AMMONIA

• The manufacture of ammonia is crucial for the

world's agricultural industry for from it all
fertilizers that contain nitrogen are produced

• The manufacture of fertilizers is by far the

most important use of ammonia. These
include urea, ammonium salts (ammonium
phosphates, ammonium nitrate, calcium
ammonium nitrate) and solutions of ammonia
The uses of ammonia
An increasing amount of
ammonia, although still
small compared with
other uses, is used as a
concentrated solution
in combating the
discharge
of nitrogen oxides
from power stations
 Annual production of ammonia
• Ammonia ranks second, to sulfuric acid, as the
chemical with the largest tonnage

• It is being increasingly made in countries which

have low cost sources of natural gas and coal
(China and Russia account for ca 40%)

• The largest plants produce about 3000 tonnes a

day and there are plans to build plants that
produce 4000-5000 tonnes a day, which would
mean that the total world output could be
managed with 100 such units
 Manufacture of ammonia

The manufacture of ammonia from

nitrogen and hydrogen takes place in
two main stages:
a) the manufacture of hydrogen
b) the synthesis of ammonia
(the Haber Process)
Figure : An ammonia plant in
Western Australia:

1 Desulfurisation units
2 Primary reformer
3 High temperature and
low temperature shift
reactors
4 Carbon dioxide absorber
5 Carbon dioxide stripper
(recovery of the pure solvent,
ethanolamine)
6 Ammonia converter
7 Ammonia storage as liquid
8 Pipeline to the ship for
export
By kind permission of Yara
International ASA.
 The manufacture of 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.

Hydrogen from natural gas (methane)

This involves two stages:
• the manufacture of synthesis gas (a mixture of carbon
monoxide and hydrogen (steam reforming))
• the removal of the carbon monoxide and production of
a mixture of hydrogen and nitrogen (the shift reaction)
 The manufacture of synthesis gas
• Whichever way the methane is obtained, it will
contain some organic sulfur compounds and hydrogen
sulfide, both of which must be removed. Otherwise,
they will poison the catalyst needed in the
manufacture of synthesis gas

• In the desulfurisation unit, the organic sulfur

compounds are often first converted into hydrogen
sulfide, 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 sulfide is
removed:

Primary steam reforming converts methane and steam to

synthesis gas, a mixture of carbon monoxide and hydrogen:

• 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
• The tubes, up to 350 in parallel, are heated in a furnace
above 1000 K and under a pressure of ca 30 atm
• 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 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%.

The gas mixture now contains about 18% carbon dioxide which
is removed by scrubbing the gas with a solution of a base, using
one of several available methods. One that is favoured is an
organic base (in the carbon dioxide absorber), a solution of an
ethanolamine, often 2,2'-(methylimino)bis-ethanol (N-methyl
diethanolamine).

The carbon dioxide is released on heating the solution in the

carbon dioxide stripper). Much of it is liquefied and sold, for
example, for carbonated drinks, as a coolant for nuclear power
stations and for promoting the growth of plants in greenhouses
The last traces of oxides of carbon are removed
by passing the gases over a nickel catalyst at 600 K:

This process is known as methanation

A gas is obtained of typical composition:
74% hydrogen, 25% nitrogen, 1% methane, together with
some argon
 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
 Hydrogen from coal
• 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 manufacture of ammonia (The Haber Process)

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
 Summary
• The whole process of producing ammonia from
methane is summarized in above Figure

• If coal or naphtha is the feedstock, extra processes

are needed

• Naphtha is converted into methane and oxides of

carbon before going into the primary reformer and
then to the shift reaction

• Coal is also converted into hydrogen and carbon

oxides and this mixture then undergoes the shift
reaction