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 Slovak Society of Chemical Engineering
Institute of Chemical and Environmental Engineering
Slovak University of Technology in Bratislava

PROCEEDINGS
41st International Conference of Slovak Society of Chemical Engineering

Hotel Hutník
Tatranské Matliare, Slovakia
May 26–30, 2014

Editor: prof. Jozef Markoš

ISBN: 978-80-89475-13-1, EAN: 9788089475131

Králik, M., Turáková, M., Mačák, I., Lehocký, P.: Aniline - catalysis and chemical engineering, Ed-
itor: Markoš, J., In Proceedings of the 41st International Conference of Slovak Society of Chemical
Engineering, Tatranské Matliare, Slovakia, 723–733, 2014.
41st International Conference of SSCHE 
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Aniline - Catalysis and Chemical Engineering

Milan Králik, Mária Turáková, Ivan Mačák, Peter Lehocký

VUCHT a.s., Nobelova 34, Bratislava (mkralik@vucht.sk, maria.turakova@stuba.sk,

imacak@vucht.sk, plehocky@vucht.sk)

Keywords: aniline, benzene, nitration, catalytic hydrogenation, deactivation of catalysts,

intrinsic reaction kinetics, mass and heat transport

Symbols and abbreviations:

AN - aniline; B – Benzene; G - gaseous phase; HOMO - the Highest Occupied Molecular
Orbital; L - liquid phase; LUMO - the Lowest Unoccupied Molecular Orbital;
NB– nitrobenzene; NOB – nitrosobenzene; PHA - N-phenylhydroxylamine; S - solid phase
(catalyst); V - vapour phase; * - catalytic centre

Abstract
Aniline (AN) is an important organic chemical commodity with an annual worldwide
production at levels of MT. Main applications are in polymer chemistry; however production
of rubber chemicals, dyes, pharmaceuticals, and other chemical specialties is also important.
Nitration of benzene (B) and hydrogenation of the generated nitrobenzene (NB) to aniline are
main chemical steps in the industrial production of AN. In spite of many attempts to replace a
classical nitric-sulphuric acid mixture for the nitration of benzene by more ecological agents,
e.g. a direct nitration with oxides of nitrogen, industrial production of NB is exclusively based
on that classical procedure. Of course, modern reactor solutions (jet mixing, intensive mass
transport, precise control of temperature, etc.) ensure high yields of NB and sophisticated
treatment of wastes (regeneration of nitration mixture, thermolysis and biological treatment of
wastewaters) minimize ecological impacts.
The catalytic reduction of NB can be carried out either in the gas/vapour phase (G-S) or
in the liquid phase (L-S). Copper catalysts are favoured for the G-S and noble metals (mainly
palladium and platinum) are preferred for the L-S system. Besides high yields of AN (more
than 99%) inevitable requirement is utilization of the reaction heat (more than 500kJ/mol).
Modern reaction routes for production of AN are based on a direct amination of
benzene these are subjects for investigations. However results obtained so far do not give
chance to compete with the nitrobenzene technology.
Together with literature and patent data, brief information about the development of
aniline technology in VUCHT is also reported. A special focus is on reaction routes in the
hydrogenation of NB, deactivation of catalysts and relationships with their physicochemical
features, as well as reactor arrangement and its influence on mass and heat transport.
Necessity to combine theoretical (calculated) results with those from a model hydrogenation
unit is a key factor for design of efficient technology.

Introduction
History of AN has started in 1826, when the German chemist Otto Unverdorben isolated
by destructive distillation of indigo a substance that he called in that time Krystallin [1].
Increasing demands for AN led to synthetic routes, which started using the so called Bechamp
reduction published in 1854 [2].

4 NO2 + 9 Fe + 4 H 2 O 4 NH2 + 9 Fe 3 O4

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Later the reduction with iron was substituted by a catalytic reduction of nitrobenzene,
firstly applied in 1871 [3,4], and it is still the most utilized procedure for the preparation of
AN [5,6].
This paper is devoted mainly to the production of AN by the reduction of NB, especially
using palladium catalysts but some alternative routes are mentioned, too.

Preparation of nitrobenzene
Nitrobenzene is industrially prepared by the electrophilic substitution of hydrogen in the
benzene ring with the nitronium ion (NO2+):

H 2SO4 + HNO3 HSO4- + H 2O + NO2+

H
+ NO2+ + NO2

H
+ NO2
+ HSO4- NO2 + H 2SO4

Scheme 1. Nitration of benzene.

The rate of nitration is proportional to concentration of NO2+, which is dependent on

concentration of sulphuric acid and nitric acid. Dilution of reaction mixture with water
strongly decreases the reaction rate; when a concentration of water is higher than 50mole%,
the concentration of NO2+ reaches zero the nitration stops [7]. Therefore, it is useful if at least
a part of the water goes out from the reaction mixture in the form of vapour, what is typical
for adiabatic nitration processes.
As listed in Table 1, the nitration of benzene is a strong exothermic process. Taking into
account oxidation capability of nitric acids and necessity to work with a concentrated nitration
mixture (H2SO4+HNO3) a technological arrangement of the process enabling high yield of
NB, safety and a good overall economy is not simple. There are two contradictory features:
1. Intensive phase contact enhances reaction rate
2. A higher reaction rate is connected with the higher generation of heat
Design of the process is either isothermal (external removal of reaction heat), or the
process is adiabatic. In both cases plug flow reactors are preferred for finishing the reaction.

Table 1. Standard molar enthalpy (heat) of formation at 298.15 K and reaction heat of the
nitration of B to NB and hydrogenation of NB to AN a.
Compound ∆fH°/kJ mol–1(L) ∆fH°/kJ mol–1(G)
B 49.1 82.9
HNO3 -174.1 -133.9
NB 12.5 67.5
H2 0.
AN 31.6 87.5
Water -285.8 -241.8

Reactions ∆rH°/kJ mol–1(L) ∆rH°/kJ mol–1(G)

B + HNO3 -> NB + H2O ‐148.3 ‐123.3 
NB + 3H2 -> AN + 2H2O -552.5 -463.6
a
Data from http://www.update.uu.se/~jolkkonen/pdf/CRC_TD.pdf

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There are only a few suppliers in the world which provide good nitration technologies.
Probably the first successful process of adiabatic nitration was presented by DuPont [8,9] who
offers competitive technologies also today:
http://dupont.t2h.yet2.com/t2h/page/techpak?id=27458&sid=330&abc=0&page=tpprint).
Meisner company (http://www.josefmeissner.com/en/nitroaromatics/mononitrobenzene-
mnb) applies adiabatic jet reactor [10] with subsequent tube rectors to ensure high contact of
organic phase (NB + B) with the nitration mixture. Formation of by-products (nitrophenols,
picric acid and dinitrobenzene) is minimized just by an optimal reactant intermixing and
negligible back mixing inside the tube reactor. Due to the adiabatic technology, the
reconcentration of the sulfuric acid can be directly in the plant. The crude NB is fed to the
washing section consisting of MEISSNER compact washers and residual B in the purified
NB is separated by means of steam? (as a steam) and returned into the process.
The next supplier of the NB technology is NORAM (http://www.noram-
eng.com/groups/nitration-group-technologies.html), who uses patented electrophilic reactor
[11]. A high dispersion of benzene in the acid phase and consequent a fast reaction rate is
achieved by jet impingement of organic and water-acid phases. It is possible to minimize
residence time and virtually stoichiometric conversion of nitric acid and benzene is attained.
A decanter is used to separate the organic and acid phases. Spent acid is reconcentrated in a
Sulfuric Acid Flash Evaporator (SAFE). Energy requirements for the process are met largely
by pre-heating B and nitric acid feeds with waste reaction heat. The crude product is taken to
downstream facilities for purification. These treatments involve both standard and proprietary
procedures for washing and B stripping.
Plinke also offers adiabatic nitration of B in the liquid phase:
http://www.plinke.de/fileadmin/user_upload/pdf/Flyer/PLINKE_NB_08-2012.pdf. The
concentration of nitration mixture is adjusted to keep safety limits (increase in temperature
due to exothermic reaction). Washing and stripping are the next steps for the production of
high quality NB.
Treatment of wastes is rather sophisticated. Meissner offers thermolysis of organic
wastes. Plinke uses treatment of waste waters with oxygen and FeSO4 as a reactant and a
catalyst and biological treatment in the next step. Outgases contain portion of organics and
some NOx and are treated using common DENOX procedures.
Despite a lot of endeavour, successful laboratory research, technological applications and
investigations, nitration of benzene still provides a space for further improvements [12].
The field of gas-phase nitration is of interest; however this process is not competitive
with liquid-phase processes using sulphuric acid. The challenge remains to find an efficient
catalyst for the gas-phase nitration with oxides of nitrogen [13,14].

Catalytic reduction of NB to AN
Catalytic reduction was firstly described by Kolbe and Zaztseff [3,4].
cat.
NO2 + 3 H 2 NH2 + 2 H 2 O

Chemical aspects of the hydrogenation of NB

A general pathways in the hydrogenation of NB are given in Scheme 2 [15,16]. The
desired route is expressed by reactions NB→NOB→PHA→AN, where NOB denotes
nitrosobenzene and PHA N-phenylhydroxylamine. However; a strong chemisorption and
reactivity of NOB (Table 2) causes that NOB is virtually not desorbed from the catalytic
surface and it undergoes further hydrogenation and condensation reactions. This led Gelder et
al., [17, 18] to modifications expressed by Scheme 3.

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NO2 HO NH2
1 6
H
2 O

NO N N
2 5 N NH2
H H H
2 2 8
NHOH
3
H N N H
2 2
H 7
NH2 2
N N
4 H H
NH 2 9
H 10 14
2
H
2
H 2O H
2
NH 2 NH O OH
11 13 NH 3
15 16
- NH 3 NH2 - NH3 NH2
H 2O
OH
- NH3
12
N H
N
17
H
2
H
2 18
N N
H H
20 19

{ High molecular weight compounds }

Scheme 2. Reaction pathways in the hydrogenation of NB.

NO2 NO NH2

NOH
H2

HO H
N NH2 NH2 NH O OH
O
H2 H2O H2
N N
- NH 3

AN - NH 3
AN - H2O H
H
NH N
N N N N
H2

H - H2 H2
NH2 N N H H
H N N

             
Scheme 3. Gelder’s [17,18] interpretation of reaction pathways in the hydrogenation of NB.

Experience from the recent years pointed out importance of quantum mechanical
modelling for reactivity elucidation. Increase in computers power together with available
modelling programs allow to calculate approximate values of charge distribution and energies
for HOMO (willingness to donate electrons) and LUMO (willingness to accept electrons)

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orbitals in a rather simple way. The very important is a difference between energies of
HUMO and LUMO; the lower is this value the higher is their reactivity. To evaluate steric
effects structures of molecules are presented in Figure 1.

Table 2. Energies of the Highest Occupied Molecular Orbital (EHOMO) and the Lowest
Unoccupied Molecular Orbital Calculated (ELUMO) using HYPERCHEM lite program with the
MP3 method considering atoms charges.

Molecule EHOMO ELUMO ELUMO -

/eV /eV EHOMO /eV
NO2B -12.80 -10.92 1.88
NOB -11.80 -11.12 0.68
NPHA -11.95 -8.32 3.63
AN -12.00 -8.33 3.67

Figure 1. Structure of NB (upper left), NOB (upper right), PHA (down left), AN (down right).

According to the work of Kochetova et al. [19], the catalytic steps of hydrogenation are
depicted in Scheme 4, where positive effect of electron withdrawing moieties on the
formation of H+ species is evident. The electron withdrawing effect can be ensured by a
support, e.g. activated carbon, or positively charged moieties (V5+, Zn2+, and other cations of
transition metals) [20].

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+H - +H+
H 2O
* δ-
* * *
H δ+
H
N δ+ N N δ- N
Hδ δ -
- H
δ-
O O O O HO Oδ - O

Hδ+ H δ+ Hδ+ Hδ+ Hδ+ Hδ+ H δ+ Hδ

+

Pd Pd Pd Pd

+H - +H + + H+ + H-
H2 O
* δ-
* *
NH NH N H H N H N
δ- δ-
O- OH O H O Hδ+ H H

H δ+ H δ+ Hδ
Pd Pd Pd Pd Pd

Scheme 4. Catalytic steps in the hydrogenation of NB.

Deactivation of catalysts in the course of NB hydrogenation

Deactivation of palladium catalysts in the presence of NB is well known [21-25]. Scheme
5 [25] and Figure 2 describe a typical situation during deactivation of a palladium catalyst.
High yields of AN and low consumption of a catalyst require: (i) a proper catalytic
strength, i.e. if the activation of NB and intermediates is too strong, the catalyst is deactivated
by coking, (ii) as much as possible low concentration of NB, (iii) good heat and mass transfer
to decrease NB concentration around catalytic particles and removal of reaction heat.

Scheme 5. Representation of palladium

leaching reactions (Turakova et al.
2014).

Figure 2. Deactivation of a palladium catalyst

by NB oxidation of palladium nanoparticles.

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Mass and heat transport in the liquid phase hydrogenation

Figure 3. depicts individual mass transports from G to L phase, from L to catalyst
surface (S) and backward. As for hydrogenation of NB this picture does not show transport of
water to the G/V phase, which decreases partial pressure of hydrogen (lower partial pressure
of hydrogen decreases the rate of hydrogenation). The hydrogenation can be carried out in
such a way that the whole amount of water is dissolved in organic phase.
Another factor influencing lifetime of the catalyst is its mechanical deterioration that
limits the reactor selection. The most intensive contact of phases with minimal catalyst
abrasion is in gas lift reactors. Reaction heat (see Table 1) is taken off by external coolers and
evaporation of reaction components (mainly water).

Figure 3. Peculiar features

of the hydrogenation in
liquid phase. 3 or 4 phase
system in case of water-
organics systems with
limited miscibility, i.e. G-L-
S, or G-L-L-S systems (H2 -
G-phase), very often –
hydrophilic catalyst.

Figure 4. Possibilities for intensification of mass transport in the G-L-S reaction systems.
Types of reactors from the left: mechanically stirred; Buss; column reactor with the recycling
of G-phase; gas lift.

Industrial realizations of NB to AN technology

The catalytic reduction of NB can be carried out either in the gas/vapour phase (G-S) or
in the liquid phase (L-S). Copper catalysts are favoured for the G-S and noble metals (mainly
palladium and platinum) are preferred for the L-S system. Besides high yields of AN (more
than 99%) inevitable requirement is utilization of the reaction heat (more than 500kJ/mol).
In Table 3. the most successful industrial applications for production of AN from NB are
listed.
From the Czecho-Slovak point of view the hydrogenation in the gas phase built up in
Ostrava (Pasek et al. [26,27] ) is one of the most successful process. It is worthy to add that
principle of quality of this process was fully exploited for making a licence. In 2003, this
aniline-production license was sold to Japan (TOSOH Aniline Plant Project) where a 150
kt/year aniline unit was built. This technology transfer is probably the largest chemical
process ever sold out of the Czech Republic - and to Japan, indisputably a great power in

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chemical industry in collaboration with BC MCHZ. A little drawback of this technology is a

gradual loose in catalytic activity (months) and necessity to change catalysts in the fixed bed
reactors.

Table 3. Industrial aniline technologies (potential licensors).

P Heat
Phase Cat. Reactor Fy
(bar) exploit.
G Cu-support 3 Fluidized Excellent BASF
G Cu-support 5-7 Series of adiabatic Good First Chemicals
reactors
G Cu-support 2-3 Tube + adiabatic reactor Very good BC-MCHZ
G Pd-alumina 2 Tube, coolled with oil Good Bayer
G Cu-Cr2O3 2 Tube Good Sumitomo
G Ni-support 2 Tube, coolled with oil Good NIOPIK Russia
L Ni-support 15 Autoclave with a stirrer Bad Tolo Chimie
L Ni-support 5 Autoclave with a stirrer Bad ICI
L Pd-Pt-Fe 17 „Plug-flow“ reactor Good Du Pont

From the point of minimizing consumption of the catalysts and energy utilization (see
Table 2) the DuPont technology represents a very significant contribution to solution of this
problem
http://dupont.t2h.yet2.com/t2h/page/techpak?id=27458&sid=330&abc=0&page=details). This
technology uses plug-flow hydrogenation reactor that contains a DuPont proprietary
supported noble metal catalyst. NB is fed together with hydrogen into this reactor and reaction
takes place in the liquid phase. The catalyst has a high selectivity and the NB conversion is
virtually 100% per pass. Excess hydrogen from the reactor effluent is vented and the reactor
product is sent to a dehydration column to remove the reaction water followed by a
purification column to produce high quality aniline product.

Alternative routes for the preparation of AN

Until around 1970 amination (formerly often called ammonolysis) of chlorobenzene with
aqueous ammonia, at 210°C and 60–70 bars, with a cuprous salt as a catalyst was employed in
the manufacture of aniline [2]. Catalytic amination of phenol at 425°C and around 200 bars
has been developed by Mitsui Petrochemical Industries of Tokyo. In the Halcon process, the
amination of phenol takes place in the vapour phase with a silica–alumina catalyst. Despite
technological/economical advantages (reduced capital costs, long catalyst lifetime and high
quality product), the main drawback is utilization of relatively expensive phenol. The last
plant in the US to produce aniline from phenol by amination was operated by Sunoco
Chemicals. It produced 140 million lbs/year, with diphenylamine as a co-product, at
Haverhill, Ohio and ceased the production in 2002.
Modern reaction routes for the production of AN are focused on a direct amination of
benzene.
cat.
+ NH3 NH2 + H2

Usually the generated hydrogen is “consumed” by oxidation to water. Interesting

procedure was proposed by Hoffmann & Muhler [28], who used a Ni catalyst as a co-reactant.
Generated H2 reacts with NiO, producing H2O and metal Ni, and the metal Ni is oxidised with
CO2 generated from hydrocarbons and oxygen. Another way is the amination of benzene by

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aqueous ammonia over platinum-loaded titanium oxide photocatalyst [29]. However, potential
industrial applications are limited due to higher costs in comparison with the classical NB
route.

Development of aniline technology in the VUCHT

In 2011 VUCHT has started a systematic research onto hydrogenation in the liquid phase
(http://www.vucht.sk/sluzby/projekty-s-podporou/projekt-hydrogenacie-v-kvapalnej-
faze/priebeh-realizacie). Besides laboratory and technological research the main output is the
model hydrogenation unit (Figure 5), which was designed using the concept [30] in
collaboration with Pasek. Going from laboratory tests, the best catalysts were used in this
model unit and their activity and selectivity was evaluated from runs lasting a few hundred
hours. Influences of: (i) catalyst concentration; (ii) residence time; (iii) pressure; (iv)
temperature and flowrate of hydrogen were studied. A high yield of AN (more than 99.5 %)
and low content of oxygen derivatives (see Scheme 2) from the hydrogenation reaction
significantly simplifies the overall technology, including separation steps.
In order to obtain a desired quality of aniline (the content of AN> 99.9 %; NB<1ppm), a
separation system has required a special attention. Vapour-liquid equilibria at increased
pressure and temperature were necessary to be measured in the VUCHT laboratories.
ASPEN-HYSYS software was used as a tool for design of the complex technological scheme
and material and energy balances.
Besides solution of the hydrogenation and separation problems, a significant research
area has been devoted to treatment of wastewaters and outgases. Maximum feeds of pollutants
were determined from tests on laboratory model of industrial wastewater plant. Operating
conditions (other pollutants, residence time, aerobic and non-aerobic sections) were
analogical to IWWP and tests lasted a few months. All the experimental and theoretical
investigations underline the reliability of the obtained data.

Figure 5. Model reaction unit for the

continuous hydrogenation in the liquid
phase. Pmax=5MPa, Tmax=250°C. The gas
lift reactor is seen in the middle. The plug
flow reactor is on the right side.
The model unit was built up as an activity in
the framework of the project:
“Hydrogenation in the liquid phase, ITMS:
26220220144, supported by the Research &
Development Operational Programme
funded by the ERDF.“

Conclusions
Probably no organic compound attracts so much interest like aniline. From its
identification in 1826, a vast research and technological applications to produce aniline were

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described. Economic, ecological and safety reasons favour the production of aniline via
nitration of benzene and its hydrogenation. Besides catalytic chemistry, mass and heat
transport and a proper reactor design are governing the success of the processes.
Based on theoretical background, laboratory research and especially results from the
continuous model hydrogenation unit allowed VUCHT to classify proper hydrogenation
catalysts and design the reactor system. High selectivity to aniline minimizes complexity of
the separation system.
A direct amination of benzene still remains as a challenge for the development of future
aniline technologies.

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Acknowledgement:
This publication is one of results of the project implementation: Hydrogenation in the liquid
phase, ITMS: 26220220144, supported by the Research & Development Operational
Programme funded by the ERDF.“

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