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Deactivation kinetics in the hydrogenation of


nitrobenzene to aniline on the basis of a coke
formation kinetics investigations in an
isothermal catalytic wall reactor
ARTICLE in CHEMICAL ENGINEERING SCIENCE FEBRUARY 2001
Impact Factor: 2.34 DOI: 10.1016/S0009-2509(00)00357-2

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Chemical Engineering Science 56 (2001) 1347}1353

Deactivation kinetics in the hydrogenation of nitrobenzene to aniline


on the basis of a coke formation kinetics * investigations in
an isothermal catalytic wall reactor
E. Klemm *, B. Amon, H. RedlingshoK fer , E. Dieterich, G. Emig
Institute of Technical Chemistry I, University Erlangen-Nuremberg, Egerlandstr, 3, D-91058 Erlangen, Germany
Siemens AG, KPW PK 5, D-96257 Redwitz, Germany
Bayer AG, PU-F/VF, D-41538 Dormagen, Germany

Abstract
The heterogeneously catalysed gas-phase hydrogenation of nitrobenzene to aniline on an -alumina supported palladium catalyst is
a highly selective reaction which however is deactivated by coking. A catalytic wall reactor (CWR) was proved to be a powerful tool
for the determination of a deactivation kinetics on the basis of a coke formation kinetics. Nitrobenzene was identi"ed as coke
precursor, whereas aniline had no in#uence neither on the kinetics of the nitrobenzene hydrogenation nor on the kinetics of coking.
The coking of the catalyst was investigated by monitoring axial coke pro"les along the coated wall of the CWR with progressing
time-on-stream. Analysing the coke formation at the coated section close to the inlet allows a fast determination of the fundamental
dependencies of coke formation on partial pressures of reactants and on temperature. For the "rst coated section partial pressures
correspond to the well-de"ned inlet values and do not depend on time. Fitting coke pro"les and the nitrobenzene outlet
concentrations allowed the conclusion that it is indispensable to di!erentiate between coke on the support and coke on the active site.
Furthermore, both coke on the support and coke on the active site were found to be responsible for deactivating the hydrogenation of
nitrobenzene. Thus, it was concluded that also the support is involved in hydrogenation of nitrobenzene due to hydrogen
spillover.  2001 Elsevier Science Ltd. All rights reserved.
Keywords: Catalytic wall reactor; Hydrogenation; Spillover; Deactivation kinetics; Coke formation

1. Introduction
In industry the heterogeneously catalysed gas-phase
hydrogenation of nitrobenzene to aniline is performed
either in "xed-bed or in #uidized-bed reactors on supported copper, nickel or palladium catalysts (Weissermel
& Arpe, 1997). It is a highly selective reaction with
selectivities normally larger than 99%. However, industrial production is a!ected by a slow deactivation due to
parallel coking (Weissermel & Arpe, 1997). Additionally,
the reduction of nitrobenzene is a highly exothermic
reaction with a reaction enthalpy of 443 kJ/mol and
a corresponding adiabatic temperature rise of about
24003C. Since the activation energy of the rate determin-

* Corresponding author. Fax: #49-9131-8527421.


E-mail address: elias.klemm@rzmail.uni-erlangen.de (E. Klemm).

ing step of the coke formation is higher than the activation energy of the rate determining step of the desired
nitrobenzene hydrogenation, hot-spots exceeding a certain maximum reaction temperature enhance coking and
must be avoided in the reactor. Thus, isothermal conditions should allow an extension of the production cycle
until regeneration with air is necessary. Especially, for
"xed-bed reactors it is di$cult to guarantee isothermal
conditions in the case of strongly exothermic reactions
even if multi-tubular reactors with low ratio of tube to
particle diameter are used. Thus, coking will occur in the
temperature hot-spot, which causes the reaction zone to
move towards the outlet of the reactor.
An unsteady-state simulation of the moving temperature and concentration pro"les for the nitrobenzene
hydrogenation in a "xed-bed reactor make it possible to
"nd new optimum operation conditions for an existing
industrial "xed-bed reactor. Perhaps an optimized timedependent inlet temperature and/or an optimized inlet

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 7 - 2

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E. Klemm et al. / Chemical Engineering Science 56 (2001) 1347}1353

hydrogen-to-nitrobenzene ratio increases the production


cycle. Therefore, it is essential, "rstly, to determine a reliable deactivation kinetics in the lab for the relevant
catalyst, and secondly, validate the overall kinetics by
long-term pilot-plant experiments. Afterwards optimization calculations can be performed. The present paper
focuses on the "rst part, which is the determination of the
deactivation kinetics. Since the deactivation time scale in
industrial practice is in the order of several thousands of
hours, in the lab experiments more severe conditions
(higher WHSV) are chosen to reduce the time scale down
to several hours. For the simulation of the industrial
reactor an extrapolation is then necessary. Thus, no
empirical correlation between activity and time can be
used, but a deactivation kinetics must be derived on the
basis of a coke formation kinetics. This has been proposed "rst by Bischo! and Froment (1961). Such a deactivation kinetics requires the measurement of the coke
formation at well-de"ned partial pressures and temperatures. As a very e$cient device a gradient free recycle
electrobalance can be used (Beinaert, Vermeulen, & Froment, 1994). In the case of an integral #ow reactor axial
concentration pro"les and axial coke pro"les occur. The
reaction must be stopped after several time-on-stream
and the catalyst discharged section by section for coke
analysis (Liu, Fung, Ho, & Rumschitzki, 1997). Another
possibility chosen in the present work is the use of a catalytic wall reactor (CWR), in which the catalyst is coated
on the inner wall of the tube. The catalyst is scratched
o! the wall sectionally to get the corresponding coke
pro"les. Compared to the usual integral "xed-bed
reactor the CWR has the additional advantage to
guarantee isothermal conditions especially in the case of
strongly exothermic reactions (Amon, Klemm, & Emig,
1999a; Amon, RedlingshoK fer, Klemm, Dietrich, & Emig,
1999b).

2. Experimental
2.1. Coating procedure (see Fig. 1)
An industrial Pd}Al O (1.1 wt%) catalyst of spheri 
cal shape with a diameter of about 5 mm was ground to
particles smaller than 250 m. The catalyst powder was
suspended in a solvent consisting of tetrahydrofurane
and xylene (1:2). While the closed tube segment was
rotated, the catalyst suspension was injected into the tube
through a hole in one of the covers. The solvent evaporated and the inner tube wall was coated with the catalyst.
Finally, the catalyst was calcinated at a temperature of
2503C for 8 h. This procedure ensured reproducible catalyst coatings with an adjustable thickness between 100
and 400 m. The coatings were thermally and mechanically stable for use in the CWR. To activate the catalyst,
10 vol% hydrogen in nitrogen was fed to the reactor at

Fig. 1. Coating procedure for the preparation of CWR segments.

reaction temperature before the hydrogenation reaction


was started.
2.2. Experimental procedure
The experimental set-up is described in detail in Amon
et al. (1999a,b). Isothermal conditions and the absence of
mass transport limitations were proved for the chosen
reaction conditions (Amon, 1999). For the measurement
of deactivation kinetics 8 cm long tubes with 10 mm
inner diameter are coated with 0.6 g catalyst. The following reaction conditions are chosen:
E atmospheric pressure;
E reaction temperatures: 548/598/648/698 K;
E inlet partial pressures of nitrobenzene: 1.69/3.38/
6.67 kPa;
E inlet partial pressures of hydrogen: 10.26/20.28/
40.45 kPa;
E nitrogen was used as balance to keep the total #ow
constant at 1095 ml/min.
The underlined values represent the reference point of the
reduced factor plan comprising 9 experiments. A gaschromatograph was used to monitor the concentrations
at the reactor outlet. The conversion vs. time plots represent the integral activity loss due to coking. To get the
corresponding coke pro"les the reaction was stopped
after certain time-on-streams (1,2,5,10,20 h), the coked
catalyst was scratched o! the tubes in intervals of 1 cm
and the carbon content of each sample was determined
by TC analysis (C-Mat 550; StroK hlein Instruments). Fig.
2 depicts for one set of reaction conditions given by the
reduced factor plan the set of measured data. The good
coincidence of the conversion vs. time curves for one set
of reaction conditions, but stopped at di!erent time-onstream proves a su$cient reproducibility of the coating
procedure.

E. Klemm et al. / Chemical Engineering Science 56 (2001) 1347}1353

1349

Table 1
Kinetic constants of the initial reaction rate
Parameter

Value of
estimation

Standard
deviation

k
(kmol/kg s)
& 
E
(kJ/mol)
 &
K (kPa\)
,
K  (kPa\ )
&

1.86;10\
10.0
1.51;10\
0.14

1.27;10\
0.9
2.98;10\
0.02

the rate determining step (Amon et al., 1999a):


kK K  p p 
, & , &
r "
.
(1)
 (1#K p #K p )
, ,
& &
Table 1 lists the determined kinetic constants of the
initial reaction rate. The rather low activation energy of
10 kJ/mol for the hydrogenation can be explained by the
fact, that the temperature dependence of the adsorption
constants was not considered explicitly and thus compensates partially the activation energy of the reaction.
The absence of mass transfer was checked both experimentally and by applying the Mears criterion (Amon,
1999). However, other authors also found low values
between 20 and 25 kJ/mol for the activation energy of the
hydrogenation (Echigoya, Nagai & Morikawa, 1971;
Datta, Sarkar, Sengupta, Gangulis & Sen, 1976). By
evaluation of the adsorption constants it can be concluded that hydrogen is strongly adsorbed by a factor
of 10.
Fig. 2. Measured coke pro"les and conversions depending on time-onstream for a given set of reaction conditions.

3. Kinetic measurements and modelling


Following the approach of Szepe and Levenspiel
(1968) the overall kinetics of the nitrobenzene hydrogenation is assumed to be separable into the kinetics on the
fresh catalyst and an activity function. Due to Bischo!
and Froment (1961) the activity function should be correlated with the coke content of the catalyst, whose formation is modelled by a coke formation kinetics.
A contribution to the deactivation by sintering of the
palladium was excluded by dispersion measurements before and after the deactivation experiments.
3.1. Kinetics of the hydrogenation on the fresh catalyst
The initial conversions and the initial reaction rates at
di!erent reaction conditions were obtained by extrapolating the conversion curves to time t"0 min. It could be
shown that hydrogenation of nitrobenzene on the fresh
catalyst follows a Langmuir}Hinshelwood mechanism
considering the surface reaction of the adsorbed nitrobenzene molecule and one adsorbed hydrogen atom as

3.2. Derivation of coke formation kinetics


At the "rst coated section close to the inlet the rate of
coke formation can be observed at well de"ned and
time-constant reaction conditions, because the partial
pressures of nitrobenzene and hydrogen match the
known inlet values. Figs. 3 and 4 clearly show the
in#uence of hydrogen and nitrobenzene partial pressures
upon the coke formation rate. Hydrogen retards and
nitrobenzene enhances the coke formation. The coke
formation itself undergoes a deactivation.
Considering these observations the following coke
formation kinetics can be derived:
w
pK
AR "k , exp(!k
w ).
(2)
AR pK
 AR AR
t
&
By "tting this coke formation kinetics with the commercial software SIMUSOLV to the measured data depicted
in Figs. 3 and 4 preliminary estimations of the kinetic
parameters can be obtained:
m "0.1$0.0015, m "2.73$0.079,


k "0.9508$0.0034,
AR
k
"1677.2$55.
 AR

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E. Klemm et al. / Chemical Engineering Science 56 (2001) 1347}1353

Fig. 3. In#uence of the hydrogen partial pressure on the rate of coke


formation.

Fig. 5. Parity plot for the measured and simulated coke pro"les.

Fig. 4. In#uence of the nitrobenzene partial pressure on the rate of coke


formation.

Various activity functions (linear, hyperbolic) have been


applied, but the exponential one indicated the most
promising result.

Fig. 6. Parity plot for the measured and simulated nitrobenzene outlet
concentrations.

3.3. Isothermal deactivation kinetics


For "tting the complete coke pro"les along the axial
coordinate and the corresponding nitrobenzene conversions at the reactor outlet, the di!erential mass balance of
the CWR has to be integrated in time and space:
p
(up )
, "!
, !Rr (t).
&
t
z

(3)

The hydrogenation rate r (t) is separated into the time


&
independent rate r (Eq. (1)) and the time-dependent

activity function a (t):
&
r (t)"r a (t).
(4)
&
 &
Assuming that the total coke deposited on the catalyst is
responsible for the loss of activity of the hydrogenation

reaction, an appropriate correlation between a (t) and


&
w has to be found. Several functions have been tested,
AR
but only an exponential one resulted in the best "t:
a (t)"exp(!k w ).
(5)
&
 AR
The parity plots clearly show that neither the measured
coke pro"les (Fig. 5) nor the measured conversions
(Fig. 6) can be modelled satisfactorily accurate within
20% in the entire observed time-domain.
With increase in both time-on-stream and coke content an obvious lack of "t can be seen. The model cannot
describe the long-term coking correctly. Thus, the model
has to be modi"ed. On the basis of experimental observation that coke is also formed on the alumina support with
a non-negligible amount especially at longer time-onstream (Klemm, Amon, RedlingshoK fer, & Emig, 1999),

E. Klemm et al. / Chemical Engineering Science 56 (2001) 1347}1353

1351

Fig. 7. Parity plot for the coke formation considering Eqs. (6)}(8).
Fig. 8. Parity plot of the measured and simulated nitrobenzene outlet
concentrations considering Eqs. (6)}(8) and (10).

two coke formation kinetics have to be considered. One


for the coke formation on the active site palladium
(marked with index a) and the other for the coke information on the support (marked with index s):
w
pK
A? "k , ) exp(!k
w ),
(6)
A?
 A? A?
t
pK
&
pK
w
AQ "k , ) exp(!k
w ),
(7)
AQ pK
 AQ AQ
t
&
w "w #w .
(8)
AR
A?
AQ
By total carbon analysis it cannot be distinguished between coke on active site and coke on support. Only the
total carbon content w is measured and must be "tted
AR
by the model equations according to Eqs. (6)}(8). Additionally, it is assumed that only the coke on palladium
deactivates hydrogenation reaction:
a (t)"exp(!k w ).
(9)
&
 A?
This assumption should be true, if nitrobenzene is hydrogenated exclusively on palladium.
For determination of the model parameters the di!erential Eqs. (3), (6) and (7) are integrated with
SIMUSOLV considering Eqs. (4) and (9) and "tting the
simulated to the measured coke pro"les and outlet concentrations in the time domain.
The parity plot for the measured and simulated coke
content now indicates a su$cient "t as can be seen in
Fig. 7.
In spite of the described improvement in modelling the
coke formation no su$cient "t of the nitrobenzene outlet
concentrations could be reached. Still the same tendency
of deviation occurs as can be seen in Fig. 6. Thus, one has
to think about the adequacy of Eq. (9) which couples the
coke formation with the hydrogenation activity. It could
be possible that not only the coke deposited on the active

Table 2
Kinetic constants of the deactivation kinetics
Parameter

Value of
estimation

Standard
deviation

m

m

k
A?
k
 A?
k
AQ
k
 AQ
k


1.7
0.4
0.264
4624
1.4;10\
0 (not signi"cant)
282

0.031
0.0024
0.019
42
1.4;10\
3.6

site, but also the coke deposited on the support deactivates the hydrogenation. Thus, in the following model it
is still di!erentiated between coke formed on palladium
and coke formed on the support according to Eqs. (6) and
(7), but the dependency of the activity upon the coke
content is changed to
a (t)"exp(!k w ).
(10)
&
 AR
With the model described above both the coke formation as well as the activity loss of the catalyst can
be described satisfactorily. Fig. 8 depicts the parity
plot for nitrobenzene outlet concentrations.
Table 2 summarizes all the determined parameter
values with their standard deviations as calculated by
SIMUSOLV software.
Interpreting the values of the parameters of the deactivation kinetics allow the conclusion that coke formation
on the palladium takes place rapidly, whereas the coke
formation on the support is much slower and dominates
in the long-term range. For the coke formation on the

1352

E. Klemm et al. / Chemical Engineering Science 56 (2001) 1347}1353

catalyst. For a reliable proof of that assumption additional experiments have to be performed.
3.4. Temperature-dependent deactivation kinetics
By including also the experimental results at higher
reaction temperatures into the "tting procedure of the
best deactivation model (total carbon responsible for
deactivation and di!erentiation between coke on active
site and on support) the following activation energies can
be determined:
Fig. 9. Investigating the in#uence of hydrogen treatment of the coked
catalyst on the nitrobenzene hydrogenation.

support no self-deactivation could be observed within


the timescale of the experiments. The coke formation
on the palladium undergoes a strong self-deactivation as
can be concluded from the large value of k
.
 A?
The modelling results also allow the conclusion that
both the coke on the active sites as well as the coke on the
support deactivate hydrogenation of nitrobenzene. Or in
other words, the support is involved in the hydrogenation of nitrobenzene. This could be explained by a spillover of atomic hydrogen from palladium to alumina
where it also can hydrogenate the adsorbed nitrobenzene. Thus, coke on the support hinders this elementary
step by mechanically blocking the surface or it can consume hydrogen in a competitive reaction. To check the
latter, nitrobenzene was shut o! at certain times in
the hydrogenation experiment in order to purge with
hydrogen during a certain time interval. Afterwards
the nitrobenzene hydrogenation was continued. As can
be seen from Fig. 9 no regeneration by hydrogen
treatment can be achieved, which means that the
coke molecules cannot be hydrogenated to volatile
compounds desorbing from the surface. Thus, hydrazo
benzene, azo benzene, or azoxy benzene which have
been postulated by some authors (Metcalfe & Rowden,
1971; Collins, Smith, & Davis, 1982) as possible intermediates also cannot be responsible for the blockage of
the surface, because they should have been hydrogenated
to aniline.
Surprisingly, the deactivation is faster after hydrogen
treatment which means that a faster coke formation
occurs. No explanation for that observation can be given
so far.
Spillover in hydrogenation reactions is a phenomenon
which is continually studied in the last three decades
(Delmon, 1994; Conner & Falconer, 1995; Roland,
Braunschweig, & Roessner, 1997). The observations in
the present work make us assume, that hydrogen spillover also has to be considered in the hydrogenation of
nitrobenzene on the -alumina supported palladium

E "50.7$2.1 kJ/mol, E "37.1$2.1 kJ/mol.


? AQ
? A?
Thus, the temperature sensitivity of the coke formation
on the support is more pronounced than the coke formation on the palladium. Both activation energies are larger
than that of the hydrogenation reaction (see Table 1)
clarifying the strong coking beginning at higher temperatures.

4. Conclusion
The CWR is an appropriate lab reactor for the determination of deactivation kinetics especially in the case of
highly exothermic reactions. For the hydrogenation of
nitrobenzene in the gas phase on an -alumina supported
palladium catalyst the deactivation could be described
satisfactorily considering both the formation of coke on
palladium as well as on the support and assuming the
total coke responsible for deactivation of the main reaction. Thus, it was concluded that the support must also
be involved in the hydrogenation step. Spillover of hydrogen atoms from the palladium to the support and
hydrogenation of the nitrobenzene can explain that observation. Coke on the support therefore hinders the
hydrogenation step taking place on the support by mechanically blockage.

Notation
a
E

H
0
K
k
k

k

p
G
r

t
u
w

activity, dimensionless
activation energy, kJ/mol
reaction enthalpy, kJ/mol
adsorption constant, variable
reaction rate constant, variable
Arrhenius factor, variable
deactivation rate constant, dimensionless
partial pressure of component i, kPa
reaction rate, kmol/kg s
temperature, K
time, s
gas linear velocity, m/s
weight fraction, dimensionless

E. Klemm et al. / Chemical Engineering Science 56 (2001) 1347}1353

X
z

conversion, dimensionless
axial coordinate, m

Subscripts
0
zero time on stream
cat
catalyst
c
coke (coking)
ca
coke (coking) on active sites
cs
coke (coking) on support
ct
total coke
H
hydrogenation
i
component i
NB
nitrobenzene

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