CHAPTER II

REVIEW OF RELATED LITERATURES

This chapter contains the cited theories, principles, concepts and facts

regarding the relevant features examined and used by the group about the feasibility of

producing ammonium nitrate.

2.0. OVERVIEW

Ammonium nitrate is not only a principal component of airborne aerosol, but it is

chiefly an important and widely used product in the chemical industry. The commercially

important applications are twofold: as a fertilizer component and as an explosive

ingredient.

Among inorganic fertilizers, AN is the most universally used because of its unique

combination of nitrogen bound as both nitrate and ammonium ions that are the only two

forms in which plants can efficiently absorb nitrogen from the soil. According to scientific

literature (Oxley et al., 2002) pure ammonium nitrate is considered as a relatively stable

chemical, since it can be preserved unaltered at ordinary temperature and pressure.

Indeed even if it melts at quite low temperature (170 C), significant thermally induced

decomposition requires temperature of more than 200 C. When fertilizer grade AN is

manufactured, it is classified as an oxidizing agent Class 5.1 for transportation purposes,

but in extraordinary situations it may detonate as an explosive. Although pure ammonium

nitrate is generally used safely, several noteworthy accidents involving AN have occurred

over the years, causing a significant number of deaths and injuries (Marlair and Kordek,

2005).
 With ammonium nitrate, three major hazardous phenomena need to be

considered: fire, decomposition and explosion. Whereas by itself AN is not combustible,

it can thermally decompose and give off gaseous products of ammonia and nitric acid

and other gases including vapors of toxic nitrogen dioxide (NO2) when exposed to

external heat. Additional factors like confinement or contamination may trigger an

explosion hazard. Indeed, the major accidents that have occurred over the years

involved mixtures of ammonium nitrate with other substances. It has been evidenced

that while combined with contaminants, the explosive sensitivity of AN may sharply

increase because ammonium nitrates stability decreases (Sun et al., 2005). As an

oxidizing agent AN can intensify the development of a fire involving combustible

materials (like wood or plastics).

With all these claims, many countries considered the termination of AN production

and participation to worlds market. Farmer switched especially to urea, the same organic

compound found in urine. It is produced synthetically for use as fertilizer and comes in

pellets, or prills, much like ammonium nitrate. Urea packs more nitrogen than

ammonium nitrate, but it has a drawback: the nitrogen tends to escape into the air, or

volatilize, before working its way to plants roots. They can easily cause the problem of

eutrophication when they're washed by rainwater into rivers, lakes, ground waters, and

other bodies of water. That loss increases in warm weather and in areas where fertilizer

is spread on top of the soil rather than plowed in. For this reason, some farmers still prefer

ammonium nitrate.

Ammonium nitrate provides much needed nitrogen to lawn grasses and garden

plants in an easily accessible form that doesn't leach out of the soil. A straight nitrogen
fertilizer typically contains 34-percent ammonium nitrate, but the amount may vary in

fertilizer blends containing other plant nutrients or with combined forms of nitrogen.

Fertilizer can explode. Ammonium nitrate is the chemical that makes these

dramatic displays possible. But creating an explosion isn't as simple as just having a pile

of ammonium nitrate let alone a pile of fertilizer sitting around. But, according to

chemist Jimmie Oxley, ammonium nitrate is a lot less dangerous than people might

guess. Despite a history of high-profile explosions, ammonium nitrate isn't considered to

be that big of a danger. In fact, Oxley called it a "marginal explosive" a chemical that

is mostly safe, but can become dangerous when the conditions are vary unpleasantly.

Furthermore, since the 1950s, ammonium nitrate-based explosives have basically

supplanted the older dynamite explosives used in mining and other industries, precisely

because they are so much safer and harder to detonate. Ammonium nitrate isn't even

classed as an explosive proven that it is very difficult to get it detonate at a reasonable

scale.

Despite the accidents and losses incurred due to mishandling of ammonium

nitrate, many believe the total eradication of this product is impossible. With its special

contribution to better crop yield, its demand globally is of figures the world market could

never resist. Ammonium nitrate as fertilizer is especially important because every amino

acid in plants requires nitrogen which is essential component for plants to manufacture

new cells. Fertilizing plants causes them to grow more rapidly and efficiently, just like

ensuring a manufacturing plant has all the raw materials it needs for a production line.
2.1. RAW MATERIALS

2.1.1 AMMONIA

Ammonia or azane is a compound of nitrogen and hydrogen with the formula NH3.

The simplest pnictogen hydride, ammonia is a colourless gas with a characteristic

pungent smell. It 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 pharmaceutical products and is used in

many commercial cleaning products.

Although common in nature and in wide use, ammonia is

both caustic and hazardous in its concentrated form. It is classified as an extremely

hazardous substance in the United States as defined in Section 302 of the

U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and is

subject to strict reporting requirements by facilities which produce, store, or use it in

significant quantities.

The global industrial production of ammonia in 2014 was 176 million tonnes

(173,000,000 long tons; 194,000,000 short tons), a 16% increase over the 2006 global

industrial production of 152 million tonnes (150,000,000 long tons; 168,000,000 short

tons). Industrial ammonia is sold either as ammonia liquor (usually 28% ammonia in

water) or as pressurized or refrigerated anhydrous liquid ammonia transported in tank

cars or cylinders.

NH3 boils at 33.34 C (28.012 F) at a pressure of one atmosphere, so the liquid

must be stored under pressure or at low temperature. Household ammonia or ammonium

hydroxide is a solution of NH3 in water. The concentration of such solutions is measured

in units of the Baum scale (density), with 26 degrees baum (about 30% (by weight)

ammonia at 15.5 C or 59.9 F) being the typical high-concentration commercial product.

Ammonia is a colourless gas with a characteristic pungent smell. It is lighter than

air, its density being 0.589 times that of air. It is easily liquefied due to the strong hydrogen

bonding between molecules; the liquid boils at 33.3 C (27.94 F), and freezes at

77.7 C (107.86 F) to white crystals. Ammonia may be conveniently deodorized by

reacting it with either sodium bicarbonate or acetic acid. Both of these reactions form an

odourless ammonium salt.

Ammonia is miscible with water. In an aqueous solution, it can be expelled by

boiling. The aqueous solution of ammonia is basic. The maximum concentration of

ammonia in water (a saturated solution) has a density of 0.880 g/cm3 and is often known

as '.880 ammonia'. Ammonia does not burn readily or sustain combustion, except under

narrow fuel-to-air mixtures of 1525% air.

When mixed with oxygen, it burns with a pale yellowish-green flame. At high

temperature and in the presence of a suitable catalyst, ammonia is decomposed into its

constituent elements. Ignition occurs when chlorine is passed into ammonia, forming

nitrogen and hydrogen chloride; if chlorine is present in excess, then the highly

explosive nitrogen trichloride (NCl3) is also formed.

2.1.2 NITRIC ACID

Nitric acid (HNO3), also known as aqua fortis and spirit of niter, is a

highly corrosive mineral acid. The pure compound is colorless, but older samples tend to

acquire a yellow cast due to decomposition into oxides of nitrogen and water. Most
commercially available nitric acid has a concentration of 68% in water. When the solution

contains more than 86% HNO3, it 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%.

Nitric acid is the primary reagent used for nitration the addition of a nitro group,

typically to an organic molecule. While some resulting nitro compounds are shock- and

thermally-sensitive explosives, a few are stable enough to be used in munitions and

demolition, while others are still more stable and used as pigments in inks and dyes. Nitric

acid is also commonly used as a strong oxidizing agent.

Commercially available nitric acid is an azeotrope with water at a concentration of 68%

HNO3, which is the ordinary concentrated nitric acid of commerce. This solution has a

boiling temperature of 120.5 C at 1 atm. Two solid hydrates are known; the monohydrate

(HNO3H2O) and the trihydrate (HNO33H2O).

Nitric acid of commercial interest usually consists of the maximum boiling

azeotrope of nitric acid and water, which is approximately 68% HNO3, (approx. 15 molar).

This is considered concentrated or technical grade, while reagent grades are specified at

70% HNO3. The density of concentrated nitric acid is 1.42 g/cm3. An older density scale

is occasionally seen, with concentrated nitric acid specified as 42 Baum.

2.1.3 ALUMINUM SULFATE

Aluminum sulfate is a chemical compound with the formula Al2(SO4)3. It is soluble

in water and is mainly used as a flocculating agent (causing contaminating particles to

clump into larger, more easily trapped particles) in the purification of drinking water and

waste water treatment plants, and also in paper manufacturing.

 Aluminum sulfate is sometimes referred to as a type of alum. It is used in water

purification and as a mordant in dyeing and printing textiles. In water purification, it causes

impurities to coagulate into larger particles and then settle to the bottom of the container

(or be filtered out) more easily. This process is called coagulation or flocculation.

Research suggests that in Australia, aluminum sulfate used this way in drinking water

treatment is the primary source of hydrogen sulfide gas in sanitary sewer systems. An

improper and excess application incident in 1988 polluted the water supply

of Camelford in Cornwall. When dissolved in a large amount of neutral or slightly alkaline

water, aluminum sulfate produces a gelatinous precipitate of aluminum hydroxide,

Al(OH)3. In dyeing and printing cloth, the gelatinous precipitate helps the dye adhere to

the clothing fibers by rendering the pigment insoluble.

Aluminum sulfate is sometimes used to reduce the pH of garden soil, as

it hydrolyzes to form the aluminum hydroxide precipitate and a dilute sulfuric acid solution.

The gardener can add aluminum sulfate to the soil to reduce the pH which in turn will

result in the flowers of the Hydrangea turning a different color (blue).

2.2. PRODUCT

2.2.1 AMMONIUM NITRATE

2.2.1A. Formula and structure: The chemical formula of ammonium nitrate is NH4NO3.

Its molecular formula is written as N2H4O3 and its molar mass is 80.052 g/mol. Ammonium

nitrate is a salt, which consists of two ions: a cation, the ammonium ion (NH 4+) and an

anion, the nitrate ion (NO3-). The cation and anion are held together by a strong ionic

bond. The structure of ammonium nitrate, composed of the two ions, is shown below:
Ammonium cation Nitrate anion

2.2.1B. Occurrence: Ammonium nitrate occurs naturally as a mineral in certain desert

regions of the world. However, it is not abundant and is found as a mixture with many

other minerals. It is easier to prepare synthetic ammonium nitrate, as described below.

2.2.1C. Preparation: Ammonium nitrate is commonly prepared by the reaction of

ammonia with nitric acid. This is a typical acid-base reaction to give a salt (NH4NO3) as

the product.

NH3 + HNO3 NH4NO3

2.2.1D. Physical properties: Its physical state is solid and it typically exists as a white,

crystalline or bead-like powder. It has a melting point of 169.6 C, boiling point of 210 C,

and a density of 1.72 g/cm3.

2.2.1D. Chemical properties: Ammonium nitrate is readily water soluble. It is also highly

hygroscopic, meaning that it readily absorbs water from the atmosphere and clumps up.

It is not particularly reactive and is fairly stable. It decomposes at high temperatures (over

200 C) to form nitrous oxide and water vapor.

2.2.1E. Uses: Ammonium nitrate is most commonly used in fertilizers (as an excellent

and inexpensive nitrogen source) and in instant cold packs. It is also used to manufacture

explosives as it acts as a strong oxidizing agent. In particular, ammonium nitrate is used

to prepare an industrial explosive called ANFO (ammonium nitrate fuel oil), which is

composed of 94% ammonium nitrate and 6% fuel oil.

2.2.1F. Health hazards/ health effects: While not severely toxic, ammonium nitrate can

cause health issues if ingested or inhaled in high concentrations. Ingesting large amounts

of ammonium nitrate can cause headache, dizziness, abdominal pain, vomiting,

weakness, irregular heart beat and convulsions, while inhalation of this powder may

cause breathing problems, coughing, sore throat, and even suffocation at high

concentrations.

2.3. PRODUCTION PROCESS

Industrial production is chemically quite simple, although technologically

challenging. The acid-base reaction of ammonia with nitric acid gives a solution of

ammonium nitrate: HNO3(aq) + NH3(g) NH4NO3(aq).

For industrial production, this is done using anhydrous ammonia gas and

concentrated nitric acid. This reaction is violent and very exothermic. It should never be

attempted by amateurs or in improvised equipment using such concentrated materials,

though with plenty of dilution by water, it could be considered easy. After the solution is

formed, typically at about 83 percent concentration, the excess water is evaporated to an

ammonium nitrate (AN) content of 95 to 99.9 percent concentration (AN melt), depending

on grade. The AN melt is then made into "prills" or small beads in a spray tower, or into

granules by spraying and tumbling in a rotating drum. The prills or granules may be further

dried, cooled, and then coated to prevent caking. These prills or granules are the typical

AN products in commerce. The processes involved are simple in principle, but certainly

not easy. The Haber process combines nitrogen and hydrogen to produce ammonia, part
of which can be oxidized to nitric acid and combined with the remaining ammonia to

produce the nitrate. Another production method is used in the so-called Odda process.

2.4. PROJECT HISTORY

Ammonium Nitrate was first prepared in the sixteenth century. Its early industrial

development was primarily for use in explosives, but beginning and above 1940 its used

as a fertilizer developed rapidly. Ammonium Nitrate is the most important ammonium

compound but during the 1980s its production decline at an average of 2.8 % per year in

the United States, European countries, and Asian regions particularly in the Agro-

industrial places to 7,611,000 short tons in 1990. This decline has been due to a decline

in the consumption of ammonium nitrate as fertilizers over recent years. During this period

production fell to a low of 6.5 million short tons in 1986 but recovered with the help of

declining imports and rice exports. Large amount of ammonium nitrate still are consumed

for explosives but the increase of demand for fertilizer has been generated through the

years.

The main process involve in the manufacture of ammonium nitrate fertilizer has

been developed. This process is known as the "Prilling Process. Prilling appears to be a

somewhat vague but commonly used technical word, at least in the industry of fertilizer

production. If we want to use it within the area of particle formation in general and

specifically as a term describing a certain type of microencapsulated, particulate material,

we obviously need a definition. We will accept "small round" only, as we associate with

droplet formation and want to avoid anything but spheres, - and "small" will have to
become something even bigger than "normal powder" particles within the drying

business.

2.5. HISTORY OF PRILLING

Starting with the first commercial application described in a German patent in 1918,

the first uses of ammonium nitrate were actually not for the fertilizers version but rather

product forms useful in formulation of explosives.

For this purpose 2-fluid- and pressure-nozzles were applied as atomizers, taking

the Particle Size Distribution (PSD hereafter) to as coarse as "95% between 400 and

2000 microns" equal to an average particle size (d50 hereafter) of 1200 microns or 1.2

mm.

The term "prills" really does not originate until 1946 with the first true fertilizer-

types, where particles in the range of 1-4 mm are needed for direct dosing onto the fields.

The prilling of the molten nitrate is done with slowly rotating discs or "buckets" (with holes),

- or by means of relatively simple "showerheads" at the top of tall "prilling towers", 30-70

meters high. The cooling, which leads to solidification, is accomplished by a counter-

current air stream.

Special metal powders, sodium hydroxide, stearic acid, fats, and certain wax

powders are also for various applications produced this way. The wax has even been

seen to carry a 50/50 payload of proteolytic enzymes for detergent use (2), - and thus we

are already at micro-encapsulation by "prilling"! The PSD, however, is as "fine" as only

the 200-500 micron (0.2-0.5 mm) range.

As already strongly indicated, prilling is also closely associated with cooling,

chilling and congealing. "Big, prilled drops are most conveniently solidified by pure
solidification of melts. Drying of big particles is a much slower and much more complicated

process, and even small prills would require long processing times and more

sophisticated equipment - or would have to be made using agglomeration techniques.

"Congealing" is therefore the normally selected process for the making of prills.
 REFERENCES

"Storing and Handling Ammonium Nitrate", UK Health and Safety Executive

publication INDG230, 1986.

Brown, Theodore E., H. Eugene LeMay, and Bruce E. Bursten. Chemistry: The
Central Science. 10th ed. Upper Saddle River, NJ: Prentice Hall, 2005. ISBN
0131096869

Chang, Raymond. Chemistry. 9th ed. New York: McGraw-Hill

Science/Engineering/Math, 2006. ISBN 0073221031

Housecroft, Catherine E., and Alan G. Sharpe. Inorganic Chemistry. 4th ed. Harlow,
UK: Prentice Hall, 2001. ISBN 0582310806

McMurry, John, and Robert C. Fay. Chemistry. 4th ed. Upper Saddle River, NJ:
Prentice Hall, 2004. ISBN 0131402080

Moore, John W., Conrad L. Stanitski, and Peter C. Jurs. Chemistry: The Molecular
Science. New York: Harcourt College, 2002. ISBN 0030320119

Smith, Roland. Conquering chemistry. Sydney: McGraw-Hill, 1994. ISBN

0074701460

UNIDO and International Fertilizer Development Center. Fertilizer Manual. Kluwer

Academic Publishers, 1998. ISBN 0-7923-5032-4

The Characterization of Ammonium Nitrate Mini-Prills

http://axpro.mines.edu/documents/AN%20Mini%20Prills.pdf

Nitric Acid Uses, Properties, Structure and Formula

http://www.softschools.com/formulas/chemistry/nitric_acid_uses_properties_structure_f
ormula/229/

Properties of Ammonia
https://www.osha.gov/SLTC/etools/ammonia_refrigeration/ammonia/