NITRATION

LEARNING OBJECTIVES

 Introduction
 Nirtating Agents
 Mechanism For Nitration
 Kinetics of Aromatic Nitration
 Equipments For Nitration Processes
 Industrial Application

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NITRATION???

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INDUSTRIAL IMPORTANCE OF
NITRO-COMPOUNDS
 Usage in solvent and explosive industry
 Nitrophenols: fungicide, intermediate in
leather industry preservatives
 Nitroltoulene: dyes, organic synthesis,
explosives

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 INTRODUCTION

The reaction between a nitrating agent and an

organic compound that results in one or more nitro
( --NO2) groups becoming chemically bonded to
an atom in this compound.

A process in which a nitro group (--NO2) becomes

chemically attached to a carbon, oxygen, or
nitrogen atom in an organic compound.

A hydrogen or halogen atom is often replaced by

the nitro group. 5
 INTRODUCTION (CONTD)
Three general reactions summarize nitration chemistry
1. C nitration, in which the nitro group attaches itself to a
carbon atom

2. O nitration in which an ON bond is formed to produce

a nitrate

3. N nitration, in which a NN bond is formed

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 NITRATING AGENTS
A variety of reagents can be used to effect nitration.
These include:

 Concentrated fuming and aqueous nitric acid

 Mixtures of nitric acid with sulfuric acid, acetic

anhydride, acetic acid, phosphoric acid and
chloroform.

 N2O5 and N2O4

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 MECHANISM
 Nitrations are highly exothermic, ie, 126 kJ/mol (30
kcal/mol). However, the heat of reaction varies with
the hydrocarbon that is nitrated.

 The mechanism of a nitration depends on the

reactants and the operating conditions.
 The reactions usually are either

1. Ionic or
2. Free-radical.

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 MECHANISM (CONTD)
 Ionic nitrations are commonly used for aromatics;
many heterocyclics; hydroxyl compounds, eg, simple
alcohols, glycols, glycerol, and cellulose; and amines.

 Nitration of paraffins, cycloparaffins, and olefins

frequently involves a free-radical reaction.

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IONIC NITRATION REACTIONS

 Acid mixtures containing nitric acid and a strong acid,

eg, sulfuric acid, perchloric acid, selenic acid,
hydrofluoric acid, boron trifluoride can be used as the
nitrating feedstock for ionic nitrations. These strong
acids are catalysts that result in the formation of
nitronium ions, NO+2.

 Sulfuric acid is almost always used industrially since it

is both effective and relatively inexpensive.

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 IONIC NITRATION
REACTIONS (CONTD)
 When sulfuric acid is present in the mixed acids,
the following ionization reactions occur. These
ionic reactions are rapid, and equilibrium
concentrations of NO+2 are likely to be present at
all times in the acid phase. NO+2 concentrations
depend mainly on the composition of the mixed
acids but decrease to some extent as the
temperature increases.

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 IONIC NITRATION REACTIONS
 Most ionic nitrations are performed at 0-120°C. For
nitrations of most aromatics, there are two liquid
phases: an organic and an acid phase.

 Sufficient pressure, usually slightly above atmospheric,

is provided to maintain the liquid phases. A large
interfacial area between the two phases is needed to
expedite transfer of the reactants to the interface and of
the products from the interface.

 The site of the main reactions is often at or close to the

interface. To provide large interfacial areas, a
mechanical agitator is frequently used. 12
13
14
15
IONIC NITRATION REACTIONS
(CONTD)

 NO+2 attacks an aromatic compound (ArH) as

follows:

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 IONIC NITRATION
REACTIONS (CONTD)
 For an alcohol, glycol, or glycerol, or for amines,
the reaction may be represented:

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KINETICS OF AROMATIC
NITRATION

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 KINETICS OF AROMATIC
NITRATION
 The kinetics of aromatic nitrations are functions of
temperature, which affects the kinetic rate constant,
and of the compositions of both the acid and
hydrocarbon phases.

 In addition, a larger interfacial area between the two

phases increases the rates of nitration since the main
reactions occur at or near the interface.

 Larger interfacial areas are obtained by increased

agitation.

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 KINETICS OF AROMATIC
NITRATION (CONTD)
 The viscosities and densities of the two phases and the
interfacial tension between the phases are important
physical properties affecting the interfacial area.

 Such properties are, of course, dependent on both

temperature and the respective compositions of the
phases.

 Temperature also changes the solubilities of various

compounds in either the acid or hydrocarbon phase
Such dissolved compounds often result in by-product
formation.
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 KINETICS OF AROMATIC
NITRATION (CONTD
 Rates of nitration determined over a range of
temperatures in two-phase dispersions have been used
to calculate energies of activation

from 59-75 kJ/mol (14-18 kcal/mol).

 Such energies of activation must be considered as only

apparent, since the true kinetic rate constants, NO+2
concentrations, and interfacial area all change as
temperature is increased.

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 KINETICS OF AROMATIC
NITRATION (CONTD
 Increased agitation of a given acid-hydrocarbon
dispersion results in an increase in interfacial areas
owing to a decrease in the average diameter of the
dispersed droplets.

 As the droplets decrease in size, the ease of

separation of the two phases, following completion
of nitration, also decreases.

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 HEALTH AND SAFETY FACTORS

The danger of an explosion of a nitrated product

generally increases as the degree of nitration increases,
e.g.,
trinitroaromatics are more hazardous as compared to
dinitroaromatics or especially mononitroaromatics.

Nitroaromatics and some polynitrated paraffins are

highly toxic when inhaled or when contacted with the
skin. All nitrated compounds tend to be highly
flammable.

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 PROCESS EQUIPMENTS FOR
NITRATION

 Batch Nitration
 Continuous Nitration

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 Advantages And Disadvantages of Batch And Continuous Reaction
Processes.
Advantage of a Batch Process Advantage of a Continuous Process
• More cost effective if large quantities of the chemical are
• A variety of different products can be made using the plant.
being made.
• Slow reactions can be carried out.
• No expensive ‘down time’ when plant is not being used.

• Can use reactants in any state including solids. • Automated process requires less labour.

Disadvantage of a Batch Process Disadvantage of a Continuous Process

• Risk of contamination if more than one than one product made • High capital cost of setting up the plant
in reaction vessel
• Costs rise if plant not operated continuously.
• Expensive down time while reactor is being filled and emptied.

• Larger workforce required.

• Can be difficult to control highly exothermic reactions.

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 BATCH VERSUS CONTINUOUS
PROCESSES:
 ADVANTAGES OF CONTINUOUS
PROCESSES:

 Lower Capital Costs

 Safety
 Labor Usage

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 BATCH NITRATION
 Nitration is usually done in closed cast iron or steel vessels.
Modern practice is to use mild carbon steel.

 Nitrator consists of a cylindrical vessel containing some kind

of cooling surface, a means of agitation, feed inlets and
product outlet lines.

 They are also equipped with a large diameter quick dumping

line for emergency use if the reaction gets out of control.

 The contents of the nitrator are dumped rapidly into a large

volume of water contained in a drowning tub.

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 BATCH NITRATION ( CONT..)
 A common accessory for the nitrator is a suction line in
the vapor space above the liquid charge to remove the
acid fumes and oxides of nitrogen which may be
liberated.

 Two factors which are of prime importance in the

design of nitrators are:

 Degree of agitations
 Control of temperature

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 BATCH NITRATION ( CONT..)
 Cooling is generally accomplished by coils of tubes through
which either cold water or brine for cooling may be circulated
or hot water and steam for heating.

 For control of temperature in nitrations, a wall jacket is usually

not sufficient enough except in the case of vessels of very
small capacity.

 Advantages of coils:
 High coolant velocity is possible
 More compact so can be installed anywhere in the tank.

 Disadvantages of coils:
 Fouling problem. Cleaning is no easy.
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 CONTINUOUS NITRATION

 The actual nitration reactions in a continuous process are

carried out in the same type of vessel as used for batch
nitration, with the exception that an overflow pipe or weir
arrangement is provided for the continuous withdrawal of
product and that continuous feed of reactants is provided.

 Automization is there is continuous processes.

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 AGITATING MECHANISM

1. Single impeller
2. Double impeller
3. Propeller or turbine with cooling sleeve,

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 1. SINGLE-IMPELLER
AGITATOR
It consists of one
vertical shaft
containing horizontal
arms. The shaft may be
placed off center in
order to create rapid
circulation past, or
local turbulence at, the
point of contact
between the nitrating
acid and the organic
compound.
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 2. DOUBLE-IMPELLER
AGITATOR

It consists of two vertical shafts rotating in opposite

directions, and each shaft has a series of horizontal
arms attached. The lower blades have an upward thrust,
whereas the upper ones repel the liquid downward.
This conformation provides a reaction mix that is
essentially homogeneous.

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 3. SLEEVE-AND-PROPELLER
AGITATION

The term is usually

applied when the nitration
vessel is equipped with a
vertical sleeve through
which the charge is
circulated by the action of
a marine propeller or
turbine.

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 NITRATORS
 Schmid Nitrator
 Biazzi Nitrator

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 SCHMID NITRATOR
 The material to be nitrated is fed into the top of the nitrator
and is immediately drawn down through the sleeve and
thoroughly mixed with the spent acid and reacting material.

 In the bottom of the nitrator fresh mixed acid is fed in and

mixed with the other reactant by means of agitator and
baffles provided.

 The reacting material then pass upwards with high velocity

through the tubes surrounded by refrigerated brine.
Product and spent acid are withdrawn continuously from
the nitrator through the overflow line.

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 BIAZZI NITRATOR
 In this apparatus the turbine type agitator provides
intensive agitation. A vortex is formed in the center
about the agitator shaft.

 The reactants fed from the top are immediately drawn

into the vortex thoroughly mixed and circulated down
through the center of the bank of cooling coils.

 The high velocity imparted to the nitrator contents makes

for efficient mixing and heat transfer. Due to throwing of
cold body on hot body flashing and evaporation takes
place so you have to provide suction line for vapors.

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