CHAPTER III

Flow Diagram of Urea Production Process

Urea is manufactured by reacting ammonia and carbon dioxide in an autoclave to form ammonium
carbamate. The operating temperature is 135oC and 35 atm pressures, the chemical reaction is an
endothermic reaction and so ammonia is maintained in excess to shift the equilibrium towards urea
formation. Urea production is based on two main reactions

Description of flow sheet:

1. Ammonia pumping: Liquid ammonia is pumped from the multistage pump which maintains the
reaction pressure in the vertical stainless steel vessel

2. Carbon dioxide compression: ammonia plant directly boosts the carbon dioxide from the compression
section as it readily forms at the CO2 section of the ammonia production plant.

3. Urea synthesis tower: It is lined with a film of oxides to protect from corrosion. Catalyst bed is placed
on the inner side of the autoclave structure and 180- 200 atm pressure at a temperature about 180-200
degrees centigrade is maintained. Plug flow operation takes places and molten urea is removed from
the top of the tower.

4. Distillation tower and Flash drum: This high-pressure slurry is flashed to 1 atm pressure and distilled
to remove excess ammonia and decomposed ammonia carbamate salts are removed and recycled.

5. Vacuum Evaporator: The solution is fed to vacuum evaporator for concentrating the slurry.

6. Prilling Tower: It is dryer where the molten slurry is passed from the top of the tower into a bucket
which rotates and sprinkles the slurry and air is passed from the bottom. All the moisture is removed as
the urea form into granules during its journey to the bottom of the tower. These granules are sent by
conveyor to the bagging section.

Process Water Treatment:

As already pointed out in the process description, the liquid effluent treatment section consists mainly
of a distillation column to purify the wastewater, a hydrolyser to decompose the small percentage of
urea into ratio NH3and CO2 which are eventually stripped in the lower section of the same column.

The condensed vapors from first and second vacuum systems, containing urea, ammonia and CO2 are
collected in the process condensate tank. In this tank, the carbonate close drain is also fed by the
centrifugal pump and is recycled.A simple description which gives an idea of the urea manufacturing
process with plant layout:
Reactor effluent:

The reactor effluent which consists of a liquid phase along with certain percentage inerts and reactants
in a vapor phase, fed to the H.P. stripper where the first carbamate decomposition occurs. The vapor
phase containing most of the inert gases then flows to the carbamate condenser together with the
carbamate recycle from the medium pressure section. Only before re-injecting the carbamate into the
reactor, the inert gases are separated from the liquid phase-in the carbamate separator and fed to the
MP decomposer.

H.P. Stripper:

It is the falling film type heat exchanger. It contains 2429 tubes with some space above the tubes and
below the tubes. In the above space, a 0.315m height pall rings bed arranged. A sieve tray is fitted above
the packed bed. The tubes are fitted with ferrules have three tangentially drilled distribution holes.
Tubes are made of titanium and shell side fluid is the medium pressure saturated steam.The reaction
product leaving the reactor flow to the steam heated falling film stripper which operates at about 144-
146Kg/cm2 pressure. The liquid from the feed distributor pipe is evenly distributed onto the packed bed
by means of a preheated sieve having 1400 holes. The mixture is heated up as it flows into the vertical
tubes of the falling film exchanger. The CO2 content of the solution is reduced by the stripping action of
the ammonia as it boils out of the solution. The carbamate decomposition heat is supplied by medium
pressure saturated steam, where the latent heat of condensation of saturated steam is taken by
carbamate solution. In the falling film exchanger, the principle advantages are a high rate of heat
transfer, no internal pressure drop, and short time of contactDecomposition is promoted by heating and
stripping CO2 by vaporized excess NH3, under the same pressure level as urea reactor. Stripper used is
falling film type, decomposed and vaporized gases and liquid effluent are therefore in counter-current
contact and CO2 concentration in the liquid is gradually reduced from the top to bottom of the stripper
tube. As NH3 rich gas (CO2lean gas) rises from the lower parts of the tube, then the gas at upper parts of
the tube becomes an NH3 rich gas as compared with the equilibrium composition and the
decomposition reaction in liquid phase corrects the deviation from the equilibrium (the stripping effect).
Decomposition at high pressure requires high temperature which means that much biuret has formed
and the liquid becomes corrosive, but excess ammonia and the use of titanium in the stripper permit
minimizing the problems. The urea solution with part of inerts is coming from the bottom of the stripper
enters into the medium pressure decomposition in urea purification section. The overhead gases from
the top of the stripper mixed with recovered solution from medium pressure absorber and then
pressurized to 180kg/cm2 in H.P. carbamate pumps and preheated in carbamate pre-heater by using
steam condensate flowing to battery limits then this mixture enters tube side of carbamate condenser
where heat of reaction of reaction-1 and condensation of carbamate gases is removed by production of
steam at 3.5 to 4.5 kgf/cm2 on the shell side by vaporization of water. The condensate from the
condenser with few inert gases is entered into the carbamate separator. Carbamate separator is the
cylindrical empty vessel in which separation of carbamate solution from inert gases will take place,
carbamate solution from the bottom of the separator is recycled to the reactor by means of an ejector.
UREA PURIFICATION:

Urea purification takes place in three stages at decreasing pressures as follows: First stage at 18kgf/cm2
Second stage at 4.5kgf/cm2 Third stage at 0.35kgf/cm2 it is pointed out that the exchangers where the
urea purification occurs are called decomposer. The upper part of the medium pressure inert washing
tower consists of three valve trays. Where the inert gases are subjected to a final scrubbing or washing
by means of some absorption water. In this way, the inerts are sent to vent stack practically free from
ammonia.

Prevention of explosion hazard by gases vented to the atmosphere :

CO2 fed to the reactor normally contains a small percentage of H2, CH4 and CO in addition to inerts like
N2 and Ar. These gases plus a few gases introduced into the plant with NH3 coming from B.L together
with CO2 contained in passivation air could give rise to explosively problems when vented into the
atmosphere from MP inerts washing tower. As a matter of fact, this problem is minimized in
Snamprogetti urea plants. Since the quantity of passivation air used is far lower than the one used in
other processes. Thus the O2 to the flammable gases ratio in the vented gases does not justify the use of
an H2 removal system on the CO2 stream from B.

L.P.Decomposer (LPD):

This is also the falling film type heat exchanger. It is also constructed the same as to MP decomposer,
the packed bed height, equipment divisions and construction are the same. The lower the pressure, the
better the prevention of NH3 and CO2 loses from the system, but the recovered solution becomes
weaker. Which means that excess water is recycled to the synthesis loop, the operating conditions of L.P
decomposer are selected at 3.5kgf/cm2 pressure decomposer (falling film type). The gases leaving the
top separator are mixed with the dilute carbon solution coining from wastewater treatment and sent to
the ammonia preheater, where they are practically absorbed and condensed. The ammonia preheater is
the shell and tube (1-4 pass) heat exchanger, in which LPD vapors are condensed and feed NH3 to the
reactor, is heated. While depressurizing (drawing tube side NH3 loop, case must be taken to avoid
freezing of water) solution on the shell side of this preheater. From the above condensate with
uncondensed gases then enter the LP condenser, where the residue absorption and condensation heat
is removed by cooling water. The liquid phase, with remaining inert gases, is sent to the carbonate
solution vessel. The carbonate solution tank is a horizontal cylindrical vessel. It is constructed with inerts
washing tower above the tank and is located slightly taper to the ground to maintain the solution head
for pumps at a low level also. In shutdown followed by emptying of high-pressure equipment, the
recovered NH3, CO2 in the low-pressure stage is also stored in their tank. The level of this tank should
be maintained low in order to recover all carbonate in case of a shutdown. The inert gases leaving from
carbonate solution tank enters into low-pressure inerts washing tower which is located on the tank with
the packed bed. The inerts are washed in this tower by using water in the countercurrent flow. The
inerts which are leaving from the washing tower are vented to stack, which is practically free from NH3.
Purification and recovery stage at 0.35kg/cm2:

Vacuum pre-concentrator:

This is also the falling film type heat exchanger. It is also constructed the same as to above decomposers
with bell distributor.The solution leaving (the bottom of low-pressure decomposer is expanded at 0.35
kgf/cm2 pressure and enters the vacuum pre-concentrator) falling film types as with the help of
tangentially inlet duct. 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 and
the required heat is supplied by the condensation of the gases coming from the medium pressure
decomposer separator. The gases leaving the pre-concentrator top are routed to the vacuum duct
where condensation takes place. The urea solution, collected at the bottom of the pre-concentrator
holder is sent to the vacuum section by using the centrifugal pump. The pre-concentrator is able to save
a lot of pressure stream in the evaporator permits to concentrate the urea solution from 70-75% to
about 85-88% wt. Low-pressure section for urea production

UREA CONCENTRATION:

As it is necessary, in order to prill urea, to concentrate the urea solution up to 99.8% wt. The simplest
and most widely used method is direct concentration, which consists of heating the solution under
vacuum to remove water. Direct concentration is operated on the basis of the equilibrium vapor
pressure of the urea solution. Theoretically, to concentrate the solution without the deposit of crystals,
the operating pressure should be kept over 0.3kh/cm2 abs.., 1360C into eh second vacuum system. The
urea solution coming from vacuum pre-concentrator holder is sent to the first vacuum concentrator
where it is heated up to above the boiling point of that liquid at the pressure of separator. The mixed
phase coming out of concentrator enters the gas-liquid separator from where vapors are extracted by
the second vacuum system, while the solution fed to the prilling section by using the centrifugal pump.
Both the 70-72% wt. urea solution from the L.P decomposer and the urea melt from the vacuum
separator can be directed to the urea solution tank, so as to face any emergency situation in both the
vacuum and prilling sections.

UREA PURIFICATION at M.P. Decomposer:

This is falling film type heat exchanger is divided into three parts. Top separator where the released flash
gases are separated, middle decomposer where the carbamate decomposition will take place and
bottom holder where the concentrated urea solution will hold. The decomposer tubes are fitted with
ferrules having four tangentially distribution holes with equispaced. Packing bed of pall ring with 1.3m
height and sieve plate for distribution is provided above the decomposer in the separator. To promote
more decomposition it is necessary to those higher temperatures or to reduce to lower levels. M.P.
Decomposed is operated at 17kgf/cm2 (g) and 156-158OC decomposed heat is being supplied from
outside of tube by M.P. steam and M.P. condensate.The solution with a low residual CO2 content,
leaving the bottom of the stripper is expanded at the pressure of 18kgf/cm2 and enters at the top of the
M.P. decomposer where the released flash gases are removed before solution enters the tube bundle.
 Where the residual carbamate is decomposed and the required heat is supplied by means of
medium pressure saturated steam and medium pressure steam condensate which is coming from the
stripper. Distribution of falling film is obtained by ferrules. After decomposition of carbamate, the
concentrated urea solution with part of inert is collected in the holder and then flows to L.P.
decomposer. The NH3 and CO2 rich gas leaving the top of the separator are sent to vacuum pre-
concentrator, where they are partially absorbed in the aqueous carbonate solution coming from the
urea purification section at 4.5kgf/cm2. The absorption and condensation of gases are removed by
evaporating water from urea solution, thus allowing a considerable saving of L/P/ steam in the
evaporation stages. Then the gases enter the M.P. condenser where the residue absorption and
condensation of the heat of gases are removed by cooling water. In the condenser, CO2 is almost totally
absorbed. The mixture of M.P. condenser flows to the medium pressure absorber.

M.P. Absorber:

It is the bubble cap tray type column contains 4 numbers of trays having bubble cap risers fitted with
bell caps. It contains a sparger pipe distributor at the bottom. The absorber performs CO2 absorption
and NH3 rectification.Reflux NH3 is drawn as part from the NH3 booster pump and fed to the absorber
on the top tray and the aqueous ammonia solution which in coming from M.P.inerts washing tower is
fed on the third tray by means of a centrifugal pump and tray washing provision is also there. Partially
condensed NH3 -CO2-H2O mixture from M.P. condenser enters the bottom of the column, where it is
distributed is carbamate solution by means of sparger pipe distributor. Uncondensed gases consisting of
NH3, CO2, H2O and inerts rising from the bottom are absorbed by cold liquid NH3 reflux in the upper
section of the column. Most of the CO2 and H2O condenses as ammonium carbamate and fall back to
the bottom. Condensation heat is removed by evaporation of ammonia. Thus a stream of inert gases
saturated with NH3 leaving the top of the absorbers rectification section. The bottom solution is
recycled to urea synthesis and high-pressure recovery section by H.P. carbonate pump. Ammonia vapors
with inert gases leaving the top of the column is partially condensed in ammonia condenser by heat
exchange with cooling water and then the liquid and gaseous ammonia phases are returned to ammonia
receiver.

Ammonia Receiver:

It is the horizontal cylindrical vessel fitted with ammonia recovery tower. The tower is installed on the
receiver with a 3m packing bed height of pall rings and contain distribution sieve tray above the packed
bed. The receiver is located slightly tapper to the ground. The ammonia which is received from battery
limits containing 5PPM oil. It causes the foaming in the synthesis section, to avoid this foaming the oil
should be separated from ammonia. In the above receiving tank, the oil will separate by density
separation and comes towards the down end of the tank. This oil will drain periodically.

• The function of this receiver tank is to receive and act as buffer storage for ammonia received from
battery limit.

• To receive ammonia recovered during plant shut down.

The inert gases containing residual ammonia leaving the receiver enters the ammonia recovery tower,
where the pure ammonia coming from B.L. is fed at the top of the tower. In the tower, the inert gases
containing NH3 and pure liquid NH3 are brought in contact with each other in countercurrent flow to
recover some ammonia from inerts. The inert gases containing residual ammonia are sent to the
medium pressure falling film absorber (inert washing tower) where they meet in a counter-current
water flow which absorbs gaseous ammonia. The heat of absorption is removed by cooling water. From
the bottom of the absorber, the water-NH3 solution is recycled back to the medium pressure absorber
by means of a centrifugal pump. Tower operating at a pressure 2.5 kgf/cm2 before entering the
distillation tower the process condensate is preheated in the exchangers where the heating medium is
the purified condensate flowing out the tower.

Since the solution is contaminated by urea, after a first stripping in the upper part of the tower, it is
pumped into the hydrolyser where the urea is decomposed by means of the stream at 37 kgf/cm2,
370oC. Before entering the hydrolyser, the solution is preheated in the exchanger with the solution
coming out from the hydrolyser.

The hydrolysis reaction of urea is the opposite of that occurring in the reactor.

NH2CONH2 + H2O ------->2NH3 + CO2 + Heat

Therefore urea decomposition is favored by high temperature, low pressure and NH3 & CO2 deficiency.
Also, a sufficiently long residence time has proved to be an important parameter. In order to eliminate
NH3 and CO2 as far as possible before feeding the hydrolyser the wastewater coming out from the
vacuum condensers is first stripped in the column. Moreover, a series of baffles in the hydrolyser
provided a plug flow effect, thus avoiding back mixing. Also, the continuous removal of hydrolysis
reaction and this encourages the decomposition of urea. Thevapors leaving the hydrolyser, jointly with
the vapors coming from the distillation tower are condensed in the distillation tower overhead
condenser. Where the condensation heat is removed by cooling water. From this condenser, the
carbonate solution flows to the reflux accumulator from part of the solution fed to the distillation
column by using the pump. The purified waste from the bottom of the distillation tower is cooled.

UREA PRILLING: PRILL TOWER:

It is a cylindrical vertical tower with a height of 100m, in which urea prilling takes place. It consists of
prill section the top and scrapper at the bottom. Prill tower contains bottom lowers (window) and top
lowers (windows) also. In the prill section bucket (Tuttle type) is there. The tower is coated inside with
anti-corrosive plant. This is a natural draft

Prill tower.

The molten urea leaving the second vacuum holder is sent to the prilling bucket by means of a
centrifugal pump. The bucket contains no. of holes to the wall. The urea coming out of the rotating
bucket in the form of drops fall along with the prilling tower and arid encounters cold air flow which
causes its solidification.The molten urea drops coming from bucket contain is at a temperature
of1330C.There will be heat transfer from drops to air, thus reducing the temperature of drops and
increasing the temperature of the air. The heated air tries to go up, due to that flow of air; some vacuum
is created at the glass. The bottom air will try to cover the above vacuum thus creating the natural draft.
The air will enter the prill tower through bottom lowers and vented to the atmosphere through top
lowers.The heated air with a few parts of urea dust enters the scrubbing section where the urea dust
will recover from the air by scrubbing of air with DM water and the free from urea dust is vented to
atmosphere.The molten urea drops from bucket fall down along the prilling tower. Due to the
countercurrent flow of air, the temperature of molten urea will decrease and form as a prill. The solid
prills falling to the bottom of the prilling tower are fed to a belt conveyor by a rotary scraper. From here
they are sent to the automatic weighing machine and to the urea storage, bagging section.

DEDUSTING SYSTEM:

The urea melt coming out of the bucket in the form of droplets and while falling inside the prill tower
encounters a countercurrent flow of cold air causes solidification. Hot air leaving prill tower top consists
of fine urea dust and free ammonia. In order to prevent pollution caused during the process of prilling.
During system has been incorporated at prill tower top. The system also recovers urea, which is recycled
back into the system.

Operation:

In the dedusting tank, air travels in two chambers and a stainless steel partition wall which is hanging
from the top separates these two chambers. The three recirculation pumps take suction deduction
chamber with the help of scrubber nozzles with an angle of 10 deg and due to this spraying action, sir is
sucked into the first chamber (annual scrubbing chamber). Urea gets dissolved while exhaust air
travelling from top to bottom in annular scrubber chamber and then it enters the second chamber of
the dedusting sump, where demister pads are provided at the top. A process condensate pump is
sprayed on demister pads. By nozzles with 90deg.angle, and this system is operated by PLC
(programmable logic control). Before taking DDS in line top louvers are be kept closed. Make up liquid
for the dedusting sump is done by a control valve and after attaining required concentration the
solution is drained to urea lumps dissolving tank. Maximum allowable urea dust to atmospheric air is
3Omg/Nm2 of air. An energy-efficient process for urea synthesis must fulfill the following parameters.

• The high conversion efficiency of CO2 in urea synthesis reactor, in order to minimize the heat required
for decomposition of unconverted carbamate. (Achieved by optimization of parameters in the urea
reactor).

• Efficient decomposition of carbamate and efficient separation of carbamate decomposition products

Ammonia- a compound of nitrogen and hydrogen with the formula NH3. A stable binary hydride, and
the simplest pnictogen hydride, ammonia is a colorless gas with a characteristic pungent smell. It is a
common nitrogenous waste, particularly among aquatic organisms, and it contributes significantly to the
nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers

Bacteria- were among the first life forms to appear on Earth, and are present in most of its habitats.
Bacteria inhabit soil, water, acidic hot springs, radioactive waste, and the deep biosphere of the earth's
crust

Concentration- is the abundance of a constituent divided by the total volume of a mixture. Several types
of mathematical description can be distinguished: mass concentration, molar concentration, number
concentration, and volume concentration

Fertilization - is the fusion of gametes to initiate the development of a new individual organism or
offspring. This cycle of fertilization and development of new individuals is called sexual reproduction.

Fertilizers- is any material of natural or synthetic origin (other than liming materials) that is applied to
soil or to plant tissues to supply one or more plant nutrients essential to the growth of plants. Many
sources of fertilizer exist, both natural and industrially produced.

Greenhouse Gas- a gas that absorbs and emits radiant energy within the thermal infrared range.
Greenhouse gases cause the greenhouse effect. The primary greenhouse gases in Earth's atmosphere
are water vapor, carbon dioxide, methane, nitrous oxide and ozone.

Haber Process- is an artificial nitrogen fixation process and is the main industrial procedure for the
production of ammonia today. It is named after its inventors, the German chemists Fritz Haber and Carl
Bosch, who developed it in the first decade of the 20th century.

Synthesis- is the act of combining elements to form something new. If you describe your bedroom
decor as a synthesis of vintage and punk, we'll know you mean a mixture of these two styles.

Prilling - is a process in which amelted substance is sprayed against upward-flowing air in a tower to
form solid particles.

Purification- to make pure; free from anything that debases, pollutes, adulterates, or contaminates: to
purify metals.

Water Treatment- is any process that improves the quality of water to make it more acceptable for a
specific end-use. The end use may be drinking, industrial water supply, irrigation, river flow
maintenance, water recreation or many other uses, including being safely returned to the environment.