at various set temperatures to achieve

this temperature, depending on the experimental conditions.
The cold water used in condenser (2) was provided by a cool-
ing tower.

2.4 Catalyst Preparation

Cobalt stearate catalyst was prepared from cobalt hydroxide

(Co(OH)2) and stearic acid (C 17H35COOH). Stoichiometric
amounts calculated according to Eq. (1) below, were weighed.
Firstly, stearic acid was heated in a water bath up to the point
where complete melting was observed. Cobalt hydroxide was
added to the molten stearic acid and mixed well. The mixture
was heated until a dark purple-brown color was obtained.
Then the mixture was further heated to ca. 230 °C, where the
water was evaporated and a hard-solid catalyst was obtained.

Co(OH)2 + 2C 17H 35COOH → Co(C17H35COOH) 2 + 2H2O

(1)

The solid catalyst was granulated to fine powder form and

was ready for use after sieving. The catalyst obtained was
weighed depending on the experimental conditions and was
dissolved in toluene, which could be charged to the reactor.

Figure 2. The dimensions of the sparger and bubble reactor. 2.5 Experimental Procedure

The temperature of the cooling circulation bath was set before

through the tubes. Both condensates are collected in the same charging the toluene to the reactor, and the cooling tower and
decanter. The decanter is made of stainless steel, in which grav- hot oil systems were switched on. The system was left un-
itational separation takes place. This unit is charged with 7 L touched until the hot oil temperature reached the desired reac-
of toluene (full volume) from valve V 13 before heating the sys- tion temperature. Then, ca. 7 L of toluene was charged to the
tem and starting the reaction. The upper layer, i.e., toluene, re- decanter and it was completely filled until toluene was ob-
turns to the reactor by gravity, whereas the lower layer, i.e., served to overflow from the decanter into the reactor. Al-
water, is discharged at the end of each run. though the volume of the reactor was 7 L, it was charged with
3.5 L of toluene, in which a certain amount of cobalt catalyst
was dissolved. Next, the hot oil input and output valves were
2.2 Materials turned on to heat the reactor. Beforethe system reached the re-
action temperature, the pressure was allowed to build up to
Since this study is concerned with the mechanism and the reac- desired value of 4 atm and maintained at a constant value, by
tion rate, great care was taken in the preparation of the materials adjusting the exit valve at the top of the pressurized cylindrical
used in the investigation. Sulfur free toluene (C7 H8), provided tube. The temperature of the reactor was measured with a
by PETKIM, a petrochemical company located in Aliaga, Izmir, thermocouple inserted in a thermowell. After the desired pres-
was carefully distilledand the fraction boiling at 110°C was used sure and temperature were attained, pure oxygen was allowed
in the investigation. Pure oxygen was provided from GÜNES to flow through the reactor at a fixed rate. Care was taken to
Company, a local gas supplier in Izmir, in cylinders with a vol- maintain constant temperature and pressure in the reactor.
ume of 8 m 3. The cobalt stearate catalyst was prepared in the The reactor pressure and temperature were controlled within
laboratory by reacting cobalt hydroxide and stearic acid at a tem- ± 0.1 atm and ± 2 °C, respectively. During the reaction, the
perature of 230 °C, as described below. Analytical reagent grade temperature, pressure and gas flow rate were checked at
sodium hydroxide was used for the determination of the concen- 5–10 min intervals.
tration of benzoic acid in the reactorat the end of the each run. When the desired batch time was completed, the hot oil sys-
tem was shut down after closing the oxygen valve, and the re-
actor was cooled by cold water coming from the cooling tower
2.3 Utilities and then the pressure was gradually released. The system was
left untouched until the temperature reached a certain value
In order to start the reaction in the oxidation of toluene, the above the freezing point of benzoic acid. Hence, the product
bubble reactor has to be heated to a predetermined tempera- can be obtained in the liquid phase without freezing.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

412 A. Gizli et al. Chem. Eng. Technol. 2008, 31, No. 3, 409–416

During the reaction, the vapor leaving the reactor was sepa- Table 1. Experimental conditions.
rated from the non-condensable gas stream with a condenser.
The condensate returning to the decanter separated into two Experiment No. Batch Mass of Co 2+ Temperaturea Flow Rate
Time(h) (g) (°C) (L/h)
layers, i.e., a lower aqueous phase and an upper toluene phase.
The toluene phase was continuously returned to the reactor by 1 3 0.188 170 212
overflow. The water phase was removed from the decanter at
2 3 0.188 170 397
the end of the reaction and measured.
3 3 0.188 170 551
4 3 0.188 152–153 397
2.6 Analysis
5 3 0.188 157–158 397
Samples of 1 mL were taken from the reaction mixture and 6 3 0.188 165 397
placed in two different flasks. For benzoic acid in the decanter
which escapes from the reactor during the reaction because of 7 3 0.376 152–153 397
low pressure, it is also necessary to take 1 mL samples from 8 3 0.376 160–161 397
the decanter and place it into two other flasks. A certain
9 1 0.188 152–153 397
amount of pure alcohol and five drops of phenolphthalein
were added. The titration proceeded with 0.1 N NaOH until a 10 1 0.188 157–158 397
pink color was observed. The consumption of the titrant was 11 1.5 0.188 152–153 397
then recorded.
Benzoic acid taken from the reactor was compared with 12 1.5 0.188 157–158 397
standard industrial products by analysis with FTIR. The com- 13 1.5 0.188 163 397
parison showed that the experimental product was similar to
the industrial product. 14 2 0.188 152–153 397
15 2 0.188 157–158 397
16 1 0.376 152–153 397
2.7 Experimental Conditions
17 2 0.376 152–153 397
The experiments carried out using the reaction conditions a
listed in Tab. 1. In all runs, the mass of Co2+ in g expressed as P = 4 atm.
0.188 g corresponds to 2 g cobalt stearate catalyst. Therefore,
1 g and 4 g cobalt stearate catalysts contain 0.094 g and
Table 2. Results of experiments.
0.376 g of Co 2+ , respectively.
Experiment No. Conversion %

1 17.52
3 Results and Discussion
2 39.15
The concentration of benzoic acid in the reactor was calculated 3 44.00
using titration analysis. The conversion is calculated by using
4 31.50
Eq. (2):
5 43.69
mass of benzoic acid produced=MWBA
%conversion  × 100 6 45.34
mass of toluene charged=MW toluene
(2)
7 32.55
8 48.53
Tab. 2 lists the calculated conversion values for each experi-
ment. Figs. 3–7 show the results of the experiments in which 9 21.69
the effect of the parameters such as pure oxygen flow rate, 10 25.51
temperature, reaction batch time, and catalyst loading, are in-
vestigated. 11 24.92
12 32.87

3.1 Process Variables Investigation 13 33.65

14 31.30
Experiments were conducted to investigate the effect of a par-
15 39.65
ticular variable while maintaining all other variables constant.
The experimental data plotted in the figures or presented in 16 18.36
the tables are the averages of at least three runs performed un-
17 29.12
der the same conditions.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eng. Technol. 2008, 31, No. 3, 409–416 413

3.2 Effect of Oxygen Flow Rate on the 60

Production of Benzoic Acid
50
Fig. 3 shows the percentage conversion as a func-
Conversion(%)

tion of pure oxygen flow rate in L/h. It is observed 40

from Fig. 3 that the conversion increases with the
flow rate of oxygen, and reaches a maximum at a 30 2 g catalyst
4 g catalyst
flow rate of 551 L/h, where it is evident that the
20
maximum value for benzoic acid conversion is
44%. However, the curve reaches a plateau at an 10
oxygen flow rate of 397 L/h. It can be concluded
that the oxygen flow rate of 397 L/h is the opti- 0
mum value from an economic viewpoint. Further 150 155 160 165 170 175
batch reaction tests were performed at this flow
Temperature(ºC)
rate.
The increased conversion can be attributed to Figure 4. Effect of reaction temperature on conversion to benzoic acid.
the increased interfacial area available for mass
transfer. The increased interfacial area results in
higher conversion since it facilitates bubbling at higher ture of ca. 160°C. If the temperature was further increased, it
flow rates. The reason for reaching a plateau at a flow rate of would be difficult to hold the benzoic acid in the reactor be-
397 L/h may be due to the reaction kinetics being the rate de- cause of the low pressure. In addition, Fig. 5 shows that there
termining step above 397 L/h, although the rate may be con- is no remarkable gain in conversion at temperatures above
trolled by mass transfer at flow rates below this value. 160 °C.

3.3 Effect of Reaction Temperature 3.4 Effect of Batch Time

The effect of temperature on the production of benzoic acid is Fig. 6 shows the conversion to benzoic acid while using two
shown in Fig. 4. The batch tests were performed at five differ- different amounts of catalyst and two different temperatures at
ent temperatures and with two different amounts of catalyst. various batch times. The results indicate that there is no signif-
By disregarding the results with 4 g of catalyst, the most rapid icant increase in conversion over 2 h batch times.
approach to high conversion, which is 43.7 %, was attained at
ca. 157 °C with 2 g of catalyst. The conversion decreases to
39 % at 170 °C. It will be shown with the reaction mechanism 3.5 Effect of Catalyst Loading
proposed in the following section, that the reactions are revers-
ible. Increments in conversion brought about by temperature The effect of catalyst loading on the production of benzoic
rises impose kinetic control on the reaction. However, the de- acid can be followed by the results presented in Tabs. 1 and 2.
crease in conversion after a certain point shows that the reac- A quantity of 1 g of catalyst was used in the preliminary
tion might be controlled by equilibrium. experiments. However, no product was detected when this
Further data to see the effect of temperature for the produc- quantity of catalyst was used. According to further results, it
tion of benzoic acid can also be found in Tabs. 1 and 2. It is is clear that the optimum value for the amount of Co stearate
shown that the maximum conversion is obtained at a tempera- is 2 g.

50 3.6 Kinetic Study

45 Temperature:170ºC
Pressure: 4 atm Many variables may affect the rate of a chemical
40 Catalyst:2g. cobalt stearate
35 reaction. In homogenous systems, the temperature,
Conversion(%)

Batch Time: 3h
30 pressure, composition and catalyst are obvious
25 variables. In heterogeneous systems, more than
20 one phase is involved, and hence, materials may
15 have to move from phase to phase during the reac-
10 tion.
5 In order to obtain kinetic data, a large number
0 of tests were performed at various temperatures,
0 100 200 300 400 500 600 i.e., 152 °C, 158 °C, and 163 °C. The experiments
were performed at 4 atm pressure. The amount of
Ox ygen Flowrate(L/h)
catalyst used and the oxygen flow rate were 2 g
Figure 3. Effect of oxygen flowrate on conversion to benzoic acid. and 397 L/h, respectively. These experiments were

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

414 A. Gizli et al. Chem. Eng. Technol. 2008, 31, No. 3, 409–416

The derivatives of the derived fitting equations

50
provide the reaction rates. Tab. 3 shows the calcu-
45
lated reaction rates and concentrations of toluene
40
and oxygen at each studied temperature range. In
35
Conversion(%)

Tab. 3, CA, C B and CBA represent toluene, oxygen

30 3h
and benzoic acid concentrations, respectively. C A
25 2h
1.5h was calculated by using the conversion of toluene,
20
1h and CB was calculated by taking into consideration
15
the steps involved in the solubility of oxygen and
10
the mass transfer of oxygen from the interface to
5
bulk liquid [20]. CBA was calculated with the help
0
of the titration results.
150 155 160 165 170 175 The data obtained between the reaction rates
Temperature(ºC) and the concentrations were used to determine the
reaction rate expression of liquid-phase oxidation
Figure 5. Effect of temperature on the production of benzoic acid at various
of toluene to benzoic acid. Three different models
batch time.
were proposed for this reaction and they were all
tested.
50 I. 1st Model
45 Oxygen flowrate: 397 L/h The reaction is only dependent on the toluene
40 Pressure: 4 atm concentration, Eq. (3):
35
Conversion(%)

30 –r A = kCAm (3)
25
20 II. 2nd Model
4 g. catalyst, 152-153 ºC
15 The reaction rate is dependent on both the tolu-
2g. catalyst, 152-153 ºC
10 ene and oxygen concentrations, Eq. (4):
2 g. catalyst, 157-158 ºC
5
0 –r A = kCAm C Bn (4)
0 0.5 1 1.5 2 2.5 3 3.5
III. 3rd Model
Batch Time(hour)
It is proposed that the reaction occurs by the fol-
Figure 6. Effect of batch time on the production of benzoic acid. lowing mechanism through the formation of a
radical [19].

benzylalcohol
repeated for different batch times, i.e., 0.5, 1, 2, and 3 h. The
conversions obtained were plotted versus the reaction times toluene peroxy radical
and the relation between the conversion and the reaction time (A)
was derived. Figs. 7–9 show the fitting curves. In addition, the
benzaldehyde benzoic acid
equations for each temperature range are shown on the fig- peroxide
ures.
Since no product other than benzoic acid is de-
tected in the reaction products, the mechanism
35 can be simplified as follows:
T = 152 ºC
30 P = 4 atm
W=2g k1
25 Toluene Radical
Conversion(%)

V = 397 L/h
k2
20 X =1/100(0.4636t 3 - 6.9293t2 + 27.153t)
k3
R2 = 0.9265 Radical+O2 Benzoic Acid
15 k4
10

5 Therefore, the reaction rate expression reflecting

this mechanism can be derived as Eq. (5):
0
k1 k3 m n q
0 0.5 1 1.5 2 2.5 3 3.5 CA C B  k4 CBA
k2
Batch Time(hour) –r A = k p
(5)
1  k3 C B
2
Figure 7. The conversion to benzoic acid at different batch times at 152°C.

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

Chem. Eng. Technol. 2008, 31, No. 3, 409–416 415

q
k1 CAm CBn  k C BA
50 –rA = p (6)
45 T = 158ºC CB
P = 4 atm
40 W=2g k4 k2
where k 
35 k3
Conversion(%)

V = 397 L/h
30
25 All the models were tested in the presence of the
20
3
X = 1/100(0.2184t - 6.1593t + 31.089t) 2
following criteria by using the experimental reac-
15 R2 = 0.9965 tion rate data and by assigning different orders to
10 the reactions.
5 I. Rate constants must be positive.
0 II. Rate constants follow Arrhenius Law.
0 0.5 1 1.5 2 2.5 3 3.5 III. Model should fit the experimental data
In the 1 st and 2nd models, the models were tested
Batch Time(hour)
with all experimental data in one step by express-
Figure 8. The conversion to benzoic acid at different batch times at 158°C. ing the rate constant using the Arrhenius equation.
However, in the third model this testing was per-
formed separately at each temperature studied.
40 The test results of the models are shown in Tab. 4.
T = 163ºC
35 P = 4 atm It can be seen from Tab. 4 that the R2 values for
30 W=2g models 1 and 2 are not satisfactory. The R 2 value
Conversion(%)

V = 397 L/h for model 3 seems quite good. For further investi-
25
gation, k 1 values obtained at different temperatures
20 were expressed by the Arrhenius equation in
X =1/100( -9.2126t2 + 36.191t)
15 R 2= 0.999 Tab. 5, and the activation energy of the reaction
10 was calculated. The good fit of k to the Arrhenius
equation can be seen in Fig. 10. The values of the
5
rate constants for the other reaction steps cannot
0 be calculated individually, and only their products
0 0.5 1 1.5 2 are listed in Tab. 5.
Batch Time(hour) The validation of model 3 with the experimental
results is shown in Fig. 11. The activation energy
Figure 9. The conversion to benzoic acid at different batch times at 163°C. of the reaction was determined as 43 kJ/mol. This
is high for a typical oxidation reaction, but the
Table 3. Results of kinetic experiments. value can be related to the low activity of the cata-
lyst.
Temperature (°C) Time (h) –rA [mol/L h]C A (mol/L) CB (mol/L) C BA (mol/L)

1 1.652 7.127 0.047 2.213 4 Conclusions

1.5 1.167 6.426 0.052 2.914
152 Investigations have been carried out to determine
2 0.747 5.949 0.056 3.391 the influences of operating variables such as oxy-
3 0.102 5.384 0.062 3.956 gen flow rate, reaction temperature, batch time
and loading of catalyst on the liquid-phase oxida-
1 1.908 6.898 0.049 2.442
tion of toluene to benzoic acid. In a series of batch
1.5 1.410 6.070 0.054 3.270 experiments carried out at 4 atm pressure, the re-
158 sults showed that:
2 0.941 5.484 0.059 3.856
– The optimum oxygen flow rate is ca. 397 L/h
3 0.096 5.42 0.067 3.920 (the corresponding molar ratio of O 2 to toluene
0.5 2.519 7.865 0.045 4.365 is ca. 2).
– The optimum reaction temperature is ca.
163 1 1.659 6.820 0.053 1.475 157 °C.
1.5 0.799 6.205 0.062 2.520 – The optimum reaction time is 2 h.
– The optimum catalyst loading is 0.57 g/L of tol-
uene.
In addition, a kinetic study was carried out while
A further simplification is introduced, and the reverse reac- maintaining the optimum reaction conditions. Three kinetic
tion of the radical formation is assumed to be slower than the models, (i) the power-rate law solely dependent on toluene
other reactions. Therefore, the first term in the denominator is concentration, (ii) the power-rate law dependent on both oxy-
dropped and Eq. (5) is simplified to give Eq. (6): gen and toluene concentrations, and (iii) the model dependent

© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

416 A. Gizli et al. Chem. Eng. Technol. 2008, 31, No. 3, 409–416

Table 4. The results of the models. on the formation of the benzyl radical, were
tested. The results showed that the third model
Model 1 Model 2 Model 3 may be feasible for the description of the catalytic
–rA = kCA6.8 –rA = kCA –0.103C B–7.594 oxidation of toluene to benzoic acid in the liquid
k1 CA C 1:5 4:5
B  k CBA
–rA= phase. The activation energy was determined as
CB
40 kJ/mol.
k4  k2
k
k3
References
k = 7.655 · 10 –3e–27788.3561/RT k = 13253.03e–112831.87/RT k1 = 2.27 · 10 5e –43108.09/RT
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© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.cet-journal.com

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