NITRATION

LEARNING OBJECTIVES

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

2
NITRATION???

3
 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 the organic 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.
 INTRODUCTION (CONTD)
Three general reactions summarize nitration chemistry
1. C nitration, in which the nitro group attaches itself to a
carbon atom to form a nitroaromatic or nitroparaffinic
compound.

2. O nitration (an esterification reaction), in which an ON

bond is formed to produce a nitrate ester.

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

nitramine is formed
 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
 MECHANISM
 Nitrations are highly exothermic, i.e. 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.
 MECHANISM (CONTD)
 Ionic nitrations are commonly used for aromatics;
many heterocyclics; hydroxyl compounds, e.g., simple
alcohols, glycols, glycerol, cellulose and amines.

 Nitration of paraffins, cycloparaffins, and olefins

frequently involves a free-radical reaction.
IONIC NITRATION REACTIONS

 Acid mixtures containing nitric acid and a strong acid,

e.g., 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.
 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.
IONIC NITRATION REACTIONS
(CONTD)

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

follows:
 IONIC NITRATION
REACTIONS (CONTD)
 For an alcohol, glycol, or glycerol, or for amines,
the reaction may be represented:
 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.
 CHEMISTRY OF
ELECTROPHILIC AROMATIC
SUBSTITUTION
• Generation of the electrophile in nitration requires
strong acid.
• An electrophile is a chemical species that forms bonds
with nucleophiles by accepting an electron pair.

• A Lewis acid is any substance, such as the H+ ion, that

can accept a pair of nonbonding electrons. In other
words, a Lewis acid is an electron-pair acceptor.

• A Lewis base is any substance, such as the OH- ion,

that can donate a pair of nonbonding electrons. A
Lewis base is therefore an electron-pair donor.

• Because electrophiles accept electrons, they are

Lewis acids.
 Electrophilic Aromatic Substitution

• The characteristic reaction of benzene is electrophilic

aromatic substitution—a hydrogen atom is replaced by an
electrophile.
• Benzene does not undergo addition reactions
like other unsaturated hydrocarbons, because
addition would yield a product that is not
aromatic.
• Substitution of a hydrogen keeps the aromatic
ring intact.
• Regardless of the electrophile used, all electrophilic aromatic
substitution reactions occur by the same two-step mechanism
—
• addition of the electrophile E+ to form a resonance-stabilized
carbocation,
• followed by deprotonation with base.
Many substituted benzene rings undergo
electrophilic aromatic substitution.
Each substituent either increases or decreases the
electron density in the benzene ring, and this affects
the course of electrophilic aromatic substitution.
• Consider toluene—Toluene reacts faster than
benzene in all substitution reactions.
• The electron-donating CH3 group activates the
benzene ring to electrophilic attack.
• Ortho and para products predominate.
• The CH3 group is called an ortho, para director.
NITRATIONS OF PARAFFINS
 FREE-RADICAL NITRATIONS OF
PARAFFINS

• Both vapor-phase and liquid-phase processes are

employed to nitrate paraffins, using either HNO3 or NO2.
• The nitrations occur by means of free-radical steps, and
sufficiently high temperatures are required to produce
free radicals to initiate the reaction steps.
 GAS-PHASE NITRATIONS

 Gas-phase nitrations fall in the 200 -440°C range.

 Gas-phase nitrations occur at atmospheric pressure, but

pressures of 0.8 -1.2 MPa (8-12 atm) are frequently
employed in industrial units.

 The higher pressures expedite the condensation and

recovery of the nitroparaffin products when cooling
water is employed to cool the product gas stream
leaving the reactor.
 LIQUID-PHASE NITRATIONS

 Temperatures of about 150-200°C are usually

required.
 Sufficient pressures are needed for the liquid-
phase processes to maintain the reactants and
products as liquids.
 Residence times of several minutes are
commonly required to obtain acceptable
conversions.
MECHANISM ( VAPOUR PHASE)
29
MECHANISM ( LIQUID PHASE)
MECHANISM ( GAS PHASE)
KINETICS OF AROMATIC
NITRATION
 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.
 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.
 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.
 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.
 PROCESS EQUIPMENTS FOR
NITRATION

 Batch Nitration
 Continuous Nitration
 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.

• Lower capital cost of setting up the plant

Disadvantage of a Batch Process Disadvantage of a Continuous Process

• Risk of contamination if more than one than one product made
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.

WHY CAPITAL COST OF CONTINUOUS
PROCESS IS LOW???

 For a given rate of production, the equipment

needed for a continuous process is smaller than for
a batch process.
 The reason for this is obvious, since it is not
necessary to accumulate material in a continuous
process anywhere, the vessels are designed with
capacities dictated by the rate of reaction process
step which they must accommodate.
 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.
 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
 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& scaling problem. Cleaning is no easy.
 AGITATING MECHANISM

1. Single shaft
2. Double shaft
3. Propeller or turbine with cooling sleeve,
 1. SINGLE-SHAFT AGITATOR
It consists of one vertical
shaft containing horizontal
arms (one or more
propellors mounted on it).
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.
 2. DOUBLE-SHAFT AGITATOR
• The 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.
 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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 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.
 NITRATORS
 Schmid Nitrator
 Biazzi Nitrator
 SCHMID NITRATOR
 The material to be nitrated is fed into the top of the nitrator
and is immediately drawn down through the sleeve and
immediately 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.
SCHMID NITRATOR
 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, both of which are fed from the top are
immediately drawn into the vortex thoroughly mixed and
circulated down through the center of the bank of
cooling coils and backup through and around the 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.
BIAZZI NITRATOR
 SAFETY MEASURES
 Safety measures which should be present in nitration
operations are similar for both the batch and continuous
processes.
 It is common to provide for automatically stopping feed
of the material to be nitrated in the event of an undue
temperature rise in the nitrator, a failure of the
refrigeration or brine circulation, or the failure of
agitation.
 It is common to require that continuous observation of
the nitrator temperature be maintained.
 Inlet valve is controlled by the measurement of the
temperature inside the nitrator.
 NITROBENZENE
MANUFACTURING
 INTRODUCTION
Nitrobenzene (oil of mirbane), C6H5NO2,
is a pale yellow liquid with an odor that
resembles bitter almonds.

Nitrobenzene is slightly soluble in water

and is readily soluble in most organic
solvents.

It is a good organic solvent.

PROCESSES FOR NITROBENZENE

Nitrobenzene is made by three processes:

1. Direct Nitration
2. Dehydrating Nitration
3. Adiabatic Nitration.

The process involves the direct nitration of benzene

using a mixture of nitric acid and sulfuric acid.
 MODE OF OPERATION

This process may be carried out by a

1. Batch or
2. Continuous process.

The continuous process is more effective for large

plants.
STEPS….
Both processes involve

a) Nitration
b) Washing of crude nitrobenzene…
c) Distillation to separate the water‚ benzene and
dinitrobenzene.
 BATCH NITRATION PROCESS

 Composition of mixed acid used is:

HNO3 32 – 39 wt %
H2SO4 60 – 53 wt %
H2 O 8 wt %

 Cast-iron nitrating vessels are used.

 The temperature of the mixture is maintained at 50-55°C

by adjusting the feed rate of the mixed acid and the
amount of cooling.
BATCH NITRATION PROCESS
(CONTD)

 The process requires a lot of agitation due

1. the formation of two phases and

2. the required mass and heat exchange.

 The batch reaction time generally is 2-4 hours. After that

nitrating acid is largely exhausted and the nitrobenzene
is separated‚ washed and distilled.

 The selectivity reaches 98 to 99%.

BATCH NITRATION PROCESS
(CONTD)

 The separation of nitrobenzene is accomplished in a

large conical bottom lead tanks, each capable of handling
one or more charges.
 The nitrator charges settle in tanks for 4-12 hrs, after
spent acid is drawn off from the bottom of the tanks.
 Nitrobenzene layer is sent to neutralization tub which
either may be a large lead conical shaped tub containing
an air spider, ( for agitation the charge during washing
process), or a standard cast iron kettle similar to the
nitrator with sleeve and propeller agitation.
BATCH NITRATION PROCESS
(CONTD)

 The charge is thoroughly agitated and warm with live

steam for 30 min, and then allowed to settle for a similar
period.
 The acid water is then run off.
 The charge is then given a neutralizing wash with warm
sodium carbonate solution, and separation of
nitrobenzene layer,
 After that a final wash with warm water is made.
 CONTINUOUS NITRATION
PROCESS
Continuous nitration process generally offers lower capital
costs and more efficient labor usage than a batch process,
most if not all of the nitrobenzene producers use continuous
processes.

Composition of mixed acid used is:

HNO3 20 to 26 wt %
H2SO4 56 to 65 wt %
H2O 15 to 18 wt %
 CONTINUOUS NITRATION
PROCESS
 Benzene is charged to the nitrator. Mixed acid is slowly
added on surface of benzene from dosing tank with stirring.
The ratio of mixed acid to benzene is kept around 2.5 : 1.0.

 So by high speed agitator and proper cooling coils reaction

temperature can maintained upto 50 – 55°C.

 By obvious agitation, the interfacial area, of the reaction

mixture is maintained as high as possible, thereby
enhancing the mass transfer of reactants and cooling coils,
which control the temperature of highly exothermic
reaction.
CONTINUOUS NITRATION PROCESS (CONTD)
 Benzene and the nitrating acid are fed into the nitrator,
which can be a stirred cylindrical reactor with internal
cooling coils and external heat exchangers or a cascade
of such reactors.

 The nitrator also can be designed as a tubular reactor,

e.g, a tube-and-shell heat exchanger with appropriate
cooling, involving turbulent flow.
 CONTINUOUS NITRATION PROCESS (CONTD)
 A slight excess of benzene is usually fed into the
nitrator to ensure that the nitric acid in the nitrating
acid is consumed to the maximum possible extent and
to minimize the formation of dinitrobenzene.

 Reaction time is only 15 – 20 minutes because of rapid

and efficient agitation.

 The temperature of the nitrator is maintained at 50

-100°C by varying the amount of cooling.
 CONTINUOUS NITRATION PROCESS (CONTD)
 Nitrobenzene and spent acid are removed from the
side reactor and send to decanter unit.

 Organic and aqueous layers are formed, where two

layers are separate in 10 to 20 minutes.

 The aqueous phase or spent acid is drawn from the

bottom and is concentrated in a sulphuric acid
reconcentration step or is recycled to the nitrator,
where it is mixed nitric acid and sulphuric acid
immediately prior to being fed into nitrator.
 CONTINUOUS NITRATION PROCESS (CONTD)
 The crude Nitrobenzene can used directly for
production of aniline if required, otherwise the crude
nitrobenzene flows through a series of washer –
separators, where residual acid is removed by washing
with a dilute sodium carbonate solution followed by
final washing with water.

 The product is then distilled to remove benzene and the

nitrobenzene can be refined by vacuum distillation.

 Theoretical yields are 96 – 99 %.

TYPICAL CONTINUOUS NITROBENZENE
PROCESS.
PFD FOR MANUFACTURE OF NITROBENZENE
 CONTINUOUS PROCESS
The continuous nitration plant which consists of a
cascade of stirred vessels (usually three nitrating
vessels) provides a stepwise‚ slowly increase in
temperature as…

35 to 40°C in the first vessel

50°C in the second and
55 to 60°C for the final reaction.
76
 ECONOMIC ASPECTS
$$ $$
 The two main areas affecting the economic
aspects for nitrobenzene production are
process related costs including raw material
costs, energy requirements, waste treatment,
etc.

 The most significant costs related to the

production process are the raw material costs.
These typically are at least 85% of the
production costs for nitrobenzene.
 HEALTH AND SAFETY FACTORS
 Nitrobenzene is a very toxic substance; the maximum
allowable concentration for nitrobenzene is 5 mg/m3.

 It is readily absorbed by contact with skin and by

inhalation of vapor.

 The primary effect of nitrobenzene is the conversion of

hemoglobin to methemoglobin; thus the conversion
eliminates hemoglobin from the oxygen-transport
cycle.
HEALTH AND SAFETY FACTORS
(CONTD)

 Exposure to nitrobenzene may irritate the skin and

eyes.

 Nitrobenzene affects the central nervous system and

produces fatigue, headache, vertigo, vomiting, general
weakness, and in some cases unconsciousness and
coma.
HEALTH AND SAFETY FACTORS
(CONTD)
 In areas of high vapor concentrations (>1 ppm),
full face masks with organic-vapor canisters or air-
supplied respirators should be used.

 Clean work clothing should be worn daily, and

showering after each shift should be mandatory.

 With respect to the hazards of fire and explosion,

nitrobenzene is classified as a moderate hazard
when exposed to heat or flame.
 USES OF NITROBENZENE

The largest end use for nitrobenzene is in the

production of aniline. Approximately 95-98% of
nitrobenzene is converted to aniline; the demand for
nitrobenzene fluctuates with the demand for aniline.

The other uses are in p-aminophenol‚ dyes and

pigments and as a chemical intermediate and
solvent.
NITRO PARAFFIN
MANUFACTURING
 PROPANE NITRATION
 Propane is commercially nitrated by vapor-phase process.
 Temperature control is a primary factor in designing the
reactor.
 Excess but controlled amounts of propane also increase
the HNO3 conversions to nitroparaffins.

 Conditions for the nitration of propane are 770 oF (410

o
C) at pressures of 115-175 psi.
 Initially the vapor phase nitration was carried out in
heated tubes through which a mixture of HNO3 vapour
and hydrocarbon was passed.
 PROPANE NITRATION
 The present plant nitrator combines the two steps, using
the heat of reaction to vaporize the nitric acid-(adiabatic
nitrator, since under perfectly balanced conditions, no heat
would have to be added or removed from the nitrator).
 In the form adopted, the nitric acid is introduced into a
stream of heated hydrocarbons by a number of spray
nozzles.
 Because of the high temperature of 750-850 oF, short
reaction time of 0.1 to 5 sec and corrosive properties of
Nitric acid serious design problems arose which have now
been resolved.
PROCESS SECTIONS
 Nitration
 Products recovery
 Products purification
 Products separation
 Reactants recovery

85
 PROPANE NITRATION

 Conditions for the nitration of propane are 770oF

(410oC)at pressures of 115-175 psi.

 The proportion of four nitroparaffins from propane are:

Nitromethane ………….. 25%
Nitroethane …………….10%
1-Nitropropane …………… 25%
2-Nitropropane ………….. 40%

86
87
 PROPANE NITRATION
 After leaving the nitrator, the product is cooled to
condense the nitroparaffins and the pressure is reduced
to atmospheric.
 The total effluent is passed through an absorber where
it is scrubbed with a suitable solvent such as hydroxyl
amine chloride which removes from the vapor phase
from ketones, aldehydes, (to prevent these chemical to
recycled to nitrator with recovered propane).
 The gases from the absorber contain oxides of nitrogen
and propane and are delivered to the reactant recovery
process.

88
 PROPANE NITRATION
 The recycling of propane and recovered HNO3 leads to
high yields of nitroparaffins based on HNO3.

 The liquid phase from the absorber is transferred to the

top of a steam-heated column called the stripper in
which the crude nitroparaffins and water are stripped
out of the solvent.
 The regenerated solvent is recycled to the absorber.
 The stripped nitroparaffins along with water and
oxidation products are condensed and form a two layer
mixture which is separated in a decanter.
 PROPANE NITRATION
 From the decanter the nitroparaffin layer is fed to the
first rectification operation called the heads column.
 Here the low boiling aldehydes, ketones are removed
and a cutoff is made for the initial boiling point of the
hydrocarbons.
 The crude nitroparaffins are taken from the bottom of
the column, condensed and subjected to a purification
process.
 PROPANE NITRATION
 The purification process is designed to trace impurities
in the nitroparaffins which lead to instability,
corrosiveness, and color development in the final
products.
 After the chemical treatment in agitated pots, a
decanting separation, water washing and another
decanting separation, the wet nitroparaffins are sent to
the separation process.
 The water is first removed in the drying column, and
then the separation is accomplished in four successive
atmospheric pressure rectifying columns, which strip
out in order nitromethane, nitroethane, 2-nitropropane,
and 1-nitropropane.