UREA

Urea is an organic compound which is the worlds most commonly used nitrogen fertilizer
because of its high concentration of 46% N, cheap, least likely to cake and easy to handle. It is
mass-produced by reacting ammonia (NH
3
) and carbon dioxide (CO
2
) to produce ammonium
carbamate (middle product) and decompose it to produce Urea (final product).
Two reactions for urea production:
2NH3 (g) + CO2 (g) ===== NH2COONH4 (s) ; exothermic

NH2COONH4 ( s) ===== NH2CONH2 (s) + H2O (l) ; endothermic

EFFECT OF VARIOUS PARAMETERS

TEMPERATURE
The formations of urea from carbon dioxide and ammonia have 2 reactions. The 1
st
is
exothermic while the 2
nd
is endothermic. With the application of Le chateliers Principle, the 1
st

reaction is favored when the temperature is low while the 2
nd
reaction is favored when it is at
high temperature. The 1
st
reaction is fast and reaches to completion but the 2
nd
reaction is slow
and it determines what the overall rate of the production of urea is. A sufficient completion of
the 2
nd
reaction is attained if an optimum temperature is maintained.

PRESSURE
With the increase of pressure, there is a reduction of volume in the overall reaction and thus
high pressure favors the forward reaction. The selection of the pressure is according to the
temperature to be maintained and NH
3
:CO
2
ratio.

CONCENTRATION
According to law of mass action, if there is a high concentration of the reactants there would be
higher forward reaction. With the CO
2
being the limiting reagent, having a higher NH
3
: CO
2
ratio
favors conversion. The dehydration of carbamate results in urea production, a lesser H
2
O:CO
2

ratio favors conversion.



RESIDENCE TIME
Since the conversion reaction of urea is slow, appropriate time should be provided to get a
higher conversion of reactants. The reactor should be design to accommodate the parameters
such as temperature, pressure and concentration.

PROCESS DESCRIPTION
There are different types of Processes use for the manufacturing of urea and these are:


Snamprogetti ammonia stripping process it is the chosen process because it involves a high
NH
3
to CO
2
ratio in the reactor which make it most efficient in converting carbamate to urea.
Four main operations for the urea production process:
1. Urea synthesis and high pressure recovery.
2. Urea purification and low pressure recovery.
3. Urea concentration.
4. Urea prilling.
UREA SYNTHESIS AND HIGH PRESSURE RECOVERY
Liquid Ammonia and gaseous Carbon dioxide is synthesized to form urea. Carbon dioxide at 1.6
atm pressure and 40 temp. is drawn from the battery limits and compressed up to 162 atm
by a centrifugal compressor. In order to protect the CO
2
compressor from corrosion, a small
quantity of air is added to passivate or coat the surface of the stainless steel. Ammonia
receiver tank collects the liquid ammonia directly from the battery limits and compressed it at
about 23 atm by a centrifugal pump. Some portion of this ammonia goes to the medium
Process Temperature
requirement
(Reactor)
Pressure
requirement
(Reactor)
%unconverted
ammonium
carbamate
Snamprogetti 190 154 atm 2-3%
Stamicarbon 190 140 atm 15%
Mitsui Toatsu
or Tokyo
Koatsu

195

240 atm

33%
pressure absorber and the remaining part enters at high pressure synthesis loop where it is
compressed at a pressure of 240 atm. This is used as driving fluid in the carbamate ejector
before it enters the reactor; the carbamate coming from carbamate separator is compressed up
to synthesis pressure. The liquid mixture of ammonia and carbamate enters the reactor where
it reacts with compressed CO
2.
At the reactor, two reactions takes place and this are:
2NH3 (g) + CO2 (g) ===== NH2COONH4 (s) ; exothermic

NH2COONH4 ( s) ===== NH2CONH2 (s) + H2O (l) ; endothermic
The first reaction is the formation of carbamate from ammonia and carbon dioxide; it occurs
rapidly and goes to completion under the reaction conditions used industrially. The second
reaction is the decomposition of carbamate to form Urea and water, it occurs slowly and does
not proceed to completion and it also determines the reactor volume. During synthesis T =
190 and P =154 atm. Ratios of various reactant, operating temperature, residence time in the
reactor and reaction pressure are factors need to be consider in determining the fraction of
carbamate that dehydrates. The ratio of NH
3
/CO
2
is around 2:1 and the mole ratio of H
2
O/ CO
2

is around 0.67:1. Plug flow type of reactor are used in the process, it has 10 no. of sieve tray in
order to avoid escape of CO
2
which must react in the lower part of the reactor and also to avoid
back mixing.
At High pressure stripper which has the same pressure as that of the reactor, urea solution
enters that contains urea, carbamate, water and unconverted CO
2
and NH
3
. The mixture is
heated as it flows down the falling film heat exchanger. As NH
3
boils out, it serves as stripping
agent to reduce the CO
2
content of the solution. Steam of 24 atm is being supplied for the
decomposition of carbamate. The total mixture of overhead gases from stripper and recovered
solution from the MP absorber flows to the high pressure carbamate condenser where it is
condensed and by means of carbamate ejector it is recycled to the reactor. Incondensable
gases consisting of inerts and little amount of NH
3
and CO
2
unreacted in the condenser coming
out from the top of the carbamate separator are sent to the bottom of MP decomposer.

UREA PURIFICATION AND LOW PRESSURE RECOVERY
There are two stages for Urea purification and these are:
1
st
stage is the MP decomposer and the working pressure is 18 atm.
2
nd
stage is the LP decomposer and the working pressure is 4.5 atm
The first stage is a falling type MP decomposer and composes of 2 parts. First is the top
separator, it is where the released flash gases remove from the solution is, and second is the
decomposition section wherein the solution enters the tube bundle and the steam condensate
at 24 atm flowing out of the stripper serves as the source of heat required for the
decomposition of residual carbamate.
The second stage is LP decomposer also a falling film type and composes of two parts. The top
separator contains the released flash gases and the decomposition section wherein the
saturated steam at 4.5 atm is the source of heat required for the decomposition of last residual
carbamate.

UREA CONCENTRATION
The main objective of this operation is to reduce the water content of urea to as low as 1%. It
has two stages and in order to achieve the objective, vacuum concentrator is provided in every
stage. At the 1
st
stage, the solution with 72% urea leaving the LP decomposer enters to the 1
st

vacuum concentrator operating at a pressure of 0.23 atm and the mixed phase coming out in
the concentrator enters at the 1
st
vacuum system where in the gas-liquid separation takes
place. The solution leaving the 1
st
vacuum system enters in 2
nd
vacuum concentrator operating
at a pressure of 0.03 atm and the mixed phase coming out enters in 2
nd
vacuum system where
in the gas-liquid separation takes place.

UREA PRILLING
The molten urea leaving the 2
nd
vacuum separator enters to the prilling bucket by means of a
centrifugal pump. In the prilling tower, Urea from the buckets fall in the form of drops and it
encounters the cold air which makes it solidify. Solidified prills(final product) passed through a
screeners when it falls down at the bottom of the prilling tower to retain lumps only. Final
product is transported by means of belt conveyor in automatic weighing machine, packaging
and storage sections.