Lecture 2 Nitration
Lecture 2 Nitration
Lecture 2 Nitration
Nitrating Agents
Mechanism For Nitration
Kinetics of Aromatic Nitration
Equipments For Nitration Processes
Industrial Application
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The reaction between a nitration agent and an
organic compound that results in one or more nitro
( --NO2) groups becoming chemically bonded to
an atom in this compound.
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A variety of reagents can be used to effect nitration.
These include:
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Nitrationsare highly exothermic, i.e. 126 kJ/mol (30
kcal/mol). However, the heat of reaction varies with
the hydrocarbon that is nitrated.
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Ionic nitrations are commonly used for aromatics;
many heterocyclics; hydroxyl compounds, e.g., simple
alcohols, glycols, glycerol, and cellulose; and amines.
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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.
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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.
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Foran alcohol, glycol, or glycerol, or for amines,
the reaction may be represented:
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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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• Generation of the electrophile in nitration requires
strong acid.
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Electrophilic Aromatic Substitution
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• 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.
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• 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.
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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.
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• 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.
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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.
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Gas-phase nitrations fall in the 200 -440°C range.
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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.
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When nitrogen dioxide is used, the main reaction steps are
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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.
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The viscosities and densities of the two phases and the
interfacial tension between the phases are important
physical properties affecting the interfacial area.
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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.
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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.
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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.
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Nitration is usually done in closed cast iron or steel vessels.
Modern practice is to use mild carbon steel.
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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.
Degree of agitations
Control of temperature
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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.
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.
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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.
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1. Single impeller
2. Double impeller
3. Propeller or turbine with cooling sleeve,
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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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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.
40
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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Schmid Nitrator
Biazzi Nitrator
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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.
43
In this apparatus the turbine type agitator provides
intensive agitation. A vortex is formed in the center about
the agitator shaft.
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Nitrobenzene (oil of mirbane),
C6H5NO2, is a pale yellow liquid with
an odor that resembles bitter almonds.
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Nitrobenzene is made by three processes:
1. Direct Nitration
2. Dehydrating Nitration
3. Adiabatic Nitration.
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This process may be carried out by a
1. Batch or
2. Continuous process.
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Both processes involve
a) Nitration
b) Washing of crude nitrobenzene…
c) Distillation to separate the water‚ benzene and
dinitrobenzene.
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Composition of mixed acid used is:
HNO3 27 to 32 wt %
H2SO4 56 to 60 wt %
H2 O 8 to 17 wt %
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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.
HNO3 20 to 26 wt %
H2SO4 56 to 65 wt %
H2O 15 to 18 wt %
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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.
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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.
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The continuous nitration plant which consists of a
cascade of stirred vessels (usually three nitrating
vessels) provides a stepwise‚ slowly increase in
temperature as…
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The two main areas affecting the
economic aspects for nitrobenzene
production are process related costs
including raw material costs, energy
requirements, waste treatment, etc.
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Nitrobenzene is a very toxic substance; the
maximum allowable concentration for
nitrobenzene is 5 mg/m3.
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In areas of high vapor concentrations (>1 ppm),
full face masks with organic-vapor canisters or air-
supplied respirators should be used.
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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.
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Propane is commercially nitrated by vapor-phase process.
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Conditions for the nitration of propane are 770oF
(410oC)at pressures of 115-175 psi.
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The total effluent is passed through an absorber where
it is scrubbed with a suitable solvent.
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