US03CICV01 Unit -1 Dr. N. K.

Patel

Natubhai V. Patel College of Pure & Applied Sciences

B.Sc. Semester III
Industrial chemistry (Vocational)
US03CICV01: Unit process
UNIT 1
Syllabus

Nitration: Introduction, nitrating agents, mechanism, batch v/s continuous nitration process
and manufacturing of Nitrobenzene (batch and continuous), m-dinitrobenzene and p-nitro
acetanilide.
Amination: Introduction of amination by reduction and by ammonolysis. Different types of
reduction reactions and manufacturing of Aniline by Bechamp reduction, m-nitro aniline and
Aniline by ammonolysis.
NITRATION

1.0 INTRODUCTION

A manufacturing chemist is concerned with industrial processes in which raw

materials are charged or separated into useful products. In any case, the products
themselves may serve as the starting materials for further changes and thus may not be the
end products but only the intermediates.
Any commercial production of chemicals is usually a combination of physical and
chemical changes e.g. cracking of petroleum involves transportation of liquids and solids,
distillation into various fractions of a definite boiling range and the chemical reactions
resulting in cracking of big molecules into small ones etc. Thus the cracking process involves
both the physical and chemical changes.
The process of manufacture of common salt from seawater involves the following
steps; Transportation of brine (aqueous solution of common and other salts), heat transfer,
evaporation, crystallization, sieving etc. None of the steps in the sequence involves any
chemical change. Thus the process here consists of only physical unit processes changes.
For the systematic study of chemical process industries the physical and chemical
changes which are important for the manufacturing processes have been classified as unit
operation and respectively
Any piece of equipment used in industry would involve doing something (operations)
and hence analysis of the operation to be performed by the equipment into fundamental
terms would simplify and unify the treatment of all processes because the unit operations are
identical in fundamentals.
1.0. 1Unit operation
They may be defined as major physical changes useful to chemical industries.
Important unit operations are heat transfer, flow of fluids, material handling, filtration,
distillation, extraction, drying etc. Relatively few of the unit operations are required in any
particular process. In majority of cases, operations are to be done to set up the condition to
carry out chemical changes. Thus very important classification of various changes useful to
chemical industries was needed to be done. This was called Unit Processes.
1.0.2 Unit process
Unit processes may be defined as major chemical transformations which are
important to the chemical industries e.g. Nitration, halogenation, sulfonation, oxidation,
reduction etc.
The study of these processes includes
The basic knowledge of a particular chemical reaction
Equipment for the reaction
Running the reaction so as to get the purest product in minimum time and at
minimum possible cost
The classification of unit operations is more systematic than that of unit processes due
to the diversity and complexity of the latter. However the regularities emerged from the study
of a particular process can be useful in setting up condition for the manufacture of a new

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chemical which may include one or more such unit processes. E.g. For the unit process
nitration (i) The reaction is always almost exothermic (ii) The physicochemical principles of
equilibrium and chemical kinetics are similar (iii) Material of construction and the equipment
for the process can be predicted.
The principles of widely varying sequence of making up a chemical process do not
depend upon the nature of the materials being worked upon and other characteristic of the
system under study. If the step of process is recognized, the process can be designed in such
a way that each step to be used can be studied individually, illustration of
Unit operations Unit processes
Distillation, drying, evaporation, Heat- Alkylation, animation, dehydration,
exchange, mixing, size-reduction, diazotization, coupling, electrolysis
transportation, separation etc. halogenation, nitration, sulfonation,
oxidation, reduction etc.
In both unit operations and unit processes the similarities within any unit operation or
unit process are separated and studied; thus drawing attention to the like qualities of a given
physical change, as in distillation or chemical change as in hydrogenation. The emphasis
thus place upon the similarities led to unifying theories and to expression by rules and
formulas of those like aspects and these in turn led to a clearer understanding of the function
and thus to improved design of the necessary equipment: This is the scientific and
engineering approach. The ultimate study by this method of the technical changes
culminated in chemical engineering formulas and laws for using the classified observations in
each unit operation or unit process. These formulas and laws are the tools for the industrial
chemist uses in designing or operating a distillation column or a hydrogenation.
In conclusion, it may be stated that the unitary concept as applied to both physical
and chemical changes, has been useful and has emphasized the fundamental systems and
principles rather than technical details.

1.1 NITRATION

Nitration is the process of introduction of one or more nitro groups in a reacting

molecule (called substrate), e.g.

R-Cl + AgNO2 R-NO2 + AgCl

Silver nitrite
R-Cl+AgNO3 R-O-NO2 + AgCl
Silver nitrate

1.2 USES OF NITRO-COMPOUNDS

The nitro compounds find applications as solvents, dyestuffs, pharmaceuticals,

explosives and as intermediate for the preparations of amines which are prepared by the
reduction of the corresponding nitro compounds.

1.3 NITRATING AGENTS

A variety of nitrating agents can be used depending upon compound to be nitrated

Dilute, concentrated or fuming nitric acid can be used.
HNO3 dissolved in acetic acid, H2SO4, acetic anhydride, CHCl3, H3PO4
Mixed acids: This is a mixture of HNO3 and H2SO4. The HNO3 may be concentrated or
fuming

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N2O5 and N2O4

1.3.1 Functions of H2SO4
It removes the water produced during nitration.
Being a stronger acid than nitric acid, it protonates nitric acid to form a nitryl ion
which is strong nitrating agent.
HNO3 + 2H2SO4 NO2+ +H3O+ + 2HSO4
1.3.2 Evidence to support the formations of nitryl ion in the mixed acid
HNO3 + 2H2SO4 NO2+ +H3O+ + 2HSO4
From the freezing point depression van't factor of HNO3 in H2SO4 is found to be 4
which indicate that the ionization of HNO3 can be represented by the above
equation.
Solution of HNO3 has three different UV spectra. In dilute aqueous solution, its
spectrum is that of NO3 (nitrate ion). In an inert weakly polar solvent e.g.CHCl3, the
spectrum is the same as that of ethyl nitrate, indicating that HNO3 exists as unionized
HNO3. A 3rd spectrum is characteristic of H2SO4 solution of HNO3 and its esters,
indicating that here that HNO3 does not exist as NO3 ion or as unionized nitric acid.
The Raman spectrum of HNO3 in H2SO4 is even more informative. Solution of HNO3 in
H2SO4 and in perchloric acid have only one Raman line owing to HNO3 which occurs
at 1400cm-1 and which is polarized.
Electrolysis of solution of HNO3 in H2SO4 posses positively charged ions migrating
towards the cathode.
Several crystalline nitryl salts have been isolated and characterized. e.g. NO2+ ,NO3
NO2+ClO4and NO2+HS2O7.

1.4 AROMATIC NITRATION

ArH +HONO2 ArNO2 +H2O

1.4.1 Orientation
Nitration is an electrophillic substitution reaction i.e. NO2+ is an electrophile. Therefore
the substituent which raises the electron density on the ring carbon towards the nitration
reaction forms o-, p-nitro products.
1.4.2 Kinetics and mechanism of aromatic nitration
Kinetics
Rate =K(HNO3) (ArH)
1 1
Overall rate = 2
Generally accepted mechanism which is compatible with the data is
HNO3 + 2H2SO4 NO2+ + H3O+ + 2HSO4 (Fast) Step - 1
ArH + NO2 ArHNO2+ ( Slow: Rate determining step) Step 2
ArHNO2 + HSO4
+ ArNO2 + H2SO4 Step - 3

1.5 NITRATION IN ORGANIC SOLVENTS

In the organic solvents like nitromethane or acetic acid, with HNO3 in large excess,
the kinetics of the nitration process depends upon the aromatic compound being nitrated.
Compounds such as nitrobenzene or ethyl-benzoate with strongly deactivating group are
nitrated at a rate which is proportional to the concentration of the substrate i.e. the reaction
is first order. Compounds which are more reactive than benzene such as toluene, xylene and
p-chloranisole react at a rate which is independent of concentration of the substrate i.e. the
reaction is zero order. The rate of reaction with all substrates which show zero-order kinetics is
the same.
The results may be interpreted in the following manner.
2HNO3 H2NNO3+ + NO3
H2NO3 H2O + NO2+ (nitryl ion)
This 1 step which represents the transfer of proton from one nitric acid molecule to
st

another is very rapid. The rate at which the 2nd step, the formation of nitryl ion takes place

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depends upon the medium. In a strongly acidic and highly polar solvent like concH2SO4 this
takes place very quickly. In less strong acidic media such as acetic acid or nitromethane this
step can be relatively slow. The zero order kinetics shown by highly reactive substrate in
these solvents indicates that the nitration step is fast compared with rate of formation of NO2.
NO2+ + ArH ArNO2 + H+
This is supported by the fact that all these highly reactive compounds are nitrated at
the same rate which is the rate of formation of nitryl ion. In the nitration of aromatic substrates
of low reactivity, the formation of the nitryl ion is fast relative to the nitration step which is rate
determining. Each compound in this class reacts at its own characteristic rate. In the nitration
of compounds of intermediate reactivity, both steps occur at comparable rate.

1.6 EFFECT OF HNO2 ON NITRATION: HNO2 (NITROUS ACID)

HNO2 or NO2 inhibits or in some cases catalyses the process of nitration: The inhibiting
effect is observed in the nitration of compounds having no activating groups, where reaction
are carried out either in strong HNO3 or in mixed acid. In these media the nitrous acid forms
the nitrosyl ion (NO+) and thus reduces the reaction rate.
HNO3 + HNO2 H2O + NO+ + NO3
HNO2 + 2H2SO4 NO+ + H3O+ + 2HSO4
The catalytic effect is observed in the nitration of reactive substrates such as anisole
or dimethyl aniline which are nitrate in relatively weak HNO3 where the nitryl ion
concentration is low. The catalysis is done to form a nitro compound according to the
following equation.
ArH + NO+ ArNO + H+
ArNO + HNO3 ArNO2 + HNO2
Because of nitorsyl ion (NO+) which is much weaker electrophillic reagent than nitryl
ion (NO2+), it is able to react only with very reactive aromatic compounds such as anisole or
dimethylaniline. Two conditions are necessary for catalysis by nitrous acid.
1. The substrate must be sufficiently reactive so that it can be easily attacked by nitorsyl
ion (NO+)
2. The reaction medium must be such that the concentration of nitryl ions is very low,
thus allowing the nitrosyl ions to complete favourably for the substrate.

1.7 OXYNITRATION

An interesting reaction occurs between benzene and 50% HNO3 containing 0.2 molar
Hg(NO3)2 (Mercuric nitrate) which yields up to 85% dinitro phenol and picric acid. This process
includes both oxidation and nitration. Hence it is called oxy-nitration. Benzene is initially
converted to phenyl mercuric nitrate which reacts with nitrogen dioxide to form
nitrosobenzene. Each of these intermediates has been isolated from reaction mixture. The
nitrosobenzene reacts in two ways
1. In nitric acid weaker than 50%, it reacts with 2 moles of nitric oxide to from phenyl
diazonium nitrate. The diazonium salt is converted to phenol by water which is
nitrated in steps to from final product.
2. In nitric acid of greater 50% concentration, the nitrosobenzene is converted directly
to p-nitrophenol which is than nitrated to give final product.

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1.8 NITRATION OF PARAFFINIC HYDROCARBON

They are inert to electrophillic reagent. It is not an electrophillic substitution reaction. It

is a free radical reaction. Classification is done as
Gas-phase nitration and
Liquid-phase nitration,
1.8.1 Gas-phase nitration
Paraffins are quite inert to electrophillic reagent such as the nitryl ion. The paraffins
are attacked by certain atoms and free radicals. Nitration of these compounds is carried out
in industries in vapour phase at 350 4500C. It is free radical reaction. Nitric acid of strength
70% or less is generally used. We can also use NO2
1.8.1.1 Nitration products of iso-pentane
A characteristic feature of reaction involving alky radical is the great variety of
product formed. This is indicated by nitration of 2-methyl butane. This gives all possible mono-
nitration products that might be formed by breaking any one of the bonds presents and
introducing a nitro group at the point of cleavage. The products are as under.

More due to nitration, mostly mono nitro compounds are formed. In otherword poly-
nitration does not occur to significant extent.
Although C C bond breaks during the reaction no rearrangement of carbon
skeleton occurs.
1.8.1.2 Facts as a result of systematic study
There is optimum temperature at which highest yield is obtained.
The addition of oxygen increases yield based on HNO3 but also increases oxidation of
alkane.
NO2 also reacts with paraffin to yield nitro-paraffin.

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Bromine has beneficial effect on both yield and conversion to nitro-paraffin using
HNO3.
Highly branched hydrocarbons undergo less fission during nitration than to their less
branched isomer. Correspondingly substitution is favoured when highly branched
structures are nitrated.
Temperature coefficient for H substitution are in order is 1 > 20 > 3
Rate of substitution is in reverse order at low temperature i.e. 30 > 20> 10.
1.8.1.3 Steps involved in nitration of paraffin
HONO2 OH + NO2

Alkyl Radical formation

R-H + OH R + H2O
R-H + NO2 R + HNO2
Nitro paraffin formation
R + NO2 R-NO2
Oxidative and cleavage steps
R-CH2 +NO2 R-CH2O + NO
R-CH2O + NO2
R-CHO + HNO2
R-CH2O R + CH2O
RCHO + NO2 RCO + HNO2
RCO R + CO
CH2O + NO2 NO + H2O + CO
Olefin formation (unsaturation)
RCH2CH2 + NO2 HNO2 + RCH=CH2
2RCH2CH2 RCH=CH2 + RCH2CH3
1.8.2 Liquid phase nitration
The reaction is less important than the gas-phase nitration because
Low yields
Low conversions
Unwanted side reaction occurs. (Oxidation and decomposition)
In this reaction, hydrogen atom is replaced by nitro group. The alkyl groups are not
replaced. The rate of formation of product is in following order 30 > 20 >10 nitro-paraffin. The
reaction is slow because of low mutual solubility of paraffin and nitration medium. Because
of higher boiling point, higher hydrocarbons can be nitrated at high temperature.
The initially formed mononitroparaffin is more soluble in the HNO3 than in hydrocarbon
and undergoes further reaction to yield polynitroparaffins and decomposition and oxidative
products including fatty acids, alcohols and oxides of carbon.
The oxidation which occurs along with the nitration reduces HNO3 to elementary
nitrogen, which cannot be usefully utilized. This makes the process expensive.

1.9 LIQUID PHASE NITRATION OF OLEFINS

NO2 is nitrating agent and air is added to oxidize any nitric oxide to dioxide.

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The initial products are dinitroparaffin and nitronitrite. The latter is unstable and is
partially oxidized to stable nitronitrate. The remaining nitronitrite is converted into nitroalcohol
by treatment of reaction product with H2O or ethanol before distillation.
The reaction is carried out by slow addition of olefin to nitrogen dioxide at
temperature -10 to 250C.
The use of ether as solvent minimizes the oxidative side reactions. Ethylene reacts
slowly but higher olefins react more rapidly and molar equivalent can be made to react
completely in 1 to 2 hrs. Total yield of separated products are 65 - 85%.

1.10 THERMODYNAMICS OF NITRATION

Nitration reaction is highly exothermic. The heat released e.g. in nitration of 1lb of
benzene is comparable to that released on condensation of 1lb of steam. The heat problem
is much more important because of heat of dilution of nitrating acid and low heat capacity
of medium. We must know how to develop and use thermodynamic data in designing
nitrating equipment and providing safe and efficient operation. Since nitration is exothermic,
its enthalpy change (H) will be -ve.
1.10.1 Heat of nitration
The nitration reaction must be controlled by systematic cooling design to withdraw
the heat energy evolved. When all the energy set free by an exothermic reaction is forced to
appear as heat, the quantity of it lost to the cooling mechanism equals the decrease in
enthalpy i.e. Q= -H where Q = heat of reaction, represent the total amount of heat lost by
the reacting system from the start of reaction till the products return to initial temperature
and pressure of the system.
1.10.2 Thermal properties of nitration acid
Heat of solution
To determine the heat evolved during nitration of hydrocarbon by mixed acid, it is
necessary to consider not only the heat of nitration but also various heats of solution.
Heat of dilution
This is the quantity of heat evolved where dilution of mixed acid is carried out.
1.10.3 Integrated heats of nitration
In nitration of hydrocarbon by means of a mixture of concentrated HNO3 + H2SO4,
total heat liberated is equal to heat of solution of initial mixed acid minus heat of solution of
final spent acid minus heat of solution of the nitric acid entering into the reaction plus heat of
nitration reaction
Although heats of nitration are relatively large, the control of reaction is closely
related to heats of dilution of nitrating acid. The simplest way to integrate heat effect
involved is to sum up the enthalpies on the both sides of complete reaction equation by the
use of heats of nitration and other experimental data.
1.10.4 Thermal data relating to the preparation and use of nitro compounds
It indicates that when nitration occurs, a considerable amount of heat is generated. It
has been found that heats of nitration decreases with increase in the number of nitro groups.

1.11 PROCESS FOR TECHNICAL NITRATION

Technical nitration can be discussed as batch processes and continuous process.

Each kind of process has advantages peculiar to itself.
1.11.1 Advantage of batch process compared to continuous processes.
Flexibility
Batch process equipment posses general usefulness because each batch of material
passing to the process is separate or nearly separate from batches which have proceeded. It
is usually easier to introduce process variations into a batch process than into a continuous
process. Furthermore batch-process equipment is often of such general applicability that a
given plant may be readily converted from production of one nitrated material to another.
Beginning production of new compound or pilot production is conveniently done by the

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batch process because of operating flexibility, even though a use of continuous of process
may be planned for completely developed process.
Labour usage
For high rates of production when large batches are used, the labour efficiency of a
batch process may be equal to a continuous process e.g. large scale industrial production of
nitro glycerine and nitro toluene.
1.11.2 Advantage of continuous processes compared to batch processes
Lower capital cost
For a given rate of production, the equipment needed for a continuous process is
smaller than batch process. This is the most striking difference between two types of
processes.
It is not necessary to accumulate material in a continuous process anywhere and
therefore vessels are designed with the capacities detected by the rate of reaction process
step which they must accommodate. Alternatively, because of the relatively small size of
continuous process equipment, it is often possible and advantageous to use materials of
construction which could be very high in cost. If stainless steel is used there is no corrosion
problem.
Safety
Because of relatively small size of continuous process equipment, there is less
material in process at any time, than at certain times in a comparable batch process. E.g. at
the completion of a batch process nitration and during its normal separation of the product
from the spent nitrating acid, the entire batch of an often hazardous compound will be
present in the material need be present in hazardous condition as needed to gain sufficient
reaction or process time. In case of high explosives made by nitration such as nitroglycerine,
this safety factor of a continuous process is very attractive.
Labour usage
A continuous process is usually a more efficient labour user than a batch process. This
is particularly true for small or medium scale production and for hazardous products, since
continuous processing minimizes the amounts of material in the process on the average, it is
possible to handle operation at one place that required physical separation in batch process
and hence requires additional labour. This discrepancy in labour efficiency disappears as
scale of operations increases.

1.12 BATCH NITRATION

1.12.1 Construction, working and safety measures of batch nitrator

Nitration is usually done in cast iron or steel vessel. Now a days mild carbon steel is
used. When nitrating with mixed acid (HNO3 + H2SO4), the life of such nitrator is satisfactory
and any shot like failure is due to more water or to low actual HNO3 content in the waste
acid. It has been found that during manufacture of mononitrotoluene, as the water content
of the waste acid increases above 26% or the actual nitric falls below 2.5%, the rate of
corrosion on mild steel becomes very rapid because alloy steels are preferred for
construction the nitrator
Nitrator consists of an upright cylindrical vessel with cooling surfaces, a means of
agitation, feed inlet or inlets and product outlet lines. Most nitrators also have a large
diameter thick dumping line for emergency use. If the reaction goes out of hand or the
temperature rises because of failure of agitation, cooling or otherwise. In such an emergency
the contents of nitrator may be dumped rapidly into a large volume of H2O contained in a
"drowning tub". A common accessory for a nitrator is suction line in the vapour space above
the liquid charge to remove the acid fumes and oxides of nitrogen which may be liberated.
The two factors of prime importance in the design of nitrators are
The degree of agitation
The control of temperature.
Agitation in general must be very efficient, even violent, in order to obtain smooth
reactions and to avoid local over-heating which could occur in strangle sports were to exist

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in nitrator is quickly and thoroughly mixed reactant which could lead to local overheating do
not occur.
Cooling or other temperature control in nitrators is accomplished by coils of tubes
through which cold water or brine for cooling may be circulated or hot water or steam is
passed for heating. For control of temperature in nitration, a wall jacket is not usually efficient
enough except in the case of vessels of very small capacity. The need for large cooling
surface and for high velocity of cooling medium and nitrator contents past the surfaces
dictates use of cooling tubes.
The most common type of agitating system used in nitrator has vertical shaft with one
more propellers mounted on it. This shaft propeller is mounted in the cylindrical shape center
of one or more banks of cooling coil. An actual cylindrical sleeve is sometimes mounted in
the center of coil banks to assure that circulation of nitrator content is as desired. When
reactant feed to the nitrator is from the top into the center of agitator sleeve, circulation by
the propellers is usually down through the center and around and up through the cooling
coils. When the fed is beneath the liquid level, at the bottom of the sleeve and cycle acid is
used; circulation is up through the sleeve and around and down through the banks of coil.
Good mixing and efficient heat transfer is obtained by this sleeve and propeller
arrangement. When cycle acid is not used, circulation is down through the sleeve so that the
hydrocarbon fed into the sleeve near the bottom is quickly disperses in mixed acid and
immediately passed over the cooling coils.
1.12.2 Batch nitration of hydrocarbons
Batch nitration of hydrocarbon such as benzene toluene, it has been common past
practice to nitrate by using a cycle acid. Here the common practice involved charging a
sleeve and propeller agitator with cycle acid to above the level of the top of cooling coils.
Hydrocarbon was than floated in on top of cycle acid. Nitrating acid was fed into the
nitrators in the cycle acid with continuous stirring near the bottom of sleeve under the
propeller. This fortified cycle acid then reacted at the inter phase of the hydrocarbon and
acid in top of the nitrator. Nitration was then completed by allowing the temperature to rise
and eventually to emulsify nitrated products and acid. More modern practice for this type of
hydrocarbons involves no cycle acid but consists of feeding the hydrocarbon under the
surface of nitrating acid in the bottom of sleeve where agitation is very thoroughly. This is
called direct nitration and is more satisfactory than the older "indirect' nitration method.

1.13 CONTINUOUS NITRATION

Continuous nitration is carried out in the same type of vessels as those used for batch
nitration with the exception that an overflow pipe or weir arrangement is provided for
continuous withdrawal of the products and that continuous feed of all the reactants is
provided. Schmid nitrator and Biazzi nitrator are continuous nitrator.
1.13.1 Schmid nitrator
This nitrator has been designed for the German Schmid Meisener system.

Figure: Schmid nitrator

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In this nitrator, the material to be nitrator is fed from top of nitrator and immediately
drawn down through sleeve and intimately and thoroughly mixed with the spent acid and
reacting materials. In bottom of nitrator, fresh mixed acid is fed and is immediately mixed
with the other reactants by means of high flow rate caused by the agitators and baffles. The
reacting materials then pass upward with the high velocity through the tubes surrounded by
refrigerated brine circulating in the jacket. Products and spent acid are withdrawn
continuously from the nitrator through the overflow line.
1.13.2 Biazzi nitrator
It is designed by Swiss form of M. Biazzi. There is a turbine type agitator provides
intensive agitation. A vortex is formed in the center about the agitator shaft. The reactants,
both of which are fed in nitrator through the top are immediately drawn into this vortex,
thoroughly mixed and circulated down through the center of bank of cooling coils and back
up through and around the coils. The high velocity makes mixing and heat transfer very
efficient.

Figure: Biazzi nitrator

In any continuous equipment, the designer must be careful to assure that no stagnant
areas can exist. Also it is quite general to specify high finishes on the interior surfaces with
complete freedom from surface pits or pockets which could trap the product. It is also
important that the apparatus must be completely drainable so that if the contents must be
dumped no product contaminated with acid remains. Alternatively upon shut down of
equipment, it is common to displace all products from the apparatus by filling the nitrator
from the bottom with spent or cycle acid. Only if the apparatus is completely free of traps or
pockets can this displacement procedure be carried out with assurance that no nitrated
product will be trapped and remain behind in the nitrator.
Safety measures are similar for both continuous and batch 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 a
failure of agitation. Continuous observation of the nitrator temperature is necessary. The feed
of reactant can be controlled by a dead man valve which can be kept open only by
manual pressure. Solenoid operated controls which "fail-Safe" are also commonly used. This
means that the operation can be carried out only when all necessary services such as
power, refrigeration or agitation are functioning.

1.14 MIXED ACID COMPOSITIONS FOR NITRATION

From the technical stand point of using mixed acid, there are two primary conditions
that must be met. These are:

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1. The amount of 100% HNO3 present in nitration must be enough to satisfy stoichiometric
requirement of the reaction. It is usually present in excess to maintain reasonably fast
overall rate of reaction (nitration).
2. The amount of 100% H2SO4 with dissolved SO3 (i.e. Oleum, H2S2O7) if needed must be
sufficient to promote the desired reaction regardless of mechanism of reaction.
Two values which are calculated from reaction stoichiometry in one case and
determined in process development in the other case are practical controlled yardsticks.
Those values are D.V.S. (dehydrating value of sulfuric acid) and the nitric ratio.
D.V.S.: It is ratio of H2SO4: H2O present at the end of reaction.
The nitric ratio (R): It is the ratio of wt. of 100% HNO3: wt. of material being nitrated.
The accumulation of water, as a result of nitration reaction would be objectionable,
in nitrating medium and the function of sulfuric acid is to make it ineffective.
1.14.1 D.V.S. calculations
Consider the following analysis report for mixed acid used for preparing nitroglycerine.
Total H2SO4 49.99% Actual HNO3 52.38 %
Total HNO3 52.44% HNOSO4 00.12 %
Actual H2SO4 49.90 % H 2O 2.40 %
The figures, given for total H2SO4, HNO3 and HNOSO4 are determined directly by
analysis. Actual H2SO4 and HNO3 are obtained by correcting their corresponding totals by
subtraction of the equilibrium to each from HNOSO4. These factors are 0.722 for H2SO4 and
0.496 for HNO3. By using these factors, the actual values listed are obtained. Total acidity is
the sum of these two actual plus HNOSO4, in this example 102.40%. The water content is than
obtained by difference.
To calculate D.V.S. from the mixed acid, the formula is:
S Where, S = % actual H2SO4
D.V.S. = --------------------------- N= % actual HNO3
EN/R + W W= % water
E = water equivalent of material to
be nitrated
R = nitric ratio
E is defined as parts by weight of water resulting from the nitration of 1 part of the
starting material. It is made up of water of reaction plus water present in the starting material,
if any. If the calculation is based on 100 lb of mixed acid then the factor EN/R may be readily
understood.
If the particular mixed acid discussed above is to be used to nitrate glycerin the
D.V.S. may be calculated as follows: In this nitration a nitric ratio of 2.30 has been widely
used. We assume 1% moisture in the actual glycerin.

C3H5(OH)3 + 3HNO3 C3H5(ONO2)3 + 3H2O

M.W: 92.06 189.06 227.06 54.06
92.06gm/mole glycerin 54.06gm/mole H2O
0.99gm/mole glycerin ?
0.581 lb from nitration
+ 0.010 lb originally present
E = 0.591 lb of total water present at the end of nitration.
The nitric ratio 2.30 provides an excess of HNO3 of about 13% over theoretical as
shown by following calculation.
92.06gm/mole glycerin 189.06gm/mole HNO3
0.99gm/mole glycerin ?
2.03 from equivalent nitric ratio (theoretically)
But practically nitric ratio used is 2.3 %

Now, for calculation of DVS

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 US03CICV01 Unit -1 Dr. N. K. Patel

S
D.V.S. = ---------------------------
EN/R + W
49.90
D.V.S = -------------------------------- = 4.51 D.V.S.
0.591 X 52.38/2.3 + (-2.4)
It is a common practice for plant control chemist to report the D.V.S. along with
mixed acid analysis as though these values were a property of acid only. We should bear in
mind that the D.V.S. applied to the system which exists in nitrator at the end of nitration when
the acid used under specified conditions.
1.14.2 Relation between D.V.S. and stability of the nitrator charge
An important consideration in nitration of glycerin and related compounds is the
stability of the nitrator charge or product in contact with its own spent or partially spent acid.
Any condition which lowers the stability is increasing the hazards because of firing in the
nitrator. High D.V.S. favours high stability of nitrator charge. Decrease in D.V.S. results in lower
stability.

1.15 NITROBENZENE

Nitrobenzene can be manufactured by

Batch Nitration with mixed acid
Continuous nitration with fortified spent acid

1.16 BATCH NITRATION WITH MIXED ACID

1.16.1 Raw Materials

Benzene: 10000lb
Mixed acid: 23300lb
Nitric acid ratio: 1.04
1.16.2 Reaction

1.16.3 Manufacture
Use of cycle acid is not essential, particularly when the problem of heat transfer has
been satisfactorily solved. The operation commence by delivering to the nitrator sufficient
cycle acid, i.e. spent acid from a previous charge in which some nitrobenzene and nitric
acid are still present, The amount of such acid required depends on the type of nitrator used.
In the sleeve and propeller type, it should cover the cooling coils; in the Hough nitrator, it
must cover and overflow through the parts of the machine. Cold water is then circulated
through the heat-exchange medium, when the temperature is 500C or lower, the charge of
benzene is pumped from the scale tank into the nitrator. The mixed acid for nitration can be
fed on the top of the hydrocarbon or under surface.
The temperature of nitration for benzene may very within moderate limits. When no
cycle acids used, the temperature below 500C is kept, when fortified spent acid is employed
the nitration temperature may be kept between 500C and 550C.
1.16.4 Separation and Neutralization
The separation of the nitrobenzene is done in large conical bottomed lead tanks,
each capable of holding one or more charges. The nitrator charge is settled here for 4 to
12 hrs., when the spent acid is drawn off from the bottom of the lead tanks and delivered to
the spent acid tanks for additional settling or for treatment with benzene next to be nitrated,
in order to extract the residual nitrobenzene. The nitrobenzene is then delivered to the
neutralizing house. The neutralizing tub may be either a large lead conical shaped tube
containing an air spider, which is used for agitating the charge of nitrobenzene during the
washing process, or a standard cast iron kettle similar to the nitrator with sleeve and propeller

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 US03CICV01 Unit -1 Dr. N. K. Patel

agitation. The neutralizing vessel is prepared with "heel" of warm water, which is delivered
from an adjacent vat, and the nitrobenzene is blown into it. The charge is thoroughly
agitated and warmed with live steam for 30 min. or until neutral to Congo and then allowed
to settle for a similar period. The supernatant acid water is then run off through side outlets
into a labyrinth where practically all the immersed nitrobenzene will settle out. The charge is
now given a neutralizing wash at 40-500C with a warm sodium carbonate solution, until
alkaline to phenolphthalein. When the nitrobenzene is intended for aniline production, this
may be followed by a wash with aniline water from the reducer house if any has to be
worked up; otherwise, a final washing with a small quantity of warm water is made.
The nitrobenzene is then delivered to its storage tanks, where it is again settled to
remove final traces of water. The crude product can now be distilled for commerce or used
directly for the preparation of aniline. In some plants where the nitrobenzene is used almost
exclusively in the aniline plant, the neutralizing and subsequent washes are omitted. The
nitrobenzene delivered to the reducer house it, consequently acid. No harmful effects on the
equipment are noticeable, if the acidity is kept below 0.5 percent.

1.17 CONTINUOUS NITRATION WITH FORTIFIED SPENT ACID

Methods for the continuous nitration of benzene have been proposed by Castner
and Mares. Both processes are base on the recognition that a slightly HNO3 - fortified spent
acid constitutes a satisfactory nitrating agent for a limited quantity of hydrocarbon. For large
scale production, it is necessary to circulated relatively large quantities of acid of low nitric
acid content high heat capacity and to remove the water of nitration continuously in an
integrated evaporator operating under reduced pressure. When the heat of sulfuric acid
hydration and the chemical heat of nitration are evolved in separate vessels by adding nitric
acid to prepared mixture of benzene, sulfuric acid and water, the hazards of nitration are
further reduced and it is feasible to operate safely at relatively high temperatures and to
utilize the sensible heat in effecting the subsequent removal of water from the spent acid.
1.17.1 Raw materials
Benzene, Nitric acid, sulfuric acid are the main raw material for continuous nitration.
1.17.2 Reaction

1.17.3 Manufacture

Hot sulfuric acid at 900C is run from the heat insulated storage tank (B) into one of a
battery of nitrator (A1 to A4). Under vigorous agitation, sufficient 63% nitric acid is added to
the nitrator to produce a mixed acid containing 4% HNO 3. Sufficient benzene is then

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delivered from its storage tank to react with all the nitric acid in the nitrator. Upon completion
of the reaction, that takes about 10 min. The agitation is stopped and the charge is
permitted to settle. While the separation of nitrobenzene and spent acid proceeds, another
nitration is started, thus providing a continuity of operations.
The crude nitrobenzene is drawn off through side outlets C on the nitrator and sent to
the neutralizer. The spent acid which is free of nitric acid but contains small amounts of
nitrobenzene is drawn off in operating sequence at the outlets (D1 to D4) located at the base
of the nitrators.
The spent acid is first directed to the acid heater (E) which is heated by low pressure
steam to maintain the sensible heat of the spent acid (72 percent H2SO4) and delivered to
the vapour separator. The evaporator, operating under vacuum of 29 inch, effectively
removes the water of nitration by virtue of the sensible heat of the spent acid and returns the
sulfuric acid to the system at its original (75 percent) strength. The small quantity of
nitrobenzene found with the water in the condenser is separated and added to the crude
charge.

1.18 m - DINITROBENENE

1.18.1 Raw materials

Benzene
Mixed acid composition
(1) For mono-nitration (2) For di-nitration
60.0% H2SO4 75.0%
32.0% HNO3 20.0%
08.0% H 2O 05.0%
03.52% D.V.S. 07.36
01.01 Nitric ratio 01.10
1.18.2 Reaction

1.18.3 Manufacture
The preparation of m-dinitrobenzene from benzene is usually accomplished in two
stages of nitration. Both may be made in the same vessel
The first stage is carried out under the conditions of nitration of benzene to form
nitrobenzene. At the conclusion of the first nitration, the spent acid is run off from the base of
the machine and is replaced by a storage nitrating acid for the second stage of nitration.
The composition of the nitrating acids for the both stages of nitration is as shown above.
It is readily seen from compositions that the second nitration required a more
concentrated acid. Moreover, the reaction must be controlled at a higher temperature i.e.
90-1000C. Although the heat of nitration for the second nitro group is not so great as for the
introduction of the first. The operation is nevertheless much slower on account of the lower
specific heat and greater integral heat of dilution of the more concentrated acids that are
used. Since the rate of feed and time of reaction are determined by the efficiency of
agitation and heat exchange, these are matters of special importance in this nitration.
In the combined operations 2,200Kgs of spent acid from a dinitration (about 80%
H2SO4) is retained in a jacketed cast-iron nitrator of 8 cu. ft. (2,112 gal) capacity that is
provided with a lead cooling coil and sleeve in which a stirrer operates at 110 rpm. To this
added 1900Kgs mixed acid analyzing 88 percent HNO3, 11% H2SO4 and 1% H2O. Then
2200Kgs benzene is introduced over a period of 4 hrs while controlling the temperature
initially at 250C and finally at 400C. The temperature is then raised to 600C in 1 hr. The charge
is permitted to stratify and the spent acid is discharged to a lead lined washer with stirrer
where it is washed with either benzene or nitrobenzene.
To the nitrobenzene retained in the nitrator, there is added over a 3 hr. period 5,000-
6000 Kg. of mixed acid (Approx 33 % HNO3, 67% H2SO4) permitting a temperature rise from
250C to 400C. The temperature is then raised to 900C and maintained there for 1 hr or until

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 US03CICV01 Unit -1 Dr. N. K. Patel

free of nitrobenzene by the steam distillation test. The charge is settled and the spent acid
run into a large washer, where several batches are washed with nitrobenzene. The
dinitrobenzene is delivered to a tile lines or stainless steel washer, provided with a lead cover
and stirrer. Here, it is washed first with 4,000 liters of hot water, then with caustic soda solution
until neutral and finally with water.
About 4,500kgs of crude molten dinitrobenzene (85% m-, 13% o-, 2% p- ) obtained
from each nitrator charge is purified by mixing thoroughly with 3,000 liters water at 800C in a
jacketed cast iron vessel. The contents are allowed to cool without heat exchange, until
about 700C when pelleting begins. Then 650kgs sodium sulfite, which converts the para and
ortho derivatives to nitramines, is added at a rate of 100kgs/15 minutes. During this period,
temperature rises to 780C. Stirring is continued for 3 hrs, when a solidification point on a
washed and filtered sample should not be less than 88.50C; if lower 25-50kgs more sodium
sulfite is added.
The molten charge is cooled by means of the water jacket to 20 - 250C. Then, while
water is introduce, the mother liquor is pumped off through a filter basket until the color of
the wash changed from dark red to clear yellow. The first wash waters are discharged and
sufficient yellow water is retained for washing the next batch. After as much water as possible
has been removed via the basket, the charge is heated to 95 0C, settled for half hour and the
oil run into a cylindrical steel steam jacked vacuum drier that is fitted with steam heated run
off cocks. The residual water is retained for the next batch. Over all yield on benzene 81.9%.

1.19 p-NITROACETANILIDE

1.19.1 Raw material

In the nitration of acetanilide, it is important in order to prevent hydrolysis, to conduct
the nitration at 3-50C. To ensure a maximum yield of product, use is made of cycle acid,
which in this instance is water-white 66 Be sulfuric acid
1.19.2 Raw materials
Acetanilide: 1000lb
Mixed acid of composition
HNO3 33 % H 2O 20 %
H2SO4 47 % HNO3 ratio 1.015
1.19.3 Reaction

1.19.4 Manufacture
In to 4,000 lb of sulfuric acid free of nitrous acid, 1,000 lb of dry acetanilide/mp 1330C)
is added very slowly. During these 3-4 hrs., the temperature is maintained at 250C. The charge
is cooled to 20C and 1,450 lb of mixed acid of the composition as above is then slowly run
into the nitrator. The rate of feed being regulated by the capacity of the brine coil to control
the temperature at 3-50C.
Agitation is continued for 1 hr longer, the entire operation consuming 10-12 hrs. When
the temperature rises above 50C during nitration, there is a distinct tendency towards the
formation of the ortho isomer. To test for complete nitration, a sample is drawn from the
nitrator and poured on ice and the p-nitroacetanilide washed with cold water. The
precipitate is hydrolyzed in a test tube with boiling dilute (caustic), and the resulting p-nitro
aniline should yield a clear yellow solution with hydrochloric acid. If the acetanilide has not
been completely nitrated, the odour of aniline may be detected.
The batch is run from nitrator on to a suction filter containing 600 gal of water and
sufficient ice (or a brine coil) to keep the temperature below 150C. It is provided with a stirrer
that is set in motion just prior to receiving the charge form the nitrator. The temperature
should be kept close to 50C otherwise, the weak mineral acid present will hydrolyze some of
the p-nitroacetanilide and the mixture will turn yellow owing to the formation of p-nitro

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anilinesulfate. The p-nitroacetanilide, which is brown as it runs from the nitrator is changed to
milky-white mass as it comes into contact with the cold water.
When the p-nitroacetanilide is to be sold, it is twice washed on the filter with cold
water until practically free of acid and then with minimum of 3 percent caustic soda or
sodium carbonate solution. The neutralized cake is finally washed to remove the excess of
alkali and then it is removed and dried.
The yield of p-nitroacetanilide is 88- 90% of theory or 160-162 lb per 100 lb acetanilide
taken.

AMINATION BY REDUCTON

1.20 INTRODUCTION

Amination by reduction involve the synthesis of amines by reductive methods. Amines

can be produced by reducing nitro, nitroso, hydroxylamino, azoxy, azo and hydrazo
compounds as well as oximes, amides, nitriles and azides. In each case, a carbon to nitrogen
bond already exists. Amines may also be formed by reacting compounds containing certain
labile groups (e.g. halogens, hydroxyl and sulfonic) with ammonia.

1.21 METHODS FOR THE PREPARATION OF PRIMARY AMINES

The reduction of nitro, nitroso, hydroxylamino, azoxy, azo and hydrazo compounds.
The reduction of nitrites, amides, oximes and azides.
The replacement of labile groups, such as nitro, halogen, hydroxyl and sulfonic acid
by reaction with ammonia or ammonia progenitors such as urea.
Intramolecular replacement of (a) hydrazobenzenes and hydroxylamines (b) amides
and (c) secondary and tertiary amines.
The hydrolysis of N-substituted amides.
Direct amination by means of hydroxylamine and sulfuric acid.
First four are the most important methods from chemical engineering point of view.

1.22 USES OF AMINES

Amines are of very great importance as intermediates in the chemical process

industries. They are used in production of dyes, rubber chemicals, nylon, pharmaceuticals,
gasoline additives, surfactants, textile auxiliaries, photographic chemicals, chelating agents,
sweetening agents, agricultural chemicals, polyurethanes, inks, plastics etc.
In recent years, the production of diamines by reductive methods has become
increasingly important. Hexamethylenediamine is a prime intermediates, together with
adipic acid, in the production of nylon 66. m-phenylenediamine is used as a crosslinking
agent in epoxy resin. Toludenediamines are intermediates in the production of toluene
disocyanates, from which are made polyurethane foam, rubbers, coatings and adhesives.

1.23 METHODS OF REDUCTION

A great variety of reduction methods have been used for the preparation of amines.
Among these are:
1. Metal and acid: Iron and acid (Bechamp method) is the major example in this
category, but other metals (tin, zinc) have also been employed. Generally,
hydrochloric acid is preferred, but sulphuric acid, acetic acid and formic acid have
also been used.
2. Metal and alkali: This method is used mainly for the production of azoxy, azo and
hydrazo compounds. The latter are important in the manufacture of the benzidine
series.
3. Metal hydrides

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 US03CICV01 Unit -1 Dr. N. K. Patel

4. Catalytic: This method involves the use of hydrogen (or hydrogen - containing gases)
and a catalyst such as nickel, copper, platinum, palladium or molybdenum sulfide.
5. Sulfide: This is used mainly for the partial reduction of polynitro aromatic compounds
to nitro-amines and for reduction of nitro-anthraquinones to amino- anthraquinones.
6. Sulfite (Piria method): The reaction of sodium sulfite and bisulfite on an aromatic nitro
compound leads to a mixture of amine and aminoaryl sulfonic acid.
7. Sodium hydrosulfite (hyposulfite).
8. Electrolytic
9. Sodium and sodium alcoholate.
10. Strong caustic oxidation-reduction.
11. Hydrogenated quinolines and naphthalene.
By a proper selection of reducing agent and careful regulation of the process,
reduction may often be stopped at intermediates states and valuable products other than
amines obtained. Metal and acid reduction is most vigorous and usually yields amines as
end products. When nitrobenzene is treated with zinc and a mineral acid, the resultant
product is aniline. When an alkaline solution is employed, hydrazobenzene is generally
obtained, but very vigorous conditions sometimes result in the formation of aniline. When
zinc dust and water are used, reaction product is phenyl hydroxylamine as shown below.

When the compound to be treated contains more than one nitro group, the product
of reduction depends upon the agents used. Thus, m-phenylenediamine is obtained by the
iron and acid reduction of m-dinitrobenzene, while the alkaline sulfide reduction yields m-
nitro aniline.

With certain compounds containing acid or alkali sensitive groups (e.g. ester or
amides), it is necessary to adjust the pH carefully to avoid decomposition and side reactions.
In such reductions on the acid side, it is generally advisable to replace the normally used
mineral acids with organic acid like acetic acid. An example of the latter is the reduction of
nitroanilides, for here the presence of mineral acids would tend to hydrolyze the anilide to an
amine.
The method to be used will therefore, depend upon the degree of reduction desired,
the sensitivity to the process of both starting material and final product, the need for
avoiding contaminants and the overall economics.
The reduction of nitro compounds involves the progressive removal and replacement
by hydrogen of the oxygen in the -NO2 group. The intermediate products in the reduction of
nitrobenzene, whose interrelationships are shown in the following figure are obtained by
control of the reduction potential of the system.

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 US03CICV01 Unit -1 Dr. N. K. Patel

Figure: Reduction products of Nitrobenzene

1.24 IRON AND ACID (BECHAMP) REDUCTION

Bechamp's discovered in 1854 that nitro compounds could be reduced in the

presence of iron and acetic acid. Parkin applied the reaction in the commercial production
of aniline. Technical progress in the application of this reaction was first made by substituting
hydrochloric acid for the acetic acid, originally employed. Subsequently, it was discovered
that the ferrous functions in such a way that reduction could be carried out with far less
than the theoretical quantity of acid.
Reaction: C6H5NO2 + 2Fe + 6HCI C6H5NH2 + 2H2O + 2FeCI3
Formula wt.:123 2(55.84) 6(36.45)
In industrial practice, less than 2 % of the amount indicated above is actually used.
Operating experience has shown that 3.0 lb of hydrochloric acid (10 lb of 30 % solution) is
sufficient to bring about a satisfactory reduction of 100 lb of nitrobenzene to aniline.
The presence of free acid has been shown to be unnecessary. It is demonstrated
that nitrobenzene could be reduced with iron powder in alcoholic or aqueous solution, in
the presence of magnesium or calcium chloride. The absence of free acid is
advantageous. It has been demonstrated that aniline hydrochloride, aluminium chloride,
sodium bisulfate or other salts derived from strong acids can be successfully employed. All
that is required is a salt that acts like an acid in water solution, liberating hydrogen ion.
1.24.1 Chemical and physical factors
1.24.1.1 Amount of iron
In plant practice, it is customary to use slightly over 2 moles Fe per mole nitro
compound to carry out the reduction process. Under such circumstances, not all the iron is
converted to the ferrosoferric oxide, some reducto - active ferrous hydroxide also being
present. In plant, practice, it has been found that when insufficient iron is present the
addition of heat or acid is not effective in carrying the reduction to completion and poorly
filtering iron oxide sludge is obtained. The introduction of some finely divided iron under
such circumstances brings about a vigorous reaction, which results in the complete
reduction of the nitro compound. The range of iron generally used is about 2.5 - 5.0 moles
per mole of nitro compound. This has been found satisfactory for a wide variety of aromatic
amines. Some operation prefers to use very finely divided iron to finish a reduction and this
practice is particularly advisable when the bulk of the iron turnings is not of good quality.

1.24.1.2 Physical condition of iron

The iron fed into the reducer not only supplies the metal absorption surface but also
enters into the reactions by providing the iron for the regeneration of the ferrous chloride
upon the hydrolysis of the phenyl ammonium chloride (aniline hydrochlorides) and also acts
as an oxygen carrier. A clean, finely divided, soft, gray cast iron yields the best results. The
rate of reduction depends on the fineness and porosity of the iron particles, the homogeneity

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of the charge in the reducer, and the degree of etching imparted to the iron by the
preliminary acid treatment. To ensure thoroughly etched iron it is customary to boil the iron
and acid suspension before adding any nitro compound. When this precaution is observed,
the reaction proceeds very readily, with no danger of a violent deferred reaction. Iron
borings, turnings or shavings are generally used. With coarse particles, the oxidation of the
iron is retarded and an excess of it must be provided. It is clear that the use of finely divided
iron shortens the time of reaction.
1.24.1.3 Amount of water
Theoretical considerations indicate the desirability of using 4-5 moles of water per
mole of nitro compound treated.
4RNO2 + 9Fe + I6H2O 4RNH2 + 3Fe(OH)2 + 6Fe(OH)3 4RNH2 + 3Fe3O4 +12H2O
Owing to the fact that part of the iron hydroxides formed losses water to form the
ferrosoferric oxide during the course of the reaction, it is entirely possible that the reduction
may be made with less than 4moles of water. Practical problems relating to (1) the agitation
of the reaction mass (2) the promotion or a smooth active reaction and (3) the conservation
of the heat of reduction make it advisable to use a slight excess. Where the nitro compound
contains a solubilizing group, such as sulfonic or carboxylic residue, and the resulting amine is
filtered from alkalinized iron oxide sludge, much more water is generally used (50-100moles)
1.24.1.4 Amount of acid
This reaction required the presence of small amounts of ferrous ion to act as a
catalyst. Generally about 0.05 - 0.22 of an equivalent of acid is used. The acids usually
employed in the reduction process are hydrochloric and sulfuric acid.
1.24.1.5 Effects of agitation
A sturdy sleeve and propeller or double impeller type of stirrer will be superior to the
slow moving plow type, speeding up the reaction considerably.
Most aromatic nitro compounds (not containing basic groups) are practically
insoluble in faintly acid solution, and through mixing is a factor of major importance. A
method involving use of rotary mills having freely moving ponderous agitators, such as iron
balls for the reduction of nitro, nitroso and azo compounds to amines with iron in aqueous
emulsion in order to effect grinding action during the reduction. Such mills are also useful in
the distillation of aromatic amines from the iron oxide sludge in vacuum.
1.24.1.6 Reaction temperature
The use of a high catalyst concentration (3 % or more compared to nitrobenzene
taken) during reduction results in a finely divided iron sludge which although it is generally a
poor filtering sludge, is of possible a commercial value (for removing sulphur compound from
illuminating gas). This result can obtain by limiting the quantity of water introduced into the
jacketed reducer and utilizing the heat of reaction to carry on the reaction. An obvious
advantage arising from operating with such concentrated solution is the fact that the
charge is easily maintained at the boiling temperature. The vigorous reflux that characterizes
such as a reduction ensures against the formation of intermediate product of reaction. The
reaction is not only rapid but is economical on account of the lower consumption of steam.
1.24.1.7 Additions of solvents
Where a very insoluble and difficulty reducible nitro compound is to be reduced, the
addition of a solvent miscible with water, such as ethyl alcohol, methanol or pyridine is often
considerable help. This makes for a smoother and more rapid reduction. In carrying out the
reduction, the alkalinized iron oxide sludge is filtered off hot and washed with hot solvent.
The resulting amine is then isolated from the filtrate. This method is used where reduction in
water alone is extremely slow or where the final amine can be isolated only by solvent
extraction.
1.24.1.8 Testing for completion
Reduction will not take place in the absence of ferrous ions, which can be
demonstrated by the lack of a black precipitates on spot testing with sodium sulfide solution.
The reaction is considered complete when an aliquot no longer increases its take up sodium
nitrite on further reduction with a stronger reducing agent, such as zinc and hydrochloric
acid.
1.24.1.9 Work up of reaction mixture

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Soluble iron is generally precipitated with alkali, using caustic soda, soda ash, lime or
magnesia. Where the amine is volatile, it may be isolated by steam distillation or by vacuum
distillation from the iron oxide cake after distilling off the water. Where the final amine is
soluble in alkaline solution the iron oxide cake is filtered off and the amine isolated from the
filtrate. When the final amine is volatile but sensitive to alkali, as is the case with some
polychloroamine the amine may be steam distilled from the slightly acid mixture.
1.24.1.10 Continuous processing
Although the Bechamp reduction is generally carried out on a batch basis, it has
been run continuously. This involves passing an acidified solution or emulsion of the nitro
compound through a suitable tower packed with iron shavings or scraps iron and kept at
the required temperature.
1.24.1.11 Recovery of by- products
In the technical preparation of amines by catalytic reduction with iron and a soluble
salt, it is not customary to recover and utilize the dissolved catalyst.
1.24.1.12 Yield of amine
In plant, yields in the range of 85-98% of theory are obtained with the Bechamp
reduction.
1.24.2 Equipment
1.24.2.1 Material of construction
Bechamp reduction is usually carried out in cast - iron vessels and alkali reduction in
carbon steel vessels of desired sizes. The larger ones (1,600 gal capacity) are favoured by
plant engineers because of the possibilities of more economical operation.
The reducers for iron and acid reductions are sometimes equipped with side and
bottom cast - iron lining plates, which may be reversed or replaced, in order to protect the
vessel against the continuous, erosive action of the iron borings. Alternatively the reducers
may be lined partially or entirely with acid resisting brick or tile. Wooden equipment is also
used, particularly for the reduction of solid nitro compounds such as p-nitro aniline.

Figure: Jacketed reducer

1.24.2.2 Agitation
In some reducers, a vertical shaft carries a set of cast iron plows, which can be
removed through the side door to the reactor. These plows travel at the rate of 30-50rpm
and serve to keep the iron particle in suspension in the lower part of the vessel. It will be
recalled that the iron and acid reduction process is a four component system e.g. reducible
organic compound, water, acid or metal salts and metal. Obviously, the best results in such a
catalytic process can be obtained only when all of the components are in intimate contact.

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1.24.2.3 Jacketing of reducers

Practically all the iron reducers employed for the Bechamp reduction of liquid nitro
compounds are equipped with jackets. Although the reduction process is distinctly
exothermic, the reaction precedes best at slightly elevated temperatures. It is customary,
therefore, to warm the reactants at the start.
When jacketed reducers are employed, the heat is applied indirectly and no dilution
of the charge occurs. Under such circumstances, the optimum quantity of water can be
delivered during the "feeding" stage and the reaction is kept active by regulating the
introduction of the reactants.
When the reaction vessels are not jacketed, as is the case with brick or tile-lined
kettles, live steam is introduced to start and maintain the reaction. Care must be taken that
the charge does not become unduly diluted. Otherwise, the concentration of acid is
lowered and the reaction rate decreased. Yields may also suffer.

1.25 MANUFACTURE OF ANILINE FROM NITROBENZENE BY BECHAMP REDUCTION

1.25.1 Raw materials

Basis: 1 metric ton aniline
Nitrobenzene: 1390 kg
Iron borings: 1600 kg
Hydrochloric acid: 125 kg
1.25.2 Reaction
HCl
4C6H5NO2 + 9Fe + 4H2O 4C6H5NH3 + 3FeO4 90 95% Yield
1.25.3 Manufacture

Figure: Manufacture of aniline from nitrobenzene by Bechamp reduction

Crude nitrobenzene is charge into a reducer (reactor) fitted with an efficient reflux
condenser. The reducer is a steam jacketed cast iron enclosed cylindrical vessel containing
an agitator. Cast iron borings (turnings) or powder (free from oil and non - ferrous metals),
water and catalyst are added gradually, in small quantities, to the nitrobenzene. Generally
10 to 20% of the total iron is added at the beginning and the mixture is heated by steam to
reflux temperature (200C). The remaining iron is added over a period of time at a rate
determined by the proper pressure temperature balance. The addition rate is fast enough to
maintain lively reflux by the heat generated from the exothermic reaction, yet slow enough
to prevent excessive hydrogen, pressure build up.

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The water required for the reaction is generally in the form of aniline water recovered
from the separator or column and is added to the reducer in bulk at the start or in small
quantities along with the iron additions. Dilute (30%) HCl acid is added along with the water
as catalyst. The acid reacts with the iron borings. Forming catalytically active iron salts.
Subsequent runs may utilize aniline hydrochloric acid mother liquor as the source of the
catalyst and some of the reaction water; the weight ratio of reactants is approximately 115
parts of iron borings, 0.27 parts of 100% hydrochloric acid and 60 parts of water per 100 parts
of nitrobenzene. After the last addition, the reaction is heated with steam to maintain lively
reflux.
At the end of the reduction (about 10 hrs. for 2250kg charge), the aniline is separated
from the reducer charge by one or more of several methods, The liquid water aniline mixture
may be separated from the solid iron oxide iron hydroxide sludge by steam distillation,
vacuum distillation, filtration, centrifugation or siphoning. For example the finished reduction
product may be neutralized with a small amount of sodium carbonate (about equal to the
amount of hydrochloric acid in the charge) and allowed to settle. Most of aniline and some
water siphoned off and the residual aniline is separated from the sludge by steam distillation.
The sludge consisting of ferric oxide, water and small amount of ferric oxide is dumped and
may be marketed after drying.
The water aniline mixture from the reducer is run to a separator where the lighter
aniline separates and is withdrawn from the upper. The top layer, which contains 3 to 5%
aniline, is partially distilled until the aniline content in the water is low. The residual aniline
water is returned to the reducer for subsequent runs. The aniline in the distillate is separated
by decantation and the water layer is redistilled to obtain the remaining aniline. An alternate
procedure is to extract aniline from the aniline water with nitrobenzene.
The aniline streams from the separator and decanter are united and vacuum distilled
to yield purified aniline. The yield based on nitrobenzene is approximately 95% by weight.

1.26 MANUFACTURE OF ANILINE FROM CHLOROBENZENE BY AMMONOLYSIS

1.26.1 Raw materials

Basis:1 ton aniline
Chlorobenzene = 2,500 lb
Ammonia solution(28%) = 7,450 lb
Cuprous oxide = 350 lb
1.26.2 Reaction
C6H5Cl + 2NH3(aq) C6H5NH2 + NH4Cl (soln)
96% yield
1.26.3 Manufacture
Chlorobenzene is charged into a series of horizontal, rotating high - pressure rolled
steel autoclave. Approximately 0.1 mole of cuprous oxide and 4 to 5moles of 28 to 30%
aqueous ammonia per mole of chlorobenzene are added. The reaction is initiated at a
temperature of 180oC and is later maintained at 210 to 220C under constant agitation. The
pressure rises to 750 to 850 psi. The active catalyst is cuprous chlorine produced from cuprous
oxide by the product ammonium chlorine as follows:
Cu2O + 2NH4CI Cu2CI2 + 2NH3 + H2O
A large excess of ammonia solution is used to suppress the phenol producing side
reaction (C6H5CI + NH3 + H2O C6H5OH + NH4CI). If the indicated ratio of reactants is
used, the rate of aniline formation is about 20 times greater than the rate of phenol
formation.

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 US03CICV01 Unit -1 Dr. N. K. Patel

Chloro - Ammonia Absorber

benzene aq.

Cu2O
Seprator
Reactor Cooler
and Column
Separator Neutralizer

Aniline

Filter

Acid

Neutralizer Column Acidifier

NaOH

Phenol
Diphenyl amine Aniline

Figure: Flowchart for production of Aniline from chlorobenzene by Ammonolysis

The reaction products are cooled below 100C and run to a separator. The free
ammonia continues to absorption and condensing system for recovery. The settled reaction
mass separates into two layers: aniline rich lower and an aqueous upper layer. The
approximate distribution of reaction products not including unreacted chlorobenzene in the
two layers is as follows: aniline layer 82% aniline, 5% phenol, and 1% diphenylamine; water
layer 5 % aniline, 0.5% phenol, 9% chlorine ion (NH4CI), 3% cuprous oxide and 14% ammonia.
The aqueous layer is drawn from the top of the separator and is run to a neutralizer,
where it is treated with sodium hydroxide or lime. A sufficient amount of alkali is used to react
with the ammonium chloride and phenol. The solution is fractionally distilled, and the
liberated ammonia expelled first is recovered in an absorption system. The second fraction
consists of aniline and water, which are separated by decantation. The residual solution of
sodium phenate and sodium chloride is filtered to remove the precipitated copper oxides,
which are reused in subsequent runs.
The aniline layer is withdrawn from the bottom of the separator and treated with 50%
sodium hydroxide solution. Approximately 0.2 percent of the volume of the aniline layer is
used. The solution is fractionally distilled, yielding first aniline -water mixture, which is further
treated as described previously. The second fraction is technically pure (97 to 90%) aniline,
the residue is steam distilled, yielding diphenylamine. The phenol is recovered by acidifying
the residue mostly sodium phenate and distilling. The yield of aniline is 96% based on
chlorobenzene.

1.27 m-NITROANILINE

100 parts of dinitrobenzene is added to 1000 parts of water at 900C contained in a

reducer fitted with reflux condenser and a propeller type stirrer. Upon emulsification, 245
parts of sodium sulfide (9H2O), dissolved in a minimum of water, is gradually run in. The dinitro
compound is gradually reduced to m-nitro aniline, the end point being determined by the
formation of a definite black streak when ferrous sulfate solution is added to filter paper
spotted with some of the reducer liquor.
A modification in the preceding process involves the use of an organic solvent, which
is immiscible with water, for the m-dinitrobenzene. Accordingly, 100 parts of technical
dinitrobenzene, 90% purity and 160 parts of either solvent naphtha or toluene are put into
reducer, and the mixture is warmed to 600C to effect solution. Then, 4000 parts of hot water is
added, and the m-dinitrobenzene solution is stirred and heated to 950C. A hot polysulfide
(Na2S3) solution made by heating 720 parts of 7% Na2S with 40 parts of flowers of sulfur is
then added rather rapidly. The reaction of polysulfide is distinctly exothermic, and the charge

23
 US03CICV01 Unit -1 Dr. N. K. Patel

boils vigorously, but overheating is avoided because of vaporization of solvent. Reduction of

the dinitrobenzene to m-nitro aniline is found to take place quickly under such conditions.
To hot reduction mass is first filtered to remove any free sulfur, and the solvent
naphtha in the filtrate is distilled with steam. The dissolved m-nitro aniline crystallizes out in the
form of bright yellow crystals when the residual liquor is cooled. After washing, the product
has a melting point of about 1130C and can be used directly in the manufacture of azo
dyes. A yield of approximately 9092% of theory is attainable, and the process is applicable
to other m-dinitro compounds, e.g., m- dinitro derivatives of toluene and xylene.

1.28 EXERCISE

1. Differentiate between unit process and unit operation 02

2. Discuss the advantages of continuous process and batch process over each 05
other
3. Describe the continuous nitration of benzene with fortified spent acid
4. Define nitration. Enlist various nitrating agents and discuss the function of 05
sulphuric acid in the mixed acid used for nitration
5. Describe the batch nitration of benzene with mixed acid 05
6. Give an account on methods of reduction for the preparation of amines. 06
Illustrate various products of reduction of nitrobenzene
7. With the help of flow diagram describe the manufacture of aniline from 05
nitrobenzene
1. By Bechamp reduction
2. by Ammonolysis from chlorobenzene
8. Explain kinetics and mechanism of aromatic nitration. What is the effect of 04
nitrous acid on nitration
9. Give various reagents used for aromatic chlorination 05
10. Describe gas phase and liquid phase nitration 05
11. Define nitric ratio, D.V.S. with example 04
12. Describe the manufacture of BHC 05
13. What is amination by reduction? State various methods of preparation of 07
amines. Write a note on Bechamp reduction
14. Describe the manufacture of p nitroacetanilide 05
15. Define unit process. Why is it so called? How do unit processes differ from unit 02
operation?
16. Give an account of oxy-nitration of benzene 03
17. Describe the manufacture of m-dinitrobenzene from benzene 05
18. Describe construction, working and uses of 06
1. Schmidt nitrator
2. Biazzi nitrator for continuous nitration process
19. Give a brief account of nitration of paraffinic hydrocarbon 05
20. Give evidence to establish the formation of nitryl ions in a nitration process 03
conducted using mixed acids

1.38 FURTHER READING

1. Unit Processes in Organic Synthesis by P. H. Grogins

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