Lecture note

Semester -6th

Subject- fertilizer technology

Subject code- PECH 5302

NAME- SUBHAN KUMAR PAL

Department of Chemical Engineering

Email id- subhankumarpal@gmail.com

 Disclaimer

This document does not claim any originality and cannot be used as a substitute for prescribed
textbooks. The information presented here is merely a collection by the committee faculty members for
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Various sources as mentioned at the reference of the document as well as freely available material
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 Syllabus
Module I

Fertilizers: Chemical Fertilizers and Organic manures, Types of Chemical Fertilizers,

Fertilizer applications and agronomic details.

Nitrogenous Fertilizers : Feedstock for production of Ammonia Gas, Associated Gas,

Coke Oven Gas, Naphtha, Fuel Oil, Petroleum Heavy Stock, Coal, Lignite, Coke, Water.
Methods of production, characteristics, specification and storage of Ammonium
sulphate, ammonium nitrate, urea, calcium ammonium nitrate and ammonium chloride.

Module II
Phosphatic Fertilizers: Raw materials - phosphate rock, sulphur, pyrites. Methods of
production, characteristics, specification and storage of single super phosphate, triple
super phosphate.

Potassic Fertilizers : Methods of production, characteristics, specification and storage of

potassium chloride, potassium sulphate and potassium nitrate.

Module III
Complex and NPK Fertilizers: Methods of production, characteristics specification and
storage of ammonium phosphate sulphate, Di-ammonium phosphate, nitro phosphates,
urea ammonium phosphate, mono ammonium phosphate and various grades of NPK
fertilizers.

Other Fertilizers: Secondary nutrients, micronutrients, Fluid fertilizers, controlled release

fertilizers.

Lecture- 01

Introduction to Plant nutrients, Fertilizer specifications,

Terminology and Definitions:

Introduction

A fertilizer is a material that furnishes one or more of the chemical elements necessary for
the proper development and growth of plants. The most important fertilizers are fertilizer
products (also called chemical or mineral fertilizers), manures, and plant residues. A
fertilizer product is a material produced by industrial processes with the specific purpose of
being used as a fertilizer. Fertilizers are essential in todays agricultural system to replace
the elements extracted from the soil in the form of food and other agricultural products.

Plant Nutrients
Chemical elements that are essential for the proper development and growth of plants are
typically referred to as plant nutrients. The list of plant nutrients recognized as being
necessary for plant growth has increased over the years and now totals sixteen.

Expression

Many countries express quantities or percentages of the primary nutrients in terms of

elemental nitrogen (N2), phosphorus pen oxide (P2O5), and potassium oxide (K2O).
Secondary nutrients and micronutrients usually are expressed on an elemental basis
although calcium and magnesium sometimes are expressed in the oxide form. However,
several countries express all plant nutrients on an elemental basis.

Classification of Elements Essential for Plant Growth:

Major elements (Available from air or water) Carbon

(Macronutrients) Hydrogen
Oxygen

Primary nutrients Nitrogen

Phosphorus
Potassium

Secondary nutrients Calcium

Magnesium
Sulphur

Minor elements Boron

(Micronutrients)
Chlorine
Copper
Iron
Manganese
Molybdenum
Zinc
Fertilizer Grade

All fertilizer labels have three bold numbers. The first number is the amount of nitrogen (N 2),
the second number is the amount of phosphate (P2O5) and the third number is the amount
of potash (K2O). These three numbers represent the primary nutrients [nitrogen (N) -
Phosphorus (P) - potassium (K)].
This label, known as the fertilizer grade, is a national standard. A bag of 10-10-10 fertilizer
Contains 10 percent nitrogen, 10 percent phosphate and 10 percent potash.
Fertilizer grades are made by mixing two or more nutrient sources together to form a blend
that is why they are called "mixed fertilizers." Blends contain particles of more than one
color. Manufacturers produce different grades for the many types of plants.

You can also get fertilizers that contain only one of each of the primary nutrients. Nitrogen
sources include ammonium nitrate (33.5-0-0), urea nitrogen (46-0-0), sodium nitrate (16-0-
0) and liquid nitrogen (30-0-0). Phosphorus is provided as 0-46-0 and potash as 0-0-60 or
0-0-50.

Fertilizer Specifications

Specifications are the requirements with which a fertilizer should conform, as

agreed upon between buyer and seller. Fertilizer specifications meet differing requirements
depending on the use or intent of the specification information.

Specifications are normally used in the contract between the buyer and seller of a
fertilizer to ensure agreement on product characteristics or more often to define the product
in sufficient detail to effect the satisfaction of both buyer and seller.

Terminology and Definitions

The below specified definitions are those given by International Association for
Standardization (ISO) and Association of American Plant Food Control Officials
(AAPFCO).

Fertilizer Material- A fertilizer that meets any of the following conditions (AAPFCO):

1. Contains important quantities of no more than one of the primary plant nutrients
(nitrogen, phosphorus, or potassium).

2. Has 85% or more of its plant nutrient content present in the form of a single
chemical compound.

3. Is derived from a plant or animal residue or by product or natural material deposit

which has been processed in such a way that its content of plant nutrients has not
been materially changed except by purification and concentration.

Fertilizer- In the simplest terminology, a material, the main function of which is to provide
plant nutrients.

Soil Conditioner Material added to soils, the main function of which is to improve their
physical and/ or chemical properties and/ or their biological activity.
Liming Material An inorganic soil conditioner containing one or both of the elements
calcium and magnesium, generally in the form of an oxide, hydroxide, or carbonate,
principally intended to maintain or raise the pH of soil.

Straight Fertilizer: A qualification generally given to a nitrogenous, phosphatic, or

potassic fertilizer having a declarable content of only one of the primary plant nutrients, i.e.
nitrogen, phosphorus, or potassium.

Compound Fertilizer: A fertilizer that has a declarable content of at least two of the plant
nutrients nitrogen, phosphorus and potassium, obtained chemically or by blending or both.

Granular Fertilizer: Solid material that is formed into particles of a predetermined mean
size.

Coated Fertilizer Granular fertilizer that is covered with a thin of a different material in
order to improve the behavior and/ or modify the characteristics of the fertilizer.
Other related terms are:

Coated Slow-Release Fertilizer (AAPFCO)- A product containing sources of water soluble

nutrients, release of which in the soil is controlled by a coating applied to the
fertilizer.

Polymer-Coated Fertilizer (AAPFCO)-A coated slow-release fertilizer consisting of

fertilizer particles coated with a polymer (plastic) resin. It is a source of slowly available
plant nutrients.

Controlled-Release Fertilizers- Fertilizers in which one or more of the nutrients have

limited solubility in the soil solution, so that they become available to thea growing plant
over a controlled period.

Nitrogen Stabilizer (AAPFCO) - A substance added to a fertilizer to extend the time that
the nitrogen component of the fertilizer remains in the soil in the ammoniacal form.

Liquid Fertilizer A term used for fertilizers in suspension or solution and for liquefied
ammonia (ISO).

Solution Fertilizers (ISO) Liquid fertilizer free of solid particles.

Suspension Fertilizer (ISO) A two-phase fertilizer in which solid particles are

maintained in suspension in the aqueous phase.

Suspension Fertilizer (AAPFCO) A fluid containing dissolved and UN dissolved plant

nutrients. The suspension of the undissolved plant nutrients may be inherent with the
materials or produced with the aid of a suspending agent of non fertilizer properties.
Mechanical agitation may be necessary in some cases to facilitate uniform suspension of
undissolved plant nutrients.
Suspension Fertilizer A liquid (fluid) fertilizer containing solids held in suspension, for
example, by the addition of a small amount of clay. The solids may be water-soluble in a
saturated solution, or they may be insoluble, or both.

Slurry Fertilizer (AAPFCO)A fluid mixture that contains dissolved and undissolved
plant nutrient materials and requires continuous mechanical agitation to assure
homogeneity.

Powder A solid substance in the form of very fine particles. Powder is also referred to as
no granular fertilizer and is sometimes defined as a fertilizer containing fine particles,
usually with some upper limit such as 3 mm nut no lower limit.

Formula A term used in some countries to express, by numbers, in the order N-P-K
(nitrogen- phosphorus- potassium), the respective content of these nutrients in a compound
fertilizer.

Bulk Qualification given to a fertilizer or soil conditioner not packed in a container

(ISO).

Guarantee (of Composition) Quantitative and/ or qualitative characteristic with which

a market product must comply for contractual or legal requirements.

Declarable Content That content of an element (or an oxide) which, according to

national legislation, may be given on a label or document associated with a fertilizer or soil
conditioner.

Fertilizer unit The unit mass of a fertilizer nutrient (in the form of the element or an
oxide) generally 1 kg.

Plant Food Ratio The ratio of the numbers of fertilizer units in a given mass of fertilizer
expressed in the order N P K.

Fundamentals of Soil Phosphorus, Soil Potassium and Soil Sulfur:

Soil phosphorus

Phosphorus compound are important in energy transfer and storage reactions since electrons are
moved via adenosine di- and triphosphate in most biochemical reactions. Phosphorus is also a
constituent of nucleic acids, which make up genetic encoded strands of DNA and RNA used for
protein synthesis. Flowering, fruiting, seed formation, and early plant development therefore rely
heavily on P supplies, as do root development and several other processes. Even though the P
content of plant tissues is about 0.1% - 0.4%, which is about one-half of the amount of N or K, P
is a critical component of particular basic to life. Phosphorus is fairly mobile in plants and is
therefore moved to the youngest tissues of plants are P deficient.
The orthophosphate form H2PO4 predominates as the form of P taken up by plants although there
are also a few organic compounds that have been shown to be taken up directly plants. The
solubility of orthophosphate compounds in the soil solution may vary from 0.05 to 3 ppmw.

Unlike N, which is supplied as NO3- by mass flow of water to plant roots, only a fraction of the P
needed by plants is supplied by mass flow with soil water. Diffusion is a much more important
mechanism by which plant roots are supplied with P, and the amounts of P in solution and its
replenishment are determined by the dissolution of relatively insoluble P compounds or minerals.

Phosphorus fixation

When water-soluble sources of P are added to soils, the orthophosphate forms are converted to
many different compounds, depending on the above elements and soil pH. In soils of moderate
pH, Ca phosphate dominates, whereas Fe and Al compounds become more important in more
acidic soils.

These compounds then revert to even more stable or soluble compounds with time.
Various sorption reactions onto metal oxides; hydroxides, and carbonate mineral surfaces also
occur; these reactions are either reversible or relatively irreversible and affect phosphate
solubility and supply. These relatively irreversible reactions of phosphate are collectively called
P fixation and are very dependent on the chemical constituents of soils.

Soils that are of near neutral reaction and sandy texture have little fixation; next would come
other neutral soils with lower levels of soluble Fe and Al. soils with the highest fixation are
acidic, clayey soils high in Fe and Al. younger soils tend to have more available-P and lower
fixation capacity although some young volcanic soils have colloidal amorphous materials that fix
large amounts of P.

The response of crops to added water soluble phosphate fertilizers is very dependent on P
fixation capacity since the amount of P which is actually available depends on the P fixation
capacity.

Soil Potassium:

Potassium is considerably different than the other fertilizer nutrients, both in its function within
plants and in the way it becomes available to plants. Unlike most nutrients, K in plants does not
become part of structural components of plants nor elements of proteins, carbohydrates, etc., but
it remains as an ion, mainly in cellular liquids.

It functions to control turbidity of cells, helps in the transport mechanisms of starches and sugar,
acts in protein synthesis, and activates enzymes. It encourages root growth, makes plant stalks
healthy and strong, and is very important in reducing the effects of drought. Frequently, the most
important benefits of good K nutrition are not in yield but also from the reduction of fungal
disease and improved quality of harvested products.
Since K is very mobile in plants, deficiency symptoms are seen in older leaves first,
usually as yellowing or browning of the leaf margins, or in some crops as brown spots on the
older leaves. Deficiency symptoms are not as readily observable as those of N, even though K is
needed in almost the same amounts as N. overall slow growth, lodging(the plant falls over from
stalk weakness), and poor grain or fruit quality are often indicators in roots and grain
development and many other aspects of plant growth and development.

Losses of K through erosion of clays from the soil surface can be very substantial. Few
measurements of runoff loss have apparently been done, but these losses are certainly important.
Since K can be lost from soils and fixed in clay minerals, yearly additions of K are more efficient
than larger, infrequent applications on some soils although few crops respond to split
applications of K in the same season as they do to N.

Plants need large amounts of K, which is removed in harvested plant parts. Plant residues left in
the field can return some K back to the soil. Animal manures are important sources of K because
they often contain as much K as N. applied K salts, as KCl or K2SO4, give the same K response,
but in some cases the crops may respond to either the Cl or S carriers.

Soil sulfur

Sulfur is needed by plants in amount similar to those of P. It is an essential constituent of three

amino acids, in building blocks of proteins and enzymes. It cycles in the soil-plant-atmospheric
system similarly to N, with reduced sulfide forms (H2S, pyrites), oxidized sulfate dioxide and
organic sulfur compounds exist in the atmosphere. As with nitrogen, organic forms of S
comprise the major storehouse for soil S.

A notate difference between N and S is that gypsum (CaSo4 2H2O) a relatively insoluble mineral,
can form in soil to maintain S in more arid soils. Insoluble sulfates also form in wetter soils and
accumulate S in sub soils. Obviously the atmosphere does not contain S as it does N2.

Sulfur deficiencies in plants look similar and are often confused with those of N. Both
deficiencies are manifest as yellowing of the plant; yet, there are clear distinctions. Deficiencies
of S are seen in the younger leaves, whereas those of N are seen mainly in the older leaves.
Sulfur deficiencies result in small, spindly plants and severely reduced nodulation for BNF in
legumes. Seed and fruit maturation is also delayed.

Sulfur deficiencies can readily develop, particularly in humid areas and areas that do not receive
S from the atmosphere or from S containing fertilizers. Atmospheric sources of S are organic S
compounds emitted from marine plankton and inorganic S from oil and coal combustion.

Because enforcement of environmental laws and better technologies have reduced the amount of
S that soils receive through acid rain, this source has decreased. In addition, since higher analysis
fertilizer have largely replaced S containing single superphosphate and ammonium sulfate,
incidental contributions of S to soils are reduced.
 Sulfur deficiencies are therefore expected to increase and sulfate containing fertilizers will
probably be needed, particularly in moist tropical areas and especially for legume and vegetable
production.

Classifications of Soil nutrients and Fundamentals of Soil

Nitrogen:

Classifications of soil Nutrients:

Concentrations of various forms of nutrients are normally low in soils, but soils have the ability
to store nutrients in many organic and inorganic molecules. They are transformed to the soluble
plant available forms at rates defined by the environmental conditions for the biotic and
abiotic reactions, amounts of the different non available forms, their rates of conversion,
and removal of various nutrient forms from soil solution.

Thus, all of the plant nutrients have ionic forms that are plant available, and soils contain an
assortment of less available forms that became available to plants through chemical and
biological reactions.

The nutrients supplied from soil have been classified in different ways: by their
functions in plants, by whether they generally need to be added to soils to optimize growth,
or by their mobility in the plant.

For agricultural production, nutrients are classified by the quantities of the nutrients needed by
plants and whether they are normally present in sufficient quantities in soils to optimize the
growth of a crop.

Macronutrients:

The elements nitrogen (N), phosphorus (P), and potassium (K) are the nutrients that most
often limit crop growth, and they are called macronutrients. Since N, P, and K are the
nutrients most widely deficient in soils, they are also called the major, primary, or the
fertilizer nutrients.

Calcium, Mg, and S are called the secondary nutrients of the macronutrients
because they are not as widely deficient as N, P, and K.
Micronutrients:

Other elements that are needed by plants in much lower amounts than the macronutrients
are called micronutrients or trace elements. They are as essential to plant growth as the
macronutrients because they perform very essential and specific roles, particularly in
molecules involved with energy transfer process, hormones, and enzymes.
Fundamentals of N, P and K:

Soil factors that affect the plant availability of the primary or fertilizer nutrients (N, P and
K) are quite complex, and different from one another. The available forms, mechanisms of
becoming plant available, forms of stored nutrients in soils, and timing of plant uptake are
different not only between the nutrients but also for individual fertilizer sources of each
nutrient.

A basic understanding of the reaction of nutrients in soils and the factors that
affect the response of crops to fertilizers is essential for people in the fertilizer industry so
that they can make informed production and marketing decisions based on what can
increase the profit from using fertilizers.

Soil Nitrogen:

Nitrogen is a component of amino acids, which make up proteins, chlorophyll (the

molecule that captures the suns energy), enzymes, and the genetic material, nucleic acids.
Therefore, this nutrient is needed in large amounts by all plants.

Plants that do not have adequate N are yellowish, have yellowing and browning older leaves, are
stunted and have poor root systems. Without additions of N, the nutrients are practically
uniformly deficient for all grasses and cultivated crops.

The only exceptions are leguminous crops that have symbiotic bacterial colonies growing within
the plant, which have the ability to meet N needs through fixation of atmospheric N 2 Excess N
can cause excessive vegetative growth, delayed maturity, and stalk breakage in small grains. The
other macronutrients do not have direct detrimental effects when applied to excess.

The availability of N to plants is largely controlled by soil microbial processes. The N cycle
in soils is complex, and under certain conditions large amounts of plant available N can be
lost from the soil in drainage water or to the atmosphere.

In this way, N is different from the other nutrients, which are not as readily lost from soils. The
rates of conversion between forms of N and the direction (immobilization and mineralization)
depend principally on the growth conditions of the microorganisms, i.e., temperature, moisture,
oxygen availability and composition of organic substrates etc, rather than simply abiotic
reactions.

Nitrogen uptake depends on the relatively small amount of available N forms in soil
solution the soils ability to replenish the available forms, and the growth conditions for the
plant. Of course, any condition that inhibits plant growth such as other nutrient deficiencies,
poor rooting conditions, poor weather, etc., will reduces N uptake.

Nitrate (NO3-) is the main form of N available to upland crops, whereas ammonium (NH4+)
is the main form taken up by plants growing under flooded conditions, notably rice. Nitrate
moves through soils with the soil water, since soils have little anion-absorbing capacity.
Therefore, NO3- can move with water to plant roots for uptake. Nitrate is also eligible for
leaching into groundwater. To reduce NO3- pollution, it is therefore important that the
amount of NO3- stored in the soil be minimized during periods in which water percolates
through the soil. Fertilizer N applications can be made more efficient by applying the N
before it is needed by the crop.

Nitrate-N is also subject to loss from the soil through microbial processes when soils
become highly anaerobic due to water saturation, which inhibits oxygen movement. When
soils become anaerobic, certain microbes use NO3- as a terminal election acceptor, and the
NO3- is converted to N2 and N2o, forms of N that cannot be used by plants.

This loss of plant available N, called de nitrification, therefore precludes NO3- use in flooded
rice culture. When soils are flooded to grow rice, the NO3- accumulated from organic matter
transformations during the period of dry season fallow is lost through de nitrification.

Upland soils, which become very wet for a week or more because of poor internal drainage
or weather conditions, can lose NO3- through de nitrification, particularly if there is readily
degradable organic material in the soil. The organic material causes O2 to be consumed
more rapidly and provides growth substances for the de nitrification organisms.

Ammonium N is a plant available from in addition to NO3-, but in normal upland soils it is
converted fairly rapidly to NO3- by a series of microbial reactions collectively called
nitrification. Most NH4+ fertilizers are converted to NO3- within a few weeks, but this
period can vary with soil temperature, moisture, O2 availability, soil pH, and the manner in
which NH4+ or NH3 was applied.

Soils of less than 5.0 nitrify more slowly than more neutral soils. Concentrated zones of NH4+
can also reduce the rate of its conversion to NO3- As a cation, NH4+ can be absorbed onto cation
exchange sites and is therefore normally not subject to leaching as is NO3-. In addition, NH4+
can move into the interior of clay lattice structures and be protected from nitrification or plant
uptake; this is called ammonium fixation.

Nitrogenous fertilizers:

Ammonia: Production and Storage:

Ammonia or azane is a compound of nitrogen and hydrogen with the formula NH 3. It is a

colourless gas with a characteristic pungent smell. Ammonia contributes significantly to the
nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers.

Ammonia, either directly or indirectly, is also a building-block for the synthesis of many
fertilizers, pharmaceuticals and is used in many commercial cleaning products. Although in
wide use, ammonia is both caustic and hazardous.

Ammonia, as used commercially, is often called anhydrous ammonia. This term

emphasizes the absence of water in the material. Because NH3 boils at 33.34 C (28.012
F) at a pressure of 1 atmosphere, the liquid must be stored under high pressure or at low
temperature.

Household ammonia or ammonium hydroxide is a solution of NH 3 in water. The

concentration of such solutions is measured in units of the Baum scale (density), with 26
degrees baum (about 30% w/w ammonia at 15.5 C) being the typical high-concentration
commercial product. Household ammonia ranges in concentration from 5 to 10 weight percent
ammonia.

Physical properties of ammonia:

Ammonia has flammable limits of 16%-25% by volume in the air and 15%-79% in oxygen.
Ammonia air mixtures is 650 Celsius. The mixture can explode if ignited. Ammonia is
readily soluble in water. A large amount of heat, about 2180kj (520kcal), is produced when
the dissolution of 1kg of ammonia gas occurs.

Physical properties of anhydrous Ammonia:

Density of Ammonia at 15c:

Production of Ammonia:

Ammonia synthesis
Ammonia is synthesised from hydrogen (from natural gas) and nitrogen (from the air).
Natural gas contains some sulfurous compounds which damage the catalysts used in this
process. These are removed by reacting them with zinc oxide, e.g.

ZnO + H2S ZnS + H2O

The methane from the natural gas is then converted to hydrogen:

CH4 +H2O 3H2 + CO
CH4 + 2H2O 4H2 + CO2
CO + H2O H2 + CO2
Air is mixed in with the gas stream to give a hydrogen: nitrogen ratio of 3:1.
Water, carbon monoxide and carbon dioxide (all of which poison the iron catalyst used in
the ammonia synthesis) are removed. The carbon monoxide is converted to carbon
dioxide for use in urea production, and the carbon dioxide removed:

CO + H2O CO2 + H2

The remaining traces of CO and CO2 are converted to methane and then the gases cooled
until the water becomes liquid and can be easily removed.

The nitrogen and hydrogen are then reacted at high temperature and pressure using an iron
catalyst to form ammonia:
N2 + 3H2 2NH3

THE AMMONIA MANUFACTURING PROCESS:

Ammonia is produced in a process known as the Haber process, in which nitrogen and
hydrogen react in the presence of an iron catalyst to form ammonia. The hydrogen is formed
by reacting natural gas and steam at high temperatures and the nitrogen is supplied from the
air.
. Other gases (such as water and carbon dioxide) are removed from the gas stream and
the nitrogen and hydrogen passed over an iron catalyst at high temperature and pressure to
form the ammonia. The process is shown schematically in Figure 1.
Fig.1- schematic diagram for production of ammonia
 production, for storage or for direct sale.

Associated gas :

Associated petroleum gas (APG), or associated gas, is a form of natural gas which is found with
deposits of petroleum, either dissolved in the oil or as a free "gas cap" above the oil in the
reservoir. Historically, this type of gas was released as a waste product from the petroleum
extraction industry. Due to the remote location of many oil fields, either at sea or on land, this gas is
simply burnt off in gas flares. When this occurs the gas is referred to as flare gas.

The gas can be utilized in a number of ways after processing: be sold and included in the natural
gas distribution networks, used for on-site electricity generation with engines or turbines, re injected
for enhanced oil recovery, or used as feedstock for the petrochemical industry.

Associated gas composition:

Coke oven gas:
a combustible gas; one of the products of coking. Its approximate composition (in perce
nt by volume) is as follows: H2, 5560; CH4, 2030;CO, 57; CO2, 2
3; N2, 4; unsaturated hydrocarbons, 23; O2, 0.4
0.8. Density at 0C and 760 millimeters of mercury (mm Hg), or 105kilonewtons per sq
m (kN/m2), 0.45
0.50 kg/m3; heat of combustion (lower limit), 17.5 megajoules per eu m (MJ/m3), or 4,00
04,500kcal/m3; heat capacity, 1.35 kJ/(m3.K); ignition temperature, 600
650C. Coke-oven gas is toxic and explosive; its explosiveconcentration in air is 6
30 percent. The yield of gas is about 300 cu m per ton of dry charge. Coke-
oven gas is used as a fuel and as rawmaterial for the synthesis of ammonia.
During the carbonization of coking coal in a coke oven battery for the production of coke, around 25-30%
of the coal charged is driven off as effluent gases rich in volatile matter and moisture. This gas is known
as coke oven gas (CO gas). In the non recovery or heat recovery coke ovens this gas is burnt in the oven
itself and provides the required heat for the carbonization of coal. In case of by product battery, the
evolved gas is removed as raw gas and is treated in a byproduct plant to give a clean fuel gas. In the
byproduct plant, condensable, corrosive and economically valuable components are removed. During the
cycle of coking, the gas is produced during majority of the coking period. The composition and rate of
evolution of the CO gas changes during the period and the evolution of CO gas is normally complete by
the time the coal charge in the battery reaches 700 deg C. The final yield of clean coke oven gas after
treatment in the byproduct plant is around 300 N Cum per ton of dry coal. The yield of gas is dependent
upon i) volatile matter in the charge coal and ii) carbonization condition. The density of CO gas at
standard temperature and pressure is 0.545 Kg/Cum.
The raw CO gas may contain hydrogen and methane, ammonia, carbon monoxide, carbon dioxide,
ethane, ethylene, benzene, oxygen and nitrogen, hydrogen sulfide, water vapor, cyclopentadiene,
toluene, naphthalene, hydrogen cyanide, cyanogen, and nitric oxide.

Typical Analysis of Coke Oven Gas:

COAL CARBONIZATION AND COKE OVEN

PLANT:

Coal carbonization is used for processing of coal to produce coke using metallurgical grade coal.
Coal carbonization involves heating of coal in the absence of air. Coke making process is
multistep complex process and variety of solid liquids and gaseous products are produced which
contain many valuable products. Various products from coal carbonization in addition to coke
are coke oven gases. coal tar, light oil, and aqueous solution of ammonia and ammonia salt.
Coke oven gases are about 310-340 cum per tone of dry coal which contains gaseous products,
coal tar vapours, light oil and water.

Carbonization can be carried out at low temperature or high temperature. Low temperature
carbonization is used to produce liquid fuels while high temperature carbonization is used to
produce gaseous products.

Low temperature carbonization (450-750oC): In low temperature carbonization quantity of

gaseous product is less while liquid products are large.

High temperature carbonization (above 900oC): In high temperature carbonization, the yield
of gaseous product is more than liquid products with production of tar relatively low.

Coke Oven Plant: various section of coke oven plant are given below-
Coking Coals: Blast furnace requires coke of uniform size, high mechanical strength, and
porosity with minimum volatile matter and minimum ash. Coking coal may be dived I on the
basis of their coking properties: prime coking coal, medium coking coal, semi coking coal. The
prime coking coal produce strong metallurgical coke while coals of other groups yield hard coke
only the concentration of moisture ash, sulphur and sometime phosphorous and ash fusion
temperature are important in determining the grade of coking coal since they influence the
quality of coke produced. Low moisture, ash, sulphur and phosphorous content in the coal are
desirable for production of good quality coke. The desired analysis of typical coal charge to coke
oven is.

Ash content : 16% 0.5%

Moisture : 6-7%
Volatile matter : 22-25%
Fixed carbon : 58-60%%
Sulphur : 0.56%
Phosphorous : 0.09%

Some of the other factors affecting quality of coke are rank of coal, particle size, bulk density,
weathering of coal, coking temperature and coking rate, soaking time, quenching practice.
By-product from Coke Oven Plant:

The high temperature carbonization is used for production of coke for use in blast furnace.
Various by-products obtained from coal carbonization are crude tar, crude benzoyl, and
ammonia. Typical yield of some important byproduct are: Tar 3.2%, ammonium sulphate 1.1%,
crude benzoyl 0.9%.

Gas Condensation section: Coke oven gas containing water vapors and chemical products of
coking (tar, ammonia, benzoyl etc. at temperature about 750-800oC from the coke oven plant is
cooled to temperature of 80-82oC. During gas cooling 65-70% of the tar is condensed. Further
cooling of gas, the water vapors and the remaining part of the target condensed along with some
ammonia and other chemicals.
Fuel oil:

Fuel oil is a fraction obtained from petroleum distillation, either as a distillate or a residue. Broadly
speaking fuel oil is any liquid petroleum product that is burned in a furnace or boiler for the
generation of heat or used in an engine for the generation of power, except oils having a flash
point of approximately 40 C (104 F) and oils burned in cotton or wool-wick burners. In this
sense, diesel is a type of fuel oil. Fuel oil is made of long hydrocarbon chains,
particularly alkanes, cycloalkanes and aromatics. The term fuel oil is also used in a stricter sense to
refer only to the heaviest commercial fuel that can be obtained from crude oil, i.e., heavier
than gasoline and naphtha.
Naphtha :

Naphtha is the name for a number of intermediary products that occur when refining crude oil. They
are liquid hydrocarbons. They are used to produce high octane gasoline products. The
petrochemical industry also uses them to make olefins and solvents.

Typical naphthas are used for:

Solvents in cleaning fluid

As an ingredient of Shoe polish
As an ingredient for some of the fuels used in lighters
Possibly one of the things in Greek fire.

Lignite :

It is often referred as brown coal, is a soft brown combustible sedimentary rock that is formed
from naturally compressed peat. It is considered the lowest rank of coal due to its relatively low
heat content.

Characteristics:

Lignite is brownish-black in color and has a carbon content of around 25-35%, a high inherent
moisture content sometimes as high as 66%, and an ash content ranging from 6% to 19% compared
with 6% to 12% for bituminous coal.

The energy content of lignite ranges from 10 20 MJ/kg (917 million BTU per short ton) on a moist,
mineral-matter-free basis. The energy content of lignite consumed in the United States averages 15
MJ/kg (13 million BTU/ton), on the as-received basis (i.e., containing both inherent moisture and
mineral matter).

Lignite has a high content of volatile matter which makes it easier to convert into gas and liquid
petroleum products than higher ranking coals. Unfortunately its high moisture content and
susceptibility to spontaneous combustion can cause problems in transportation and storage. It is
now known that efficient processes that remove latent moisture locked within the structure of brown
coal will relegate the risk of spontaneous combustion to the same level as black coal, will transform
the calorific value of brown coal to a black coal equivalent fuel while significantly reducing the
emissions profile of 'densified' brown coal to a level similar to or better than most black coals.

Coke:
Coke is a fuel with few impurities and a high carbon content, usually made from coal. It is the
solid carbonaceous material derived from destructive distillation of low-ash, low-sulfur bituminous
coal. Cokes made from coal are grey, hard, and porous. While coke can be formed naturally, the
commonly used form is man-made. The form known as petroleum coke, or pet coke, is derived from
oil refinery coker units or other cracking processes.

Properties:
The bulk specific gravity of coke is typically around 0.77. It is highly porous.

The most important properties of coke are ash and sulfur content, which are linearly dependent on
the coal used for production. Coke with less ash and sulfur content is highly priced on the market.
Other important characteristics are the M10, M25, and M40 test crush indexes, which convey the
strength of coke during transportation into the blast furnaces; depending on blast furnaces size,
finely crushed coke pieces must not be allowed into the blast furnaces because they would impede
the flow of gas through the charge of iron and coke. A related characteristic is the Coke Strength
After Reaction (CSR) index; it represents coke's ability to withstand the violent conditions inside the
blast furnace before turning into fine particles.

The water content in coke is practically zero at the end of the coking process, but it is often water
quenched so that it can be transported to the blast furnaces. The porous structure of coke absorbs
some water, usually 3-6% of its mass. In more modern coke plants an advanced method of coke
cooling uses air quenching.

Uses:
Coke is used as a fuel and as a reducing agent in smelting iron ore in a blast furnace. The carbon
monoxide produced by its combustion reduces iron oxide (hematite) in the production of
the iron product.

Since smoke-producing constituents are driven off during the coking of coal, coke forms a desirable
fuel for stoves and furnaces in which conditions are not suitable for the complete burning
of bituminous coal itself. Coke may be combusted producing little or no smoke, while bituminous
coal would produce much smoke.

Ammonium sulphate:
Ammonium sulfate, (NH)SO, is an inorganic salt with a number of commercial uses. The most common
use is as a soil fertilizer. It contains 21% nitrogen and 24% sulfur.

Formula: (NH4)2SO4
Molar mass: 132.14 g/mol
Melting point: 235 C
Density: 1.77 g/cm
IUPAC ID: Diazanium sulfate
Soluble in: Water
Classification: Sulfates

The majority of its production is coming from coking of coal as a byproduct. Ammonium
sulphate is produced by the direct reaction of concentrated sulphuric acid and gaseous ammonia
and proceeds according to the following steps.

1. Reaction of Ammonia and Sulphuric Acid:

Liquid ammonia is evaporated in an evaporator using 16 bar steam and preheated using
low pressure steam.
The stiochiometric quantities of preheated gaseous ammonia and concentrated sulphuric
acid (98.5% wt/wt) are introduced to the evaporator crystallizer (operating under
vacuum). These quantities are maintained by a flow recorder controller and properly
mixed by a circulating pump (from upper part of the crystallizer to the evaporator).

2. Crystallization
The reaction takes place in the crystallizer where the generated heat of reaction causes
evaporation of water making the solution supersaturated. The supersaturated solution
settles down to the bottom of crystallizer where it is pumped to vacuum metallic filter
where the Ammonia & Sulphuric crystals are separated, while the mother liquor is recycled to
the crystallizer.

3. Drying of the wet Ammonium Sulphate Crystals

The wet A.S crystals are conveyed (by belt conveyors) to the rotary dryer to be dried
against hot air (steam heated) and then conveyed to the storage area where it naturally
cooled and bagged.

The following presents the process block diagram for ammonium sulphate production.
Uses:

The primary use of ammonium sulfate is as a fertilizer for alkaline soils. In the soil the ammonium ion
is released and forms a small amount of acid, lowering the pH balance of the soil, while contributing
essential nitrogen for plant growth. The main disadvantage to the use of ammonium sulfate is its low
nitrogen content relative to ammonium nitrate, which elevates transportation costs.

It is also used as an agricultural spray adjuvant for water soluble insecticides, herbicides,
and fungicides. There, it functions to bind iron and calcium cations that are present in both well water
and plant cells. It is particularly effective as an adjuvant for 2,4-D (amine), glyphosate, and
glufosinate herbicides.

Ammonium nitrate:
The chemical compound ammonium nitrate, the nitrate salt of ammonium, has the chemical formula
NHNO, simplified to NHO. It is a white crystalline solid which is highly soluble in water.

Formula: (NH4)(NO3)
Molar mass: 80.052 g/mol
Density: 1.73 g/cm
Melting point: 169.6 C
Boiling point: 210 C
IUPAC ID: Ammonium nitrate
Soluble in: Water

The chemical compound ammonium nitrate, the nitrate salt of ammonium, has the chemical
formula NH4NO3, simplified to N2H4O3. It is a white crystalline solid which is highly soluble in water. It
is predominantly used in agriculture as a high-nitrogen fertilizer. The compound is used
as explosives in mining, and also sometimes in improvised explosive devices. It is the main
component of ANFO, a popular explosive, which accounts for 80% explosives used in North
America. It is used in instant cold packs, as hydrating the salt is an endothermic process.

Ammonium nitrate is an important fertilizer with the NPK rating 34-0-0 (34% nitrogen). It is less
concentrated than urea (46-0-0), giving ammonium nitrate a slight transportation disadvantage.
Ammonium nitrate's advantage over urea is that it is more stable and does not lose nitrogen to the
atmosphere. During warm weather it is best to apply urea soon before rain is expected to minimize
nitrogen loss.

The main advantages of ammonium nitrate are as follows:

It is quite hygroscopic;
There is some risk of fire or even explosions unless suitable precautions are taken;
It is less effective for flooded rice than urea or ammoniacal nitrozen fertilizers;
It is more prone to leaching immediately after application than ammoniacal products.

Production :
The production process comprises three main unit operations: neutralization, evaporation,
solidification (prilling and granulation).

Neutralization:
Anhydrous liquid ammonia is evaporated in an evaporator using cooling water. The
stoichiometic quantities of nitric acid (55% concentration wt/ wt) and gaseous ammonia
are introduced by an automatic ratio controller to a neutralizer. The reaction between
Ammonia and nitric acid produces ammonium nitrate solution according to the following
exothermic reaction.
Neutralization can be performed in a single stage or in two stages. The neutralizer can be
carried out at atmospheric (either normal or low emission neutralizers where the
temperature does not exceed 105C and pH will be 6 and 3 respectively) or at elevated
pressure of almost 4 atmospheres. The normal neutralizers are usually followed by flash
evaporation in order to increase the out let A.N concentration to 70%. In case of pressure
neutralizers the temperature will be in the range of 178C and the steam generated from
the heat of reaction will be utilized in the subsequent step namely concentration of A.N
solution.

During evaporation some ammonia is lost from the solution. The steam which is boiled
off is contaminated. The control of the neutralizer is important. The pH and the
temperature must both be strictly controlled to limit the losses from the neutralizer. All
installations must include pH and temperature controls. At the operating temperature of
the neutralizer, impurity control is of great importance because a safety incident will also
be a significant environmental incident. The ammonium nitrate solution from neutralizer
may be fed to storage without further processing but, if it is used in the manufacture of
solid ammonium nitrate, it is concentrated by evaporation.

1. Evaporation to Concentrate the A.N

The outlet from the neutralizer is received in an intermediate tank. The solution should be
made alkaline before being pumped (no need for pumps in case of pressure neutralizers
since the pressure will maintain the flow) to the evaporation section (multi-effect)
running under vacuum. The solution will be steam heated in the multi effect evaporation
section. The solution will be concentrated up to 97.5-99.5% (normally over 99 %)
depending on whether ammonium nitrate will be granulated or prilled.

2. Mixing the Filling Material:

In order to reduce the nitrogen content of A.N from 35% to 33.5%, the proper filling
material is added (about 4% by weight of powdered limestone or dolomite or even kaolin).

3. Prilling or Granulation
The hot concentrated melt is either granulated (fluidize bed granulation, drum granulation
etc) or prilled. Ammonium nitrate is formed into droplets which then fall down a fall
tower (prill tower) where they cool and solidify. Granulation requires more complicated
plant than prilling and variety of equipment. The main advantage of granulation with
respect of environment is that the quantity of air to be treated is much smaller and
abatement equipment is cheaper.

4. Drying, Screening
The ammonium nitrate (prills or granules) is dried (usually in drums) using hot air (steam
heated), then screened to separate the correct product size. The oversize and undersize
will be recycled either in the mixing tank (in case of prilling) or to the granulator.
5 Final Cooling
The hot proper size granules, are then cooled (against cooled and humid free air) down to
40C and treated with anti-caking (usually amines) and then coated with an inert material
(usually, kaolin, limestone or dolomite) and then conveyed to the storage.

Ammonium nitrate can also be made via metathesis reactions:

(NH4)2SO4 + 2 NaNO3 2 NH4NO3 + Na2SO4
(NH4)2SO4 + Ca(NO3)2 2 NH4NO3 + CaSO4

Sodium sulfate is removed by lowering the temperature of the mixture. Since sodium sulfate is much
less water-soluble than ammonium nitrate, it precipitates, and may be filtered off. For the reaction
with calcium nitrate, the calcium sulfate generated is quite insoluble, even at room temperature.

Urea:

Urea is in many ways the most convenient form for fixed nitrogen. It has the highest nitrogen content
available in a solid fertilizer (46 %).It is easy to produce as prills or granules and easily transported in

bulk or bags with no explosive hazard. It leaves no salt residue after use on crops. Its specific gravity
is 1.335, decomposes on boiling and is fairly soluble in water.

The principal raw materials required for this purpose are NH3 & CO2.Two reactions are

involved in the manufacture of urea. First, ammonium carbamate is formed under pressure by

reaction between CO2 & NH3.

CO2 + 2NH3 NH2COONH4 H= -37.4 Kcal

This highly exothermic reaction is followed by an endothermic decomposition of the

ammonium carbamate.

NH2COONH4 NH2CONH2 + H2O H= + 6.3 Kcal

Uses of Urea:

About 56 % of Urea manufactured is used in solid fertilizer.

About 31 % of Urea manufactured is used in liquid fertilizer.

Urea-formaldehyde resins have large use as a plywood adhesive.

Melamine-formaldehyde resins are used as dinnerware & for making extra hard surfaces.

PROPERTIES OF UREA:
PHYSICAL PROPERTIES OF UREA: Urea is a white, odorless, hygroscopic solid. It is non-
corrosive.

CHEMICAL PROPERTIES OF UREA:

Molecular weight 60.05

Relative humidity 60 %

Maximum Nitrogen content 46.6 %

Specific gravity 1.335

Heat of fusion 60 Cal/gm (endothermic)

Heat of solution, in water 58 Cal/gm (endothermic)

Bulk density 0.74 gm/cc

PROCESS TECHNOLOGY:

Urea is made from ammonia and carbon dioxide. The ammonia and carbon dioxide are fed into the reactor at high

pressure and temperature, and the urea is formed in a two step reaction

2NH3 + CO2 NH2COONH4 (ammonium carbamate)

NH2COONH4 H2O + NH2CONH2 (urea)

The urea contains unreacted NH3 and CO2 and ammonium carbamate. As the pressure is reduced and heat applied

the NH2COONH4 decomposes to NH3 and CO2. The ammonia and carbon dioxide are recycled. The urea solution is

then concentrated to give 99.6% w/w molten urea, and granulated for use as fertilizer and chemical feedstock.

Step 1 - Synthesis

A mixture of compressed CO2 and ammonia at 240 bar is reacted to form ammonium carbamate. This is an
exothermic reaction, and heat is recovered by a boiler which produces steam. The first reactor achieves 78%

conversion of the carbon dioxide to urea and the liquid is then purified. The second reactor receives the gas
from the first reactor and recycle solution from the decomposition and concentration sections.
Conversion of carbon dioxide to urea is approximately 60% at a pressure of 50 bar. The solution
is then purified in the same process as was used for the liquid from the first reactor.
 Fig. schematic representation of urea synthesis
Step 2 - Purification
The major impurities in the mixture at this stage are water from the urea production reaction
and unconsumed reactants (ammonia, carbon dioxide and ammonium carbamate). The
unconsumed reactants are removed in three stages 3. Firstly, the pressure is reduced from 240
to 17 bar and the solution is heated, which causes the ammonium carbamate to decompose
to ammonia and carbon dioxide:
NH2COONH4 2NH3 + CO2
At the same time, some of the ammonia and carbon dioxide flash off. The pressure is then
reduced to 2.0 bar and finally to -0.35 bar, with more ammonia and carbon dioxide being
lost at each stage. By the time the mixture is at -0.35 bar a solution of urea dissolved in
water and free of other impurities remains.
At each stage the unconsumed reactants are absorbed into a water solution which is recycled
to the secondary reactor. The excess ammonia is purified and used as feedstock to the
primary reactor.

Step 3 - Concentration
75% of the urea solution is heated under vacuum, which evaporates off some of the water,
increasing the urea concentration from 68% w/w to 80% w/w. At this stage some urea
crystals also form. The solution is then heated from 80 to 110 oC to re dissolve these crystals
prior to evaporation. In the evaporation stage molten urea (99% w/w) is produced at 140 oC.
The remaining 25% of the 68% w/w urea solution is processed under vacuum at 135 oC in a
two series evaporator-separator arrangement.
Step 4 - Granulation
Urea is sold for fertilizer as 2 - 4 mm diameter granules. These granules are formed by
spraying molten urea onto seed granules which are supported on a bed of air. This occurs in
a granulator which receives the seed granules at one end and discharges enlarged granules at
the other as molten urea is sprayed through nozzles. Dry, cool granules are classified using
screens. Oversized granules are crushed and combined with undersized ones for use as seed.
All dust and air from the granulator is removed by a fan into a dust scrubber, which removes
the urea with a water solution then discharges the air to the atmosphere. The final product is
cooled in air, weighed and conveyed to bulk storage ready for sale.

Calcium ammonium nitrate:

Calcium ammonium nitrate or CAN, also known as nitro-limestone, is a widely used

inorganic fertilizer, accounting for 4% of all nitrogen fertilizer.

Physical & chemical properties:

Calcium ammonium nitrate is hygroscopic. Its dissolution in water is endothermic, leading to its use
in some instant cold packs.

Use :

Most calcium ammonium nitrate is used as a chemical fertilizer. Fertilizer grade CAN contains
roughly 8% calcium and 21-27% nitrogen. CAN is preferred for use on acid soils,as it acidifies soil
less than many common nitrogen fertilizers It is also used in place of ammonium nitrate where
ammonium nitrate is banned.

Calcium ammonium nitrate is used in some instant cold packs as an alternative to ammonium
nitrate.

Calcium ammonium nitrate has seen increasing use in improvised explosives.

Production :
Calcium ammonium nitrate is made by adding calcium carbonate to a slurry of nitrate, resulting in a
mixture of calcium nitrate and residual ammonium nitrate. It crystallizes as a hydrated double salt:
5Ca(NO3)2NH4NO310H2O.

Calcium ammonium nitrate, often abbreviated CAN, is a fertilizer which is a blend of

about 20%-30% CaCO3 and 70%-80% Ammonium nitrate. CAN is produced by mixing
concentrated ammonium nitrate solution with ground calcite or dolomite limestone, chalk
marl, or precipitated calcium carbonate from nitro phosphate production. The mixing should
be done quickly to avoid decomposition of the ammonium nitrate:

2NH4NO3 +CaCO3 Ca(NO3)2 + 2NH3 + CO2 + H2O

Ammonium chloride:

Ammonium chloride, an inorganic compound with the formula NH4Cl, is a white crystalline salt,
highly soluble in water. Solutions of ammonium chloride are mildly acidic. Sal ammoniac is a name
of the natural, mineralogical form of ammonium chloride. The mineral is commonly formed on
burning coal dumps, due to condensation of coal-derived gases. It is also found around some types
of volcanic vents. It is used as a flavoring agent in some types of liquor ice. It is the product from the
reaction of hydrochloric acid and ammonia.

Formula: NH4Cl
Molar mass: 53.491 g/mol
IUPAC ID: Ammonium chloride
Melting point: 338 C
Density: 1.53 g/cm
Soluble in: Water

Sources:
It is a product of the Solvay process used to produce sodium carbonate.
CO2 + 2 NH3 + 2 NaCl + H2O 2 NH4Cl + Na2CO3

In addition to being the principal method for the manufacture of ammonium chloride, this method is
used to minimize ammonia release in some industrial operations. Ammonium chloride is prepared
commercially by combining ammonia (NH3) with either hydrogen chloride (gas) or hydrochloric
acid (water solution)
NH3 + HCl NH4Cl

Ammonium chloride occurs naturally in volcanic regions, forming on volcanic rocks near fume-
releasing vents (fumaroles). The crystals deposit directly from the gaseous state, and tend to be
short-lived, as they dissolve easily in water.

Reactions:
Ammonium chloride appears to sublime upon heating. However, this process is
actually decomposition into ammonia and hydrogen chloride gas.
NH4Cl NH3 + HCl

Ammonium chloride reacts with a strong base, e.g. sodium hydroxide, to release ammonia gas:
NH4Cl + NaOH NH3 + NaCl + H2O

Similarly, ammonium chloride also reacts with alkali metal carbonates at elevated temperatures,
giving ammonia and alkali metal chloride:
2 NH4Cl + Na2CO3 2 NaCl + CO2 + H2O + 2 NH3

A 5% by weight solution of ammonium chloride in water has a pH in the range 4.6 to 6.0.
Some of ammonium chloride's reactions with other chemicals are endothermic, for example its
reaction with barium hydroxide, and its dissolving in water.

Production methods:
Several methods for producing ammonium chloride are used: the order of importance is follows:

1. The dual-salt process, whereby ammonium chloride and sodium carbonate are
produced simultaneously.

2. Direct neutralization of ammonia with hydrochloric acid.

The sodium bicarbonate is separated by centrifuging or filtration and calcined to produce sodium
carbonate and CO2; the latter is recycled to the system.

The Direct-neutralization Method- Ammonium chloride of high purity can be made by

the direct reaction between anhydrous ammonia vapor and hydrochloric acid gas, according
to the reaction.

The reaction is exothermic (42,000cal/g-mole). In most cases, neutralization is undertaken

at reduced pressures of 250-300mm of mercury in one or more rubber-lined steel vacuum
reaction vessels protected with an additional inner lining of inert brick. Concentrated
hydrochloric acid gas is passed through an aspirator, wherein it is diluted with air to about
20% concentration and enters the reaction vessel via a vertical sparser tube. According to
preference, ammonia gas is introduced either by a second sparser or by tangential nozzles
in the base of the reaction vessel. Agitation is provided by the large volume of air entering
the reactor with the hydrochloric acid vapor; thus, the need for a mechanical agitator with
its additional power requirements and maintenance problems is avoided.

Similarly, operation under vacuum not only provides excellent cooling but simultaneously
prevents escape of noxious vapors and eliminates the need for hydrochloric acid-vapor
blowers, plus their attendant cost and maintenance charges. A reduced pressure of 250-
330mm of mercury and a corresponding slurry temperature of 75-80C represent typical
operating conditions.

Mother liquor the centrifuge is pumped back to the saturator(s) via a storage tank. Saturator
off gases must be well scrubbed before entering the vacuum pump or ejector unit to prevent
corrosio0n and to eliminate air pollution. A two-stage scrubbing system is usually
employed and may consist of a direct, barometric scrubber condenser followed by a wetted,
packed tower. Liquor from the scrubber-condenser is returned to the mother liquor tank and
is evaporated in the saturator, thus providing a means of temperature control and recovery.

As with other processes involving reactions between hydrochloric acid (or chlorides) and
ammonia, traces of free chlorine in the acid feed can lead to disastrous explosions caused
by the formation of nitrogen tri chloride in the saturator. Hence, adequate safety precautions
must be installed whereby the HCl gas feed is monitored and the flow discontinued when
chlorine is detected. This can be accomplished by such means as bypassing a small stream
of gas through a photocell- calorimeter unit containing potassium iodide or using a modern
continuous gas analyzer of the absorption or chromatographic type.

After separation and drying, the crystalline ammonium chloride is bagged as quickly as
possible to minimize subsequent storage and application difficulties.

Applications:

Ammonium chloride is used as a flux in preparing metals to be tin coated, galvanized or soldered. It
works as a flux by cleaning the surface of work pieces by reacting with the metal oxides at the
surface to form a volatile metal chloride. For this purpose, it is sold in blocks at hardware stores for
use in cleaning the tip of a soldering iron and can also be included in solder as flux.

Ammonium chloride is used as an expectorant in cough medicine. Its expectorant action is caused
by irritative action on the bronchial mucosa. This causes the production of excess respiratory tract
fluid which presumably is easier to cough up. Ammonium salts are an irritant to the gastric mucosa
and may induce nausea and vomiting.

Ammonium chloride is used as a systemic acidifying agent in treatment of severe

metabolic alkalosis, in oral acid loading test to diagnose distal renal tubular acidosis, to maintain
the urine at an acid pH in the treatment of some urinary-tract disorders.
Ammonium chloride is used in a ~5% aqueous solution to work on oil wells with clay swelling
problems. It is also used as electrolyte in zinccarbon batteries. Other uses include in hair shampoo,
in the glue that bonds plywood, and in cleaning products. In hair shampoo, it is used as a thickening
agent in ammonium-based surfactant systems, such as ammonium lauryl sulfate. Ammonium
chloride is used in the textile and leather industry in dyeing, tanning, textile printing and to luster
cotton.

Ammonium chloride is used to spice up dark sweets called salty liquorice, in baking to give cookies
a very crisp texture, and in the vodka Salmiakki Koskenkorva for flavoring. In India and Pakistan, it is
called "Noshader" and is used to improve the crispness of snacks such as samosas and jalebi.

Phosphatic fertilizers:
The raw materials required for production of phosphatic fertilizer are phosphate rock, sulphur
and pyrites.

Phosphate rock:

Phosphorite, phosphate rock or rock phosphate is a non-detrital sedimentary rock which contains
high amounts of phosphate bearing minerals. The phosphate content of phosphorite is at least 15 to
20%, which is a large enrichment over the typical sedimentary rock content of less than 0.2%. The
phosphate is present as fluorapatite Ca5(PO4)3F (CFA) typically in cryptocrystalline masses (grain
sizes < 1 m) referred to as collophane. It is also present as hydroxyapatite Ca5(PO4)3OH or
Ca10(PO4)6(OH)2, which is often dissolved from vertebrate bones and teeth, whereas fluorapatite can
originate from hydrothermal veins. Other sources also include chemically dissolved phosphate
minerals from igneous and metamorphic rocks. Phosphorite deposits often occur in extensive layers,
which cumulatively cover tens of thousands of square kilometres of the Earth's crust.

Sulphur:
Sulfur or sulphur is a chemical element with symbol S and atomic number 16. It is
an abundant,multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic
molecules with chemical formula S8. Elemental sulfur is a bright yellow crystalline solid when at room
temperature. Chemically, sulfur can react as either an oxidant or a reducing agent.
It oxidizes most metals and several nonmetals, including carbon, which leads to its negative charge
in most organosulfur compounds, but it reduces several strong oxidants, such
as oxygen and fluorine.

Elemental sulfur is mainly used as a precursor to other chemicals. Approximately 85% is converted
to sulfuric acid (H2SO4):
2 S + 3 O2 + 2 H2O 2 H2SO4
 Pyrites:
The mineral pyrite, or iron pyrite, also known as fool's gold, is an iron sulfide with the
chemical formula FeS2. This mineral's metallic luster and pale brass-yellow hue give it a
superficial resemblance to gold, hence the well-known nickname of fool's gold. Pyrite is
the most common of the sulfide minerals.

Pyrite is usually found associated with other sulfides or oxides in quartz veins, sedimentary rock,
and metamorphic rock, as well as in coal beds and as a replacement mineral in fossils. Despite
being nicknamed fool's gold, pyrite is sometimes found in association with small quantities of gold.
Gold and arsenic occur as a coupled substitution in the pyrite structure. In the Carlintype gold
deposits, arsenian pyrite contains up to 0.37 wt% gold.

Single super phosphate:

Single superphosphate (SSP) was the first commercial mineral fertilizer and it led to the
development of the modern plant nutrient industry. This material was once the most commonly
used fertilizer, but other phosphorus (P) fertilizers have largely replaced SSP because of its
relatively low P content.

Features:
Supplies sulphate sulphur and calcium.
The ratio of phosphorus and sulphur suits many crop and pasture needs.
Both the phosphorus and sulphur are in readily available forms.
Can be blended with other fertilizer products (except Urea & DAP)
Can be stored easily for long periods, without taking up moisture.
Contains calcium and sulphur (mostly as gypsum) and helps keep soil in good shape by maintaining soil
structure.
SSP provides a balance of P, S and Ca that mimics pasture growth requirements and is the best
balanced P, S and Ca fertilizer for Australian pastures.

Process technology:
Single Superphosphate is produced by reacting naturally occurring phosphate rock with sulphuric acid.
This process converts insoluble phosphates into forms more readily available to plants.

Phosphate Rock + Sulphuric Acid Single Superphosphate

The figure given below presents the block flow diagram for manufacturing of mono
superphosphate fertilizers and the related raw materials and pollution sources.

The manufacturing process depends on reacting phosphate rock with sulfuric acid and the
fertilizer contains about (16- 20 %) P2O5. The net reaction proceeds as follows:

The process can be divided into two stages as follows:

The first stage represents the diffusion of sulfuric acid to the rock particles accompanied by a
rapid chemical reaction on the particle surface, which continues until the acid is completely
consumed, and crystallization of calcium sulphate.

The second stage represents the diffusion of the formed phosphoric acid into the pores of the
rock particles which did not decompose. This stage is accompanied by a second reaction.

In this process ground phosphate rock is transported from the storage site to automatic
weight, by a system of belt and screw conveyors and elevators, which feed the continuous
action double conical mixer.

The sulfuric acid is continuously diluted with water in a batch mixer to a 75 % concentration,
then fed to the mixer to react with ground phosphate rock where a first reaction takes place. This
reaction ends in the reaction mixer in 30- 60 minutes, during the period of settling and hardening
of the superphosphate slurry, which is caused by the relatively rapid crystallization of the low
solubility calcium sulphate. The next stage of the process is ageing of the superphosphate, i.e. the
formation and crystallization of mono calcium phosphate in the den.

The formed slurry is transported to the continuous-action reaction den which has a very low
travel speed to allow for solidifying (see fig 2), where formation of superphosphate takes place
(settling and hardening of the slurry in the first stage of ageing). Considerable quantities of
fluoride compounds are evolved from the acidulation, they are sent to the scrubbers.
 The superphosphate powder, from the den, is transferred for ageing by a belt conveyor, located
below the den, to the pile storage for curing, or completion of chemical reaction, which takes 2-6
weeks to a P2O5 availability acceptable for plant nutrient. The raw fertilizer is uniformly
distributed by a scattering device and in order to accelerate the ageing operation, the
superphosphate is agitated during storage by means of a grab-bucket crane. The end product still
contains a certain amount of uncombined phosphoric acid, which makes the fertilizer more
hygroscopic. Neutralizing admixtures are used to remove the free acid of the superphosphate, or
it is treated with gaseous ammonia. These procedures improve the physical properties of the
superphosphate. They lower the moisture content, the hygroscopic and the tendency to cake. If
ammonia treatment is used, an additional nutritional component (N2) is also introduced into the
fertilizer.

During reaction of the phosphate with sulphuric acid in the den, hydrogen fluoride evolves and
reacts with the silica contained in the phosphates and forms gaseous silicon-tetra fluoride (SiF4)
and fluo slicic acid (H2SiF6). The continuous den is, therefore, enclosed so that fumes of these
compounds do not escape into the working place. The fluoride gases, containing H 2SiF6 vapors,
are withdrawn through an opening in the den roof into a ventilation pipe to an absorption unit
and are utilized for making sodium fluoride silicates.

Superphosphate is granulated in drum granulators to improve its physical properties. In the

granulator, the superphosphate powder (after being cured for 2-6 weeks) is wetted with water fed
into the drum through nozzles, and rolled into granules of different size which are then dried,
screened into size fractions cooled and the product is bagged in plastic (polyethylene) bags. The
over size granules are ground and recycled, with the undersize granules, to the den.

Uses:

The product is a low cost source of phosphorus and sulphur in a wide range of pasture situations. SSP is
a traditional product for supplying phosphorus and sulphur to pastures, the main two nutrients required for
pasture production. Generally mixed with Sulphate of Ammonia and Muriate of Potash, but can be
blended with other fertilizers.

Storage and handling:

Can be stored for relatively long periods (0 6 months).

Does not take up moisture from the air.
Can be used in a wide range of spreading and sowing equipment.

Triple super phosphate:

Triple superphosphate is a fertilizer produced by the action of concentrated phosphoric acid

on ground phosphate rock. The active ingredient of the product, mono calcium phosphate, is
identical to that of superphosphate, but without the presence of calcium sulfate that is
formed if sulfuric acid is used instead of phosphoric acid. The phosphorus content of triple
superphosphate (17 - 23% P; 44 to 52% P2O5) is therefore greater than that of
superphosphate (7 - 9.5% P; 16 to 22% P2O5). It is produced in granular and non granular
form and is used both in fertilizer blends (with potassium and nitrogen fertilizers) and by
itself.

Chemical Properties

Chemical formula: Ca(H2PO4)2H2O

Fertilizer analysis: 45% P2O5 (0-45-0)
15% Ca
Water-soluble P: Generally >90%
Solution pH 1 to 3

Process technology:

The figure below shows the block flow diagram for manufacturing of triple
superphosphate. This type of fertilizers is much more concentrated than the ordinary
superphosphate, containing 45- 46 % of available P2O5. Triple superphosphate is
manufactured by the action of phosphoric acid on phosphate rock. The main reaction is:

A process similar to single superphosphate production is used, in which pulverized

phosphate rock is mixed with phosphoric acid in a two-stage reactor. The resultant slurry is
sprayed into the granulator. The slurry is sprayed into the drum granulation co-current with
flue gases of fired fuel (natural gas or fuel oil and air). The product is screened and off-size
is recycled back to the granulator. The on-size product is cooled and stored ready for being
bagged. The exhaust gases from the reactor, granulator and cooler are scrubbed to remove
fluoric compounds.
 Uses:
As a low cost source of phosphorus, TSP is the main substitute for Single Superphosphate in cropping
blends.
The product is used mainly in blends with DAP and MOP.
It is a source of phosphorus in situations where no nitrogen is required, for example, good fallow after
clover dominant pasture.
It is also used in horticultural blends where the phosphorus content needs boosting.
 Storage and handling:

TSP has excellent physical qualities. It stores, handles and flows through all types of equipment
extremely well.
Does not take up moisture in storage or in the field.
Spread very evenly.
TSP flows significantly quicker than other fertilizers, approximately 15 to 20% faster than DAP so care
must be taken in calibration, before sowing.

Potassic fertilizers:

Potassium chloride or Muriate of Potash (MOP):

The chemical compound potassium chloride (KCl) is a metal halide salt composed
of potassium and chlorine. In its pure state, it is odorless and has a white
or colorless vitreous crystal appearance. The solid dissolves readily in water and its solutions have a
salt-like taste. KCl is used in medicine, scientific applications, and food processing. It occurs
naturally as the mineral sylvinite and in combination with sodium chloride as sylvinite.

Potash is a mixture of potassium containing compounds with a high KCl content. Unlike white-
colorless KCl, potash varies in color from pink or red to white depending on the mining and recovery
process used. White potash, sometimes referred to as soluble potash, is usually higher in analysis
and is used primarily for making liquid starter fertilizers. Potassium chloride was historically known
as "muriate of potash". This name is occasionally still encountered in association with its use as
a fertilizer.

Chemical properties:

In chemistry and physics, it is a common standard, for example for calibration of the electrical
conductivity of (ionic) solutions, since KCl solutions are stable, allowing for reproducible
measurements. In aqueous solution, it is essentially fully ionized into solvated K+ and Cl- ions. Such
solutions serve as a source of chloride ion. When treated with silver salts, one observes the
characteristic precipitation of silver chloride:
KCl(aq) + AgNO3(aq) AgCl(s) + KNO3(aq)

Although potassium is more electropositive than sodium, KCl can be reduced to the metal by
reaction with metallic sodium at 850 C because the potassium is removed by distillation.
KCl(l) + Na(l) NaCl(l) + K(g)
 This method is the main method for producing metallic potassium. Electrolysis (used for sodium)
fails because of the high solubility of potassium in molten KCl.

Manufacture:
Occurs as a natural salt and after processing to cleanse out unwanted salts (especially common salt), it is
usually compacted into chips and screened to meet size specifications.

Features and benefits:

Potassium stimulates the growth of strong stems and gives the plant some disease resistance by
promoting thickness of the outer cell walls.
Adequate potassium can reduce moisture loss from growing plants, thereby giving some drought
resistance.
Potassium improves color, flavor and storing quality of fruit and vegetables.
MOP is the most concentrated form of granular potassium and typically the most cost effective.
The even granule size of MOP allows for accurate spreading.
MOP is commonly blended with SSP to supply major nutrients for pasture based systems

Uses:

The majority of the potassium chloride produced is used for making fertilizer, since the growth of
many plants is limited by their potassium intake. As a chemical feedstock, it is used for
the manufacture of potassium hydroxide and potassium metal. It is also used in medicine, lethal
injections, scientific applications, food processing, and as a sodium-free substitute for table salt for
persons concerned about its health effects.

It is sometimes used in water as a completion fluid in petroleum and natural gas operations, as well
as being an alternative to sodium chloride in household water softener units.

Potassium chloride is used in some de-icing products that are designed to be safer for pets and
plants, though these are inferior in melting quality to calcium chloride [lowest usable temperature
12 F (11 C) v. 25 F (32 C)]. It is also used in various brands of bottled water, as well as in
bulk quantities for fossil fuel drilling purposes.

Storage and handling:

MOP (Muriate of Potash or KCl) stores well in bulk or in bags. It is not hygroscopic. MOP is particularly
corrosive and so metal parts should be protected. After use, wash out equipment.

Potassium sulphate or sulphate of potash(SOP):

Potassium sulfate is a non-flammable white crystalline salt which is soluble in water. The chemical is
commonly used in fertilizers, providing both potassium and sulfur.
 Formula: K2SO4
Molar mass: 174.259 g/mol
Melting point: 1,069 C
Density: 2.66 g/cm
Boiling point: 1,689 C
Soluble in: Water

Natural resources:

The mineral form of potassium sulfate, arcanite, is relatively rare. Natural resources of potassium
sulfate are minerals abundant in the Stassfurt salt. These are co crystallizations of potassium sulfate
and sulfates of magnesium calcium and sodium.

The minerals are:

Kainite, MgSO4KClH2O
Schnite, K2SO4MgSO46H2O
Leonite, K2SO4MgSO44H2O
Langbeinite, K2Mg2(SO4)3
Glaserite, K3Na(SO4)2
Polyhalite, K2SO4MgSO42CaSO42H2O

From some of the minerals like kainite, the potassium sulfate can be separated, because the
corresponding salt is less soluble in water.

Kieserite, MgSO4H2O, can be combined with a solution of potassium chloride to produce potassium
sulfate.

Features and benefits:

SOP provides both potassium and sulphur in soluble forms.

SOP contains no chloride and hence has a much lower salt index than MOP. Where soils are saline and
where irrigation water may have high chloride levels SOP is the preferred form of potassium to use.
Where seeds or transplants are placed in direct contact with fertilizer, SOP is much less likely to cause
root burn of plants.
Potassium stimulates the growth of strong stems and gives the plant some disease resistance by
promoting thickness of the outer cell walls. Adequate potassium can reduce moisture loss from growing
plants, thereby giving some drought resistance. Potassium improves color, flavor and storing quality of
fruit and vegetables.

Potassium sulfate is the second largest tonnage potassium compound and it is also used primarily
as a fertilizer. The sulfate or other non chloride forms of potassium are preferred for certain
crops that do not tolerate the chloride ion well, e.g., tobacco and some fruits and vegetable.
Non chloride potash sources are also needed in areas where chloride accumulate or in areas of
very intensive agriculture, potassium sulfate may be preferred because of its sulfur content where
soils are deficient in both potassium and sulfur.

Production technology:

The process for manufacturing potassium sulfate is similar to that used for the manufacture
of sodium sulfate.

Potassium sulfate can be synthesized by reaction of potassium chloride with sulfuric acid according
to the Leblanc process. Potassium sulfate is produced according to the following reaction:
2 KCl + H2SO4 2 HCl + K2SO4

The Hargreaves process uses sulfur dioxide, oxygen and water and potassium chloride as the
starting materials to produce potassium sulfate. Hydrochloric acid evaporates off. SO 2 is produced
through the burning of sulfur.
Mannheim Process Historically potassium sulfate has been made primarily from KCL and
sulfuric acid (and a small amount from KCL and SO2) when the byproduct HCL was the
dominant product. However, over the year the HCL market has had more competition and
natural K2SO4 with lower capital and operating coasts has begun to dominate its production in
some countries with natural complex salts.

The Mannheim process was originally developed from sodium sulfate production by reacting
NaCl with sulfuric acid. Replacing NaCl with KCl produces potassium sulfate. The reaction is
two-stage:
The potassium chloride reacts during slow mixing in the heated Mannheim furnace with sulfuric
acid, producing gaseous HCl and K2SO4. The furnace is heated by natural gas or fuel oil. The
product K2SO4 is cooled in a cooling drum. Lump material from the cooler is crushed and
finished or can be compacted and granulated as with KCl.

The HCl gas is cooled in a graphite in a graphite heat exchanger and absorbed in water in two
stages to produce 30% hydrochloride acid as a byproduct. The process gives an excellent quality
that contains over 50% K2O and less than 1% chlorine. Emissions are well controlled.

Recovery of Potassium Sulfate From Natural Complex Salts The chief natural complex
salts that are the source of the potassium sulfate are;

Kainite (KCl . MgSO4 . 3H2O)

Langbeinite (K2SO4 . 3MgSO4)
Carpathian polmineral ores
The natural process involves the initial conversion with recycled K2SO4 end liquor mined
kainite or langbeinite to form an intermediate product schoenite. All processes are based on
intercrystalline reactions of ion exchange.

The Process comprises four basic units:

Preparation of the ore and flotation;

Production of schoenite and its recovery;
Leaching of the schoenite to potassium sulfate;
Liquor treatment.

The kainite is re pulped with recycled brine, screened, and directed to ball mills and
Hydro classifiers. Overflows go to a thicker and main filter and underflows to flotation and
filtration. Float material, after filtration, is combined with the solid fraction from the main filter
and directed to the schoenite reactors and separating cyclones. After a two step hydro separation,
centrifugation, and filtration, schoenite is directed to the to the leaching reactors. After
decomposition of the schoenite, product is directed to final centrifuges and a dryer; the overflows
are cooled and crystallized. After additional thickening, the product is centrifuged and dried. The
product specification ensures that the K2O content is not lower than 50% and the chlorine
content is less than 1%.

In the recovery unit,talkali forms syngenite to moderately increase the recovery of schoenite
from the plant end liquor. The brine from the schoenite filter is reacted with main flow to be
leaching reactors.

Other processes involve adding sylvite to kainite, langbeinite kieserite, etc. The schoenite
intermediate can be formed kieserite, etc. the schoenite intermediate can be formed by reacting
KCl with mined kieserite or the epsomite. Where solar or plant evaporation can be done
economically, the yields can be further improved by evaporating the schoenite or glaserite end
liquor and recycling the salts.

A complex process can production of potassium sulfate from ores can been implemented on an
industrial scale. The naturals ores are composed of calcium sulfate anhydride, epsomite, halite,
kainite, kieserite, langbeinite, polyhalite, sylvite and clay. The treatment of such an ore requires
permanent analytical services and the development of a large number and for the kind of salts
intended to be produced, additional sylvite must be added in varying amounts to maintain the
right proportions for crystal formation. The basic process concept is to produce schoenite from
all available salts. The remaining products or processes are subjugated to his basic process.

The Carpathian ore contains about 9% potassium and 15% clay. The ore is leached with hot
synthetic kainite solution in a dissolution chamber. The langbeinite, polyhalite and halite remain
undissolved chamber containing salts and clay is directed to a Dorr-Oliver settler where clay is
settled and directed to a washer and discarded. The solution is crystallized at the proper cation
and anion proportions to produce crystalline schoenite. To avoid crystalline of potassium
chloride and sodium chloride, the saturated solution of potassium and magnesium sulfates is
added to the Dorr-Oliver settler. The slurry of schoenite is filtered and crystals are leached with
water to produces K2SO4 crystals, which are centrifuged and recycled and a liquor of potassium
and magnesium sulfates. Also liquid phase from filter is recycled and added to the schoenite
liquor from vacuum crystallization. Part of the schoenite liquor is evaporated to produce
crystalline sodium sulfate and discard the magnesium chloride liquid end products. The slurry
from the evaporation unit is recycled as synthetic kainite. This process permits the use of the
Carpathian ores to produce several commercially valuable products such as potassium sulfate,
potassium-magnesium sulfate, potassium chloride, sodium sulfate and magnesium chloride
liquors.

The production of potassium sulfate from langbeinite is possible with a large amount of
muriate of potash is possible with a large amount of nitrate of potash by mixing langbeinite
and sylvite.
The langbeinite ore is separated from sylvite and halite by selective washing, froth
flotation, or heavy media separation. The commercial langbeinite used in the process must
pulverized in ball mills, and fine powder is mixed with a solution of the muriate of potash.
The muriate of potash is dissolved and clarified in a separate unit. The reaction in the
presence of water yield potassium sulfate in a crystalline form and brine. Crystals are
 centrifuged or filtered, dried in a rotary dryer, sized and finished. The finished methods
either produce coarse material or granulated product. The mixed salts are added to the
sulfate reactor the liquor is discard as a waste.

Uses:
The principal use of potassium sulfate is as a fertilizer. K2SO4 does not contain chloride, which can
be harmful to some crops. Potassium sulfate is preferred for these crops, which include tobacco and
some fruits and vegetables. Crops that are less sensitive may still require potassium sulfate for
optimal growth if the soil accumulates chloride from irrigation water.[6]

The crude salt is also used occasionally in the manufacture of glass. Potassium sulfate is also used
as a flash reducer in artillery propellant charges. It reduces muzzle flash, flareback and blast
overpressure.

Sometimes used as an alternative blast media similar to soda in soda blasting as it is harder and
similarly water soluble.

Potassium sulphate (SOP) can be a more expensive source of potassium than MOP and so its uses are
often restricted to five main areas.
Where soil or irrigation water salt levels are high and MOP is undesirable.
Where chloride sensitive crops are being grown; for example, berries and vines.
Where high chloride levels occur in irrigation water.

Storage and handling:

Potassium sulphate can be stored in bulk bags. It does not bond in the heap. Potassium sulphate is
slightly hygroscopic and is neutral in reaction. All potassium fertilizers are corrosive and care should be
taken when the fertilizer is in contact with metal. After application wash all machinery out with water.

Potassium nitrate:

Potassium nitrate is a chemical compound with the chemical formula KNO. It is an ionic salt of potassium
ions K and nitrate ions NO. It occurs as a mineral niter or nitre and is a natural solid source of nitrogen.

Formula: KNO3
Molar mass: 101.1032 g/mol
IUPAC ID: Potassium Nitrate
Melting point: 334 C
Density: 2.11 g/cm
Boiling point: 400 C
Soluble in: Water, Glycerol, Ammonia

Properties:
Potassium nitrate has an orthorhombic crystal structure at room temperature, which transforms to a
trigonal system at 129 C. Upon heating to temperatures between 550 and 790 C under an oxygen
atmosphere, it loses oxygen and reaches a temperature dependent equilibrium with potassium
nitrite:
2 KNO3 2 KNO2 + O2

Potassium nitrate is moderately soluble in water, but its solubility increases with temperature. The
aqueous solution is almost neutral, exhibiting pH 6.2 at 14 C for a 10% solution of commercial
powder. It is not very hygroscopic, absorbing about 0.03% water in 80% relative humidity over 50
days. It is insoluble in alcohol and is not poisonous; it can react explosively with reducing agents, but
it is not explosive on its own.

Process technology:
Potassium nitrate can be made by combining ammonium nitrate and potassium hydroxide.
NH4NO3 (aq) + KOH (aq) NH3 (g) + KNO3 (aq) + H2O (l)

An alternative way of producing potassium nitrate without a by-product of ammonia is to

combine ammonium nitrate and potassium chloride, easily obtained as a sodium-free salt substitute.
NH4NO3 (aq) + KCl (aq) NH4Cl (aq) + KNO3 (aq)

Potassium nitrate can also be produced by neutralizing nitric acid with potassium hydroxide. This
reaction is highly exothermic.
KOH (aq) + HNO3 KNO3 (aq) + H2O (l)

On industrial scale it is prepared by the double displacement reaction between sodium nitrate and
potassium chloride.
NaNO3 (aq) + KCl (aq) NaCl (aq) + KNO3 (aq)

Uses:
Potassium nitrate is used in fertilizers as a source of nitrogen and potassium two of
the macronutrients for plants. When used by itself, it has an NPK rating of 13-0-44.

Used in some toothpastes for sensitive teeth. Recently, the use of potassium nitrate
in toothpastes for treating sensitive teeth has increased and it may be an effective treatment.
Used historically to treat asthma. Used in some toothpastes to relieve asthma symptoms.
Used in Thailand as main ingredient in Kidney Tablets to relieve the symptoms
of cystitis, pyelitis and urethritis.
Combats high blood pressure and was once used as a hypotensive.
 Electrolyte in a salt bridge

Active ingredient of condensed aerosol fire suppression systems. When burned with the free
radicals of a fire's flame, it produces potassium carbonate.
Component (usually about 98%) of some tree stump removal products. It accelerates the
natural decomposition of the stump by supplying nitrogen for the fungi attacking thewood of
the stump.
In heat treatment of metals as a medium temperature molten salt bath, usually in
combination with sodium nitrite. A similar bath is used to produce a durable blue/black finish
typically seen on firearms. Its oxidizing quality, water solubility, and low cost make it an ideal
short-term rust inhibitor.
To induce flowering of mango trees in the Philippines.
Thermal storage medium in power generation systems. Sodium and potassium nitrate salts
are stored in a molten state with the solar energy collected by the heliostats at
the Gemasolar Thermosolar Plant. Ternary salts, with the addition of calcium
nitrate or lithium nitrate, have been found to improve the heat storage capacity in the molten
salts.

Complex or compound and NPK fertilizers:

Compound fertilizers, which contain N, P, and K, can often be produced by mixing straight fertilizers.
In some cases, chemical reactions occur between the two or more components. For example mono
ammonium and di ammonium phosphates, which provide plants with both N and P, are produced by
neutralizing phosphoric acid (from phosphate rock) and ammonia (from a Haber facility):
NH3 + H3PO4 (NH4)H2PO4

2 NH3 + H3PO4 (NH4)2HPO4

NPK fertilizers:

NPK fertilizers are three-component fertilizers providing nitrogen, phosphorus, and potassium.

NPK rating is a rating system describing the amount of nitrogen, phosphorus, and potassium in a
fertilizer. NPK ratings consist of three numbers separated by dashes (e.g., 10-10-10 or 16-4-8)
describing the chemical content of fertilizers. The first number represents the percentage of nitrogen
in the product; the second number, P2O5; the third, K2O. Fertilizers do not actually contain P2O5 or
K2O, but the system is a conventional shorthand for the amount of the phosphorus (P) or potassium
(K) in a fertilizer. A 50-pound bag of fertilizer labeled 16-4-8 contains 8 pounds of nitrogen (16% of
the 50 pounds) an amount of phosphorus and potassium equivalent to that in 2 pounds of P 2O5 (4%
of 50 pounds) and 4 pounds of K2O (8% of 50 pounds). Most fertilizers are labeled according to this
 N-P-K convention, though Australian convention, following an N-P-K-S system, adds a fourth
number for sulfur.

di-ammonium phosphate (DAP):

Di-ammonium phosphate is one of a series of water-soluble ammonium phosphate salts that can be
produced when ammonia reacts with phosphoric acid.

Formula: (NH4)2HPO4
Molar mass: 132.07 g/mol
Density: 1.62 g/cm

(NH4)2HPO4(s) NH3(g) + NH4H2PO4(s)

Features:

High analysis source of phosphorus.

N:P ratio of 1:1 makes it an effective source of nitrogen.
DAP releases free ammonium. Nitrogen in the ammonium form resists leaching and is a slower release
form of nitrogen.
The free ammonium gives a higher pH reaction immediately around the granule.
The low cost of nitrogen in DAP makes it a cost effective source of nitrogen if Phosphorus is also
required.

Uses:
DAP is used as a fertilizer. When applied as plant food, it temporarily increases the soil pH, but over
a long term the treated ground becomes more acidic than before upon nitrification of the ammonium.
It is incompatible with alkaline chemicals because its ammonium ion is more likely to convert
to ammonia in a high-pH environment. The average pH in solution is 7.58. The typical formulation
is 18-46-0 (18% N, 46% P2O5, 0% K2O).

DAP can be used as a fire retardant. It lowers the combustion temperature of the material,
decreases maximum weight loss rates, and causes an increase in the production of residue or
char. These are important effects in fighting wildfires as lowering the pyrolysis temperature and
increasing the amount of char formed reduces that amount of available fuel and can lead to the
formation of a firebreak. It is the largest component of some popular commercial firefighting
products.

DAP is also used as a yeast nutrient in winemaking and brewing mead; as an additive in some
brands of cigarettes purportedly as a nicotine enhancer; to prevent afterglow in matches, in
purifying sugar; as a Flux for soldering tin, copper, zinc and brass; and to control precipitation of
alkali-soluble and acid-insoluble colloidal dyes on wool.
 One of the major cropping fertilisers used in Australia as a source of both phosphorus and nitrogen. The
high phosphorus content makes it a true high analysis fertiliser. DAP and DAP blends are used on a
range of crops in broad-acre farming, cereals, sugar cane, sowing pastures, dairy pastures, fodder crops
and also in horticultural crops; for example, vegetables and tree crops.

Storage and handling:

Does tend to take up moisture, both in storage and in the field.
Storage in a bulk shed is the preferred storage method. Covering with a tarp may reduce any moist air
uptake.
The use of augers may damage the fertiliser and increase any handling problems.
Do not leave exposed to moist air.
Either fill or empty (completely), the drill or air-seeder fertiliser box overnight.
Cover seeding equipment with a tarp.
Raise the equipment tines from the soil to stop moisture moving up the tubes.

Nitro phosphates:

Nitro phosphate is the generally accepted term for any fertilizer that is produced by a
process involving treatment of phosphate rock with nitric acid.

Fundamentals of Nitro phosphates

The basic (and simplified) acidulation reaction can be represented by the following
Reaction equations:
Ca3 (PO4)2 + 4 HNO3 2 Ca (NO3)2 + Ca(H2PO4)2 + 20.2 kcal

Ca (H2PO4)2 + 2 HNO3 Ca (NO3)2 + 2 H3PO4 + 2.05 kcal

Overall
Ca3 (PO4)2 + 6 HNO3 3 Ca (NO3)2 + 2 H3PO4 + 22.25 kcal

After separation of the insoluble material, phosphoric acid is neutralized with ammonia to
produce a fertilizer. If the calcium nitrate is left in the solution, it reverts to di calcium
phosphate ammonium following the reaction:

2H3PO4 + Ca (NO3)2 + 4NH3 CaHPO4 + (NH4)2HPO4 + 2NH4NO3 + 66.67 kcal

Calcium is non-nutrient in terms of N, P, and K and is therefore seen as a diluents. For

these reasons alone, it is desirable to remove calcium from the solution. But there is
another, more important reason. If the calcium nitrate is left in the solution, when it is
neutralized the N:P ratio will be fixed. To produce grades with lower N:P ratios, it is
necessary to remove calcium nitrate, whereas if higher nitrogen grades are required, the
removed calcium nitrate can be converted to ammonium nitrate and returned to the solution.
Therefore, most nitro phosphate processes include some means of removing calcium nitrate from
the solution.

The nitro phosphate process (also known as the Odda process) was a method for the industrial
production of nitrogen fertilizers.

The process involves acidifying phosphate rock with nitric acid to produce a mixture of phosphoric
acid and calcium nitrate.
Ca3 (PO4)2 + 6 HNO3 + 12 H2O 2 H3PO4 + 3 Ca(NO3)2 + 12 H2O

The mixture is cooled to below 0 C, where the calcium nitrate crystallizes and can be separated
from the phosphoric acid.
2 H3PO4 + 3 Ca (NO3)2 + 12 H2O 2 H3PO4 + 3 Ca(NO3)24H2O

The resulting calcium nitrate produces nitrogen fertilizer. The filtrate is composed mainly of
phosphoric acid with some nitric acid and traces of calcium nitrate, and this is neutralized
with ammonia to produce a compound fertilizer.
Ca (NO3)2 + 4 H3PO4 + 8 NH3 CaHPO4 + 2 NH4NO3 + 3(NH4)2HPO4

If potassium chloride or potassium sulfate is added, the result will be NPK fertilizer. The process was
an innovation for requiring neither the expensive sulfuric acid nor producing gypsum waste.

The calcium nitrate mentioned before, can as said be worked up as calcium nitrate fertilizer but often
it is converted into ammonium nitrate and calcium carbonate using carbon dioxide and ammonia.
Ca (NO3)2 + 2 NH3 + CO2 + H2O 2 NH4NO3 + CaCO3

Both products can be worked up together as straight nitrogen fertilizer.

Due to the byproduct ammonium nitrate which has lower value, the production of ammonium nitro
phosphate fertilizer is not economical compared to di ammonium phosphate which is produced from
cheaper sulfuric acid or gypsum.

Mono ammonium phosphate:

Ammonium di hydrogen phosphate, or mono ammonium phosphate, NHHPO, is formed when a
solution of phosphoric acid is added to ammonia until the solution is distinctly acidic. It crystallizes in
tetragonal prisms.

Density: 1.80 g/cm

Chemical Properties:

Chemical formula: NH4H2PO4

P2O5 range: 48 to 61%
N range: 10 to 12%
Water solubility (20) 370 g/L
 Solution pH 4 to 4.5

Features:

MAP is a high analysis source of phosphorus.

A cost effective granular product.
Low in heavy metals.
Good handling characteristics.
The nitrogen in MAP is in the ammonium form, which resists leaching and is a slower release form of
nitrogen.
The product has an acid reaction in the soil which can be an advantage in neutral and high pH soils.
Therefore MAP is used in preference to DAP on alkaline soils.

Ammonium di hydrogen phosphate (ADP), or mono ammonium phosphate, NH4H2PO4, is

formed when a solution of phosphoric acid is added to ammonia until the solution is distinctly acidic.
It crystallizes in tetragonal prisms. Mono ammonium phosphate is often used in the blending of dry
agricultural fertilizers. It supplies soil with the elements nitrogen and phosphorus in a form usable by
plants. The compound is also a component of the ABC powder in some dry chemical fire
extinguishers. This substance is also supplied in an emerald green, amethyst, or aquamarine crystal
growing box kit for children.

Solid mono ammonium phosphate shows a dissociation pressure of ammonia of 0.05 mm Hg at

125 C based on the decomposition reaction as follows: ammonia gas is combined with phosphoric
acid, granulated, dried and screened.
NH4H2PO4(s) NH3(g) + H3PO4(l)

ADP is a widely used crystal in the field of optics due to its birefringence properties. As a result of its
tetragonal crystal structure, this material has negative uniaxial optical symmetry with typical
refractive indices no =1.522 and ne = 1.478 at optical wavelengths.

ADP crystals are piezoelectric, a property required in some active sonar transducers (the alternative
being transducers that use magnetostriction). In the 1950s ADP crystals largely replaced
the Quartz and Rochelle Salt crystals in transducers because they are easier to work than Quartz
and, unlike Rochelle Salt, are not deliquescent.

Uses:
One of the major cropping fertilizers used in Australia as a source of phosphorus and nitrogen, MAP and
MAP blends are used extensively in cropping systems and for sowing pastures. The low level of nitrogen
makes it useful as a starter fertilizer and as there is no free ammonia, the risk of affecting germinating
seeds is minimal.
 Storage and handling:
Will store freely in shed storage for extended periods with little concern about moisture uptake.
Covering with a tarp will greatly reduce any moist air uptake.
The use of augers may damage the fertilizer and increase any handling problems.
Do not leave exposed to moist air.
Either fill or empty (completely), the drill or air-seeder fertilizer box overnight.
Raise the equipment tines from the soil to stop moisture moving up the tubes.

Various grades of NPK fertilizers:

Straight fertilizers such as Calcium Ammonium Nitrate (CAN), Ammonium Nitrate (AN),
Ammonium Sulphate (AS), Urea, Single Superphosphate (SSP), Triple Superphosphate
(TSP), Potash (Potassium Chloride) (MOP) and combined types such as Mono-
Ammonium Phosphate (MAP), Di-Ammonium Phosphate (DAP) are well-defined products
made using well-defined processes. Compound or complex fertilizers such as NPK, are
more difficult to define as there is an infinite number of N/P/K-ratios and the processes
applied in their production are numerous.

The product name NPK is normally followed by three numbers to indicate the percent of
N, P2O5 and K2O which the product contains, e.g. 24612 indicates that this particular
grade contains 24% N (nitrogen compounds), 6% P2O5 (phosphorus compounds) and 12%
K2O (potassium compounds). In addition, the fertilizer may contain magnesium, boron,
sulphur, micro-nutrients, etc. The typical content of nutrients (N + P2O5 + K2O) will
normally be in the range of 40-60%.

Grades with no P2O5 or no K2O are also included in the NPK product range but they are
normally named NP and NK fertilizers. These types of fertilizers can normally be produced
in NPK plants and emission levels will typically be within the limits valid for NPK grades.

The labeling of fertilizers varies by country in terms of analysis methodology, nutrient labeling, and
minimum nutrient requirements. The most common labeling convention shows the amounts of
nitrogen, phosphorus, and potassium in the fertilizer.

Macronutrient fertilizers are generally labeled with an NPK analysis, based on the relative content of
the chemical elements nitrogen (N), phosphorus (P), and potassium (K) that are commonly used
in fertilizers. However, numbers used in this labeling scheme do not directly represent the source
composition or absolute nutrient content of the fertilizer. The N value is the percentage of elemental
nitrogen by weight in the fertilizer. The values for P and K represent the amount of P 2O5 and K2O that
would be present if all the phosphorus and potassium in the fertilizer appeared in these forms.

For example, the fertilizer potash is a naturally occurring mineral composed of nearly pure potassium
chloride (KCl). As such, its composition is 1:1 potassium to chloride or 52% potassium and 48%
chlorine by weight (owing to differences in molecular weight between the elements). Traditional
analysis of 100 g of KCl would yield 60 g K2O. The percentage yield of K2O from the original 100 g of
fertilizer is the number shown on the label. A potash fertilizer would thus be labeled 0-0-60, not 0-0-
52.
Converting nutrient analysis to composition:

The factors for converting from P2O5 and K2O values to their respective P and K elemental values are
as follows:

P2O5 consists of 56.4% oxygen and 43.6% elemental phosphorus. The percentage (mass
fraction) of elemental phosphorus is 43.6% so elemental P = 0.436 x P2O5
K2O consists of 17% oxygen and 83% elemental potassium. The percentage (mass fraction) of
elemental potassium is 83% so elemental K = 0.83 x K2O
Nitrogen values represent actual nitrogen content so these numbers do not need to be
converted.

Using these conversion factors, an 185120 fertilizer contains by weight:

18% elemental (N)

22% elemental (P), and
17% elemental (K)

NPK values for various synthetic fertilizers:

15-00-00 Calcium nitrate

21-00-00 Ammonium sulfate
30-00-00 to 40-00-00 Sulfur-coated urea (slow release)
31-00-00 Iso butyldene di urea (~90% slow release)
33-00-00 to 34-00-00 Ammonium nitrate
35-00-00 Urea form (~85% slow release, sparingly soluble urea formaldehyde)
40-00-00 Methylene urea (~70% slow release)
46-00-00 Urea (U-46)
82-00-00 Anhydrous ammonia
10-34-00 to 11-37-00 Ammonium polyphosphate
11-48-00 to 11-55-00 Mono ammonium phosphate
18-46-00 to 21-54-00 Di ammonium phosphate
 13-00-44 Potassium nitrate
00-17-00 to 00-22-00 Superphosphate (Mono calcium phosphate monohydrate with gypsum)
00-44-00 to 00-52-00 Triple superphosphate (Mono calcium phosphate monohydrate)

NPK values for mined fertilizer minerals:

11-08-02 to 16-12-03 bird guano

00-3-00 to 00-8-00 Raw Phosphate Rock (would be 00-34-00 if it were soluble)
00-00-22 Potassium magnesium sulfate (K-mag)
00-00-60 Potassium chloride

Secondary nutrients:

There are three secondary plant nutrients namely calcium(Ca), magnesium(Mg), sulphur(s).Out
of the three secondary nutrients needed at lower levels than NPK, calcium (Ca) is perhaps the most
important. Calcium strengthens cell walls, helping to reduce bruising and disease in fruit, salad
and vegetable crops. This means that a good supply of calcium produces food crops that are less
prone to damage and have a longer shelf life. Crops short in calcium will have growth disorders
such as corky skin.

Fruit and vegetables containing higher levels of calcium also have a higher nutritional value for
example, vitamin C and antioxidants in tomatoes. This means that eating fresh fruit with strong skins
and a great, crisp bite will help provide us with the calcium we need for strong bones.

Magnesium (Mg) is also important for crop quality, but is also a key component of leaf chlorophyll
and the enzymes that support plant growth. Low magnesium leads to reduced photosynthesis, which
severely limits crop yields.

Grain fill in rice and dry matter content of potatoes can be significantly reduced if magnesium is
undersupplied.

Sulfur (S) is an essential part of many amino acids and proteins. Without both S and Mg, crops
suffer; growth slows and leaves turn pale or yellow. Sulfur is particularly important for ensuring the
protein content of cereal crop grains.

Micronutrients:
Micronutrients are nutrients required by humans and other organisms throughout life in small
quantities to orchestrate a range of physiological functions. For people, they include dietary trace
minerals in amounts generally less than 100 milligrams/day - as opposed to macro minerals which
are required in larger quantities. The micro minerals or trace elements include at
least iron, cobalt, chromium, copper, iodine, manganese, selenium, zinc and molybdenum.
Micronutrients also include vitamins, which are organic compounds required as nutrients in tiny
amounts by an organism, as well as phytochemicals. Micronutrients reinforce and supplement the
strong plant growth and structures provided by major and secondary nutrients.

Micronutrients for plant:

There are about seven nutrients essential to plant growth and health that are only needed in very
small quantities. Though these are present in only small quantities, they are all necessary:

Boron is believed to be involved in carbohydrate transport in plants; it also assists in metabolic

regulation. Boron deficiency will often result in bud dieback.

Chlorine is necessary for osmosis and ionic balance; it also plays a role in photosynthesis.

Copper is a component of some enzymes. Symptoms of copper deficiency include browning of

leaf tips and chlorosis.

Iron is essential for chlorophyll synthesis, which is why an iron deficiency results in chlorosis.

Manganese activates some important enzymes involved in chlorophyll formation. Manganese

deficient plants will develop chlorosis between the veins of its leaves. The availability of
manganese is partially dependent on soil pH.

Molybdenum is essential to plant health. Molybdenum is used by plants to reduce nitrates into
usable forms. Some plants use it for nitrogen fixation, thus it may need to be added to some
soils before seeding legumes.

Zinc participates in chlorophyll formation, and also activates many enzymes. Symptoms of zinc
deficiency include chlorosis and stunted growth.

Fluid fertilizers:

Fluid fertilizers are the inorganic substances, produced industrially and introduced into a soil in a liquid
state.
Liquid fertilizers include nitrogenous fertilizers,anhydrous liquid ammonia, aqueous ammonia, ammoniat
es, concentrated solutions of ammonium nitrate and urea, and complex fertilizerscontaining two or three
basic plant food elements (nitrogen, phosphorus, and potassium) in various proportions.

Nitrogenous liquid fertilizers (ammonia solution 16.520.5 percent, anhydrous liquid ammonia 82.2 percent
, ammonia liquors 3545 percent)contain nitrogen mainly or exclusively in the form of ammonia (NH;}), whi
ch bonds firmly with the soil particles and is not washed out by rain or melted snow water.

Thus, liquid fertilizers can be applied not only in spring but also in late summer (under a winter crop) and
in theautumn (under the following years spring crop). Liquid fertilizers are introduced into the soil to a spe
cific depth (to avoid ammonia loss) bytrailer or tractormounted machines with plows or cultivators.

Ammonia solution and liquors are introduced at a depth of 10to12 cm, andanhydrous liquid ammonia at
1520 cm (depending on the mechanical state of the soil). Since ammonium nitrate and urea solutions (up
to30to32 percent) do not contain ammonia, they can be put in the top dressing and sprayed over the soil
s surface. Liquid fertilizer doses (interms of nitrogen) are the same as those of solid nitrogen fertilizers.

Liquid fertilizer containing free ammonia is stored and transported in airtight vessels. Steel tanks that can
withstand high vapor pressurereaching 2 meganewtons per sq m (20 atmospheres) are used for anhydro
us ammonia. Tanks used for tractor fuel are suitable for aqueousammonia. Ammoniates require vessels t
hat are made of stainless steel, aluminum, or plastic or have an anticorrosion coating. Nitrogenliquid fertili
zers are considerably cheaper than solid ones, and less labor is needed to apply them.

Complex liquid fertilizers are aqueous solutions containing up to 27 percent nitrogen, phosphorus, and po
tassium. With stabilizing additives(colloidal clay, bentonite) to prevent crystallization, it is possible to incre
ase the concentration of food substances in the fertilizer to 40percent. Since complex fertilizers do not co
ntain free nitrogen they can be applied to the surface during plowing, cultivating, or harrowing,and during
sowing in a drill row.

UAN is a solution of urea and ammonium nitrate in water used as a fertilizer. The combination of urea
and ammonium nitrate has an extremely low critical relative humidity (18% at 30 C) and can therefore
only be used in liquid fertilizers. The most commonly used grade of these fertilizer solutions is UAN
32.0.0 (32%N) also known as UN32 or UN-32, which consists of 45% ammonium nitrate, 35% urea and
only 20% water. Other grades are UAN 28, UAN 30 and UAN 18. The solutions are quite corrosive
towards mild steel (up to 500 milli inches per year on C1010 steel) and are therefore generally equipped
with a corrosion inhibitor to protect tanks, pipelines, nozzles, etc. Ureaammonium nitrate solutions
should not be combined with calcium ammonium nitrate (CAN-17) or other solutions prepared from
calcium nitrate. A thick, milky-white insoluble precipitate forms that may plug nozzles and pipelines.
Controlled release fertilizers:

A controlled-release fertilizer (CRF) is a granulated fertilizer that releases nutrients gradually into
the soil (i.e., with a controlled release period). The slowness of the release is determined by the low
solubility of the chemical compounds in the soil moisture. Since conventional fertilizers are soluble in
water, the nutrients can disperse quickly as the fertilizer dissolves. Because controlled-release
fertilizers are not water-soluble, their nutrients disperse into the soil more slowly. The fertilizer
granules may have an insoluble substrate or a semi-permeable jacket that prevents dissolution while
allowing nutrients to flow outward.

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 semi-permeable coatings, occlusion, protein
materials, or other chemical forms, by slow hydrolysis of water-soluble low molecular weight
compounds, or by other unknown means.
Stabilized nitrogen fertilizer: A fertilizer to which a nitrogen stabilizer has been added. A nitrogen
stabilizer is a substance added to a fertilizer which extends the time the nitrogen 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.
Urease inhibitor: A substance that inhibits hydrolytic action on urea by the enzyme urease.

Implementation:
The fertilizer is administered either by topdressing the soil, or by mixing the fertilizer into the soil
before sowing.

One of the advantages of CRF is reduced incidence of fertilizer burn. Other important advantages
are economical benefits (labor savings) due to less applications and mostly less overall fertilizer
amount. The results (yield) are in most cases improved by > 10%.

Incorporating CRF into growing media, especially during soil mixing, requires no extra application
labor. It is easy to vary the amount of CRF applied to crops with different feeding needs. Because
CRFs provide nutrients slowly and constantly and in a manner that is not tied to irrigation
frequency, they provide more consistent nutrition for plants making it possible to maintain more
consistent quality. Application of a CRF results in lower root zone pH or electrical conductivity
compared to water soluble fertilizers as long as crops are properly irrigated (less stress).
Depending on rate and crop, CRFs may produce more compact plants that require less use of growth
regulators. CRFs continue to feed plants under cool weather conditions. This is especially important
during the busy shipping season. Depending on the rate and product selected, CRFs continue to feed
plants while theyre displayed at retail outlets, and often, long after their eventual purchase by
consumers.
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