SUMMARY

Urea is in many ways the most convenient form for fixed nitrogen.
He/She has the most

nitrogen content available in a solid fertilizer (46%). It is easy to

produce in the form of pellets or

granules and easily transported in bulk or bags without risk of explosion.

It leaves no salt residues after its use in crops. Its specific weight is
At 1.335, it decomposes at the boiling point and is quite soluble in water.

The main raw materials required for this purpose are NH3 and CO2. Two
reactions are involved in the production of urea. Firstly,
ammonium carbamate forms under

pressure due to the reaction between CO2 and NH3.

CO2 + 2NH3 → NH2COONH4

H= -37.4 Kcal

This highly exothermic reaction is followed by a decomposition.

endothermic of

ammonium carbamate.

The various processes for the manufacture of urea are:

1) Snamprogetti ammonia extraction process

2) Stamicarbon CO2 separation process

3) Once through the urea process

4) total process MitsuiToatsu urea recycling

We chose the Snamprogetti ammonia separation process for manufacturing

of urea.

In this process, ammonia and CO2 are compressed and fed into the reactor.
The unconverted carbamate is separated and recovered from the effluent solution of the
urea synthesis reactor at reactor pressure, condensed to a solution
aqueous in a high pressure condenser production and recycling of
return to the reactor by steam gravity. Part of the reactor feed
Liquid NH3, vaporized in a heated steam exchanger, is used
as an inert gas for decomposing and ammonium carbamate throw in the
high pressure steam separator heated.
A balance of energy and material is made for the plant. The capacity
selected from the

The plant is 450,000 tons/year with a production of 62,500 kg/h of urea.

with 98% purity urea. Urea reactor and vacuum evaporator are designed.
The reactor volume is calculated and found to be 195 m3. The length and
the reactor diameter is 40 m and 2.5 m respectively. The evaporator
used is from the long tube type movie climbing.

Snamprogetti ammonia-urea extraction process is selected because

it implies a high ratio of NH3 to CO2 in the reactor, which ensures the high
conversion of carbamate into urea. The operation of ammonia separation
highly efficient drastically reduces the recycling of carbamate and the
team size in carbamate decomposition. Technology
Snamprogetti differs from its competitors in that it is based on the use of
excess ammonia to prevent corrosion, as well as promote the
decomposition of unconverted carbamate into urea.

Uses of Urea:

About 56% of manufactured urea is used in solid fertilizers.

Approximately 31% of manufactured urea is used in liquid fertilizers.

urea-formaldehyde resins have a wide use as an adhesive for

plywood.

melamine-formaldehyde resins are used as tableware and to make more

hard

superficies.

Chapter 1

INTRODUCTION

1.1 MANUFACTURE OF UREA [1]

Urea is an important nitrogen fertilizer. Its use is increasingly

greater, let it be

the preferred nitrogen fertilizer worldwide. It is used in fertilizer

solid, 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 a
organic compound from an inorganic compound. In 1870, Bassarow produces
urea by heating ammonium carbamate in a sealed tube
it was the first synthesis of urea by dehydration. The chemical formula of,
NH2CONH2 indicates that urea can be considered as the amide of acid.
carbamic acid NH2COOH, or the diamide of carbonic acid (OH) 2.

Fertilizer is generally defined as 'any material, organic or

inorganic, natural or synthetic, that provides one or more of the elements
chemicals necessary for the growth of plants. The main objective of
the fertilizer industry is to provide the primary nutrients and
secondary nutrients that are necessary in quantities of primary macronutrients are
are usually supplied through chemical fertilizers. They are compounds
chemicals that contain one or more of the primary nutrients and are produced
generally by chemical reactions. Whatever the compounds may be
chemicals, their most important ingredient for plant growth is
the nutrient content. The primary nutrients are nitrogen, phosphorus and
potassium. However, its concentration in a chemical fertilizer is expressed
as a percentage of total nitrogen (N), available phosphate (P2O5), and K2O
soluble. The grade of a fertilizer is expressed as a set of three
numbers in the order of one hundred N, P2O5, and K2O. If a nutrient is absent in
a fertilizer, which is represented by a zero. Therefore, the sulfate of
ammonium 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 resistant to corrosion.

CHEMICAL PROPERTIES OF UREA

Molecular weight 60.05

Relative humidity 60%

46.6%
Maximum nitrogen content
Specific weight 1.335

Heat of fusion 60 Cal / g (endothermic)

The heat of the solution, in the water 58 Cal/g (endothermic)

The apparent density 0.74 g / cc

Table 1.1 - SPECIFIC HEAT OF UREA

Temperature, °C Specific heat, kJ / kg °C

0 1.398
50 1.66
100 1.89
150 2.11
1.3 USES OF UREA

Around 56% of manufactured urea is used in solid fertilizers.

About 31% of manufactured urea is used in liquid fertilizers.

urea-formaldehyde resins have a wide use as an adhesive of

plywood.

Melamine-formaldehyde resins are used as tableware and to make more

hard

surface.

1.4 TECHNOLOGICAL PROCESS

Although there are several processes currently used for the production of urea,
the underlying principle for all processes is the same. The two
the main reactions involved are:

1) CO2 + 2NH3 ↔ NH2COONH4 ∆ H = -37.4 kcal / mol g

2) NH2COONH4 ↔ NH2CONH2 + H2O ∆H = + 6.3 Kcal / mol g

Undesirable secondary reactions take place in:

3) 2NH2CONH2 ↔ NH2CONHCONH2 + NH3

Biuret

Both the first and second reactions are equilibrium reactions. The first
reaction almost completed at 185-190 °C and 180 to 200 atm. The second reaction
(decomposition reaction) is slow and determines the speed of the reaction.
The unconverted CO2 and NH3 along with un decomposed carbamate must be
recovered and reused. This is a problematic step. The synthesis is
it complicates even more due to the formation of a dimer called biuret,
NH2CONHCONH2, which must be kept low, as it negatively affects the
growth of some plants.

1.5 GENERAL PROCESS.

Ammonia and CO2 are compressed separately and fed to the high
pressure (180 atm)

The autoclave as shown in fig-1.1 must be cooled with water

due to the highly exothermic nature of the reaction. a mixture of
urea, ammonium carbamate, H2O and unreacted (NH3 + CO2) are produced.

This liquid effluent is at 27 atm. And is fed into a flash-

special evaporator that contains a gas-liquid separator and the condenser.
Without reacting, NH3, CO2, and H2O are removed and recycled in this way.
aqueous solution of carbamate-urea is transferred to the evaporation drum
atmospheric where the additional decomposition of carbamate takes place.
The exhaust gases from this step can be recycled or sent to the
NH3 processes for the manufacture of chemical fertilizers The solution of
80% aqueous urea can be used as is, or sent to an evaporator.
empty to obtain molten urea that contains less than 1% water. The mass
molten metal is then sprayed in a granulation tower. To avoid the
formation of biuret and keep it below 1%, the temperature must
stay just above the melting point for the times of
processing of 1-2 seconds in this phase of the operation.

THE VARIABLES THAT AFFECT AUTOCLAVE REACTIONS ARE [2]:

[Fig-1.2]

Process temperature (185 °C) favors equilibrium yield at a

given pressure (180 atm). The conversion of ammonium carbamate to urea
it gradually increases as the temperature rises. However,
after a particular temperature, depending on the pressure, the
conversion drops suddenly with an additional rise in temperature.
The pressure corresponding to this temperature is generally at the
range of 175 to 185°C, is known as the decomposition pressure which is of
approximately 180 atm.

2) Pressure [Fig-1.3]:

The main reaction is sufficiently slow at atmospheric pressure. Without

embargo, it starts almost instantly under a pressure of around 100 atm and the
temperature of 150 °C. There is a reduction in volume in the overall reaction and
such high pressure favors the forward reaction. This pressure is
select according to the temperature that is maintained and the NH3 ratio:
CO2.
3) Concentration:

The greater the concentration of the reactants, the greater the direct reaction will be.
according to the law of mass action. CO2 being the limiting reactant
the NH3:CO2 ratio favors the conversion. Since the dehydration of
the results of carbamate in the production of urea, in lesser proportion
H2O: CO2 favors conversion. Therefore, water consumption in the
reactor must be minimal.

4) The residence time:

Given that the reaction of urea is slow and takes about 20 minutes to
reach the balance, the sufficient time to be provided to obtain
a higher conversion. Reactor is designed to accommodate this with
regarding the other parameters of temperature, pressure, and concentration.

5) the formation of biuret:

A problem faced during the manufacture of urea is the formation of

biuret during the production of urea. It is not a desirable substance, as
negatively affects the growth of some plants. Its urea content
it should not be more than 1.5% by weight.

2NH2CONH2 ↔ NH2CONHCONH2 + NH3

(Biuret)
Figure 1.1 Conversion percentage vs temperature graph for the
urea production
Figure 1.2 Conversion percentage Vs pressure graph for production of
urea

Although urea production is high at high pressure and high temperature, the
the reaction does not operate at maximum temperature and pressure because:

1) Increase in pressure raises capital and operating costs of

compression equipment and the reaction.

2) increase in temperature accelerates the decomposition of urea to biuret, a

compound that negatively affects the growth of some plants.

The conditions stipulated above produce corrosion rates

intolerable issues, and a compromise design must be chosen.

1.6 MAIN ENGINEERING PROBLEMS

carbamate decomposition and recycling

There are many processes that can be used for the production of urea.
the main difference in the competitors' processes is in the design of
recycling. Given that the conversion is only 40-50% per pass, the gases of
escape that have not reacted must be recirculated or used
economically in other places. Exhaust gas recompression is
practically impossible due to corrosion and carbamate formation
solid in the compressors.

Granular urea production:

Biuret formation is another problem. Vacuum evaporation of urea from

80% to approximately 99%, the spraying cools in the air and solidifies
it should be done just above the melting point of urea and for a time
minimum residence in the interval of several seconds.

3) Heat dissipation in the autoclave:

The exothermic heat of the reaction can be removed by coils or

wall cooling.

Corrosion:

This has been the main reason why the NH3-CO2 process was
developed slowly. High silver cost line tracers or tantalum are
They use in autoclaves with hastelloy C, titanium, stainless steel (SS 321), and
aluminum alloys used in other parts of the plant. Pressure and
Minimum conditions with excess NH3 are desirable for temperature
reduce the rates of severe corrosion. Under these conditions, steel
stainless steel can be used in the autoclave.

Chapter 2

Various methods of urea production, along with flow sheets.

2.1 VARIOUS PROCESSES FOR MANUFACTURING

UREA [3]

The urea synthesis reactor always contains carbamate that has not
reacted and more or less the excess of ammonia, depending on the
composition of food. This raises the practical problem of separating the
unreacted material from the urea solution and its reuse
non-reactive material. Depending on the method of reusing the material
without reacting, commercial urea synthesis processes are divided into the
following main categories:

1) Once the urea process through:

The unconverted carbamate decomposes into NH3 and CO2 gas by
heating of the effluent mixture from the urea synthesis reactor at low
pressure. The NH3 and CO2 gas separates from the urea solution and is used for
to produce ammonium salts by absorbing NH3, whether in acid
sulfuric or nitric.

Once through the urea process [Fig-2.1]:

In this process, liquid NH3 is pumped through a piston pump.

high pressure and gaseous CO2 is compressed through a compressor until the
pressure of the urea synthesis reactor in a molar feed ratio
from NH3 CO2 of 2/1 or 3/1 a. The reactor normally operates in a range of
temperature from 175 to 190 °C. The reactor effluent is disappointment in the
pressure at approximately 2 atm and the carbamate decomposes and is stripped of
the urea product solution in a heat exchanger heats the shell
and steam pipes. The wet gas, separated from the urea product solution.
of 85-90%, and contains about 0.6 tons of gaseous NH3 per
ton of urea produced is normally sent to an ammonium nitrate or
ammonium sulfate adjacent production plant for recovery. It
achieves an average conversion of carbamate to urea of approximately
60%. The excess heat is removed from the reactor through a coil of
low pressure vapor producers in an amount of approximately 280
000 cal / Kg of urea produced.
Figure 2.1 Once through the urea process

2) Urea recycling process Solution:

The NH3 and CO2 gas recovered from the effluent mixture of the reactor either in
one or in several pressure stages decomposition sections is absorbed
in water and are recycled back to the reactor in the form of an aqueous solution
ammoniacal ammonium carbamate.

3) Internal urea recycling carbamate process:

The unreacted carbamate and the excess ammonia are removed from the
effluent from the urea synthesis reactor using hot gaseous CO2 or
NH3 in the reactor pressure, instead of letting the reactor effluent
up to a much lower pressure. The NH3 and CO2 gas, thus recovered at the
reactor pressure, it is condensed and returned to the reactor by means of flow through
gravity for recovery.

Snam Progetti (Italy) [Fig-2.2]

This process is based on the principle of internal recycling technique
carbamate and is commonly called the Snam NH3 separation process.
basic difference between the Snam process and conventional processes
urea recycling solution carbamate is the fact that in this case the
unconverted carbamate is separated and recovered from the effluent solution of the
urea synthesis reactor at reactor pressure, condensed to a solution
aqueous in a high-pressure steam condenser production, and recycles from
new to the reactor by gravity. Part of the reactor feed NH3
liquid, vaporized in a heated steam exchanger, is used as
inert gas to decompose and ammonium carbamate strip in the separator
high-pressure steam heated.

The reactor operates at approximately 130 atm and 180-190 °C. The separator
operates at approximately 130 atm and 190 °C. The gas separator of
escape condenses in a shell and tube vertical condenser, which
operates at approximately 130 atm and 148 to 160 °C. low pressure steam
It occurs in the high-pressure carbamate condenser. The solution
urea product, leaving the separator and still containing 2-3% of
residual carbamate without reacting, is more degassed in a system of
low pressure absorption decomposition. The ammoniacal solution
Recovered ammonium carbamate is pumped back into the reactor.

Figure 2.2 Snamprogetti process

b) Stamicarbon (Holland) [Fig-2.3]

The novelty of the CO2 separation process lies in the fact that the
The reactor effluent is not allowed to go to a lower pressure as in the process.
conventional liquid urea recycling, but it is eliminated under pressure synthesis by the
power supply current of the gaseous CO2 reactor in a heated steam
vertical heat exchanger.

The high-pressure separator operates at around 140 atm and 190 °C.
urea solution stripped still contains approximately 15% of
non-converted carbamate, and it is left for about 3 atm for more than
degassing in the low pressure heated decomposer at
approximately 120 °C. The recovered gas supply is condensed with
cooling water in the low-pressure condenser, which operates at about
65 °C and 3 atm. The solution thus obtained is pumped to the high condenser.
pressure through the high-pressure carbamate pump. The gas outside
recovered from the high-pressure separator condenses in the condenser of
high pressure, operating at approximately 170 °C and 140 atm. The heat of
condensation is removed on the housing side of the condenser through the
vaporization of the equivalent amount of condensate. The water vapor 3.4
ATM thus produced can be reused

The gas and liquid mixture emitted from the high-pressure condenser is
feeds the reactor for the total condensation of CO2 into carbamate and subsequent
conversion to urea. The inerts are vented from the reactor through a
water-cooled ventilation condenser. The effluent from the reactor, in
return to 185 °C and 140 atm, is fed to the high-pressure separator as

described above.
Figure 2.3 Stamicarbon process

c) MitsuiToatsu oToyo Koatsu process (Japan) [Fig-2.4]

This total urea recycling process is a recycling solution.

conventional carbamate with three decomposition systems and
recovery of pressure-carbamate - stages. The reactor is operated at
approximately 195 °C, 240 atm, and with an NH3 to CO2 molar ratio of
approximately 4.3. Around 67% of the total ammonium carbamate
present in the reactor is converted into urea.

The unconverted carbamate decomposes and separates from the solution of

urea, along with the excess of NH3 in a series of three decomposer stages
of pressure, which operate respectively at around 18 atm and 150 °C, 3.06
atmospheric pressure is 130 °C, and atmospheric pressure is 120 °C. The main characteristic of
the MitsuiToatsu process is the fact that the gas phase at each stage of
decomposition comes into contact in countercurrent flow with the solution
urea product that comes from the previous decomposition stage.
Any of a filler section or a mesh tray section is
is used for this purpose. The effect is that the gaseous mixture of NH3 and CO2
obtained from the decomposition of carbamate is reduced
considerably in the steam content. Thus, the amount of recycled water
the reactor is maintained at a relatively low level and a relatively high level
conversion in the reactor is reached. The exhaust gas from each stage of
decomposition condenses into the solution in its respective condenser
cooled by water and the solution thus obtained is pumped at high pressure from the
next scene condenser.

The excess NH3 is separated from the aqueous solution of carbamate and washed off.
the latest traces of CO2 in countercurrent flow with the reflux liquid,
NH3, fed to the top of the high-pressure absorber. The excess
the pure NH3 thus obtained is condensed into liquid with cooling water and is
recycle to the reactor. The carbamate solution is recycled back to the reactor to
total recovery.
Figure 2.4 Total urea recycling process of MitsuiToatsu

2.2 SELECTION OF THE PROCESS [Figure 2.5]

Snamprogetti's urea-ammonia extraction process is selected because

it implies a high ratio of NH3 to CO2 in the reactor, which ensures the high
conversion of carbamate into urea. The operation of ammonia separation
highly efficient drastically reduces the recycling of carbamate and the
size of the team in carbamate decomposition. Technology
Snamprogetti differs from its competitors in that it is based on the use of
excess ammonia to prevent corrosion, as well as promote the
decomposition of unconverted carbamate into urea.

The formation of urea from ammonia and carbon dioxide takes place at
through reversible reactions with the formation of ammonium carbamate as
intermediate product. Now, the success of any urea MFG process
it depends on how we can economically recycle carbamate to the reactor.
Snamprogetti's urea manufacturing process accomplishes the previous task by the
extraction process.

NH2COONH4 (s) ===== 2NH3 (g) + CO2 (g) Δ H = + 37.4 Kcal / g-mol

This reaction involves an increase in volume and the absorption of heat. Thus, this
reaction is favored by a decrease in pressure and an increase in
temperature. On the other hand, the decrease in the partial pressure of any
The products will also promote the forward reaction. Process
based on the first principle of pressure decrease and decrease in
temperature is called the conventional process, while the process on the
base for increase / decrease of the partial pressures of NH3 or CO2 is
call separation process. According to the previous equation we have:

K = (pNH3) 2 * (pCO2) [where, K = equilibrium constant]

The extraction is carried out at synthesis pressure using CO2 or NH3 as

separation agent. If CO2 is selected, it is to be supplied to the
decomposers / separator as in Stamicarbon separation process
CO2. While if NH3 is selected, it is to be obtained from the
own system because the excess of NH3 is present in the reactor as in the
Snam process. CO2 extraction is an advantage, as is the introduction of CO2.
increases pCO2. Thus pNH3 will be reduced to maintain constant P as P = pCO2
+ pNH3.

At a particular temperature, K is constant so that when pNH3 decreases

to keep K constant, carbamate will be reduced much faster by
decomposition as pNH3 appears in the equilibrium equation with a
power of two. Selection of decomposition first stage must be such
way that water evaporates min because the recovered gases go
along with the reactor carbamate anew and if the water enters into production
the reactor will be negatively affected due to the hydrolysis of urea. Thus, the
Stepwise decomposition of carbamate is done. Second consideration to
the favor of isobaric extraction is that greater results of the pressure of
recycling of carbamate in the condensation at higher temperature and that the
recovery in the form of steam at low pressure. This is why it was agreed upon
stages of pressure reduction

Figure 2.5 Snamprogetti process for urea manufacturing

Chapter 3
Selected process: ammonia separation process Snamprogetti

SNAMPROGETTI AMMONIA separation process

3.1 MANUFACTURING PROCESS [4]

In the reactor, when liquid ammonia reacts with compressed CO2 (in
162 ATA) high temperature and pressure gives urea according to the following
reactions:

2NH3 + CO2 ======= NH2COONH4 exothermic

NH2COONH4 ======= NH2CONH2 + H2O endothermic

Since reactions are reversible in nature, only the

partial conversion in the reactor.

Urea solution consisting of urea, carbamate, water, and unconverted CO2 and
NH3 is introduced into the separator where the extraction action of NH3 favors the
decomposition of the carbamate, and therefore 80% of carbamate is
decomposes here. Pressure in the separator is the same as that of the reactor.

Urea solution from the separator is sent to the pressure decomposer.

media, where the purification of urea is carried out by dehydration of the
Carbamate solution. Urea is further purified in a decomposer.
low pressure. Off gases from the decomposer MP & LP
decomposer is sent to the medium pressure condenser and absorber of
media pressure for the recovery of unconverted ammonia. From this
this way it is sent to the vacuum concentrators that operate in two stages
71.12% of urea solution resulting from decomposing LP:

vacuum evaporator first.

second vacuum evaporator

Finally, 98% of molten urea is sent to the Granulation towers where

urea globules are formed by passing a stream of cold air in the tower
from the bottom. Properly sized urea granules are sent to
through the bagging section of the conveyor belts. In the section
in bagging, coating of urea granules can be done if it is
necessary. Large urea granules or lumps are sent to group together
dissolution tank.

Urea synthesis

NH3 and CO2 react under low concentration, temperature, and pressure to the
specific conditions

to form urea as per the following reactions:

CO2 (g) + 2NH3 (g) ⇌ NH2COONH4 (s) H = -37.64 kcal / mol

g

2) NH2COONH4 (s) => NH2CONH2 (s) + H2O (l); H = 6.32 kcal / mol
gm

------------------------------------------------------------------------------------------------------------

CO2 (g) + 2NH3 (g) ===== NH2CONH2 (s) + H2O (l) H = -31.32 kcal / mol
g

Thus, the synthesis of urea is generally exothermic, releasing heat of 31.32 kcal/
mol gm at standard conditions of pressure of 1 atm and 25 °C. But of heat
The real available in a synthesis reaction of urea will be only 5.74 kcal/mol.
gm due to heat loss in the evaporation of liquid NH3, evaporation
of water and urea fusion. This is based on the actual data from the plant.

In addition to the energy consumed in the feeding of CO2 and NH3 at high
temperature and pressure, in the recycling of carbamate, in the concentration of
empty of urea, for the operation of different pumps and compressors,
etc., which together makes the consumption of urea for energy production.

3.2 EFFECT OF VARIOUS PARAMETERS

[Fig-1.2]

In the previous reactions, the first reaction is exothermic and the second one is
endothermic. Thus, according to the first reaction of Le Chatelier's Principle, it ...
favors low temperature and secondly one at high temperature. In addition, the
Reaction number 1 is fast and goes to the end, but reaction number 2 is slow and
determine the overall rate of urea production. To finalize sufficient of
No. 2 optimal temperature reaction is maintained. It is observed that the conversion
equilibrium max occurs between 190 to 200 °C. If the temperature
An increase above 200 °C increases the corrosion rate.

NH2COONH4 (s) => 2NH3 (g) + CO2 (g) H = -ve (K1)

NH2COONH4 (s) => NH2CONH2 (s) + H2O (l) H = -ve (K2)

Both reactions are favored at high temperature, but our goal

it is to maximize the second reaction as the first reaction is undesirable in the
reactor. Therefore, our operating zone must be in the region
where K2 > K1.

PRESSURE [Fig-1.3]:

In general, the synthesis reaction of urea is given as follows:

CO2 (g) + 2NH3 (g) ====== NH2CONH2 (s) + H2O (l)

There is no reduction in the volume of the overall reaction and such high pressure.
it favors the direct reaction. This pressure is selected according to the temperature.
be maintained and NH3: CO2 ratio.

CONCENTRATION:

The greater the concentration of the reactants, the greater the direct reaction will be.
according to the law of mass action. CO2 being the limiting reactant greater than NH3:
CO2 relationship favors the conversion. Given that, the dehydration of the
carbamate results in urea production, lower H2O: relationship of
CO2 favors the conversion, therefore the intake of water to the reactor must be
min.

RESIDENCE TIME:
Since the urea conversion reaction is slow, enough time will be
provide to achieve a higher conversion. Reactor is designed to
to accommodate this with respect to the other parameters of temperature, pressure
and concentration.

3.3 SNAMPROGETTI separation process [4]

The formation of urea from ammonia and carbon dioxide takes place at
through reversible reactions with the formation of ammonium carbamate as
intermediate product. Now, the success of any manufacturing process of
urea depends on how we can economically recycle carbamate
Snamprogetti reactor urea manufacturing process accomplishes the previous task
through the extraction process.

NH2COONH4 (s) ====== 2NH3 (g) + CO2 (g) ∆ H = + 37.4 Kcal / g-

mol

This reaction involves an increase in volume and heat absorption. Thus, this
reaction is favored by a decrease in pressure and an increase in
temperature. On the other hand, the decrease in the partial pressure of any
the products will also promote the forward reaction. Process
based on the first principle of pressure decrease and decrease of
temperature is called a conventional process, while the process on the
base of increase / decrease of the partial pressures of NH3 or CO2 is
call separation process. According to the previous equation we have:

K = (pNH3) 2 * (pCO2) [where, K = equilibrium constant]

The extraction is carried out at synthesis pressure using CO2 or NH3 as

separation agent. If CO2 is selected, it is to be supplied to the
decomposers / separator as in Stamicarbon separation process
CO2. While if NH3 is selected, it is to be obtained from the
own system because the excess of NH3 is present in the reactor as in the
Snam process. CO2 extraction is an advantage, as is the introduction of
increase in CO2 pCO2. Thus pNH3 will be reduced to maintain constant P as
P = pCO2 + pNH3.
At a particular temperature, K is constant so that when pNH3 is reduced
to keep K constant, carbamate will be reduced much faster by
decomposition as pNH3 appears in the equilibrium equation with a
power of two. Selection of decomposition first stage must be such
so that the water evaporates min because the recovered gases go
together with the carbamate in the reactor again and if the water enters the reactor, the
production will be negatively affected due to urea hydrolysis. Thus,
the stage decomposition of carbamate is done. Second consideration to
The favor of isobaric extraction is that it results in higher pressure outcomes.
recycling of carbamate in the condensation at higher temperature and that the
recovery in the form of low-pressure steam. This is why it is practiced by
stages of pressure reduction.

3.4 DESCRIPTION OF THE PROCESS

The urea production process is carried out through the following

main operations:

1) the synthesis of urea and recovery at high pressure.

2) the purification of urea and low-pressure recovery.

3) The concentration of urea.

4) formation of urea pearls.

UREA SYNTHESIS AND HIGH PRESSURE RECOVERY

Urea is synthesized from liquid ammonia and carbon dioxide gas.

The carbon dioxide extracted from battery limits is around 1.6.
pressure is compressed in a compressor at approximately 40 °CTemp
centrifugal up to 162 ata. A small amount of air is added to the suction
of the CO2 compressor in order to passivate stainless steel surfaces. By
both the corrosion protection due to both the reagent and the product of
reaction.

The liquid ammonia coming directly from the battery limits is

Collects in the ammonia receiver tank from where it is extracted to &
compressed to about 23 atm pressure using a centrifugal pump. Part of
this ammonia is sent to the medium pressure absorber and the remaining part enters
in the high-pressure synthesis loop. The NH3 from this synthesis loop is
compresses at a pressure of approximately 240 ata. Before entering the
Reactor is used as a conducting fluid in the carbamate ejector, where
the carbamate from the carbamate separator is compressed until the
synthesis pressure. The liquid mixture of ammonia and carbamate enters the
reactor where it reacts with compressed CO2.

In the reactor, NH3 and CO2 gas react to form amm.

Carbamate, part of which is dehydrated to form urea and water.
the fraction of carbamate that dehydrates is determined by the proportions
of various reagents, operating temperature, residence time
in the reactor and the reaction pressure. The molar ratio of NH3 / CO2 is
around 2:1, the molar ratio of water to CO2 is about 0.67:1.

2NH3 (g) + CO2 (g) ===== NH2COONH4 (s) exothermic

NH2COONH4 (s) ====> NH2CONH2 (s) + H2O (l) endothermic

Under the synthesis conditions (T = 190 °C, P = 154 atm), the first reaction
it occurs rapidly and has been completed. The second reaction occurs
slowly and determine the volume of the reactor.

The urea is a plug flow reactor with 10 NO.S of perforated plates.

to avoid mixing again and to prevent the escape of gaseous CO2 that
it must react at the bottom of the reactor.

Stage decomposition is carried out to reduce the water that will be transferred to the
reactor that could negatively affect the conversion

Urea solution containing urea, carbamate, H2O and unconverted CO2 and NH3
enter

the high-pressure separator where the pressure is the same as that of the reactor.
mix

It heats up as it flows down the film exchangers.

descending. The CO2 content of the solution is

reduced by the action of NH3 separation as it boils out of the solution.

The carbamate

The decomposition heat is supplied by 24 steam tons. The gases of

separator head and

the solution recovered from the absorber MP, all the flow at high pressure
carbamate

condenser through the mixer, total mix, except for a few

inert gas condenses and
Recycle to the reactor via carbamate ejector. Condensation of the gases.
the high

temperature and pressure allow for the recovery of condensation heat in the
water vapor production at 4.5 ata in the high carbamate condenser
pressure.

From the top of the gas carbamate separator not

Condensables consist of inerts and a small amount of NH3 and CO2
without reacting in the capacitor. These are sent to the bottom of MP
disassembler

Figure 3.1 urea process Snamprogetti

UREA PURIFICATION AND LOW PRESSURE RECOVERY

Urea purification is carried out in two stages at decreasing pressure as

continues:

First stage at 18 ata pressure, that is, MP decomposer

Second stage at 4.5 pressure, that is, LP decomposer

Purification of the first stage and recovery stage at 18 ata:

The type of MP decomposition film is falling apart. It is divided into 2 parts:

upper separator, where the gases released in flash, the solution enters in the
beam tube section and the decomposition, where the residual carbamate is
decomposes and necessary heat is supplied through 24 condensed ata
of steam that comes out of the separator.

Second purification and recovery stage at 4.5 ata:

The solution leaving the lower part of MP decomposition was expanded in

4.5 pressure hits and enters LP decomposition (the drop in film type).
This is divided again into two parts: the upper part of the separator where
the flash gases released before the solution enters the
tube rays. Decomposition section where the last residual carbamate
it decomposes and the required heat is supplied by means of saturated steam
a 4.5 ata.

Urea concentration

The next section is the concentration of urea and the goal is to reduce the content.
of urea water at a price as low as 1%. For this purpose
provides a two-stage vacuum concentrator. The solution that comes out of the
decomposing LP background with approximately 72% urea is sent to the
First vacuum concentrator operates at a pressure of 0.23 ata. The phase
mixed that goes into the liquid gas separator, from where the vapors are
they extract through the vacuum system first, while the solution enters the
The second vacuum concentrator operates at a pressure of 0.03 ata. The two
Concentrators are supplied with saturated steam at 4.5 ata. The mixed phase
what comes out enters the gas-liquid separator, where the vapors are
extracted by the empty second system.

Prilling UREA

The molten urea leaving the second vacuum separator is sent to the bucket of
formation of pearls through a centrifugal pump. The urea that comes out of the
Buckets in the shape of droplets fall along the granulation tower and are
Find a flow of cold air that causes its solidification. The granules
solids that fall to the bottom of the granulation tower are sent to
through the crushers to retain lumps only, and then to the conveyor
conveyor that brings the product to the automatic weighing machine and to the
urea storage sections. Bags of urea by means of conveyor belt
carriers are recycled into the underground tank, where they dissolve.

Chapter 4

Material balance

MATERIALS BALANCE

Selected capacity: 450,000 tons/year

Number of working days: 300

Daily production: 450,000 / 300 = 1,500 tons / day

Urea 62.500 Kg / h of 98% purity

Composition of the final product:

98% (61,250 Kg / hr)

1% (625 Kg / hr)

Water: 1% (625 Kg / hr)

Assumption: the global conversion to urea is assumed to be 95%.

Main reactions:

CO2 + 2NH3 ==== NH2COONH4

(44) (17) (78)

NH2COONH4 -> NH2CONH2 + H2O

(60) (18)

CO2 + 2NH3 ==== NH2CONH2 + H2O (general reaction)

Secondary reaction:

2NH2CONH2 ===> NH2CONHCONH2 + NH3

(103)

625 Kg / h of Biuret produced by = (120/103) * 625 = 728 kg / h of urea

(reaction 4)

Thus, urea produced by the reaction (2) = 61,250 + 728 = 61,978 Kg/hr

61.978 Kg / h of urea produced by = (34/60) * 61.978 = 35.120 kg / h of NH3

(44/60) * 61.978 =
45.450 Kg / hr

Assuming a 95% conversion, we obtain

NH3 really necessary = 35120 / 0.95 = 36.968 kg / h

Necessary CO2 = 45450 / 0.95 = 47.842 Kg / hr

Now, taking into account reaction (4):

If reaction (3) is 100% complete,

The produced urea = (60/44) * 47.842 = 65.239 kg/h

But, for 95% conversion

The produced urea = 0.95 * 65,239 = 61.977 kg/h

Therefore, urea was converted to Biuret and NH3 = 61.977 - 61.250 = 727 kg/h

Thus, starting from reaction (4)

Biuret produced = (103/120) * 727 = 624 kg / h

The water produced in reaction (2) = (18/60) * 61.978 = 18.593 kg / h

In the reactor output (Urea = 34%)

Flow rate = 61.250 / 0.34 = 1,80,147 kg/h of flow

NH3 reacts in the reaction (1) = (34/60) * 61.977 = 35.120 Kg / hr

NH3 produced in reaction (4) = (17/120) * 727 = 103 Kg / hr

Thus, unreacted NH3 = 36968 at 35.120 + 103 = 1951 kg / h

CO2 reacts in the reaction (1) = (44/60) * 61.977 = 45.450 Kg / hr

Therefore, the unreacted CO2 = 47842-45450 = 2392 kg/h

Now,

Flow rate at the reactor outlet - (urea rate + CO2 + NH3 +

water + biuret flow = carbamate flow rate

1,80,147- (61.250 + 2392 + 1951 + 18.593 + 624) = 95.337 kg / h

4.1 REACTOR

Fig 4.1 Material flow through the reactor

Table 4.1 Material flow through reactor

ENTRY

MATERIAL FLOW (kg / h) MATERIAL% FLOW (kg / h)%

Non-reactive feeding

NH3 (liq) 36.968 43.59 NH3 (liq) 1.951 1.08

47.842

Total of 84810 100

Recycle

Carbamate 95337 100 products

UREA 61250 34

WATER 18.593 10.32

BIURET 624 0.36

CARBAMATE 95.337 52.92

Total180147100180147100

4.2 STRIPPER

Fig 4.2 Material flow through separator

Since the reaction takes place in the separator and only carbamate is formed
recycle back to the reactor. Therefore, the amount of ammonia, dioxide of
carbon, water, and biuret in the outlet stream of the separator will be equal to
it was in the input current.

Table 4.2 Material flow through separator

ENTRY

MATERIAL FLOW RATE (kg/h) MATERIAL% FLOW RATE (kg/h)%

Background product

NH3 1.951 1.08 1.951 2.30 NH3

CO2 2.392 1,32 2.392 2,82 CO2

95.337

UREA

WATER

BIURET 624 0.36 Total of 84,810 100

TopProduct

Ammonium 95337 100

carbamate

180147
4.3 MEDIUM PRESSURE SEPARATOR

Fig 4.3 Material flow through the medium pressure separator

The amount of ammonia, carbon dioxide, water, and biuret will remain
constant as no reaction takes place.

50% of ammonia and carbon dioxide is supposed to escape from the part
superior of the separator and the rest goes with the background product. Amount of water and
biuret remains constant as no reaction takes place.

Table 4.3 Material flow through the medium pressure separator

ENTRY EXIT

MATERIAL FLOW (kg / h)

NH3 1,951 2.3 NH3 976 1,18

2.392 2.82 1.196 1.44 CO2

UREA 61.250 72.22 61.250 74.11 UREA

WATER WATER 18.593 21.9 18.593 22.49

BIURET 624 0.76 624 0.78 BIURET

Total82639100

Losses

NH3 975 44.91

1.196

84812

4.4 LOW PRESSURE SEPARATOR

Figure 4.4 Material flow through low pressure separator

Remaining ammonia and carbon dioxide are supposed to escape from the part
superior.

Table 4.4 Material flow through low pressure separator

entry

MATERIAL FLOW (kg / h)

NH3 976 1.18

1,196 1,44

UREA 61.250 74.11 61.250 76.11 UREA

WATER WATER 18.593 22.49 18.593 23

BIURET 624 0.78 624 0.79 BIURET

Total of 80467 100

Losses

NH3 975 44.91

1.196 55.09

Total826391002171100

EVAPORATOR 4.5 VACUUM

Fig 4.5 Flow of material through vacuum evaporator

Let's x & y be the mass fractions of urea in the feed (F) and
product (P) resp.

x = 0.7611 (76.11%)

y = 0.9788 (97.88%)

Taking stock of the urea:

F.x = p.y

80.467 * 0.7611 = 0.9788 P *

P = 62.574 kg / h
Overall material balance of:

F=P+E

E = 80.467 - 62.574

E = 17.893 kg / h

Table 4.5 Material flow through the vacuum evaporator

ENTRY

MATERIAL FLOW RATE (kg / h)

61.250 76.11 61.250 97.88 UREA

WATER WATER 18593 23.10 700 1.11

BIURET 624 0.79 624 1.01 BIURET

Total of 62574 100

Losses

17893 WATER 100

Total80467100

4.6 prilling TOWER

Fig 4.6 Material flow through granulation tower

Let's x & y be the mass fractions of urea in the feed (F) and
product (P) resp.

x = 0.9788 (97.88%)

y = 0.9796 (97.96%)

Making a balance of urea:

F.x = p.y
62.574 * 0.9788 = 0.9796 P *

P = 62.524 kg / h

Table 4.6 Material flow through the granulation tower

ENTRY

MATERIAL FLOW (kg / h)

UREA 61.250 97,88 61.250 97,96 UREA

WATER WATER 700 1.11 650 1.11

BIURET 624 1.01 624 0.93 BIURET

Total62524100

Losses

WATER 50 100

Total62574100

Chapter 5

Energy balance

ENERGY BALANCE

Asunción: temperature Date = 0 ° C

5.1 REACTOR [5]

Fig 5.1 Energy through the reactor

POWER ENTRY

Specific heat of the material at 40 °C

NH3 0.53 cal / g ° C = 2.219 kJ / KgoC

CO2 0.22 cal / g ° C = 0.9211 kJ / kg °C

specific heat at 180°C

Carbamate 0.62 cal / g ° C = 2.596 kJ / kg °C

The heat input

MCP? t

NH3: 3.6968 x 10^4 x 2.219 x 40 = 0.328 x 10^7 kJ / hr

CO2: 4.7843 x 0.9211 x 104 x 40 = 0.176 x 107 kJ / hr

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

The heat input = 4.959 x 10^7 kJ / hr

? HR = -31.32 kcal / mol g

-0.013 X 107 kJ / kmol of urea formed.

Amount of urea formed during the reaction = 1,020.83 Kmol / hr

? HR = 1,020.83 x 0.013 x 107 kJ / hr

= 13.27 x 107 kJ / hr

Output current

Specific heat of the material in mole fractions 180°C (x) Flow (Kmol /
hr)

NH3 0.55 cal / g °C = 39.15 kJ / KmoloC 0.033 114.76

CO2 0.23 cal / g ° C = 42.37 kJ / Kmol °C 0.0158 54.36

Carbamate 0.62 cal / g ° C = 202.49 kJ / KmoloC 0.354 1,222.3

Urea 0.4828 cal / g ° C = 121.32 kJ / Kmol °C 0.296 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.299 1,032.94

Biuret 183.8 Kj / KmoloC 0.002 6.07

Total=3,451.3

Mixing Cp = ? xiCpi

Thus, Cp = 0.033 x + 0.0158 39.15 x 42.37 x 0.296 + 121.32 + 202.49 + 0.354

x 0.002 x
183.8 + 0.299 x 75.37 = 132.46 kJ / KmoloC

Thus, the heat carried by the output current = MCP? T

3,451.3 x 132.46 x 180

8.229 x 10^7 kJ / hr

Heat input + HR - Heat output = rate of accumulation

4.959 x 10^7 + 13.27 x 10^7 to 8.229 x 10^7 = accumulation rate

accumulation rate = 10 x 107 kJ / hr

Assumption: Cooling water at 25 °C is used to remove heat from

Reactor. The output is water vapor at an absolute pressure of 4.5 bar (Ts =
147.9 °C

Thus, the heat gained from cooling the water = 10 x 107 kJ / hr

MCP? t + m? = 10 x 107 Kj / hr

o, m (Cp? t +?) = 10 x 107

m [4,187 x (147.9 to 25) + 2120.6] = 10 x 107 kJ / hr

(Here? = 2120.6 kJ / kg and = 4.187 kJ / kg °C)

m = 108 / 2635.18

m = 37.948 kg / h

5.2 STRIPPER [6]

Flow of figure 5.2 Energy through separator...

m = 37.948 kg / h
.

5.2 STRIPPER [6]

Figure flow of 5.2 Energy through separator

Total heat input = 8.229 x 10^7 kJ / hr

Output current

Liquid

Specific heat of the material at [185°C] [5] mole fractions (x) Flow rate

(Kmol / hr)

NH3 0.58 cal / g ° C = 41.31 kJ / KmoloC 0.05 114.76

CO2 0.24 cal / g ° C = 44.22 kJ / Kmol °C 0.024 54.36

Urea 0.5385 cal / g ° C = 135.3 kJ / KmoloC 0.46 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.463 1,032.94

Biuret 183.8 Kj / KmoloC 0.003 6.07

2,228.96

Mixing Cp =? xiCpi

Thus, Cp = 0.05 x 41.31 x 44.22 + 0.024 + 0.46 x 135.3 x 183.8 + 0.003 +

34.86601

100.81 kJ / KmoloC

Thus, the heat carried by the outgoing current = MCP? T

2,228.96 x 100,81 x 185

4.157 x 10^7 kJ / hr

2) steam flow: ammonium carbamate

Specific heat of the material at [185°C] Flow

(Kmol / hr)

Carbamate 0.62 cal / g ° C = 202.49 kJ / Kmol°C 1222.3

For carbamate? = 210 Kj / Kg

Thus, the heat transported by carbamate = m Cp? T + m?

1222.3 x 202.49 x 185 + 95,336 x 210

6.581 x 10^7 kJ / hr

In this case, water vapor is used at 24 atm (Ts = 221.8 °C).

? of steam = 1855.3 kJ / kg

The heat supplied by the steam outlet = Heat - The heat input

(6,581 + 4,157 to 8,229) x 107 kJ / hr

m? = 2.509 x 10^7 kJ / hr

m = 2.509 x 107 / 1855.3

m = 13.523 kg / h

5.3 CONDENSER CARBAMATE [6]

Figure 5.3 Energy through the carbamate condenser

Energy balance

mv? Cp v = ms (Ts-25) + m? s

Put the values that we obtain:

95337 x 210 = 4.187 ms [x (147.9 to 25) + 2120.6] [? Where s = 2120.6 kJ / kg]

Therefore, ms = 7,597.5 kg / h

5.4 MEDIUM PRESSURE SEPARATOR [5]

Figure 5.4 Energy through the medium pressure separator

The heat input = 4.157 x 10^7 kJ / hr

Liquid

Output current

Specific heat of the material at [140°C] mole fractions (x) Flow rate

(Kmol / hr)

NH3 0.54 cal / g °C = 38.4 kJ / KmoloC 0.027 57.4

0.23 cal / g °C = 42.37 kJ / Kmol °C 0.0127 27.182

Urea 0.493 cal / g ° C = 123.84 kJ / Kmol ° C 0.476 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.4815 1,032.94

Biuret 170.92 kJ / KmoloC 0.0028 6.07

2,144.42

Cp of mixture =? xiCpi

Thus, Cp = 0.027 x 38.4 + 0.0127 x 42.37 + 0.476 x 123.84 + 0.0028 x 170.92

+ 0.4815 x

75.37 kJ / KmoloC

97.29 kJ / KmoloC

heat output = 2,144.42 x 97.29 x 140 kJ / hr

2.921 x 10^7 kJ / hr

2) For the gases that escape from the top

Material? at 140°C mole fractions (x) Flow

(Kmol / hr)

NH3 320 cal / g ° C = 22.777 x 10^3 Kj / KmoloC 0.6785 57.35

CO2 110 cal / g ° C = 20.265 x 10^3 Kj / Kmol oC 0.3215 27.182

84.53

? of mix =? xi? i

Therefore, ? = (0.6785 x 22.777 + 0.321 x 20.265) x 103 Kj / KmoloC

= 21,969 x 103 Kj / Kmol

Specific heat of the material at [140°C] mol fractions (x) Flow rate

(Kmol / hr)

NH3 0.54 cal / g ° C = 38.4 kJ / KmoloC 0.6785 57.35

CO2 0.23 cal / g °C = 42.37 kJ / Kmol °C 0.3215 27.182

84.53

Mixing Cp =? xiCpi

Thus, Cp = 0.6785 x 38.4 + 0.321 x 42.37 kJ / KmoloC

= 39.676 kJ / kmol °C

The heat escapes from the mains = m (Cp? T +?)

= 84.53 (39.676 x 21.969 x 140 + 103)

0.2327 x 107 kJ / hr

Asunción: The cooling water enters at 25°C and exits at 50°C.

Thus, the heat gained by the inlet cooling of the water = Heat - outlet of
heat

(4.157 - 2.921 a 0.2327) x 107 kJ / hr

MCP? t = 1.00 x 10^7 kJ / hr

m = 1.00 x 10^7 / (4.187 x 25)

m = 95,533.8 kg / hr

5.5 LOW PRESSURE SEPARATOR [5]

Fig flow of 5.5 Energy through low-pressure separator

The heat input = 2,921 x 10^7 kJ / hr

Liquid

Output current

Specific heat of the material at [80°C] mole fractions (x) Flow rate

(Kmol / hr)

Urea 0.429 cal / g ° C = 107.76 kJ / KmoloC 0.496 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.5 1,032.94

Biuret 149 Kj / KmoloC 0.004 6.07

2059.8

Mixture Cp = ? xiCpi

Thus, Cp = 0.496 x 107.76 x 75.37 + 0.5 + 0.476 x 123.84 + 0.004 x 149 kJ /

KmoloC

= 91.73 kJ / KmoloC

heat output = 2059.8 x 91.73 x 80

1.51 x 10^7 kJ / hr

2) For the gases that escape from the top

Material? at 140°C mol fractions (x) Flow rate

(Kmol / hr)

NH3 260 cal / g ° C = 18.51 x 10^3 Kj / KmoloC 0.679 57.41

CO2 85 cal / g ° C = 15.66 x 10^3 Kj / Kmol oC 0.321 27.182

84.59

? of mixture = ? xi? i

Therefore,? = (0.679 x 0.321 x 18.51 + 15.66) x 103 KJ / KmoloC

17.6 x 10^3 Kj / Kmol

Specific heat of the material at [140°C] mole fractions (x) Flow rate

(Kmol / hr)

NH3 0.52 cal / g ° C = 37.013 Kj / KmoloC 0.027 57.41

CO2 0.21 cal / g ° C = 38.69 kJ / Kmol oC 0.0127 27.182

84.59

Mixture Cp =? xiCpi

Thus, Cp = 0.679 x 37.013 + 0.321 x 38.69 kJ / Kmol°C

37.55 kJ / KmoloC

The heat escapes from the mains = m (Cp? T +?)

= 84.59 (37.55 x 17.7 x 80 + 103)

0.1743 x 107 kJ / hr

Asunción: The cooling water enters at 25°C and exits at 50°C.

Thus, the heat gained by the cooling of the incoming water = Heat - output of
heat

(2.921 - 1.51 - 0.1743) x 107 kJ / hr

MCP? t = 1.2367 x 10^7 kJ / hr

m = 1.2367 x 10^7 / (4.187 x 25)

m = 1.18,146 kg / h

[5]

Fig flow of 5.6 Energy through the evaporator

For the product stream that comes out of the evaporator first:

Specific heat of the material at [85°C] mole fractions (x) Flow rate

(Kmol / hr)

Urea 0.435 cal / g °C = 109.28 kJ / kmol °C 0.75 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.245 333.33

Biuret 149 Kj / KmoloC 0.005 6.06

Total=1360.223

Cp of the mixture =? xiCpi

Thus, Cp = 0.75 x + 109.28 0.245 x 75.37 + 0.005 x 149 Kj / KmoloC

101.17 kJ / KmoloC

? t MCP = 1360.223 x 101.17 x 85

1.17 x 10^7 kJ / hr

Heat balance

First evaporator:

The heat input (supply) + heat input from steam = heat

transported by steam + energy from

background product

The heat input (supply) + S1? S1 = E1HE1 + energy of the product

in the background

1.537 x 10^7 + S1 x 2123.2 = 12.593 x 2,614.97 + 1.17 x 10^7

13.781 kg / h

Second evaporator:

Heat input (supply) + heat input from steam = heat

transported by water vapor + energy of the

background product
The heat input (supply) + S2? S2 = E2HE2 + product energy
in the background

1.17 x 10^7 + S2 x 2123.2 = 5300 x 2545.7 + 1065.8 x 96.84 x 27

S2 = 2157 kg / h

5.7 prilling TORRE [5]

Fig equilibrium 5.7 Energy through granulation tower

The heat input = 1065.8 x 96.84 x 27 = 0.279 x 107 kJ / hr

Output current

Specific heat of the material at [30 °C] mole fractions (x) Flow

(Kmol / hr)

Urea 0.3758 cal / g ° C = 94.41 kJ / KmoloC 0.96 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.034 36.11

Biuret 133.02 kJ / KmoloC 0.006 6.07

1,063.01

Mixing Cp = ? xiCpi

Thus, Cp = 0.96 x 94.41 x 75.37 + 0.034 + 0.006 x 133.02 Kj / KmoloC

93.99 kJ / KmoloC

Heat output = 1,063.01 x 93.99 x 25

= 0.250 x 107 kJ / hr

Assuming, the humidity of the air at 25 °C = 0.01

Heat brought in by the air intake = heat - heat production

(? MCP t) dry air = (,279-0,250) x 107

m = 0.029 x 107 x /(1.009 1)

m = 28.74,133 kg / h

Thus, the air rate = 28,74,133 kg/h of flow

Chapter 6
The design of the team:

Reactor and evaporator design

DESIGN OF EQUIPMENT

6.1 REACTOR DESIGN [7]

Figure 6.1.1 Urea reactor

From fig-6.1.2, for NH3 to the CO2 ratio of 2 corresponding yield of the
urea is 50%. From gura

6.1.3, the 50% performance of urea has a residence time of 40

min.

t = 40 min

Figure 6.1.2 Performance graph % of urea molar ratio of NH3 Vs CO2

Figure 6.1.3 Performance% graph of urea vs residence time.

Now, t = V / F (Ref: Chemistry design-Peter reactor Harriott, Pg-90)

Where, t = residence time

Flow rate F = volumetric in the reactor in m3 / hr.

V = Volume of the reactor in m3.

Now,

Density of the liquid NH3 = 618 Kg / m3 (Ref: JH Perry)

Density of CO2 gas at 40 °C = 277.38 Kg / m3 (density = PM / RT, p = 162

atm, T = 313 K

Density of carbamate = 1600 Kg / m3 (Ref: http://www.inorganics.basf.com

Thus, NH3 flowing in the reactor = 36.968 / 618 = 59.82 m3 / hr

CO2 flowing in the reactor = 47842 / 277.38 = 172.478 m3 / hr

Carbamate flowing in the reactor = 95.337 / 1.600 = 59.59 m3 / hr

Total flow in the reactor = 59.82 + 172.478 + 59.59

291.89 m3 / hr

Since, t = V / F

Therefore, V = T x F
=(40 x 291.89) / 60

V = 194.59 m3

For the design purpose V = 195 m3

Now, the volume of the reactor = (? D2 / 4) L = 195 [D = 2.5 m (given)]

(Ref: Design Team-Brownell &Young; Pg-80)

o, L = 195 x 4 / (3.14 x 2.52)

39.75 m

o, L = 40 m

6.1.1 SHELL THICKNESS [8]

Available data:

The temperature inside the reactor = 180 °C

The pressure inside the reactor = 154 atm

Construction materials:

Low alloy carbon steel (Ref: Fertilizers Factories - ME Pozin)

Material specifications:

IS: 2002-1962 Grade 2B (Ref: BC Bhattacharya, Ping-A1, Pg-261)

1.18 x 10^8 N / m2

Reactor diameter = 2.5 m

(Ref: Fertilizers Factories - ME Pozin, Pg-263, because plants have the

capacity of 450,000

tons / year

Now, the volume of the reactor = (? D2 / 4) L = 195

(Ref: Design Team-Brownell & Young; Pg-80)

o, L = 195 x 4 / (3.14 x 2.52)

39.75 m

o, L = 40 m
Also, L / D = 40 / 2.5 = 16 which is consistent with the actual relationship that is
between 14 to

20.

Now,

t = PDI / (2fj - p) [Ref: Design team - MV Joshi, Pg-96]

where, t = thickness of the shell

Di = inner diameter

J = joint efficiency

p = design pressure

f = allowable effort

154 atm = 1.56 x 10^7 N/m²

The design pressure p = (10% additional)

= 1.1 x 1.56 x 10^7 N / m2

1.716 x 10^7 N / m2

J = 1 [For class 1 pressure vessels, BIS-2825]

f = 1.18

Di = 2.5 m

Thus, t = 1.716 x 10^7 x 2.5 / (2 x 1.18 x 10^8 x 1 to 1.716 x 10^7)

t = 0.196 m

= 196 mm

o, t = 200 mm

6.1.2 DESIGN LEAD [10]

For 2: 1 ellipsoidal distributed head

º = PDV / 2fJ [ref: Design team - MV Joshi, Pg-106, Eq-5.24]

where p = internal design pressure

D = major axis of the ellipse

Factor V = tension intensification = (2 + k2) / 4

k = major axis / minor axis

Thus, º = 1.716 x 10^7 x 2.5 x 1.5 / (2 x 1.18 x 10^8 x 1)

t = 0.273 m

o, t = 273 mm

o, t = 300 mm

6.1.3 diameter of the tubes [11]

We know it,

(Di) opt = 0.0144 x (m`) 0.45 / (?) 0.32

For inlet pipes:

NH3 = 0.0144 x 36968^0.45 / 618^0.32

0.2093 m

8.24 inches

Standardize the use of table-11, PHT, D Q Kern we obtain:

NPS = 10

Programe no. = 60

OD = 10.75 inches

ID = 9.75 inches

(Di) of CO2 = 0.0144 x (47842) 0.45 / (277.38) 0.32

0.3037 m

11.95 inches

Standardize the use of table-11, PHT, D Q Kern we obtain:

NPS = 12

Program no. = 30

OD = 12.75 inches

ID = 12.09 inches

Carbamate = 0.0144 x (95337) 0.45 / (1600) 0.32

0.2364 m

= 9,307 inches

Standardize the use of table-11, PHT, D Q Kern we obtain:

NPS = 10

Program no. = 60

OD = 10.75 inches

ID = 9.75 inches

(Di) output current = 0.0144 x (1,80,147) 0.45 / (1283.97) 0.32

0.3378 m

13.29 inches

Standardize the use of table-11, PHT, D Q Kern we obtain:

NPS = 16

Program no. = 30

OD = 16 inches

ID = 15.25 inches

6.1.4 REACTOR SKIRT SUPPORT [10]

Reactor weight = weight of construction material + weight of contents

of the reactor

=? DTL? + Weight of the reactor contents

=? x 2.5 x 0.2 x 44 x 7,857 + 180,147 [? = 7857 kg / m3]

W = 722 tons

= 7,085 x 107 N

Construction materials:

IS: 2002-1962 Grade 2B (Ref: BC Bhattacharya, Ping-A1, Pg-261)

Allowable tensile effort = 1.18 x 10^8 N / m2

2.55 x 10^8 N/m2

The wind pressure up to = 1300 N / m2

The stress due to dead weight:

fd = W / (? tsk Dok)

where,

Stress

? W = dead weight of the ship

Dok = Outer diameter of the skirt

tsk = thickness of the skirt

7,085 x 107 / (3.14 x 2.5 x tsk)

= 9.025 x 106 / tsk N / m2

Assuming that the height of the skirt = 5 m

fwb = Mw / Z = 4 MW / (? D2

ok tsk) [Ref: equation 13.22, M V Joshi]

Mw = Plw (h1 / 2) + Puw (h1 + h2 / 2)

Plw = kP1h1Do [where k = 0.7]

Puw = kP2h2Do

FWB = 0.7 x 1300 x 20 x 2.5 x (20/2) x 4 / (3.14 x 2.52 x tsk) +

0.7 x 1300 x 20 x 2.5 x 30 x 4 / (3.14 x 2.52 x tsk)

3.709 x 10^5 / tsk N / m2

Stress due to seismic load:

fsb = (2/3) x CWH / (? Rok tsk) [here C = 0.08]

(2/3) * (0.08 * 7.085 * 107 * 40) / ((3.14 * (2.5 / 2) * tsk)

fsb = 3.85 x 10^7 / tsk N / m²

The maximum tensile stress = fsb - fd

= 3.85 x 10^7 / tsk - 0.9025 x 10^7 / tsk

(Ft) Max = 2.9475 x 10^7 / tsk

Now, the permissible tensile stress = 1.18 x 10^8

N / m2

tsk = 2.9475 x 10^7 / (1.18 x 10^8)

0.2498 mm

The maximum compressive stress: [Ref: Equation 13.29, Pg-326, MV Joshi]

(Fc) Max = 3.85 x 10^7 / tsk + 0.9025 x 10^7 / tsk

(Fc) Max = 4.7525 x 107 / tsk

(Fc) admissible

Y.P

x 2.55 x 10^8 N/m²

o, tsk = 4.7525 x 10^7 / (0.85 x 10^8)

559.1 mm

Thus, the thickness that must be used = 600 mm

6.2 EVAPORATOR DESIGN [5]

Figure 6.2.1 Urea evaporator (long tube vertical evaporator falling film)

Vapor pressure = 0.23 atm

Vapor temperature of space = 63.1 oC

21.9 °C

[Ref: Kirk Othmer, Encyclopedia of Chemical Technology, Vol-21]

Liquid boiling point = 85 °C

For the product stream that comes out of the evaporator first:

Specific heat of the material at [85°C] mole fractions (x) Flow rate

(Kmol / hr)

Urea 0.435cal / g °C = 109.28 kJ / Kmol °C 0.75 1,020.83

Water 1 cal / g ° C = 75.37 kJ / KmoloC 0.245 333.33

Biuret 149 Kj / KmoloC 0.005 6.06

Total=1360.223

Mixing Cp =? xiCpi

Thus, Cp = 0.75 x + 109.28 0.245 x 75.37 + 0.005 x 149 Kj / KmoloC

101.17 kJ / KmoloC

? t MCP = 1360.223 x 101.17 x 85

1.17 x 10^7 kJ / hr

Heat balance

First evaporator:

The heat input (supply) + steam heat input = heat

transported by water vapor + energy of the

background product

The heat input (supply) + S1? S1 = E1HE1 + energy of the product

of background

For steam at 147.165 °C, S1 = 2123.2 kJ/kg

Put the values that we obtain

1.537 x 10^7 + S1 x 2123.2 = 12.593 x 2.614.97 + 1.17 x 10^7

13.781 kg / h

Economía = 12.593 / 13.781 = 0.914

Now,

Value U1 is obtained from fig-6.2.2. At 63.1oC (145.58oF) the value of U1 is

270

Btu / hr.sq.ft.oF. Multiplying this value by 5.6783 gives the value of U1 in W /

m2K.

A1 = S1? S1 / U1? T1

? T1 = application (T?) - BPR1

= 147.165 - 63.1 to 21.9

62.165 °C

Thus, A1 = 13781 x 2123.2 / 1533 x 62.165

307.03 m2

In the same way,

A2 = S2? S2 / U2? T2

? T2 = application (T?) - BPR2

= 147.165 - 23.77- 3.48

119,915 °C

Thus, A2 = 2,157 x 2123.2 / 738 x 119.915

51.75 m2

(Ref: values of U1 and U2 from Perry's manual, 10-35)

Figure 6.2.2 Graph to determine the heat transfer coefficient

6.2.1 DESIGN:

Assuming:

Length = 6 m [Ref: M V Joshi, Pg-220]

ODTube = 1 inch [Table-10, PHT, D Q Kern]

Tube ID = 0.834 inches [14 BWG]

Minimum pitch = 1.25 x OD

= 1.25 x 25 = 31.25 mm [Ref: M V Joshi, Pg-220]

Stop step = 32 mm square step

307.03 m2

Number of tubes (N):

307.03 =? x 0.025 x 6 x N

N = 651,8

o, N = 652

Let OTL = D

Therefore, (? / 4) x D2 = 652 x (0.032) 2

922 cm
Now, ddI = OTL + 2C

0.922 + 0.075 x 2

1.072 m

The D standardization using Table-B4, Pg271, BC Bhattacharya

1100 mm

6.2.2 WALL THICKNESS CALCULATION [10]

Construction materials: Mild steel

Specification: ES 2002-1962 Grade-1 [Ref: BC Bhattacharya, Pg-261, Appendix

A]

fall = 0.93 x 108 N / m2

C = 0 mm

J = 0.85

t = PDDI / (2fj - p) + C [Ref: Design Team - MV Joshi, Pg-96]

where, t = thickness of the shell

inner diameter

J = joint efficiency

pd = design pressure

f = allowable effort

subsidy Corrosion

pd = 1.1 x ps

4.5 ata

pd = 4,854 x 10^5 N / m2

t = (4.854 x 10^5 x 1.1) / (2 x 0.93 x 10^8 x 0.85 up to 4.854 x 10^5)

= 3.3876 mm

Assuming, t std = 5 mm [Ref: PG-269, AC Bhattachrya]

Check this thickness for the critical buckling pressure:

Pc = critical external buckling pressure

Pc = [2.42E / (1-μ2) 3/4] x [(t / Do) 02.05 / {L / DO - 0.45 x (t / Do) 1/2}]

[Ref: M V Joshi, eqn- 5.14, Pg-100]

E = 2 x 10^6 N / cm2 [For mild steel]

μ = 0.30 [Ref: BC Bhattacharya, Pg-269, mesa-A-8]

L=6m

Haga = Di + 2 x t

1.5 + 2 x 0.006

1,512 m

Putting the values into the previous equation of Pc we obtain

Pc = 1.316 Kg / cm2

Taking safety factor = 4

Pall = Pc / 4 = 1.316 / 4 = 0.329 Kg / cm²

What is less than 1 Kg / cm2

Therefore, this thickness is not acceptable.

Once again, having TSTD = 6 mm [Ref: BC Bhattacharya, Pg-269]

We obtain,

Pc = 2.072 Kg / cm2

Pall = 2.072 / 4 = 0.518 Kg / cm2

What is less than 1 Kg / cm2

Therefore, this thickness is also not acceptable.

Once again, having TSTD = 7 mm [Ref: BC Bhattacharya, Pg-269]

We obtain,

Pc = 3.0387 Kg / cm2

Pall = 3.0387 / 4 = 0.75 Kg / cm2

What is less than 1 Kg / cm2

Therefore, this thickness is also not acceptable.

Once again, having TSTD = 8 mm [Ref: BC Bhattacharya, Pg-269]

We obtain,

4,234 Kg / cm2

Pall = 4.234 / 4 = 1.05 Kg / cm2

What is superior to 1 Kg / cm2

Therefore, this thickness is acceptable.

Thus, Tmin = 8 mm

6.2.3 SEPARATOR [10]

Upper head (elliptical head)

For 2: 1 ellipsoidal divided head

Di = 1 m [Ref: Table B-4, Pg-271, B C Bhattachrya]

L = 4 m [Ref:Table B-2, Pg-269, B C Bhattachrya]

º = PDV / 2fJ [ref: Design Team - MV Joshi, Pg-106, Eq-5.24]

where p = internal design pressure

D = major axis of the ellipse graph to determine heat transfer

coefficient

Factor V = tension intensification = (2 + k2) / 4

k = major axis / minor axis

p = 0.23 ata = 0.226 x 10^5 N/m2

j = 0.85

1.6 m

k=2

V = 1.5

By internal pressure:

º = (0.226 x 105 x 1.5 x 1) / (2 x 0.93 x 0.85 x 108)

2.144 x 10^-4 m

0.214 mm
For external pressure:

1 Kg / cm2

Corresponding internal pressure used to calculate TH = 1.67 x Pext

Thus, paint = 1.67 Kg / cm2

Therefore,

º = 4.4 x Rc [3 x (1 - μ2)] x 1/2 (p / 2E) 1/2 [Ref: MV Joshi, eqn- 5.26, Pg-107]

where, p = External pressure design

Radio Rc = Corona for torispherical and hemispherical heads and

equivalent corona radio for the elliptical head.

E = modulus of elasticity

Poisson relationship μ =

Put the values we obtain

º = 0.0061 mm

Thus, TSTD = 5 mm [Ref: B C Bhattacharya, Pg-269]

6.2.4 INFERIOR head design [10]

Assuming a vertex angle of 90 degrees

Because, conical head

D=1m

º = PDV / 2fJCos? [Ref: M V Joshi, Pg-106]

Here,? = The angle of half vertex

Because, internal pressure:

p = 0.226 x 105

º = (0.226 x 105 x 1.5 x 1) / (2 x 0.93 x 108 x 0.85 x 0.707)

= 0.3032 mm

For the external pressure:

p = 1.67 x Pext
1.67 x 1 kg / cm2

Therefore,

º = (1.67 x 10^5 x 1.5 x 1) / (2 x 0.93 x 10^8 x 0.85 x 0.707)

= 2,241 mm

TSTD = 5 mm [Ref: B C Bhattacharya, Pg-269]

Verification of this thickness for the critical buckling pressure:

Pc = [2.42E / (1-μ2) 3/4] x [(t / Do) 02.05 / {L / DO - 0.45 x (t / Do) 1/2}]

[Ref: M V Joshi, eqn- 5.14, Pg-100]

Here, L = D / 2

Put the values we obtain,

Pc = 19.11 kg / cm2

Thus, Pall = Pc / 4

19.11 / 4

4,778 kg / cm2

What is greater than 1 kg/cm2

Therefore, this thickness is acceptable

Therefore, Tmin = 5 mm

Chapter 7

Results and discussion

RESULTS AND DISCUSSION

The capacity of the selected plant is 450,000 tons/year based on

300 days of work. The

The granulation tower product contains 98% urea. Critical review of

all the

manufacturing processes have been presented. Snamprogetti process has been

selected for

the project. The process of ammonia urea stripping Snamprogetti involves a

high NH3 at
CO2 concentration in the reactor, which guarantees high conversion of
carbamate in urea. The highly

an efficient ammonia extraction operation drastically reduces the

recycling of carbamate and

the size of the team in the carbamate decomposition. It differs from technology
Snamprogetti

of the competitors based on the excessive use of ammonia to

prevent corrosion, thus

how to promote the decomposition of untransformed carbamate into urea.

Material and energy balance has been done for each of the equipment.
reactor is

designed and its volume was found to be 195 m3. The length and diameter of the
reactor has

it has been found to be 40 m and 2.5 m respectively. The L / D ratio of the

reactor is found to be

16 which is consistent with the actual plant data. The L / D ratio of the
urea reactor

According to the actual plant data, it is between 14 and 20.

Movie escalated, a long vertical evaporator tube is used for the

urea concentration. The

The length of the heat exchanger was found to be 6 m. The diameter and the
the height of the separator is

1 m and 4 m respectively. 652 number of pipes with an outer diameter of 1

inch, 14 BWG and 6 m long (Area =

307 m2 have been used.

REFERENCES:

1) Shreeve R N. Process Industries. Chemistry, third edition. New York:

McGraw

Company book Hill, 1967

2) Dryden. Outlines of Chemical Technology, 3rd edition. New Delhi: Affiliated

Pulse East Orient Private Limited, 2004

3) Othmer Kirk, Encyclopedia of Chemical Technology, Vol.- 21. New York: John

Wiley & Sons, 2004

4) NFL-Guna (P.F), the data of the plant.

Perry R H. Chemical Engineers Handbook, sixth edition. New York: McGraw

Hill Book Co, 1984

www.basf.com

Fertilizers Manufacturing

Brownell LE & Young E H. Process Equipment Design. New York: John Wiley

& Sons, 1968

9) Bhattacharyya B C. chemical equipment Design, first edition. New

Delhi: CBS, 2003

10) Joshi MV. Equipment Design Process, third edition. New Delhi:
Mcmillan India

Limited, 2001

Transfer Kern D Q. Process Heat.