KWAME NKRUMAH UNIVERSITY OF SCIENCE AND

TECHNOLOGY

COLLEGE OF ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

BSc. PETROCHEMICAL ENGINEERING

A REPORT ON:

PRODUCTION OF FERTILISERS

BY:

BOAKYE GLOGINA

INDEX NUMBER: 9404417

NOVEMBER 2020
 TABLE OF CONTENTS

1.0 INTRODUCTION ............................................................................................................... 1

2.0 LITERATURE REVIEW .................................................................................................... 2

1. ACCORDING TO EFFICIENCY ......................................................................................... 3

i. Straight Fertilisers ........................................................................................................... 3

ii. Auxiliary Substances ...................................................................................................... 4

2. ACCORDING TO PHASE .................................................................................................... 4

i. Solid Fertilisers................................................................................................................ 4

ii. Liquid Fertilisers ............................................................................................................ 5

3. ACCORDING TO ORIGIN .................................................................................................. 5

i. Organic Fertilisers ........................................................................................................... 5

ii. Mineral Fertilisers .......................................................................................................... 7

3.0 FERTILISER MANFACTURING PROCESS .................................................................. 12

3.1 SOURCES OF RAW MATERIALS .......................................................................... 12

3.2 MAJOR EQUIPMENT USED IN MANUFACTURING FERTILISER ........... 12

4.0 ENVIROMENTAL IMPACT OF FERTILISER .............................................................. 36

1. Biology of water bodies ....................................................................................................... 36

2. Depletes the quality of the soil............................................................................................. 36

3. Human health ....................................................................................................................... 36

4. Nitrates ................................................................................................................................. 37

5. Oxygen depletion ................................................................................................................. 37

5.0 CONCLUSION .................................................................................................................. 38

REFERENCES ........................................................................................................................ 39

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 TABLE OF FIGURES

Figure 1 : A rotary drum granulator ......................................................................................... 13

Figure 2 : A chain crusher ........................................................................................................ 13

Figure 3 : A vertical mixer ....................................................................................................... 14

Figure 4 : A belt conveyor ....................................................................................................... 14

Figure 5 : A drum screener machine ........................................................................................ 15

Figure 6 : A granules fertiliser making machine ..................................................................... 15

Figure 7 : A drum fertiliser dryer ............................................................................................. 16

Figure 8 : A Drum Fertiliser Cooler ........................................................................................ 16

Figure 9 : Fertiliser production routes for nitrogen and phosphorus based fertilisers ............. 17

Figure 10 : Ammonium nitrate fertiliser .................................................................................. 22

Figure 11 : Urea fertiliser ......................................................................................................... 24

Figure 12 : Ammonium sulphate fertiliser ............................................................................... 26

Figure 13 : Process flow diagram for producing nitrogen based fertilisers ............................. 27

Figure 14 : Phosphorus based fertiliser .................................................................................... 29

Figure 15 : Process flow diagram for the manufacture of some phosphorus based diagram . 31

Figure 16 : Potassium based fertilisers .................................................................................... 32

Figure 17 : Process flow diagram for KCl fertiliser production .............................................. 33

Figure 18 : Key global fertiliser products ................................................................................ 34

Figure 19 : Nutrient application by crop ................................................................................. 35

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 CHAPTER ONE

1.0 INTRODUCTION

Fertilisers, whether organic or inorganic, have greatly contributed and supported people all

over the world. It has allowed for the mass production of food/agricultural produce on a very

large scale to support the survival of the increasing global population. (Trade Finance Global,

2020)

Since the discovery of fertiliser over 100 years ago, it has provided man with a way of

increasing crop yield without necessarily increasing land mass as it boosts the nitrogen content

in the soil. This discovery, along with others, and the subsequent increase in yields that they

brought defined what is now known as the ‘Green Revolution’ – a shift in industrial agriculture

that made continued population growth possible. Presently, about 50% of global food yields

can be credited to fertiliser. (Trade Finance Global, 2020)

Fertilisers provide mineral ions needed for healthy growth in plants. As plants grow, they

absorb mineral ions from the water in the soil through their root hair cells. As time progresses,

the concentration of these ions decreases, so that there is the need to apply fertilisers to the soil

to supply the nutrients that are lacking. (BBC, 2020)

It goes without saying that the economics of fertilisers have a huge effect on wider food markets

and understanding its place within the wider agricultural commodities marketplace can help

traders to make better decisions about their investments and manage risk. (Trade Finance

Global, 2020)

With the increasingly use of fertilisers and its benefits however, they should be applied in the

right amounts as needed by plants. Thus, excessive use of these fertilisers on plants and the soil

can have adverse effects on both plants and soil as well as human health.

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 CHAPTER TWO

2.0 LITERATURE REVIEW

Fertilisers are organic or inorganic substances containing nutrients for nutrition of crop plants

and forest trees, to maintain or improve soil fertility and positive influence on yield or quality

of production. They contain the building blocks for foliar and fruit production, bloom

formation, and root and general plant health. In poor soils, they are very essential for plant

vigour.

Nutrients needed by plants are of two main categories: macronutrients and micronutrients.

Nitrogen (N), Phosphorus (P), Potassium (K), Calcium (Ca), Sulphur (S), Magnesium (Mg),

Oxygen (O), Hydrogen (H), and Carbon (C) are the macronutrients. Nitrogen, Phosphorus, and

Potassium are however considered the three major macronutrients. The micronutrients include

Molybdenum (Mo), Iron (Fe), Zinc (Zn), Copper (Cu), Boron (B), Chlorine (Cl), Manganese

(Mn), and Nickel (Ni). While macronutrients are needed in higher quantities by plants,

micronutrients are only needed in minute quantities. Micronutrients support the growth,

development, and overall health of plants in the fields. (BBC, 2020)

 Nitrogen is responsible for the growth of the leaf and plant and is commonly used in

the middle of the life of the plant. Its fertiliser type holds the largest share of the global

fertiliser market. It is the main constituent of proteins and determines a plant’s growth,

vigour, colour, and yield.

 Phosphorus is needed throughout the whole life cycle of the plant; it is vital for adequate

root development and aids the plant resist drought. It improves the fruiting/flowering

of the plant and helps it to absorb the nitrogen in the soil. Its fertiliser type holds the

second largest share of the global fertiliser market

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  Potassium helps plants with photosynthesis and nutrient absorption. It also helps

improve crop quality and crop resistance to lodging, disease, and drought. It holds the

third largest share the fertiliser market globally. (Trade Finance Global, 2020)

 Sulphur is important in the initial growth stages to produce essential amino acids,

proteins and oils.

 Magnesium is needed for photosynthesis, converting light into chemical energy for

nutritional purposes.

 Calcium is important for the yields, quality, and shelf life of fruit and vegetables.

(Yara, 2018)

A bag of fertiliser has a ratio of the macronutrients N, P, and K displayed on it. For instance,

the ratio 10:5:6 (20) indicates 10% N, 5% P, and 6% K. The number in the bracket tells of the

percentage of NPK in the bag of fertiliser. Hence, such a fertiliser bag has 20% of its contents

being N, P, and K; the remaining 80% consists of micronutrients and other chemicals.

Fertilisers are divided into three main aspects:

 According to efficiency

 According to phase

 According to origin

1. ACCORDING TO EFFICIENCY

i. Straight Fertilisers

They are also known as simple fertilisers. These fertilisers comprise one of the three main

nutrients: nitrogen, phosphorus, and potassium, as they usually contribute a single nutrient.

They may however comprise two nutrients. Some straight fertilisers include urea, rock

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phosphate, ammonia, ammonium sulphate and muriate of potash. They have the advantage of

low prices in the market compared to other fertilisers. (Faul, 2020)

ii. Auxiliary Substances

They contain plant nutrients in larger quantities, and hence do not supply nutrients to plants,

but allow the improving of nutrition by affecting the metabolism of plants so that the plants

can utilise larger quantities of nutrients to yield formation.

Auxiliary fertilisers may be divided into:

i. Auxiliary soil substances: these substances are without effective amount of

nutrients which would biologically, chemically or physically affect the soil,

improving the soil state or increasing the efficiency of fertilisers.

ii. Plant preparations: these are substances without effective amount of nutrients which

otherwise favourably affect the development of cultivated plants or the quality of

plant products.

(Faul, 2020)

2. ACCORDING TO PHASE

i. Solid Fertilisers

Solid fertilisers may be powdery or granular depending on the particle size. Powdery fertilisers

have prevalent particle sizes smaller than 1 mm while granular fertilisers have particle sizes

ranging from 1–4 mm. These are dry fertilisers that are made in the form of pellets, and often

blended together to get the desired ratio of nutrients needed for the fields. By this, a farmer can

control the exact amount of Nitrogen, Phosphorus, and Potassium added to the field. Granular

fertilisers can be applied via broadcasting directly onto the field, planting in a band with crops,

or applied to the crops as a side-dress where it is cultivated into the soil. (Twin State, 2020)

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 ii. Liquid Fertilisers

They are produced as clear solutions or suspensions. These fertilisers can either be applied to

the soil or to the crops (foliar application). When they are applied to the soil, it results in the

plant roots absorbing the nutrients from the soil. On the other hand, when they are applied to

the plants themselves, it is the leaves that absorb the nutrients and make them readily available

for immediate use. (Twin State, 2020)

3. ACCORDING TO ORIGIN

i. Organic Fertilisers

Organic fertilisers consist of natural materials, such as bacteria, moulds, insects, worms, and

other organisms. In order to become available to plants as nutrition, they need to be converted

by certain soil organisms. These fertilisers indirectly ensure the plant’s resistance for plagues,

viruses and diseases (Royal brinkman, 2020). Most organic fertilisers are high in one of the

three major macronutrients and low in the other two.

Some organic fertilisers include:

i. Blood meal. This is dried, powdered blood collected from cattle slaughterhouses.

It is very rich in nitrogen for which reason it is to be applied carefully in order not

to cause plant burns due to over-application. Blood meal is applied just before

planting to stimulate green leafy growth.

ii. Bone meal. A finely ground bone which is a by-product from animal

slaughterhouses. It is a great source of calcium and contains up to 15% phosphate.

It promotes strong root systems and flowering. Bone meal is often used when

growing flowers, bulbs and fruit trees.

iii. Bat guano. This is usually used as a foliar spray and may be used as a top dressing

or diluted in a tea. Bat guano is ideal for organic gardening, and most effectively

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 used at the root zone to heighten flower and root development. It is rich in soluble

nitrogen, phosphorus and trace elements, and usually powdery.

iv. Shellfish fertiliser/meal. Made from crushed bones or shells from crab or other

shellfish, it is a great source of calcium, in addition to phosphorus and many other

trace minerals. It is advantageous in that it contains chitin which encourages the

growth of organisms that inhibit harmful pest nematodes.

v. Rock phosphate. This is a calcium based phosphate rock which is usually ground

to the consistency of small crumbs. This rock powder contains over 30% phosphate

and a large number of trace elements. It does not leach out of the soil, and hence

remains unchanged until it is taken up by the roots.

vi. Greensand. This is an iron potassium silicate that gives the minerals in which it

occurs a green tint. Mined from an ancient New Jersey sea bed deposit of shells,

Greensand is rich in iron, potassium and numerous micronutrients.

vii. Fish emulsion. It is a partially decomposed blend of finely pulverised fish. It can

smell, although some deodorised versions have been developed. Like blood meal,

it should be used sparingly in order not to burn plant roots due to the high nitrogen

content.

(Vinje, 2020)

Organic fertilisers have numerous advantages including:

- Soil structure: Organic fertiliser improves the soil structure due to the organic matter

present. As a result, the soil’s ability to hold on to water and nutrients increases. This

also enables more air to get to plant roots, thereby improving soil aeration.

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 - Microbes thrive: Organic fertiliser contains carbon, nitrogen, phosphorus and

potassium that feeds microbes and enables them to make nutrients readily available for

plants in a naturally occurring biological process.

- Sustainable and Environmentally Friendly: Organic fertilisers do not run off easily

into waterways harming marine life and water quality. According to the Organic Trade

Association, organic fertiliser also increases species biodiversity by 30% compared

with inorganic fertiliser.

- Plant Damage Threat Avoided: Organic fertilisers are less likely to cause plant burns

and damage compared to the inorganic ones.(Ersek, 2017)

Some disadvantages however associated with the use of this fertiliser are:

- Not all products are created equally: For this reason, many organic fertilisers produce

inconsistent results.

- Nutrient Levels are low: The nutrient levels in organic fertilisers are low as these

nutrients are usually complexed in organic chemical structure.

- Slow release of nutrients: They may also not release enough of their principal nutrients

at a time because they depend on soil organisms to be broken down for use by plants.

Most organic fertilisers are hence effective only when the soil is moist and warm.

(Ersek, 2017)

ii. Mineral Fertilisers

These are also known as inorganic or chemical fertilisers, and they include all fertilising

substances manufactured outside the agricultural plant. Unlike the organic fertilisers, mineral

fertilisers can be taken in by plants instantly without the need for conversion by

microorganisms. Mineral fertilisers may be divided into:

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 - One-component (straight) fertilisers which contain one nutrient as a major. They may

also comprise accompanying ions, respectively microelements. These fertilisers are

divided into nitrogen fertilisers, phosphoric acid fertilisers, potassium fertilisers,

calcium fertilisers, and magnesium fertilisers.

- Multi-component (compound) fertilisers which contain at least two or more major

nutrients. They may as well include accompanying ions and microelements. According

to nutrient content, they are divided into double ones containing two of the major

nutrients (NP, NK, and PK), triple fertilisers (NPK) with micronutrients, and special

group consists of sulphur-containing fertilisers. (Faul, 2020)

Some advantages of these fertilisers include:

i. Fast acting since the nutrient-rich salts dissolve quickly and are immediately

available to the plants depending on them to provide essential nourishment in the

form of nitrogen, phosphorus, and potassium.

ii. Precise content of nutrients which is guaranteed by law. Unlike organic fertilisers,

mineral fertilisers have the plant nutrients broken down and provided as a

percentage which is usually displayed on mineral fertiliser bags. The nutrient

breakdown could be 15-15-15, 12-20-6, and many others.

iii. Ease of Use. These fertilisers come in several easy-to-use formulations also

allowing for easy transportation compared to organic fertilisers such as manure.

iv. Lower cost as they are mass produced. Particularly, dry granular controlled-release

inorganic fertilisers are a very cost-efficient option for home gardeners because they

provide complete nutrition and do not require repeated applications.

Some disadvantages however are as follows:

i. The soil’s live is not effectively contributed to by mineral fertilisers.

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 ii. The amount of sodium in mineral fertilisers is higher than in organic fertilisers.

Sodium if not used correctly can pile up and cause damage in the roots of plants

(Royal brinkman, 2020)

DIFFERENCES BETWEEN ORGANIC AND INORGANIC FERTILISERS

ORGANIC INORGANIC

COMPOSITION Contain only plant or animal Artificially manufactured

based materials that are and contain minerals or

either a by-product or end synthetic chemicals.

product of naturally

occurring processes, such as

manures, leaves and compost

NUTRIENT SOURCE Crop residues and animal Nitrogen from air, Phosphate

manures and Potassium from

deposits/mines

NUTRITIONAL CONTENT Low High

REALEASE OF Slow, thereby reducing the Rapid, increasing the risk of

NUTRIENTS risk of leaching leaching

COST High Low

RELEASE OF Low High

GREENHOUSE GASES

INTO THE ATMOSPHERE

QUALITY Often inconsistent, Traceable and consistent

dependent on source

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 NPK RATIO About 14% 20 to 60%

SOURCE MATERIALS Manure, leaves, sticks, Rocks, sand, petroleum, air,

fruits, bone, flour, flowers natural gas, methane

(Miller, 2018)

Inorganic fertilisers may burn up plants and build up toxic salt concentrations in the soil.

Organic fertilisers on the other hand though may cause concentration of some nutrients, toxic

build up is unlikely as long as the organic material is able to fully decompose. (Miller, 2018)

Selecting an appropriate fertiliser for a plant is dependent on several factors such as the type

of substrate, nutritional need and sensitivity of the crop, as well as the preferable mode of

application of the fertiliser. The price of fertilisers in the market is dependent on a couple of

factors:

i. Prices of crops: The price of fertilisers increase with a corresponding increase in

crop prices. This can be attributed to the fact that a large portion of the production

costs of wheat, corn, and other crops comes from fertiliser. Hence, high fertiliser

prices will cause a rise in crop prices; likewise, higher crop produce will increase

the demand for fertiliser and cause fertiliser prices to rise.

ii. Natural Gas/Energy Prices: Since natural gas is involved in the production of

fertiliser, lower natural gas prices result in lower fertiliser price, and higher natural

gas prices result in higher fertiliser price.

iii. Population Growth: As the population grows, the demand for food rises. As such

the prices of fertiliser rise correspondingly as they are applied to crops for early and

mass production.

iv. Weather/Climate: Crop production is heavily dependent on weather conditions for

which reason some crops are preferably planted in the wet season while others are

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 planted in the dry season. Hence, climate change and unpredictable weather

conditions can influence the growth and yield of crops especially if there are

unexpected climate/weather changes. Fertilisers are therefore resorted to

complement these situations and increase the crop yield when the weather

conditions are unfavourable. Higher demand of fertilisers therefore leads to higher

fertiliser prices.

v. Other demand factors: The prices of fertilisers are further influenced by such other

factors as currency fluctuations, planted acres, crop inventories, alternative crop use

market changes, and dietary patterns.

(Trade Finance Global, 2020)

Despite the enormous benefits gained from fertilisers, it is imperative that they are rightly

applied in the right season in order to achieve the most from them. Though different plants

require different application of fertilisers at particular times, the umbrella rule for annual

application of fertiliser is to apply in early spring. This encourages leafy growth, and helps in

the production of flowers and fruits. Fertilisers are most effective when used on plants at their

peak growing cycle, thus, when the plant is leafing out for deciduous species, flowering, or

putting on new growth after leaving the dormant water stage. (Grant, 2020b)

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 CHAPTER THREE

3.0 FERTILISER MANFACTURING PROCESS

3.1 SOURCES OF RAW MATERIALS

Raw materials for manufacturing fertilisers are basically nitrogen, phosphorus, and potassium.

Nitrogen is sourced from the air as it contains about 78% nitrogen. However, since plants

cannot access nitrogen directly from the air, it is needful that it is made available to the soil so

it is absorbed by the plant roots. (Yara International ASA, 2018)

Phosphorus/Phosphate is originated from insoluble calcium phosphate rocks commonly

referred to as “rock phosphate”. Rock phosphate is made available for the plant usually through

a chemical process to create plant friendly fertilisers. The world’s largest deposits of phosphate

rocks are present in China, Russia, and Morocco. (Yara International ASA, 2018)

Potassium is originated from oil sea and lake beds formed millions of years ago. Potassium

fertilisers are based on naturally occurring potassium chloride. Since potassium sources are

often located far below the soil surface (1-2 km depth), plant roots are unable to reach them

naturally. The world’s biggest potassium producers are Canada, Russia, Belarus, and China.

(Yara International ASA, 2018)

3.2 MAJOR EQUIPMENT USED IN MANUFACTURING FERTILISER

Below is some equipment used in the manufacture of NPK fertilisers production line:

i. Rotary Drum Granulator

This works by tumbling material in a rotating drum, typically in the presence of a

binder which causes the fines to become tacky and allows them to pick up additional

fines. This leads to the formation of agglomerates in a process known as

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 coalescence. The tumbling action helps to round the agglomerates and create a

homogenous mixture.

Figure 1: A rotary drum granulator

ii. Chain Crusher

Chain crusher is used to crush various materials into small granules where the

grinding medium may be fertiliser, concrete, or rocks.

Figure 2: A chain crusher

iii. Vertical Mixer

It uniformly blends particles and materials of different sizes, bulk density, and

moisture content to attain perfect mixing in which any sample taken from the

resultant mixture should have exactly a similar composition.

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Figure 3: A vertical mixer

iv. Belt Conveyor

It is used in the transportation of products of large volumes through a process. It

may transport regular and irregular shaped, large or small, as well as light or heavy

objects. It transports materials like grains, ore, coal, sand, and many others in a

straight line or through changes in elevation or direction.

Figure 4: A belt conveyor

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 v. Drum screener machine

Also known as trammel screen or rotary drum screen, it is used for classifying, size

splitting and pre-sorting bulk materials into one or more fractions.

Figure 5: A drum screener machine

vi. Granules Fertiliser Packing Machine

It is suitable for quantitative packaging of powder and granular martials. This

machine is the last part of the organic fertiliser production plant used to ensure high-

efficiency bagging process.

Figure 6: A granules fertiliser making machine

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 vii. Drum Fertiliser Dryer

This machine is an ideal drying equipment in the fertiliser industry for both

compound and organic fertilisers production. It is used to reduce the moisture

content of fertilisers.

Figure 7: A drum fertiliser dryer

viii. Drum Fertiliser Cooler

It is used for cooling fertiliser with a certain temperature and particle size in the

fertiliser industry. It can be used in combination with the dryer to remove the dust

and clean the exhaust together, which can improve the cooling efficiency and the

rate of thermal energy utilisation, reduce labour intensity, and further remove

moisture from the fertiliser.

Figure 8: A Drum Fertiliser Cooler

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 (hqhifertilisermachine, 2018)

3.3 FERTILISER MANUFACTURING

Figure 9: Fertiliser production routes for nitrogen and phosphorus based fertilisers

NITROGEN BASED FERTILISERS

Nitrogen comes in many forms. It may be taken in by plants through the roots or from the stoma

in the leaves and stems. Some nitrogen based fertilisers include ammonia liquor, ammonium

nitrate, ammonium sulphate, anhydrous ammonia, aqua ammonia, and urea. For nitrogen-based

fertilisers, nitrogen is obtained from air by mixing it with hydrogen from natural gas at high

temperature and pressure to create ammonia; the ammonia is produced by the Haber-Bosch

process. Approximately 60% of the natural gas is used as raw material, with the remainder

employed to power the synthesis process. The ammonia produced is then used to produce nitric

acid by the Ostwald process, with which it is mixed to produce nitrate fertilisers such as

ammonium nitrate (AN). Ammonia may also be mixed with liquid carbon dioxide to create

urea; both products can be further mixed together with water to form urea ammonium nitrate

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(UAN) solution. With the contact process, sulphuric acid is produced and mixed with ammonia

to form ammonium sulphate fertiliser. Raw materials for making nitrogen based fertilisers are

nitrogen from air and hydrogen from natural gas. (Fertilisers europe, 2019)

PROCESS DESCRIPTION

 Nitrogen production from air

In the obtaining of nitrogen from air, air is first filtered to remove dust, and then cooled in

stages till a temperature of -200°C is reached. At this temperature, air is now liquid. In the

liquid state, water vapour condenses and is removed using absorbent filters, carbon dioxide is

removed as it freezes at -79°C. However, oxygen and nitrogen liquefy at -183°C and -196°C

respectively and are separated by fractional distillation. The liquefied air is now passed into

the bottom of a fractionating column which is warmer at the bottom than at the top. Gaseous

nitrogen is distilled at the top of the column while liquid oxygen exits the bottom of the column.

(BBC, 2020)

 Hydrogen production from natural gas

Hydrogen, essential for the manufacture of ammonia and nitrogen based fertilisers is the most

abundant element on earth but rarely can it be found in its pure state; hence the need to extract

it from its compound. Hydrogen may be extracted from fossil fuels such as natural gas and

coal, biomass, non-food crops, nuclear energy, and renewable energy sources such as wind,

solar, geothermal, and hydroelectric power. However, steam–methane/natural gas reforming is

currently the most widely used method and least expensive way of producing hydrogen.

With steam–methane reforming, synthesis gas which is a mixture of hydrogen, carbon

monoxide, and a relatively small amount of carbon dioxide is produced by reacting methane,

with high-temperature steam (700 °C to 1000 °C) under 3–25 bar pressure. This reaction is

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endothermic. To produce further hydrogen, carbon monoxide is reacted with water in the water-

gas shift reaction which is exothermic. (EIA, 2020)

Equation of reaction: 𝐶𝐻4 + 𝐻2 𝑂 → 𝐶𝑂 + 3𝐻2

Water-gas shift reaction: 𝐶𝑂 + 𝐻2 𝑂 → 𝐶𝑂2 + 𝐻2

 Haber – Bosch Process

Nitrogen and Hydrogen after they have been produced are used for the synthesis of ammonia.

The ammonia produced is then used in the synthesis of different nitrogen fertilisers. In this

process, nitrogen and hydrogen are reacted in the presence of an iron catalyst at low

temperature and high pressure. The reaction proceeds at a temperature range of 400 – 650 °C

and a pressure range of 200 – 400 atm. The lower the temperature and the higher the pressure

used, the greater the yield of ammonia. The forward reaction is exothermic. (Augustyn et al,

2020)

𝐹𝑒
Equation of reaction: 𝑁2 + 3𝐻2 ↔ 2𝑁𝐻3 + ℎ𝑒𝑎𝑡

 Ostwald Process

This process is used in the production of nitric acid. Developed by the German chemist

Wilhelm Ostwald in 1901, the manufacture of nitric acid primarily involves three steps:

i. Catalytic oxidation of ammonia

Here, ammonia gas is oxidized to nitric oxide (NO) in the presence of platinum or

rhodium gauze catalyst. This reaction occurs at a temperature range of 800 – 900°C

and an operating pressure of 3–4 atm. In this step, about 95% ammonia is oxidised

to nitric oxide. The equation of reaction is given as:

𝑃𝑡/𝑅ℎ
4𝑁𝐻3(𝑔) + 5𝑂2(𝑔) ⇔ 4𝑁𝑂(𝑔) + 6𝐻2 𝑂(𝑔) ∆𝐻 = −905.2 𝑘𝐽⁄𝑚𝑜𝑙

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 ii. Oxidation of nitric oxide

Nitric oxide produced in the first step is further oxidized to nitrogen dioxide. The

hot nitric oxide is passed through a heat exchanger where the gas is cooled to about

150 °C. Nitric oxide after cooling is transferred to another oxidising tower where at

about 50 °C, it is oxidised to nitrogen dioxide (NO2). The reaction equation is given

as:

2𝑁𝑂(𝑔) + 𝑂2(𝑔) ↔ 2𝑁𝑂2 (𝑔) ∆𝐻 = −114 𝑘𝐽⁄𝑚𝑜𝑙

iii. Absorption of nitrogen dioxide into water

The nitrogen dioxide is then cooled in a condenser to less than 100 °C. Water vapour

formed condenses and absorbs some nitrogen dioxide fed into the condenser to form

nitric acid (HNO3). Below is the reaction equation:

3𝑁𝑂2(𝑔) + 𝐻2 𝑂(𝑙) ↔ 2𝐻𝑁𝑂3(𝑎𝑞) + 𝑁𝑂(𝑔) ∆𝐻 = −117 𝑘𝐽⁄𝑚𝑜𝑙

The nitric acid obtained is very dilute and is recycled in an absorption tower so that

more and more NO2 get absorbed. HNO3, after recycle, becomes about 68%

concentrated. In order to increase the concentration of HNO3, vapours of HNO3 are

passed over concentrated sulphuric acid (H2SO4). H2SO4 is a dehydrating agent and

absorbs water from HNO3 thereby making it concentrated. (World of Chemicals,

2020)

In a distillation tower, unreacted nitric oxide and nitrogen dioxide are distilled to form nitric

acid. Here, a fine spray of deionised water is released from the top of the tower. The unreacted

gas mixture is drawn from the bottom of the tower and absorbed into the water.

AMMONIUM NITRATE (NH4NO3) FERTILISER

In processed fertilisers, ammonium nitrate fertiliser is one of the easiest forms of nitrogen

available for plants uptake due to the strong chemical bond in nitrogen which is difficult for

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uptake by plants. It contains 33 – 34% Nitrogen and has a water solubility of 1,900 g/L at 20

°C. Ammonium nitrate fertiliser is an odourless, volatile and nearly colourless crystal salt. Use

of this fertiliser in gardens and large scale agricultural fields enhances plant growth and

provides a ready supply of nitrogen for which plants can draw. (Grant, 2020)

Its production on a large scale began in the 1940s when it was used for munitions during

wartime. Its use as a commercial fertiliser began after the end of World War II. In the

production of ammonium nitrate, ammonia gas is neutralised with nitric acid to form a

concentrated solution and considerable heat.

The reaction equation is given as: 𝑁𝐻3(𝑔) + 𝐻𝑁𝑂3(𝑙) → 𝑁𝐻4 𝑁𝑂3(𝑙) ∆𝐻 = −110 𝐽⁄𝑚𝑜𝑙

Depending on the pressure and concentration of the nitric acid, 83% of ammonium nitrate

solution can be obtained. After the formation of the solution, the excess water is evaporated off

to leave an ammonium nitrate (AN) content of 95 – 99.9% concentration (AN melt) depending

on grade. The AN melt is then made into prills 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.

Low-density prills are more porous than high-density prills and are preferred for industrial use,

while high-density prills are used as fertiliser. Granular ammonium nitrate is produced by

repeatedly spraying the concentrated solution onto small granules in a rotating drum. The solid

fertiliser is normally coated with an anti-caking compound to prevent sticking and clumping.

Before this fertiliser is solidified, small quantities of carbonate minerals are sometimes added,

and this eliminates the explosive properties of ammonium nitrate. The additives also reduce

the Nitrogen concentration and are sparingly soluble, making the modified product less suitable

for application through an irrigation system (fertigation). (Mosaic, 2020)

21
This fertiliser is an almost instantly useable form of nitrogen due to its porosity and solubility.

It makes nitrogen available from both the ammonia and the nitrate. It is applied by the broadcast

spreading of the granules which rapidly melt in water to allow the release of nitrogen into the

soil. The rate of application is 2/3 to 11/3 cup (157.5 – 315 mL) of ammonium nitrate fertiliser

per 1000 square feet (93 square meter) of land. It is then tilled in or watered in very thoroughly;

this allows the nitrogen move quickly through the soil to the roots of the plant for rapid uptake.

This fertiliser is commonly used in vegetable gardens and in hay and pasture fertilisation due

to the high nitrogen content. (Grant, 2020)

Figure 10: Ammonium nitrate fertiliser

UREA (NH2CONH2)

Urea is the most important nitrogenous fertiliser in the market with the highest Nitrogen content

(about 46%). It is a white crystalline organic chemical compound, neutral in pH, and can adapt

to almost all kinds of soils. Urea fertiliser is applied primarily to provide the plants with

nitrogen to promote green leafy growth and make the plants look lush. It also aids the

photosynthesis process of plants.

22
Urea is made when carbon dioxide (CO2) is reacted with anhydrous ammonia, leading to the

production of ammonium carbamate (NH2COONH4) which is then dehydrated. In this process,

ammonia and carbon dioxide are fed into a synthesis reactor at 180 – 210 °C and 150 bar

pressure. This reaction is exothermic, and heat is recovered by a boiler which produces steam.

Equations of reaction: 2𝑁𝐻3(𝑔) + 𝐶𝑂2(𝑙) ⇌ 𝑁𝐻2 𝐶𝑂𝑂𝑁𝐻4(𝑙)

𝑁𝐻2 𝐶𝑂𝑂𝑁𝐻4(𝑙) ⇌ 𝐻2 𝑂(𝑙) + 𝑁𝐻2 𝐶𝑂𝑁𝐻2(𝑙)

The reaction mixture containing ammonia, ammonium carbamate, and urea is first stripped off

the ammonia and the resultant solution of ammonium carbamate and urea passes through a

chamber of decomposers operating at progressively reduced pressures. Here, the unconverted

carbamate is decomposed back to ammonia and carbon dioxide and then recycled to the reactor.

The produced urea solution is concentrated by evaporation or crystallisation, where the crystals

are melted to yield pure urea in the form of prills or granules. Prills are made by spraying

molten urea from the top of a high tower through a counter current air stream. Granular urea is

formed by spraying molten urea into a mixture of dried urea particles and fines in a rotating

drum. (I.C.I.S, 2010)

Dry urea is very soluble and must be kept away from moisture until its use. This fertiliser

should be applied at the time of sowing and should not come in contact with the seeds. It should

also be used in combination with earth or sand before application due to the high nitrogen

content. Urea should not be applied when the soil contains free water or likely to remain wet

for three or four days after application.

23
Figure 11: Urea fertiliser

AMMMONIUM SULPHATE [(NH4)2SO4]

This fertiliser was one of the first and most widely used nitrogen fertilisers for crop production.

Though it is currently less common, it is still valuable where both nitrogen and sulphur are

required.

Ammonium sulphate is produced by reacting sulphuric acid (H2SO4) with heated ammonia.

The reaction equation is given as:

2𝑁𝐻3 + 𝐻2 𝑆𝑂4 → [(𝑁𝐻4 )2 𝑆𝑂4 ]

The ammonia required for this process is produced by the Haber process while the sulphuric

acid used is produced by the Contact process. The raw materials for the Contact process include

sulphur (S), air, and water. Sulphur is available from fossil fuels and sulphide ores. Sulphur is

reacted with oxygen in air to produce sulphur dioxide (SO2) in the equation:

𝑆(𝑠) + 𝑂2(𝑔) → 𝑆𝑂2(𝑔)

The sulphur dioxide gas produced is used to make sulphur trioxide. Here, sulphur reacts with

more oxygen in the equation:

24
 2𝑆𝑂2(𝑔) + 𝑂2(𝑔) ⇌ 2𝑆𝑂3(𝑔)

This reaction proceeds at a temperature of 450 °C and an approximate pressure of 2 atm in the

presence of a vanadium (V) oxide (V2O5) catalyst.

Sulphur trioxide produced is now reacted with water to form sulphuric acid in the equation:

𝑆𝑂3(𝑔) + 𝐻2 𝑂(𝑙) → 𝐻2 𝑆𝑂4(𝑎𝑞)

In the manufacture of ammonium sulphate, an ammonia gas – water vapour mixture is

introduced into a reactor containing a saturated solution of ammonium sulphate and about 2 –

4% (v/v) fee sulphuric acid at 60 °C. This solution is kept acidic by adding concentrated

sulphuric acid. Dry, powdered ammonium sulphate may be formed by spraying sulphuric acid

into a reaction chamber filled with ammonia gas. The heat of reaction evaporates all of the

water present in the system with the resulting formation of a dry powdery salt. (Speight, 2017)

Ammonium sulphate crystals are formed by circulating the solution through an evaporator

where it thickens. A centrifuge separates the crystals from the mother liquor. The crystals

containing 1 – 2.5% moisture are dried in a fluidised bed or rotary drum dryer. The dryer

exhaust gases are sent to a particulate collection system to control emissions and recover

residual product. The coarse and fine granules are separated by screening before they are stored

or shipped. This fertiliser contains 21% nitrogen and 24% sulphur. (Speight, 2017)

25
Figure 12: Ammonium sulphate fertiliser

26
Figure 13: Process flow diagram for producing nitrogen based fertilisers

27
PHOSPHORUS BASED FERTILISERS

Phosphorus based fertilisers are produced from mined ores. Phosphate rock is primarily treated

with sulphuric acid to produce phosphoric acid (54% P2O5) also known as green acid, which is

either concentrated or mixed with ammonia to make a range of phosphate (P2O5) fertilisers.

Due to the corrosiveness of phosphoric acid, it is used to manufacture other fertilisers such as

Diammonium Phosphate (DAP), Monoammonium Phosphate (MAP), Single Super Phosphate

(SSP), Triple Super Phosphate (TSP), and NPKs though phosphate is not the base of this

product as it is included with potassium and nitrogen to create a variety of NPK blends.

(Fertilisers europe, 2019)

Mined phosphate rock is separated from the unwanted materials via a wet process, and the

resulting material is first dried in a rotary dryer. The dry phosphate ore is then most commonly

processed into ammoniated phosphates by reacting the phosphate rock with sulphuric acid to

produce phosphoric acid. The phosphoric acid is then reacted with ammonia to produce the

ammoniated phosphate MAP or DAP. However, the phosphoric acid and ammonia are pre-

neutralised in tanks to form a slurry which is fed into a rotary granulator. Here, the product

forms granules as it tumbles through the drum and solidifies. (Capitane and Carison, 2020)

The granules are then carried via conveyor to a rotary dryer where they are dried into their final

form. The tumbling action of the dryer further rounds and polishes the granules which then exit

the dryer into a screening process for separation of over- and under-size granules. Oversize

granules are crushed via a chain mill and fed with the undersize granules back into the process

as recycle. On-size product moves on to cooling, which is carried out using a rotary cooler.

Cooling helps prevent caking during storage, and is necessary when material exiting the dryer

is too hot for subsequent material handling equipment. (Capitane and Carison, 2020)

28
Figure 14: Phosphorus based fertiliser

MONOAMMONIUM PHOSPHATE (MAP)

This is a widely used source of phosphorus and nitrogen. Monoammonium phosphate with the

chemical formula (NH4)(H2PO4) is also known as ammonium, dihydrogen phosphate (ADP).

It is made of two constituents common in fertiliser industry and contains the most phosphorus

o any common solid fertiliser. It is water-soluble and dissolves rapidly in adequately moist soil.

Upon dissolution, the two basic components of the fertiliser separate again to release

ammonium (NH4+) and phosphate (H2PO4-), both of which give plants healthy and sustained

growth. MAP is a desirable fertiliser in neutral and high-pH soils since the pH of the solution

surrounding the granule is moderately acidic.

In its production, a 1:1 ratio of ammonia (NH3) and phosphoric acid (H3PO4) is reacted and the

resulting slurry of MAP is solidified in a granulator. The reaction equation is given as:

𝑁𝐻3 + 𝐻3 𝑃𝑂4 → 𝑁𝐻6 𝑃𝑂4 + ℎ𝑒𝑎𝑡

Granular MAP is applied in concentrated bands beneath the soil surface in proximity of

growing roots or in surface bands. It is also commonly applied by spreading it across the field

and mixing it in the surface soil via tillage. (Mosaic, 2020)

- its ability to blend well with other products

- it provides added source of Nitrogen, which is in a readily available form for plant

uptake

- it has the highest Phosphorus concentration among standard dry fertilisers.

- provision of high quality plant products.

One major drawback however is that:

- it does not mix well with calcium products

DIAMMONIUM PHOSPHATE (DAP)

This fertiliser is also known as diammonium hydrogen phosphate with the chemical formula

[(NH4)2HPO4]. It is the world’s most widely used phosphorus fertiliser. It is made from two

common constituents in the fertiliser industry, and its relatively high nutrient content and

excellent physical properties make it a popular choice in farming and other industries.

Diammonium phosphate is produced in a controlled reaction of phosphoric acid with ammonia

where the hot slurry is cooled, granulated, and sieved. It has a relatively high standard nutrient

grade of 18-46-0. The reaction equation is given as:

2𝑁𝐻3 + 𝐻3 𝑃𝑂4 ⇌ 𝑁2 𝐻9 𝑃𝑂4

DAP fertiliser is an excellent source of Phosphorus and Nitrogen for plant nutrition. It is highly

soluble and hence dissolves quickly in soil to release plant-available phosphate and ammonium.

30
A notable property of DAP is its alkaline pH that develops around the dissolving granule.

(Mosaic, 2020)

Figure 15: Process flow diagram for the manufacture of some phosphorus based diagram

31
POTASSIUM BASED FERTILISERS

These fertilisers are also produced from mined ores. Several chemical processes can be used to

convert the potash rock into plant food, including potassium chloride, sulphate and nitrate.

(Fertilisers europe, 2019)

Muriate of potash, Potassium sulphate, Potassium nitrate, Sulphate potash magnesia, and

Kainite are some fertilisers based on potassium. However, the usual potassium fertilisers are

two main types in which K+ is combined with either chloride (muriate of potash) or sulphate

(sulphate of potash). The fertiliser type to use in order to obtain high yields and good quality

plants depends on the needs of the plant, soil conditions, and climatic factors. (Scherer, 2005)

Figure 16: Potassium based fertilisers

POTASSIUM CHLORIDE (KCl)

This fertiliser type is available in three different grades: 50% K, 41% K, and 33% K. The two

latter forms however contain substantial amounts of sodium chloride (NaCl) and are

recommended as K+ fertilisers for natrophilic crops. (Scherer, 2005)

Potassium chloride is produced by extracting the sylvinite ore which is a mixture of sylvite

mixed with halite (sodium chloride). The ore is then transported to a processing facility where

32
it is crushed and the K salts are separated from the sodium salts. At the processing site, the ore

is ground into fine sizes and screened to get the desired sizes. The ore is then dissolved in hot

water and a solution of NaCl is added to obtain a mixture. The temperature of the mixture is

then increased so that more of the ore dissolves till a saturated solution of KCl is obtained. The

saturated solution of both KCl and NaCl is suddenly cooled in a vacuum where the KCl

precipitates as crystals. The KCl crystals are then dried, powdered, and used.

The colour of KCl can vary from red to white, depending on the source of the sylvinite ore

though there are no agronomic differences between red and white KCl. The reddish tint comes

from trace amounts of iron oxide. Some KCl is however produced by injecting hot water deep

into the ground to dissolve the soluble sylvinite mineral and then pumping the brine back to

the surface, where the water evaporates.

This fertiliser is the most widely applied potassium (K) fertiliser due to its relatively low cost

and because it includes more K than most other sources.

Figure 17: Process flow diagram for KCl fertiliser production

33
POTASSIUM SULPHATE (K2SO4)

Potassium sulphate is frequently used for crops where additional chloride from more common

potassium chloride (KCl) fertiliser is undesirable. This fertiliser type usually contains 43% K.

Potassium sulphate fertiliser may be manufactured for kainite or langbeinite though langbeinite

is commonly used. Langbeinite and KCl are reacted according to the equation:

𝐾2 𝑆𝑂4 . 𝑀𝑔𝑆𝑂4 + 2𝐾𝐶𝑙 → 2𝐾2 𝑆𝑂4 + 𝑀𝑔𝐶𝑙2

Langbeinite is ground to pass through a 200 mesh sieve and mixed with KCl. The salt mixture

is then recycled with water and fresh quantity of the langbeinite. The reactions occur in

interconnected tanks and the crystallised K2SO4 is separated by means of centrifuge. The wet

K2SO4 is dried and conveyed to storage.

Figure 18: Key global fertiliser products

34
Figure 19: Nutrient application by crop

35
 CHAPTER FOUR

4.0 ENVIROMENTAL IMPACT OF FERTILISER

Though fertilisers help in boosting the growth and yield of plants, they have their drastic side

effects in the long run. Some of the effects of fertilisers on the environment include:

1. Biology of water bodies

Excessive use of fertilisers on the soil leads to eutrophication, which is the gradual

increase in the concentration of phosphorus nitrogen, and other plant nutrients in an

aging aquatic ecosystem such as a lake. These nutrients tend to become toxic for the

aquatic life, hence, increasing the excessive growth of algae in the water bodies and

decreasing the oxygen levels. This leads to death of fish and other aquatic fauna and

flora. It also alters the food chain as the different kinds of fishes in the water bodies

tend to be the food source for various birds and animals.

2. Depletes the quality of the soil

Excessive use of fertilisers can alter the fertility of the soil by increasing its acidity. For

this reason, it is recommended that a soil test is done at least once every three years in

order to keep a track of whether or not the right amount of fertilisers is used.

3. Human health

Nitrogen and other chemicals present in fertilisers can also affect the ground waters and

waters that are used for drinking purposes. One common effect of this can be the

development of blue baby syndrome which occurs in infants whose skin tissues are low

in oxygen. The use of lawn fertilisers and pesticides can also cause health risks such as

cancer and chronic diseases in humans, especially in children.

(Environment News South Africa, 2014)

36
4. Nitrates

High levels of nitrates can be toxic to livestock and humans. Nitrates are not adsorbed

into soil materials, so they may leach to groundwater. In some instances, stored or land-

applied manures or nitrogen fertilisers have caused high concentrations of nitrates in

water. Because nitrates freely leach down the soil profile, nitrogen that is not used for

crop or plant growth can reach the groundwater easily. (Meehan, 2017)

5. Oxygen depletion

Manure or commercial fertilisers stimulate microorganism growth when they enter

surface water. The growth and reproduction of these microorganisms reduce the

dissolved oxygen content of the water body thereby reducing the availability of oxygen

in the water. Fish and other aquatic species suffocate and hence degrade the water

quality. (Meehan, 2017)

37
 CHAPTER FIVE

5.0 CONCLUSION

With the world’s population expected to grow short of ten billion by 2050, having so many

mouths to feed across the globe will create upward pressure on demand for food. This, in turn,

puts upward demand on fertilisers as they are a crucial component in the production of many

food products. Between 2018 and 2023, the compound annual growth rate of the global

fertiliser market is predicted to reach 3.8%. Demand for bio-fertilisers is therefore expected to

rise exponentially with a 14% annual growth rate between 2018 and 2023 due to the issue of

soil pollution caused by the excessive use of chemical fertilisers. (Trade Finance Global, 2020)

Hence, there is the need to balance the use of chemical and organic fertilisers in order to achieve

optimum plant growth and maximum benefit from plants.

38
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