Lecture

Urea Synthesis
Urea
• Urea (NH2CONH2) is of great importance to the
agriculture industry as a nitrogen-rich fertilizer.
• It is the most convenient form for fixed N2.
• Highest N2 content available in a solid fertilizer,
i.e. 46%.
Some Characteristics
• Easy to produce in the form of prills or granules
and easy to transport in bulk or bags.
• Dissolves easily in water.
• Leaves no salt residue after use on crops.
Some Uses
• Most of the ammonia is used on site in the
production of urea.
• The urea is used as a fertilizer, and as such is of
great importance in agriculture
Other Uses
• In addition to fertilizer use, it is used as:
• A protein food supplement for ruminants.
• In melamine production
• As an ingredient in the manufacture of resins,
plastics, adhesives, coatings, textile anti-shrink
agents and ion-exchange resins.
• It is an intermediate in the manufacture of
ammonium sulfamate, sulfamic acid and
pthalocyanines.
• It is also used as a component in the manufacture of
resins for timber processing and in yeast
manufacture.
Urea Synthesis
• Urea is produced from NH3 and CO2.
• 2 equilibrium reactions are:
1. Ammonium Carbamate production under
pressure by reaction between CO2 and NH3.
2 NH 3  CO2  NH 2COONH 4
2. Decomposition of Ammonium Carbamate.
NH 2COONH 4  NH2CONH 2  H 2O
• Among these reactions first one is highly
exothermic while the second one is
endothermic.
• While the process is designed in such a way to
maximize the urea production and inhibit biuret
formation:
2 NH 2CONH 2  NH 2CONHCONH 2  NH3
• This reaction is undesirable because it lowers the
yield of urea and also biuret burn the leaves of
the plants.
Block Flow Diagram for Urea Synthesis
Step 1 - Synthesis
• A mixture of compressed CO2 and NH3 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. 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.
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).
Removal of Unconsumed Reactants
• The unconsumed reactants are removed in three
stages.
1. 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:
NH 2COONH 4  2 NH 3  CO2
• 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 re-
dissolve 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 fertilizer 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 granules
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.
Assignment
• Differentiate between Prilling and Granulation
Tower.
Manufacturing Processes for Urea
 Urea
Manufacturing

Conventional Stripping
Processes Processes

Once Recycle Stamicarbo Snamprogetti

ACES Isobaric
Through Processes n CO2 Ammonia and
Process Double Recycle
Self-Stripping
Once-Through Process
• In the very first processes, non-converted NH3 was neutralized
with acids(e.g. nitric acid)to produce ammonium salts (such
as ammonium nitrate) as co-products of urea production.
• In this way, a relatively simple urea process scheme was
realized.
• The main disadvantages of the once-through processes are:
• the large quantity of ammonium salt formed as co-product
and the limited amount of overall carbon dioxide conversion
that can be achieved.
• A peculiar aspect of this historic development is a partial
“revival” of these combined urea
ammonium nitrate production facilities
Conventional Recycle Processes
• Once through processes were soon replaced by
total-recycle processes, where essentially all of
the non-converted ammonia and carbon dioxide
were recycled to the urea reactor.
• In the first generation of total-recycle processes,
several licensors developed schemes in which
the recirculation of non-converted NH3 and CO2
was performed in two stages.
• The first recirculation stage was operated at
medium pressure (18-25bar); the second, at
low pressure (2–5bar).
• The first recirculation stage comprises at least a
decomposition heater, in which carbamate
decomposes into gaseous NH3 and CO2, while excess
NH3 evaporates simultaneously. The off-
gas from this first decomposition step was subjected
to rectification, from which relatively pure NH3 (at
the top) and a bottom product consisting of an
aqueous ammonium carbamate solution were
obtained. Both products are recycled separately to
the urea reactor.
Stripping Processes
• In the 1960s, the Stamicarbon CO2-
stripping process was developed, followed later by other
processes.
• Characteristic of these processes is that the major part of the
recycle of both non-converted NH3 and non-converted CO2
occurs via the gas phase, such that none of these recycles is
associated with a large water recycle to the synthesis zone.
• Another characteristic difference between conventional and
stripping processes in terms of the recycle scheme, can be
found in the way heat is supplied to there circulation zones.
The energy balance of the conventional processes. In this first
generation urea process, the heat supplied to the urea
synthesis solution was used only once; therefore, this type of
process can be referred to as an N =1 process. Such a process
required about 1.8t of steam per tonne of urea.
Stamicarbon CO2 – Stripping Process
Snamprogetti Ammonia and Self-
Stripping Processes
ACES Process (Advanced process for Cost and Energy Saving

urea production.)