THE HABER-

BOSCH PROCESS
Synthesis of ammonia
 Steps involved in the Haber-Bosch
process

There are two stages involved in the Haber-Bosch process:

1.The production of a purified mixture of nitrogen and

hydrogen
2.The synthesis of ammonia- Haber process.
age 1: Production of hydrogen
Sulphur compounds will poison the
Removal of hydrogen sulphide and organic
catalysts used in the later production of
sulphur compounds from natural gas. the nitrogen/hydrogen mixture
Why?

Primaryreforming- methane reacts with steam at 700-1100 C

at 20 atm to form syngas (mixture of gases containing carbon
monoxide and hydrogen.
(g) CO(g)(g)

Secondary reforming- products obtained are mixed with air.

Since nitrogen constitutes approximately 71% of air,
nitrogen can be obtained.
2H2(g) + 02(g) 2H2O(g)
Production of hydrogen contd

Shift reaction- carbon monoxide reacts with steam

produced in the previous step at 130 C in the presence
of a nickel oxide catalyst.
C0(g) + H2O(g) CO2(g) + H2(g)

Unwanted carbon dioxide are removed by passing the

gases through an alkaline solution, e.g. concentrated
potassium carbonate.

The gases are dried to produce a mixture containing

74% hydrogen, 25% nitrogen and traces of argon.
Fractional distillation of liquefied
air
1. Air, the raw material, is first passed through a filter to remove dust.
2. It is then compressed and chilled to 6 C where most of the moisture condenses.
3. The cool air passes through chemicals which absorbs carbon dioxide and any
remaining moisture.
4. The air is then cooled even further to -200 C where air becomes liquefies using
cooled gases from the distillation column and further more by compression and
expansion. It is important to note that the cooling occurs in steps and there are
certain milestones. The cooling process removes any remaining carbon dioxide
which condenses and is extracted at -79C; oxygen is liquefied at -183 while
argon at -186 and nitrogen at -196.
5. The liquids nitrogen, argon and oxygen are separated by fractional distillation. As
liquefied air is passed into the column, it is gently warmed. As it reaches -196
nitrogen begins to boil and rises up the column. It is then extracted off at the top
of the column.
Stage 2: The Haber process
Produced by
fractional
distillation of
liquefied air.
Steps involved in the Haber process:
1. The purified sample of nitrogen and hydrogen in a 1:3 ratio are mixed
and compressed to 200 atm.
2. The gaseous mixture is then heated to 400C and passed through a
finely divided iron catalyst promoted by aluminium oxide and potassium
oxide.
3.The reactant gases are first adsorbed on the surface of the iron catalyst
by the donation of electrons to the vacant d orbitals of the iron catalyst.
This process is called chemisorption. On adsorption, the nitrogen triple
bonds and the hydrogen single bonds are broken; this process is called
dissociative adsorption.
4.After, three N-H bonds are formed to synthesize ammonia. Ammonia
desorbs from the surface of the catalyst and condenses.
5.Ammonia leaves the system as liquefied ammonia.
6.The ammonia yield produced is approximately 15%
7.The unreacted nitrogen and hydrogen gases are recycled.
8.Eventually, a yield of approximately 97% of ammonia is obtained by
recycling the hydrogen/nitrogen mixture.
Equilibrium, Le Chateliers principal and the Haber process

Le Chateliers principal states that if there is a change in a

equilibrium system, the system will shift so as to minimize that
change.

Three conditions are implemented in the Haber-Bosch process in

consideration of the equilibrium system to maximize the percentage
of ammonia obtained:
1. Condensation of ammonia as quickly as it is produced.
2. Low temperature
3. High pressure
Equilibrium, Le Chateliers principal and Haber
process

Graph showing the effect of temperature and pressure on the

yield of ammonia
 The removal of ammonia as quickly as it is produce decreases the
concentration of ammonia in the system. The system minimizes this change
by shifting to the right; hence, producing more ammonia.

The forward reaction is exothermic and therefore releases heat. Therefore,

the production of a higher yield of ammonia is favoured by low
temperatures. Lowering the temperature of the reactions will shift the
reaction to the right, releasing more heat. However, 400C is hardly a low
temperature!

The production of a higher yield of ammonia is favoured by a high pressure.

On the left side of the equilibrium there are four moles of gases, while on
the right, they are two moles of gases. According to Le Chateliers principal,
increasing the pressure would favour the reactions with fewer moles of
gases. Thus, the equilibrium shifts to the right.
The compromise between the equilibrium conditions and
industry
Low temperatures will increase the production of ammonia according to Le
Chateliers principal. However, 400C is hardly a low temperature! Low
temperatures hinder the rate of the reaction, so a compromise was needed
between temperature and the rate. Chemists chose a suitable temperature
(400C) that would give an acceptable yield of ammonia (15%) at an
acceptable rate.

Le Chateliers principal also states that a high pressure would favour the
formation of ammonia. Yet, high pressures are very difficult and expensive to
maintain. High pressure increases the risk of gases exploding out of the
reaction vessel; the cost of making pipelines and vessels to withstand such
high pressure is extremely high and a lot of energy is needed to generate
high pressures. Therefore, a compromise of 200 atm was accepted.
Uses of ammonia
Nitrogen is an essential nutrient in plant growth. Plant roots absorb nitrogen
form the soil in the form of nitrates. It is required for the formation of proteins,
chlorophyll and nucleic acids. Over a number of years, after repeated use, the
ammonia content in the soil is drastically reduced and has to be replenished.
Approximately 80% of ammonia is made into ammonia salts which can then
by applied to the soil. Ammonium nitrate (sold commercially as NITRIM) is the
most widely used fertilizer. Ammonium sulphate and ammonium phosphate
are also produced. Liquid ammonia is also commonly applied to the soil.

NH3(aq) + H2SO4(aq) (NH4)2SO4(aq) NH3(aq) + HNO3(aq) NH4NO3(aq)

A large portion of the remaining ammonia goes towards making explosives,

such as trinitrotoluene (TNT) and nitro-glycerine.
 Used in commercial and household cleaners and detergents e.g. glass
and window cleaners i.e. are used to clean, bleach, and deodorize. The
ammonia sold for household use is a dilute water solution of ammonia
in which ammonium hydroxide is the active cleansing agent. It should
be used with caution!
Ammonia is used in large amounts in the Ostwald process for the
synthesis of nitric acid and also used in theSolvay processfor the
synthesis of sodium carbonate
Used in livestock feeds as a source of nitrogen for protein production.

Used n the manufacture of plastics, fabrics, dyes and pharmaceuticals.

 Impacts of the Ammonia Industry
on the Environment
Nitrate Fertilizers- nitrate fertilizers are soluble compounds which can be
leached and washed off the topsoil by rain and into groundwater. These can
then flow into streams and lakes and promote the growth of aquatic plants.
The nutrients in the water system increases which can then promote the
growth of algae bloom. This widespread growth prevents light from
penetrating the lower layers of the water. When these plant die, there is an
increase in bacteria in the water which in turn competes with the aquatic life
for dissolved oxygen. The lesser dissolved oxygen a body of water has, the
least likely it is to support aquatic life; hence, fishes and other aquatic
organisms which depend on oxygen for respiration die out.
Impact of the ammonia industry
contd
Soilacidification- ammonia in the atmosphere can react with water
in the soil and is converted to ammonium ions (NH4+) which are
then converted by bacteria in the nitrogen cycle to nitrates and
nitrites and hydrogen ions (H+). The hydrogen ions decrease the
soil PH and make it difficult for some plants to grow.
Preventing pollution in the Haber-Bosch
process
Use alternative source of hydrogen rather than the process outlined. During the
production of hydrogen, carbon dioxide is produced as a product of reactions,
e.g. the shift reaction. One can instead use the hydrogen produced form previous
experiments (e.g. from the petroleum industry) to synthesize ammonia.
Nutrient management:Applying fertilizers in the proper amount, at the right time
of year and with the right method can significantly reduce the potential for
pollution.
Cover crops:Planting certain grasses, grains or clovers can help keep nutrients
out of the water by recycling excess nitrogen and reducing soil erosion.
Buffers:Planting trees, shrubs and grass around fields, especially those that
border water bodies, can help by absorbing or filtering out nutrients before they
reach a water body.
Conservation tillage:Reducing how often fields are tilled reduces erosion and soil
compaction, builds soil organic matter, and reduces runoff.
Preventing pollution contd
The wet scrubber (termed absorbers since they
remove gaseous pollutants), specifically the packed
tower scrubber, can be used to control gas emissions.
The polluted gas stream is fed into the tower where
there is a bed of specialized packing material. Nuzzles
spray scrubbing liquid onto the top of the packing
material and the liquid travels down the packing
material. Eventually, the scrubbing liquid and the gas
molecules come in contact and the molecules are
adsorbed. The contaminated liquid then drains down
the packing bed and out through the bottom of the
tower. The gas stream flows out through the top of the
packing material, through the nuzzles and through a
mist eliminator before exiting the tower.
Factors that influence the location of the ammonia
Industry
Availability of energy- enormous amounts of energy is required for the
generation of high temperatures and pressure. Ammonia plants should be built
near an abundant source of energy, e.g. hydropower plant or solar farm or the
petroleum industry.
Environmental reserves- more than likely, continuing production of ammonia
will result in the surroundings being affected. The plant owner needs to choose
his/her plant site wisely and skilfully to prevent damages to the environment
and possibly disagreements with environmentalists in the future.
Skilled labour force- The Haber-Bosch process is a dangerous and hazardous
process which largely needs experienced workers.
Should the plant be built next to the vicinity of a city or not? Cities are densely
populated area with a lot of structures that can be corroded e.g. (bridges,
marble stones, steel structures) with acid rain. Plant owners need to think
twice before building next to a city!
Health and safety in the ammonia
industry
Ammonia can irritate the lungs and change the pH of the blood, which can
alter the uptake of oxygen by haemoglobin. Therefore, wash bottles and gas
masks should be available and should be placed in strategic locations
throughout the industry in case of any accidental spills.
Liquid ammonia should be kept in a cooling system at all times below -33 C.
The cooling system should be properly maintained.
Ammonia containers must have proper hazardous signs during transport in
route to consumers or elsewhere.
Fires and explosives- at concentration of 16-25% of ammonia gas, it is
explosive. Proper storage and regulations should be strictly enforced and the
air should be continuously monitored for ammonia concentration.