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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.
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
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80
a..
c
0
v;
(jj
>
c
40
0
()
60
20
the
(1)
3 H2
____.
PNA
600 .
1200
1800
2400
Time,(s)
+
PPD
(2)
80
~
::2
60
c:
0
'(ii
MNA
MBD
Qj
>
c:
40
()
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
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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
(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)
(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.
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
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-3.1 , - - - - - - - - - - - - - - - - - - ;
... (II)
-3.3
... (12)
.:Z
.s
CH 2o CM NAo
-3.7
... (13)
-3.9
-4.1 -+-------r------.----------r'
2.9
3
3.1
3.2
where,
4,------------------
Conclusion
4 .8
-5.2
-5.6
~+-----.----.-----.----~
2.28
2.32
2.38
2.4
2.44
(Iff)* 10+3 (K 3 )
630
Nomenclature
3
CrNAo
CPNA
c;NA
C MNAo
CMNA
cMNA
C11 ,
"o
K,
K2
r2
r20
10
11
12
13
References
I
2
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