Nitration

Submitted by:
Name: Subhan Ahmad
ID: 2020-CH-42

Submitted to:
Prof. Abdul Gaffar

NITRATION

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Table of Contents
1. Introduction of Nitration.......................................................................................................3
1.1. Example of Pentaerythritol tetranitrate.......................................................................3
1.2. Mixed Acid.......................................................................................................................3
2. Scope of Nitration in chemical Industry...............................................................................3
2.1. Nitroglycerin....................................................................................................................3
2.1.1. Structure of Nitroglycerin..........................................................................................3
2.1.2. Utility.........................................................................................................................4
2.2. Nitro guanidine................................................................................................................4
2.2.1. Structure.....................................................................................................................4
2.2.2. Utility.........................................................................................................................4
2.3. Trinitrophenyl methylnitramine...................................................................................4
2.3.1. Structure.....................................................................................................................4
2.3.2. Utility.........................................................................................................................5
3. Production at Industrial Scale...............................................................................................5
3.1. Trinitrotoluene................................................................................................................5
3.1.1. Structure.....................................................................................................................5
3.1.2. Scope of Trinitrotoluene............................................................................................5
3.1.3. Reaction.....................................................................................................................5
3.1.4. Block Flow Diagram..................................................................................................6
3.1.5. Explanation of Process..............................................................................................6
3.2. Nitrocellulose...................................................................................................................7
3.2.1. Structure.....................................................................................................................7
3.2.2. Utility.........................................................................................................................7
3.2.3. Reaction.....................................................................................................................7
3.2.4. Block Flow Diagram..................................................................................................7
3.2.5. Explanation of Process..............................................................................................8
4. Application in Pakistani Market...........................................................................................8
4.1. Trinitrotoluene................................................................................................................8
4.2. Nitrocellulose...................................................................................................................8
5. Reference List.........................................................................................................................8

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List of Figures
Figure 1 Structure of Nitroglycerin.................................................................................................3
Figure 2 Structure of Nitro guanidine..............................................................................................4
Figure 3 Structure of Trinitrophenyl methylnitramine....................................................................4
Figure 4 Structure of Trinitrotoluene...............................................................................................5
Figure 5 Process Line of Trinitrotoluene.........................................................................................6
Figure 6 Structure of Nitrocellulose................................................................................................7
Figure 7 Process Line of Nitrocellulose..........................................................................................7

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1. Introduction of Nitration
“A reaction in which a nitro group (–NO2) replaces a hydrogen on a carbon atom by the use of nitric
acid or mixed acid.”[ CITATION Haw16 \l 1033 ]
1.1. Example of Pentaerythritol tetranitrate
For example, PETN (pentaerythritol tetranitrate), is an old explosive made from acetaldehyde and
formaldehyde that reacts by condensation under basic catalysis followed by a crossed Cannizaro
reaction.
H2 H2
O O
Ca(OH)2 HO C C OH
+ 4 C
C C
HO C C OH
H3 C H H H
H2 H2
The nitration of pentaerythritol takes place by adding concentrated nitric acid at 25-300C to produce
PETN.

O O
H2 H2 H2 H2
HO C C OH HNO3 O N O C C O N O
C C
HO C C OH O N O C C O N O
H2 H2 H2 H2
O O
Pentaerythritol PETN

PETN is not very soluble in nitric acid or water and is easily filtered from solution. [ CITATION Muh05 \l
1033 ]

1.2. Mixed Acid

Mixed Acid is also known as nitrating acid, which is a mixture of Sulfuric acid and Nitric acid. It
comprises of 36% nitric acid and 61% sulfuric acid.[ CITATION Haw16 \l 1033 ]

2. Scope of Nitration in chemical Industry

Nitro compounds has a very high scope and utility in the chemical industry from manufacturing to cosmetic
products, giving shinny effect to paints to usage in production of ammunition and explosives. Few example of
nitro compounds are given as follow.

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2.1. Nitroglycerin
2.1.1. Structure of Nitroglycerin
O

N
O O
O
O O O
N
N
O
O

Figure 2-1 Structure of Nitroglycerin

2.1.2. Utility
It is still one of the most widely produced nitrate esters. Nitroglycerine is a very powerful explosive
with a high brisance, that is, shattering effect. It is used in dynamite. [ CITATION Muh05 \l 1033 ] In the
medical field, it is used for treatment of narrow blood vessels by improving flow of blood.
Nitroglycerine is also thickened or gelatinized by the addition of a small percentage of nitrocellulose. It
provides a source of high energy in propellant compositions. Nitroglycerine is insoluble in water but
readily dissolves in most organic solvents.

2.2. Nitro guanidine

2.2.1. Structure
NH
H O
H2 N C N N
O
Figure 2-2 Structure of Nitro guanidine

2.2.2. Utility
Nitro guanidine, also known as picrate, has been used as an industrial explosive but not as a military
explosive because of its relatively low energy content and difficulty of initiation. Nitro guanidine can
also be used in flashes and propellants because of the low heat and temperature of explosion. Nitro
guanidine combined with nitrocellulose, nitroglycerine, and nitro di-ethylene glycol forms a colloidal
gel.[ CITATION Muh05 \l 1033 ]

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2.3. Trinitrophenyl methylnitramine
2.3.1. Structure
O

H3 C N
O
N
O
O
N N
O
O

N
O O

Figure 2-3 Structure of Trinitrophenyl methylnitramine

2.3.2. Utility
Tetryl or 2,4,6-trinitrophenyl methylnitramine, was frequently used as a base charge in blasting caps, as
the booster explosive in high-explosive shells, and as an ingredient of binary explosives. Tetryl is now
replaced by PETN or RDX. Tetryl is a very toxic chemical.[ CITATION Muh05 \l 1033 ]

3. Production at Industrial Scale

Two organic examples of nitration such as TNT and Nitrocellulose are discussed in the succeeding section.

3.1. Trinitrotoluene
3.1.1. Structure
CH3
O
O
N N
O
O

N
O O

Figure 3-4 Structure of Trinitrotoluene

3.1.2. Scope of Trinitrotoluene

TNT has the advantages of low manufacturing costs and cheap raw materials, safe handling, a low
sensitivity to impact and friction, high explosive power, and also has good chemical and thermal
stability. TNT is widely used in commercial explosives and is much safer to produce and handle than

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nitroglycerine and picric acid. TNT has the advantages of low manufacturing costs and cheap raw
materials, safe handling, a low sensitivity to impact and friction, high explosive power, and also has
good chemical and thermal stability.[ CITATION Muh05 \l 1033 ]
3.1.3. Reaction
The Reaction is done in presence of 3 parts of nitric acid and 1 part of sulfuric acid.

CH3
CH3 O
O
N N
O
O
+ 3HNO3  + H2 SO4 + 3H2 O + H2 SO4

N
O O
TNT

3.1.4. Block Flow Diagram

Figure 3-5 Process Line of Trinitrotoluene

3.1.5. Explanation of Process

The production of TNT by nitration of toluene is a 3-stage process performed in a series of reactors, as
shown in Figure 6.3-2. The mixed acid stream is shown to flow countercurrent to the flow of the
organic stream. Toluene and spent acid fortified with a 60 percent HNO3 solution are fed into the first
reactor. The organic layer formed in the first reactor is pumped into the second reactor, where it is
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subjected to further nitration with acid from the third reactor fortified with additional HNO3. The
product from the second nitration step, a mixture of all possible isomers of di-nitro toluene (DNT), is
pumped to the third reactor. In the final reaction, the DNT is treated with a fresh feed of nitric acid and
oleum (a solution of sulfur trioxide [SO3] in anhydrous sulfuric acid). The crude TNT from this third
nitration consists primarily of 2,4,6-trinitrotoluene. The crude TNT is washed to remove free acid, and
the wash water (yellow water) is recycled to the early nitration stages. The washed TNT is then
neutralized with soda ash and treated with a 16 percent aqueous sodium sulfite solution to remove
contaminating isomers. The waste solution (red water) from the purification process is discharged
directly as a liquid waste stream, is collected and sold, or is concentrated to a slurry and incinerated.
Finally, the TNT crystals are melted and passed through hot air dryers, where most of the water is
evaporated. The dehydrated product is solidified, and the TNT flakes packaged for transfer to a storage
or loading area.[ CITATION RNS67 \l 1033 ]
3.2. Nitrocellulose
3.2.1. Structure

H2 C N O

H
H
H
O O O
O N H
O
O

H O
N
O

Figure 3-6 Structure of Nitrocellulose

3.2.2. Utility
Nitrocellulose compositions used in explosive application such as ammunition vary from 10 to 13.5
percent of nitrogen.[ CITATION Muh05 \l 1033 ] It is also used in giving shinny appeal to cosmetic
products such as nail polish and in paints. It is usually stored after being wet by isopropanol.
3.2.3. Reaction

C6 H7 O2 (OH)3  + 3HNO3  + H2 SO4  C6 H7 O2 (ONO2 )n  + 3H2 O + H2 SO4

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3.2.4. Block Flow Diagram

Figure 3-7 Process Line of Nitrocellulose

3.2.5. Explanation of Process

Cotton linters, or wood pulp high in α-cellulose, are purified by boiling in Kiers (vats) with dilute
caustic soda solution and Bleaching is effected with NaOCl, or Ca(OCl)2. After that, the cotton is
dried, fluffed, weighed and Mixed acid is made up from fortifying acid and spent acid, brought to
proper temperature and run into the nitrator. Nitration (esterification) is usually conducted under
carefully controlled conditions in a “mechanical dipper” ‘nitrator. One nitrator charge is formed by
14.5 kg of purified cellulose. The cellulose 's agitated with approximately 682 kg of mixed acid at 30O
C for about 25 min. The entire nitrator charge is dropped into a centrifuge, where the spent acid is
centrifuged from the nitrated cellulose. The spent acid is partly fortified for reuse and partly sold or
otherwise disposed of, e.g., by de-nitration and concentration of the H2SO4. The nitrated cellulose is
drowned with water, washed by boiling, and again washed in a beater. Nitrated cellulose is broken and
mixed with other drying agents. Grains of nitrocellulose are obtained.[ CITATION RNS67 \l 1033 ]

4. Application in Pakistani Market

4.1. Trinitrotoluene
 It is used Explosive, intermediate in dyestuffs and photographic chemicals.
 TNT has a tendency to convert into its Dinitrotoluene which is its isomer. DNT is used in
detergent coating, water proofing and plasticizer.
 Mixture of TNT and Nitroglycerin have very scattering effect which heated. Hence it is used in
preparation of dynamite. Instead of Nitroglycerin, Ammonium Nitrate can also be used.
 It is also used in grenades and rockets.
4.2. Nitrocellulose
 Fast-drying automobile lacquers, high explosives and collodion.
 It is also used as a rocket propellant, printing ink base and propellant powder.
 Coating of bookbinding cloth, leather finishing, manufacture of “Celluloid” is also done by
nitrocellulose.[ CITATION Haw16 \l 1033 ]

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 It usage is also found as a gun cotton. It is stored in Iso-propanol.
 Di-butyl phthalate which is used a dense colloidal is manufactured by nitrocellulose. [ CITATION
RNS67 \l 1033 ]

5. Reference List

[1] Hawley, " Chemical Dictionary," in Hawley`s Condensed Chemical Dictionary, New Jersey, John
Wiley & Sons, 2016, p. 1595.
[2] M. F. Ali, " Industrial Chemistry," in Handbook of Industrial Chemistry, Dhahran, McGraw-Hill,
2005, p. 677.
[3] R.N.Shreve, Chemical Process Industries, New York: Mc-Graw Hill, 1967.

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