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CHAPTER 1

INTRODUCTION
Point No.

Subject

Page No.

1.1

Physical & Chemical properties of Urea

1.2

Uses of Urea

1.3

Process Technology

1.3.1

Once Through Process

1.3.2

Partial Recycle Process

1.3.3

Total Recycle Process/Liquid Carbamate Solution Process

1.3.4

Stripping process

1.3.5

Theory of Stripping

1.4

Major Commercial Process

1.4.1

Toyo-Koatsu Process (Total Recycle Process)

1.4.2

Stripping process

1.4.2.1

Stamicarbon Stripping process

1.4.2.2

SNAM Progetti Process

1.4.2.3

ACES Process

1.5

Effect of Process Variables

1.5.1

Effect of NH3/CO2 ratio

1.5.2

Effect of Water/CO2 ratio

1.5.3

Effect of Pressure and Temp.

1.5.4

Residence Time

1.6

Biuret in Urea

LIST OF DIAGRAMS
Fig. No.
No.

Description

1.

Stami Carbon Process Flow Diag.

2.

Snam progetti Process Flow Diag.

3.

Effect of NH3/CO2 ratio

4.

Effect of H2O/CO2 ratio

5.

Effect of Pressure and Temp.

6.

Effect of Residence Time

7.

Biuret in Urea

Page

INTRODUCTION

Urea Synthesis is of historical importance, it is being the first organic compound to be


synthesized from inorganic compounds in a laboratory. Wholer in 1828, obtained Urea
from Ammonium cyanate. Previous to this, urea had been separated from Urine and the
experiment by Wholer showed that organic material could be prepared from an inorganic
chemical.
Commercial production of Urea was started in 1920 by I.C. Farben in Germany based on
Ammonium Carbamate process. Since then, considerable ingenuity was used to
overcome process difficulties such as corrosion problem, recovery of off-gases,
controlling effluents which resulted in present day development.
The various commercial manufacturing processes of urea, today use reaction between
liquid Ammonia and Carbon dioxide gas to form Ammonium Carbamate and subsequent
dehydration of carbamate to yield urea and water.
Ammonia and carbon dioxide are usually available from same site, as CO 2 is a by
product of Ammonia plant using hydrocarbons as feed stock.

1.1

PHYSICAL & CHEMICAL PROPERTIES OF UREA:


Molecular weight

60.05

Melting Point

132.60

Boiling Point

Decomposes at atmospheric
pressure before boiling.

Sp. Gravity (Crystal) at 20C

Heat of combustion (Solid) :

2531 Cal.gm.

Heat of solution in water

-57.8 Cal./gm

Critical Humidity

1.355

70.1%

Viscosity at 150C

2.16 CPS

Crystallization Heat

47.0 Kcal/Kg.

Fusion Heat

59.95

Thermal conductivity

0.191 kcal/sec/cm/C

0.321

Specific Heat (Cal/gm/C)


At 20C

At 98C

0.158

At 120C

0.194

At 160C

0.224

At 220C

0.288

Solubility in water (wt%)


Temperature C

00

20

40

60

80

100

120

Urea(gms.per of water)

67

105

163

24

396

725

2244 gms

Urea is a white crystalline chemical product & is readily soluble in water. On


heating beyond its melting point, it decomposes giving CO 2, NH3 and other
complex compounds of Carbon, Nitrogen, Oxygen. At 160C it decomposes
toyield Ammonia, Biuret and higher condensation products, the longer the urea is
held above its melting point, further the reaction proceeds.
Urea is in fact the diamide of carbonic acid with a chemical formula represented
by:
N =H2
|
O=

C
|
N =H2

1.2

USES OF UREA:
Its main applications are:

a)

As fertilizer in agriculture:

Due to high nitrogen content of urea, the

demand for fertilizer grade urea is rising rapidly. Urea today accounts for a
large percentage of Nitrogenous fertilizer.

b)

As cattle feed: Urea is used as cattle feed in western countries. Sheep


and cattle are capable of digesting urea upto about 40%.

c)

As raw material: For a number of industrial/house hold products like urea


formaldehyde, melamine and urea furfural. Urea also finds extensive use in
preparation of adhesives, textile antishrink compounds, ion exchange
resins and as an intermediate in the preparation of pigments.
5

1.3

PROCESS TECHNOLOGY:
Urea is produced by synthesis from liquid Ammonia and gaseous carbon dioxide,
Ammonia and carbon dioxide react to form Ammonium Carbamate, a portion of
which dehydrates to form urea and water. The fraction of Ammonium carbamate
that dehydrates is determined by the ratio of various reactants i.e. the operating
pressures, temperature and the residence time in reactor.
The reaction of Ammonia and carbon dioxide to produce urea takes place in two
stages at elevated pressure and temperature.

1)

2 NH3

Liquid Ammonia
2)

CO2

Gaseous
Carbon dioxide

NH2COONH4

NH2COONH4

+ 38.1 Kcal/gm.Mol.

Ammonium
carbamate
NH2CONH2 + H2O - 7.1 Kcal/gm.Mol.

Ammonium
Carbamate

Urea

Water

The first reaction is strongly exothermic and therefore heat is liberated as this
reaction occurs. With excess NH 3, the CO2 conversion to carbamate is almost
100%, provided solution pressure is greater than decomposition pressure.
The decomposition pressure is the pressure at which carbamate will decompose
back into CO2 and NH3 i.e.
NH2COONH4

2 NH3

CO2

Decomposition pressure is a function of NH 3 concentration in the feed & the


solution temperature. It increases if either temperature or NH 3 recycle is
increased. It is desirable to operate at higher pressure with high mole ratio of NH 3
to CO2 provided reactor operating pressure is quite high to prevent carbamate
decomposition into NH3 to CO2. This will maximize CO2 conversion to urea and
towards the reaction (2).
The second reaction is endothermic, therefore heat is required for this reaction to
start. The heat for this reaction comes from the formation of carbamate. This
reaction is a function of temperature and ammonia concentration in the feed.

The solution effluent from the reactor being a mixture of urea solution, ammonium
carbamate, un-reacted ammonia, water and CO 2 is extremely corrosive in nature.
The subsequent stages of process consist of decomposition of unconverted
carbamate, resulting recovery of ammonia and carbon dioxide for recycle,
concentration and prilling of urea melt.
1.3.1 Once through process:
This process is simplest in operation. In this process, ammonia and CO 2 are fed
to the reactor and effluent solution is stripped off the unconverted ammonia and
CO2. The solution is processed further for concentration and the production of
urea prills.
The off gases containing Ammonia and CO 2 are neutralised with acids for the
production of other Ammonium fertilizers. Because this process requires an
investment for another plant to use the more expensive Ammonia, the capital cost
of the urea producing unit will go up.
Although the initial cost of Urea Plant is low and conversion efficiency is high, the
once through process is no longer an economic proposition. Besides the
exceedingly huge demand of high Nitrogen fertilizer has pushed the once through
process in back ground.
1.3.2 Partial Recycle Process:
In this process the CO2 from the Off gases is absorbed in Monoethanol Amine.
Excess Ammonia is recovered by condensation and recycled whereas CO 2 is
regenerated and vented.
This process gives a better temperature control of the reaction but suffers from the
defect that CO2 is lost and MEA used for CO2 absorption gets partially degraded.
1.3.3 Total Recycle or Liquid Carbamate Solution Recycle Process:
Today all the conventional total recycle (solution) processes are almost the same.
All use similar reactor conditions, reactor pressure of about 200 kgcm 2 and a
temp. of about 185/190C. They maintain a NH 3 / CO2 mole ratio of upto about 4:1
in the synthesis section. A conversion of about 64% per pass is obtained.

Reactor effluent solution is let down and decomposition of carbamate is carried


out by heating with steam. The off gases are condensed and recycled as solution
to the reactor. The excess ammonia used is recovered, condensed and fed back
to reactor.
Major variation however, exists in recycle system in temperature and pressure
levels. The various solution recycle processes endeavour
a)

to maximize heat revovery

b)

to minimize the amount of carbamate solution recycled and the amount of


water recycled to reactor.

c)

To minimize power requirement

d)

To maximize ammonia recovery

e)

To minimize investment.

These put

together amounts to find a balance between utility consumption,

maintenance and investment.


1.3.4 Stripping Process :
Efforts to find some additional driving force beyond the usual addition of heat and
reductions in pressure to decompose carbamate from urea reactor effluents have
met with great success.
In this process decomposition of Ammonium carbamate is done at the synthesis
pressure by using either CO2 (Stamicarbon CO2 stripping process, ACES process)
or NH3 vapours (Snamprogetti NH3 stripping process ACES process in a falling
film type decomposer normally called stripper. The reactor effluents are allowed
to fall through the stripper tubes in the form of liquid film from the top while the
stripping agent is introduced from the bottom which travels upwards.
Medium pressure steam condensing on the shell side of the stripper supplies heat
for decomposition of Ammonium carbamate.

Currently, Snamprogetti process

does not require injection of Ammonia vapours at stripper bottom, only higher
mole ration of NH3 / CO2 is maintained in the reactor. At higher NH 3 / CO2 ratio,
Ammonia liberated in stripper is adequate to carry out stripping effectively. Since
the reactor, stripper & condenser system operates at nearly same pressure, it is

possible to feed recycle carbamate

either by gravity flow which however

necessitates the installation of carbamate condenser at a much higher elevation


so as to give the required head or to use a recycle ejector using a part of the feed
reactants as a motive fluid. Snamprogetti was the first to develop use of such
recycle ejector and locate condensers at ground level. Since a major portion of
unconverted carbamate is decomposed and recycled to reactor at synthesis
pressure, load on down stream decomposition and recovery section is
comparatively much less resulting in lower utility consumption.
Further, since the synthesis pressure in the stripping process is lower, it is
possible to employ steam driven centrifugal CO2 compressor which has lower
maintenance and operating cost.

In all the stripping processes low pressure

steam is generated in carbamate condenser which has results in lower


consumption of steam and cooling water.
1.3.5 Stripping Theory:
The Theory of stripping is based on Henrys law. The concentration of a
component in solution while in equilibrium with vapour phase is directly
proportional to the partial pressure of the component in the vapour phase. By
changing partial pressure of a component, concentration of solute can be
changed. This can be illustrated as follows. Let us assume that A & B are two
components.
CA

Concentration of Comp. A in Solution

CB

Concentration of Comp. B in Solution

PA & P B

Partial pressure of the respective components of the solution.

Total Pressure

PA + P B

In Ammonia stripper process, excess ammonium present in reactor effluent is


released as vapour by heating in stripper. This ammonia vapour increases partial
pressure of ammonia over the solution inside stripper tubes. As the total pressure
remains same, partial pressure of CO2 reduces to a lower value. In accordance to
Henrys low, the concentration of CO 2 in solution decreases by allowing CO 2 to
strip off from solution. Ammonium carbamate then decomposes to increase the

CO2 concentration in solution.

The heat of decomposition is supplied by

condensation of medium pressure steam in stripper.


In CO2 stripping process, the stripping is carried out by increasing partial pressure
of CO2 over the solution.

1.4

MAJOR COMMERCIAL PROCESS :

1.4.1 Toyo-Koatsu Process (Total Recycle Process)


Urea is synthesized in urea reactor under reaction condition of 200 0C & 250
kg/cm2g, from CO2, liq. NH3 and recycles carbamate. Urea synthesis reactor is
lined with titanium. The reaction product leaving Urea reactor consists of Urea,
water, ammonium carbamate & excess ammonia.
Urea reactor effluents are let down to an intermediate pressure through a letdown
valve and then passes through a decomposer. The solution pressure is further let
down and solution is sent to low pressure carbamate decomposer. Overhead
gases from the decomposers are absorbed in the respective absorber namely,
high pressure absorber cooler, High pressure absorber, Low pressure absorber &
off gas condenser and finally recycled back to Urea synthesis reactor.
The mixture from the reactor expanded to 18.5 ata enters the upper part of High
pressure decomposer (H.P.D.) where the flashed gas is separated and the liquid
is heated in the reboiler of High pressure decomposer.
The overhead gas from H.P.D. goes to High pressure absorber cooler.

The

bottom solution from H.P.D. expanded at 3.5 ata & enters low pressure
decomposer (L.P.D.) The operation of L.P.D. is similar to that of H.P.D.
A small amount of CO2 gas is injected at the bottom of L.P.D. which acts as a
stripping agent and fixes the NH3 released in this decomposer. Almost all the
excess NH3 and ammonium carbamate are separated from the solution in the gas
separator (G.S.).
The overhead gas from L.P.D. is sent to low pressure absorber. The remaining
very small amount of NH3 and CO2 are removed completely by pressure reduction
10

in upper part of Gas Separator and by heating in lower part of Gas Separator
(G.S.) The overhead gases, NH3, CO2 & water vapour are completely condensed
and / or absorbed in the off gas absorbing system.
The Urea solution leaving the lower part of G.S. contains approx. 73% Urea &
then, sent to crystallization section.

The crystallization system consists of

crystallizer which is divided into two parts, the upper part is vacuum evaporator
and the lower part is a crystallizer.
The Urea solution is first filtered to remove any contaminants & flows directly to
the lower part of crystallizer.
Crystals that are formed in a vacuum crystallizer, are centrifuged.

In the

centrifuges Urea crystals are separated from mother liquor & dried in fluidizing
dryer.
The mother liquor from centrifuges flows down to mother liquor tank. A centain
amount of mother liquor is recycled to recovery section and finally sent back to
reactor where the biuret is converted back to urea in the presence of excess NH3,
Dry crystals are raised to prill tower top while passing through pneumatic
conveyor and fed to melter by screw conveyors. The molten urea then flows
through distributor & falls down the prilling tower in the form of prill and is cooled
down by the up coming air from a blower through fluidized bed.
The prilled Urea coming from the bottom of the tower is screened to remove
oversize prills & then stored in bulk storage.
The Toyo Koatsu process was popular during sixties and early seventies. The
process has quite a few Variations & the latest variant is more economical in
utilities than earlier ones.
1.4.2 Stripping Process:

11

Efforts to find some additional driving force beyond the usual addition of heat and
reduction in pressure to decompose carbamate from Urea reactor effluents have
met with great success.
In this process, decomposition of ammonium carbamate is done at the synthesis
pressure by using either CO2 (Stamicarbon Striping) or NH3 vapours
(Snamprogetti Stripping Process) in a falling film type decomposer normally called
stripper. The reactor effluents are allowed to fall through the stripper tubes in the
form of liquid film from the top while the stripping agent is introduced from the
bottom which travels upwards. Medium pressure steam condensing on the shell
side of the stripper supplies heat for decomposition of ammonium carbamate.
Currently Snam Progetti Process, does not require injection of ammonia vapours
at stripper bottom. Only higher mole ratio of NH 3/ CO2 is maintained in the reactor.
At higher mole (NH3/CO3) ratio, ammonia liberated in stripper is adequate to carry
out stripping effectively. Since the reactor stripper condenser system operates at
nearly same pressure, it is possible to feed recycle carbamate their by gravityflow
which however necessitates the installation of carbamate condenser at a much
higher elevation so as to give the required head or to use a recycle ejector using a
part of the feed reactants as a motive fluid. Snam Progetti was the first to develop
use of such recycle ejector & locate condensers at ground level. Since a major
portion of unconverted carbamate is decomposed and recycled to reactor at syn.
Pressure, load on down stream decomposition and recovery section is
comparatively much less resulting in lower utility consumption.
Further since the synthesis pressure for the stripping process is lower, it is
possible to employ steam driven centrifugal carbondioxide compressor which has
lower maintenance and operating cost. In both Snam Progetti and Stamicarbon
Stripping Processes low pressure steam is generated in carbamate condenser
which has resulted in lower consumption of steam and cooling water.

1.4.2.1

Stamicarbon Stripping Process:

In the reactor, operating at 135-148 atm (g) with temperature of 175-185C and at
an overall NH3/ CO2 ratio of 2.8-2.9, a part of the incoming NH 3and CO2is reacted
to form ammonium carbamate which together with the incoming carbamate

12

already formed in the high pressure (H.P.) condenser, is partly converted in to


urea & water. Reactor effluent is stripped with fresh CO2 at synthesis pressure in
a specially developed stripper with external heat supply.
In the stripper, the bulk of non-converted carbamate is decomposed and also the
bulk of the excess NH3 is vaporized. The resulting gases, NH 3 & CO2 are recycled
to H.P. condenser. Fresh liq. NH 3 and recycle carbamate from down stream low
pressure recovery system is fed in to the H.P. Condenser Ammonium Carbamate
is formed in the H.P. condenser. Exothermic heat of reaction of carbamate
formation is recovered as low pressure steam which is used in the Urea
manufacturing process. This carbamate and the non condensed gas, together are
fed to the reactor where urea is formed.
The stripped Urea solution (still containing small quantities of NH 3 & CO2) is let
down to 2 to 5 atm (g) pressure in a rectification column where required heat is
provided in a recirculation heater. Resulting gases from rectification column are
removed and condensed in a low pressure carbamate condenser.
70% Urea solution from the recovery section is stored in a Urea solution tank and
is then concentrated by evaporation in two stages. The molten Urea containing
approximately 0.2% water from the second evaporator is pumped to the top of the
prill tower where it passes in to a rotating prill bucket.
Prills formed in prill tower are collected at the base and prill tower scraper
transfers the prills into the prill tower conveyor.
The recent development of Stamicarbon technology is the inclusion of pool
condenser and pool reactor.

1.4.2.2

Snam Progetti Stripping Process:

Ammonia and CO2 react at a pressure of 160 Kg/cm2 (g) to yield Urea and
Ammonia Carbamate. The carbamate content of the reactor effluent is
decomposed in stripper and condensed in H.P. Condenser. An ejector (feed
ammonia is the driving medium) supplies the motive power to return the high

13

pressure carbamate solution from H.P. condenser to the reactor. This system
facilitates H.P. carbamate condenser to be installed at lower level.
The Urea solution containing excess of NH 3 flowing out of the reactor is sent to
carbamate decomposer (stripper). The excess ammonia acts as a stripping
medium & helps dissociation of ammonium carbamate to ammonia & CO 2. The
overhead vapours from the stripper are condensed in H.P. Carbamate condenser.
Heat of condensation permits production of L.P. steam which is used in the
process.
Reactor operates at 160 Kg/cm2 pressure and at a temp 1850C with NH3/CO2
feed mole ration of 3:6:1. Stripper solution effluent is let down in two stages at
successively lower pressure (18 ata and 4.5 ata) and is heated to remove NH 3 &
CO2 from the solution. The bulk of NH 3 is sent to a recovery tank and is recycled
as anhydrous NH3 to the reactor along with make up. The small amount of CO 2
and recovered ammonia is recycled as ammonium carbonate solution to
carbamate condenser.
70% Urea solution coming from the low pressure section is concentrated in two
stage vacuum concentration system and then prilled as mentioned in stamicarbon
process.

1.4.2.3

ACES Process :

The ACES process (Advanced process for cost and energy saving) was
developed by Toyo Engineering Corporation (TEC), Japan for Urea Synthesis and
granulation.
Make up liquid ammonia and make up CO 2 gas along with anticorrosive air (0.5%
O2 ) and recycle carbamate solution are fed to a vertical urea reactor having nine
trays. Reactor is operated at 175 kg/cm 2g, 1900C and at NH3/CO2 molar ratio of
4.0 and H2O/CO2 molar ratio of 0.65.

The urea solution after attaining CO 2

conversion of 67% is fed to stripper by gravity. The stripper has trays at the upper
part with a falling film heat exchanger at the bottom. Major part of CO 2 is fed to
stripper which strips off ammonium carbamate and excess ammonia from the urea
solution. The overhead gas of stripper is condensed in two parallel condensers.
14

The condensation heat is utilized in generating 6 ata steam in one condenser and
for heating the stripper outlet urea in other condenser.

Reactor top gas,

containing small quantities of ammonia and CO2, is sent to scrubber for recovery.
Stripper outlet urea solution is let down to two stages at successively lower
pressure (18.5 ata and 3.5 ata) and is heated to remove unconverted ammonium
carbamate and ammonia.
70% Urea solution from the low pressure section is further purified in two vacuum
stages and prill through prill bucket.
1.5

EFFECT OF PROCESS VARIABLES :


Carbamate formation takes place with liberation of heat and urea formation takes
place with absorption of heat. The former reaction is rapid and the later is slow.
The equilibrium conversion to urea will be favoured under the following conditions:
i)

Higher NH3 concentration

ii)

Less H2O concentration

iii)

Higher temperature

iv)

Higher pressure

v)

Higher residence time.

1.5.1 Effect of NH3 / CO2 Ratio :


Theoretical mole ratio of NH 3/CO2 is 2. But in this condition Urea yield is only
around 43.44% at 170 atm., and 155 0C. This low yield can be improved by
changing NH3/CO2 ratio. When the excess ratio of NH 3 is increased to 280% urea
yield changes from 43.5% to 85.2%.
On other hand, when excess ratio of CO 2 is changed from 0 to 300% urea yield
increases only from 43.5% to 46%.

The effect of excess CO 2 is very small.

Moreover, in the CO2 rich conditions, the solution becomes very corrosive. In
general almost all the urea plants are operated under NH 3/CO2 mole ratio around
2.5 to 5.0.
1.5.2

Effect of Water / CO2 Ratio :


15

Water is a product of urea formation. One mole of water is formed when one mole
of urea is produced. In the presence of excess water, equilibrium reaction shifts in
reverse direction and yield of urea, is poor. However water has to be added for
recycling unconverted NH3 and CO2 back to reactor. Lower the amount of water in
reactor, higher is the yield of urea. Too low water concentration in low pressure
recovery section results in higher carbamate concentration and this causes
pumping problem and clogging in piping system.
Excess water in reactor also reduces effective volume for urea formation and
additional energy is required to get rid of this water. Study shows that presence of
one mole of excess water per mole of carbamate reduces equilibrium yield of urea
to half.
1.5.3 Effect of Pressure and Temperature:
As per Le Chatliers principle, higher pressure favours carbamate formation. At
the operating condition carbamate formation is almost instantaneous and reaction
tends to completion, provided reaction heat is removed simultaneously. Lower
temperature favours carbamate formation, being an exothermic reaction. In case
of urea formation, higher temperature is favorable because the reaction is
endothermic. The relation is such that when temperature increases the conversion
increases proportionally. Max. equilibrium conversion is achieved at around 190
to 2000C.

Reactants are highly corrosive at higher temperature.

Operating

pressure is totally dependent on temperature at which conversion takes place.


Urea conversion takes place in liquid phase. So equilibrium pressure becomes
increasingly higher when the temperature rises.
1.5.4 Residence Time :
Urea conversion reaction is slow and takes 20 minutes to attain equilibrium.
Considering the slowness of the reaction, urea reactor is so designed that
residence time should be more than 20 minutes Higher residence time favours
equilibrium conversion and normally reactors are designed for residence time of
30 minutes to one hour depending upon other operating parameters. 68% urea
conversion takes place with residence time of 30 minutes at a mole ratio of 4:1
and temperature of 1880C almost a residence time of 55 minutes is required.

16

Residence time in Urea reactor plays an important role on equilibrium conversion.


Where operating parameters including mole ratio are not favourable for a good
yield higher residence time compensates to some extent to achieve a better yield.
But this is done by providing higher reactor volume which increases capital
investment.
1.6

BIURET IN UREA:
A problem facing every urea manufacturer is the formation of Biuret during the
production process. It is not a desirable substance as it is toxic to the plants. It
should not exceed more than 1.5% in urea as per fertilizer control order.
When urea solution is heated in the absence of free Ammonia an objectionable
ingredient called Biuret is formed according to following reaction:
2 NH2 CONH2 ----------------------------- NH2 CO.NH. CONH2 + NH3
Urea

Biuret

Ammonia

The formation of Biuret is favoured under the following condition:


1)

Higher temperature

2)

Higher residence time

3)

Higher concentration of solution

4)

Lower Ammonia concentration.

17