Nitration

Addition of nitro-group by replacing a number of

different monovalent atoms or groups of atoms,
(especially hydrogen atom).
1-Nitro group attached to carbon atom (Nitroaromatic
/nitroparaffinic compounds) CNO2
2- Attached to oxygen atom(Nitrate ester) CONO2

3-Nitro-group attached to nitrogen

atom(Nitroamine/Nitroamide) NNo2
 Nitration Products
Solvents, dyestuffs, pharmaceuticals and
explosives
Also useful intermediates for the preparation of
other compounds.
Nitrating agents:
HNO3(fuming,concentrated,aqueous)
Mixed acid(HNO3 & H2SO4)
HNO3 & acetic anhydride
HNO3 & acetic acid
Cont
HNO3 & phosphoric acid
HNO3 & chloroform
Nitrogen tetraoxide & pentaoxide
NO2+ion: HNO3 exists in conc.H2SO4
(mixed acid) as nitryl ion.
The nitration of aromatic compounds
can be represented by the eqn:
ArH+HNO3=ArNO2+H2O
Kinetics and Mechanism of Aromatic Nitration

The Kinetics of nitration reaction depends

upon the reaction medium (Aromatic
compound and Nitrating agent etc.)

Let us first consider the reaction in a

strong H2SO4 medium.

The rate of all aromatic nitration process

is proportional to the concentration of
added nitric acid & of organic substrate .

Mathematically, this behavior can be

written as follows,
 Rate [HNO3] [ArH]
Rate = K[HNO3] [ArH]

The most accepted mechanism for the nitration

process is regarded as follows,

The organic compounds with intermediate reactivity

show fractional dependence on the concentration of
organic compound , the kinetics of the reaction are
therefore, intermediate between zero and one.

Various mechanism proposed further reactions

referred to above are as follows.
Cont
The effect of the amounts of H2O upon
the rxn rate is that the rxn rate rises
sharply with increasing content H2SO4
ration & reaches a maximum at about
90% H2SO4 & then falls off at higher acid
concentration.
The rise is due to increase in nitryl ion.
Rxn mechanism in conc. H2SO4
Cont
HNO3+ 2H2SO4NO2+ + H3O+2HSO4-
ArH + NO2ArHNO2+
ArHNO2+ HSO4-ArNO2+ H2SO4
1. Condition - A

i. HNO3 is in large excess.

ii. Deactivating group (NO+2) attached with nucleus of organic
compound.
iii. Highly polar organic solvent such as sulfuric acid etc.

The mechanism is as follows,

i. 2HNO3 H2NO+3 + NO-3 (Fast)
ii. H2NO+3 H2O + NO+2 (Fast)
iii. ArH + NO+2 ArNO2 + H+ (Slow) (R.D.S)

The First step (representing the transfer of a proton from one

molecule of HNO3 to another )is very rapid.
Rate of second step depends upon the medium.
 Hence highly reactive aromatic compounds are nitrated at the same rate
which is the rate of formation of nitryl ion.

In the nitration of less reactive aromatic compounds,the formation of nitryl

ion is fast relative to the nitration step(RDS)

Shows first order dependence on the organic substrate.

Therefore, step ii, involving the formation of nitronium ion (NO+2) should
be faster than reaction No. iii. On the basis of this mechanism, the rate
expression conforms to the observed behavior.
2. Condition - B

i. HNO3 is in large excess.

ii. Activating group (-CH3) attached with nucleus of organic compound.
iii. Medium, Organic solvent.

For such reactions, the mechanism which could be compactable

with to observed behavior is represented as follows,

i. 2HNO3 H2NO+3 + NO-3 (Fast)

ii. H2NO3 H2O + NO+2 (Slow)
iii. ArH + NO+2 ArNO2 + H+ (Fast) (RDS)
3. Condition - C

i. Large excess of HNO3,

ii. Organic compound containing average reactivity and medium containing
organic solvent under these conditions, the reaction is thought to
proceed via two paths.

a. Independent of organic solvent (substrate)

b. The other path is assumed as which does not involve the organic
compound.

The extent of any of two steps would have direct impact on the order of
reaction.
Nitration in Organic Solvent
With amount of HNO3 in large excess and in the
presence of Organic solvent such as (non-aqueous) acetic
acid, the kinetics of the nitration process depend directly
on the Concentration of the organic compound. Thus when
nitrobenzene ( NO 2) is nitrated in the presence
of organic solvent. The system is 1st order w.r.t. organic
compound.

It is thus clear that organic compounds possessing the

deactivating groups (e.g Nitrobenzene) show, the 1st order
dependence.
 On the contrary, the organic compounds containing
activating group (Toluene, Xylene) do not show any effect
on the rate of reaction. The order of reaction for such
system is zero. The rate of reaction with all substrate
(organic compound) with zero order dependence has been
found the same. This thing indicate that the rate
determining step in all such nitration reactions is the
same.
i. HNO3 + 2H2SO4 NO+2 + H3O+ + 2HSO-4
ii. ArH + NO2+ Ar HNO+2 (Intermediate)
iii. Ar HNO+2 + HSO4 Ar NO2 + H2SO4

It has been observed that the rate of reaction rises sharply with
increasing sulfuric acid concentration and reaches a maximum at
about 90% H2SO4 and then falls off at higher acid concentration.

The aspect of decrease in the rate of reaction with in the

concentration of H2SO4 above 90% is however not explained by
mechanism given above, except that the step No. (ii).
 It was first suggested that the rise in rate with increasing acid
strength when the acid is less then 90% is due to the increase in
the concentration of nitrylion (NO+2).

A plausible explanation for the decrease in rate at higher acidity

(when H2SO4 > 90%) has been given by Gillespie and Millen.
An interaction occurs between the organic substrate (e.g.
nitrobenzene) and the sulfuric acid which decrease the electron
density in the ring and hence decreases the reactivity.
The interactions is probably a hydrogen bond formation.
The hydrogen bond between nitrobenzene and sulfuric acid can be
pictured. O

ArN

O - - HOSO3H

The strength of a hydrogen bond increases with the acidity of the

hydrogen donor, which is this case is sulfuric acid.
 THE EFFECT OF ADDITION OF HNO2 IN NITRATION PROCESS

Nitrous acid (HNO2) or Nitrogen Dioxide in certain instances exerts two

types of effects,

1) Inhibiting effect
2) catalytic effect

INHIBITING EFFECT

The inhibiting effect is observed in the nitration of compounds having no

activating group; these reactions are necessarily carried out either in
strong HNO3 or in mixed acids

In this media nitrous acid forms nitrosyl ion (NO)+

HNO2 + HNO3 NO-3 + NO+ + H2O

HNO2 + 2H2SO4 H3O+ + 2HSO-4 + NO+
So, nitrosyl ion decreases the concentration of nitryl ion and thus
reduces the reaction rate.

CATALYTIC EFFECT:

The catalytic effect is observed in the nitration of reactive substrate

such as anisole (Methyl Phenyl ether (CH3OC6H5) or dimethl aniline,
which is nitrated, in weak acid where nitryl ion concentration in low.

The catalysis is due to the formation of nitroso compound, which is

oxidized to nitro compound.

ArH + NO+ ArNO + H+

ArNO + HNO3 ArNO2 + HNO2
 Because nitrosyl ion is much weaker electrophonic reagent than nitryl,
ion is able to react only with very reactive aromatic compounds such
as anisole or dimethylaniline.

Two conditions are necessary for catalysis by HNO2.

1) The substrate must sufficiently reactive to attack by nitrosyl ion.

2) The reaction mediums have concentration of nitryl ion very low thus
allowing the nitrodyl ion to compete favorably for substrate.

OXYNITRATION

An interesting reaction occurs between benzene and approximately

50 percent nitric acid containing 0.2 molar mercuric nitrate which
yields up to 85 percent dinitrophenol and picric acid. This process is
known as oxynitration.
NITRATION OF PARAFFINIC HYDROCARBONS

Gas Phase Reaction

In contrast to aromatic hydrocarbons, which are

susceptible to attack by electrophilic reagents such as the nitryl ion,
the paraffins are quite inert to such reagents. The paraffins, on the
other hand, are susceptible to attack by certain atoms and free
radicals. The nitration of these compounds are practiced commercially
is carried out in the vapor phase and at temperature of 350 450 C;
it is undoubtedly a free radical reaction. Nitric Acid of 70% strength or
less is generally used, although Nitrogen Dioxide can also be used. A
characteristic feature of reactions involving alkyl radicals is the great
variety of product formed. This is clearly shown by the nitration of 2
methyl pentane which yields all the possible mononitrations products
that might be formed by breaking any one of bonds present and
introducing a nitro group at the pint of cleavage.
The products are:-

1) Nitro methane
2) Nitro ethane
3) 2 nitro propane
4) 2 nitric butane
5) 1 nitro isobutene
6) 1- nitro 3 methyl butane
7) 2- nitor-3-methylbutane

The nitration produces only mononitroparaffins and no significant

amounts of polynitro compounds. Although cleavage of the carbon
skeleton occurs, as shown above, on rearrangement of the carbon
skeleton has been found to occur.
 The reaction is carried out by passing the reactants through the
reaction chamber in a flow system. The products are condensed and
distilled. As a result of a systematic study, the following facts have
emerged.

1) There is an optimum temperature at which the highest yield is

obtained. Using butane and concentrated nitric acid is molar ratio of
15:1, and a contact time of 1.6 sec, the result shown in the
accompanying table were obtained.

Temperature C 405 425 435

% Conversation of nitric acid 15 36 22
% Yield of RNO2 based on butane 1 2.9 1.4

2) The addition of oxygen increases the yield based on nitric acid but also
increases the oxidation of butane. The effects are shown in fig. oxygen
also increase the yield of nitro methane and nitro ethane and
decreases the yield of nitro butane.
3) Nitrogen dioxide also reacts with paraffins to yield nitroparaffins. At 325
C, a contact time of 1.9 min, and propane: NO 2 = 4.2, the percent
conversion of NO2 is 16.6 and the yields based on the moles of
hydrocarbons is 51 percent. The addition of oxygen lowers the
optimum temperature and improves conversion and yields. At 285 C,
contact time 3 min, and O2 : NO2 = 0.75, the conversion is 29 percent
and the yield is 71 percent.

4) Bromine has a beneficial effect on both yields and conversions to

nitroparaffins using nitric acid. At 423 C, a contact time of 1.5 sec, and
the following rations of reactants, propane: O2 = 8.2, propane: nitric
acid = 9.9, water: nitric acid = 15 and Br2:HNO3 = 0.015, the percent
conversion of nitric acid is 47.7 and the yield based on propane is 55.5
percent. The yield of other products are follows: CO 2 = 0, CO = 3.6,
C3H6 = 9.7, C2H4 = 4.1, aldehydes and ketones = 27 percent. The
effect of chlorine is similar to that of the bromine.
5) Highly branched hydrocarbons undergo less fission during nitration
than they do their less branched isomers. Correspondingly, hydrogen
substitutions are favored when highly branched structure is nitrated. As
can be seen from the data in table, in which ha comparison is made of
the nitration of isomeric butanes and pentanes the molar ratio of the
product resulting from fission so that resulting from hydrogen
substitutions decreases as the carbon skeleton becomes more highly
branched.
Hydrocarbons Temp Mole% of Products Ratio
fission C
products
substitution
products

Butanes 420 10.5 nitro methane 0.463

15.8 nitro ethane
5.3 1-nitroprepane
44.2 2-nitrobutane
24.2 1-nitrobutane

2-Methylpropane 420 5.8 nitro methane 0.407

23.1 2-nitropropane
7.0 2-methyl, 2-nitrobutane
64.1 2-methyl, 1-nitrobutane
N-Pentane 400 2.3 nitro methane 0.475
10.9 nitro ethane
16.7 1-nitroprepane
12.8 1-nitrobutane
18.9 1-nitropentane
18.2 2-nitropentane
20.2 3-nitropentane
2-Methylbutane 420 3.9 nitro methane 0.628
8.8 nitroethane
16.1 2-nitropropane
2-methyl, 1-nitropropane
9.8 2-nitrobutane
12.2 2-methyl-2-nitrobutane
14.0 3-methyl-2-nitrobutane
24.1 2-methyl-1-nitrobutane
11.1 3-methyl-1-nitorbutane
2,2-Demethylpropane 410 14.0 nitro methane 0.370
13.0 2-methyl-2-nitropropane
73.0 2,2-dimethyl1-1-nitropropane
The benzene is initially converted to phenyl mercuric nitrate which
reacts with nitrogen dioxide to yield nitrosobenzene. Each of these
intermediates has been isolated from the reaction mixture. The
nitrosobenzene can react in two ways. In nitric acid weaker than 50
percent, it reacts with 2 moles of nitric oxide to form phenyldiazonium
nitrate, a reaction first discovered by Bamberger. The diazonium salt is
converted by water to phenol, which is nitrated in steps to the final
products. In nitric acid of greater than 50 percent concentration, the
nitrosobenzene is converted directly to p-nitro phenol without going
through the diazonium compound. The p-nitro phenol is then nitrated
further to give the dinitrophenol and picric acid.
N-NITRO COMPOUNDS

The n-nitro compounds include the nitramines, which have the

structure (A), and the nitramides, which have the structure (B).

NO2 NO2
(A) (B)

R N R RCO N R

Where R is an alkyl or aryl group and R is H, alkyl or aryl. The primary

nitramides are those in which R is H. N-nitro compounds find their
greatest use as explosives and propellants. Trimethylenetrinitramine,
which is known as RDX, is used as an explosive as is 2,4,6 trinitro
N-nitro N-methyl aniline, which is known as tetryl. Nitroguanidine is
used in solid propellant formulations.
 H2 H 3C N NO2

O2N N N NO2 O 2N NO2

NH

H2C CH2
H 2N C
NHNO2
N
NO2

NO2
RDX Tetryl Nitroguaidine
Methods of Preparation

Primary nit amines can not be prepared by the direct, nitration of primary
amines. Because of their sensitivity towards acid, they probably do not
survive in the strongly acidic environment of the nitration. They are gently
made by alkaline hydrolysis of nit amides.
HNO2 OH

RCORHCH2 RCON(NO2)CH RCOOH + HN(NO2) CH2

The nitramides are readily prepared by nitration of the amide with 100%
nitric acid or with nitric acid, acetic anhydride, acetic acid mixture.
Primary nitramines can also be prepared from the appropriate urethane.
CICOOEt HNO 3 NH 3

CH2NH2 CH3NHCOOEt CH3(NO2)COOEt

CH3NHNO2 + NH2COOEt
Secondary nitro mines are prepared by the nitrolysis of secondary
amides or of N, N-dialkyl ureas.
HNO2

RCON(CH3)2 RCOOH + (CH3)2 N NO2

RCNO HNO3

R2NH R2NCONH2 R2NNO2

Dialhyl Urea Sec. Nitramine

Mr. G. W right and coworkers showed that nitramines could be obtained

directly from secondary amines by using a nitrating mixture, which
contains chloride ions. Thus by treating the amine nitrate with acetic
anhydride containing zinc chloride, the nitramines of dimethylamine,
diethylamine, piperdine and morholine were obtained in yields of 60-70
percent.
Aromatic nitramines undergo a rearrangement in which the nitro group
migrates to the benzene ring. Such a rearrangements is believe to
occur in the synthesis to tetryl, which is made by the nitration and
nitrolysis of dimethylaniline with mixed acid. The reaction steps are as
follows:-
H2C N CH2 CH2 N CH2 H2C N NO2 H2C N H H2C N NO2

NO2 NO2 NO2 NO2

The earlier process for making RDX consisted of reacting hexamine

(hexamethylenetetramine) or its dinitrate salt with 98-100 percent nitric
acid the yield of this method are not good because of the formation of
RDX is accompanied by the formation of formaldehyde, which is
oxidized by the nitric acid. Greatly improved yields (70-80%) can be
obtained by means of the Bachman process, which employs hexamine,
98 percent nitric acid, ammonium, nitrate, and
Acetic anhydride. In the Bachman process a by product having the
structure I also formed in yields up to 10%. The mechanism of these
reactions is not thoroughly understood.

CH2 CH2 NO2

N N O2N N N NO2 CH2 N CH2

CH2 CH2

O2N N N NO2

CH2 CH2 CH2 H 2C CH2

CH2 N CH2

N
NO2
N NO2

Hexamine RDX I
 PROCESS EQUIPMENT FOR TECHNICAL
NITRATIONS

Types of Process Equipment

Nitrations, as technical industrial processes, have evolved from bath-

type operations using stoneware vessels and hand operations to
automatically controlled continuous type processes carried out in gleaming
stainless steal vessels.

The high heat of reaction and dilution involved in nitration, originally

absorbed by the placing the stone ware vessels in a water bath, are now
taken up by coils or jackets cooled by refrigerated brine.

Controls have evolved from none at all to completely automatic

systems, which may be so elaborate as to permit operation from remote
locations. The idea of remote control has always appealed to the designer of
equipment for the manufacture of hazardous, explosive compounds, which
often are result of nitration processes.
It will be convenient to discuss technical nitrations from the standpoint,
1st of bath processes and 2nd of continuous processes. This is the
historical order of development. However it should not be concluded
that batch processes have been rendered obsolescent by continuous
ones or that they surely will be superseded. Each kind of process has
advantages peculiar to itself.

In broad terms, batch processes have the following advantages

compared to continuous processes.

Flexibility: Batch process equipment possesses general usefulness

because each batch of material passing through the process is
separate, or nearly separate, from batches which have preceded or
which will follow it. It is usually easier to introduce process variations
into the batch process than into a continuous one. Furthermore, batch
processing 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 a new compound a pilot production
is conveniently done by the batch process by the operating flexibility,
even through the use of a continuous process may be planned for the
completely developed process.

Labor Usage: For high rates of production when large batches are
used the labor efficiency of a batch process may be just as good as that
for a continuous process. This appears to be true for the large scale
industrial production of nitroglycerine and nitortoluene, for example:-

Continuous processes, in general will be found to have to following

advantages over batch processes.

Lower Capital Costs: For a given rate of production, the

equipment needed for a continuous process is smaller than for a
batches process. This is usually the most striking difference between
the two types of process.
The reason for this is obvious, Since it is not necessary to accumulate
material in the continuous process anywhere, the vessels are designed
with capacities dictated by the rate of reaction process step, which they
much accommodate. Alternatively, because of the relatively small size of
continuous process equipment, it is often possible and advantageous to
use materials of construction, which would be excessively high in cost
for batch scale equipment. Thus, for example, corrosion resistance
alloys such as the appropriate stainless steels may be used for a
continuous plant, whereas ordinary mild steal may be dictated for a
batch plant because of cost. In the case of the stainless steel, corrosion
problems may be completely eliminated.

Safety: Because of the relatively small size of continuous process

equipment, there is a less material in process at any time than at certain
times in a comparable batch process. For example, at the completion of
a batch process nitration and during its normal separation of the product
from spent nitrating acid. The entire batch of an often hazardous
compound will be present in the equipment. In the continuous process,
Only as much material needed to gain sufficient reaction or process
time. In the case of high explosives made by nitration, such as
nitroglycerine, this inherent safety factor of a continuous process is very
attractive.
CONTINUOUS NITRATION WITH FORTIFIED
SPENT ACID

Methods for the continuous nitration of benzene have been proposed

by Castner and Mares. Both processes are based on the recognition
that a slightly HNO3- fortified spent acid constitutes a satisfactory
nitrating agent for a limited quantity of hydrocarbon. To obtain volume
production, it is necessary to circulate relatively large quantities of acid
of low nitric acid content and high heat capacity and to remove the
water of nitration continuously in an integrated evaporator operating
under reduced pressures. When the heat of sulfuric acid hydration and
the chemical heat of nitration are evolved in separate vessels by adding
nitric acid to a 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.
As shown in Fig. 4-14 the operation proceeds as follows:-

Hot sulfuric acid at 90 C is run from the heat insulated storage tank (B)
into one of a battery of nitrators (A1 to A4). Under vigorous agitation,
sufficient 63 percent nitric acid is added to the nitrator to produce a
mixed acid containing 4 percent HNO3. Sufficient benzene is then
delivered from its storage scale tank to react with al the nitric acid in the
nitrator. Upon completion of the reaction, which takes about 10 minutes,
the agitation is stopped and the charge permitted to settle. While the
separation of the nitrobenzene and spent acid proceeds, another
nitration is started, thus providing a continuity of operations.
PREPARATION OF A-NITRO NAPHTHALENE

NO2

+ HNO2 + H 2O

When naphthalene is nitrated under optimal conditions, the product

consists principally of -nitro naphthalene. The reaction takes place
vigorously; and unless precautions are taken, polynitro compounds are
formed. If impure naphthalene is used, the nitration product will be
unsatisfactory; and inasmuch as it is difficult to isolate -nitro
naphthalene in a pure state, it is advisable to prevent further
complications and to use a pure raw material.
When the nitration is made without the use of cycle acid, a mixed acid
of the following composition may be used:

H2SO4 . 59.55%
HNO3 ... 15.85%
H2O .. 24.60%
HNO3 ratio .. 1.01
D.V.S. .. 2.04

This will yield a product consisting of 95 percent -nitro naphthalene

together with some unchanged naphthalene and very little dinitro
derivative. By using cycle acid to dissolve the naphthalene to be
nitrated an then proceeding with the nitration in the usual way, the
operating steps are as follows: The naphthalene-1,280 Ib-is suspended,
in 4,500 Ib of dilute sulfuric acid or spent acid containing about 65
percent H2SO4. The whole is thoroughly stirred, and 2,350 Ib of mixed
acid of the following composition is slowly added:
 H2SO4 . 56.60%
HNO3 ... 28.30%
H3O .. 15.10%
HNO3 ratio .. 1.03

During the addition of the acid, the temperature is kept at 35-50 C; but
after the whole of the acid has been run in, the temperature is raise
slowly to 65-70 C and maintained at that period for 1 hr. The agitation
is then stopped and the nitro naphthalene which floats on the surface is
decanted with part of the spent acid and delivered to a separator, a
heel of acid being left for the next nitration. After settling for 3 hr, the
spent acid is removed and the crude nitro naphthalene is delivered to
the washing and granulation kettle. Here it is made free for acid by
repeated washings with boiling water and alkali. Any free naphthalene
that may be present is removed by steam during the washing process.
The crystallizing point must be between 52 and 52.5 C.
The purification of the crude product is accomplished also by re-
crystallizing it from 10 percent of its weight of ligroin or solvent naphtha.
The success of the purification depends upon certain details of
manipulation, which include (1) use of a minimum of solvent and (2)
constant agitation while re-crystallization take place in order to assure
the formation of small crystals. The nitro naphthalene is dissolved in 10
percent of its weight of solvent naphtha and heated above the melting
point of the crude, i.e., above 50 C, until a homogeneous mixture is
formed. The resulting solution is cooled to 25 C with constant agitation,
and the thick slurry that is formed is centrifuged. The -nitro
naphthalene obtained in this manner has a solidifying point above 54.4
C. This is not yet pure, as the chemically pure material comes as
glistening yellow crystals which melt at 61 C.
PREPARATION OF NITROPARAFFINS

The development of the preparation of nitroparaffins from laboratory

scale through pilot plant to full scale operation covered a 20 year long
effort by Commercial Solvents Corporation. A full scale plant with a
capacity of more than 10,000,000 Ib per year went on stream in 1955.
by a process of nitration of propane, the main production of
nitroparaffins includes nitro methane, nitro ethane, 1-nitropropane and
2-nitropropane. The nitration is done in the vapor phase. A flow diagram
illustration the process is shown in fig. There are five process sections
in the nitroparaffins preparation. These involve (1) nitration, (2)
products recovery (3) products purification (4) products separation and
(5) reactants recovery. A report by Schecter and Kaplan states that
conditions for the nitration of propane are 777 F (410 C) at pressure
of 115-175 psi, initially the vapor phase was carried out in heated tubes
through which a mixture of HNO3 vapor and hydrocarbon was passed.
The present plant nitrator combines the two steps, using the heat of
reaction to vaporize the nitric acid. Since, under perfectly balanced
Conditions, no heat would have to be added to, or removed from, the
nitrator, it is called an adiabatic nitrator. In the form adopted, the nitric
acid is introduced into a stream of heated hydrocarbon by a number of
spray nozzles. Because of the high temperatures of 750-850 F, short
reaction times of 0.1-5.0 sec, and the corrosive properties of nitric acid,
serious problems of design arose which have now been solved.

The conditions of nitration can be varied widely, but these have been
worked out to the optimum values of temperature, pressure, reaction
time, ration of reactants, and the like. The proportion of the four nitro
paraffins from propane is said by Bachman and Pollack to be about as
follows:-
Nitro methane 25%
Nitro ethane 10%
1-Nitro propane . 25%
2-Nitro propane . 40%
Nitrations in the vapor phase such as these are always accompanied by
competing oxidative and decomposition reactions which may produce
such organic materials as aldehydes, ketones, alcohols, carboxylic
acids, olefins, nitrolefins, and polymers. Such simple compounds as
CO2 and CO, NO, and H2O are also end products of the nitration
reaction. The nitrator is operated to minimize production of nitrogen, and
little excess nitric acid appears in the effluent stream.

After leaving the nitrator, the product is cooled to condense the

nitroparaffins and the pressure is reduced to atmospheric. The total
effluent is then passed through an absorber, where it is scrubbed with a
suitable solvent such as hydroxylamine hydrochloride which removes
from the vapor phase the ketones, aldehydes, etc. This is done so that
these will not be recycled to the nitrator with recovered propane. The
gas from the absorber contain oxides of nitrogen and propane and are
delivered to the reactants recovery process. The recycling of propane
and recovered HNO3 leads to high yields of nitro paraffin based on
HNO3. It is reported that over 90 moles of nitroparaffins may be obtained
per 100 moles of HNO3 consumed. The liquid phase from the absorber
is transferred to the top of a steam heated column called the stripper in
which the crude nitro paraffins and water are stripped out of the solvent.
The regenerated solvent is recycled to the absorber. The stripped nitro
paraffins along with water and the oxidation products are condensed
and form a two layer mixture which is separated in a decanter. From the
decanter the nitroparaffins layer is fed to the first rectification operation
called the heads column.