Urea 2
Urea 2
Urea 2
INTRODUCTION
Point No.
Subject
Page No.
1.1
1.2
Uses of Urea
1.3
Process Technology
1.3.1
1.3.2
1.3.3
1.3.4
Stripping process
1.3.5
Theory of Stripping
1.4
1.4.1
1.4.2
Stripping process
1.4.2.1
1.4.2.2
1.4.2.3
ACES Process
1.5
1.5.1
1.5.2
1.5.3
1.5.4
Residence Time
1.6
Biuret in Urea
LIST OF DIAGRAMS
Fig. No.
No.
Description
1.
2.
3.
4.
5.
6.
7.
Biuret in Urea
Page
INTRODUCTION
1.1
60.05
Melting Point
132.60
Boiling Point
Decomposes at atmospheric
pressure before boiling.
2531 Cal.gm.
-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
At 98C
0.158
At 120C
0.194
At 160C
0.224
At 220C
0.288
00
20
40
60
80
100
120
Urea(gms.per of water)
67
105
163
24
396
725
2244 gms
C
|
N =H2
1.2
USES OF UREA:
Its main applications are:
a)
As fertilizer in agriculture:
demand for fertilizer grade urea is rising rapidly. Urea today accounts for a
large percentage of Nitrogenous fertilizer.
b)
c)
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
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.
b)
c)
d)
e)
To minimize investment.
These put
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
CB
PA & P B
Total Pressure
PA + P B
1.4
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.
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
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
1.4.2.2
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.
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.
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
ii)
iii)
Higher temperature
iv)
Higher pressure
v)
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
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.
Operating
16
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
Higher temperature
2)
3)
4)
17