Stamicarbon bv

1. This document contains a simplified/general “Process Description” of the Urea

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Description of the urea process

Contents

1. Introduction.
2. Ammonia and carbon dioxide compression
3. Synthesis
4. Low pressure recirculation stage
5. Pre-evaporation and evaporation
6. Process condensate treatment

1. Introduction

Urea is produced by reacting liquid ammonia and gaseous carbon dioxide at about 170 - 185 C and
135 - 145 bar according to the following reactions:

2 NH3 + CO2 <=====> NH2COONH4 (1)

NH2COONH4 <=====> NH2CONH2 + H2O (2)

In the first reaction, carbon dioxide and ammonia are converted into ammonium carbamate. This reaction is
fast and exothermic. In the second reaction, which is slow and endothermic, the ammonium carbamate
dehydrates to produce urea and water.

2. Ammonia and Carbon dioxide compression

Liquid ammonia is supplied from battery limits to the high pressure ammonia pump and compressed to
about 165 bar. It is then sent to the high pressure carbamate condenser via the high pressure ammonia ejector.
Carbon dioxide from battery limits is supplied, together with a small amount of air, to the carbon dioxide
compressor before it is compressed to about 150 bar. A hydrogen converter is integrated in the carbon
dioxide compressor. In this converter the hydrogen, present in the carbon dioxide, is removed by catalytic
combustion. A portion of the supplied air is used for this catalytic combustion while the remainder being
used to passivate the equipment of the synthesis section and so prevent corrosion. The dehydrogenated
carbon dioxide is introduced into the bottom part of the high pressure stripper. The two feedstocks, ammonia
and carbon dioxide, are fed to the synthesis section at a molar ratio of 2:1.

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 3. Synthesis

The dehydration of ammonium carbamate into urea and water takes place in the pool condenser and
subsequently in the reactor. The reactor effluent is distributed over the tubes of the high pressure stripper,
which is a falling film type shell and tube heat exchanger. Here, the reactor effluent is contacted counter
currently with carbon dioxide, causing the partial ammonia pressure to decrease and the carbamate to
decompose. The heat, required for this purpose, is supplied by passing saturated high pressure steam
around the tubes of the high pressure stripper. This steam pressure is controlled by a pressure control valve
so that the liquid, leaving the high pressure stripper, contains about 12 % by weight of ammonia. The urea
solution from the high pressure stripper, flows to the medium pressure recirculation section whilst the
high pressure stripper off gases are sent to the pool condenser which is special design U-tube type heat
exchanger. In the pool condenser condensation of strip gasses takes place through the principle of pool
condensation, i.e. the gases are dispersed into a pool of liquid, where the heat of condensation is being
dissipated by submerged heat exchanger tubes. This heat of condensation is used to generate low pressure
steam of about 4.5 kg/cm2-a. This steam is used for heating and desorption as well as for the vacuum
ejectors. The steam pressure at the tube side of the high pressure carbamate condenser is controlled by a
pressure control valve in the steam discharge line of the steam drum. A change in this pressure will change
the steam condensate temperature and hence the temperature difference between the shell side and the
tube side. The steam drum pressure is set to such a value that the synthesis pressure is about 145 kg/cm2-
a measured in the liquid NH3 feed to the pool condenser. The pool of liquid in the pool condenser allows
for a considerable amount of urea formation to take place here. The formed urea, non-converted
carbamate, excess ammonia and some non-condensed ammonia and carbon dioxide are subsequently
introduced into the bottom of the reactor where further conversion of carbamate into urea takes place. The
reactor volume allows sufficient residence time for the reaction to approach equilibrium. The heat,
required for the conversion and for heating the solution in the reactor, is supplied by additional
condensation of ammonia and carbon dioxide. The reactor contains a number of high efficiency trays to
ensure that the flow of liquid through the reactor approaches plug flow. Moreover the trays are designed
such that negative effects (such as back-mixing, by-passing and stagnant zones in the reactor) are avoided.
The reactor effluent goes through the down comer to the high pressure stripper. The inert, introduced with
the carbon dioxide and part of the unreacted ammonia and carbon dioxide, go overhead to the off gas line
of the adiabatic flash tank in the MP section.

4. Medium pressure section

The urea solution, leaving the high-pressure stripper in the synthesis section, is expanded at a pressure of
about 25 kg/cm2-a in the adiabatic flash tank. Because of the expansion a substantial part of the carbamate

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in that solution is decomposed into ammonia and carbon dioxide vapour. That vapor together with the
carbamate from the low-pressure recirculation section and the off gas of the reactor is introduced into the
shell of the pre-evaporator where the vapor is condensed, evaporating water from the urea solution at the
tube side. In case the water in the urea solution is not sufficient to ensure enough condensation at the
condensing side of the pre-evaporator the pressure in the MP section will increase. To deal with this,
ammonia water can be added to the urea solution to enhance the condensing capacity. The carbamate
solution from the pre-evaporator is elevated by a high-pressure carbamate pump and introduced into the
pool condenser. The non-condensed vapor together with the inert gas in the shell of the preevaporator is
sent to the medium pressure absorber. The urea solution leaving the adiabatic expansion is sent to the low-
pressure recirculation section.

5. Low pressure recirculation section

In this section essentially all of the small amounts of non-converted ammonia and carbon dioxide are
recovered from the urea/ carbamate solution, leaving the bottom of medium pressure adiabatic flash tank.
This solution is expanded to about 4 kg/cm2-a. As a result a portion of the carbamate, left in the solution,
decomposes and evaporates. The remaining liquid is divided onto a bed of Pall rings in the rectifying
column. The urea/ carbamate solution is sent from the bottom of the rectifying column to a heater where
its temperature is raised to about 135 °C in order to decompose the remaining carbamate. The heat required
is supplied by low pressure steam. In the separator (i.e. the bottom part of the rectifying column) the gas
phase is separated from the liquid phase. The gases are sent to the rectifying column where they are cooled
by the colder urea/ carbamate solution. This causes a portion of the water vapor contained in the gases to
condense. The gases leaving the rectifying column are introduced into the bottom part of the low pressure
carbamate condenser where they are condensed almost completely. The heat of condensation is dissipated
into tempered cooling water. Process condensate is also supplied to the low pressure carbamate condenser
together with the condensed overhead vapors from the first desorber in order to control the water
concentration in the carbamate solution. The optimum ammonia/ carbon dioxide ratio allows the water
concentration to be as low as 32 % by weight. The pressure in the low pressure carbamate condenser is
controlled at about 4.3 kg/cm2-a. From the level tank of the low pressure carbamate condenser, the
carbamate solution flows to the medium pressure carbamate pump where its pressure is raised to about 25
kg/cm2-a and from where the carbamate solution is carried to the pre-evaporator heater. The urea solution,
leaving the bottom of the rectifying column, flows to an atmospheric flash, where the pressure difference
causes the solution to flash, causing water to evaporate. Off gas from this flash is sent to a condenser. Non
condensing vapor from this condenser is discharged to the atmospheric absorber. Urea solution from the
atmospheric flash flows to the pre-evaporator heater and separator via a level control valve, in this pre-
evaporator the urea solution is heated by heat exchange with condensing medium pressure carbamate gas
in the shell, and a portion of the water evaporates and some ammonia, carbon dioxide and inert are

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liberated. These vapors are partly condensed in the first stage evaporator condenser and the remaining
ammonia and carbon dioxide are scrubbed from the inert in the atmospheric absorber by means of
circulating process condensate and steam condensate. Condensate from first stage evaporator condenser
is sent to the ammonia water tank.
Off gases from the atmospheric absorber and the LP absorber are sent to an acidic scrubber, where by
means of sulfuric acid the remaining ammonia is removed from the off gas before it is discharged to the
atmosphere. The ammonium sulfate which is formed is discharged to battery limit.

6. Evaporation

The urea solution from the pre-evaporator is sent to the urea storage tank. The urea solution is pumped
from the urea solution tank to the first stage evaporator where the urea solution is concentrated to about
95 % by weight. The sub-atmospheric pressure in this evaporator is about 0.33 kg/cm2 and the temperature
of the solution leaving this evaporator about 130°C. This urea solution is sent to a second stage evaporator
in which the solution is concentrated to a melt. The urea concentration in this melt is 98.5 % by weight.
The sub atmospheric pressure in the second stage evaporator is 0.15 kg/cm2 and the temperature of the
melt leaving this evaporator is about 140°C. The urea melt is then sent via the urea melt pump to the
granulator. The overhead vapor of both evaporators is condensed in the evaporator condensers and the
process condensate leaving the condensers is collected in the ammonia water tank. Non condensed vapors
leaving the condensation section are sent to an absorber, operating at atmospheric pressure, where
ammonia left in the vapor is absorbed almost completely.

7. Finishing / Granulation

In the Stamicarbon fluid bed granulation process, granular urea is produced by low pressure ‘film’
spraying of liquid urea melt onto seed material in fluidized state. The basic characteristics of this process
are: • the liquid urea is a concentrated solution (melt) • the liquid urea is sprayed inside a fluidized bed by
means of a large number of spray nozzles • the particle size enlargement is achieved by scale granulation,
i.e., growth of the seed or nucleus granules by continuous solidification of very thin layers of urea melt
onto the initial particles • formaldehyde (in the form of urea formaldehyde pre-condensate) is added to
the urea melt before spraying, acting as a process aid and anti-caking agent. In order to spray onto a large
number of solid particles simultaneously and to prevent agglomeration, it is necessary to keep the particles
apart. Fluidization is a suitable method to avoid contact between particles over a long period of time until
they are cooled down sufficiently. During the entire residence time in the granulation zone of the
granulator, each granule is repeatedly covered with a thin film of urea melt. The particle size growth is
uniform and progressive with the residence time and results in a uniform shape and good quality granules.

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 8. Process condensate treatment

Process condensate from the evaporator condenser, containing ammonia, carbon dioxide and urea, is
collected in the ammonia water tank and used as absorbent in the 4 bar absorber and the atmospheric
absorber. Next the process condensate is pumped from the ammonia water tank to the first desorber via a
desorber heat exchanger. In the first desorber the bulk of the ammonia and carbon dioxide is stripped off by
means of the overhead vapours of the second desorber and hydrolyser. The bottom effluent of this first
desorber is pumped via a hydrolyser heat exchanger, where this condensate is heated from approximately
136 C to 190 C, to the top of the hydrolyser column. In the hydrolyser, the urea is decomposed into
ammonia and carbon dioxide while being heated by means of live high pressure steam, to about 190 C. To
obtain very small urea concentrations in the hydrolyser effluent (< 1 ppm), the process condensate is counter
current contacted with the live steam. On leaving the hydrolyser the process condensate, containing traces
of urea, goes via the hydrolyser heat exchanger to the second desorber. The overhead vapours of the
hydrolyser being sent to the first desorber. After cooling the hydrolyser effluent in the hydrolyser heat
exchanger to about 145 C, this condensate is fed to the top of the second desorber. Here, the remaining
ammonia and carbon dioxide is stripped off by means of live low pressure steam. The process condensate,
leaving the second desorber, is cooled in the desorber heat exchanger and subsequently in the waste water
cooler. It contains very small amounts of urea and ammonia (< 1 ppm ammonia and 1 ppm urea) and can
be used for several purposes i.e. for boiler feed water or cooling water make up. The overhead gases from
the first desorber are condensed in the reflux condenser and are transferred as a carbamate solution to the
low pressure carbamate condenser. The non-condensed vapours are sent to the atmospheric absorber.

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