Lecture 2 Nitration

NITRATION
LEARNING OBJECTIVES
 Introduction
 Nirtating Agents
 Mechanism For Nitration
 Kinetics of Aromatic Nitration
 Equipments For Nitration Processes
 Industrial Application
Ch.E-305 Muhammad Asif Akhtar 2

NITRATION???

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

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

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.

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.

 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
mechanicalCh.E-305
agitator is frequently used.
Muhammad Asif Akhtar 10
(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

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.

• Generation of the electrophile in nitration requires
strong acid.

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.

Considering inductive effects only, the NH2 group
withdraws electron density and CH3 donates electron
density.

Electrophilic Aromatic Substitution and
Substituted Benzenes.
• A substituent affects two aspects of the electrophilic aromatic
substitution reaction:
1. The rate of the reaction—A substituted benzene reacts
faster or slower than benzene itself.
2. The orientation—The new group is located either ortho,
meta, or para to the existing substituent. The identity of
the first substituent determines the position of the
second incoming substituent.

• 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.

• The principles of inductive effects and resonance
effects can now be used to predict carbocation
stability.

The reactivity and directing
effects of common substituted
Benezene.

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.

CHEMISTRY
When nitrogen dioxide is used, the main reaction steps are

WHY AROMATIC COMPOUNDS FOLLOW
IONIC REACTION MECHANISM AND
PARAFFINS FREE RADICAL..??
WHY AGITATION IS REQUIRED IN THE

NITRATION OF AROMATIC
COMPOUNDS..??

KINETICS OF AROMATIC
NITRATION

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.

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.
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.

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.

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.
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

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.
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.

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

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.
2. DOUBLE-IMPELLER
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.

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
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.

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.

PREVIOUS LECTURE
REVIEW…??

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 first 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 27 to 32 wt %
H2SO4 56 to 60 wt %
H2O 8 to 17 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 denser
nitrobenzene is separated‚ washed and distilled.
 The selectivity reaches 98 to 99%.

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 (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,

eg, 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.
The temperature of the nitrator is maintained at

50 -100°C by varying the amount of cooling

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.

PFD FOR MANUFACTURE OF NITROBENZENE

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.

 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.
(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.

(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 amounts of propane are used to help provide a

heat sink and help moderate the temperature.
 Excess but controlled amounts of propane also increase

the HNO3 conversions to nitroparaffins.
 A significant amount of steam is also present in the

reactor as a heat sink whenever HNO3 is used as the
nitrating agent.

Lecture 2 Nitration

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Lecture 2 Nitration

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NITRATION

Ch.E-305 Muhammad Asif Akhtar 2

Ch.E-305 Muhammad Asif Akhtar 3

The reaction between a nitration agent and an

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

A hydrogen or halogen atom is often replaced by

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

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

Ch.E-305 Muhammad Asif Akhtar 5

 Concentrated fuming and aqueous nitric acid

 Mixtures of nitric acid with sulfuric acid, acetic

 N2O5 and N2O4

Ch.E-305 Muhammad Asif Akhtar 6

 The mechanism of a nitration depends on the

Ch.E-305 Muhammad Asif Akhtar 7

 Nitration of paraffins, cycloparaffins, and olefins

Ch.E-305 Muhammad Asif Akhtar 8

 Acid mixtures containing nitric acid and a strong acid,

 Sulfuric acid is almost always used industrially since it

Ch.E-305 Muhammad Asif Akhtar 9

 Sufficient pressure, usually slightly above atmospheric,

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

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

Ch.E-305 Muhammad Asif Akhtar 11

Ch.E-305 Muhammad Asif Akhtar 12

Ch.E-305 Muhammad Asif Akhtar 13

Ch.E-305 Muhammad Asif Akhtar 14

• The characteristic reaction of benzene is electrophilic

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Both vapor-phase and liquid-phase processes are employed

Ch.E-305 Muhammad Asif Akhtar 27

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

 Gas-phase nitrations occur at atmospheric pressure, but

 The higher pressures expedite the condensation and

Ch.E-305 Muhammad Asif Akhtar 28

 Temperatures of about 150-200°C are usually

Ch.E-305 Muhammad Asif Akhtar 29

When nitrogen dioxide is used, the main reaction steps are

Ch.E-305 Muhammad Asif Akhtar 30

WHY AGITATION IS REQUIRED IN THE

Ch.E-305 Muhammad Asif Akhtar 31

Ch.E-305 Muhammad Asif Akhtar 32

 In addition, a larger interfacial area between the two

 Larger interfacial areas are obtained by increased

Ch.E-305 Muhammad Asif Akhtar 33

 Such properties are, of course, dependent on both

 Temperature also changes the solubilities of various

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

 Such energies of activation must be considered as only

Ch.E-305 Muhammad Asif Akhtar 35

 As the droplets decrease in size, the ease of

Ch.E-305 Muhammad Asif Akhtar 36

The danger of an explosion of a nitrated product

Nitroaromatics and some polynitrated paraffins are