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8 Citations 32 References 5 Figures
Article (PDF Available) in Chemical Engineering & Technology 31(3) · March 2008 with 924 Reads
DOI: 10.1002/ceat.200700140
Ali Gizli
Guelin Aytimur
3.03 · 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.
+1
Experimental Set-up. . Experimental conditions. The dimensions of the sparger . Results of experiments.
and bubble reactor.
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 2. The dimensions of the sparger and bubble reactor. 2.5 Experimental Procedure
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
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.
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
414 A. Gizli et al. Chem. Eng. Technol. 2008, 31, No. 3, 409–416
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
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)
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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trial Derivatives, Elsevier, Amsterdam 1992.
R2 = 0.73 R2 = 0.78 R2 = 0.95
[2] Kirk-Othmer Encyclopedia of Chemical Technol-
ogy, 3rd ed., Wiley, New York 1978.
[3] Encyclopedia of Chemical Processing and Design
Table 5. The Arrhenius equation results for Model 3.
(Ed. J. J. Mc Ketta), Marcel Dekker, New York
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[4] W. Warren Kaeding, Ind. Eng. Chem. Process
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y = -5185x + 12.332
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lnk
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0 0.5 1 1.5 2 2.5
–rA experimental
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