urea is manufactured by reacting ammonia and carbon dioxide in

8
Urea is manufactured by reacting ammonia and carbon dioxide in autoclave to form ammonium carbamate. The operating temperature is 135 0 C and 35 atm pressure, the chemical reaction is endothermic reaction and so ammonia is maintained in excess to shift the equilibrium towards urea formation. Urea production consists of main two re actions. 1. Formation of ammonium carbamate 2. Dehydration of ammonium carbamate to pr oduce molten urea Urea Production from NH 3 and CO 2 Description of flow sheet: 1. Ammonia pumping : Liquid ammonia is pumped from the multistage pump which maintain the reaction pressure in the vertical stainless steel vessel 2. Carbon dioxide compression:ammonia plant directly boost the carbon dioxide from the compression section as it readily form at the CO 2 section of ammonia production plant. 3. Urea synthesis tower: It is lined with film of oxides to protect form corrosion. Catalyst bed is placed in the inner side of the autoclave structure and 180- 200 atm pressure at temperature about 180-200 deg centigrade is maintained. Plug flow operation take 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 carbamated 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 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 it journey to the bottom of the tower. This gra nules are sent by conveyor to t he bagging section.

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Page 1: Urea is Manufactured by Reacting Ammonia and Carbon Dioxide In

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Urea is manufactured by reacting ammonia and carbon dioxide in autoclave to form ammonium

carbamate. The operating temperature is 1350C and 35 atm pressure, the chemical reaction is

endothermic reaction and so ammonia is maintained in excess to shift the equilibrium towards urea

formation. Urea production consists of main two reactions.

1. Formation of ammonium carbamate

2. Dehydration of ammonium carbamate to produce molten urea

Urea Production from

NH3 and CO2 

Description of flow sheet:

1. Ammonia pumping : Liquid ammonia is pumped from the multistage pump which maintain the reaction

pressure in the vertical stainless steel vessel

2. Carbon dioxide compression:ammonia plant directly boost the carbon dioxide from the compressionsection as it readily form at the CO2section of ammonia production plant.

3. Urea synthesis tower: It is lined with film of oxides to protect form corrosion. Catalyst bed is placed in

the inner side of the autoclave structure and 180- 200 atm pressure at temperature about 180-200 deg

centigrade is maintained. Plug flow operation take 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 carbamated 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 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 it journey to the bottom of the tower. This granules are sent by conveyor to the

bagging section.

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A simple description which give an idea of the urea manufacturing processwith plant layout: 

Low pressure section for urea production 

REACTOR EFFLUENT:The reactor effluent which consists of a liquid phase along with a certain percentage inerts and reactants

in a vapour phase, fed to the H.P. stripperwhere the first carbamate decomposition occurs. The vapour

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 containing 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 with 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 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 high rate of heat transfer,

no internal pressure drop, short time of contact.

Decomposition 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 countercurrent contact and CO2 concentration in 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 mediumpressure 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/cm2in 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 into the carbamate separator. Carbamate separator is the cylindrical

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empty vessel in which separation of carbamate solution from inert gases will take place, carbamate

solution from bottom of separator is recycled to reactor by means of ejector.

The non-condensate gases from the top of the separator consist mainly of inert gases, with a small

amount of NH3 and CO2 are passed through the split range controller to the medium pressure

decomposer holder to utilize the heat of these for that decomposition.

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 IN 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 the small quantity of gases introduced into the plant with NH3 coming from

B.L together with CO2 contained in passivation sir could give rise to explosively problems when vented

into 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 flammable gases ratio in the vented gases does not justify the use of a

H2 removal system on the CO2 stream from B.L

PURIFICATION AND RECOVERY STAGE AT 4.5 kg/cm2:

L.P.Decomposer:

This is also the falling film type heat exchanger. It is also constructed same as to MP decomposer, the

packed bed height, equipment divisions and construction are 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 waste

water 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 vapours are

condensed and feed NH3 to reactor is heated. While depressurizing(drawing tube side NH3 loop, case

must be taken to avoid freezing of water) solution on shell side of this preheater.

From the above condensate wit 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.

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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 low

level also. In shutdown followed by emptying of high pressure equipment, the recovered NH 3, CO2 in 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 shutdown.

The inert gases leaving from carbonate solution tank enters into low pressure inerts washing tower which

is located on the tank with packed bed. The inerts are washed in this tower by using water in the counter

current flow. The inerts which are leaving from the washing tower are vented to stack, which are

practically free from NH3.

PURIFICATION AND RECOVERY STAGE AT 0.35 kgf/cm2

VACUUM PRE CONCENTRATOR:

This is also the falling film type heat exchanger. It is also constructed same as to above decomposers

with bell distributor.

The solution leaving(the bottom of low pressure decomposer is expanded at 0.35 kgf/cm2 a 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 pre-concentrator holder is sent to the vacuum section

by using centrifugal pump. The pre-concentrator is able to save a lot of pressure stream in the evaporatorpermits to concentrate the urea solution from 70-75% to about 85-88% wt.

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 in heating the solution under

vacuum to remove water. Direct concentration is operated on the basis of the equilibrium vapour 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.., 136

0

C int eh second vacuum system.The urea solution coming from vacuumpre-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 vapours are extracted by the second vacuum system, while the solution

fed to the prilling section by using 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.

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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 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 centrifugal

pump. Bucket contains no. of holes to the wall. The urea coming out of the rotating bucket in the form of

drops fall along the prilling tower and arid encounters cold air flow which causes its solidification.

The molten urea drops coming from bucket contains 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 air. The heated air try 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 air by scrubbing of air with DM water and the free from urea dust is vented to atmosphere.

The molten urea drops from bucket falls down along the prilling tower. Due to the counter current 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 scrapper. From here they are sent to the automatic

weighing machine and to the urea storage, bagging section.

Biuret Formation:

Two moles of urea are converted into one mole of biuret and one mole of NH 3 by hetaing.

2 NH2CONH2-------------> NH2CONHCONH2 + NH3 Because the biuret is injurious to germinating seeds, and pine apple and citrus trees wither when the

fertilizer is sprayed on the leaf. The biuret content in fertilizer grade urea on the world market is required

to be below 1.0%. biuret forms almost everywhere in urea production steps.

The following conditions are favorable for biuret formation.

• High residence times. 

• High temperature. 

• Low amount of water. 

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 waste water, a hydrolyserto 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 CO 2 are

collected in the process condensate tank. In this tank the carbonate close drain is also fed by the

centrifugal pump and are recycled .

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

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holder where the concentrated urea solution will holding. 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 separator. To promote more

decomposition it is necessary to that 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.

Urea medium pressure

section flow sheet 

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 areremoved 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 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 heat of gases is removed by

cooling water. In the condenser CO2 is almost totally absorbed. The mixture from 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 sparger pipe distributor at bottom. The absorber perform CO2 absorption and

NH3 rectification.

Reflux NH3 is drawn as part from the NH3 booster pump and fed to the absorber on 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 centrifugal pump and tray washing provision is also there.

Image of medium pressure 

section of urea production 

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

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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 CO2and 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 vapours with inert

gases leaving the top of column is partially condensed in ammonia condenser by heat exchange withcooling 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 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

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 a buffer storage for ammonia received from

battery limit.

• To receive ammonia recovered during plant shut down. 

• To receive ammonia condensed in the recovery system.  

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 a counter current 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. Theheat of absorption is removed by cooling water. From the bottom of the absorber water-NH3solution is

recycled back to the medium pressure absorber by means of 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 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 sufficient 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 waste water 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.

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Urea High

Pressure section 

The vapours leaving the hydrolyser, jointly with the vapours 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 pump. The purified waste from the bottom of distillation

tower is cooled.

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 consistsof 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 dedusting tank air travels in two chambers and a stainless steel partition wall which is hanging fro 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 traveling from top to

bottom in annular scrubber chamber and then it enters the second chamber of dedusting sump, where

demister pads are provided at the top. 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 dedsuting 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.

• 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(CO2 and NH3 ), as well as of excess ammonia .(Optimization of process parameters in the

stripper and decomposer)

• Maximum recovery and efficient utilization of heat formed by absorption and reaction of NH 3 and

CO2 released from the stripper and decomposition. (Optimization of process parameters in the carbamatecondenser ,the MP decomposes and MP absorber).