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University of basra for

oil and gas

1- chapter one

 Introduction
 Physical and chemical properties of aniline
 Aniline production process
 Uses
 History
 Hazard of aniline
 Flow sheeting
 Introduction

ANILINE.
Aniline is found already formed in coal tar. M. Runge
enumerated among the alkaline products of coal tar, pyrrhol,
aniline (called by him cyanol), and leukoline. Picoline, naphthalin,
and paranaphthalin were also found by MM. Anderson
and Anders. The aniline in tar is the product of the action
of phenic acid on ammonia. At first these two substances
yield a compound phenate of ammonia
NH 4O . C12H 5O
Ammonia. Phenic acid.
which at a high pressure is transformed into aniline and
water,
NH 4O, C12 H5 O = CI2H7N + 2HO.
Phenate of ammonia. Aniline. Water.
By treating the heavy hydrocarbons with dilute hydro
chloric acid aniline is dissolved from them in the form of
hydroehlorate, which can be obtained in the dry state by
evaporating the solution. From this salt aniline may be
easily got by distillation with lime or potash. In the tar
oils a small quantity of this substance remains, but much
too small to allow it to be extracted profitably. Hence
aniline must be produced artificially. Analogous to the probable
formation of aniline from the phenate of ammonia, this
salt may be submitted to high .

 Physical and chemical properties


 Physical Properties

Chemical formula C6H7N

Molar mass 93.13 g. mol-1

Appearance Colorless to yellow liquid

Density 1.0217 g/mL

Melting point -6.3 © (20.7 0F,266.8 k)

Solubility in water 3.6 g/100 mL at 20 0C

Boiling point 184.13 0C ,363.43 0F ,457.28 K)

Vapor pressure 0.6 mmHg(200C)

Acidity (pka ) 4.6 (for the conjugated acid )

Freezing point © -6.03

 Chemical properties
aromatic amines are usually weaker bases than aliphatic amines by the difference in
pka of the conjugate acids of aniline .pka of aniline is 4.63 and pka of cyclo hexyl amine
is 10.66 .

this is due to resonance effect .aniline is stabilized by sharing its lone-pair electrons
with the aromatic ring .
 Aniline is an aromatic amine which is mainly used as feedstock for
polyurethanes.
 It ignites readily, burning with a smoky flame characteristic of aromatic
compounds.
 Aniline is colorless, but it slowly oxidizes in air, giving a red-brown tint to
aged samples.
 It is used to manufacture dyes, drugs, photographic and rubber chemicals,
explosives and plastics.
 Aniline production processes

1 .production of aniline from benzene

Exothermic catalytic

nitration Nitro Hydrogenation


benzene Aniline
benzene

C6H6 + HNO3 → C6H5NO2 + H2O

C6H5NO2 + 3H2 → C6H5NH2 + 2H2O

is the process of introducing the amino group (–NH2) into an


organic compound as, for example, the production of aniline (C6H5NH2)
by the reduction of nitrobenzene (C6H5NO2) in the liquid phase
or in the vapor phase in a fluidized bed reactor . For many
decades, the only method of putting an amino group on an aryl nucleus
involved adding a nitro (–NO2) group, then reduction to the amino
(–NH2) group.
Without high-pressure vessels and catalysts, reduction had to be done
by reagents that would function under atmospheric pressure

RNO2 + 3H2 → RNH2 + 2H2O


reducing agents available under these restrictions are:
1. Iron and acid
2. Zinc and alkali
3. Sodium sulfide or polysulfide
4. Sodium hydrosulfite
5. Electrolytic hydrogen
6. Metal hydride
2 .Another methods of production aniline

Amination is also achieved by the use of ammonia (NH3), in a process


referred to as ammonolysis. An example is the production of aniline
(C6H5NH2) from chlorobenzene (C6H5Cl) with ammonia (NH3). The reaction
proceeds only under high pressure.
The replacement of a nuclear substituent such as hydroxyl (OH),
chloro, (–Cl), or sulfonic acid (–SO3H) with amino (–NH2) by the use of
ammonia (ammonolysis) has been practiced for some time with feedstocks
that have reaction-inducing groups present thereby making
replacement easier. For example, 1,4-dichloro-2-nitrobenzene can be
changed readily to 4-chloro-2-nitroaniline by treatment with aqueous
ammonia. Other molecules offer more processing difficulty, and pressure
vessels are required for the production of aniline from chlorobenzene or
from phenol

C6H5CI + NH3 C6H5NH2 + H2O


C6H5OH + NH3 C6H5NH2 + H2O

Ammonia is a comparatively low cost reagent, and the process can


be balanced to produce the desired amine.
Phenol
Ammonia
Catalytic
reactor
Ammonia recovery column
Dehydrating column
Purification column
Bottoms removal column
Ammonia recycle Water Aniline Azeotrope
Azeotrope recycle Diphenylamine.

 Selection process

The first method is the most widely used in industrial chemical processes for the
following reasons :

 Dealing with phenol is not easy ,so gasoline is best used to produce
aniline
 Phenol requires an acidic medium while the stimulating medium causes
erosion
 Gasoline freezes at 5 © and evaporates at 40

 Phenol is more dangerous and causes burns and wounds of user .

 Uses

 Aniline is predominantly used as a chemical intermediate for the dye,


agricultural, polymer, and rubber industries.
 It is also used as a solvent, and has been used as an antiknock compound for
gasoline. .
 Illustrative of the drugs prepared from aniline is paracetamol
(acetaminophen, Tylenol )
 The principle use of aniline in dye industry is as a precursor to indigo ,the
blue

 Historical View

Aniline was first isolated 1826 by Otto Unverdorben by destructive distillation of


indigo. He called it crystalline. In 1834, Friedlieb Runge isolated a substance from
coal tar that turned a beautiful blue color when treated with chloride of lime. He
named it kyanol or cyanol. In 1840 , Carl Julius Fritzsche (1808-1871) in indigo with
caustic potash and obtained an oil that he named aniline, after an andigo-yielding
plant.

In 1842, Nikolay Nikolavich Zinin reduced nitrobenzene and obtained a base that he
named benzidam. In 1843, August Wilhelm von hofmann showed that these were all
the same substance, known thereafter as phenylamine or aniline.

 Hazard of aniline
 Hazard Summary

Exposure to aniline may occur from breathing contaminated outdoor air, smoking
tobacco, or working or
being near industries where it is produced or used. The acute (short-term) and
chronic (long-term) effects
of aniline in humans consist mainly of effects on the lung, such as upper respiratory
tract irritation and
congestion. Chronic exposure may also result in effects on the blood. Human cancer
data are insufficient
to conclude that aniline is a cause of bladder tumors while animal studies indicate
that aniline causes
tumors of the spleen. EPA has classified aniline as a Group B2, probable human
carcinogen.

 Health Hazard Information

Acute Effects:
 Acute inhalation exposure to high levels of aniline in humans has resulted in
effects on the lung, such as
 upper respiratory tract irritation and congestion. (1,2)
 Aniline has been classified as very toxic in humans, with a probable oral lethal
dose in humans at 50 to 500
 milligrams per kilogram body weight (mg/kg). (2)
 milligrams per kilogram body weight (mg/kg). (2)
 Aniline is considered to have high acute toxicity, based on short-term animal
tests in rats. (3)

Chronic Effects (Noncancer):


 The major effects from chronic inhalation exposure to aniline in humans is the
formation of
 methemoglobin, which can cause cyanosis (interference with the oxygen-
carrying capacity of the blood).
 (1,2)
 Aniline is severely irritating to mucous membranes and affects the eyes, skin,
and upper respiratory tract in
 humans. (1,2)
 Significant amounts of aniline can be absorbed through the skin. (2)
 Animals studies have reported a dose-related decrease in red blood cell count,
hemoglobin levels, and hematocrit.
 Flow sheeting
The process

Nitrobenzene is fed to a vaporiser, where it is vaporised in a stream of hydrogen


(three
times stoichiometric). The mixture is passed into a fluidness bed reactor containing
copper
on silica gel catalyst, operated at a pressure, above the bed, of 20 psig (140 kN/m2).
The
contact time, based on superficial velocity at reaction temperature and pressure and
based
on an unexpanded bed, is 10 seconds. Excess heat of reaction is removed to
maintain the
temperature at 270© by a heat-transfer fluid passing through tubes in the catalyst
bed.
The exit gases pass through porous stainless-steel candle filters before leaving the
reactor.
The reactor gases pass through a condenser/cooler, and the aniline and water are
condensed. The excess hydrogen is recycled, except for a purge to maintain the
impurity
level in the hydrogen to not more than 5 per cent at the reactor inlet. The crude
aniline
and water are let down to atmospheric pressure and separated in a liquid/liquid
separator,
and the crude aniline containing 0.4 per cent unreacted nitrobenzene and 0.1 per
cent
cyclo-hexylamine as well as water, is distilled to give refined aniline. Two stills are
used,
the first removing water and lower boiling material, and the second removing the
higher
boiling material (nitrobenzene) as a mixture with aniline. The vapour from the first
column
is condensed, and the liquid phases separated to give an aqueous phase and an
organic
phase. A purge is taken from the organic stream to remove the cyclo-hexylamine
from the
system, and the remainder of the organic stream recycled. The cyclo-hexylamine
content
of the purge is held to not greater than 3 per cent to avoid difficulty in phase
separation.
In the second column, 8 per cent of the feed is withdrawn as bottoms product.
The purge and the higher boiling mixture are processed away from the plant, and
the
recovered aniline returned to the crude aniline storage tank. The aniline recovery
efficiency
in the purge unit is 87.5 per cent, and a continuous stream of high-purity aniline
may be
assumed.