Urea

Urea Manufacturing Process
by
Syed Kamal Zafar

THE UREA MANUFACTURING PROCESS
• Urea is produced from ammonia and carbon dioxide in two equilibrium reactions:
• 2NH3 + CO2 ↔ NH2COONH4
• ammonium carbamate
• NH2COONH4 ↔ NH2CONH2 + H2O
• urea
• The urea manufacturing process, shown schematically in Figure , is designed to
maximise these reactions while inhibiting biuret formation:
• 2NH2CONH2 ↔ NH2CONHCONH2 + NH3
• biuret
• This reaction is undesirable, not only because it lowers the yield of urea, but
because biuret burns the leaves of plants.
• This means that urea which contains high levels of biuret is unsuitable for use as a
fertiliser.
• Biuret is a chemical compound with the chemical formula C 2H5N3O2. It is also known as carbamylurea. It is the result of condensation of
two molecules of urea and is an impurity in urea-based fertilizers. This white solid is soluble in hot water
Step 1 - Synthesis
• A mixture of compressed CO2 and ammonia at 240
barg is reacted to form ammonium carbamate.
• This is an exothermic reaction, and heat is recovered
by a boiler which produces steam.
• The first reactor acheives 78% conversion of the
carbon dioxide to urea and the liquid is then purified.
• The second reactor recieves the gas from the first
reactor and recycle solution from the decomposition
and concentration sections.
Step 1 - Synthesis
• Conversion of carbon dioxide to urea is
approximately 60% at a pressure of 50 barg.
• The solution is then purified in the same
process as was used for the liquid from the
first reactor.
Urea Synthesis
Step 2 - Purification
• The major impurities in the mixture at this stage are water from the urea production
reaction and unconsumed reactants (ammonia, carbon dioxide and ammonium
carbamate).
• The unconsumed reactants are removed in three stages3.
• Firstly, the pressure is reduced from 240 to 17 barg and the solution is heated, which
causes the ammonium carbamate to decompose to ammonia and carbon dioxide:
• NH2COONH4 ↔ 2NH3 + CO2
• At the same time, some of the ammonia and carbon dioxide flash off.
• The pressure is then reduced to 2.0 barg and finally to -0.35 barg, with more
ammonia and carbon dioxide being lost at each stage.
• By the time the mixture is at -0.35 barg a solution of urea dissolved in water and free
of other impurities remains.
• At each stage the unconsumed reactants are absorbed into a water solution which is
recycled to the secondary reactor.
• The excess ammonia is purified and used as feedstock to the primary reactor.
Step 3 - Concentration
• 75% of the urea solution is heated under vacuum, which
evaporates off some of the water, increasing the urea
concentration from 68% w/w to 80% w/w.
• At this stage some urea crystals also form.
• The solution is then heated from 80 to 110 C to redissolve
these crystals prior to evaporation.
• In the evaporation stage molten urea (99% w/w) is produced
at 140 C.
• The remaining 25% of the 68% w/w urea solution is
processed under vacuum at 135 C in a two series evaporator-
separator arrangement.
Step 4 - Granulation
• Urea is sold for fertiliser as 2 - 4 mm diameter granules.
• These granules are formed by spraying molten urea onto seed granules which
are supported on a bed of air.
• This occurs in a granulator which receives the seed gransules at one end and
discharges enlarged granules at the other as molten urea is sprayed through
nozzles.
• Dry, cool granules are classified using screens.
• Oversized granules are crushed and combined with undersized ones for use as
seed.
• All dust and air from the granulator is removed by a fan into a dust scrubber,
which removes the urea with a water solution then discharges the air to the
atmosphere.
• The final product is cooled in air, weighed and conveyed to bulk storage ready
for sale.
Urea granule specifications
UTILITIES
• The ammonia and urea manufacturing facilities are
separate, so each has its own utilites. These are listed below.
• Ammonia manufacture
• Heat recovery
• The heat of the gas from the primary reformer (Step 1) is
used to produce steam for the primary reformer using a
boiler. The gas is then discharged. Heat from the process gas
from the secondary reformer (Step 2) is used to produce
steam for a turbogenerator.
• A turbo generator is the combination of a turbine directly connected to an electric generator for
the generation of electric power. Large steam-powered turbo generators provide the majority of
the world's electricity and are also used by steam-powered turbo-electric ships
UTILITIES Ammonia manufacture
• Water recycling
• Excess water from the water gas shift
converter, the methanator and the ammonia
synthesis loop is used for boiler feed water
and as the absorbing water for ammonia
recovery.
• Carbon dioxide stripper
• The used UCARSOL is sent to the carbon dioxide
stripper.
• Here the UCARSOL is heated to remove a mixture
of CO2 and water, cooled and reused.
• The water is removed from the CO2 by
condensation and the pure CO2 sent directly to
the urea plant for compression and use in urea
synthesis.
• Ammonia recovery
• Gases purged from the ammonia synthesis loop and gases
collected during ammonia decompression are mixed and sent to
the ammonia recovery system.
• Here the gas mixture is introduced at the bottom of a column and
passes up through a counter-current of cold water.
• 96% of the ammonia in the gas is absorbed into the water, leaving
a gas mixture that is used as a fuel gas to heat the primary
reformer.
• The ammonia is distilled out of the ammonia water mixture,
condensed and pumped to join the rest of the ammonia from the
ammonia synthesiser.
Urea manufacture
• Heat recovery
• The heat of the reaction in which ammonium
carbamate produces steam at 7 barg.
• This is used in the decomposition and
evaporation sections for heating.
Urea manufacture
• Ammonia and carbon dioxide recovery
• During urea decomposition a mixture of gaseous
carbon dioxide and ammonia is collected and
absorbed into a dilute aqueous urea solution.
• This mixture is recycled by being fed back into
the secondary urea reactor.
• The excess ammonia is condensed and used as
feedstock to the primary reactor.
Urea manufacture
• Water recycling
• Evaporated water from the concentration step
is used during the third stage of
decomposition as the initial recycle solution.
THE ROLE OF THE LABORATORY
• Ammonia production
• • The laboratory monitors the gaseous mixture exiting each vessel at each stage
in the process using gas chromatography.
• The concentration of each component during the process is kept at a
precalculated design figure and laboratory results are compared to these figures.
• Adjustments are made to the process based on the laboratory results to bring
the process back to the design figures.
• • The UCARSOL solution is analysed daily to determine the solution strength.
• The solution strength must be kept within a defined range and additions to the
system are made according to laboratory results.
• • Liquid ammonia product is analysed to ensure that impurity concentrations are
below maximum levels set.
• The sample solution injected into the instrument enters a gasstream which transports the sample into a separation
tube known as the "column." (Helium or nitrogen is used as the so-called carrier gas.) The various components are
separated inside the column
THE ROLE OF THE LABORATORY
• Urea Production
• • The laboratory carries out analysis at various stages of
granulation for size distribution.
• The process is adjusted accordingly to meet final product size
specifications.
• • The final product is analysed for moisture, biuret, formaldehyde
and pH as a check on the process and to ensure customer
specifications are met.
• In addition, boiler and cooling waters are analysed to ensure that
their composition is such that corrosion is minimised.
• Trouble shooting is often required to source biuret or excessive
moisture during intermediate stages of the urea process.
ENVIRONMENTAL IMPLICATIONS
• The ammonia and urea complex is operated in accordance with
stringent safety and environmental standards.
• The Petrochem complex produces effluent in the form of storm
water and waste water from the manufacturing process.
• All effluent is directed to large holding ponds where it is treated
and carefully checked as to its composition prior to discharge.
• The effluent is spray irrigated onto Petrochem’s pastures
surrounding the complex.
• Many waste minimisation measures are carried out during the
process, resulting in the plant having little effect on the
environment.

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Urea Manufacturing Process

Syed Kamal Zafar

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