Chemical Engineering Science 56 (2001) 1299}1304

Hydrogenation of nitrobenzene to p-aminophenol in a four-phase

reactor: reaction kinetics and mass transfer e!ects
C. V. Rode*, M. J. Vaidya, R. Jaganathan, R. V. Chaudhari
Homogenous Catalysis Division, National Chemical Laboratory, Pune 411008, India

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 Many other patents describe the use of various cationic

surfactants to enhance the rate of hydrogenation and
p-Aminophenol (PAP) is a commercially important in- selectivity to PAP (Spiegler, 1956; Sathe, 1979). The in-
termediate for the manufacture of analgesic and anti- formation in the patents and few publications (Rylander,
pyretic drugs such as paracetamol. Conventionally, PAP 1985; Juang, Hwang, Ho, & Chen, 1988; Rode, Vaidya,
is manufactured by iron}acid reduction of p-nitro- & Chaudhari, 1999) mainly address the e!ect of type and
chlorobenzene or p-nitrophenol, which are multistep pro- composition of catalysts and process conditions on the
cesses. The major disadvantage of iron}acid reduction is activity and selectivity behavior. This process involves
the generation of large amount of Fe/Fe oxide sludge initial reduction of nitrobenzene to
-phenylhyd-
(1.2 kg/kg of product). A single-step catalytic hydrogen- roxylamine (PHA) as an intermediate followed by in situ
ation of nitrobenzene to PAP using supported noble metal rearrangement to PAP in the presence of an acid, and
catalyst in the presence of aqueous acid medium (7%) is formation of aniline is the main competing side reaction
gaining more importance because (i) it is a single-step in this process (Scheme 1).
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). Scheme 1. Hydrogenation of nitrobenzene to p-aminophenol.

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 C. V. Rode et al. / Chemical Engineering Science 56 (2001) 1299}1304
This is a multiphase catalytic system consisting of four
phases, viz., gaseous (H ), organic (nitrobenzene), aque-

ous and solid (catalyst). The overall rate would be in-
#uenced by gas}liquid, liquid}liquid and liquid}solid
mass transfer and interfacial areas. The complex hydro-
dynamics, distribution of Pt/C catalyst in organic/
aqueous phases and liquid}liquid dispersion are also
important. Therefore, the aim of this work was to investi-
gate the kinetics of both aniline and PAP formation and
various mass transfer e!ects on the rate of reaction.
Initial rate data were obtained at di!erent temperatures,
catalyst loading, speed of agitation and partial pressure
of hydrogen in a stirred high-pressure slurry reactor.
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.
2.2. Apparatus
All hydrogenation experiments were carried out in
a 300 cm hastelloy reactor, a schematic of which is
shown elsewhere (Rode & Chaudhari, 1994). The reactor
was supplied by M/s Parr Instruments (USA), consisting
of an agitated vessel equipped with gas inlet/outlet
system, cooling coil, automatic temperature control,
variable agitation speed, safety rupture disc, high-pres-
sure cut o! and pressure recording by a transducer.
A storage reservoir for H gas was used along with

constant pressure regulator, which allowed the measure-
ment of hydrogen consumption as a function of time,
while maintaining the reactor at a constant desired
pressure.
2.3. Procedure
In a typical hydrogenation experiment, 11.5 g nit-
robenzene, 35 mg catalyst, 5 g H SO and 84 cm water
 
were charged to a clean, dry reactor. The contents were
#ushed with nitrogen "rst and then with hydrogen (2}3
times) and were heated to a desired temperature. The
reactor was pressurized with hydrogen and H gas ab-

sorption was noted by observing the decrease in pressure
in the reservoir. The analysis of liquid samples for the
quantitative estimation of reactant and products was
carried out using HP model 1050 liquid chromatograph
equipped with an ultraviolet detector. The analytical
column, lichrospher RP 18 (125;4 mm), supplied by
Hewlett-Packard was used for analysis. The separation
of nitrobenezene hydrogenation products was achieved
with 30% acetonitrile}water as a mobile phase at 253C
and #ow rate of 1 ml/min. Samples of 10
l were injected
into the column through the septum and analyzed at
254 nm.
3. Results and discussion
The main objective of the present work was to study
the intrinsic kinetics of hydrogenation of nitrobenzene to
PAP and performance of a semibatch slurry reactor.
Some initial experiments on hydrogenation showed
that the main reaction products observed were p-
aminophenol and aniline with 60}90% selectivity to
PAP depending on the reaction conditions. However, the
presence of
-phenylhydroxylamine could not be detec-
ted by analysis, indicating the rearrangement of PHA to
PAP is an instantaneous reaction in the aqueous phase.
Hence, the reaction scheme 1, can be shown as
B#3APE#W, (1)
B#2APP#W, (2)
where, A"hydrogen, B"nitrobenzene, E"aniline,
P"p-aminophenol and W"water.
The product PAP was recovered as a solid and it's
yield matched very well with the HPLC analysis. It was
observed that the material balance of the reactants, i.e.
hydrogen and nitrobenzene consumed and the products
formed agreed to the extent of 95}96% as per the
stoichiometry shown by Eqs. (1) and (2). Therefore, initial
rates were calculated from the hydrogen consumed vs.
time data. No hydrogenation was observed without cata-
lyst, indicating the absence of any homogeneous reaction.
Some experiments on catalyst recycle were carried out,
and it was observed that the activity of the catalyst and
selectivity to p-aminophenol remained constant even
after 4 recycles indicating the consistency of the catalyst
activity during the run.
3.1. Initial rate data
The e!ects of various reaction parameters like nit-
robenzene 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 resist-
ance 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
 C. V. Rode et al. / Chemical Engineering Science 56 (2001) 1299}1304
Fig. 1. E!ect of catalyst loading on initial rate of hydrogenation of
nitrobenzene to p-aminophenol. Reaction conditions: nitrobenzene:
0.934 kmol/m; temperature: 353 K; pressure: 2.72 MPa; water:
84;10\ m; acid: 5%w/w; agitation: 700 rpm.
Fig. 2. E!ect of hydrogen pressure on initial rate of hydrogenation of
nitrobenzene to p-aminophenol. Reaction conditions: nitrobenzene:
0.934 kmol/m; catalyst: 0.15 kg/m; acid: 5% w/w; water:
84;10\ m; agitation: 700 rpm.
zero order at higher partial pressure of hydrogen as
shown in Fig. 2. The e!ect of speed of agitation at
0.15 kg/m catalyst loading at 2.72 MPa and 353 K tem-
perature is shown in Fig. 3. The initial rates were found to
be independent of agitation at 353 K. However, at higher
catalyst loading of 0.35 kg/m, hydrogen partial pressure
of 2.72 MPa and at 353 and 373 K, initial rate increased
1301
Fig. 3. E!ect of speed of agitation on hydrogenation of nitrobenzene to
p-aminophenol. Reaction conditions: nitrobenzene: 0.934 kmol/m;
water: 84;10\ m; acid: 5% w/w; temperature: 353 K; pressure:
2.72 MPa.
with increase in speed of agitation. These observations
indicate that gas to liquid mass-transfer resistance is
signi"cant at these reaction conditions.
3.2. Kinetic modeling
For the purpose of kinetic study, it was important to
ensure that the rate data were obtained under the kineti-
cally controlled regime. For the present system,
gas}liquid, liquid}solid and intraparticle di!usion resist-
ances are likely to exist. In order to analyze the contribu-
tion of these mass transfer steps, quantitative criteria
described in detail in the previous work by Rode and
Chaudhari (1994) were used and it was found that the
data at 323}353 K for catalyst loading of 0.15 kg/m was
in the kinetic regime. For this purpose, the values of
solubility of hydrogen in nitrobenzene and water were
taken from Radhakrishnan, Ramchandran, Brahme, and
Chaudhari (1983) and Stephen and Stephen (1963), re-
spectively. In case of hydrogenation of nitrobenzene to
aniline the rate of hydrogenation was found to be of zero
order with respect to both hydrogen and nitrobenzene
concentrations. Based on the hydrogen pressure e!ect
and other trends discussed above, a single site Lan-
gmuir}Hinshelwood rate model is proposed for
hydrogenation of nitrobenzene to PAP and rates of
hydrogenation for Eqs. (1) and (2) can be written as
r "wk , (3)
 
wk A
r "  , . (4)
 1#K A
 ,
1302 C. V. Rode et al. / Chemical Engineering Science 56 (2001) 1299}1304

3.3. Evaluation of kinetic parameters

In order to evaluate the kinetic parameters in Eqs. (3)

and (4), a batch reactor model was used. Under iso-
thermal conditions, the variation of the liquid-phase
concentration of nitrobenzene, aniline and PAP can be
represented by the following set of mass balance
equations:

dBl r r
! " # , (5)
dt 3 2

dEl r
" , (6)
dt 3

dP r
" . (7)
dt 2

The initial conditions are at t"0, B "B and

 
E "P "0.
 
Eqs. (5)}(7) can be solved to obtain the liquid-
phase concentrations of reactant and products as a
function of time using Runge}Kutta method. Since,
the hydrogen consumption is also related by
stoichiometry, the hydrogen consumed at any time can
be calculated as
Fig. 4. Hydrogen consumption vs time pro"les at di!erent temper-
atures for hydrogenation of nitrobenzene. Reaction conditions: nit-
robenzene: 0.934 kmol/m; catalyst: 0.15 kg/m; water: 84;10\ m;
acid: 5% w/w; pressure: 2.72 MPa; agitation: 700 rpm.
3.4. Reactor performance under mass-transfer controlled
conditions

(3El #2Pl )<l , (8) As mentioned in the previous section, data under
certain conditions (higher catalyst loading) were found to
where <l is the volume of the liquid-phase reactants. be in mass-transfer controlled regime. Therefore, a
The rate parameters in Eqs. (3) and (4) were evaluated reactor performance model under such conditions was
by simulating the experimental hydrogen consumption- developed. It was observed experimentally, that the cata-
time data by non-linear least-squares regression analysis. lyst was present only in the organic phase, similar to the
Data at di!erent temperatures (323, 338 and 353 K) in earlier reports (Yamada et al., 1996). However, under
the kinetic regime were simulated and the values of rate stirring the organic phase and the catalyst were found to
parameters are presented in Table 1. The results compar- be uniformly dispersed in the aqueous phase (continuous
ing the experimental and predicted hydrogen con- phase). The following assumptions were made for devel-
sumption-time data behavior are shown in Fig. 4. The oping a reactor model under mass-transfer controlled
proposed model also predicted the selectivities of PAP at conditions: (1) isothermal conditions prevail (2) liquid}
various temperatures which were within $10% error solid mass transfer and intraparticle di!usion resistances
(Table 2). These data clearly show a good agreement are absent as very "ne catalyst particle size (
50
) was
between the model predictions and the observed results. used. The various steps involved in a four-phase system
Temperature dependence of rate constants as an are: (a) mass transfer of A from gas phase to the two
Arrhenius plot is shown in Fig. 5, and energies of activa- immiscible phases (Nitrobenzene and water), (b) mass
tion were evaluated as 47 and 49.8 KJ/mol for reactions transfer of A from nitrobenzene phase (NB) to the surface
(1) and (2), respectively. of solid, (c) reaction on solid surface in nitrobenzene
medium, and (d) mass transfer of A from nitrobenzene
phase to aqueous phase. Mass balance in the nitroben-
Table 1 zene phase reaction can be given as
Values of kinetic parameters at di!erent temperatures
R "k a (AH !A l )!k a (A l !A l ), (9)
Temperature k k K  * , , ** ** , U
  
(K) (kmol/kg/s) (m/kg/s) (m/kmol) wk A l
R "wk #  , . (10)
  1#K A l
323 0.00049 0.15 42.78  ,
338 0.00090 0.35 65.38
353 0.00220 0.73 97.00
Since, the hydrogenation reaction takes place only in the
organic phase, the liquid}liquid mass transfer can be
 C. V. Rode et al. / Chemical Engineering Science 56 (2001) 1299}1304 1303

Table 2
Comparison of predicted and experimental selectivity of PAP and aniline

Temperature (K) p-aminophenol (%) Aniline (%)

Experimental Predicted Experimental Predicted

323 82 90 18 10
338 86 88 14 12
353 88 82 12 18

Fig. 5. Temperature dependence of rate constants. Reaction conditions: Fig. 6. Comparison of experimental and predicted results for hydro-
nitrobenzene: 0.934 kmol/m; catalyst: 0.15 kg/m; water: 84;10\ m; genation of nitrobenzene at 373 K. Reaction conditions: nitrobenzene:
acid: 5% w/w; pressure: 2.72 MPa; agitation: 700 rpm. 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.

ignored. Hence, Eq. (9) can be simpli"ed as

4. Conclusion
R "k a (AH !A l ). (11)
 * , ,
Combining Eqs. (10) and (11), we obtain The kinetics of single-step hydrogenation of nitroben-
zene to p-aminophenol in acidic medium using 3% Pt/C

 
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 hydro-
gen 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).
catalyst has been studied in a slurry reactor, over a tem-
perature range of 323}373 K. The rate of reaction
showed a zero-order dependence with respect to nit-
robenzene 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 in-
clude gas}liquid and liquid}liquid mass-transfer steps.
The intrinsic kinetic parameters were evaluated by simu-
lation of the experimental hydrogen consumption-time
data. From the temperature dependence of the rate con-
stant, 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 C. V. Rode et al. / Chemical Engineering Science 56 (2001) 1299}1304

resistance was signi"cant and the model predictions were Chaudhari, R. V., Gholap, R. V., Emig, G., & Hofman, H. (1987).
in good agreement with experimental data under these Gas}liquid mass transfer in dead end autoclave. Canadian Journal of
conditions also. Chemical Engineering, 65, 744}751.
Derrenbaker, E. L. (1981). Process for the selective preparation of
p-aminophenol from nitrobenzene. US patent 4,307,249.
Greco, N. P. (1976). Hydrogenation of nitrobenzene to p-aminophenol.
Notation US patent 3,953,509.
Henke, C. O., & Vaughen, J. V. (1940). Reduction of aryl nitro com-
AH concentration of hydrogen at the gas liquid in- pounds. US patent 2,198,249.
Juang, T. M., Hwang, J. C., Ho, H. O., & Chen, C. Y. (1988). Selectivity
terface, kmol/m in the phase transfer catalytic hydrogenation of nitrobenzene by
A l concentration of hydrogen in nitrobenzene,
, transition VIII metals. Journal of the Chinese Chemical Society, 35(2),
kmol/m 135.
k rate constant, kmol/kg s Radhakrishnan, K., Ramchandran, P. A., Brahme, P. H., & Chaudhari,
 R. V. (1983). Solubility of hydrogen in methanol, nitrobenzene, and
k rate constant, m/kg s
 their mixtures. Experimental data and correlation. Journal of Chem-
K adsorption constant, m/kmol
 istry Engineering Data, 28, 1}4.
k a volumetric gas}liquid mass transfer coe$cient,
* Rode, C. V., & Chaudhari, R. V. (1994). Hydrogenation of m-nitro-
s\ chlorobenzene to m-chloroaniline: Reaction kinetics and modeling
k a volumetric liquid}liquid mass transfer coe$c- of a non-isothermal slurry reactor. Industrial Engineering Chemistry
** ** Research, 33, 1645}1653.
ient, s\
Rode, C. V., Vaidya, M. J., & Chaudhari, R. V. (1999). Synthesis of
R overall rate of hydrogenation, kmol/m s
 p-aminophenol by catalytic hydrogenation of nitrobenzene. Organic
r rate of hydrogenation for aniline, kmol/m s
 Process Research and Development, 3, 465}470.
r rate of hydrogenation for PAP, kmol/m s Rylander, P. N. (1985). Hydrogenation methods. Academic Press: New
 York, p. 107.
w catalyst loading, kg/m
Rylander, P. N., Karpenko, I. M., & Pond, G. R. (1970). p-aminophenol
from nitrobenzene. US patent 3,715,397.
Sathe, S. S. (1979). Process for preparing p-aminophenol in the presence
Acknowledgements of dimethyldodecylamine sulfate. US patent 4,176,138.
Shi, L., Zhou, X., & Shi, B. (1992). Manufacture of p-aminophenol. CN
One of the authors, MJV, is grateful to the Council of patent 1,087,623; Chemical Abstracts (1995), 123: 111663w.
Scienti"c and Industrial Research for the award of Senior Spiegler, L. (1956). Aromatic p-hydroxyamines. US patent 2,765,342.
Stephen, H., & Stephen, T. (1963). Solubilities of inorganic and organic
Research Fellowship. compounds, Vol. 1, Binary systems part-I (p.81). London: Per-
gamon press.
Yamada, H., Tagawa, T., & Goto, S. (1996). Hydrogenolysis for de-
References protection of aminoacid in a stirred tank reactor containing
gas}liquid}solid four phases. Journal of Chemical Engineering of
Caskey, C. C., & Chapman, D. W. (1986). Process for preparing p- Japan, 29(2), 373}376.
aminophenol and alkyl substituted p-aminophenol. US patent
4,571,437.