20

ANILINE AND NITROBENZENE

20.1. ANILINE

Aniline (also know as aminobenzene and benzamine) was first produced in

1826 by Unverdorben by the dry distillation of indigo the oldest known vat dye.
Fritsche also obtained aniline from indigo by heating it with potash and
he named it aniline. Hofmann obtained aniline by the reduction of nitrobenzene
in 1843 and was able to prove the structure. Aniline is a colorless oily
flammable liquid that is slightly soluble in cold water and infinitely soluble in
alcohol and ether. Its physical properties are summarized in Table 20.1.

Table 20.1. Physical Properties of Aniline

Property Value
Molecular Weight 93.12
Boiling point. C
101.3 kPa (760 mm Hg) 184.4
4.4 kPa (33 mm Hg) 92
1.2 kPa (9 mm Hg) 71
Melting point C -6.15
Density d
at 20/4C 1.02173
at 20/20C 1.022
Viscosity at 20C mPas (= cP) 4.423-4.435
Dissociation constant pK
at 20C 4.60
at 60"C 8.88
Enthalpy of dissociation
kJ/mol (kcal/mol) 21.7(5.19)

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Table 20.1. Physical Properties of Aniline - continued

Property Value

Heat of combustion
kJ/ mol (kcal/mol) 3389.72 (810.55)
Specific heat 20-20C 0.518
Latent heat of vaporization
J/g (cal/g) 476.3 (113.9)
Flash point (closed-cup) C 76
Autoignition Temperature C 615
Flammable Limits in Air (% by Volume)
LEL 1.3
UEL 11.0
Vapor Density (Air = 1) 3.22
Solubility (g in 100 g Water @ 20C) 3.5
Odor Threshold ppm 1.1

20.1.1. Aniline Processes

The aniline processes that are being used in 2003 include:

1) Hydrogenation of nitrobenzene
2) Nitrobenzene reduction with iron filings and
3) Ammonolysis of phenol.

Almost 97% of the nitrobenzene produced in the United States is converted

to aniline between the hydrogenation process and the iron filings process137.

20.1.1.1. Hydrogenation of Nitrobenzene

The primary aniline production process in the world is the hydrogenation

of nitrobenzene. BASF DuPont ChemFirst (purchased by DuPont in 2002) and
Rubicon use this process in the United States. This technology is also used by
all Western European aniline producers and all but one Japanese aniline
producer.

The catalytic gas-phase hydrogenation processes for nitrobenzene can be

carried out using a fixed-bed or a fluidized bed reactor. Bayer and Allied work
with nickel sulfide catalysts at 300C to 475C in a fixed bed. The selectivity to
aniline is more than 99%. The catalytic activity slowly decreases due to carbon