AMMONIA

Submitted in fulfilment of the requirements

for

SECOND YEAR ENGINEERING

In

CHEMICAL ENGINEERING

By

ABHINAV TYAGI 204048

URJA MALADKAR 204025

VAISHNAVI NAMBIAR 204032

BHUPENDRA 204049
VATANDAR

Under the guidance of:

DR. TRUPTI DHARMARAO

Associate Professor, Department of Chemical Engineering Department, TSEC

Thadomal Shahani Engineering College

University of Mumbai 2020 – 2021

1
 CERTIFICATE

This is to certify that the project entitled

“Ammonia”

is the work of

ABHINAV TYAGI 204048

URJA MALADKAR 204025

VAISHNAVI NAMBIAR 204032

BHUPENDRA 204049
VATANDAR

Dr. Trupti Dharmarao

Guide

Dr. Anita Kumari Dr G.T. Thampi

Head of Department Principal

 Project Report Approval for S.E.

Project report entitled

“Ammonia”

By

ABHINAV TYAGI 204048

URJA MALADKAR 204025

VAISHNAVI NAMBIAR 204032

BHUPENDRA 204049
VATANDAR

Is approved for the degree of “SECOND YEAR ENGINEERING” in

“CHEMICAL ENGINEERING”
Examiners:

1.

2.

3.

4.

Date:
 DECLARATION

I declare that this written submission represents my ideas in my own words and
where others’ ideas or words have been included, I have adequately cited and
referenced the original sources. I also declare that I have adhered to all
principles of academic honesty and integrity and have not misrepresented or
fabricated or falsified any idea/data/fact/source in our submission. I understand
that any violation of the above will cause for disciplinary action by the Institute
and can also evoke penal action from the sources which have thus not been
properly cited or from whom paper permission has not been taken when needed.

1. 2.

Abhinav Tyagi (204048) Urja Maladkar (204025)

3. _ 4.

Vaishnavi Nambiar (204032) Bhupendra Vatandar (204049)

 INDEX

Page No.

General Characteristics 6

Physical & Chemical Properties of Ammonia 7

Chemical Reactions in Ammonia Process 10

Different Processes of Manufacturing Ammonia 17

Description of Most Commonly Used Process with 25

Process Flow Diagram

Applications of Ammonia 32

Market Survey 34

Important Industries Manufacturing Ammonia 44

 1.General Characteristics
Ammonia is a compound of nitrogen and hydrogen with the formula NH3. A stable binary
hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct
characteristic of a pungent smell. It is a common nitrogenous waste, particularly among
aquatic organisms, and it contributes significantly to the nutritional needs of terrestrial
organisms by serving as a precursor to food and fertilizers. Ammonia, either directly or
indirectly, is also a building block for the synthesis of many pharmaceutical products and is
used in many commercial cleaning products. It is mainly collected by downward
displacement of both air and water.

Although common in nature – both terrestrially and in the outer planets of the Solar System –
and in wide use, ammonia is both caustic and hazardous in its concentrated form. It is
classified as an extremely hazardous substance in the United States, and is subject to strict
reporting requirements by facilities which produce, store, or use it in significant quantities.[12]

The global industrial production of ammonia in 2018 was 175 million tonnes,[13] with no
significant change relative to the 2013 global industrial production of 175 million tonnes.
[14]
 Industrial ammonia is sold either as ammonia liquor (usually 28% ammonia in water) or as
pressurized or refrigerated anhydrous liquid ammonia transported in tank cars or cylinders.[15]

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

stored under pressure or at low temperature. Household ammonia or ammonium hydroxide is
a solution of NH3 in water. The concentration of such solutions is measured in units of
the Baumé scale (density), with 26 degrees Baumé (about 30% (by weight) ammonia at
15.5 °C or 59.9 °F) being the typical high-concentration commercial product.
 2. Physical and Chemical Properties
Physical Properties
Ammonia is a colourless gas with a characteristically pungent smell. It is lighter than air, its
density being 0.589 times that of air. It is easily liquefied due to the strong hydrogen
bonding between molecules; the liquid boils at −33.3 °C (−27.94 °F), and freezes to white
crystals[19] at −77.7 °C (−107.86 °F).

Ammonia may be conveniently deodorized[clarification needed] by reacting it with either sodium

bicarbonate or acetic acid. Both of these reactions form an odourless ammonium salt.

Solid
The crystal symmetry is cubic, Pearson symbol cP16, space group P213 No.198, lattice
constant 0.5125 nm.[23]

Liquid
Liquid ammonia possesses strong ionising powers reflecting its high ε of 22. Liquid ammonia
has a very high standard enthalpy change of
vaporization (23.35 kJ/mol, cf. water 40.65 kJ/mol, methane
8.19 kJ/mol, phosphine 14.6 kJ/mol) and can therefore be used in laboratories in uninsulated
vessels without additional refrigeration. See liquid ammonia as a solvent.

Solvent properties
Ammonia readily dissolves in water. In an aqueous solution, it can be expelled by boiling.
The aqueous solution of ammonia is basic. The maximum concentration of ammonia in water
(a saturated solution) has a density of 0.880 g/cm3 and is often known as '.880 ammonia'.

Combustion
Ammonia does not burn readily or sustain combustion, except under narrow fuel-to-air
mixtures of 15–25% air. When mixed with oxygen, it burns with a pale yellowish-green
flame. Ignition occurs when chlorine is passed into ammonia, forming nitrogen and hydrogen
chloride; if chlorine is present in excess, then the highly explosive nitrogen trichloride (NCl3)
is also formed.
Decomposition
At high temperature and in the presence of a suitable catalyst, ammonia is decomposed into
its constituent elements. Decomposition of ammonia is slightly endothermic process
requiring 23 kJ/mol (5.5 kcal/mol) of ammonia, and yields hydrogen and nitrogen gas.
Ammonia can also be used as a source of hydrogen for acid fuel cells if the unreacted
ammonia can be removed. Ruthenium and platinum catalysts were found to be the most
active, whereas supported Ni catalysts were the less active.

Chemical Properties
Thermal stability: Ammonia is highly stable. However, it can be decomposed into hydrogen
and nitrogen by passing over heated metallic catalysts or when electric discharge is passed
through it.

Combustibility: Ammonia is combustible in air. However, it will burn in an atmosphere of

oxygen.

Nitric oxide is obtained when a mixture of ammonia and air is passed over platinum -
rhodium catalyst at 800°C

Basic character: Ammonia molecule has a strong tendency to donate its lone pair of
electrons of nitrogen to other molecules. Thus, it acts like a strong Lewis base. In aqueous
solutions, NH3 ionizes in accordance with the reaction.
The equilibrium constant for this reaction at 298 K is 1.8 x 10^-5. Thus, ammonia ionizes to a
very small extent in aqueous solution. The aqueous solution of ammonia acts as a weak base
due to the presence of OH- ions therein. Therefore, ammonia turns red litmus blue and reacts
with acids to form salts.
 3. Chemical Reactions in Ammonia Process
Typical modern ammonia-producing plant first converts natural gas, liquified petroleum gas
or petroleum naphtha into gaseous hydrogen. Hydrogen is produced from a variety of
feedstocks, mostly from natural gas, coal or naphtha. The ways in which hydrogen is
obtained from these feedstocks are dealt with separately.

The method for producing hydrogen from hydrocarbons is known as steam reforming. The
hydrogen is then combined with nitrogen to produce ammonia via the Haber-Bosch process.

Part A : Seperation of Hydrogen

A. Hydrogen from natural gas (methane).

This involves two stages:

i) SYN GAS: the manufacture of synthesis gas (a mixture of carbon monoxide and
hydrogen (steam reforming)

 DESULPHURISATION: Whichever way the methane is obtained, it will contain

some organic sulphur compounds and hydrogen sulphide, both of which must be
removed. Otherwise, they will deactivate and poison the catalyst needed in the
manufacture of synthesis gas. In the desulfurization unit, the organic sulphur
compounds are often first converted into hydrogen sulphide, prior to reaction with
zinc oxide. The feedstock is mixed with hydrogen and passed over a catalyst of

mixed oxides of cobalt and molybdenum on an inert support (a specially treated

alumina) at ca 700 K.

Then the gases are passed over zinc oxide at ca 700 K and hydrogen sulphide is
removed:
 PRIMARY (steam) REFORMING • Reforming is the process of converting
natural gas in to hydrogen, carbon monoxide and carbon dioxide. Steam and
natural gas are combined at a three-to-one ratio. This mixture is preheated and
passed through catalyst – filled tubes in the primary reformer.

Catalytic steam reforming of the sulphur produces synthesis gas (hydrogen and
carbon monoxide). using methane as an example.

High temperatures and low pressures favour the formation of the products (Le
Chatelier's Principle). In practice, the reactants are passed over a catalyst of nickel,
finely divided on the surface of a calcium oxide/aluminium oxide support
contained in vertical nickel alloy tubes.

 SECONDARY STEAM REFORMING: reacts oxygen from the air with some of
the hydrogen present and the resulting mixture is passed over a nickel catalyst. The
 steam and heat produced from the combustion reforms most of the residual
methane. Among the key reactions are:

The emerging gas from this net exothermic stage is at ca 1200 K and is cooled in
heat exchangers. The steam formed from the water used in cooling the gases is
used to operate turbines and thus compressors and to preheat reactants.
Some recent designs use waste heat from the secondary reformer directly to
provide heat for the primary reformer. At this stage the gas contains hydrogen,
nitrogen, carbon monoxide and carbon dioxide and about 0.25% methane. As air
contains 1% argon, this also accumulates in the synthesis gas.

ii) THE SHIFT REACTION:

 This process converts carbon monoxide to carbon dioxide, while generating more
hydrogen. It takes place in two stages. In the first, the high temperature shift
reaction, the gas is mixed with steam and passed over an iron/chromium (III)
oxide catalyst at ca 700 K in a fixed bed reactor. This decreases the carbon
monoxide concentration from 11%:

In the second stage, the low temperature shift reaction, the mixture of gases is
passed over a copper-zinc catalyst at ca 500 K. The carbon monoxide
concentration is further reduced to 0.2%.

 PURIFICATION: The gas mixture now contains about 18% carbon dioxide
which is removed either by scribbling with water, aqueous monoethanolamine
solution or hot potassium carbonate solution. CO is an irreversible poison for the
catalyst used in the synthesis reaction, hence the need for its removal the synthesis
gas is passed over another catalyst bed in the methanator, where remaining trace
 amounts of carbon monoxide and dioxide are converted back to methane using
hydrogen.

This process is known as methanation. A gas is obtained of typical composition:

74% hydrogen, 25% nitrogen, 1% methane, together with some argon.

B. Hydrogen from naphtha

If naphtha is used as the feedstock, an extra reforming stage is needed. The naphtha is
heated to form a vapour, mixed with steam and passed through tubes, heated at 750 K
and packed with a catalyst, nickel supported on a mixture of aluminium and
magnesium oxides. The main product is methane together with oxides of carbon, and
is then processed by steam reforming, as if it was natural gas, followed by the shift
reaction.

C. Hydrogen from coal

If coal is used, it is first finely ground and heated in an atmosphere of oxygen and
steam. Some of the coal burns very rapidly in oxygen (in less than 0.1 s) causing the
temperature in the furnace to rise and the rest of the coal reacts with the steam:

The gas emitted contains ca 55% carbon monoxide, 30% hydrogen, 10% carbon
dioxide and small amounts of methane and other hydrocarbons. This mixture is
treated by the shift reaction.
The main problems of using coal includes the large amounts of sulphur dioxide and
trioxide generated in burning coal and the significant amounts of other impurities such
as arsenic and bromine, all of which are very harmful to the atmosphere and all of
which are severe poisons to the catalysts in the process. There is also a massive
problem with disposal of the ash.
 D. Hydrogen from biomass
Synthesis gas can be produced from biomass.

Part B : The Manufacturing of Ammonia ( Haber’s Process)

1. Ammonia converter

After leaving the compressor, the gaseous mixture goes through catalyst beds in the
synthesis converter where Ammonia is produced with a three-to-one hydrogen-to-
nitrogen stoichiometric ratio. However, not all the hydrogen and nitrogen are
converted to ammonia. The unconverted hydrogen and nitrogen are separated from
the ammonia in the separator and re-cycled back to the synthesis gas compressor and
to the converter with fresh feed. because the air contains argon which does not
Participate in the main reaction, purging it minimizes its Build up in the recycle loop.

2. Ammonia separation

The removal of product ammonia is accomplished via mechanical refrigeration or

absorption/distillation. the choice is made by examining the fixed and operating costs.
Typically, refrigeration is more economical at synthesis pressure of 100 atm or
greater. At lower pressures, absorption/distillation is usually favoured.

3. Ammonia storage

Ammonia is stored in tanks as a refrigerated liquid. some ammonia is used directly as

a fertilizer. Most ammonia is converted in to downstream processes to urea (46%
nitrogen) or ammonium nitrate (34% nitrogen) for use as fertilizer.

The heart of the process is the reaction between hydrogen and nitrogen in a fixed bed
reactor. The gases, in stoichiometric proportions, are heated and passed under pressure
over a catalyst.
 
 Figure 3 A diagram illustrating a conventional synthesis reactor (a converter).

The proportion of ammonia in the equilibrium mixture increases with increasing pressure
and with falling temperature (Le Chatelier's Principle). To obtain a reasonable yield and
favourable rate, high pressures, moderate temperatures and a catalyst are used.

Pressure/atm Percentage ammonia present at equilibrium at a range of temperatures

  373 K 473 K 573 K 673 K 773 K 973 K

10 - 50.7 14.7 3.9 1.2 0.2

25 91.7 63.6 27.4 8.7 2.9 -

50 94.5 74.0 39.5 15.3 5.6 1.1

100 96.7 81.7 52.5 25.2 10.6 2.2

200 98.4 89.0 66.7 38.8 18.3 -

400 99.4 94.6 79.7 55.4 31.9 -

1000 - 98.3 92.6 79.8 57.5 12.9

 Table 1 Percentage, by volume, of ammonia in the equilibrium mixture for the reaction
between nitrogen and hydrogen at a range of temperatures and pressures.
 
A wide range of conditions are used, depending on the construction of the reactor.
Temperatures used vary between 600 and 700 K, and pressures between 100 and 200
atmospheres. Much work is being done to improve the effectiveness of the catalyst so that
pressures as low as 50 atmospheres can be used.
As the reaction is exothermic, cool reactants (nitrogen and hydrogen) are added to reduce
the temperature of the reactors.

4. Different Processes of Manufacturing Ammonia

A. Conventional Ammonia Production

HABER-BOSCH:

 The currently adopted ammonia production process basically employs the system

invented by Fritz Haber and Carl Bosch about 100 years ago. Therefore, this
system is well known as Haber–Bosch process. About 85% of total production of
ammonia worldwide is produced by this process [5]. The ammonia synthesis occurs
according to reaction .

3 H2 + N2 ⇋ 2 NH3 ΔH°27 °C = −46.35 kJ/mol 

 Ammonia synthesis is an exothermic reaction (negative enthalpy change), and it

occurs spontaneously at low temperatures (negative entropy change). Although it
is favoured at room temperature, the reaction rate at which the reaction occurs at
room temperature is too slow to be applicable for at an industrial scale.
 To effectively synthesize ammonia from its main components (hydrogen and
nitrogen), the reaction should be performed at a relatively high temperature and
pressure of 400–500 °C and 10–30 MPa, respectively, with the assistance of an
iron-based catalyst. This condition is demanded due to the high dissociation
energy (941 kJ/mol) of triple-bonded nitrogen. However, to bring the reaction
under this high temperature and pressure, about 30 MJ/kg-NH 3 of energy is
required [6].

An ammonia production system from any primary source, such as natural gas, is considered
complex, as it includes many combined processes.
Above diagram shows the schematic diagram of conventional ammonia production from
natural gas. The system consists of different processes: steam reformation, the water–gas shift
reaction, CO2 removal, syngas purification, and ammonia synthesis and separation.
Therefore, efforts to reduce the total energy consumption require the improvement of the
whole process involved.

B. Electrochemical Processing

 Although electrochemical processing is significantly under-developed compared to

the Haber–Bosch process, it is expected to realize higher energy performance. The
energy consumed by this process is about 20% lower than the Haber–Bosch process .

 Above figure shows the schematic flow diagram of electrochemical ammonia

synthesis. The process is considered simple; therefore, its application is considered to
potentially reduce system configuration and control complexity. In addition, the
investment cost can be lower compared to currently adopted ammonia synthesis
systems.
  The reactions at both cathode and anode in proton conducting cells are shown in
reactions (I) and (II), respectively. The reactions at each cathode and anode are
basically reversible.

N2 + 6 H+ + 6 e− ⇌ 2 NH3……….(I)

3 H2 ⇌ 6 H+ + 6 e−…………….(II)

 Four different types of electrolytes are currently available:

(a) Liquid electrolytes

Liquid electrolytes can operate under atmospheric temperature and pressure [22]. There are
some potential liquid electrolytes, including LiClO4 (0.2 M) in tetrahydrofuran [22],
LiClO4 in ionic liquid, LiClO4 in H2SO4 and Li2SO4 in H2SO4

(b) Molten salt

A molten salt type electrolyte is generally operated at a temperature range of 300–500

°C .There are some potential chemicals for use as electrolytes, such as LiCl, KCl and CsCl,
with dissolved Li3N 

(c) Composite membranes

As the representative of composite electrolytes, alkali metal carbonate (such as LiCO 3) and
oxide (such as LiAlO2) and CeO2 doped with Sm2O3 have shown the expected properties,
including oxygen ion, carbonate ion and proton conductivity 

(d) Solid state electrolytes.

The system with solid electrolytes generally operates in very wide operating temperatures,
from room temperature to about 800 °C. There are different materials which can be included
in this type of electrolyte. These include perovskites (cerate and zirconate), fluorites (doped
zirconia, ceria and thoria), pyrochlores (calcium doped lanthanum zirconate) and other
materials (including brownmillerite, eulytite and monazite). 

C.Thermochemical Cycle of Ammonia Production

 As an alternative process for ammonia production, a process employing the

thermochemical cycle has been developed. The system consists of two circulated
processes: reduction (nitrogen activation) and steam-hydrolysis (ammonia formation).
Both reactions are summarized as follows:

Al2O3 + 3C + N2 → 2 AlN + 3 CO    ΔH°25 °C = 708.1 kJ/mol

2AlN + 3 H2O → Al2O3 + 2 NH3    ΔH°25 °C = −274.1 kJ/mol

Figure 4. Schematic diagram of the thermochemical cycle of ammonia production .

Above figure shows the schematic diagram of the thermochemical cycle of ammonia
production.

 The primary energy sources are pre-treated and converted to carbon before being fed
to the thermochemical cycle process. In the first reduction process , the AlN is
 produced through the carbothermal reduction of Al2O3 and nitrogen. This reaction is
endothermic and occurs under a reaction temperature of about 1500 °C.
 Moreover, in the second reaction, which is steam-hydrolysis (reaction (5)), the AlN
produced in the first reduction process is reacted with steam (H 2O) producing Al2O3.
The produced Al2O3 from this second reaction is then circulated to the first reduction
process. Detailed reaction kinetics have been analysed in detail in [31].

Advantages:

Unlike the Haber–Bosch process, this thermochemical cycle can be carried out at
atmospheric pressure and without a catalyst. The process allows independent reaction control
for nitrogen activation (reaction (4)) and ammonia formation (reaction (5)). Furthermore, as
could be observed from reaction (4), the system can produce ammonia directly from
carbonized material, instead of pure hydrogen. Therefore, this system is expected to be able
to reduce the energy consumption during ammonia production

Disadvantages:

However, this system has the biggest challenge related to its very high operating
temperature, leading to limited heat sources and materials. Various ideas have been suggested
for the heat supply, including the utilization of concentrated solar heat

MANUFACTURING PROCESS (used commercially in

industries)
A. Imperial chemical industries

 Hydrocarbon feed is subjected to steam reforming in two stages to form oxides of

Carbon, methane and hydrogen. In the secondary reformer air is mixed with the gases
to get a N2: H2 ratio of 1:3. Carbon monoxide is removed by shift conversion. Carbon
dioxide is removed by absorption into or Potassium Carbonate solution. Traces of CO
and CO2 are removed by conversion into methane. Synthesis gas is used to produce
ammonia.
 Advantages of ICI Process • Intensive heat recovery • Generation of steam which can
be imported. • Less dependency on electricity • Capital cost is least.

B. Haber-bosch process

 The Haber–Bosch process, is the industrial implementation of the reaction of nitrogen

gas and hydrogen gas. It is the main industrial procedure to produce ammonia:
N2 + 3 H2 → 2 NH3 (ΔH = −92.4 kJ·mol−1)

  Parameters • Temperature: 450˚C, moderately high. • Pressure: 200-1000 atm.

Catalyst: Iron, As the rates are increased, the temperature used need not be so high as
that which would be required in the absence of a catalyst. By allowing a lower
temperature to be used, the position of equilibrium is more favourable as the Haber
process is exothermic in the forward direction.

C. Braun purifier process

 Braun Purifier Process • In this process Synthetic ammonia (NH3) refers to ammonia
that has been synthesized from natural gas. Natural gas molecules are reduced to
carbon and hydrogen. The hydrogen is then purified and reacted with nitrogen to
produce ammonia.
 The first stage is purification where impurities, mainly sulphur compounds, are
removed from the gas stream.
 Steam reforming is performed in two stages. In the primary stage, the endothermic
reactions take place at pressures around 30 bar and temperatures of 800°C or higher.
This is followed by an exothermic secondary reformer where air is added to the
partially reformed gas stream.
 The carbon monoxide in the gas leaving the secondary reformer is converted to
carbon dioxide in the shift reactors and then removed by scrubbing from the gas
stream. Any residual carbon oxides are then converted back to methane by
methanation before compression of the hydrogen and nitrogen to ammonia synthesis
pressure.
 The final reaction stage is ammonia synthesis where the hydrogen and nitrogen
combine to form ammonia. This reaction stage takes place at high pressure (100-350
bar) and is highly exothermic.
 5. Description of the most commonly used process
with process flow diagram
Haber–Bosch process or just Haber process is one of the most efficient and successful
industrial procedures to be adopted for the production of ammonia. German chemists Fritz
Haber along with his assistant in the 20th century developed high-pressure devices and
catalysts to carry out the process on a laboratory scale.

Later, Carl Bosch in the year 1910 took the design and created a machine for industrial-level
production. This was indeed an important development in the field of science.

Ammonia is produced on a large scale by the Haber process with capacities of up to 3,300

tonnes per day.

Process and Conditions

In the Haber process, “the atmospheric nitrogen (N2) is converted to ammonia (NH3) by
reacting it with hydrogen (H2)”. Here a metal catalyst is used and high temperatures and
pressures are maintained.

1. Raw Materials

The raw materials for the process are

 Air, which supplies the nitrogen.

 Natural gas and water which supply the hydrogen and the energy needed to heat the
reactants.
Ni Catalyst
CH4(g) + H2O(g)----------------> CO(g) + 3H2(g)
700oC
Enough steam is used to react with about 45% of the methane (CH4), the rest of the
methane is reacted with air:
Ni Catalyst
2CH4(g) + O2(g) + 4N2(g) (air) --------------> 2CO(g) + 4H2(g) + 4N2(g)

All the carbon monoxide (CO) in the mixture is oxidized to CO2 using steam and an
iron oxide catalyst:
 iron oxide catalyst
CO(g) + H2O(g) ------------------> H2(g) + CO2(g)

The carbon dioxide (CO2) is removed using a suitable base so that only the nitrogen
gas (N2) and hydrogen gas (H2) remain and are used in the production of ammonia
(NH3).

 Iron which is the catalyst and does not get used up.

2. Catalyst

The catalyst is actually slightly more complicated than pure iron. It has potassium
hydroxide added to it as a promoter - a substance that increases its efficiency.

The catalyst has no effect whatsoever on the position of the equilibrium. Adding a
catalyst doesn't produce any greater percentage of ammonia in the equilibrium
mixture. Its only function is to speed up the reaction.

In the absence of a catalyst the reaction is so slow that virtually no reaction happens in
any sensible time. The catalyst ensures that the reaction is fast enough for a dynamic
equilibrium to be set up within the very short time that the gases are actually in the
reactor.

3. Temperature

In order to produce the maximum possible amount of ammonia in the equilibrium

mixture, the equilibrium needs to be shifted as far as possible to the right.

The forward reaction (the production of ammonia) is exothermic.

According to Le Chatelier's Principle, this will be favoured if the temperature is lowered. The
system will respond by moving the position of equilibrium to counteract this - in other words
by producing more heat.
In order to get as much ammonia as possible in the equilibrium mixture, the temperature
needs to be as low as possible. The lower the temperature you use, the slower the reaction
becomes.

400 - 450°C is a compromise temperature producing a reasonably high proportion of

ammonia in the equilibrium mixture (even if it is only 15%), but in a very short time.

4. Pressure

There are 4 molecules on the left-hand side of the equation, but only 2 on the right.

According to Le Chatelier's Principle, if the pressure is increased, the system will respond by
favouring the reaction which produces fewer molecules. That will cause the pressure to fall
again.

In order to get as much ammonia as possible in the equilibrium mixture, as high as possible a
pressure is needed. 200 atmospheres is a high pressure, but not extremely high.

Increasing the pressure brings the molecules closer together. In this particular instance, it will
increase their chances of hitting and sticking to the surface of the catalyst where they can
react. The higher the pressure, the better in terms of the rate of a gas reaction.

Very high pressures are very expensive to produce on two counts.

 You have to build extremely strong pipes and containment vessels to withstand the
very high pressure. That increases your capital costs when the plant is built.

 High pressures cost a lot to produce and maintain. That means that the running costs
of the plant are very high.

200 atmospheres is a compromise pressure chosen on economic grounds. If the pressure

used is too high, the cost of generating it exceeds the price you can get for the extra
ammonia produced.
 5. The proportions of nitrogen and hydrogen

The mixture of nitrogen and hydrogen going into the reactor is in the ratio of 1
volume of nitrogen to 3 volumes of hydrogen.

Avogadro's Law says that equal volumes of gases at the same temperature and
pressure contain equal numbers of molecules. That means that the gases are going into
the reactor in the ratio of 1 molecule of nitrogen to 3 of hydrogen.

That is the proportion demanded by the equation.

There is always a down-side to using anything other than the equation proportions. If
you have an excess of one reactant there will be molecules passing through the reactor
which can't possibly react because there isn't anything for them to react with. This
wastes reactor space - particularly space on the surface of the catalyst.

Process
 1. In the Haber process, nitrogen gas is taken from the air and combined with hydrogen
atom obtained from natural gas in the ratio 1:3 by volume.

2. The gases are passed through four beds of catalyst with cooling between each pass for
maintaining a reasonable equilibrium constant.

3. Different levels of conversion occur in each pass where unreacted gases are recycled.
At each pass of the gases through the reactor, only about 15% of the nitrogen and
hydrogen converts to ammonia. (This figure also varies from plant to plant.) By
continual recycling of the unreacted nitrogen and hydrogen, the overall conversion is
about 98%.

4. Normally an iron catalyst is used in the process, and the whole procedure is conducted
by maintaining a temperature of around 400 – 450oC and a pressure of 150 – 200 atm.

5. The process also involves steps like shift conversion, carbon dioxide removal, steam
reforming, and methanation.

6. In the final stage of the process, the ammonia gas is cooled down to form a liquid
solution which is then collected and stored in storage containers. When the gases
leave the reactor they are hot and at a very high pressure. Ammonia is easily liquefied
under pressure as long as it isn't too hot, and so the temperature of the mixture is
lowered enough for the ammonia to turn to a liquid. The nitrogen and hydrogen
remain as gases even under these high pressures, and can be recycled.

7. During industrial production of ammonia, the reaction never reaches equilibrium as

the gas mixture leaving the reactor is cooled to liquefy and remove the ammonia. The
remaining mixture of reactant gases is recycled through the reactor. The heat released
by the reaction is removed and used to heat the incoming gas mixture.

Reaction Rate and Equilibrium

The Haber process for the synthesis of ammonia is based on the reaction of nitrogen and
hydrogen. The reaction is an exothermic reaction, one where there is a release of energy.

N2(g) + 3H2(g) → 2NH3(g)

Nitrogen in the reaction is obtained by separating nitrogen from the air through liquefaction
and hydrogen is obtained from natural gas by steam reforming.

CH4(g) + H2O → H2(g) + CO(g)

According to Le Chateleir principle, the production of ammonia is favoured by high pressure

and low temperature. The Haber process is typically carried out at pressures between 200 and
400 atmospheres and temperature of 500oC. In the commercial production of ammonia, NH3
is continuously removed as it is produced. Removing the products causes more nitrogen and
hydrogen to combine according to Le Chatelier’s principle.

The reaction is a reversible reaction. However, the reaction is affected by changes in

temperature, pressure and catalyst used mainly in the composition of the equilibrium mixture,
the rate of the reaction and the economics of the whole process.

Mechanism
The mechanism of ammonia synthesis contains the following seven elementary steps:

1. Transport of the reactants from the gas phase through the boundary layer to the
surface of the catalyst.
2. Pore diffusion to the reaction center.
3. Adsorption of reactants

4. Reaction
5. Desorption of product

6. Transport of the product through the pore system back to the surface
7. Transport of the product into the gas phase

 The reaction mechanism involves the following steps:

1. N2 (g) → N2 (adsorbed)
2. N2 (adsorbed) → 2 N (adsorbed)
3. H2 (g) → H2 (adsorbed)
4. H2 (adsorbed) → 2 H (adsorbed)
5. N (adsorbed) + 3 H (adsorbed) → NH3 (adsorbed)
6. NH3 (adsorbed) → NH3 (g)
Process flow diagram

6. Applications of Ammonia
Industry Use
Fertiliser production of:
 ammonium sulfate, (NH4)2SO4
 ammonium phosphate, (NH4)3PO4
 ammonium nitrate, NH4NO3
  urea, (NH2)2CO,also used in the production of barbiturates
(sedatives), is made by the reaction of ammonia with carbon
dioxide

Chemicals synthesis of:

 nitric acid, HNO3, which is used in making explosives such
as TNT (2,4,6-trinitrotoluene), nitroglycerine which is also
used as a vasodilator (a substance that dilates blood vessels)
and PETN (pentaerythritol nitrate)
 sodium hydrogen carbonate (sodium bicarbonate), NaHCO3
 sodium carbonate, Na2CO3
 hydrogen cyanide (hydrocyanic acid), HCN
 hydrazine, N2H4 (used in rocket propulsion systems)
Explosives ammonium nitrate, NH4NO3
Fibres & Plastics nylon, -[(CH2)4-CO-NH-(CH2)6-NH-CO]-,and other polyamides
Refrigeration used for making ice, large scale refrigeration plants, air-conditioning
units in buildings and plants
Pharmaceuticals used in the manufacture of drugs such as sulfonamide which inhibit
the growth and multiplication of bacteria that require p-
aminobenzoic acid (PABA) for the biosynthesis of folic acids, anti-
malarials and vitamins such as the B vitamins nicotinamide
(niacinamide) and thiamine.
Pulp & Paper ammonium hydrogen sulfite, NH4HSO3, enables some hardwoods
to be used
Mining & used in nitriding (bright annealing) steel, used in zinc and nickel
Metallurgy extraction
Cleaning ammonia in solution is used as a cleaning agent such as in 'cloudy
ammonia
 7. Market Survey

Market Overview
Global Ammonia Market is projected to register a CAGR of 4.02% to reach USD 68,354.5
Million by the end of 2028.

Ammonia is a colorless inorganic compound of nitrogen and hydrogen with a characteristic

pungent smell. It is mainly produced using natural gas, the Haber process, in which nitrogen
and hydrogen react in the presence of an iron catalyst to form ammonia.

The global demand for ammonia is mainly driven by the growth of the fertilizer industry.
Around 60% of the ammonia produced is consumed by the fertilizer industry. Some of the
common fertilizers produced through ammonia include urea, ammonium nitrate, ammonium
sulfate, ammonium phosphate, diammonium phosphate, monoammonium phosphate, nitric
acid, sodium bicarbonate, and sodium carbonate. According to the United Nations, the
world’s population is likely to exceed 8.6 billion by 2030. Thus, the increasing demand for
food coupled with the growing consumption of protein-rich diets, fruits, and vegetables is
expected to boost the demand for fertilizers in the agricultural industry.

Segmentation
Global Ammonia Market has been categorized based on three forms, namely liquid, gas, and
powder. Among these, the liquid form segment accounted for more than 40% of the global
market share in 2018; and is projected to register a CAGR of 4.08% during the assessment
period. This is attributed to the high demand for the product in almost all the major
applications such as refrigerants, chemicals, and pharmaceuticals. Moreover, the liquid form
of ammonia is applied to the soil by the surface injection method. It quickly vaporizes but is
captured by soil and water. Ammonia is mostly used in the liquid form. It is majorly used in
fertilizers and industrial & household cleaning. For application in fertilizers, it is compressed
into a liquid and then mixed with different plant enhancers. In the gaseous form, it combines
with moisture present in the dirt, which in turn results in ammonia-enriched fertilizer soil.
Anhydrous ammonia is the purest form of ammonia, which does not contain any water
molecule. It is a pungent gas with suffocating fumes, which is primarily used as a fertilizer. It
is compressed into a colorless and clear liquid when used as an agricultural fertilizer.

By the Sales Channel, the market is bifurcated into direct channel and distribution channel.
The direct sales channel segment was valued at USD 35,727.2 million in 2018.

Application Insights
Based on Application, the global market has been segmented into fertilizers, chemicals,
refrigeration, fibers and plastics, pharmaceutical, pulp and paper, and others. The fertilizer
segment emerged as the leading and fastest-growing segment; exhibiting a CAGR of 4.39%
during the forecast period. The significant growth of the fertilizer industry and constantly
rising demand for food due to the growing global population are expected to boost the growth
of the segment.
Global Ammonia Market Revenue, By Application

Fig. 1

Other application industries include textiles, pharmaceuticals, industrial & household

cleaning, food and beverages, metallurgical processes, water and wastewater treatment,
rubber, pulp & paper, and leather. Ammonia is being used as a refrigerant owing to several
benefits such as high efficiency, environmentally-friendly, smaller pipe size, better heat
transfer properties, and cost.
 Fig.2

Regional Insights
The Global Ammonia Market has been studied across five regions, namely Asia-Pacific,
North America, Europe, Latin America, and the Middle East & Africa. The market in Asia-
Pacific held the largest market share of over 50% in 2018, with a market value of around
USD 24,798.0 million. This is mainly attributed to the increasing demand for ammonia for
producing fertilizers in the major economies of India, China, Thailand, and Indonesia. In
China, ammonia is mostly produced from coal gasification, whereas globally it is mostly
obtained from natural gas. In terms of production, China is followed by India and Indonesia.
Globally, the capacity is anticipated to increase significantly. The major capacity addition is
projected to be in the Middle East & Africa, Central & South America, and Southeast Asia.
The largest addition is anticipated to be in Indonesia and China.
 Fig. 3

The industry is witnessing continuous fall in prices from the past two years on a global level.
This is mainly due to the increasing supply and demand gap in the region. The rising supply
owing to increasing capacity and weaker demand is the major reason for the gap in the
market. This weaker demand is due to lower crop & food prices, poor economic prospects,
fluctuating energy prices, and rising competition.

The U.S. is among the major producers of ammonia globally. The country had over 13
companies that produced the product at their 20 production plants in 2015. In the U.S.,
approximately 45% of the product is consumed in nitrogen fertilizer and the remaining is
used for producing synthetic fibers plastics, resins, and various other chemical compounds.
As the natural gas accounts for around 50% of the production cost for nitrogen fertilizer, the
availability of cheap natural gas in the country is expected to be a major driving factor for
industry growth in the region.

Global Ammonia Market, by Region

 North America

o US

o Canada
 Europe

o France

o Belgium

o Germany

o Spain

o Italy

o UK

o Poland

o Netherlands

o Russia

o Rest of Europe

 Asia-Pacific

o China

o Japan

o India

o Australia & New Zealand

o Indonesia

o South Korea

o Thailand

o Vietnam

o Rest of Asia-Pacific

 Latin America

o Mexico
 o Brazil

o Argentina

o Rest of Latin America

 Middle East & Africa

o Turkey

o Egypt

o GCC

o Israel

o Rest of Middle East

Key Market Trends

Agriculture Industry to Dominates the Market

 Ammonia, also known as NH3, is one of the most efficient and widely used sources
of nitrogen for plant growth. The advantages of ammonia's relatively easy application
and ready availability have led to its increased use as a fertilizer. Ammonia is a basic
building block for ammonium nitrate fertilizer, which releases nitrogen, an essential
nutrient for growing plants, including farm crops and lawns. Moreover, it can be
converted into a variety of common N fertilizers.

 The agriculture industry dominates the global ammonia market, with an estimated
market share of around 80%. Ammonia is majorly used in fertilizers, and its usage has
only been increasing through the years, thereby, driving its usage in the agriculture
market throughout the forecast period.

 Fertilizers are plant nutrients that are required for the growth of crops. The fertilizers
market is also expected to expand, with agriculture production growing through the
years (primarily owing to the growing population, increasing urbanization, and rising
disposable income of individuals). Consumption of meat, dairy products, fish, sugar,
 fruits, and vegetables has been experiencing rapid growth, compared to the
consumption of cereals.

 Urea is a dry nitrogen material produced by reacting ammonia with carbon dioxide. It
contains the highest percentage of nitrogen among the commonly used dry fertilizers
and is rapidly replacing ammonium nitrate in the recent years.

 After a slow growth of 1.3% in 2018, the demand for agriculture is seen as dropping
by 1% in 2019. This is due to combination of low international prices for most crops;
unfavorable weather in important agricultural and fertilizer consuming areas; currency
depreciation in some fertilizer-importing countries trade tensions between China and
the US and between Russia and Ukraine; sanctions against Iran; and increasing
emphasis on the more efficient use of fertilizers in developed countries and China.

 Although medium-term outlook for world agriculture remains broadly unchanged,

however agricultural production growth rates are steadily declining. Additionally,
expectations to improve fertilizer use efficiency and recycle more organic nutrient
sources will put pressure on fertilizer demand in developed countries and an
increasing number of emerging economies.

 Although the global fertilizer demand seem to have slow growth, the demand for
ammonia-based products are faring better. The largest growths are projected in South
Asia, Latin America and Southeast Asia. Significant increases in urea demand are
expected to contribute to this growth especially in Latin America and East Asia,
including China for its industrial sectors. Overall, these factors are expected to
influence the demand for the global ammonia market.
 Fig. 4

Asia-Pacific to Dominate the Ammonia Market

 Asia-Pacific dominated the ammonia market, accounting for more than half of the
consumption globally.

 In the Asia-Pacific region, China is the largest economy in terms of GDP. The country
witnessed about 6.1% growth in its GDP during 2019, even after the trade disturbance
caused due to its trade war with the United States. The economic growth rate of China
in 2020 was initially expected to be moderate as compared to the previous year.

 China accounts for approximately 7% of the overall agricultural acreage, globally,

thus, feeding 22% of the world population. The country is the largest producer of
various crops, including rice, cotton, potatoes, and among other vegetables. Hence,
the demand for ammonia which is used as a fertilizer is rapidly increasing owing to
the large-scale agricultural activities in the country.

 The agricultural sector in the country is expected to grow for various reasons, as
China’s urban consumers have the intent to eat more freshly produced and processed
fruits, vegetables, juices, etc., and the demand for freshly produced food items may
continue to grow, due to population shifts from rural areas to the cities.
 China has the largest agricultural output among all other countries in the world. In
China, about 10% of its land is suitable for cultivation. The limited space for
cultivation has led to serious food shortages in the past. China is planning to
modernize and upgrade agriculture in the next 10 years. China's agriculture
development will shift from increasing production to improving quality.

 India is a growing economy and holds great potential for future market opportunities.
The country has the tenth-largest arable land resources in the world. The gross
irrigated area under food grains was 64.8 million hectares in 2019, from 61.63 million
hectare in 2013. The growing investments in irrigation have enhanced the gross
irrigated area, thus, creating a demand for pesticides and fertilizers, stimulating the
demand for the market studied.

 The Indian textile and apparel sector is expected to achieve decent growth in 2021.
According to the Indian Textpreneurs Federation (ITF), the textile industry had
benefited from the volumes in the market in the first 10 months of 2020.

 Furthermore, the government launched a production-linked incentive scheme to

provide incentives for the manufacture and export of specific textile products made
using man-made fiber.

 Overall, the market for ammonia in Asia-Pacific region is anticipated to grow

significantly through the forecast period.
 Fig. 5

Covid-19 Impact
The COVID-19 outbreak is likely to bring several short-term and long-term consequences in
various industries, such as agriculture, textiles, mining, and other end-user industries, which
may affect the ammonia market. The agriculture industry was widely impacted due to supply
chain disruption and halt in the production of fertilizer manufacturing companies due to
lockdown and workforce shortages, thus, adversely affecting the ammonia market. For
instance, across the world, the lockdowns in Europe have greatly disrupted food supply
chains. According to Syngenta, about 46% of large European farming businesses have been
impacted by the COVID-19 pandemic.
 8. Important Industries Manufacturing Ammonia

Key Players
Key Players operating in the Global Ammonia Market include Yara (Norway), CF Industries
Holdings Inc. (US), Nutrien Ltd. (Canada), Group DF (Ukraine), OCI NV (Netherlands),
EuroChem Group AG (Switzerland), SABIC (Saudi Arabia), Acron (Russia), Orica Limited
(Australia), Uralchem JSC (Russia), AB ”Achema” (Lithuania), Togliattiazot (Russia), Indian
Farmers Fertiliser Cooperative Limited (India), Qatar Fertiliser Company (Qatar), and Koch
Fertilizer, LLC (US).
Competitive Landscape
The global market is highly competitive in nature and is currently witnessing constant price
fluctuations. The industry is marked by the presence of global as well as regional market
players. The global players are investing in the research & development activities for
innovating new and developed processes. The global ammonia market is fragmented, with the
inclusion of international and local players in different regions. The major manufacturers in
the market include CF Industries Holdings Inc., Yara, Nutrien Ltd, OCI Nitrogen, Ostchem
(Group DF), followed by other prominent players. These players account for a majority of the
global market share owing to their large production capabilities, global revenue base,
availability of low-cost raw material, patented production facilities, and global distribution
network.

Players in this market are focused on strategic growth initiatives such as expansion,
agreement, and acquisition to remain at the forefront to meet the growing demand for
ammonia.

Fig. 6

Recent Developments
 In March 2021, OCI NV entered into an agreement with MAN Energy Solutions,
Hartmann Group, and Eastern Pacific Shipping to establish a marine value chain and
begin commercializing ammonia and methanol as future shipping fuels by 2023-24.

 In August 2020, Industries Qatar, one of the region's industrial behemoths, reported
that the company's Board of Directors approved the proposed acquisition of Qatar
Petroleum's 25% stake in Qatar Fertiliser Company (QAFCO) at its meeting on
August 23, 2020. The acquisition of QP's stake in QAFCO is in line with IQ's strategy
to expand its downstream presence and create value.

 In April 2018, BASF SE inaugurated the new ammonia production facility at Texas,
United States, in collaboration with Yara with a combined investment of USD 600
million. This production facility has the capacity to produce 750,000 metric tons of
ammonia per year.