UNIVERSITY OF ENGINEERING

AND TECHNOLOGY, LAHORE

SUBMITTED BY: MUHAMMAD ANS

REGESTRATION ID: 2020-CH-12
SUBMITTED TO: Dr. ABDUL GHAFFAR
 TABLE OF CONTENTS

1. Introduction of Nitration 3
1.1. Examples 3
1.1.1. Nitrobenzene 3
1.1.2. 2,4,6 – Trinitrotoluene 3
1.1.3. 3 – Nitrobenzoic acid 3
2. Scope of Nitration in Chemical Industry 4
3. Production at industrial scale 4
3.1. Nitrocellulose 4
3.1.1. Scope of Nitrocellulose 4
3.1.2. Reactants 5
3.1.3. Reaction 5
3.1.4. Explanation of preparation 5
3.1.5. Block flow diagram 6
3.2. Nitroglycerine 6
3.2.1. Scope of Nitroglycerine 7
3.2.2. Reactants 7
3.2.3. Reaction 7
3.2.4. Explanation of preparation 7
3.2.5. Block flow diagram 8
4. Applications in Pakistani market 9
4.1. Nitrocellulose 9
4.2. Nitroglycerine 9
5. References 9

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 LIST OF FIFURES

1. Formation of Nitrobenzene 3
2. Formation of 2,4,6 – Trinitrotoluene 3
3. Formation of 3 – Nitrobenzoic acid 3
4. Formation of Nitrocellulose 5
5. Block flow diagram for Nitrocellulose 6
6. Formation of Nitroglycerine 7
7. Block flow diagram for Nitroglycerine 8

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1. INTRODUCTION OF NITRATION
The introduction of NO2 group by the replacement of one or more H atoms in an organic compound
is termed as Nitration (3).

1.1 EXAMPLE

1.1.1 Nitrobenzene

Nitrobenzene

Figure 1 formation of Nitrobenzene

1.1.2 2,4,6 - Trinitrotoluene

NO2
3HNO3

2,4,6 - Trinitrotoluene

Figure 2 formation of 2,4,6 - Trinitrotoluene

1.1.3 3 – Nitrobenzoic acid

3 – Nitrobenzoic acid
Figure 3 formation of 3 - Nitrobenzoic acid

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2. SCOPE OF NITRATION IN CHEMICAL INDUSTRY
In general, there are many industrial applications of nitration; among which, the most important is
• The production of nitroaromatic compounds such as nitrobenzene, 2- Bromonitrobenzene,
nitrocellulose, ortho & para nitrotoluene and different type of fertilizers which have high
solubility and bio-degradability(1).
• Such processes are mainly used for the production of explosives like TNT (2,4,6-
trinitrotoluene) and different types of propellants (2).
• In case of fertilizers, this process is mainly useful in the manufacturing of Ammonium Nitrate
(NH4NO3) and Potassium Nitrate (KNO3) fertilizers which contains about 33 – 33.5 % and 13
– 14 % of nitrogen respectively.
• Nitrates are also used for medication purposes like they help to increase the diameter of blood
vessels and allow more blood to get to the heart due to which the chances of heart attack
decrease along with the enhancement of Metabolic reactions (3).
• In auto-mobile paint industry, to produce high nitrogen, high quality and viscosity paint is
produced.

3. PRODUCTION AT INDUSTRIAL SCALE

Two organic examples of nitration such Nitrocellulose and Nitroglycerine are to be discussed here:

3.1. NITROCELLULOSE
Nitrocellulose is a highly flammable compound having appearance like yellowish white in the
form of cotton filaments. It is formed by the reaction of cellulose with a mixture of nitric acid and
sulfuric acid(1). It is also known as cellulose nitrate, flash cotton, guncotton and pyroxylin with
molecular formula C6H9(NO2)O5)n (mononitrocellulose), (C6H8(NO2)2O5)n (dinitrocellulose) and
(C6H7(NO2)3O5)n (trinitrocellulose). It was known as "mother-in-law silk” which plays a vital role
in the export of a country (2).
3.1.1 SCOPE OF NITROCELLULOSE
• The membranes of nitrocellulose are sticky, used for the immobilization of nucleic acids and
proteins (3).
• Nitrocellulose is widely used in diagnostic tests where antigen-antibody binding occurs like
CRP tests and U-albumin tests etc.
• Collodion is a solution, formed by the solubility of nitrated cellulose in ether and alcohol, used
for wounds, warts and topical skin problems(2).
• It is used in the coating of playing cards and to hold staple pins together used in office staplers
and Nail polish which is inexpensive, dries quickly and not damaging the skin(1).
• The mesh of nitrocellulose is used to capture the cells in liquid or gaseous solutions.
• It is used as propellants in rockets, leather finishing and printing inks (3).
• A mixture of nitrocellulose and camphor is used to manufacture billiard balls and Table tennis
balls.

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3.1.2 REACTANTS FOR THE PRODUCTION OF NITROCELLULOSE

1. Ordinary cotton (cellulose)

2. Mixture of concentrated nitric and sulfuric acids (mixed acid, which is a mixture of Sulfuric
acid (61%) and Nitric acid (36)

3.1.3 REACTION
The reaction is carried out between cellulose and HNO3 (1:3) in the presence of conc.H2SO4 to
produce nitrocellulose with the elimination of water molecule (1).

Figure 4 Formation of Nitrocellulose

3.1.4 EXPLAINAITION OF PREPARATION

Nitrocellulose is produced by causing the cellulose to react with a mixture of nitric acid and
sulfuric acid. The acids from the storage tank are sent to the reactor where the Nitration of the
cellulose took place. The product obtained from the reactor vessel is nitrocellulose which is
separated from the acid and separated acid is sent to the recovery tower and then again to the
storage tank (1). The product from the tower is then sent to the pre-stabilization chamber where the
nitrocellulose is distilled and then pressurized boiling of the product is done to remove any
entrapped gases present in the structure. Then it is sent to the post-stabilization chamber where the
nitrocellulose temperature and pressure become low down to normal and a specific amount of
alcohol is added depending upon the company and industry which is producing it to give special
perfection to the product then it is sent to the packaging and bagging section where it is coated and
then packed and sent to the market (2).

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3.1.5 BLOCK FLOW DIAGRAM

Figure 5 Block flow diagram for Nitrocellulose

3.2. NITROGLYCIRINE
Nitroglycerin is a colorless, dense, oily and explosive liquid having pale yellow color (2). It is most
commonly produced by treating glycerol with nitric acid under appropriate conditions i.e. in the
presence of H2SO4. Chemically, the Nitroglycerin compound is an organic nitrate compound rather
than a nitro compound(1). It is also known as nitroglycerine, trinitroglycerin (TNG) and glyceryl
trinitrate (GTN). In IUPAC, it is named as 1,2,3-trinitroxypropane with molecular formula
C3H5N3O9

3.2.1. SCOPE OF NITROGLYCIRINE

• The major use of nitroglycerin is in the industry of explosives such as dynamite and propellants
because when it is subjected to heat, shock, or flame, it explodes (2).

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• It is a useful ingredient of various types of smokeless powder because when it burns, it
produces no visible smoke practically.
• It is an important constituent of soap industry to manufacture Liquid hand soaps and cosmetics
industry to manufacture Colored lip products (1).
• It plays a vital role in the production of insect and pests repellent i.e., in insecticides and
pesticides.
• Nitroglycerin is used in those medications which ensure the enhancement of flow rate of blood
and oxygen to the heart and ultimately corrects the imbalance between the flow of oxygen and
blood to the heart and the heart’s energy demand due to which the chances of cardiovascular
diseases decrease (3).
• Nitroglycerine ointment is used to treat the chest pain (3).

3.2.2 REACTANTS FOR THE PRODUCTION OF NITROGLYCEROL

1. Glycerol or glycerin
2. Mixture of concentrated nitric and sulfuric acids

3.2.3 REACTION
The reaction is carried out between glycerol and HNO3 in the presence of conc. H2SO4 to form
nitroglycerine with the elimination of water molecule (2).

H2SO4
+ 3HNO3 + 3H2O

Glycerol Nitroglycerine

Figure 6 Formation of Nitroglycerine

3.2.4 EXPLAINAITION OF PREPARATION

The industrial manufacturing of nitroglycerine involves not only continuous Nitration but also
continuous separation and washing of nitroglycerine. There is an acid-resistant Steel nitrator in
which the main reaction i.e., nitration of glycerin is carried out at about 25 - 30 0C. Nitrator is
mechanically stirred along with the slow introduction of glycerin and mixed acids. The nitration
of glycerin is exothermic in nature that is why the cooling system is installed by using refrigerating
coils, having cooling surface area 4 times larger than in the usual nitrates. The propellers of the
mechanical stirrer revolve at a speed of 200 to 300 RPM and above these propellers, steel plates
are installed and fixed in order to promote the better circulation of the liquid in the nitrator tank.
If there is any decomposition of the nitroglycerine occurs, then the contents are discharged into a

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drowning tank the separator is an inclined cylinder that is made of an acid-resistant sheet of steel.
the mixture from the nitrator enters from the top of the separator baffles and cooling coils are
installed in order to facilitate the separation of nitroglycerine. the spent or separated acids are
recovered and collected in the lower region while the nitroglycerine is collected in the upper region
of the separator. The washing of nitroglycerine is carried out in the towers that work in a
continuous way (2). These towers contain perforated plate shelves. the nitroglycerine leaves the
separator and enters the injector which is fed with water or a solution of sodium carbonate or of
ammonia and emulsion is then formed and enters the tower from below. Compressed air is injected
into the tower to facilitate mixing, the contents flow into the separator where the emulsion forms
separate layers water flows out from the top, and nitroglycerine from the bottom. For the washing
of nitroglycerine two types of towers are commonly used one where it is washed with water and
the other where it is washed with a sodium carbonate solution or with the dilute aqueous ammonia
(3)
. After the washing process, the product is dried and sent to the packaging and bagging section
where it is coated and then packed and sent to the market.

3.2.5. BLOCK FLOW DIAGRAM

Figure 7 Block flow diagram Nitroglycerine

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4 APPLICATIONS IN PAKISTANI MARKET

4.1. Nitrocellulose

• In paper and ink industry, to manufacture printing inks and paper lacquers with high odorless
solvent content which have high demand in packaging and flexographic printing industry (1).
• In wood finishing industry, nitrocellulose-based lacquers are extensively used which dry
rapidly having high quality finishing properties (2).
• In leather and fabrics industry, it is used to manufacture highly flexible, strong and matt
finishing leather and fabrics goods in order to enhance their appearance and tensile strength (3).
• In cosmetics industry, it is used in the formation of nail varnishes having high standards of
quality and purity along with rapid drying process (1).
• In the manufacturing of a dense colloidal known as Di-butyl.

4.2. Nitroglycerine

• In mining industry, nitroglycerin is used as explosives in form of dynamite and in propellants

to extract the minerals from mines and in the drilling of highways and railroad tunnels.
• In oil and gas industry, it is used to recover oil and gas from shale formations(2).
• In sports industry, it is used in the production of sporting powders to manufacture soccer ball,
cricket bat, tennis ball and athletic apparel (1).
• In pharmaceutical industry, it is used in the manufacturing of drugs known as nitrates, which
like isosorbide dinitrate and isosorbide mononitrate and many ophthalmological ointments(3).

5 REFERENCES

1. R.N.Shreve, Chemical Process Industries, New York: Mc-Graw Hill, 1967

2. Urbanski, Tadeusz, “Chemistry and Technology of Explosives”, Oxford Pergamon Press 1965
3. Eberlin Esteves, "Electrophilic Aromatic Nitration: Understanding Its Mechanism and
Substituent Effects", volume 3, 2006