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Abstract
The kinetics of catalytic hydrogenation of nitrobenzene in acid medium to p-aminophenol was investigated in a batch slurry reactor
in a temperature range of 323}353 K. Aniline was formed as a byproduct (upto 20%). The initial rate data were analyzed to assess the
mass transfer e!ects and it was found that gas}liquid mass transfer resistance was important under certain reaction conditions.
A Langmuir}Hinshelwood type rate model has been proposed based on the initial rate data in the kinetic regime and considering the
reaction taking place in both organic as well as aqueous phase. Since this was a four-phase system, the rate equation was suitably
modi"ed to include gas}liquid and liquid}liquid mass transfer steps. The kinetic parameters evaluated from a semibatch reactor
model were found to represent the observed experimental data very well indicating the applicability of the proposed rate
model. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Catalytic hydrogenation; p-Aminophenol; Kinetics; Mass transfer; Four-phase system; Reaction engineering
1. Introduction
p-Aminophenol (PAP) is a commercially important intermediate for the manufacture of analgesic and antipyretic drugs such as paracetamol. Conventionally, PAP
is manufactured by iron}acid reduction of p-nitrochlorobenzene or p-nitrophenol, which are multistep processes. The major disadvantage of iron}acid reduction is
the generation of large amount of Fe/Fe oxide sludge
(1.2 kg/kg of product). A single-step catalytic hydrogenation of nitrobenzene to PAP using supported noble metal
catalyst in the presence of aqueous acid medium (7%) is
gaining more importance because (i) it is a single-step
process, (ii) environmentally acceptable, (iii) more e$cient
since the work up of reaction crude is simple, and (iv)
byproduct aniline is also a value-added product.
Henke and Vaughen (1940) were the "rst to disclose
a process for PAP by hydrogenation of nitrobenzene
using Pt/C catalyst and a mineral acid. Sul"des of Mo
and W and catalysts such as PtO and Pd have been
reported for this hydrogenation reaction (Greco, 1976;
Derrenbaker, 1981; Rylander, Karpenko, & Pond, 1970;
Shi, Zhou, & Shi, 1992; Caskey & Chapman, 1986).
* Corresponding author.
E-mail address: rode@dalton.ncl.res.in (C. V. Rode).
0009-2509/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 3 5 2 - 3
1300
2. Experimental
2.1. Materials
The catalyst used for hydrogenation was 3%Pt/C
available commercially from M/s Aldrich, USA. The
hydrogen gas with purity '99.9% was supplied by M/s
Indian Oxygen Ltd., Mumbai and was used directly from
the cylinder. Nitrobenzene, sulfuric acid and aniline were
procured from M/s SD Fine Chemicals Ltd. (India) while
p-aminophenol was obtained from Aldrich, USA.
(1)
B#2APP#W,
(2)
2.3. Procedure
The e!ects of various reaction parameters like nitrobenzene concentration, temperature, partial pressure
of hydrogen and catalyst loading on the initial rate of
hydrogenation are discussed below.
The e!ect of catalyst loading on the initial rate of
hydrogenation of nitrobenzene at 323}353 K is shown in
Fig. 1. The rate of hydrogenation was found to vary
linearly indicating that gas}liquid mass transfer resistance is not signi"cant under these reaction conditions.
The rate of hydrogenation was found to be of "rst order
with respect to hydrogen at lower pressure range and
2.2. Apparatus
1301
(3)
wk A
, .
r "
1#K A
,
(4)
1302
(5)
dEl r
" ,
3
dt
(6)
dP r
" .
dt
2
(7)
(8)
Table 1
Values of kinetic parameters at di!erent temperatures
Temperature
(K)
k
(kmol/kg/s)
k
(m/kg/s)
K
(m/kmol)
323
338
353
0.00049
0.00090
0.00220
0.15
0.35
0.73
42.78
65.38
97.00
Fig. 4. Hydrogen consumption vs time pro"les at di!erent temperatures for hydrogenation of nitrobenzene. Reaction conditions: nitrobenzene: 0.934 kmol/m; catalyst: 0.15 kg/m; water: 84;10\ m;
acid: 5% w/w; pressure: 2.72 MPa; agitation: 700 rpm.
1303
Table 2
Comparison of predicted and experimental selectivity of PAP and aniline
p-aminophenol (%)
Temperature (K)
323
338
353
Aniline (%)
Experimental
Predicted
Experimental
Predicted
82
86
88
90
88
82
18
14
12
10
12
18
Fig. 6. Comparison of experimental and predicted results for hydrogenation of nitrobenzene at 373 K. Reaction conditions: nitrobenzene:
0.934 kmol/m; catalyst: 0.35 kg/m; water: 84;10\ m; acid: 7.5%
w/w; pressure: 2.72 MPa; agitation: 700 rpm.
(11)
AH !R /k a
,
*
R "wk #wk
.
(12)
1#K (AH !R /k a )
,
*
Eq. (12) was solved for R by using Newton}Raphson
method and substituting for R in Eq. (11), to obtain
A l . This value of dissolved concentration of hydrogen
,
in nitrobenzene was used in Eqs. (5)}(7) to obtain hydrogen consumption vs. time data. For this purpose, value of
k a was estimated by simulating the experimental hy*
drogen consumption vs. time data at 353 and 373 K at
a higher catalyst loading of 0.35 kg/m. The comparison
of model predictions and the experimental data for 373 K
is shown in Fig. 6. The values of k a for 353 and 373 K
*
were 0.1 and 0.13 s\, respectively, which are in good
agreement with the literature values (Chaudhari, Gholap,
Emig, & Hofman, 1987).
4. Conclusion
The kinetics of single-step hydrogenation of nitrobenzene to p-aminophenol in acidic medium using 3% Pt/C
catalyst has been studied in a slurry reactor, over a temperature range of 323}373 K. The rate of reaction
showed a zero-order dependence with respect to nitrobenzene while, it showed a "rst-order dependence on
hydrogen pressure up to a pressure of 4.76 MPa, beyond
which it was zero order. On the basis of these data in the
kinetic regime, a Langmuir}Hinshelwood-type rate
equation has been proposed. Since this was a four-phase
system, the rate equation was suitably modi"ed to include gas}liquid and liquid}liquid mass-transfer steps.
The intrinsic kinetic parameters were evaluated by simulation of the experimental hydrogen consumption-time
data. From the temperature dependence of the rate constant, the activation energy was found to be 49.8 kJ/mol
for nitrobenzene to PAP reaction. It was found that
for higher catalyst loading, the gas}liquid mass transfer
1304
Notation
AH
Acknowledgements
One of the authors, MJV, is grateful to the Council of
Scienti"c and Industrial Research for the award of Senior
Research Fellowship.
References
Caskey, C. C., & Chapman, D. W. (1986). Process for preparing paminophenol and alkyl substituted p-aminophenol. US patent
4,571,437.