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Articles

Indian Journal of Chemical Tech nology


Vol. 10, November 2003, pp. 627-631

Catalytic hydrogenation of p-nitroaniline and 2-methoxy-5-nitroaniline


Sunil P Bawane & Sudhirprakash B Sawant*
Un iversity Institute of Chemical Tec hnology, University of Mumbai , Matunga, Mumbai 400 019, India

Received 27 August 2002; revised received 3 1 March 2003; accepted 28 April 2003

Catalytic hydrogenation of p-nitroaniline (PNA)' to p-phenylenediamine (PPD) was carried out in methanol
using 5% Pd/C as a catalyst at h~drogen pressures in the range of200-1000 kPa, reaction temperatures 313-333 K,
catalyst loadings 200-500 mg dm and PNA concentrations 0.3-1.02 mol dm"3 Catalytic hydrogenation of 2-methoxy5-nitroaniline (MNA) to 4-methoxy-1,3, benzenediamine (MBD) was carried out in dimethylformamide as a solvent
using 5% Pd/C as catalyst at hydrogen pressures 1000-2000 kPa, reaction temperatures 413-433 K, catalyst loadings
200-600 mg dm"3 and MNA concentrations 0.22-1.7 mol dm3 Speed of agitation beyond 17 rps had no effect on the
progress of the reaction. The study shows that PNA and MNA can be selectively hydrogenated to PPD and MBD,
respectively and the initial rate of hydrogenations showed first order dependence on the reactant concentration,
hydrogen partial pressure, and the catalyst loading for both the reactions. The activation energies for the catalytic
hydrogenation ofPNA and MNA were found to be 37.26 and 93.73 kJ mor 1, respectively.

The hydrogenation of nitro aromatic compound to the


corresponding anilines is an example, where, a
process change is necessary for prevention of
environ mental pollution. Reduction using iron-acid,
sulphides or polysu lphides is known to generate
substan tial waste. Therefore, catalytic hydrogenation
is the method of choice for the large-scale
manufacture of many aromatic and aliphatic amines
from the corresponding nitro compounds. The
objective of the present work was to study the
catalytic hydrogenation of p- nitroani line (PNA) topphenylenediamine
(PPD)
and
2-methoxy-5nitroaniline (MNA) to 4-methoxy-1,3, benzenediamine (MBD) using 5 % palladi um on carbon
catalyst under a wide range of operating conditions.
PPD is useful in the photographic and dye industri es
and widely used as antioxident and antiozonants for
elastomers, plastics and petroleum products. MBD is
used as an intermediate in the dyes industry. Various
methods have been described in the literature for the
sy nthesis of PPD 1. 10 . However, very limited kinetic
information concerning the hydrogenation reaction of
PNA to PPD has been published. Practically no
literature is available regarding the catalytic
hydrogenati on of MNA to MBD . The synthesis of
MBD by catal ytic hydrogenation of 2,4-dinitroanisole
using Pd/C as a catalyst has been reported 11
*For correspondence (E- mail : s bs@ udct.e rn et. in ;
Fax: +91-22-24145614)

Experimental Procedure
Materials
PNA and MNA were obtai ned from Arati
Industries Ltd, Mumbai, India. Methanol and
dimethylformamide used were of laboratory reagent
grade and obtained from s. d. fine chemicals Ltd.,
Mumbai, Indi a. Hydrogen (purity, 99.98%) was
obtained from Indi a Oxygen Limited, Mumbai , India
and used as such. Commercially prepared 5 % Pd/C
was obtained from Parekh Platinum Ltd, Mumbai,
Indi a.
Method
Experiments were carried out in an autoclave
(diameter = 65 mm, 100 mL capacity). The reactor
had provisions for automatic te mperature control,
variab le agitatio n speed, a safety rupture disk and the
sampl in g of the liquid phase. Methanol and
dimethylformamide were used as a solvent for the
catalytic reduction of PNA and MNA, respectively.
The appropriate quantities of the reactant, the solvent
and the catalyst were added to the clean and dry
autoc lave. Before heating the autoclave to the
required temperature, it was repeatedly purged first
with nitrogen and then with hydrogen at room
temperature without stirring. Once the required
temperature was reached, it was pressurized with
hyd rogen to get the desired partial pressure of
hyd rogen and stirring was started. As the reaction

Articles

Indi an J. Chern. Techno!., November 2003

proceeded, the hydrogen consumed was made up , so


as to maintain a constant pressure. Samples (2-3 mL)
were withdrawn through the sampl e outlet at regular
time intervals and analyzed on a GC using a SS
column, which was 2 m long and packed with 5 % SE30 on chromosorb WHP materi al. The conditions of
analysis for both the reaction mi xtures were: FID
temperature: 573 K; injection temperature: 573 K;
co lumn temperature: 443 K; carri er gas, N2 : 1.9x 10-5
m3 min-' .

80

a..

c
0
v;
(jj

>
c

40

0
()

Results and Discussion


The stoichi ometric reacti ons in volved in
catalytic hydrogenation of PNA and MNA are:

60

20

the

(1)

3 H2

____.

PNA

600 .

1200

1800

2400

Time,(s)
+

PPD

Fig. !-Effect of impeller speed on the conversion of PNA


I 0 rps
0 17 rps
x 24 rps
Reacti on temperature: 333 K ; Hydrogen partial pressure:
1000 kPa; Catalyst loading: 360 mg dm-3 ; PNA co nce ntration: 0.6
mo l dm-3

(2)
80
~

::2

60

c:
0

'(ii

MNA

MBD

Qj
>
c:

40

()

Initial experiments on catalytic hydrogenation of


PNA and MNA were carried out to establish the
material balance of reactants consumed and products
formed and the balance to the ex tent of minimum
98% as per the stoichiometry given by reaction l and
2 was established for the organi c reactants and
products . For kinetic experiments, progress of the
reaction was monitored by analyzing the reaction
mixture and calcul ating the moles of the reactants
consumed as a function of time in each run. Based on
the moles of reactants consumed, the initial rates were
calc ul ated graphicall y usi ng third o rder pol y no mi al
equation.

Effect of speed of agitation


The effect of impeller speed o n the convers ion of
PNA and MN A in the range 10-24 rps is show n in

628

~
0

20

0
0

1200

2400

3600

4800

Time, (s)
Fig . 2- Effect of impeller speed on the conversion of MNA
I 0 rps
0 17 rps
x 24 rps
Reacti o n temperature: 433 K; Hydrogen partial pressure:
2000 kPa; Catalyst loading: 600 mg dm- 3 ; MNA co ncentration:
0.22 mol dm-3

Figs I and 2, respectively . The conversion was found


to increase when the speed increases from 10 to 17
rps. This indicates that gas to liquid and/or liquid to
solid mass transfer resistance is significant between
10-17 rps. The impell er speed was not observed to
have any effect on the convers ion after 17 rps,

Articles

Bawane & Sawant: Catalytic hydrogenation of p-nitroaniline and 2-methoxy-5-nitroaniline

indicating absence of external


mass-transfer
limitation, beyond the speed of agitation of 17 rps.

Effect of catalyst loading


The catalyst loading was varied between 200 to 500
mg dm3 for the catalytic hydrogenation of PNA and
200 to 600 mg dm- 3 for the catalytic hydrogenation of
MNA. The initial rate of reaction was found to
increase linearly with the catalyst loading.

Effect of hydrogen partial pressure

Table !--Optimum conditions for the catalytic hydrogenation of


PNAand MNA
Parameter

Substrate concentration
(mol dm-3)
Temperature (K)
Hydrogen partial press ure
(kPa)
Catalyst loading
(mg dm"3 )
Time for complete
conversion (s)
Seeed (res)

PNA
hydrogenation

MNA
hydrogenation

0.6

0.22

333

433

1000

2000

360

600

2400

5800

24

24

The effect of hydrogen partial pressure was studied


in the range of 200-1000 kPa for the catalytic
reduction of PNA and in the range of 1000-2000 kPa
for the catalytic hydrogenation of MNA. The rate was
found to increase linearly with the hydrogen partial
pressure. The result indicates first order dependence
of the initial rate of reaction on the hydrogen partial
pressure

The rate equation for the catalytic hydrogenation of


PN A when the surface reaction between the adsorbed
species controls the progress of the reaction can be
written as,

Effect of reactant concentration

fj =Ki a pc *H, c *PNA

(1 )

CH, HC*H,

(2)

CPNA HC*PNA

(3)

C *H, =KaCH,

(4)

The reactant concentration was varied from 0 .31.02 mol dm3 for the catalytic hydrogenation of PNA
and from 0.22-1.7 mol dm3 for the catalytic
hydrogenation of MNA . The initial rate was found to
increase with increasing the reactant concentration
and showed a first order dependence on the reactant
concentration .

K \ c PNA

(5)

'i =KiapKaK\ CH, C PNA

(6)

c PNA =

. . . (7 )

Effect of temperature
The
reactions
were
studied
at
different
temperatures in the range of 313-323 K for the
catalytic hydrogenation of PNA and in the range of
413-433 K for the catalytic hydrogenation of MNA. It
was found that the initial rate of catalytic
the
hydrogenation
increases
with
increasing
temperature.
The optimum reaction conditions to get maximum
hydrogenation of PNA and MNA are li sted in
Table I. All the experim ents were carri ed out to
eliminate the external mass- transfer res istances by
operating at hi gh impeller speed (24 rps). It was found
that temperature has stro ng effect on th e initi al rate of
the reacti on and initial rate of reacti o n vari es linearly
with the hydrogen parti al pressure as we ll as with the
reactant concentrati on. Intraparti cle d iffusion was
12
eliminated by usi ng very fin e catalyst particles
Hence, on the basis of above observations it can be
assumed that surface reacti on is the rate-contro ll ing
step.

Taking the initial values,

cH cPNAo

... (8)

2.,

. . . (9)

where,

Solubili ty of hydrogen in
methano l and
dimeth ylformamide was estimated by a correlati on for
hydrogen so lubility given by Shaw 13 .
The Arrheniu s pl ot of In k 1 versus liT gave a
straight line as shown in Fig. 3, and an activati on
629

Articles

Indi an J. Chern. Techno!., November 2003

-3.1 , - - - - - - - - - - - - - - - - - - ;

... (II)

-3.3

Taking the initial values,


-3.5

... (12)

.:Z

.s

CH 2o CM NAo

-3.7

... (13)
-3.9

-4.1 -+-------r------.----------r'
2.9
3
3.1
3.2

where,

( Iff)* 10+3 (K- 1)

Fig. 3---Arrhenius plot for the catal ytic hydrogenation of PNA


PNA concentration: 0.6 mol dm.3 ; Hydrogen parti al pressure:
1000 kPa; Agitation speed: 24 rps; Catalyst loading : 360 mg dm3

4,------------------

The Arrhenius plot of In k 2 versus liT gave a


straight line (Fig. 4), and value of activation energy as
93.73 kJ mor' for catalytic hydrogenation of MNA.
These high values of activation energies indicate that
the reactions are kinetically controlled.

Conclusion

4 .8

-5.2

-5.6

~+-----.----.-----.----~
2.28

2.32

2.38

2.4

2.44

(Iff)* 10+3 (K 3 )

Fig. 4-Arrhenius plot for the catalytic hydrogenation of MN A


MNA concentrati on: 0.22 mol dm.3 ; Hydrogen partial pressure:
3
2000 kPa; Agitation speed: 24 rps; Catalyst loading: 600 mg dm

energy of 37 .26 kJ mor' for catalytic hydrogenation


ofPNA.
Similarly, the rate equation for the catalytic
hydrogenation of MNA, when the surface reaction
between the adsorbed species controls the progress of
the reaction , can be written as,
... (10)

630

p-nitroaniline and 2-methoxy-5-nitroaniline can be


selectively hydrogenated to p-phenyle nediarnine and
4-methoxy 1,3, benzenediamine, respectively using
5% Pd/C as a catalyst. The initial rate of
hydrogenation had first order dependence with respect
to the reactant concentration, hydrogen partial
pressure, and the catalyst loading for both the
reactions . The activation energies for the catalytic
hydrogenation of p -nitroaniline and 2-methoxy-5nitroaniline were found to be 37.26 and 93.73 kJ
mol- 1, respectively.

Nomenclature
3

CrNAo

=initi al concentration of PNA, mol dm"

CPNA

=liquid phase concentration of PNA, mo l dm3

c;NA

=adsorbed concentration of PNA, mol dm3


3

C MNAo

=initi al concentration ofMNA, mol dm

CMNA

=l iquid phase concentration of MNA, mol dm

cMNA

=adso rbed concentration of MNA, mo l dm

C11 ,

= concentration of hydrogen in liquid phase, mol dm3

C' 11 , = adsorbed concentrati on of hydrogen, mo l dm3


C11 20 =initial concentration of hydrogen in liqu id phase, mol
dm3
= rate of the catalytic hydrogenation of PNA. mol dm3 s- 1

Bawane & Sawant: Catalytic hydrogenation of p-nitroaniline and 2-methoxy-5-nitroaniline

"o

K,

=initial rate of catalytic hydrogenation of PNA, mol


dm-3 s- 1
=rate of the catalytic hydrogenation of MNA, mol
dm-3 s-1
=initial rate of catalytic hydrogenation of MNA, mol
dm- 3 s 1
=rate constant for catalytic hydrogenation of PNA

K2

= rate constant for catalytic hydrogenation of MN A

r2

r20

K, ,K',,K'2 =equilibrium constants


aP

= specific surface area of the catalyst, m2 m3

Shigeo Y, Tsukasa T, Takafumi A, Eiji S & Hiroyuki H, Jpn


Kokai Tokkyo Koho Jp, 62 (1985) 12; Chern Abstr, 107
(1987) 96425 .

Tsukasa T, Takafumi A, Shigeo Y & Hiroyuki H, Jpn Kokai


Tokkyo Koho Jp, 62 (1987) 7; Chern Abstr, 107 (1987 )
218216.

Tsukasa I, Jpn Kokai Tokkyo Koho Jp, 60 (1984) 3; Chern


Abstr, 104 (1986) 50637.

Kataoka H, Jpn Kokai Tokkyo Koho Jp, 59 (1983) 5; Chern


Abstr, 101 (1984) 170869.

Atsuo M, Kiichi F & Hiroshigeo M, Jpn Kokai Tokkyo Koho


Jp, 78 (1977) 7; Chern Abstr, 90 (1979) 103596.

10

Kiichi F & Atsuo M, Jpn Kokai Tokkyo Koho Jp, 79 (1977)


4; Chern Abstr, 90 ( 1979) 203661.

11

Zhao X, Xing C & Lubai C, Jingxi Huagong , 14 (1997) 41 ;


Chern Abstr, 127 ( 1997) 331240.

12

Ramchandra P A & Chaudhari R V, Three Phase Catalytic


Reactors (Gordon and Breach Science Publication, New
York), 1983.

13

Shaw J M, Can J Chern Eng, 65 (1987) 293.

References
I
2

Sarmah P & Barua N C, Tetrahedran Lett, 31 (1990) 4065.


Sivanandaiah K M, Guresiddappa S & Gowda D C, Indian J
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Hideki M, Takeshi N, Masaru W & Teruyuki N, Jpn Kokai
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Hiroyuki A, Jpn Kokai Tokkyo Koho Jp , 003 (1989) 6; Chern
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