Chapter-1

Nitrogen Industries & Agro-

chemical Industries
 Ammonia Synthesis
• Ammonia or azane is a compound of nitrogen and hydrogen with the
formula NH3. It is acolourless gas with a characteristic pungent smell.
Ammonia contributes significantly to the nutritional needs of
terrestrial organisms by serving as a precursor to food and fertilizers.
• Ammonia, either directly or indirectly, is also a building-block for the
synthesis of many fertilizers, pharmaceuticals and is used in many
commercial cleaning products. Although in wide use, ammonia is both
caustic and hazardous. In 2006, worldwide production was estimated
at 146.5 million tonnes.

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Flow Chart of the Haber Process

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• At the beginning of the 20th century there was a shortage of naturally occurring,
nitrogen-rich fertilizers, such as Chile saltpetre, which prompted the German
Chemist Fritz Haber, and others, to look for ways of combining the nitrogen in the
air with hydrogen to form ammonia, which is a convenient starting point in the
manufacture of fertilizers .
• This process was also of interest to the German chemical industry as Germany
was preparing for World War I and nitrogen compounds were needed for
explosives.
• The hydrogen for the ammonia synthesis was made by the water-gas process (a
Carl Bosch invention) which involves blowing steam through a bed of red hot
coke resulting in the separation of hydrogen from oxygen. The nitrogen was
obtained by distillation of liquid air, then by cooling and compressing air.

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 Enough steam is used to react with about 45% of the methane (CH4), the
rest of the methane is reacted with air:

Ni catalyst
CH4(g) + H2O(g) ----------> CO(g) + 3H2(g)
700oC

O2(g) + 4N2(g) Ni catalyst

2CH4(g) + 2CO(g) + 4H2(g) + 4N2(g)
(air) --------->

All the carbon monoxide (CO) in the mixture is oxidised to CO2 using
steam and an iron oxide catalyst:
iron oxide catalyst
CO(g) + H2O(g) H2(g) + CO2(g)
------------------>

The carbon dioxide (CO2) is removed using a suitable base so that only
the nitrogen gas (N2) and hydrogen gas (H2) remain and are used in the
production of ammonia (NH3).
In ammonia production the hydrogen and nitrogen are mixed together in
a ratio of 3:1 by volume and compressed to around 200 times
atmospheric pressure.
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 In 1909 Fritz Haber established the conditions under
which nitrogen, N2(g), and hydrogen, H2(g), would
combine using
• medium temperature (~500 deg C)
• very high pressure (~250 atmospheres, ~351kPa)
• A catalyst (a porous iron catalyst prepared by
reducing magnetite,Fe3O4).Osmium is a much better
catalyst for the reaction but is very expensive.
• This process produces an ammonia, NH3(g), yield of
approximately 10-20%.
• The Haber synthesis was developed into an industrial
process by Carl Bosch.

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 Ammonium Nitrate
• Ammonium nitrate is a chemical compound, the nitrate salt of
the ammonium cation. It has the chemical formula NH4NO3.
• It is a white crystal solid and is highly soluble in water. It is predominantly
used in agriculture as a high-nitrogen fertilizer.
• Its other major use is as a component of explosive mixtures used in mining,
quarrying, and civil construction.
• It is the major constituent of ANFO, a popular industrial explosive which
accounts for 80% of explosives used in North America; similar formulations
have been used in improvised explosive devices.
• Many countries are phasing out its use in consumer applications due to
concerns over its potential for misuse

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Ammonium Nitrate Production

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 Nitric acid
• Nitric acid (HNO3), also known as aqua fortis (strong water) and spirit
of niter, is a highly corrosive strong mineral acid. The pure compound
is colourless, but older samples are yellowish in colour due to the
accumulation of oxides of nitrogen.
• Commercially available nitric acid having concentration of 68%
HNO3, while the solution containing more than 86% HNO3, is referred
to as fuming nitric acid. Depending on the amount of nitrogen dioxide
present, fuming nitric acid is further characterized as white fuming
nitric acid or red fuming nitric acid, at concentrations above 95%.

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Ostwald's process or Ammonia oxidation process

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Ammonium Sulphate

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Ammonium Phosphates

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Sodium Nitrate

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 Potassium nitrate
• Potassium nitrate (KNO3) is a soluble source of two major essential plant
nutrients. It’s commonly used as a fertilizer for high-value crops that benefit
from nitrate (NO3-) nutrition and a source of potassium (K+) free of
chloride (Cl-).
Production
Potassium nitrate fertilizer (sometimes referred to as nitrate of potash or NOP
by reacting potassium chloride (KCl) with a nitrate source. Depending on the
objectives and available resources, the nitrate may come from sodium nitrate,
nitric acid or ammonium nitrate. The resulting KNO3 is identical regardless
of the manufacturing process. Potassium nitrate is commonly sold as a water-
soluble, crystalline material primarily intended for dissolving and applying
with water or in a prilled form for soil application.
Traditionally, this compound is known as saltpeter.

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Cyanide

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 Mixed Fertilizers
• Mixed fertiliser typically refers to a fertiliser containing two or more of the elements of nitrogen,
phosphorus and potassium (NPK) which are essential for promoting plant growth and high crop
yields. They are obtained by thoroughly mixing the ingredients either manually or mechanically.
NPK mixture fertilisers are formulated and recommended by agricultural scientists to enhance the
output of crops by giving it specific and exclusive blend of plant nutrients. They are slow releasing
by nature and remain in the field for a long time. They are tailor made as per the soil and are crop
specific.
Mixed fertilisers have a number of advantages, a few of them being:
• Use of mixed fertilisers results in reduction of labour costs as applying a mixture consumes lesser
time as compared to applying the components separately.
• Micro nutrients which help in increasing soil organic matter content are applied in small amounts
to the soil. They can be incorporated in fertiliser mixtures. This facilitates uniform soil application
of plant nutrients.
• If a proper mixture suits a particular soil type and crop, the use of a fertiliser mixture leads to
balanced manuring. It results in higher crop yield.
• Being in granulated form, mixtures have a better physical condition and hence their application is
easier.
• Residual acidity of fertilisers can be controlled by using neutralisers in the mixture.
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Types of Mixed Fertilisers:
A mixed fertiliser means a mixture of two or more straight fertilisers.
For example, ammonium sulphate and single super phosphate may be
thoroughly mixed to get a mixed fertiliser. Mixed fertilisers are
marketed as wheat fertiliser mixtures, paddy fertiliser mixtures etc.
Mixed fertilisers are of two kinds:
1. Open formula mixed fertiliser: In this case, the manufacturing firms
disclose the names and quantities of the straight fertilisers that are
constituents of the mixed fertilizer.
2. Close formula mixture: In this case, the manufacturing firms do not
disclose the names and quantities of the straight fertilisers that are
constituents of the mixed fertiliser.

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Disadvantages of a Mixed Fertiliser:
1. The use of mixed fertiliser does not permit application of individual
fertiliser elements, which may be required by the crop at specific times.

2. The illiterate farmer cannot effectively control the quantity of plant

food present in the mixture. He has to rely entirely on the grade
advertised by the firms.

3. The firms charge for mixing the fertilisers.

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Materials Used to Make Mixed Fertilisers:
The following materials are required to make the mixed fertiliser:
(i) Straight fertilisers are the primary materials used for making the
mixed fertiliser. They supply the fertiliser element required in the proper
amount to the soil.
(ii) Some low grade organic materials are added @ 100 pounds per ton
to the mixed fertiliser in order to prevent caking, and to maintain them
in a good physical condition. These organic materials (peat, paddy husk
etc.) are called conditioners.
(iii) Some basic material like Dolomite is added to neutralize acidity if
the fertiliser mixture produces acids.
(iv) Some materials like finely ground ash, soil etc. are added to make
up the difference between the weight of the fertiliser necessary to supply
the plant nutrients and the desired quantity of fertiliser mixture.

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 Pesticides
• Pesticides are chemical compounds that are used to kill pests,
including insects, rodents, fungi and unwanted plants (weeds).
Pesticides are used in public health to kill vectors of disease, such as
mosquitoes, and in agriculture, to kill pests that damage crops. By
their nature, pesticides are potentially toxic to other organisms,
including humans, and need to be used safely and disposed of
properly.

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There are many different types of pesticides, each is meant to be effective against specific pests. The term "-
cide" comes from the Latin word "to kill."

1. Algaecides are used for killing and/or slowing the growth of algae.

2. Antimicrobials control germs and microbes such as bacteria and viruses.

3. Biopesticides are made of living things, come from living things, or they are found in nature.

4. Desiccants are used to dry up living plant tissues.

5. Defoliants cause plants to drop their leaves.

6. Disinfectants control germs and microbes such as bacteria and viruses.

7. Fungicides are used to control fungal problems like molds, mildew, and rust.

8. Herbicides kill or inhibit the growth of unwanted plants, aka weeds

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9. Illegal and Counterfeit Pesticides are imported or sold illegally.

10. Insecticides are used to control insects.

11. Insect Growth Regulators disrupt the growth and reproduction of insects.

12. Minimum Risk Pesticides are exempt from EPA registration, but many states require them to be registered.

13. Miticides control mites that feed on plants and animals. Mites are not insects, exactly.

14. Molluscicides are designed to control slugs, snails and other molluscs.

15. Mothballs are insecticides used to kill fabric pests by fumigation in sealed containers.

16. Natural and Biological Pesticides control pests using things found in nature, or man-made versions of
things found in nature.

17. Ovicides are used to control eggs of insects and mites.

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18. Pheromones are biologically active chemicals used to attract insects or
disrupt their mating behavior. The ratio of chemicals in the mixture is
often species-specific.

19. Plant Growth Regulators are used to alter the growth of plants. For
example, they may induce or delay flowering
20. Repellents are designed to repel unwanted pests, often by taste or smell.

21. Rodenticides are used to kills rodents like mice, rats, and gophers.

22. Synergists make certain pesticides more effective, but they are not
effective when used alone.

23. Wood Preservatives are used to make wood resistant to insects, fungus
and other pests.

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