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 2, 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. The structure of these compounds is shown in Figure 3.

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.

CO 2 NH 3

Synthesis
urea, excess NH3,
carbamate, H 2O

heat NH3, CO2

Decomposition Recovery cooling

urea, H2O

heat Concentration H 2O H 2O

urea

Granulation

Urea granule

Figure 2 – Schematic representation of urea synthesis

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from the decomposition and concentration sections. 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.
H2NO- NH4+
H2N NH2 H2NC NH NH C C
2
O O O
C
O

Figure 3 - Some chemicals of interest in urea production

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 110oC to redissolve these crystals
prior to evaporation. In the evaporation stage molten urea (99% w/w) is produced at 140oC.
The remaining 25% of the 68% w/w urea solution is processed under vacuum at 135oC 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.
 3
This three step process is used to discourage two undesirable reactions — urea hydrolysis:
NH2CONH2 + H2O ! 2NH3 + CO2
and biuret formation:
2NH2CONH2 ! NH2CONHCONH2 + NH3

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Table 3 - Urea granule specifications
Component Concentration

Nitrogen 46 % minimum by weight

Biuret 1.0 % maximum by weight

Moisture content 0.3 % maximum by weight

Sizing 90% 2 - 4 mm by weight

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.

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 ammoniawater

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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.

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.

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.

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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FINANCIAL CONSIDERATIONS

The process uses three main raw materials: natural gas, air and water. Petrochem’s plant is
situated adjacent to the Kapuni gas treatment plant so natural gas is readily accessible.
Natural gas is used for both fuel gas and as a source of carbon dioxide and hydrogen for the
process. Air is, of course, in abundant supply. Water is pumped from the nearby
Waingongoro stream for head water to the boilers, cooling water and process water. This
water is treated after exiting the process and returned to the stream. Thus all raw materials
are cheap and readily available.

Costs are minimised throughout the process by using waste heat boilers and heat exchangers.
There is a co-generation plant and turbogenerator on site which together produce around 80%
of the power needed to run the plant.

Petrochem has undergone an upgrade to increase the production capacity of the plant. When
this expansion is fully commissioned, production capacity will increase to 750 tonnes of urea
per day.

Article written by J. C. Copplestone (Petrochem) and Dr. C. M. Kirk (Taranaki Polytechnic)

with revisions by S. L. Death, N. G. Betteridge and S. M. Fellows (all of Petrochem) and
editing by Heather Wansbrough.

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