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 20/4°C 1.02173
at 20/20°C 1.022
Viscosity at 20°C‚ mPa·s (= cP) 4.423-4.435
Dissociation constant‚ pK
at 20°C 4.60
at 60"C 8.88
Enthalpy of dissociation‚
kJ/mol (kcal/mol) 21.7(5.19)

361
362 SYNTHETIC NITROGEN PRODUCTS

Table 20.1. Physical Properties of Aniline - continued

Property Value

Heat of combustion‚
kJ/ mol (kcal/mol) 3389.72 (810.55)
Specific heat‚ 20-20°C 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 @ 20°C) 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 300°C to 475°C in a fixed bed. The selectivity to
aniline is more than 99%. The catalytic activity slowly decreases due to carbon
ANILINE AND NITROBENZENE 363

deposition. However‚ the catalyst can be regenerated with air at 250°C to 350°C
and subsequent treatment. Similar processes are operated by ChemFirst
which uses a copper on pumice catalyst from Lonza; ICI with Cu‚ Mn or Fe
catalysts with various modifications involving other metals; and by Sumitomo
with a Cu-Cr system46. A typical process diagram is shown in Figure 20.1137.
The gas-phase hydrogenation of nitrobenzene with a fluidized-bed catalyst
is used in a process from BASF. The BASF catalyst consists of Cu‚ Cr‚ Ba and
Zn oxides on a support. The hydrogenation is conducted at 270°C to 290°C
and 1 to 5 bar in the presence of a large excess of hydrogen
9 to 1). The high heat of reaction is removed by a cooling system that is built
into the fluidized bed. The selectivity to aniline is 99.5%‚ and the nitrobenzene
conversion is quantitative. The catalyst must be regenerated with air
periodically46.

20.1.1.2. Nitrobenzene Reduction with Iron Filings

The older Bechamp method for iron oxide pigment production gives aniline
as a co-product and is operated by Bayer in West Virginia. Nitrobenzene is
reduced by reaction with iron filings in the presence of a hydrochloric acid
catalyst. The iron is oxidized to the ferrous or ferric state‚ and the aniline-water
mixture is separated from the iron-hydroxide sludge. The heavier aniline layer
is removed and vacuum distilled to yield pure aniline. The yield is 90% to 95%
of theoretical. The reactions are represented as follows138, 255:

This process would have been replaced much earlier by more economical
reduction methods if it had not been possible to obtain valuable iron oxide
pigments from the iron oxide sludge. However the increasing demand for
aniline has far surpassed the market for iron pigments‚ so this process is no
longer preferred46.
364 SYNTHETIC NITROGEN PRODUCTS
ANILINE AND NITROBENZENE 365

20.1.1.3. Ammonolysis of Phenol

Aniline can also be produced when phenol is subjected to gas-phase

ammonolysis at 200 bar and 425°C in an adiabatic‚ fixed-bed reactor. This is the
Halcon/Scientific Design process. The chemistry is:

The catalysts are (possibly as zeolites) and oxide mixtures of

Mg‚ B‚ Al and Ti. These can be combined with additional co-catalysts such as
Ce‚ V or W. With a large excess of ammonia‚ the selectivity to aniline is 87% to
90% at a phenol conversion of 98%. The by-products are diphenylamine and
carbazole. This technology is used at one plant by Sunoco (previously Aristech
Chemical) in Ohio and at another plant in Japan. The economics of this process
are favorable if low-cost phenol is available‚ and high-purity aniline is desired.
Capital costs are low because benzene nitration is avoided. A typical process
sketch along with a material balance is shown in Figure 20.2139.

20.1.2. Aniline Production

MDI [4‚4’-methylenebis (phenylisocyanate)] has been the driving force

behind the recovery of the aniline business since 1982 when the industry had a
capacity utilization rate of less than 50%. By 1996‚ capacity utilization had
approached 95% in some regions138.
Aniline’s global production capacity in 1999 was 2.9 million tonnes‚ and
demand in 2000 was estimated to be 2.68 million tonnes per year. The capacity
in 1999 was found in these regions: Western Europe - 47%‚ North America -
30% and Asia / Pacific - 19%140,256. In 2000 China had over 20 aniline producers
with a total capacity that exceeded 200‚000 tonnes per year. Aniline production
in 1999 in China was 142‚700 for a utilization rate of around 70%. Historical
production in the United States is summarized in Table 20.2255.

Table 20.2. Aniline Supply and Demand

Million of Pounds
1995 1996 1997 1998 1999 2000 2001b
Capacity 1380 1420 1535 1745 1745 2310 2310
Total Prod. 1388 1395 1339 1545 1588 1866 1975
Imports – 24 60 42 26 11 12
Exports 67 41 19 43 38 58 65
Demanda 1321 1378 1380 1544 1574 1819 1922
a
Demand equals production plus imports minus exports.
b
Forecast
(Reproduced by permission of Mannsville Chemical Products Corp.)
366 SYNTHETIC NITROGEN PRODUCTS
ANILINE AND NITROBENZENE 367

Aniline consumption grew at a rate of 5.5 percent per year from 1995 to
2000. It is expected to grow at 3.9 percent per year from 2001 through 2004262.
Aniline pricing tends to track benzene pricing rather closely. In general the
aniline price will move 1.2 cents per pound for each 10 cents per gallon
movement in benzene price. Between 1995 and 2001‚ the aniline sales price
varied from $US 0.35 per pound to $US 0.40 per pound255.

20.13. Aniline Uses

MDI [4‚4’-methylenebis (phenylisocyanate)] accounted for almost 85% of

the worldwide demand for aniline in 2000. MDI is used primarily to make rigid
polyurethane foam and polyurethane elastomers. MDI growth is expected to be
6% to 8% per year during the 2000’s as its use continues to increase in the
construction industry (the largest user of rigid polyurethane foam) and the auto
industry (the largest user of reaction-injection molding plastics). The aniline
uses are shown in Table 20.3255 .

Table 20.3. Aniline Uses255‚ 262

Application %
Isocyanate 85%
Rubber Chemicals 9%
Agricultural Chemicals - Pesticides 3%
Dyes & Pigments 2%
Specialty Fibers 1%
Miscellaneousa 1%
a
Miscellaneous includes explosives‚ epoxy curing agents and pharmaceuticals .

The use of aniline in rubber chemicals will closely track the Gross
Domestic Product growth in the United States‚ while its use in agricultural
chemicals is expected to slowly decline. Aniline-based dyes and pigments are
forecast to have little growth255.
Aniline is considered a suspect carcinogen. It is absorbed through the skin‚
lungs or mucous membranes‚ and it can produce serious burns. In 2001 the
ACGIH recommended exposure limit is 2 ppm. The odor of aniline can usually
be detected in concentrations as low as 0.5 ppm. Aniline is combustible‚ but it is
not explosive or spontaneously flammable in air255.

20.2. NITROBENZENE

Nitrobenzene‚ also known as oil of mirbane‚ is a pale yellow liquid with an

odor resembling that of bitter almonds. It was first synthesized in 1834 by E.
368 SYNTHETIC NITROGEN PRODUCTS

Mitscherlich by treating benzene with fuming nitric acid and has commercial
importance as the major precursor to aniline46‚ 258.

20.2.1. Nitrobenzene Processes

Nitrobenzene is made by three processes: direct nitration‚ dehydrating

nitration and adiabatic nitration. The first process involves the direct nitration of
benzene using a mixture of nitric acid and sulfuric acid46, 258.

The sulfuric acid promotes the formation of the nitrating agent (the
nitronium ion) and prevents the dissociation of nitric acid into an oxidizing
ion by binding water as a hydrate. It also enhances the solubility between the
aqueous and organic phases46.
This process may be carried out by a batch or a continuous process. The
continuous process is more effective for large plants. Both processes wash the
crude nitrobenzene with water. The crude nitrobenzene is fed to a distillation
system to separate the water‚ benzene and dinitrobenzene. This process requires
reactor cooling and a system for sulfuric acid reconcentration. Yields by the
continuous process are 95% to 96% of theoretical. Bayer used this process in
the United States until it discontinued nitrobenzene production in 1994258 .
In the batch process‚ the nitrating acid (a mixture of 32 to 39 wt %
53 to 60 wt % and 8 wt % flows into the benzene‚ and the
chemicals react in cast-iron nitrating vessels at 50 to 55°C. The process requires
a lot of agitation due 1) the formation of two phases and 2) the required mass
and heat exchange. After a residence time of several hours‚ the nitrating acid is
largely exhausted and the denser nitrobenzene is separated‚ washed and distilled.
The selectivity reaches 98 to 99%46.
The continuous nitration plant consists of a cascade of stirred vessels
(usually three nitrating vessels) with a stepwise‚ slowly increasing temperature
(35 to 40°C in the first vessel‚ 50°C in the second and 55 to 60°C for the final
reaction. The largest units are the final settling and washing vessels46.
DuPont developed a dehydrating nitration process by which water produced
in the mixed acid nitration reaction is removed by humidification of the inert gas
stream. This eliminates the energy-intensive sulfuric acid process258.
American Cyanamid and ICI Canada jointly developed a process to
adiabatically produce mononitrobenzene. This process uses the heat of reaction
to reconcentrate the spent acid stream. The process development was completed
and commercialized by Kvaerner Chemetics and ICI Canada. As of 2003‚ a
total of seven (7) adiabatic mononitrobenzene plants have been constructed‚
with the largest being rated at 227‚000 tonnes per year. A process sketch is
shown in Figure 20.3290.
ANILINE AND NITROBENZENE 369
370 SYNTHETIC NITROGEN PRODUCTS

In the adiabatic mononitrobenzene (MNB) process‚ benzene is nitrated in

the presence of a large volume of mixed acid‚ such that the total heat of nitration
and dilution is absorbed by the acid as sensible heat. The process utilizes this
energy in a vacuum sulphuric acid evaporator to reconcentrate the spent acid‚
which is then returned to the nitration section.
Nitration is carried out in a series of stages. Mixed sulphuric and nitric
acids together with benzene are introduced at the bottom of the first stage. The
reaction takes place while the fluids flow upwards through the reactors.
The organic and acid phases are separated in a static separator located at the
top of the process building. From the separator the acid phase discharges to the
vacuum concentrator‚ while the organic phase passes to the washing section.
The vacuum sulphuric acid concentrator consists of a single stage
evaporator. The vacuum is maintained by a two-stage steam ejector system
utilizing shell and tube inter-and after-condensers. Most of the heat required to
reconcentrate the sulphuric acid is recovered as sensible heat from the reaction
and is contained in the spent acid. The balance is added through a tantalum
bayonet heater immersed in the evaporator body.
In the washing process‚ acids and nitrophenols are removed from the crude
MNB by means of an alkaline wash. Condensate from the acid concentrator
may be used as wash water. The washing section of the plant employs specially
designed equipment for space saving‚ minimum use of wash water and
elimination of circulation pumps.
In the subsequent product stripping section‚ the product is stripped free of
benzene and water using a live steam stripper or a reboiler column. The effluent
discharged from the washing area is steam-stripped to recuperate MNB.
There is a single vent stack in the plant. The stack gases are treated in a
benzene scrubber to remove benzene vapours prior to incineration or other
means of treatment290.

20.2.2. Nitrobenzene Production

MDI has been the driving force behind the recovery of the aniline business‚
and consequently nitrobenzene‚ since the early 1980’s. Nitrobenzene production
capacity in the United States in 2002 was 2.96 billion pounds. Demand has
grown from 2.235 billion pounds in 1999 to 2.526 billion pounds in 2000.
Production grew at a rate of 6.5 percent per year from 1995 to 2000. And from
2000 through 2004 production is expected to continue growing‚ but at a slower
growth rate of 3.9 percent per year. The slowdown in growth is due to a
downturn in the United States economy. However the forecast growth rate is
still higher than the rate of growth in the gross domestic product. The supply
side of nitrobenzene is in excellent shape. Plant operating rates are about 85
percent‚ and feedstock supplies of benzene‚ nitric acid and sulfuric acid are
adequate to meet demand. Foreign trade is negligible263.
Between 1996 and 2001‚ the nitrobenzene sales price varied from $US 0.30
per pound to $US 0.35 per pound263.
ANILINE AND NITROBENZENE 371

20.2.3. Nitrobenzene Uses

Aniline accounted for almost 97% of the United States demand for
nitrobenzene in 2001. The other three percent is used in p-aminophenol‚ dyes
and pigments and as a chemical intermediate and solvent.