1

MANUFACTURE OF UREA

A REPORT SUBMITTED IN PARTIAL FULFILMENT

OF THE REQUIREMENTS FOR THE DEGREE OF
Bachelor of technology
In
Chemical Engineering

By
Prasanta Saren

Department of Chemical Engineering

University of Calcutta
 2

Certificate

This is to certify that report entitled “MANUFACTURE OF

UREA” submitted by Prasanta Saren partial fulfilments
for the requirements for the award of Bachelor of
Technology Degree in Chemical Engineering at University
of Calcutta is an authentic work carried out by him under
my supervision and guidance.
To the best of my knowledge, the matter embodied in
the thesis has not been submitted to any other
University/Institute for the award of any Degree or
Diploma.
Date Dr.Barnali Mandal
Assistant Professor
Department of Chemical
Engineering
University of Calcutta
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Acknowledgement
I wish to express our deep sense of gratitude and
indebtedness to Assistant Prof. Barnali Mandal,
Department of chemical Engineering, University of
Calcutta for introducing the present topic and for her
inspiring guidance, constructive criticism and valuable
suggestion throughout this project work.
I would like to express our gratitude to Prof. Amitava
Bandyopadhyay ( Head of the Department) for his
constant support and encouragement. I'm also thankful
to all staff members of Department of Chemical
Engineering of University of Calcutta.

Date. Prasanta Saren

Roll no: T91/CE/ 184002
5th Semester
Paper code: PIIA 508
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CONTENTS. PAGES
1.Introduction 6
1.1 manufacture of urea 6
1.2 Properties of urea 7
1.3 Uses of urea 8
1.4 Process technology 8
1.5 Process in general 9
1.6 Variable that affects the Autoclave 10
Reaction
1.7 Major Engineering problem. 13

2.Various Methods Of Manufacture 15

Of Urea
Various processes for the manufacture of urea. 15

3. Selected process :Snamprogetti. 16

ammonia stripping process
3.1 process 16
3.2Process description 17
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4. Material balance 23
4.1 Around reactor 25
4.2 Around stripper 26
4.3 Around medium pressure separator 28
4.4 Around low pressure separator 29
4.5 Around Vacuum evaporator 30
4.6 Around Prilling tower 31

5. Energy balance 34
5.1 Around reactor

6. Conclusion 38
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Introduction

1.1Manufacture of urea:
Urea is an important nitrogenous fertilizer. Its utilization is
increasing steadily, it being the preferred nitrogen fertilizer
worldwide. It is used in solid fertilizer, liquid fertilizer,
formaldehyde resins and adhesives. Rouelle first discovered
urea in urine in 1773. His discovery was followed by the
synthesis of urea from ammonia and cyanic acid by Woehler in
1828. This is considered to be the first synthesis of an organic
compound from an inorganic compound. In 1870, Bassarow
produced urea by heating ammonium carbamate in a sealed
tube in what was the first synthesis of urea by dehydration.The
chemical formula of, NH2CONH2, indicates that urea can be
considered to be the amide of carbamic acid NH2COOH, or the
diamide of carbonic acid CO(OH)2.
Fertilizer is generally defined as “ any material, organic or
inorganic, natural or synthetic, which supplies one or more of
the chemical elements required for the plant growth”. The
main aim of the fertilizer industry is to provide the primary and
secondary nutrients which are required in macro quantities.
Primary nutrients are normally supplied through chemical
 7

fertilizers. They are chemical compounds containing one or

more of the primary nutrients and are generally produced by
chemical reactions. Whatever may be the chemical compounds,
its most important ingredient for plant growth is the nutrient
content. The primary nutrients are Nitrogen, Phosphorus and
Potassium. However, their concentration in a chemical fertilizer
is expressed as a percentage of total nitrogen (N), available
phosphate (P2O5) and soluble K2O. The grade of a fertilizer is
expressed as a set of three numbers in the order of percent N,
P2O5 and K2O. If a nutrient is missing in a fertilizer, it is
represented by a zero. Thus ammonium sulphate is
represented by 20.6-0-0.
1.2 PROPERTIES OF UREA :
PHYSICAL PROPERTIES OF UREA
Urea is a white, odorless, hygroscopic solid. It is non-corrosive.
CHEMICAL PROPERTIES OF UREA
Molecular weight 60.05
Relative humidity 60 %
Maximum Nitrogen content 46.6 %
Specific gravity 1.335
Heat of fusion 60 Cal/gm (endothermic)
Heat of solution, in water 58 Cal/gm (endothermic)
Bulk density 0.74 gm/cc
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Table-1.1 SPECIFIC HEAT OF UREA

Temperature, oC Specific heat, Kj/kg oC
0 1.398
50 1.66
100 1.89
150 2.11

1.3 USES OF UREA

• About 56 % of Urea manufactured is used in solid fertilizer.
• About 31 % of Urea manufactured is used in liquid fertilizer.
• Urea-formaldehyde resins have large use as a plywood
adhesive.
• Melamine-formaldehyde resins are used as dinnerware & for
making extra hard
surfaces.
1.4 PROCESS TECHNOLOGY
Although there are several processes currently used for the
manufacture of urea, the underlying principle for all the
processes is same. The two main reactions involved are:
1) CO2 + 2NH3 ↔ NH2COONH4 ∆H= -37.4 Kcal/gm mol
2) NH2COONH4 ↔ NH2CONH2 + H2O ∆H= + 6.3 Kcal /gm mol
 9

Undesirable side reaction taking place is:

3) 2NH2CONH2 ↔ NH2CONHCONH2 + NH3
. (Biuret)
Both 1st & 2nd reactions are equilibrium reactions. The 1st
reaction almost goes to completion at 185-190 oC & 180-200
atms. The 2nd reaction (decomposition reaction) is slow and
determines the rate of the reaction. Unconverted CO2 & NH3,
along with undecomposed carbamate, must be recovered and
re-used. This is a troublesome step.
The synthesis is further complicated by the formation of a
dimer called biuret, NH2CONHCONH2, which must be kept low
because it adversely affects the growth of some plants.
1.5 PROCESS IN GENERAL:
Ammonia & CO2 are compressed separately and fed to the high
pressure (180 atms) autoclave as shown in fig-1.1 which must
be water cooled due to the highly exothermic nature of the
reaction. A mixture of urea, ammonium carbamate, H2O and
unreacted ( NH3+CO2) is produced.
This liquid effluent is let down to 27 atms and fed to a special
flash-evaporator containing a gas-liquid separator and
condenser. Unreacted NH3, CO2 & H2O are thus removed &
recycled. An aqueous solution of carbamate-urea is passed to
the atmospheric flash drum where further decomposition of
carbamate takes place. The off gases from this step can either
 10

be recycled or sent to NH3 processes for making chemical

fertilizer.
The 80 % aqueous urea solution can be used as it is, or sent to a
vacuum evaporator to obtain molten urea containing less than
1 % water. The molten mass is then sprayed into a prilling
tower. To avoid formation of biuret and keep it less than 1 %,
the temperature must be kept just above the melting point for
processing times of 1-2 seconds in this phase of the operation.
1.6 VARIABLES THAT AFFECT THE AUTOCLAVE
REACTIONS ARE :
1) Temperature
Process temperature (185 oC) favours equilibrium yield at a
given pressure (180 atm). The conversion of ammonium
carbamate to urea gradually increases as the temperature
increases. However, after a particular temperature, depending
upon the pressure, the conversion suddenly drops with further
increase in temperature. The pressure corresponding to this
temperature which is usually in the range of 175-185oC, is
known as the decomposition pressure which is about 180 atm.
2) Pressure
The main reaction is sufficiently slow at atmospheric pressure.
However, it starts almost instantaneously at pressure of the
order of 100 atm and temperature of 150 oC. There is reduction
in volume in the overall reaction and so high pressure favours
 11

the forward reaction. This pressure is selected according to the

temperature to be maintained & NH3:CO2 ratio.
3) Concentration
Higher the concentration of the reactants, higher will be the
forward reaction according to the law of mass action. CO2
being the limitimg reagent higher NH3:CO2 ratio favors
conversion. Since, dehydration of carbamate results in urea
production, lesser H2O:CO2 ratio favors conversion. Water
intake to the reactor should therefore be minimum.
4) Residence time
Since, urea reaction is slow and takes about 20 mins to attain
equilibrium, sufficient time is to be provided to get higher
conversion. Reactor is designed to accommodate this with
respect to the other parameters of temperature, pressure and
concentration.
5) Biuret formation
Aproblem faced during manufacture of urea is the formation of
biuret during the production of urea. It is not a desirable
substance because it adversely affects the growth of some
plants. Its content in urea should not be more than 1.5 % by
weight.
2NH2CONH2 ↔ NH2CONHCONH2 + NH3
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(Biuret)

Although the production of urea is high at high pressure and

high temperature, the reaction is not operated at maximum
temperature and pressure because:
• Increased pressure increases capital & operating costs of
compression and
• reaction equipment.
• Increased temperature accelerates decomposition of urea
to biuret, a compound
• that adversely affects the growth of some plants.
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• The above stipulated conditions produce intolerable

corrosion rates, and a compromise design must be chosen.
1.7 MAJOR ENGINEERING PROBLEMS
1) Carbamate decomposition and recycle:
There are many processes that can be used for the
manufacture of urea. Main difference in competing processes is
in the recycle design. Since, conversion is only 40-50 % per
pass, the unreacted off gases must be recirculated or used
economically elsewhere. Recompression of off gases is virtually
impossible because of corrosion and formation of solid
carbamate in compressors.
2) Production of granular urea:
Biuret formation is another problem. Vacuum evaporation of
urea from 80% to about 99% ,spraying to air cool and
solidification must be done just above the melting point of urea
and with a minimum residence time in the range of several
seconds.
3) Heat dissipation in the autoclave:
The exothermic heat of reaction can be removed by coils or
wall cooling
4) Corrosion:
This has been the major reason why the NH3-CO2 process was
slow to develop. High cost silver or tantalum liners are used in
the autoclaves with hastealloy C, titanium, stainless steel (321
 14

SS), and aluminium alloys used in other parts of the plant.

Minimum pressure and temperature conditions with excess
NH3 are desirable to reduce the severe corrosion rates. Under
these conditions, stainless steel can be used in the autoclave.
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Various method of
manufacturing process of
Urea
There are generally 4 manufacturing process of Urea. Those
are :

• Snamprogetti ammonia stripping process

• Stamicarbon CO2 stripping process
• Once through urea process
• Mitsui Toatsu total recycle urea process

Here, Only Snamprogetti (Now saipem) is discussed here.

.
 16

SNAMPROGETTI
AMMONIA STRIPPING
PROCESS

3.1 PROCESS
NH3 & CO2 react under specific concentration , temperature
& pressure conditions to form Urea as per the following
reactions:
1) CO2 (g) + 2NH3 ( g) ===== NH2COONH4 (s) ; H = -37.64
kcal/gm mol
2) NH2COONH4 (s) ===== NH2CONH2 (s) + H2O (l) ; H=6.32
kcal/gm mol
---------------------------------------------------------------------------------
---------------------------
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CO2 (g) + 2NH3 (g) ===== NH2CONH2 (s) + H2O (l); H = -

31.32 kcal/gm mol
So, overall urea synthesis is exothermic, releasing heat of
31.32 kcal/gm mol at standard conditions of 1 atm pressure
& 25°C. But actual heat available in an urea synthesis
reaction will be only 5.74 kcal/gm mol because of the heat
lost in evaporation of liquid NH3, evaporation of water &
melting of urea. This is based on the actual plant data.
Further energy is consumed in feeding CO2 & NH3 at high
temperature & pressure , in recycling of carbamate , in
vacuum concentration of urea , for operating different
pumps & compressors etc. which altogether makes the urea
production energy consuming.
3.2 PROCESS DESCRIPTION
The urea production process takes place through the
following main operations :
• Urea synthesis & high pressure recovery.
• Urea purification & low pressure recovery.
• Urea concentration.
• Urea prilling.
UREA SYNTHESIS & HIGH PRESSURE RECOVERY
Urea is synthesized from liquid ammonia & gaseous carbon-
di-oxide. . The carbon dioxide drawn from battery limits at
about 1.6 ata pressure & about 40°C temp is compressed in
a centrifugal compressor upto 162 ata . A small quantity of
 18

air is added to the CO2 compressor suction in order to

passivate the stainless steel surfaces . Thus protecting them
from corrosion due both to the reagent & the reaction
product .The liquid ammonia coming directly from battery
limits is collected in the ammonia receiver tank from where
it is drawn to & compessed at about 23 ata pressure by
means of centrifugal pump. Part of this ammonia is sent to
medium pressure absorber & remaining part enters the high
pressure synthesis loop . The NH3 of this synthesis loop is
compressed to a pressure of about 240 ata . Before entering
the reactor it is used as a driving fluid in the carbamate
ejector, where the carbamate coming from carbamate
separator is compressed upto synthesis pressure . The liquid
mixture of ammonia & carbamate enters the reactor where
it reacts with compressed CO2 . In the reactor the NH3 &
gaseous CO2 react to form amm. Carbamate , a portion
of which dehydrates to form urea & water . The fraction of
carbamate that dehydrates is determined by the ratios of
various reactants , operating temp , the residence time in
the reactor & reaction pressure . The mole ratio of NH3 /
CO2 is around 2:1 , the mole ratio of water to CO2 is around
0.67 : 1 .
2NH3 (g) + CO2 (g) ===== NH2COONH4 (s) ; exothermic
NH2COONH4 ( s) ===== NH2CONH2 (s) + H2O (l) ;
endothermic In the synthesis conditions ( T= 190°C , P= 154
atm) , the 1st reaction occurs rapidly & is completed . The
 19

2nd reaction occurs slowly & determines the reactor volume

.
Urea reactor is a plug flow type with 10 no.s of sieve trays
to avoid back mixing & to avoid escape of gaseous CO2
which must react in the lower part of the reactor .
Stagewise decomposition is carried out to reduce water
carry over to the reactor which could adversely affect
conversion . Urea solution containing urea , carbamate ,
H2O & unconverted CO2 & NH3 enters the high pressure
stripper where the pressure is same as that of the reactor .
The mixture is heated as it flows down the falling film
exchangers . The CO2 content of the solution is reduced by
the stripping action of NH3 as it boils out of the solution .
The carbamate decomposition heat is supplied by 24 ata
steam . The overhead gases from stripper and the recovered
solution from the MP absorber, all flow to the high pressure
carbamte condenser through mixer, where total mixture ,
except for a few inerts is condensed &recycled to the reactor
by means of carbamate ejector . Condensing the gases at
high temp & pressure permits the recovery of condensation
heat in the production of steam at 4.5 ata in the high
pressure carbamate condenser.
From the top of the carbamate separator the incondensable
gases come out consisting of inerts & a little quantity of NH3
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& CO2 unreacted in the condenser . These are sent to the

bottom of MP decomposer.

UREA PURIFICATION & LOW PRESSURE RECOVERY

Urea purification takes place in two stages at decreasing
pressure as follows :
• 1st stage at 18 ata pressure, i.e, MP decomposer
• 2nd stage at 4.5 ata pressure ,i.e, LP decomposer
 21

• 1st stage purification & recovery stage at 18 ata:

It is falling film type MP decomposer . It is divided into 2
parts : Top separator, where the released flash gases ,
the solution enters the tube bundle & decomposition
section where the residual carbamate is decomposed &
required heat is supplied by means of 24 ata steam
condensate flowing out of the stripper .
• 2nd purification & recovery stage at 4.5 ata:
The solution leaving the bottom of MP decomposer is
expanded at 4.5 ata pressure& enters the LP
decomposer (falling film type). This is again divided in
to two parts :top separator where the released flash
gases are removed before the solution enters the tube
bundle . Decomposition section where the last residual
carbamate is decomposed & the required heat is
supplied by means of steam saturated at 4.5 ata.
UREA CONCENTRATION
Next section is urea concentration & objective is to reduce
water content of urea to as low as 1 % . For the purpose a
vacuum concentrator in two stages is provided . The solution
leaving the LP decomposer bottom with about 72% urea is
sent to the 1st vacuum concentrator operating at a pressure
of 0.23 ata .The mixed phase coming out enters the gas
liquid separator, wherefrom the vapours are extracted by
the 1st vacuum system, while the solution enters the 2nd
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vacuum concentrator operating at a pressure of 0.03 ata .

The two concentrators are fed by saturated steam at 4.5 ata
. The mixed phase coming out enters the gas liquid separator
, wherefrom the vapours are extracted by the 2nd vacuum
system .
UREA PRILLING
The molten urea leaving the 2nd vacuum separator is sent to
the prilling bucket by means of a centrifugal pump . The urea
coming out of the bucket in the form of drops fall along the
prilling tower & encounters a cold air flow which causes its
solidification . The solid prills falling to the bottom of the
prilling tower are sent through the screeners to retain lumps
only , & then to belt conveyor which carries the product to
the automatic weighing machine & to the urea storage
sections . Urea lumps by the means of belt conveyor are
recycled to the underground tank, where they are dissolved .
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Material balance

Selected capacity : 4,50,000 tons/year

No. of working days: 300
Daily production : 4,50,000/300 = 1500 tons/day
Urea 62,500 Kg/hr of 98 % purity
Composition of the final product :
Urea : 98 % (61,250 Kg/hr)
Biuret : 1 % (625 Kg/hr)
Water : 1 % (625 Kg/hr)
Assumption : Overall conversion to urea is assumed to be
95%.
MAIN REACTIONS:
1) CO2 + 2NH3 ==== NH2COONH4
(44) (17) (78)
2) NH2COONH4 ==== NH2CONH2 + H2O
(60) (18)
3)CO2 + 2NH3 ==== NH2CONH2 + H2O (Overall reaction)
 24

Side reaction:
4)2NH2CONH2 ==== NH2CONHCONH2 + NH3
(103)

625 Kg/hr of Biuret produced by = (120/103)*625 = 728

Kg/hr of urea (reaction 4) So, urea produced by reaction (2)
= 61250 + 728 = 61978 Kg/hr 61978 Kg/hr of urea produced
by = (34/60)*61978 = 35,120 Kg/hr NH3
Similarly, CO2 reacted in reaction (1) = (44/60)*61978 =
45,450 Kg/hr Assuming 95 % conversion we get
NH3 actually required = 35120/0.95 = 36,968 Kg/hr
CO2 actually required = 45450/0.95 = 47,842Kg/hr
Now, considering reaction (4) :
If reaction (3) is 100 % complete then, Urea produced =
(60/44)*47842 = 65,239 Kg/hr
But, for 95 % conversion Urea produced = 0.95*65,239 =
61,977 Kg/hr
Therefore, Urea converted to Biuret & NH3 = 61,977 –
61,250 = 727 Kg/hr
So, from reaction (4) Biuret produced = (103/120)*727 = 624
Kg/hr .Water produced in reaction (2) = (18/60)*61978 =
18,593 Kg/hr
At reactor’s exit (Urea = 34 %)
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Flow rate of stream = 61,250/0.34 = 1,80,147 Kg/hr

NH3 reacted in reaction (1) = (34/60)*61977 = 35,120 Kg/hr
NH3 produced in reaction (4) = (17/120)*727 = 103 Kg/hr
So, NH3 unreacted = 36968 – 35120 + 103 = 1951 Kg/hr
CO2 reacted in reaction (1) = (44/60)*61977 = 45450 Kg/hr
Therefore, CO2 unreacted = 47842 – 45450 = 2392 Kg/hr
Now,
Flow rate of stream at reactor’s exit – (flow rate of
urea+CO2+NH3+water+biuret) = Flow rate of carbamate
1,80,147- (61,250 + 2392 + 1951 +18,593 + 624) = 95,337
Kg/hr
4.1 REACTOR
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Table Flow of material across reactor

4.2 STRIPPER
 27

Since, no reaction takes place in the stripper & only carbamate

gets recycled back to the reactor. Therefore, the amount of
ammonia ,carbon-di-oxide ,water & biuret in the outlet stream
of stripper will be same as it was in the inlet stream.
 28

The amount of ammonia ,carbon-di-oxide ,water & biuret will

remain constant as no reaction is taking place. 50 % of
ammonia & carbon-di-oxide are assumed to escape from the
 29

top of the separator & rest goes with the bottom product.
Amount of water & biuret remains constant as no reaction
takes place.

4.4 LOW PRESSURE SEPARATOR

 30

4.5 evaporator:

Let x & y be the mass fractions of Urea in feed (F) & product (P)
resp.
x= 0.7611 (76.11 %)
 31

y= 0.9788 (97.88 % )
Making urea balance:
F.x = P.y
80467*0.7611 = P*0.9788
P = 62574 Kg/hr
Overall material balance gives:
F=P+E
80467 = 62574 + E
E = 17893 Kg/hr

4.6 Prilling tower

 32

Let x & y be the mass fractions of Urea in feed (F) & product (P)
resp.
x= 0.9788 (97.88 %)
y= 0.9796 (97.96 %)
Making urea balance:
F.x = P.y
62574*0.9788 = P*0.9796
P = 62524 Kg/hr
33
 34

Energy balance

Assumption : Datum temperature = 0℃

5.1REACTOR

INLET STREAM
Material. Specific heat at 40℃
NH3 0.53 cal/gm ℃ = 2.219 Kj/Kg℃
CO2 0.22 cal/gm ℃ = 0.9211 Kj/Kg ℃.
Specific heat at 180℃
Heat input
mCp∆t
NH3 : 3.6968 x 104 x 2.219 x 40 = 0.328 x
107 Kj/hr
 35

CO2 : 4.7843 x 104 x 0.9211 x 40=0.176 x

107 Kj/hr
Carbamate:. 9.5336 x 104 x 2.24 x 180= 4.455 x
107 Kj/hr

Heat input = 4.959 x 107 Kj/hr

∆HR = - 31.32 Kcal/gm mol

= -0.013 x 107 Kj/Kmol of Urea formed.
Amount of urea formed during the reaction = 1020.83 Kmol/hr
∆HR = 1020.83 x 0.013 x 107 Kj/hr
= 13.27 x 107 Kj/hr
OUTLET STREAM
Material heat at 180oC. mol fractions (x) Flow
rate
(Komol/hr)
NH3. 0.55 cal/gm oC = 39.15 Kj/KmoloC 0.033 114.76
CO2 0.23 cal/gm oC = 42.37 Kj/Kmol oC 0.0158. 54.36
Carbamate. 0.62 cal/gm oC = 202.49 Kj/KmoloC 0.354 . 1222.3
Urea 0.4828 cal/gm oC=121.32 Kj/KmoloC 0.296 1020.83
Water 1 cal/gm oC = 75.37 Kj/KmoloC 0.299 1032.94
 36

Biuret 183.8 Kj/KmoloC 0.002 6.07

Total = 3,451.3
Cp of mixture = ∑ xiCpi
So, Cp= 0.033 x 39.15 + 0.0158 x 42.37 + 0.296 x 121.32 + 0.354
x 202.49 + 0.002 x
183.8 + 0.299 x 75.37 = 132.46 Kj/KmoloC

So, heat carried by outlet stream = mCp∆t

= 3,451.3 x 132.46 x 180
= 8.229 x 107 Kj/hr
Heat input + ∆HR - Heat output = rate of accumulation
4.959 x 107 +
13.27 x 107
--
8.229 x 107 = rate of accumulation
rate of accumulation = 10 x 107 Kj/hr
Assumption : Cooling water at 25oC is used to remove heat
from the reactor. The outlet is
steam at an absolute pressure of 4.5 bar (Ts = 147.9 oC).
So, heat gained by cooling water = 10 x 107 Kj/hr
mCp∆t + mλ = 10 x 107 Kj/hr
 37

or, m (Cp∆t + λ ) = 10 x 107

m [ 4.187 x (147.9-25) + 2120.6 ] = 10 x 107 Kj/hr

( Here λ = 2120.6 kj/kg & =4.187 Kj/kg oC)

m = 108
/2635.18
m = 37,948 Kg/hr
 38

Conclusion

The selected capacity of the plant is 4,50,000 tons/year based

on 300 working days. The product from the prilling tower
contains 98 % urea. Critical review of all the manufacturing
processes has been presented. Snamprogetti process has been
selected for the project. The Snamprogetti ammonia-stripping
urea process involves a high NH3 to CO2 ratio in the reactor,
ensuring the high conversion of carbamate to urea . The highly
efficient ammonia stripping operation drastically reduces the
recycling of carbamate and the size of equipment in the
carbamate decomposition . Snamprogetti technology differs
from competitors in being based on the use of excess ammonia
to avoid corrosion as well as promote the decomposition of
unconverted carbamate into urea.