Contents

Introduction to Ammonia..........................................................................................1
Physical Properties....................................................................................................1
Chemical Properties of Ammonia.............................................................................2
Uses of Ammonia......................................................................................................3
The AMMONIA Synthesis........................................................................................4
Hydrogen Production..........................................................................................4
Nitrogen Addition................................................................................................5
Removal of Carbon Oxides.................................................................................5
Synthesis of Ammonia........................................................................................5
Reactor Technologies Used.......................................................................................8
HALDOR TOPSOE............................................................................................8
1. Topse S-200 Converter......................................................................................9
2. Topse S-300 Converter......................................................................................9
KBR Kellogg Advanced Ammonia Process (KAAP)..............................................11
Effect of Temperature and Pressure on Ammonia Conversion...............................14
Environmental Impacts ofAmmonia.......................................................................16

Introduction to Ammonia
Ammonia or azane is a compound of nitrogen and hydrogen with the formula NH3. 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 pharmaceuticals and is used in many commercial cleaning products. Although in wide use,
ammonia is both caustic and hazardous. The global industrial production of ammonia for 2012 is
anticipated to be 198 million tonnes, a 35% increase over the estimated 2006 global output of
146.5 million tonnes.
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 NH3 in water. The concentration of such
solutions is measured in units of the Baum scale(density), with 26 degrees baum (about 30%
(by weight) ammonia at 15.5 C) being the typical high-concentration commercial product

Physical Properties
Ammonia is a colourless gas with a characteristic 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, and freezes at 77.7 C to white crystals.
Ammonia may be conveniently deodorized by reacting it with either sodium bicarbonate or
acetic acid. Both of these reactions form an odorless ammonium salt.
Liquid ammonia possesses strong ionising powers reflecting its high 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. Physical Properties table is given below

Tab. Physical Properties of Ammonia

Chemical Properties of Ammonia

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 800C

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, NH 3 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.
For example,

Uses of Ammonia

In the manufacture of rayon and urea

In the manufacture of fertilizers such as urea diammonium phosphate, ammonium nitrate,

ammonium sulphate etc.

In ice plants, as a refrigerant

In furniture industry, as a cleansing agent for furniture and glass surfaces.

In the manufacture of nitric acid by Ostwald's process.

In the manufacture of sodium carbonate by Solvay's process.

The AMMONIA Synthesis

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.

Hydrogen Production

Hydrogen is produced by the reaction of methane with water. However, before this can be carried
out, all sulfurous compounds must be removed from the natural gas to prevent catalyst
poisoning. These are removed by heating the gas to 400oC and reacting it with zinc oxide:
ZnO + H2S ZnS + H2O
Following this, the gas is sent to the primary reformer for steam reforming, where super-heated
steam is fed into the reformer with the methane. The gas mixture heated with natural gas and
purge gas to 770oC in the presence of a nickel catalyst. At this temperature the following
equilibrium reactions are driven to the right, converting the methane to hydrogen, carbon dioxide
and small quantities of carbon monoxide:
CH4 + H2O 3H2 + CO
CH4 + 2H2O 4H2 + CO2
CO + H2O H2 + CO2
This gaseous mixture is known as synthesis gas
.

Nitrogen Addition

The synthesis gas is cooled slightly to 735 oC. It then flows to the secondary reformer where it is
mixed with a calculated amount of air. The highly exothermic reaction between oxygen and
methane produces more hydrogen. Important reactions are:
CO + H2O CO2 + H2
O2 + 2CH4 2CO + 4H2
O2 + CH4 CO2 + 2H2
2O2+ CH4 2H2O + CO2
In addition, the necessary nitrogen is added in the secondary reformer.
As the catalyst that is used to form the ammonia is pure iron, water, carbon dioxide and carbon
monoxide must be removed from the gas stream to prevent oxidation of the iron. This is carried
out in the next three steps.

Removal of Carbon Oxides

The gases are then pumped up through a counter-current of UCARSOL solution Carbon dioxide
is highly soluble in UCARSOL, and more than 99.9% of the CO 2 in the mixture dissolves in it.
The remaining CO2(as well as any CO that was not converted to CO 2 in Step 3) is converted to
methane (methanation) using a Ni/Al2O3 catalyst at 325oC:
2CO + 3H2 CH4+ H2O
CO2+ 4H2 CH4+ 2H2O
The water which is produced in these reactions is removed by condensation at 40 oC as above.
The carbon dioxide is stripped from the UCARSOL and used in urea manufacture. The
UCARSOL is cooled and reused for carbon dioxide removal.

Synthesis of Ammonia

The gas mixture is now cooled, compressed and fed into the ammonia synthesis loop (see Figure
1). A mixture of ammonia and un reacted gases which have already been around the loop are
mixed with the incoming gas stream and cooled to 5 oC. The ammonia present is removed and
the unreacted gases heated to 400oC at a pressure of 330 bar and passed over an iron catalyst.
Under these conditions 26% of the hydrogen and nitrogen are converted to ammonia. The outlet
gas from the ammonia converter is cooled from 220 oC to 30oC. This cooling process condenses
6

more the half the ammonia, which is then separated out. The remaining gas is mixed with more
cooled, compressed incoming gas. The reaction occuring in the ammonia converter is:
N2+ 3H2 2NH3
The ammonia is rapidly decompressed to 24 barg. At this pressure, impurities such as methane
and hydrogen become gases. The gas mixture above the liquid ammonia (which also contains
significant levels of ammonia) is removed and sent to the ammonia recovery unit. This is an
absorber-stripper system using water as solvent. The remaining gas (purge gas) is used as fuel for
the heating of the primary reformer. The pure ammonia remaining is mixed with the pure
ammonia from the initial condensation above and is ready for use in urea production, for storage
or for direct sale. Ammonia product specifications are given in Table 2.

Fig: Diagram of an Ammonia Plant

Reactor Technologies Used

There are two technolgies are working with the ammonia manufacture in pakistan which are
HALDOR TOPSOE
KBR

HALDOR TOPSOE
For more than 60 years, Topse has been the main supplier of catalysts and technology for the
ammonia industry.Today, Topses ammonia synthesis technology is based on radial flow
converters where the synthesis of ammonia from hydrogen and nitrogen takes place.
Topse pioneered radial flow converters with the installation of the first radial flow converters in
the 1960s. Since then, continuous development has resulted in a comprehensive portfolio of
radial flow converter designs to meet the multifaceted require-ments in the industry.
Topses converters offer a number of benefits:

100% radial flow through the catalyst beds to obtain a low pressure drop and higher conversion
with small sized high activity catalyst particles

indirect cooling of the gas in the heat exchangers between the catalyst beds instead of quenching
to achieve maximum conversion

total converter feed flow passes through all beds fully utiliz-ing the total installed catalyst volume

stable operation with high flexibility in operating range

optimized temperature control

excellent flow distribution

easy installation and start-up

1.

Topse S-200 Converter

Topse was the first technology licensor to introduce the multi-bed radial flow converter design,
thereby improving conversion per pass compared to known technology.
The Topse S-200 ammonia synthesis converter is a two-bed radial flow converter with indirect
cooling between the cata-lyst beds. Since the introduction of the S-200 converter type
in 1976, it has been used in more ammonia plants than any other converter design, with more
than 130 converters installed worldwide.

2.

Topse S-300 Converter

Topses S-300 converter is the latest development in Topses ammonia converter portfolio and
is the recommended converter design for all new plants. The advantages of the S-300 radial flow
converter are proven by more than 50 installations world-wide, making it the benchmark within
the ammonia industry today.
Compared to the S-200 converters, the presence of three catalyst beds offers higher conversion
into ammonia and hence increased production efficiency. Alternatively, the catalyst volume can
be reduced, which lowers investment costs compared to the previous generation of converter
design. When the S-300 basket is installed in an existing ammonia converter pressure shell as
part of a revamp project, significant energy savings can be achieved. These advantages can be
obtained in connection with the revamp of both Topse and non-Topse designed converter
types.
Two versions of the S-300 converter are available: One version has an integral feed-effluent heat
exchanger at the exit of the third catalyst bed, allowing the heat of reaction to be used for
preheating boiler feed water downstream of the ammonia con-verter. The second version is
designed without a feed-effluent heat exchanger, meaning that the outlet gas from the third bed
can go directly to a boiler for the production of high-pressure steam.
With the number of ammonia converter basket installations constantly increasing, Topse has
achieved an unequaled refer-ence situation. With over 60 years of experience in the ammonia
industry, Topse provide flexible and highly efficient ammonia converter solutions.

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KBR Kellogg Advanced Ammonia Process

(KAAP)

In 1979, British Petroleum approached M.W. Kellogg to participate in the development of a new
ruthenium-based catalyst. It was known at that time that replacing the conventional iron-based
catalyst, which was used for over 80 years, with this new catalyst would increase productivity.
Several pilot plant tests were performed using ruthenium supported on a proprietary carbon
structure with various co-promoters.) It was evident that significant economic benefits would be
attained with this new catalyst, and so it was chosen to be an integral part of what is now known
as

the

Kellogg

Advanced

Ammonia

Process

(KAAP).

KAAP can be implemented in one of three ways: as an expansion to an already existing plant, as
a retrofit design to an already existing plant, or as a grassroots design when building a brand new
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plant. In 1988, KAAP had its first commercial exposure after Ocelot Ammonia Company in
Kitimat, British Colombia (now known as Pacific Ammonia Incorporated or PAI), contracted
M.W. Kellogg to evaluate its existing ammonia plant for potential capacity increases and to
provide

suitable

retrofit

design..

The KAAP system was successfully started up in November of 1992. It consisted of a KAAP
reactor which was installed downstream from the magnetite converter already in existence. This
KAAP reactor was a two-bed radial flow converter with a unique proprietary sealing system
which avoided hot spots within the catalyst bed. The KAAP catalyst was loaded in its oxidized
state, just as most catalysts are, although it is only active in the reduced state. Therefore, fresh
synthesis gas, which heated the catalyst bed to ~300o, was used to for the reduction process. The
synthesis loop operated at the original design pressure of 2000 psia. Partially preheated feed exits
a 2-bed Kellogg converter loaded with magnetite catalyst and enters a steam superheater and
generator, which generates a pressure of 3000 psia. This feed stream, containing 15% ammonia,
then passes into the KAAP converter through a side inlet to the first bed. When the gas leaves the
second bed, ammonia concentration is increased to about 19%. A continuous purge is required in
this retrofit because the expanded plant contains more inerts than in the original synloop. After
the entire KAAP retrofit was completed, PAI had an energy savings of 0.6 mmBTU/mt.(8) This
more efficient and highly flexible system has been very easy to operate and has paved the way
for

grassroots

facilities.

Grassroots designs are different from retrofit and expansion designs in that they use 3 and 4 bed
intercooled reactors. The first bed uses conventional iron catalyst while the remaining beds
utilize the highly active KAAP catalyst. The reason for this is so that the iron catalyst can take
advantage of high ammonia reaction rates at low ammonia concentrations. As the reaction
progresses, however, the ammonia concentrations increase, and the iron catalyst loses its
effectiveness. The KAAP catalyst is then used to produce high exit ammonia concentrations at
low

pressures,

since

it

can

be

used

at

high

ammonia

concentrations.

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Keq

[NH3]2
Keq =
[N2][H2]3

This
energy

Temperatu
re (oC)

on

synthesis loop is also advantageous in that it uses

25

6.4 x 102

200

4.4 x 10-1

300

4.3 x 10-3

400

1.6 x 10-4

more efficiently by recovering heat at a much higher

temperature, yielding a 40% decrease in energy
conversion relative to conventional designs.

Effect of Temperature and Pressure

Ammonia Conversion

500
1.5 x 10
The
reaction between nitrogen gas and hydrogen gas to
produce ammonia gas is an exothermic equilibrium reaction, releasing 92.4kJ/mol of energy at
298K (25oC).
-5

N2(g)
3H2(g)
+
nitrogen hydrogen

heat,pressure,
catalyst

2NH 3(g
)
ammonia

H = -92.4 kJ
mol-1

OR
N2(g)
nitrogen

3H2(g)
hydrogen

heat,

pressure,

catalyst 2NH3(g)
ammonia

+ 92.4 kJ mol-1

By Le Chetalier's Principle:

increasing the pressure causes the equilibrium position to move to the right resulting in a
higher yeild of ammonia since there are more gas molecules on the left hand side of the
equation (4 in total) than there are on the right hand side of the equation (2). Increasing
the pressure means the system adjusts to reduce the effect of the change, that is, to reduce
the pressure by having fewer gas molecules.

decreasing the temperature causes the equilibrium position to move to the right resulting
in a higher yield of ammonia since the reaction is exothermic (releases heat). Reducing
the temperature means the system will adjust to minimise the effect of the change, that is,
it will produce more heat since energy is a product of the reaction, and will therefore
produce
more
ammonia
gas
as
well
However, the rate of the reaction at lower temperatures is extremely slow, so a higher
temperature must be used to speed up the reaction which results in a lower yield of
ammonia.

13

As the temperature increases, the equilibrium constant decreases as the yield of ammonia
decreases.

Rate considerations:

A catalyst such as an iron catalyst is used to speed up the reaction by lowering

theactivation energy so that the N2 bonds and H2 bonds can be more readily broken.

Increased temperature means more reactant molecules have sufficient energy to

overcome the energy barrier to reacting (activation energy) so the reaction is faster at
higher temperatures (but the yield of ammonia is lower as discussed above).
A temperature range of 400-500oC is a compromise designed to achieve an acceptable
yield of ammonia (10-20%) within an acceptable time period.

At 200oC and pressures above 750atm there is an almost 100% conversion of reactants to
the ammonia product.
Since there are difficulties associated with containing larger amounts of materials at this
high pressure, lower pressures of around 200 atm are used industrially.
By using a pressure of around 200atm and a temperature of about 500 oC, the yield of
ammonia is 10-20%, while costs and safety concerns in the biulding and during operation of
the plant are minimised
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 are recycled through the reactor. The heat released by the reaction is
removed and used to heat the incoming gas mixture.

14

Environmental Impacts of Ammonia

Ammonia is as stated above, a toxic chemical. When spilled on land or in water it can be
potentially devastating to the local environment, but methods have been devised for the safe
clean up of the ammonia spills. If spilled on land then a pond, pool type structure should be dug
to contain the liquid ammonia, and then filled in with sandbags, or possible foamed concrete.If
spilled in water it should have dilute acid added to it to negate the effects. The water should not
be consumed however. In the manufacturing of ammonia, there arises a need to vent gases and to
remove condensates. These liquid and gaseous effluents and the chemicals used in the process
may tend to pollute the environment.
The main sources of gaseous ammonia emission are from the inert gas purge and from the
ammonia storage section of the ammonia plant. In the case of non functioning or breakdown of
the equipment large quantity of ammonia emission increases ammonia concentration in the
atmosphere. The liquid effluents contain dissolved ammonia and dissolved Carbon dioxide. The
toxic effect of ammonia depends upon the concentration of free ammonia. Its presence in water
leads to suffocation of aquatic life forms. Also there is the possibility of emission of particulate
matter like Carbon oxides of Sulfur etc. These may removed by electrostatic precipitation or
vacuum filtration.

15