NITRATION

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.
NITRATION

1.0 INTRODUCTION

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A manufacturing chemist is concerned with industrial processes in which raw
materials are charged or separated into useful products. In any case, the products

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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

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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

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resulting in cracking of big molecules into small ones etc. Thus the cracking process involves
both the physical and chemical changes.
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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
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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
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operation and respectively

Any piece of equipment used in industry would involve doing something (operations)
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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
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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
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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
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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
¾ The basic knowledge of a particular chemical reaction
¾ Equipment for the reaction
¾ 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, sulphonation,
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

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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

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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

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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.

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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
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principles rather than technical details.

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

molecule (called substrate), e.g.
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R-Cl + AgNO2 R-NO2 + AgCl

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

¾ Dilute, concentrated or fuming nitric acid can be used.
¾ HNO3 dissolved in acetic acid, H2SO4, acetic anhydride, CHCl3, H3PO4

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 ¾ Mixed acids: This is a mixture of HNO3 and H2SO4. The HNO3 may be concentrated or
fuming
¾ N2O5 and N2O4
1.3.1 Functions of H2SO4
¾ It removes the water produced during nitration.
¾ 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¯
¾ 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.
¾ 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

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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.

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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.

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¾ Electrolysis of solution of HNO3 in H2SO4 posses positively charged ions migrating
towards the cathode.

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¾ Several crystalline nitryl salts have been isolated and characterized. e.g. NO2+ ,NO3¯
NO2+ClO4¯and NO2+HS2O7¯.
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1.4 AROMATIC NITRATION
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ArH +HONO2 ArNO2 +H2O

1.4.1 Orientation
Nitration is an electrophillic substitution reaction i.e. NO2+ is an electrophile. Therefore
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the substituent which raises the electron density on the ring carbon towards the nitration
reaction forms o-, p-nitro products.
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1.4.2 Kinetics and mechanism of aromatic nitration

Kinetics
Rate =K(HNO3) (ArH)
1 1
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Overall rate = 2
Generally accepted mechanism which is compatible with the data is
HNO3 + 2H2SO4 NO2+ + H3O+ + 2HSO4¯ (Fast) Step - 1
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ArH + NO2 ArHNO2+ ( Slow: Rate determining step) Step – 2

ArHNO2 + HSO4¯ ArNO2 + H2SO4 Step - 3
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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¯

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 H2NO3 H2O + NO2+ (nitryl ion)
This 1 step which represents the transfer of proton from one nitric acid molecule to
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another is very rapid. The rate at which the 2nd step, the formation of nitryl ion takes place
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)

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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

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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¯

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HNO2 + 2H2SO4 NO+ + H3O+ + 2HSO4¯
The catalytic effect is observed in the nitration of reactive substrates such as anisole

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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
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following equation.
ArH + NO+ ArNO + H+
ArNO + HNO3 ArNO2 + HNO2
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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.
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1. The substrate must be sufficiently reactive so that it can be easily attacked by nitorsyl
ion (NO+)
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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
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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
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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
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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

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They are inert to electrophillic reagent. It is not an electrophillic substitution reaction. It
is a free radical reaction. Classification is done as
¾ Gas-phase nitration and

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¾ Liquid-phase nitration,
1.8.1 Gas-phase nitration

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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
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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
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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
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introducing a nitro group at the point of cleavage. The products are as under.
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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
¾ There is optimum temperature at which highest yield is obtained.
¾ The addition of oxygen increases yield based on HNO3 but also increases oxidation of
alkane.
¾ NO2 also reacts with paraffin to yield nitro-paraffin.
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 ¾ Bromine has beneficial effect on both yield and conversion to nitro-paraffin using
HNO3.
¾ Highly branched hydrocarbons undergo less fission during nitration than to their less
branched isomer. Correspondingly substitution is favoured when highly branched
structures are nitrated.
¾ Temperature coefficient for H substitution are in order is 1° > 20 > 3°
¾ 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 ºOH + NO2

Alkyl Radical formation

R-H + ºOH Rº + H2O
R-H + NO2 Rº + HNO2
Nitro paraffin formation
Rº + NO2 R-NO2
Oxidative and cleavage steps
R-CH2º +NO2 R-CH2Oº + NO

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R-CH2O + NO2
º R-CHO + HNO2
R-CH2Oº Rº + CH2O

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RCHO + NO2 RCOº + HNO2
RCOº Rº + CO
CH2O + NO2 NOº + H2O + CO

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Olefin formation (unsaturation)
RCH2CH2º + NO2 HNO2 + RCH=CH2
2RCH2CH2 º

1.8.2 Liquid phase nitration

RCH=CH2 + RCH2CH3
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The reaction is less important than the gas-phase nitration because
¾ Low yields
¾ Low conversions
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¾ 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
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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.
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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
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nitrogen, which cannot be usefully utilized. This makes the process expensive.

1.9 LIQUID PHASE NITRATION OF OLEFINS

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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,

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its enthalpy change (ΔH) will be -ve.
1.10.1 Heat of nitration

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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

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enthalpy i.e. Q= -ΔH 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 el
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¾ 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.
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¾ 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
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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
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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
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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
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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.
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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.
¾ 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.
¾ 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
¾ 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

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problem.
¾ Safety

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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

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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

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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.
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¾ 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
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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
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scale of operations increases.

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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 day’s mild carbon steel is
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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
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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
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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
¾ The degree of agitation
¾ 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.

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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

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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

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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.
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Hydrocarbon was than floated in on top of cycle acid. Nitrating acid was fed into the
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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
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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
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called direct nitration and is more satisfactory than the older "indirect' nitration method.
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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
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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
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This nitrator has been designed for the German Schmid Meisener system.
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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.

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Figure: Biazzi nitrator

In any continuous equipment, the designer must be careful to assure that no stagnant
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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
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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
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product will be trapped and remain behind in the nitrator.

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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.
¾ D.V.S.: It is ratio of H2SO4: H2O present at the end of reaction.
¾ 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 %

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Actual H2SO4 49.90 % H 2O –2.40 %
The figures, given for total H2SO4, HNO3 and HNOSO4 are determined directly by

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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

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the sum of these two actual plus HNOSO4, in this example 102.40%. The water content is than
obtained by difference.

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To calculate D.V.S. from the mixed acid, the formula is:
S = % actual H2SO4
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D.V.S. = --------------------------- N= % actual HNO3
EN/R + W W= % water
E = water equivalent of material to
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be nitrated
R = nitric ratio
E is defined as parts by weight of water resulting from the nitration of 1 part of the
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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
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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.
A

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

M.W: 92.06 189.06 227.06 54.06
r.

92.06gm/mole glycerin 54.06gm/mole H2O

0.99gm/mole glycerin ?
D

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 %

11
now, for calculation of DVS
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

d
stability.

ag
1.15 NITROBENZENE

Nitrobenzene can be manufactured by

m
¾ Batch Nitration with mixed acid
¾ Continuous nitration with fortified spent acid

1.16 BATCH NITRATION WITH MIXED ACID el

bo
1.16.1 Raw Materials
Benzene: 10000lb
A

Mixed acid: 23300lb

Nitric acid ratio: 1.04
1.16.2 Reaction
ed
hm

1.16.3 Manufacture
Use of cycle acid is not essential, particularly when the problem of heat transfer has
A

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
r.

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
D

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
12
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
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

d
equipment are noticeable, if the acidity is kept below 0.5 percent.

ag
1.17 CONTINUOUS NITRATION WITH FORTIFIED SPENT ACID

Methods for the continuous nitration of benzene have been proposed by Castner

lm
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
e
acid content high heat capacity and to remove the water of nitration continuously in an
bo
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
A

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
ed

Benzene, Nitric acid, sulfuric acid are the main raw material for continuous nitration.
1.17.2 Reaction
hm
A

1.17.3 Manufacture
r.
D

13
 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% HNO3. Sufficient benzene is then
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

d
nitrobenzene found with the water in the condenser is separated and added to the crude
charge.

ag
1.18 m - DINITROBENENE

m
1.18.1 Raw materials
Benzene
Mixed acid composition
(1) For mono-nitration el
(2) For di-nitration
bo
60.0% H2SO4 75.0%
32.0% HNO3 20.0%
08.0% H2O 05.0%
A

03.52% D.V.S. 07.36

01.01 Nitric ratio 01.10
1.18.2 Reaction
ed
hm

1.18.3 Manufacture
The preparation of m-dinitrobenzene from benzene is usually accomplished in two
A

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
r.

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.
D

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

14
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
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

d
washed and filtered sample should not be less than 88.50C; if lower 25-50kgs more sodium
sulfite is added.

ag
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

m
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 950C, settled for half hour and the

el
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%.
bo
1.19 p-NITROACETANILIDE
A

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,
ed

which in this instance is water-white 66 Be sulfuric acid

1.19.2 Raw materials
hm

Acetanilide: 1000lb
Mixed acid of composition
HNO3 33 % H2O 20 %
H2SO4 47 % HNO3 ratio 1.015
A

1.19.3 Reaction
r.
D

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.
15
 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
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.

1.20 EXERCISE
1. Differentiate between unit process and unit operation

d
2. Discuss the advantages of continuous process and batch process over each other
3. Describe the continuous nitration of benzene with fortified spent acid

ag
4. Define nitration. Enlist various nitrating agents and discuss the function of sulphuric acid in
the mixed acid used for nitration

m
5. Describe the batch nitration of benzene with mixed acid
6. Explain kinetics and mechanism of aromatic nitration. What is the effect of nitrous acid on
nitration
7. Define nitric ratio, D.V.S. with example el
8. Define unit process. Why is it so called? How do unit processes differ from unit operation?
bo
9. Give an account of oxy-nitration of benzene
10. Describe construction, working and uses of
A

1. Schmidt nitrator
2. Biazzi nitrator for continuous nitration process
11. Give evidence to establish the formation of nitryl ions in a nitration process conducted
ed

using mixed acids 03

hm
A
r.
D

16