PART-2

FERTILIZER
NITROGENEUS FERTILIZER
AMMONIA
NITRIC ACID
 FERTILIZER
• In the same way that humans need to eat
properly to stay healthy, so plants need certain
nutrients to grow properly
• Fertilizer is a substance added to soil to improve
plant’s growth and yield. Basically it is a
chemical or natural substance is added to soil or
land to increase its fertility.
• Fertilizers are food supplements for plants and
need 16 nutrients to be healthy
 COMPLETE VS. INCOMPLETE
• Complete has all three primary nutrients-
nitrogen phosphorous & potassium
• Examples: 10-10-10, 15-30-15, 20-5-20
• Incomplete DOES NOT have all three primary
nutrients
• Examples: 20-0-0, 0-20-0, 12-0-44
 BASIC FORMS OF FERTILIZERS:
• Granular- designed to be scratched into the
soil and water soluble.
• Powdered- designed to be dissolved in water
for liquid feeding to soil and foliage
• Liquid- usually a concentrated form to be
mixed with water
 CLASSIFICATION OF FERTILISERS
1. Straight fertilizers
• Straight fertilizers are those which supply only one primary
plant nutrient (N, P & K).
• E.g. Urea, Ammonium sulphate, Potassium chloride and
Potassium sulphate
2. Complex fertilizers
• Complex fertilizers contain 2 or 3 primary plant nutrients of
which two primary nutrients are in chemical combination.
• Usually produced in granular form.
• Diammonium phosphate, Nitrophosphates, Ammonium
phosphate
3. Mixed fertilizers
• Mixed fertilizers are physical mixtures of
straight fertilisers.
• They contain two or three primary plant
nutrients.
• made by thoroughly mixing the ingredients
either mechanically or manually
BASED ON CONCENTRATION OF PRIMARY PLANT
NUTRIENTS (N, P & K) IN FERTILISERS:
LOW ANALYSIS HIGH ANALYSIS
FERTILISERS FERTILISERS
• Fertilisers contain less • Total content of primary
than 25% of primary nutrients is above 25%.
nutrients. • Example- Urea (46% N) ,
• Example- SSP(16% Anhydrous ammonia
P₂O₅), Sodium nitrate (82.2% N) , Ammonium
(16% N) phosphate (20% N
+20% P₂O₅)
CLASSIFICATION BASED ON PHYSICAL FORM

• SOLID FERTILIZERS • LIQUID FERTILIZERS

• Powder(single • Liquid form fertilizers are
superphosphate) applied with irrigation water
• or for direct application.
Crystals (Ammonium
sulphate) • 2 types-
• Prills (Urea, Diammonium • 1- clear liquid fertilisers (when
the fertilisers are completely
phosphate,
dissolved in water)
superphosphate)
• 2- Suspension liquid fertilisers
• Granules (Holland granules)
(when fertilisers are
• Supergranules (Urea suspended as fine particles in
supergranules) water)
• Briquettes (Urea briquettes)
BASED ON THE NATURE OF FERTILISERS:
Acid Forming Fertilisers Alkaline Forming
• Fertilisers which leave an Fertilisers Or Basic
acid residue in the soil. Fertilisers
• Apply acid forming • Fertilisers which leave
fertilisers to alkaline soil. an alkaline residue in
• The amount of calcium the soil.
carbonate required to • Apply acid forming
neutralize the acid fertilisers to alkaline
residue is called its Acid soil.
equivalent.
 Nitrogenous Fertilisers
• The fertilizer materials containing nitrogen are
called nitrogenous fertilisers.
• They may contain secondary nutrients like
Calcium and Sulphur
 Ammonia
• Ammonia is a colourless gas with a chemical formula NH 3.
• It consists of hydrogen and nitrogen. In its aqueous form, it is
called ammonium hydroxide. This inorganic compound has
a pungent smell. In its concentrated form, it is dangerous
and caustic.
• Ammonia is lighter than air with a density of 0.769  kg/m3 at
STP.
• It is widely used as a fertilizer. It is also used in the
manufacturing of explosives such as nitrocellulose and TNT.
• Also, it is used in the production of soda ash and in the
Ostwald process to get nitric acid.
• Ammonia is known to behave as a weak base
since it combines with many acids to form
salts. 
• For example, when it is reacted with
hydrochloric acid, ammonia is converted
into ammonium chloride.
• All the salts that are produced from such acid-
base reactions are known to contain
the ammonium cation, denoted by NH4+.
 Preparation of Ammonia – NH3

• Ammonia is easily made in the laboratory by heating an

ammonium salt, such as ammonium chloride NH 4Cl with a
strong alkali, such as sodium hydroxide or calcium
hydroxide.
• 2NH4Cl + Ca(OH)2 → CaCl2 + 2H2O + 2NH3(g)
• The gas may also is made by warming concentrated
ammonium hydroxide.
• The principal commercial method of production of ammonia
is the Haber Process the direct combination of nitrogen and
hydrogen under high pressure in the presence of a catalyst.
 NH3 Uses (Ammonia)

• It is used as fertilizers as it increases the yield of crops

• It is used in the household as a cleaner – NH 3 is mixed with water to
clean stainless steel and glass
• It is used in food products as an antimicrobial agent
• It is used in the fermentation industry
• It is used as a refrigerant
• It is used as a pH adjuster in the fermentation process
• It is used to neutralize pollutant like nitrogen oxides emitted from
diesel engines
• It is used as a fuel for rocket engines
• It is used in textile industries
• It is used in the manufacture of synthetic fibre like rayon and nylon
 Introduction to Ammonia Production
• Ammonia is critical in the manufacturing of fertilizers, and is
one of the largest-volume synthetic chemicals produced in the
world.
• Most people associate the pungent smell of ammonia (NH3)
with cleaners or smelling salts
• However, the use of ammonia in these two products
represents only a small fraction of the total global ammonia
production, which was around 176 million metric tons in 2014.
• Ammonia has been known for more than 200 years.
• Joseph Priestley, an English chemist, first isolated gaseous
ammonia in 1774
• Its composition was ascertained by French chemist
Claude Louis Berthollet in 1785.
• In 1898, Adolph Frank and Nikodem Caro found that
N2 could be fixed by calcium carbide to form calcium
cyanamide, which could then be hydrolyzed with water
to form ammonia
• CaO + 3C ↔ CaC2 + CO
• CaC2 + N2 ↔ CaCN2 + C
• CaCN2 + 3H2O ↔ CaCO3 + 2NH3
• The production of significant quantities of ammonia
using the cyanamide process did not occur until the early
20th century. Because this process required large
amounts of energy, scientists focused their efforts on
reducing energy requirements.
• German chemist Fritz Haber performed some of the most important work
in the development of the modern ammonia industry. Working with a
student at the Univ. of Karlsruhe, he synthesized ammonia in the
laboratory from N2 and H2.
• Meanwhile, Walther Nernst, a professor of physical chemistry at the Univ.
of Berlin, developed a process to make ammonia by passing a mixture of
N2 and H2 across an iron catalyst at 1,000°C and 75 barg pressure.
• He was able to produce larger quantities of ammonia at this pressure
than earlier experiments by Haber and others at atmospheric pressure.
• Nernst concluded that the process was not feasible because it was
difficult or almost impossible (at that time) to produce large equipment
capable of operating at that pressure.
• Nonetheless, both Haber and Nernst pursued the high-pressure route to
produce ammonia over a catalyst.
• Haber finally developed a process for producing commercial quantities of
ammonia, and in 1906 he was able to achieve a 6% ammonia
concentration in a reactor loaded with an osmium catalyst. 
• In the mid-1960s, the American Oil Co. installed a
single-converter ammonia plant engineered by
M.W. Kellogg (MWK) at Texas City, TX, with a
capacity of 544 m.t./day.
• The single-train design concept was so
revolutionary that it received the Kirkpatrick
Chemical Engineering Achievement Award in
1967.
• The plant used a four-case centrifugal compressor
to compress the syngas to a pressure of 152 bar,
and final compression to an operating pressure of
324 bar occurred in a reciprocating compressor.
 Plant designs in the 21st century

• During the first few years of the 21st century, many

improvements were made in ammonia plant
technology that allow existing plants to increase
production rates and new plants to be built with larger
and larger capacities
• Competition between technology suppliers is quite
fierce.
• Three technology licensors — KBR (Kellogg Brown and
Root), Haldor Topsøe, and ThyssenKrupp Industrial
Solutions (TKIS) — currently dominate the market. 
 Kellogg process
• MW Kellogg technology accounts for a large proportion of the world's
ammonia capacity, and with yet more capacity being planned - the
group is getting set to build more plants, reports Muriel Cozier.
• The name of Kellogg has long been associated with ammonia
technology and since 1965 more than 150 ammonia plants have been
built using the contractor's technology, accounting for a significant
portion of worldwide capacity.
• The Kellogg Advanced Ammonia Process (KAAP) and the Kellogg
Reforming Exchanger System (KRES) are the latest technologies offered
by Kellogg, and KAAP, according to the company, represents the first
significant advance in ammonia synthesis catalyst technology since an
iron catalyst was first used for ammonia manufacture more than 80
years ago.
Raw Materials
• The Ammonia Plant Process is operated using
basic raw materials of Natural Gas, Water and Air.
• The different reactions in the process require
specific catalysts.
• Natural Gas is Methane, and used as a fuel in the
furnace for heating the exterior of the primary
reformer tubes. It’s used as process material
inside the primary reformer tubes for the
production of Hydrogen.
• It’s delivered to site by pipeline at 25bar. It must
be pressurized to over 40 bar to run the process.
• Fresh Water
• Potable Water is delivered to site by pipeline from a
local authority. It must be de-mineralized before
conversion to steam. It is used in the primary
reformer as steam with natural gas where they both
react to form hydrogen and carbon oxides.
• The water treatment plant , water is de-mineralized
using as a first step, one of three parallel cationic
streams. The cationic and anionic units are
regenerated each shift and the mixed beds are
regenerated weekly depending on the sodium and
silica slippage from the cation and anion exchangers
respectively.
• Air is also used for combustion of natural gas
in the primary reformer and is supplied to the
burners by a forced draught fan
• The temperature of the combustion gases is
1050°C at the primary-reformer- furnace so
heat recovery is an essential part of the
process.
• There are several heat recovery units in this
waste heat recovery section of the plant
reducing the temperature from 1050°C to
135°C at the discharge point.
Reaction :
• 2CH4 + O2  2CO + 4H2
• 2CO + O2  2CO2
• N2 + 3H2  2NH3
Manufacturing process:
• Natural gas is used for production of nitrogen &
hydrogen
• The purified nitrogen and hydrogen is thus reacted to
give ammonia gas.
• In commercial production sulfur free natural gas is mixed
with steam in the volume based rartio of 3:7:1 and
compressed to 40 atm
• Mixture is preheated with the recycled flue or effluent
gases and fed into the furnace
• At 800 – 850 C in the presence of iron catalyst promoted with
other metal oxides conversion of methane takes place with the
formation
• Residue gas is mixed with air and fed into shaft converter to get
complete conversion
• Waste heat is utilized for the steam generation and ethanolamine
which are used in CO2 & H2S removal.
• Exit gas containing poison was regenerated in the methanator at
280-350 c which ultimately used foe heating the feed water.
• Purified N2 & H2 mixture was compressed to 300 atm at 320 to 380
c in the presence of catalyst converted to NH3
• 14-20 % conversion achieved.
• Nh3 condensed and separated from exit gas, whereas unconverted
N2 & H2 gases were recycled along with the fresh gases.
 Design aspects of Ammonia converters used
in haldor topsoe process
• This is two bed radial flow converter with indirect cooling between
the beds.
• Features of the S-200 incude efficient use of converter volume & low
pressure drop and high conversion per pass due to indirect cooling.
• It involves installation of a new converter, basket in an existing
pressure shell with full opening closure
• Will result in a reduction in specific energy consumption of about 0.3
gcal/tonne of ammonia and a apacity increase of up to 20 %
• S-50 bed catalyst bed inlet temp is controlled by the amt of steam
superheating that occurs upstream of s-50
• S-300 has an internal heat exchanger installed between the second
and third catalyst beds.
 Storage & transportation
• Storage of liquid ammonia:
• Storage at ambient temperature & equivalent
pressure in cylindrical vessels
• Storage under pressure in spherical vessels.
• This type of storage is often referred to as
semi-pressure or semi-refrigerated
• Storage at atmospheric pressure.
• Transportation of liquid ammonia
• It is used by down stream plants directly or
transferred to storage tanks.
• From these ammonia can be transferred to
road tankers, rail tank cars or ships.
• Large volume of ammonia by pipe line over a
great distances is far more economical than by
river or rail.
 Nitric acid
• Nitric acid (HNO3).
• A colorless liquid that is used in the manufacture of
inorganic and organic nitrates and nitro compounds for
fertilizers, dye intermediates, explosives, and many
different organic chemicals.
• Continued exposure to vapor may cause chronic bronchitis;
chemical pneumonitis may occur
• NITRIC ACID, RED FUMING is a pale yellow to reddish
brown liquid generating red-brown fumes and having a
suffocating odor. Very toxic by inhalation. Corrosive to
metals or tissue.
• There are approximately 50 privately owned plants
producing nitric acid in this country. The total annual
productivity capacity of these commercial plants is
estimated to be on the order of 4.1 million tons
• Government facilities in stand-by condition or
operation have an additional capacity of about 2.3
million tons per year. Production of nitric acid (100%
basis) in 1961 as reported by the U. S. Department
of Commerce was 3,378,000 tons
• The largest use of nitric acid is in the production of
fertilizers. This usage accounts for 75% of all the
nitric acid produced.
• About 15% of the production is used in the
manufacture of explosives and 10% is distributed
among a wide variety of outlets. These include the
manufacture of synthetic fibers, dyes, and plastics.
• In 1991, there were approximately 65 nitric acid
(HNO ) manufacturing plants in the U. S. with a 3
total capacity of 11 million tons of HNO per year.
• The plants range in size from 6,000 to 700,000 tons
per 3 year.
• About 70 percent of the nitric acid produced is
consumed as an intermediate in the manufacture of
ammonium nitrate (NH NO ), which in turn is used in
fertilizers.
• Nitric acid is a key industrial chemical for the production of
fertilizers.
• In 2013, annual production capacity was ca. 78 million
tonnes (Mt) and actual manufacturing ca. 58.5 Mt.
Production growth of 2.3% is anticipated, considering an
annual production of 65.5 Mt in 2018.
• The current production route of nitric acid is known as “the
Ostwald process” and has been used for nearly a century.
• In this process, ammonia is combusted (oxidized) in air, to
nitric oxide (NO). This highly exothermic reaction is carried
out over a highly selective platinum–rhodium catalyst. The
temperature ranges between 800 and 930 °C. The
pressure, on the other hand, varies from ambient to 15 bar,
depending on the technology. 
 PHYSICAL PROPERTIES
• Appearance: Colorless, yellow or red
• Odor: Acrid, suffocating
• Density: 1.5129 g cm-3
• Melting point: −42 °C (−44 °F; 231 K)
• Boiling point: 83 °C (181 °F; 356 K)
• Solubility : Completely miscible
• Vapor pressure: 48 mmHg (20 °C)
 CHEMICAL PROPERTIES
• Stability : Pure nitric acid is not very stable. Even at
ordinary temp. in presence of sunlight it undergoes
slight decomposition.
4 HNO3 → 2 H2O + 4 NO2 + O2
• Oxidizing properties : Nitric acid is a strong oxidizing
agent as shown by its large positive E◦ values.
NO3- (aq) + 2H+ (aq) e- → NO2 (g) + H2O (l) E◦ = 0.79 V
NO3- (aq) + 4H+ + 3e- → NO (g) 2H2 (l) E◦ = 0.96 V
• Reactions with metals : Nitric acid dissolves most
metals including iron, copper, and silver, with
generally the liberation of lower oxides of nitrogen
rather than hydrogen. It can also dissolve the noble
metals with the addition of hydrochloric acid.
Cu + 4HNO3 → Cu(NO3)2 + 2NO2 + 2H2O
• Reactions with nonmetals: Reaction with non-metallic
elements, with the exception of silicon and halogen,
usually oxidizes them to their highest oxidation states
as acids with the formation of nitrogen dioxide for
concentrated acid and nitrogen oxide for dilute acid.
C + 4HNO3 → CO2 + 4NO2 + 2H2O
 USES
• As a starting material in the manufacture of nitrogen fertilizers
such as ammonium nitrate & ammonium etc. Large amounts
are reacted with ammonia to yield ammonium nitrate.
• It is commonly used in science laboratories at schools for
experimenting when specifically testing for chloride
• As a nitrating agent in the preparation of explosives such as
TNT, nitro-glycerine, cellulose poly-nitrate, ammonium picrate
• It is used as a medicine to remove chancres and warts.
• Used in fibers, plastics and dyestuffs industries
• Used in metallurgy and in rocket fuel production.
• It is used in calorimetric test to distinguish between heroin and
morphine
 Manufacturing of Nitric Acid by Pressure
ammonia oxidation process and Intermediate
pressure ammonia oxidation process
Raw material:
• Basis: 1000kg nitric acid
• Ammonia : 290 kg
• Air : 3000 n/m3
• Platinum : 0.001 kg
• Water : 120000 Kg
• Steam credit : 1000 kg
• Power : 10-30 kwh
Major reaction :
4NH3 + 5O2 4 NO + 6 H2O ,∆H = -216.6 Kcal
2NO + O2 2NO2, ∆H = -27.1 kcal
Side reaction:
4NH3 + 3O2 2N2 + 6H2O, ∆H=-302.7 kcal
Nitrous Oxide Oxidation AND Absorption
2NO + O2 2NO2, ∆H=-27.1 Kcal
3NO2 + H2O 2HNO3 + NO , ∆H=-32.2 Kcal
 PROCESS:
• Nitric acid is made by the oxidation of ammonia using
platinum ot platinum-rhodium (10%) as catalyst
followed by the reaction.
• The process involves four steps:
• Catalytic oxidation of ammonia with atmospheric oxygen
to yield nitrogen monoxide
• Oxidation of nitrogen monoxide product to nitrogen
dioxide or dinitrogen tetroxide
• Absorption of the nitrogen oxides to yield nitric acid
• Concentration of nitric acid
• Compressed air is mixed with anhydrous ammonia
fed to a shell and tube converter designed so that
the preheater and steam heat recovery boiler –
superheater are within the same reactor shell.
• Converter section consists of 10-30 sheets of pt-rh
alloy in the form of 60-80 mesh wire gauge
packed in layers inside the tube
• Product gases from the reactor which contain 10-
12 % NO are sent through heat recovery units
consisting of heat recovery boiler
• Air added to convert NO to NO2 at 40-50 C
• Product from water absorption system is 57-
60 % HNO3 sol
• Nitric acid concentrated by two chemicals
• 93 % sulfuric acid
• 70-75 % magnesium nitrate sol