International Journal of

Chemical Reactor Engineering

Volume Article A
Kinetics of Adiponitrile
Hydrogenation Over
Rhodium-Alumina Catalysts
Renzo Di Felice

Aldo Bottino

Gustavo Capannelli

Antonio Comite

Tommaso Di Felice

University of Genova, difelice@dichep.unige.it

aldo.bottino@unige.it

gustavo.capannelli@unige.it

antonio.comite@unige.it

tommaso.difelice@unige.it
ISSN 1542-6580
Copyright c 2005 by the authors.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted, in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of the publisher, bepress, which
has been given certain exclusive rights by the author.
Kinetics of Adiponitrile Hydrogenation Over
Rhodium-Alumina Catalysts
Renzo Di Felice, Aldo Bottino, Gustavo Capannelli, Antonio
Comite, and Tommaso Di Felice
Abstract
The catalytic hydrogenation of adiponitrile is generally carried out industri-
ally at high temperature and pressure over Ni-Raney catalysts, which have the
disadvantages of possessing low mechanical resistance and of being pyrophoric.
In this work adiponitrile was hydrogenated in a three phase stirred slurry reac-
tor using rhodium over alumina powder as a catalyst instead. Catalysts were
prepared with a ion exchange technique by contacting 100 micron alumina pow-
der with a solution of hydrate rhodium cloride for 36 h. The reaction runs were
conducted in a 100 cc vessel at a pressure of 3 MPa and temperatures of 72 92

C varying the initial concentration of adiponitrile. A variety of series-parallel

reactions took place when adiponitrile was contacted with hydrogen in our re-
actor. Attention was concentrated on hexamethylenediamine, the nal product,
and on aminocapronitrile, a very interesting intermediate which could be used
subsequently for caprolactam production (and from this the direct synthesis of
nylon). Samples were withdrawn from the reactor at xed interval of time and
analysed with a gas-chromatograph so that time dependency of reactant con-
version and product selectivity could be determined. The results showed the
expected qualitative behaviour: adiponitrile conversion increased with time, as
did the hexamethylenediamine selectivity, whereas aminocapronitrile selectivity
showed a clear maximum and then decreased to negligible values. The Chem-
ical reaction engineering approach was used and proved sucient to describe
quantitatively the observed kinetic behaviour of the reactor.
KEYWORDS: ADN hydrogenation, Rhodium catalysts, conversion, selectiv-
ity
1. INTRODUCTION
The hydrogenation of adiponitrile (ADN) represents the main route for the industrial production of
hexamethylenediamine (HMD) which is an important intermediate for the production of nylon 6,6 (Buehler et
al., 1969). The demand of compounds useful to produce nylons is constantly increasing in Europe and with
very high growth rates in Southeast Asia (Smiley, 1989). The hydrogenation of adiponitrile can be carried out
with a severe process (high temperature and pressure and usually in fixed bed reactors) using Iron or Cobalt
catalysts or in milder conditions (liquid phase, lower temperature and pressure) on Raney Ni based catalysts
(Balladur et al., 1995, De Bellefon and Fouilloux, 1994). Today the most industrially used process is the second
one. The literature about the hydrogenation of adiponitrile is not abundant and many information are "know
how" of the manufacturers. Only in recent years some studies about the kinetic behaviour and the mass transfer
effects in the reactor with Raney Ni catalyst were reported (Gavroy et al., 1995, Joly-Vuillemin et al., 1994,
Dietrich et al., 1992, Mathieu et al., 1992, Joly-Vuillemin et al., 1996).
Although Raney Ni is a very effective catalyst, adiponitrile manufacturers need to search alternative
catalysts to improve the safety of the process (e.g. Raney Ni in dry conditions is pyrophoric) and the
technology of hydrogenation of ADN (e.g. to use fixed bed reactors). During the hydrogenation of adiponitrile
is possible to tune the operating conditions to co-produce 6-aminocapronitrile (ACN). Recently BASF AG
(Germany) patented a novel simple process to convert 6-aminocapronitrile to -caprolactam (Bassler et al.,
2003) avoiding the production of the large undesired amounts of ammonium sulphate present in the traditional
processes. 6-aminocapronitrile can be obtained as co-product of hexamethylenediamine by tuning the operating
conditions in the hydrogenation of adiponitrile. However the separation of 6-aminocapronitrile from
hexamethylenediamine is very difficult (very similar physical properties) and expensive.
Mares et al. (1998) showed that the Rh/MgO is a potential catalyst for the selective hemi-
hydrogenation of adiponitrile to 6-aminocapronitrile. In recent studies carried out in our laboratories we
showed that Rh supported on Al
2
O
3
is an effective catalyst for the selective hydrogenation of adiponitrile to 6-
aminocapronitrile (Alini et al., 2003a, 2003b) or to hexamethylenediamine by choosing properly the reaction
conditions. The catalytic performance of the catalyst was found to be dependent on the preparation conditions
and methods that in turn affect the characteristics of the final catalyst (Rh loading, metal dispersion). Therefore
a preparative technique to obtain the catalyst with higher performance was developed (Alini et al., 2005).
In this paper further data of reactivity of adiponitrile hydrogenation over the Rh/Al
2
O
3
catalyst will be
shown and an attempt to develop a simple kinetic expression to interpret these data will be reported.
2. EXPERIMENTAL
The Rh/Al
2
O
3
catalyst was prepared by the adsorption technique (Alini et al., 2004) from a weakly
acidic aqueous solution of RhCl
3
3H
2
O (100 mg/L, pH = 5). Alumina was kept in contact with the precursor
solution at room temperature for 36 h. Then the powder was filtered, washed with deionized water and dried
overnight at 60 C. The reduction of the adsorbed precursor to metal was carried out with gaseous molecular
hydrogen at 300 C. Table 1 reports the main properties of the catalyst used; details about its characterisations
will be not reported here having already been illustrated at length somewhere else (Alini et al., 2005). The very
high metal dispersion obtained (defined as the ratio between the Rh superficial atoms directly accessible and
the Rh atoms in the bulk of the catalytic metal particle), necessary for the best utilisation of the active catalytic
material, is worth noticing.
Table 1. Main characteristics of the Rh/Al
2
O
3
catalyst
Specific Surface Area BET 166 m
2
/g
Rhodium loading 0.5-1.5% w/w
Metal Dispersion > 95 %
Average Rh particle dimension 0.5 nm
Rh/Al
2
O
3
granule size 100 m
1 Di Felice et al.: ADN hydrogenation over Rh catalysts
Produced by The Berkeley Electronic Press, 2005
Figure 1 - SEM picture Al
2
O
3
Alfa Aesar particles
Figure 2 - TEM micrography of a Rh/Al
2
O
3
catalysts surface showing good Rh dispersion
Figure 1 depicts a SEM picture of the catalyst support. The solid grains have a diameter of the order of
100 m, are roughly spherical and with a rough surface. Figure 2 shows a typical TEM micrography of the
catalyst surface after Rhodium deposition. The Rhodium dispersion looks very good with clusters of the order of
1 nm.
The hydrogenation of adiponitrile was performed in a 0.1 L stirred autoclave ("bmc dr", Bchi;
Germany) depicted in Figure 3. The reactor was equipped with a low-volume sampling valve from which small
aliquots of the reactant mixture could be removed during the reaction. The experiments were carried under a
constant hydrogen pressure without venting the non reacted hydrogen. The circulation of hydrogen inside the
liquid phase was assured by a gas-inducer impeller. A vacuum system allowed for fast and complete purging of
the reactor between the introduction of the different gases into the reactor. The catalyst was introduced in a
established amounts (from 0.25 to 4.5 g of support material) with 20 mL of absolute ethanol (reaction solvent),
then the autoclave was purged with helium, heated to 50 C and pressurised to 1 MPa with hydrogen. This
activation step was carried out for 1 h, then other 20 mL of ethanol and a proper amount of adiponitrile were
added. The reaction was carried out at temperatures of 72 and 92 C and at constant hydrogen pressure (3 MPa).
The samples of the reaction mixture taken during the course of the reaction (the total sample volume was never
larger than 3 mL) were analysed using a gas chromatograph (Autosystem, Perkin Elmer) equipped with a FID
and a capillary column (SPB-1 Alltech). Table 2 summarises the relevant experimental conditions used
throughout this investigation.
Table 2 Relevant experimental conditions
Pressure 3 MPa
Rh loading (w/w %) 0.5-1.4
Solvent Ethanol, 40 mL
Reaction volume 45 mL
ADN initial concentration 0.15 1.5 kmol/m
3
Temperature 72 92 C
Reaction time 4 - 6 h
Stirring speed 120 rpm
Overall sample volume < 3 mL
Gas phase Pure H
2
2 International Journal of Chemical Reactor Engineering Vol. 3 [2005], Article A34
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Figure 3 - Scheme of the slurry reactor.
3. QUALITATIVE RESULTS AND DISCUSSION
The complete reaction scheme, as inferred from a literature survey (Joly-Vuillemin et al., 1994), is depicted in
the following Figure 4.
Figure 4 Suggested reaction pathway.
It is represented by a train of series-parallel reaction. However, only three of the chemical compounds
depicted in Figure 4 were experimentally quantified, specifically ADN, ACN and HMD.
In order to study the catalyst effectiveness in carrying out the wanted reaction and infer valuable
information on the chemical kinetics, a first experiment was carried out to verify that the slurry reactor setup was
indeed working in the kinetic regime. To this end three different batches of supported catalyst were prepared by
Rhodium deposition on the alumina support. The amount of Rhodium charged was different for the three
batches, ranging from 0.5 to 1 to 1.4 % by weight. Identical reaction runs were then carried out (temperature 72
C, reaction time 4 h, initial ADN concentration 1.4 kmol/m
3
) and the overall ADN conversion (defined as the
ratio of ADN moles consumed over ADN moles charged in the reactor) measured for each run. The results are
depicted in Figure 5: conversion is clearly a linear function of the overall amount of active catalyst used, strongly
indicating that the process is kinetically limited as expected. These results were also found not to be dependent
on the stirring rate (investigated values ranged from 60 to 400 rpm).
Safety
valve
Thermocouple Manometer
H
2
Inert gas
Vacuum
pump
Thermostatic
bath
Vent
Catalyst
Sampling
CN
NC
C
H
NC
NH
N H
2
H
2 H
2
ADN
ACN
HMD
NH
2
NC
C
H
C
H
NH
N H
C
H
N H
AHI
H
2
H
2
H
2
H
2
NH
2
NH
2
3 Di Felice et al.: ADN hydrogenation over Rh catalysts
Produced by The Berkeley Electronic Press, 2005
0.00 0.01 0.02
0.0
0.2
0.4
0.6
0.8
1.0
Catalysts (Rh %)
0.5
1
1.4
A
D
N

c
o
n
v
e
r
s
i
o
n
Rhodium weight (g)
Figure 5 Overall ADN conversion function of catalysts weight.
Experimental runs were carried out varying temperature and initial reactant concentration. The two
temperature investigated influenced only qualitatively the behaviour of the reacting mixture. Figure 6 reports
measured reactant and products concentrations function of time for the highest ADN initial concentration
utilized at the two temperatures of 72 and 92 C, Figure 7 the same results for the intermediate reactant
concentration and whereas Figure 8 depicts measured concentrations for most dilute system.
These results confirm that the reacting process occurs indeed through a consecutive reaction pathway,
as suggested in the previous reaction scheme. As expected ADN concentrations decrease with time for all the
cases studied, and for the two less concentrated systems ADN disappears completely before the reaction is
stopped. When enough time is allowed (or equivalently when initial concentrations are relatively small) the
semi-hydrogenated product (ACN) passes through a maximum and then reduces to nearly zero (Figure 7 and 8).
In summary, reactant conversion and product distribution will depend on the initial reactant concentration and on
the reaction time. As for a typical series reaction train, there will be a specific reaction time (function of the
operating parameters) for which the yield of the intermediate product will have a maximum value.
When the process (in the adopted operating conditions) is given sufficient time, the rhodium based
catalyst can also give HMD as its main product. A greater temperature gave a higher conversion of adiponitrile
and the selectivity to HMD (selectivity here is defined as the ratio of moles of a product to the ADN moles
charged in the reactor) increased at the expense of ACN, although this phenomenon is less evident when the
smaller amount of ADN was charged in the reactor where probably the sampling time was too large in relation
with the reaction behaviour. Moreover it should be stressed that the maximum temperature used in our
experiments was always less than those used in literature indicating a potentially very interesting property of the
catalysts used.
4 International Journal of Chemical Reactor Engineering Vol. 3 [2005], Article A34
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0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
ADN
ACN
HMD
c
o
n
c
e
n
t
r
a
t
i
o
n
s

[
k
m
o
l
/
m
3
]
time (h)
Figure 6(a) Component concentration in the reactor
function of time. T = 72 C
Initial ADN concentration 1.426 kmol/m
3
0 1 2 3 4 5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
ADN
ACN
HMD
c
o
n
c
e
n
t
r
a
t
i
o
n
s

[
k
m
o
l
/
m
3
]
time (h)
Figure 6(b) Component concentration in the reactor
function of time. T = 92 C
Initial ADN concentration 1.250 kmol/m
3
0 1 2 3 4 5
0.0
0.1
0.2
0.3
0.4
0.5
ADN
ACN
HMD
c
o
n
c
e
n
t
r
a
t
i
o
n
s

[
k
m
o
l
/
m
3
]
time (h)
0 1 2 3 4 5 6
0.0
0.1
0.2
0.3
0.4
0.5
ADN
ACN
HMD
c
o
n
c
e
n
t
r
a
t
i
o
n
s

[
k
m
o
l
/
m
3
]
time (h)
Figure 7(a) Component concentration in the
reactor function of time. T = 72 C
Initial ADN concentration 0.440 kmol/m
3
Figure 7(b) Component concentration in the
reactor function of time. T = 92 C
Initial ADN concentration 0.440 kmol/m
3
5 Di Felice et al.: ADN hydrogenation over Rh catalysts
Produced by The Berkeley Electronic Press, 2005
0 1 2 3 4
0.00
0.05
0.10
0.15
0.20
ADN
ACN
HMD
c
o
n
c
e
n
t
r
a
t
i
o
n
s

[
k
m
o
l
/
m
3
]
time (h)
Figure 8(a) Component concentration in the reactor
function of time. T = 72 C.
Initial ADN concentration 0.167 kmol/m
3
0 1 2 3 4
0.00
0.05
0.10
0.15
0.20
ADN
ACN
HMD
c
o
n
c
e
n
t
r
a
t
i
o
n
s

[
k
m
o
l
/
m
3
]
time (min)
Figure 8(b) Component concentration in the reactor
function of time. T = 92 C
Initial ADN concentration 0.167 kmol/m
3
On the basis of reaction scheme suggested earlier, very reactive aldimines could be formed as well as
producing a variety of undesired by-products. Chromatographic analyses showed that the by-product
hexamethyleneimine was always present with the Rh/Al
2
O
3
catalyst. A limited quantity of hexamethyleneimine
formed with the present operating conditions. Other by-products with a higher molecular weight than HMD also
formed. These by-products derived from secondary reactions between the HMD amino group and the aldimine
imino group.
The results obtained by us are comparable to those reported by other authors (Mathieu et al., 1992) who
have found that the kinetic data for the reaction in hand when carried out over Ni-Raney catalysts can be
interpreted with the Langmuir-Hinselwood reaction mechanism. They suggested a very comprehensive kinetic
law of the type:
( )
( ) ( ) [ ]
2
5 . 0
2 1
1 1
2
H H ACN ACN ADN ADN
H H ACN ACN ADN ADN
c K c K c K
c K c K k c K k
r
+ + +
+
= (1)
The present data are not in contrast with that reaction mechanism, although they are not sufficient to
support it unequivocally given the large number of numerical parameters in eq. (1) relative to the number of the
experimental data. Although the performance of other catalysts can be found in literature no other kinetic studies
other than for Ni Raney systems were reported for the hydrogenation of adiponitrile in liquid phase.
Mares et al. (1998) studied the effect of the support on the Rh catalysts performance and they found that
magnesium was the best one (ADN conversion of 82% and ACN selectivity 89%). With the Rh/alumina catalyst
(with a metal loading of 5%) they obtained an ADN conversion equal to 80% and a selectivity to ACN of about
76%.
With the Ni Raney catalyst it is also possible to increase the selectivity of ACN and lowering that of
HMD. The performance of the Ni Raney catalyst to produce ACN is not easily available in the open literature,
nevertheless from an analysis of the data of Joly-Vuillemin et al. (1994) ACN selectivity is smaller than 60 % for
ADN conversion of about 60%. The use of the Rh/Al
2
O
3
catalyst can therefore be economically advantageous
when the target product is ACN because the costs of separation of ACN from HMD and from the unreacted
ADN can be considerably reduced.
6 International Journal of Chemical Reactor Engineering Vol. 3 [2005], Article A34
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3. THE CHEMICAL REACTION ENGINEERING APPROACH
The system considered in the present investigation is represented by a train of series-parallel reaction depicted in
Figure 4. Each reaction will proceed with a speed quantified by a kinetic law; it is very likely that they will
follow a Langmuir-Hinselwood kinetic law, represented in eq. (1). It is obvious that the above kinetic
expression, even if correct, is of very little practical use at the present stage given the large number of numerical
parameters to be experimentally determined.
It was therefore decided to follow, for the time being, a completely different approach, specifically that
suggested by Levenspiel (2002): the chemical reaction engineering modelling. Without having the presumption
to describe in detailed manner the physics of the phenomenon, this approach describe the kinetic with very
simple laws (keep things as simple as possible but not simpler!); from this derived law indications on the
behaviour of the system are then easily derived.
The first simplification introduced consists in a much simpler reaction scheme: for our purpose only
three of the chemical compounds depicted in Figure 4 were taken into consideration and quantified, e.g. ADN
ACN and HMD, the other being neglected as not relevant. This assumption has been possible by experimentally
observing that the overall material balance was verified by at least 90% if the three compounds mentioned above
were considered. The reaction scheme therefore simplifies to:
HMD ACN ADN (2)
With the declared objective of using simple expressions, and with a posteriori experimental
verification, it was assumed here that the first reaction would follow a zero order kinetic with respect to ADN
and that the second reaction would follow a first order kinetics with respect to ACN. It should be stressed here
that these simplification are not without any physical basis: it is well known that Langmuir-Hinselwood kinetic
law would simplify to a zero order kinetic when the reactant concentration is high and, on the other hand, would
simplify to first order kinetic when the reactant concentration is low.
The rate of disappearance of ADN is therefore given by
1
) ( k r
ADN
= (3)
and the net rate of ACN formation by
ACN ACN
C k k r
2 1
= (4)
Consequently, ADN concentration will change with time in a STR of volume V charged with a weight W of
catalysts as
t k
V
W
C C
ADN ADN 1 0 ,
= (5)
and ADN will disappear completely after a time t*, which depends on the operating conditions,
1
0 ,
*
Wk
V C
t
ADN
= (6)
7 Di Felice et al.: ADN hydrogenation over Rh catalysts
Produced by The Berkeley Electronic Press, 2005
ACN concentration can also be easily calculated. For time smaller than t* is given by

= t
V
Wk
k
k
C
ACN
2
2
1
exp 1 (7)
At t = t* ACN concentration will reach a maximum

=
0 ,
2
1
2
1
max ,
exp 1
ADN ACN
C
k
k
k
k
C (8)
and will thereafter decrease with the following law
( )

= t t k
V
W
C C
ACN ACN
* exp
2 max ,
(9)
Analytical expressions for the third component, HMD, will not be reported explicitly as they are obtainable from
the simple overall material balance:
ACN ADN ADN HMD
C C C C =
0 ,
(10)
Typical concentration profiles obtained with the present assumptions are reported in Figure 9.
t*
c
o
n
c
e
n
t
r
a
t
i
o
n
s
reaction time
ADN
ACN
HMD
Figure 9 Typical calculated concentration profile function of reaction time.
From Figure 9, ADN concentration decrease linearly whereas ACN goes through a maximum which take place,
as already said, at time t*.
8 International Journal of Chemical Reactor Engineering Vol. 3 [2005], Article A34
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Kinetic constants k
1
and k
2
were estimated with the help of a minimising software routine from the data
presented in Figure 6 (those obtained at higher ADN initial concentrations). They are summarised in Table 3 for
the two temperatures investigated(95% confidence interval shown).
Table 3 Estimated kinetic parameters
k
1
[kmol/(kg
cat
h) ] k
2
[m
3
/(kg
cat
h)]
T = 72 C 0.25 0.02 0.27 0.04
T = 92 C 0.65 0.07 1.30 0.25
The kinetic parameters calculated for that specific case were then shown to be capable of satisfactorily
describe the component time dependent concentrations for all the other cases, confirming in this way the validity
of the simplifying assumptions previously made. This check is summarised in Figures 10 and 11. The advantage
of this simple approach is evident: for example once the operating conditions are know (temperature, rector
volume, catalysts loading, initial reactant concentration) it is straightforward to estimate the optimum reaction
time that would to maximise, let say, ACN productivity.
.
0 1 2 3 4 5 6
0.0
0.5
1.0
1.5
A
D
N

c
o
n
c
e
n
t
r
a
t
i
o
n

(
k
m
o
l
/
m
3
)
reaction time (h)
C
ADN,0
exp. model
1.426
0.440
0.167
Figure 10 (a) Experimental and calculated ADN
concentration function of time. T = 72 C.
0 1 2 3 4 5 6
0.0
0.5
1.0
1.5
A
D
N

c
o
n
c
e
n
t
r
a
t
i
o
n

(
k
m
o
l
/
m
3
)
reaction time (h)
C
ADN,0
exp. model
1.250
0.440
0.167
Figure 10 (b) Experimental and calculated ADN
concentration function of time. T = 92 C.
9 Di Felice et al.: ADN hydrogenation over Rh catalysts
Produced by The Berkeley Electronic Press, 2005
0 1 2 3 4 5 6
0.0
0.1
0.2
0.3
0.4
0.5
A
C
N

c
o
n
c
e
n
t
r
a
t
i
o
n

(
k
m
o
l
/
m
3
)
reaction time (h)
C
ADN,0
exp. model
1.426
0.440
0.167
Figure 11 (a) Experimental and calculated ACN
concentration function of time. T = 72 C.
0 1 2 3 4 5 6
0.0
0.1
0.2
0.3
0.4
0.5
A
C
N

c
o
n
c
e
n
t
r
a
t
i
o
n

(
k
m
o
l
/
m
3
)
reaction time (h)
C
ADN,0
exp. model
1.250
0.440
0.167
Figure 11 (b) Experimental and calculated ACN
concentration function of time. T = 92 C.
4. CONCLUSIONS
Rh/Al
2
O
3
is an interesting and alternative catalyst respect with the traditional and Raney based catalyst for the
hydrogenation of adiponitrile in liquid phase. Nevertheless the very high price of Rh (about 2000 US$ /troy Oz)
imposes simple preparation methods for a catalyst with very high metal dispersion and high catalyst utilisation in
the reactive process. In previous works we studied the preparation and the performance of the Rh/Al
2
O
3
catalyst.
In the present paper further reaction runs were presented and on their basis using the chemical engineering
approach simple phenomenological rate expression were obtained to interpret the kinetics of the hydrogenation
of adiponitrile on the Rh/Al
2
O
3
catalyst. It was found the ADN rate of consumption follows a zero order kinetic
law and that the reaction of formation of HDM is of first order with respect to the ACN concentration. The
kinetic equations found are in agreement with the general Langmuir-Hinselwood scheme proposed in literature
for the same reaction catalysed by Ni Raney
ACKNOWLEDGEMENTS
The financial support of the Ministero dellUniversita e della Ricerca Scientifica (MIUR) is gratefully
acknowledged.
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11 Di Felice et al.: ADN hydrogenation over Rh catalysts
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