INTRODUCTION

In 1828, WOHLER discovered that urea can be produced

from ammonia and cyanic acid in aqueous solution. Since
then, research on the preparation of urea has continuously
progressed.

In 1907, urea was produced on a limited industrial scale
by dehydration of Cyanamid, which was obtained from
calcium Cyanamid:

CaCN2 + H2O + CO2 CaCO3 + CNNH2

CNNH2 + H2O CO (NH2) 2

THEORY OF REACTION
In all commercial processes, urea is produced first by
reacting ammonia and carbon dioxide, in gaseous phase, at
high temperature (165 170C), and high pressure (132
148 bar) in presence of ammonia- carbamate saturated
solution in which the carbamate, in liquid phase is formed.
The reaction is fast and exothermic:

2NH3 + CO2 NH2COONH4 (1)

H = - 117 k j/mol

In the second reaction, which is slow and endothermic,
the ammonium carbamate dehydrates to produce urea and
water.

NH2COONH4 NH2CONH2 + H2O (2)

H = + 15.5 k j/mol
Urea Synthesis

UREA PROCESSES

1- The Snamprogetti (SNAM) process
In this process NH3 and CO2 are converted to urea via
ammonium carbamate at a pressure of 150 to 160 bar and a
temperature of 180C to 190C.
An molar ratio of NH3 to CO2 3.5 is used in the reactor to give
a CO2 conversion of 65%. The reactor effluent enters a
falling-film stripper where a large part of the unconverted
carbamate is decomposed by the stripping action of the
excess NH3 . Because of the high stripping temperatures
(200-210C), bimetallic tubes (made of zirconium and 25-22-
2 stainless steel) are needed to avoid corrosion in the tubes
and erosion near the bottom of the stripper.
Residual carbamate and CO2 are recovered downstream of
the stripper in two successive stages. The first stage
operates at 17 bar, and the second stage operates at 3.5
bar. Ammonia and CO2 vapors from the stripper top are
mixed with the recovered carbamate solution from the High
Pressure (HP) / Low Pressure (LP) sections, condensed in
the HP carbamate condenser and fed to the reactor. The
urea solution that leaves the LP decomposition stage is
concentrated in the evaporation section to make a urea melt.

2- Stamicarbon (STAC) process:
3-The Toyo Engineering-ACES (Advanced Process for
Cost and Energy Saving) process :

In this process the synthesis section operates at 175 bar with an
NH3 to CO2 molar ratio of 4.0 and a temperature of 185 to 190C.
Liquid ammonia is fed directly into the reactor while gaseous CO2
is sent from the centrifugal CO2 compressor at the bottom of the
stripper.
The reactor effluent is stripped at essentially reactor pressure
using CO2 as the stripping agent. The overhead gas mixture from
the stripper is fed to two carbamate condensers in parallel. Here
the gases are condensed and recycled under gravity to the
reactor along with absorbent solutions from the HP scrubber and
absorber. The heat generated in the first carbamate condenser is
used to generate 5.0 bar steam, and the heat from the second
condenser is used to heat the solution leaving the stripper bottom
after pressure reduction.
The ACES stripper uses a ferrite-austenite stainless steel as do
the carbamate condensers. The reactor and scrubber are
constructed with 316L urea-grade stainless steel.
The inerts in the synthesis section are purged to the scrubber
from the reactor top for recovery and recycle of NH3 and CO2
Unreacted NH3 and CO2 from several sources are eventually
recycled to the reactor via HP and LP absorbers.
The urea solution that leaves the stripper bottom is further purified
in HP (17.5 bar) and LP (2.5 bar) decomposers. The urea solution
is first concentrated to 88.7% in a vacuum concentrator and then
to the required concentration for prilling or granulating.
4- The Heat Recycle Urea Process (HRUP):
In this process ammonia, recycled carbamate and about 60%
of the make-up CO2 feed are charged to the top of an open-
ended reactor coil at 3200 psig (220 bar). Ammonium
carbamate is formed within the coil, exits the coil at the
bottom and flows up and around it. The exothermic heat of
carbamate formation in the coil drives the endothermic
dehydration of carbamate to urea on the outside of the coil.
This isothermal reactor design allows the conversion rate to
reach 77%. The reactor has a uniform temperature profile that
eliminates corrosion in the bottom of the reactor.
The decomposers produce a 68 to 70 wt% urea solution that
is concentrated under low vacuum in the Urea Concentrator
to an 88 wt%. An atmospheric, airswept, falling-film
evaporator then evaporates the 88 wt% urea product to make
a 99.7 wt% urea melt product that is ready for prilling or
granulation.
2- Stamicarbon (STAC) process:

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. 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). 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
Stamicarbon developed a fluid bed system in 1976.
The basic principle of the process involves the spraying of the
melt onto recycled seed particles or prills circulating in the
granulator. These seed particles gradually increase in size as
the process continues. The heat of solidification is removed
by cooling air. Since the contact time between liquid urea and
air is much lower than in prilling, the dust formed in
granulation processes is much coarser, and it is easier to
remove.
All granulation processes require the addition of
formaldehyde to the urea before it is sprayed on the crystal
seed surface. Formaldehyde serves as and anti-caking agent
during the granulation process and slows the release function
so that the fertilizer efficiency is higher
The Theory Concept of Granulation Process
The granulation process is basically depends on increasing in
the size of the seed particle, and that can be done one of the
following methods: -
a) Agglomeration
Binding of the particle together by the melt or solution, and that
led to non-homogeneity in the formation, and low mechanical
properties for the formed granule.
b) Stratification
The size of seed particle is increased simulteancy with
accumulation of the layers around the kernel and this method is
celled abo onion formation.
c) Accretion
The size of the seed particle is increased by the continuous
evaporation of the solution and the crystallization of very small
particles on the kernel.
All Hydro Agri fluidized bed granulation; depend on the
second method for the formation of urea granules.
Their granules are homogenous and have very high mechanical
properties and low moisture content.



Theory of Condensation
The condensation reaction is the first reaction that takes
place in urea plant. The reaction may achieve in two common
types of condensers:
I- The falling film condenser or vertical type
II- The pool condenser or horizontal type
The condensation capacity of the two types of condenser
is determined by the heat transfer coefficient, the surface area
of the tube bundle and the temperature difference between
the process side and cooling side.

The theory of condensation is depending on the
following items:
1- Pressure of condensation
2- Temperature of the reactants on the top tube sheet
3- Temperature of the cooling medium in the shell
4- NH3: CO2 molar ratio (1.8:1)
5- H2O: CO2 molar ratio
6- Gas: liquid molar ratio
As seen from equation (1), three moles are reacted to
yield only one mole. According to the decrease in volume in
the direction of carbamate formation, the pressure will
promote the reaction. In the most cases, applying pressure of
142 - 148 bar is optimum.
The gas feed temperature must be enough to evaporate a
considerable amount of ammonia dissolved in the (CO2 - NH3
- H2O) liquid feed. The temperature of the (CO2 - NH3 - H2O)
liquid feed is 105 120 C.
As seen also from equation (1), the condensation of CO2
and NH3 is an exothermic reaction. To promote this reaction,
a cooling for the reactants must be built in the shell of the
condenser. The cooling medium in the shell side of the high
pressure condenser must be of a temperature of a value that
adjusts the rate of condensation reaction. Below this value,
the carbamate formed will crystalline.
A cooling medium of a temperature of 145- 150 C being
optimum to increase the condensation reaction, in the liquid
phase, without crystalline formation of carbamate which
usually takes place below 145 150 C, at pressure of 142 -
148 bar .
Theory of Conversion
In the next step of the formation of urea, 75% of the gases
in the top of the carbamate condenser are condensed through
the vertical tubes, while 25% of the gases are sending,
associated with that condensed, to the reactor. The chemical
interaction between NH3 and CO2 results in a strongly
azeotropic behaviour of the binary system NH3 - CO2. An
approach to the description of the phase equilibria if urea and
H2O are added to the NH3 - CO2 system was given by
KAASENBROOD and CHERMIN. They found that, the
equilibrium in the NH3 - CO2 - H2O urea system under a
pressure of 142 - 148 bar and NH3 : CO2 of 3 : 1 show the
maximum CO2 conversion at high temperature.
In the NH3 - CO2 - H2O system, the urea conversion
according the equation (2) is a slow endothermic reaction. As
a result, the conversion of CO2 into urea will be slowly
independently of the chemical reaction rate. In this way, a
significant residence time will be needed before all the
vapours can be transported into the liquid phase, where the
heat being realized and the global equilibrium can be
reached. On this fact, it can be concluded that in the majority
of the urea reactors the equilibrium is not reached, as there is
strong evidence that gases of NH3 and CO2, in big amount,
are still present at reactor outlet.
The literatures on this conversion clarify that the
conversion of carbamate into urea need at least 18 25
minutes at temperature profile of 176 183 C.
Theory of Scrubbing
In this step of reaction, the reactor gas effluent, the non
reacted NH3 : CO2, are let to react at a lower temperature,
compared with reactor, at the same high pressure also. As in
the high pressure carbamate condenser, the condensation of
the rest of the gases takes place in presence of a hypothetical
mixture or initial mixture (CO2 - NH3 - H2O) liquid feed of a
concentration lower than that fed to the high pressure
carbamate condenser. The reaction is also takes place in a
vertical set of tubes. The two phases are located in the
bottom of the tubes set, in which the reaction started. The
theory of the carbamate condenser is also applied, in which a
cooling medium must be applied to promote the reaction.
Increasing the ratio of H2O : CO2 molar ratio in the mixture
results in a dramatic decrease in the reaction between the
gases of NH3 and CO2, but of course increases the reaction
between the gas of NH3 and the H2O in the liquid state. For
this reason, the molar ratio of NH3 : CO2 in the gas mixture
must be high enough to keep the ratio of gaseous NH3 : CO2
over 2: 1 after completing the reaction between the gas of
NH3 and the H2O in the liquid state.
In general cases, the H2O : CO2 ratio of the hypothetical
mixture, fed to scrubber, from recirculation, is of 2 - 2.5 : 1,
which indicates that: the NH3 : CO2 molar ratio in the gas
mixture fed to scrubber must be, at least of 4.5 :1
The reaction in this stage usually proceeds as follow:
1. The gases are fed with the hypothetical mixture in the
bottom of the scrubber
2. The gas liquid mixture goes up through pipes, in
which the absorption for ammonia, in gas phase, into the
liquid phase takes place to a certain limit
The reaction of H2O and CO2, then, takes place in the
ammonia rich liquid mixture and the heat of reactions are
propagated to the cooling medium in the shell of the scrubber,
which flows in countercurrent with the passage of reaction in
tubes, to propagate the reaction
Theory of Stripping
From the late fifties until now, the energy requirements of
urea plants have been reduced dramatically; steam
consumption was in the order of 2 tons per ton of urea,
excluding the energy to drive the carbon dioxide compressor.
At present, this figure is 0.6 to 0.7 tons per ton, depending
of course on steam quality.
The steam pressure needed in these old urea plants was
admittedly lower. Typically steam of approximately 12 bar was
required while todays stripping plants need a steam pressure
of at least about 20 bar. This large difference is mainly due to
improvements made in the process itself rather than the
increases in plant size that have since taken place.
When the stripping process in the mid-sixties introduced,
a saving of more than 40 per cent over the best existing
conventional urea process was achieved.



References :
1- Synthetic Nitrogen Products
Gary R. Maxwell
DuPont Chemical Solutions Enterprise
Memphis, Tennessee
2- Manual of Urea Plant
Abu Qir Fertilizers Company