Saran University

Faculty of Engineering
Department of chemical Engineering
Petrochemical industry
Fertilizer

8/6/2020

Supervisors: [Link] Hosen

INTRODUCTION
Fertilizer is something that you may not know too much about, but almost all of us undoubtedly
depend on it; over half the food we eat today is grown with the assistance of some kind of
fertilizer. We get all of our food from the earth, it may have a few steps of processing before it
reaches your plate but, it all can be traced back to a plant. After hundreds of years of growing
plants on the same plots of land, all the nutrients get removed without being naturally
replenished. That is where soil amendments and fertilizers come in handy; a soil amendment is
a substance that helps improve plant growth and health and, a fertilizer is a natural or chemical
substance that is added to a soil to increase its fertility.

The most common natural fertilizer you may be familiar with is compost; a combination of
decaying organic material like old banana peels, eggshells and manure. Other organic options of
fertilizer include blood meal from slaughterhouses or fish fertilizer. However, the most common
fertilizers are chemicals substances, for example the small bottle of Miracle Gro you might
spray on your garden to help your tomatoes grow or more industrially used chemical mixtures
like urea that are produced in factories and used by large scale farmers.

Land fertility decreases over time because we interrupt the natural cycle of growth and decay;
we grow the food on the farm, but we dispose of it elsewhere. Therefore, the vital nutrients that
the soil needs are never returned and the soil becomes dependent on external sources of fertility,
whether that source is a chemical or natural one is up to us to decide. As the global population
and food demand on this planet continue to increase and, soil fertility continues to decrease, the
requirement for a powerful, sustainable and non chemical fertilizer is becoming absolutely
fundamental.
Types of Fertilizer
(I) Direct Fertilizer:

The direct fertilizers are those which the green plants directly absorb from the land like nitrogen
phosphorous etc. the green plants may take all nutrients from those fertilizers.

(II) Indirect Fertilizers:

The indirect fertilizers provides not only necessary nutrients to land but also it provides the
fertilizer which increases the fertility of land by mixing potash and hydrogen inside the land and
it is necessary for the development of plant. That type of fertilizers is termed as indirect
fertilizer. Line, silicone and boron are main examples of these fertilizers.

(III) Complete Fertilizer:

The fertilizer which provides necessary every element like Carbon, Hydrogen, and Oxygen etc
for the healthy development of plants is termed as complete fertilizer.

(IV) Incomplete Fertilizer:

The fertilizer which consist only one of two necessary nutrients elements is called incomplete
fertilizers. Ammonia phosphate is one of the best examples of this fertilizer .
Fertilizer on the Basis of Source:
The fertilizers which are used in the farming are included in this type there are mainly two types
of fertilizers as below:

(I) Natural Fertilizes:

It is also called traditional fertilizers. This fertilizer is obtained normally by the way of
naturally. In which human beings and animal dung and urine is used. Besides this oil cake
fertilizer, fish fertilizers chilly salt fertilizers and potassium fertilizers are also included. In this
fertilizers chemical are not added.

(II) Chemical Fertilizer:

In this fertilizer many chemical are included. This fertilizer mainly created in factories. Many
material combines together to form mix fertilizers. But in practice the fertilizer contain nitrogen
phosphorus and potash used widely.
Types of Chemical Fertilizer:
1-Nitrogen

Nitrogen has quick, outstanding effect on plant growth whenever it is used in moderately large
quantities. Its first effect is to stimulate the growth o f leaf and stem. It gives decidedly a dark
green color to leaves whereas lack of sufficient nitrogen is often indicated by a yellowish color
o f the leaves and short growth o f the stalk or stem. Nitrogen applied in too large quantities
causes’ trouble more often than do the other elements. Excessive use of nitrogen may have
severe detrimental effects. It may delay ripening by causing too much vegetative growth of
crops.

2-Phosphorus

Phosphorus is one of the essential major nutrients besides nitrogen and potassium and is needed
in adequate amounts in the available forms for the growth and reproduction of plants. As Pierre,
(1938) put forth, phosphorus is also known as the “Master key” element in crop production
which is associated with several vital ftinctions and is responsible for many characteristic of
plant growth such as utilization o f sugar, starch and photosynthesis, nodule formation and cell
division and organization, fat formation and transfer of heredity. Phosphorus is absolutely
essential in many phases o f plant growth. Generally seeds are rich in phosphorus than other
parts of the plant. It appears therefore to have an important function in seed development.
Phosphorus plays an important role in ripening of fruits, which is very important with such
crops as com and tomatoes which are having short growing seasons.

3-Potassium

Available potassium in proper quantity has much to do with vigorous growth. Like phosphorus
it increases the plants natural resistance against disease through balancing the effect of nitrogen
and phosphorus. Potassium is needed for the formation of the green part of plants called
chlorophyll, which with the help of sunlight bring about starch formation. Potassium in
extremely heavy application in mineral soils may sometime be harmful to crop causing heavy
damage to the crop grown on some peat soils.

4-Calcium, magnesium and sulphur Fertilizers

Calcium (Ca), magnesium (Mg) and sulphur (S) are essential secondary plant nutrients. They
are not usually applied as straight fertilizers but in combination with the primary nutrients N, P,
and K.

Sulphur is often added to straight N fertilizers such as ammonium nitrate or urea. Other sulphur
sources are single superphosphate (SSP), potassium sulphate (SOP) and potassium magnesium
sulphate (Kainite), the latter also containing magnesium.

Kieserite is a magnesium sulphate mineral that is mined and also used as fertilizer in
agriculture, mainly to correct magnesium deficiencies. Calcium is mainly applied as calcium
nitrate, gypsum (calcium sulphate) or lime/dolomite (calcium carbonate), of which calcium
nitrate is the only readily plant available source of calcium.

5-Micronutrient fertilizers

Today, a large number of special fertilizers are available to supply plants with important
micronutrients such as iron, manganese, boron, zinc and copper. These can be either inorganic
or organic compounds, with the inorganic varieties further divided into water-soluble and non-
soluble products.
Nitrogen Fertilizer:
Nitrogen is a key component of amino acids and proteins. It is also a part of the chlorophyll
molecule, which controls photosynthesis, the solar energy capturing reaction of green plants.
Nitrogen and Mg are the only elements in the chlorophyll molecule that come from the soil.
Adequate supplies of N are needed to support photosynthesis and to produce proteins in
harvested crops. Nitrogen occurs in a variety of forms in the soil, and may be taken up in
different forms by growing plants. Throughout the growing season, and even between seasons,
N is transformed from one form to another by various chemical and biological processes. It can
also be reacted by lightning and deposited in rainfall. Some of these processes make it more
available to plants, while others reduce its availability. Nitrogen is also lost from the local
production systems in various forms. It may be lost into the atmosphere from the soil or from
growing plants as N2 gas, ammonia (NH3 ), nitrous oxide (N2 O), or NOx gases; it may be lost
as nitrate (NO3 - ) in soil water through leaching or runoff from the soil surface. In short, N is a
very reactive element as summarized in the N cycle diagram, forms numerous biochemical
compounds in plants, and plays a variety of significant roles in plant growth and development.
This makes it complicated to manage, but also provides many opportunities for managing N.
While it is one of the most studied nutrients, in many ways it remains one of the least
understood. But its significance in crop production and in resulting animal and human food
makes it a very important part of nutrient management. As a major component of amino acids
and proteins, as well as other major food components, N deserves significant attention. Nitrogen
is also important because of its impact on the environment. In surface water bodies, nitrate-N is
a major nutrient that supports growth of algae and aquatic plants, which as they die and
decompose, tie up oxygen in the water, creating a hypoxic condition which starves aquatic
animals for oxygen. Nitrogen in the soil can also be released into the atmosphere as N2 O which
is over 300 times as potent as CO2 as a greenhouse gas. An important goal of fertilizer best
management practices (FBMPs) for N is to reduce the release of reactive forms of N (forms
other than N2 ) into the environment. The “plow layer” of most soils contains between 0.08 and
0.4% N, with a representative average of 0.15% N. That equates to about 3,360 kg/ha of N
naturally occurring in the soil, mostly in organic compounds, which are slowly broken down so
that the N is available for plant growth. The total fertilizer N applied, while often more readily
available, is a small fraction of the total N in the soil. Applied N fertilizer merely contributes to
the total N pool in the soil. The dynamic changes in form of N in the soil make N management a
very complex process. Separately accounting for which source of N contributes to crop growth,
which to atmospheric losses, and which to water contamination, is nearly impossible. Since all
of these processes draw from the same N pool, it is difficult to show conclusively how
managing one N source can impact any of the processes or its outcomes. It is all part of one
dynamic N system. This makes any attempts to monitor and control losses of N from production
fields an extremely difficult task. But farmers still can benefit from making a serious effort to
properly manage that portion for which they do have some control. Figure 4 illustrates the
relationships among some of the many forms, processes, and reactions of N in crops, soils, and
the atmosphere. Nitrogen dynamics in soils are very complex. The important process of
nitrification (transformation of ammonium to nitrate by bacteria) proceeds rather quickly when
temperatures are warm. Denitrification, another bacterial process, converts nitrate into N2 gas,
which is released to the atmosphere. The N Cycle (Figure 5) shows the interactions among the
N forms in the soil-cropatmosphere system of crop production. The reactive N in these systems
is in a constant dynamic exchange among the various forms.j

Figure 2 The “Nitrogen Cascade” illustrating the interaction of various N forms in the N cycle
N fertilizer sources and formulations
Nitrogen fertilizers are manufactured in a variety of formulations, each with different properties
and uses for crop production systems. These all essentially begin with anhydrous ammonia
which is manufactured from air and natural gas by the Haber-Bosch process through the
chemical reaction [3H2 +N2 → 2NH3 ] under high temperature and pressure. This process,
developed in Germany just before World War I, is sometimes considered the most important
technological development of the 20th

Figure 3. Amounts of N commonly found in each form in the N cycle

Some of the more common N formulations are described below.

Anhydrous ammonia (NH3

is the most concentrated commercial fertilizer N source (82% N). Since the most common
source of energy for manufacturing ammonia is the natural gas (methane), ammonia production
facilities are usually located near natural gas supplies. The ammonia is transported world-wide
by pipelines, truck, railroads, and ships, as a liquid under pressure and/or refrigeration to keep it
below its boiling point (-33o C, -27o F). Ammonia is usually applied to the soil by injection at a
depth of 10 to 20 cm (4 to 8 in) as a pressurized liquid that immediately vaporizes, and reacts
with soil water to convert to ammonium (NH4 + ). This ion then gets attached to negatively
charged cation exchange site on clay minerals and organic matter in the soil. Aqua ammonia (20
to 24% N) is produced by mixing ammonia with water. This form can be added to irrigation
water as an alternate means of application.

Ammonium sulphate

[(NH4 )2 SO4 ] (21% N) is produced as an industrial byproduct and is one of the oldest
manufactured N fertilizers. It comes from manufacturing of steel, nylon, and other processes
that use sulphuric acid. It is often used as a carrier for herbicide application, helping to enhance
efficacy. It also contains 24% S, making it a useful choice where S is needed.

urea

fertilizer involves controlled reaction of ammonia gas (NH3 ) and carbon dioxide (CO2 ) with
elevated temperature and pressure. The molten urea is formed into spheres with specialized
granulation equipment or hardened into a solid prill while falling from a tower. During the
production of urea, two urea molecules may inadvertently combine to form a compound termed
biuret, which can be damaging when sprayed onto plant foliage. Most commercial urea fertilizer
contains only low amounts of biuret due to carefully controlled conditions during
manufacturing. Urea is an excellent nutrient source to meet the N demand of plants. Because it
readily dissolves in water, surfaceapplied urea moves with rainfall or irrigation into the soil.
Within the soil, urea moves freely with soil water until it is hydrolyzed to form NH4 +.

Nitrophosphate
(variable grades) is made by treating rock phosphate with nitric acid instead of sulphuric acid.
It has the advantage of not producing the calcium sulphate (gypsum) byproduct that becomes a
disposal issue. Two additional byproducts, calcium nitrate and calcium ammonium nitrate, are
also generated in the process. Nitrophosphates can be mixed with other nutrients to make
uniform pellets of fertilizer containing multiple nutrients.

Ammonium nitrate

(NH4 NO3 ) was initially produced in the 1940s as a munition product. It contains 33 to 34% N.
Ammonium nitrate is produced as a concentrated solution by reacting ammonia gas with nitric
acid. The solution (95 to 99% ammonium nitrate) is dropped from a tower and solidifies to form
prills, which can be used as fertilizer or made into granular ammonium nitrate by spraying
concentrated solution onto small granules in a rotating drum. Since half of the N is in the
ammonium form, it may be taken up directly by roots, or gradually converted to nitrate by
microbes, providing a delayed-release of N. The other half of the N is in the nitrate form and is
immediately available to plants. Its high solubility makes it well-suited for fertigation and foliar
application.

Urea ammonium nitrate

(UAN) (28% N) is commonly used as a liquid fertilizer N source, applied as a broadcast

application, as a carrier for herbicides and as a side-dress application for row crops, such as
maize.

Calcium cyanamide,

in addition to its fertilizer value, has herbicidal and fungicidal properties due to intermediate
decomposition products.
The different forms of N when applied to soil give almost similar crop yield responses.
Efficiency of some products may be reduced due to leaching losses of nitrates or volatilization
of ammonia under certain temperature and soil moisture situations. Surface applied urea or
UAN solutions are especially susceptible to such losses. Most N fertilizers tend to be available
quickly and are subject to loss before the N can be taken

Figure 4. The need for supplemental N fertilizer depends on early season weather.

up by the crop. But slow-release or controlled-release enhancement products can help reduce
those losses as well. In a wet spring under tropical climate, soil N may be lost due to leaching
and denitrification, resulting in a larger amount of side-dress N fertilizer being required to meet
crop needs. Split-application of fertilizer N should be a good way to manage such situations
(Figure 4). The N supply from slow- and controlled-release fertilizers is theoretically better
adapted to the curve of N uptake but depends on temperature.
Nitrogen fertilizer characteristics

Different N fertilizers are valued according to their total N-content, the different N-forms
(which determine the rate of action), and side-effects if any (Box 4). Regardless of the
formulation of the fertilizer applied, most are converted in the soil to nitrate and ammonium, the
predominant plant-available forms of N. Nitrate N in the soil solution is immediately available
and thus acts quickly but is most liable to losses via leaching and/or denitrification. Plants take
up N mainly in nitrate form. Ammonium-N, although fully available, has a somewhat slower
effect, because it is first adsorbed on soil particles and then only gradually released and
nitrified. This can be beneficial to N use efficiency, because N in the ammonium form attached
to soil particles is much less susceptible to leaching and other losses. Some plants can absorb
ammonium directly, while others require that it is first converted to nitrate. At a temperature of
20-25° C, an application supplying 50-100 kg/ha (20-40 lb/A) N would nitrify in about two
weeks. Nitrification can be delayed for several weeks by adding nitrification inhibitors to the
fertilizer. This can be useful for preventing undesirable accumulation of nitrate in vegetable
crops or reducing loss by leaching. Several different formulations, coatings, and additives are
available to help farmers manage fertilizer N more efficiently. These are broadly classified as
stabilizers, inhibitors, slow-release, and controlled-release products.

 Slow- or controlled-release fertilizer: A fertilizer containing a plant nutrient in a form

which delays its availability for plant uptake and use after application, or which extends
its availability to the plant significantly longer than a reference ‘rapidly available
nutrient fertilizer’ such as ammonium nitrate or urea, ammonium phosphate or
potassium chloride. Such delay of initial availability or extended time of continued
availability may occur by a variety of mechanisms. These include controlled water
solubility of the material by semipermeable coatings, occlusion, protein materials, or
other chemical forms, by slow hydrolysis of water-soluble low molecular weight
compounds, or by other unknown means.
 Stabilized N fertilizer: A fertilizer to which a N stabilizer has been added. A nitrogen
stabilizer is a substance added to a fertilizer, which extends the time the N component of
the fertilizer remains in the soil in the urea-N or ammoniacal-N form.
 Nitrification inhibitor: A substance that inhibits the biological oxidation of ammoniacal-
N to nitrate-N.

Figure 5 nitrogen fertilizer flow shee

Reference :
4R Plant Nutrition Manual, English and metric versions. 2012. International Plant Nutrition Institute,
Peachtree Corners, Georgia, US.

Alley, M. M, and B. Vanlauwe. 2009. The Role of Fertilizers in Integrated Plant Nutrient Management.
International Fertilizer Industry Association, Paris, France. 59 pp.

Arnon D.I. and P.R Stout. 1939. The essentiality of certain elements in minute quantity for plants with
special reference to copper. Plant Physiol. 14: 371-375.

Brown, C.A. 1942. Justus von Liebig–Man and teacher and Liebig and the Law of the Minimum. In:
Liebig and After Liebig: A century of progress in agricultural chemistry. Am. Assoc. Adv. Sci. The Science
Press Printing Co., Lancaster, PA, US.

Brown, P.H., R.M. Welch, and E.E. Cary. 1987. Nickel: A micronutrient essential for higher plants. Plant
Physiol. 85: 801‐803.

Buresh, R.J., C. Witt, and M.F. Pampolino. 2006. SSNM: An Approach for Optimizing Nutrient Use in
Intensive Rice Production. International Rice Research Institute, Los Baños, Philippines.

Dobermann, A. 2006. Reactive Nitrogen and the Need to Increase Fertilizer Nitrogen Use Efficiency.
Proceedings of 13th Agronomy Conference, Perth, Western Australia.