NAME PROJECT

Production of nitrobenzene by
nitration direct benzene

introduction
1-History
The earliest aromatic nitro compounds Were Obtained by
MITSCHERLISH

in 1834 by treating hydrocarbons derived

from
coal tar with fuming acid [1, 2, &3]. By 1835 LAURENT was
working on the nitration of naphthalene, the most readily available
pure aromatic hydrocarbon at that time. DALE reported on
mixed
nitro compounds derived from crude benzene at the 1838 annual
meeting of the British Association for the Advancement of Science.
Not until 1845, however, did HOFMANN and MUSPRATT report
their systematic work on the nitration of benzene to give monoand dinitrobenzenes by using a mixture of nitric and sulfuric
acids .
Conclusion It Nitrobenzene was first synthesized in 1834 by treating
Benzene with Fuming Nitric Acid, and it was produced commercially
in England in 1856. The relative case of aromatic nitration has
contributed significantly to the large and varied industrial application
of nitrobenzene and its derivative .The first small-scale production of
nitrobenzene was carefully distilled to give a yellow liquid with a
smell of bitter almonds for sale to soap and perfume manufacturers
as essence of mirbane.[1].
The number of naturally occurring nitro aromatic compounds is small;

This discovery stimulated investigations into the role of nitro group in

pharmacological activity, following the earlier (1943) discvery of the
antibacterial activity of nitrofuran derivatives. Many synthetic pharmaceuticals
and agrochemicals contain nitro aromatic groups, although the function of the
nitro group is often obscure [1]. Nitrobenzene is one of the important raw
materials for the dye manufacture and most nitrobenzene produced is used
directly or indirectly in dye manufacture. It is manufactured on large scale
only by aniline manufactures. Ref[1]. The choice of nitro compounds covered
here is influenced strongly by their commercial application of compounds in
the 1981 European core Inventory. Most nitro compounds, or their derivatives,
are intermediates for colorants, agrochemicals, pharmaceuticals, or other fine
chemicals with a few major volume outlets for synthetic materials and
explosives [1]

Specifications of Nitrobenzene
Nitrobenzene [98-95-3](oil of mirbane),C6H5NO2, is colourless to pale
yellow oily liquid with on odour resembling that of bitter almonds or "shoe
polish." Depending on the purity, its color varies from pale yellow to
yellowish brown [2 & 3].
Product specifications have been developed for technical-grade nitrobenzene
and for distilled-grade nitrobenzene.

Table 1-1 Specification for technical-Grade Nitrobenzene [4]

Appearance

Pale yellow oil with a characteristic order. It may

be slightly hazy owing to the presence of small
globules of free water

Water content

0.5% (maximum)

Specific gravity (15.5/15.5oC)

1.206-1.209

Dinitrobenzene content

0.1% (maximum)

0.25% (maximum)

Low-boiling impurities (benzene+aliphatic

hydrocarbons)
Sulfur- containing impurities (CS2 + nitrothiophene

2.5 ppm (maximum, as sulfur)

+elementary sulfur)

Identity [5]
Common name:

nitrobenzene

Chemical formula:
C6H5
NO2 Chemical structure:
Relative molecular mass:
CAS name:
IUPAC name:

123.11
nitrobenzene
nitrobenzen

CAS registry number:

e 98-95-3

NIOSH RTECS

DA6475000

Synonyms:

nitrobenzol, mononitrobenzol, MNB, C.I.

solvent black 6, essence of mirbane,
essence of myrbane, mirbane oil, oil of
mirbane, oil of myrbane, nigrosine spirit
soluble B

Physical properties
Nitrobenzene is a colorless to pale yellow oily liquid with an odor resembling that of
bitter almonds or "shoe polish." It has a melting point of 5.7C and a boiling point
of 211C. Its vapor pressure is 20 Pa at 20C, and its solubility in water is 1900
mg/liter at 20C. It represents a fire hazard, with a flash point (closed cup method)
of 88C and an explosive limit (lower) of 1.8% by volume in air [3].
Table 1-3 Some Physical Properties of Nitrobenzene [1,2,3&5]
5.58
210.9

Mp.oC
Viscosity
Bp.oC pa.sec
Thermal conductivity W/moC
Surface

tension

(20oC)

mN/m Specific heat J/goC

oC
At
At 25
30
oC

1.900599219*10-3
0.14473
43.35
1.473
1.418

Latent heat of fusion J/g

Latent heat of vaporization J/g
constant
volume)MJ/mol
Heat of combustion
(at
Flash point (closed cup) oC

94.1
331
3.07
4
88

Auto ignition temperature oC

482
1.8

Explosive limit in air (93 oC)vol%

At
20 opressure
C
Vapor
pa
o
At 25 C
At 30 oC in water
Solubility
mg/liter At 20 oC
At 25 oC

20
38
47
1900
2090

Chemical properties [ ]
1.

Nitrobenzene reactions involve substitution on the aromatic ring

and reactions involving the nitro group.

2.

Under electrophilic conditions, the substitution occurs at a slower

rate than for benzene and the nitro group promotes met substitution

3.

Nitrobenzene can undergo halogination,sulfonation and nitration, but

it does not undergo Friedel-crafts reactions.

4.

Under nucleophilic conditions, the nitro group promotes ortho

and para substitution.

5.

The reaction of nitro group to yield aniline is the most commercially

important reaction of nitrobenzene.

6.

Depending on the conditions, the reduction of nitrobenzene canlead

to a variety of products.

Table 1-4 Reduction products of nitrobenzene [2]

Reagent

Product

Fe, Zn or Sn + HCL

aniline

H2 + metal catalyst + heat (gasphase or

aniline

solution)
SnCL2 + acetic acid

Zn + NaOH
Zn + H2O
Na3AsO3
LiALH4
Na2S2O3 + Na3PO4

aniline
hydrazobenzene, azobenzene
N-phenylhydroxylamine
azoxybenzene
azoxybenzene
Sodium phenylsulfamate,
C6H5NHSO3Na

USES
Nitrobenzene is used primarily in the production of aniline, but it is also
used as a solvent and as an ingredient in metal polishes and soaps. In the
USA, around 98% of nitrobenzene produced is converted into aniline; the
major use of aniline is in the manufacture of polyurethanes. Nitrobenzene is
also used as a solvent in petroleum refining, as a solvent in the manufacture of
cellulose ethers and cellulose acetate (around 1.5%), in Friedel-Crafts
reactions to hold the catalyst in solution (it dissolves anhydrous aluminium
chloride as a result of the formation of a complex) and in the manufacture of
dinitrobenzenes and dichloroanilines (around 0.5%). It is also used in the
synthesis of other organic compounds, including acetaminophen [3]. The
largest end use of nitrobenzene is in the production of aniline.approximtely 9598% of nitrobenzene is converted to aniline the demand for nitrobenzene
fluctuates with the demand for aniline production grew at an average annual
rate of almost 5% from 1984 to1988 but dropped by over 4% during the 19891990 economic downturnRef[4]. For 1990,96% of the 532972 metric tons of
nitrobenzene left were used to produce variety of other products, such as paraaminiphenol and nigrosine dyes. The U.S. producers of PAP are
MALLINCHRODT,INC., RHONE- POULENC, and Hoechst cleanse with
combined production capacities >35000 metric tons. Mallinckrodt is the
largest producer, with over 50% of capacity PAP primarily is used as an
intermediate for acetaminophen.[4]

According to the BUA (1994), nitrobenzene is used in Western

Europe for the purposes shown in Table 5-1 [5].

Main application areas or chemical

manufacture
Aniline

Nitrobenzene
consumption (tones/year) in
Western Europe
380 000

m-Nitrobenzenesulfonic acid

5 000

m-Chloronitrobenzene

4 300

Hydrazobenzene

1 000

Dinitrobenzene

4 000

Others (solvents, dyes)

4 000

Total

398 300

Production Methods of Nitrobenzene

General
World production of nitrobenzene in 1994 was estimated at 2 133 800
tones; about one-third was produced in the USA [5]. In the USA, there has
been a gradual increase in nitrobenzene production, with the following
production/demand amounts, in thousands of tones, reported: 73 (1960), 249
(1970), 277 (1980), 435 (1986), 533 (1990) and 740 (1994). Based on
increased production capacity and increased production of aniline (the
major end-product of nitrobenzene), it is likely that nitrobenzene production
volume
will continue to increase [5].
Production of nitrobenzene in Japan was thought to be around 70 000 tones
in 1980 and 135 000 tones in 1990. Patil & Shinde (1989) reported that
production of nitrobenzene in India was around 22 000 tones per year [5].
Nitrobenzene is produced at two sites in the United Kingdom with a total
capacity of 167 000 tones per year. It has been estimated that a maximum of
115 400 tones of aniline was produced in the United Kingdom in 1990. If it is
assumed that 98% of the nitrobenzene in the United Kingdom is used to
make aniline, then the total amount of nitrobenzene used in the United
Kingdom would be around 155 600 tones per year [5].
Capacities for nitrobenzene production are available for several Western
European countries and are shown in Table 3-1 Production for Western Europe
was reported as 670 000 tones in 1990 [5].

1985

Table 2-1 nitrobenzene production capacities in European countries in

Country
Capacity (tones)
Belgium

200 000

Germany

240 000

Italy

18 000

Portugal

70 000

Switzerland

5 000

United Kingdom

145 000

USA

434 000

Japan

97 000

Nitrobenzene is manufactured by the direct nitration of benzene using a

mixture of nitric acid and sulfuric acid [2, 4]. This commonly is referred to as
mixed acid or nitrating acid. Because two phases are formed in the reaction
mixture and the reactants are distributed between them, the rate of nitration is
controlled by mass transfer between the phases as well as by chemical kinetics.
The reaction vessels are acid-resistant, glass-lined steel vessels equipped with
efficient agitators. By vigorous agitation, the interfacial area of the heterogeneous
reaction mixture is maintained as high as possible, thereby enhancing the mass
transfer of reactants. The reactors contain internal cooling coils which control the
temperature of the highly exothermic reaction Nitrobenzene can be produced by
either a batch or continuous process [2&3].
There are a variety of methods used to produce nitrobenzene.
1 Batch process
2 Tubular Reactor process
3 Continuous process
4 Adiabatic Continuous Process

5 Isothermal Continuous Process

6- Non-Industrial Sources

Nitrobenzene is prepared by direct nitration of benzene, using a nitric acidsulphuric acid mixture. The reaction vessel or nitrator is a specially built castiron or steel

kettle fitted with an efficient agitator. The kettle is jacketed and

generally contains internal cooling coils for proper control of the exothermic
reaction[ ]. Advantages of the way ( Easy to prepare , little , lower cost, A few
bugs compared deterring., You do not need many workers, as well as the
availability of raw materials).

Nitrobenzene can be produced by either a batch or a continuous

process with a typical batch, the reactor is charged with benzene A few
bugs
compared deterring., and the nitrating acid (56- 60% H2SO4,27-32wt
% HNO3 and 8-17%wt% H2O) is added slowly below the surface of the
benzene. The temperature of the mixture is maintained at 55-55C by adjusting
the feed rate of the mixed acid and the amount of cooling. the temperature can
be raised to 90C towards the end of the reaction to promote completion of
reaction. The reaction mixture is fed into separator where the spent acid settles
to the bottom and is drawn off to be refortified. The crude nitrobenzene is
drawn from the top to the separator and washed in several steps. depending on
the desired purity of the nitrobenzene the product can be distilled. Usually a
slight excess of the benzene is used to ensure that little or no nitric acid
remains in spent acid. Yield is about 98%.[ ]
Benzene nitrating acid (56-65 wt% H2SO4,20-26%HNO3 & 1518wt% water) are fed into the nitrator, which can be a stirred cylindrical reactor
with internal cooling coils and external heat exchangers or cascade of such
reactors. [ ]

The nitator also can be designed as a tubular reactor e.g. tube and shell heat
exchangers with appropriate cooling coils involving turbulent flow. Generally, with
a tubular reactor the reaction mixture is pumped through the reactor cycle
loop and a portion of the mixture is withdrawn and fed into the separator In
addition to laundry costs prohibitive and costly is also considered a huge process
and talked so much wrong.[ ]
In adiabatic process, the heat of reaction is not dissipated by cooling during
the process, but instead is subsequently used for evaporating the water of reaction,
so that a sulfuric acid suitable for recirculation obtained. One factor common to all
the processes which have been proposed for this purpose is that they require new
installations of special corrosion-resistant materials to accommodate the
high
process temperatures (up to 145oC.) and they alsorequire considerably
stringent

safety measures.

more

This offsets

the
potential advantages of these processes . that considerable
economic
and ecological advantages are obtained over the state-of-the-art .[ ]

PROCESS DESCRIPTION
Nitration, which is introduction of nitro group or the NO2 group into the
molecule, is achieved by bringing mixed acid and the compound to be nitrated
into intimate contact under vigorous agitation. Care must be taken to remove the
heat of nitrating. The acid left on completion of the nitration reaction is called
spent acid. In benzene nitration of the reaction is heterogeneous; benzene and
nitrobenzene have very low solubility in the mixed and spent acids. The overall
stoichiometry for the reaction of benzene and nitric acid to form nitrobenzene and
water is
N
O
2
+ HNO3

+ H2O

Ho = -34.825 Kcal/g.mol 1.3

H 2 SO 4

Sulfuric acid is a catalyst in the nitration reaction and does not enter directly into
the stoichiometry of Equation 1.3. The role of sulfuric acid is two fold: it acts as a
dehydrating agent by absorbing the water formed in the nitration reaction and it
is responsible for the dissociation of nitric acid and through which the reactive
species, the nitronium ion, is formed. The positively charged nitronium ion, NO2,
reacts with the aromatic compound by electrophilic attack to form a positively
charged complex.
This complex breaks down fast through reaction of the proton with an anion such
as The reaction mechanism is described through the
HSO4.
stoichiometric
following
equations[4]:

Equations 1.4 to 1.7 add up to Equation 1.3. The rate-controlling

reaction is that of Equation 1.5. The rate of nitration reaction is a function
of
many variables, but most importantly it is a function of sulfuric acid
strength,

which is capable of changing the rate by several orders of

magnitude. The steep increase of the nitration rate with the sulfuric acid
strength is generally

though to be due to the parallel increase in the

concentration of the nitronium ion in the mixed acid. It is the nitronium ion
which is the reactive species in the rate-controlling Equation 1.5 [4].
The nitronium ion is also present in strong nitric acid, and benzene can be
nitrated using nitric acid alone. The incentive for this process is that it would
eliminate the sometimes costly disposal or reconcentration of the spent
sulfuric acid. No commercial plant appears to be operating using a nitric acid
only process.[4].
The main by-products formed in commercial nitrobenzene plants are
dinitrobenzene (C6H4 (NO2)2), dinitrophenol (C6H3OH (NO2)2), and picric
acid (C6H2OH (NO2)2.

16

Summary process [ ]

A slight excess of benzene usually is fed into the nitrator to

ensure that the nitric acids in the nitrating mixture is consumed to
maximum possible extent and to minimize the formation of dinitrobenzene. the temperature of the nitrator is maintained at 50-100C by
varying the amount of cooling.
The reaction mixture flows from the nitrator into separator are
centrifuged here is separated into two phases. The aqueous phase or spent
acid is drawn from the bottom and concentrated in a sulfuric acid
reconcentrated step or recycled to the nitrator where it is mixed with
nitric and sulfuric acid immediately prior to being fed into the nitrator.
The crude nitrobenzene is washed and distilled to remove
water and benzene and if required nitrobenzene can be refined by
vacuum distillation.[3]

17

SPECIFICATION AND TEST METHODS

Specification and test Methods:
Specification for double-distilled nitrobenzene are give in table
below,
Property

Value

Purity ,%

> 99.8

Color

Clear, light yellow to brown

Freezing Point, 0C

> 5.13

Distillation range (First drop), 0C

> 207
212

Dry point 0C
Moisture,%

<0.1

Acidity As nitric acid, %

<0.001

18

Several qualitative spot tests are applicable to nitrobenzene and

depend on characteristic color developed by its reaction with certain
reagent. In general, calorimetric methods are subject to interferences from
aromatic nitro compounds. Certain colorimetric methods are based on
the
nitration of nitrobenzene to m- nitrobenzene and subsequent
determination by the generation of a red-violet color with acetone and
alkali. A general micrometric method for the determination of aromatic
nitro compounds is based on reduction with titanium(lll) sulfate or
chloride in acidic solution followed by back titration of excess titanium
(lll) ions with a standard ferric alum solution. Now days most modern
techniques use instrumental methods such as gas chromatography and
high pressure liquid chromatography.[ ]

19

PROCESS FLOW DIAGRAM

20

C6 H6

Mixed Acid HNO3(H2SO4)

C6H5NO2
H2SO4

nitrator

Unrect C6H6
Seprato
r and
washed

H2SO4
HNO3

DISTILLATI
ON
COLUM

Mixer

SPENT ACID

C6H5NO2

FLOWSHEET NITRATION PROCESS

21

MATERIAL BALANCE

22

23