TECHNOLOGICAL UNIVERSITY OFTHE PHILIPPINES- TAGUIG CAMPUS

Km. 14 East Service Road Western Bicutan, Taguig City

Prduction Of Urea By Ammonium

Carbamate Dehydration
First Draft

Aug 27, 2015

Bryan Jesher S. Dela Cruz

3B1
Ria Rose Fundimera
3B2

Submitted to:
Dr. Emmanuel Ferrer

RESEARCH REPORT OUTLINE / CONTENT

Title Of the Report: Production Of Urea By Ammonium Carbamate Dehydration
Legend : n 1st Accomplished n -2nd Accomplished
i. TABLE of CONTENTS
ii. LIST of FIGURES
a.) Figure 1 : Schematic representation of the ammonia synthesis process
b.) Figure 2 : Detailed plant layout model of process plant used for production of ammonia and
urea from natural gas, along with utilities and treatment sections.
c.) Figure 3 : Percentage Conversion Vs. Temperature Graph For the yield Urea
d.) Figure 4 : Percentage Conversion Vs. Pressure Graph For the yield Urea
e.) Figure 5 : Block Diagram of a Total Recycle CO2 Stripping Urea Process
f.) Figure 6 : Figure 2 Block Diagram of a Total Recycle NH3 Stripping Urea Process
g.) Figure 7 : Block Diagram for Urea Granulation and Prilling Processes.
iii. LIST of TABLES
a.) Table 1 - Composition of the gas stream after each process step (Ammonia Production)
b.) Table 2: Ammonia Specification

i.

Table Of Contents:

1. BACKGROUND
1.1. Significance of the study
1.2. Timeline of Development
1.2.1.
1.2.2.
1.2.3.
1.2.4.

1727 Noticed amount of Urea from Human Urine by Herman Boerhaave

1773 Obtained Crystals from urine assumpted as Urea by HM Rouelle
1778 - Rediscovery of Urea by H.M. Rouelle
1799 Invention of the term Urea by Antoine Franois, comte de Fourcroy and Louis
Nicolas Vauquelin
1.2.5. 1817 Determination of the chemical composition of the pure substance
1.2.6. 1828 - Accidental synthesis of Urea from an inorganic Material by Friedrich Wohler
1.2.7. 1828 - Theory of Vitalism, derived from the discovery of Urea
1.2.8. 1870 Production of Urea by heating ammonium carbamate in a seal vessel
1.2.9. 1922 Standard method developed for the production of Urea by Bosch-Meiser process
1.2.10. 1932 Reaction in the mammalian liver for Urea synthesis by Hans A. Krebs and Kurt
Henseleit
1.2.11. 1950 Urea application as an Osmotic agent for the reduction of brain volume
1.2.12. 1960 Replacement of Urea by Mannitol asthe hypersmolar agent

2. PROPERTIES
2.1. Physical Properties
2.2. Chemical Properties
2.3. Health Hazards
2.3.1. Oral Exposure
2.3.2. Inhalation Exposure
2.3.3. Dermal Exposure
2.3.4. Chronic Effects on Animals
2.3.5. Effect on Reproduction
2.3.6. Carcinogenicity
2.4. Environmental Hazards
3. USES and APPLICATIONS
3.1. Commercial Purposes
3.1.1.
3.1.2.
3.1.3.
3.1.4.
3.1.5.

For Agriculture
Niche
Laboratory Uses
Medical Uses
Pharmaceutical

3.2. Industrial Purposes

3.2.1.
3.2.2.
3.2.3.
3.2.4.

For the Manufacture of Resins for Marine Plywood Production

For Explosives
For Automobile Systems
For separation of racemic mixture

4. DETAILED MANUFACTURING PROCESS or PROCESS OPERATION

4.1. Urea Plant Installation
4.1.1.
4.1.2.

Urea Plant Layout Description

Factors which Influence the Plant Layout

4.2. Step by Step or Stage by Stage Detailed Process Description

4.2.1.
4.2.2.

Urea Process Description

The Variables That Affect The Autoclave Reactions

4.2.2.1. Temperature
4.2.2.2. Pressure
4.2.2.3. Concentration
4.2.2.4. Residence time

4.2.3.

First Process: Production Of Feed For Urea Plant

4.2.3.1. Production Of Ammonia

4.2.3.1.1.
4.2.3.1.2.

Haber Process Schematic Representation (Ammonia Synthesis )

Hydrogen Production
a.) Natural gas in Desulfurizer
b.) Desulfurized Gas in Steam Reformer
4.2.3.1.3. Nitrogen Addition
a.) Air Reformer
4.2.3.1.4. Removal Of Carbon Monoxide
4.2.3.1.5. Water Removal
4.2.3.1.6. Removal Of Carbon Oxides
4.2.3.1.7. Synthesis Of Ammonia
4.2.3.1.8. Material Balance
a.) Material Balance around Desulfurizer
b.) Material Balance around Steam Reformer
c.) Material Balance around Air Reformer
d.) Material Balance around CO2 Stripper
e.) Material Balance around Decompressor
4.2.3.1.9. Energy Balance
a.) Energy Balance around Desulfurizer
b.) Energy Balance around Steam Reformer
c.) Energy Balance around Air Reformer
d.) Energy Balance around CO2 Stripper
e.) Energy Balance around Decompressor
4.2.3.2. Recycling Carbon dioxide from Ammonia Production Plant
4.2.4.

Second Process: Storage and Transfer Equipment

a.) Ammonia
b.) Carbon Dioxide
c.) Conditioning Agent

4.2.5.

Third Process: Urea Synthesis Tower

4.2.5.1. Ammonia and Carbondioxide Reaction

4.2.5.2. Material Balance at Reactor
4.2.5.3. Energy Balance at Reactor
4.2.6. Fourth Process: Stripping
4.2.6.1. Options:
a.) Carbon dioxide Stripping Process
b.) Ammonia Stripping Process
c.) Advance Cost and Energy Saving (ACES ) Process
d.) Isobaric Double Recycle ( IDR ) Process
4.2.6.2. Selection Of the Process
4.2.6.3. Material Balance at Stripper
4.2.6.4. Energy Balance at Stripper

4.2.7. Fifth Process: Decomposition / Purification and Recovery

4.2.7.1. Stages Of Purification and Recovery
a. First Stage: Purification and Recovery Stage at 18 ata Medium Pressure
Decomposer/Separator
b. Second Stage: First Stage: Purification and Recovery Stage at 4.5 ata Low Pressure
Decomposer/Separator
4.2.7.2. Material Balance
a. Material Balance at Medium Pressure Decomposer / separator
b. Material Balance at Low Pressure Decomposer / separator
4.2.7.3. Energy Balance
a. Energy Balance at Medium Pressure Decomposer / separator
b. Energy Balance at Low Pressure Decomposer / separator
4.2.8.

Sixth Process: Urea Concentration

4.2.8.1. Evaporation
4.2.8.2. Material Balance at Vacuum Evaporator
4.2.8.3. Energy Balance at Vaccum Evaporator
4.2.9.

Seventh Process: Final Processing

a.) For Urea Production
1.) Options for final product
1.1. Prilling
1.2. Granulation
2.) Material Balance at Prilling tower
3.) Energy Balance at Prilling tower
b.) For Water Treatment

5. PRODUCT QUALITY MONITORING/ TESTING / CONTROL / ASSURANCE

5.1. Alkalinity
5.2. Biuret Analysis
5.3. Chloride Analysis
5.4. Formaldehyde
5.5. Free Ammonia Content
5.6. Water Analysis (Moisture Content)
5.7. Total Nitrogen Analysis
5.8. pH analysis
5.9. Screening
5.10. Borden Test
6.FUTURE DEVELOPMENTS and RECOMMENDATIONS
7. REFERENCES

I. Background
1.2. Timeline of Development

1727 Notice Urea from Human Urine by Herman Boerhaave

Before Wohler, it was still possible to get hold of urea but it doesn't sound pleasant Herman Boerhaave
purified urea from urine 100 years earlier. Boerhaave, from Leiden in the Netherlands, is best known
now as a physician and the founder of clinical teaching, and at the time he did not consider himself to
be much of a chemist. In fact, he only published his chemistry work because he was forced to when his
students published it on his behalf. He even wrote in his book: 'Nothing was formerly further from my
thoughts than that I should trouble the world with anything in chemistry.'
1773 Obtained Crystals from urine assumpted as Urea by HM Rouelle
French chemist Hilaire Rouelle discovered urea crystals from the urine of several animals, including
humans. Accordingly, he isolated that colorless, odorless, crystalline substance in 1773 by boiling
urine (Myers 2007).
In 1799, French chemists Antoine Franois de Fourcroy (1755-1809) and Louis Nicolas Vauquelin
(1763-1829) named the substance urea (Richet 1988).

1817 Determination of the chemical composition of the pure substance

According to Rosenfeld (2003), even before 1727 Boerhaave already obtained a crystalline residue
from urine by heating, filtering, washing, and evaporating. He called it the native salt of urine.
He noted that it differed from the sea salt (sodium chloride) which is also present in urine. Further,
according to the same author, Rouelles extract was impure and that it was British physicianchemist William Prout (1785-1850) who, in 1817, isolated pure urea from urine.

1828 Accidental synthesis of Urea from aninorganic Material by Friedrich Wohler

1828 Theory of Vitalism, derived from the discovery of Urea

Vitalism
Until the early 19th century, people - including many scientists - believed in a theory called vitalism.
Those who believed in this theory held that life was not subject to the laws of physics and chemistry.
They believed that there was an unknown, even divine principle, that governed living organisms, called
the 'life spark'.
Because of this belief, it was thought that chemicals found in plant and animal bodies - like proteins
and carbohydrates - were completely different from other chemicals like salts, acids and gases.
Therefore, people thought that 'organic' chemicals (because they came from organs) could not be made
artificially, but had to be extracted from living animals. This theory also stopped people from using
inorganic chemicals to treat diseases.

The breakthrough came in 1828. And like many major discoveries in science, it was accidental.
Friedrich Wohler (pictured) was a scientist at the polytechnic school of Berlin, who was then famous as
the discoverer of aluminium. He was trying to make ammonium cyanate by mixing ammonium
chloride with silver cyanate.
AgNCO + NH4Cl NH4NCO + AgCl
But when he examined the resulting crystals closely, the compound he got did not behave like
ammonium cyanate should. The crystals behaved like the ones Hilaire Rouelle had got - urea.
Therefore Wohler came to a radical conclusion, as he wrote in a letter to the famous chemist Berzelius
- I... must tell you that I can make urea without the use of kidneys, either man or dog. Ammonium
cyanate is urea.
In 1870 urea was produced by heating ammonium carbamate in a sealed vessel. This provided the basis
of the current industrial process for its production.

1922 Standard method developed for the production of Urea by Bosch-Meiser process

1932 Reaction in the mammalian liver for Urea synthesis by Hans A. Krebs and Kurt
Henseleit

The basic process, developed in 1922, is also called the BoschMeiser urea process after its
discoverers. The various commercial urea processes are characterized by the conditions under which
urea formation takes place and the way in which unconverted reactants are further processed. The
process consists of two main equilibrium reactions, with incomplete conversion of the reactants.
The first is carbamate formation: The fast exothermic reaction of liquid ammonia with gaseous carbon
dioxide (CO2) at high temperature and pressure to form ammonium carbamate (H2N-COONH4)
2NH3 + CO2

H2N-COONH4

The second is urea conversion: the slower endothermic decomposition of ammonium carbamate into
urea and water:
H2N-COONH4

(NH2)2CO + H2O

In 1828, Friedrich Whler, a German physician and chemist by training, published a paper that
describes the formation of urea, known since 1773 to be a major component of mammalian urine, by
combining cyanic acid and ammonium in vitro. In these experiments the synthesis of an organic
compound from two inorganic molecules was achieved for the first time. These results weakened
significantly the vitalistic hypothesis on the functioning of living cells, although Whler, at that time,
was more interested in the chemical consequences of isomerism than in the philosophical implications
of his finding. However, the chemical synthesis observed by Whler does not represent the reaction
which is employed in the mammalian liver for urea synthesis. The mechanism of this process was

elucidated by the German physician Hans A. Krebs and his medical student Kurt Henseleit in 1932 and
was shown to include the ornithine cycle.

1950 Urea application as an Osmotic agent for the reduction of brain volume
1960s Replacement of Urea by Mannitol asthe hypersmolar agent

Urea was first used as an osmotic agent for the reduction of brain volume in 1950. It was associated
with greater efficacy and consistency than alternatives such as hyperosmolar glucose. Its use became
the standard of clinical practice by 1957, in both the intensive care unit and operating room, to reduce
intracranial pressure and brain bulk and was the first hyperosmolar compound to have widespread use.
However, the prime of urea was rather short lived. Reports of side effects and complications associated
with urea emerged. These included coagulopathy, hemoglobinuria, electrocardiography changes, tissue
necrosis with extravasation, and a significant potential for rebound intracranial hypertension. Mannitol
was introduced in 1961 as a comparable and potentially superior alternative to urea. However,
mannitol was initially purported to be less effective at rapidly reducing intracranial pressure. The
debate over the two compounds continued for a decade until mannitol eventually replaced urea by the
late 1960s and early 1970s as the hyperosmolar agent of choice due to the ease of preparation,
chemical stability, and decreased side effect profile. Although urea is not currently the standard of care
today, its rise and eventual replacement by mannitol played a seminal role in both our understanding of
cerebral edema and the establishment of strategies for its management.
II.

Properties

Chemical Properties
Molecular Formula
Molecular Weight
Melting Point
Density
Boiling point

CH4N2O
60.06 g/mole
133 C
1.335 at room temperature
Decomposes

Physical Properties
Physical state
Appearance
Odor
Solubility in water

Health Hazards
Eye: Causes eye irritation

Crystals
White
Odorless solid
Soluble

Skin: Causes skin irritation

Ingestion: Causes gastrointestinal irritation with nausea, vomiting and diarrhea. May cause cardiac
disturbances, May cause disturbed blood electrolyte balance
Inhalation: Inhalation of dust causes irritation of the nose and throat, coughing and sneezing
Chronic: Prolonged or repeated exposure may cause adverse reproductive effects. Laboratory
experiments have resulted in mutagenic effects. Prolonged exposure or exposure to high concentrations
may cause eye damage
First Aid measures
Eyes: Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the
upper and lower eyelids. Get medical aid.
Skin: Get medical aid. Immediately flush skin with plenty of soap and water for at least 15 minutes
while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion: If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by
mouth to an unconscious person. Get medical aid.
Inhalation: Remove from exposure to fresh air immediately. If not breathing, give artificial
respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician: Treat symptomatically and supportively. Weak acids such as acetic acid and
propionic acid can be used as chemical antidotes, demulcents and stimulants.
Handling and Storage
Handling: Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use
with adequate ventilation. Minimize dust generation and accumulation. Avoid breathing dust, vapor,
mist, or gas. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion
and inhalation.
Storage: Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from
incompatible substances.
Environmental hazards
No environmental hazard assessment was conducted as urea is not a hazardous substance

III.

Uses and Applications

3.1 Commercial Purposes

Fertilizers
The most common application of this compound outside of metabolic functioning is as a type of
fertilizer. Over 90% of the world's production of the substance is done for fertilizer-related products.
When used in this way, it usually takes the form of granules or crystals. These may be manually
distributed by farmers or scattered with the aid of farming equipment. It is also often used in fertilizing
solutions, since it is highly water soluble, and often comes packed within soil and potting mixes.

Fig.1 Urea Fertilizer

Resins and Plastics (Urea Formaldehyde)
This compound is also frequently used as a base product in the manufacture of resins and commercial
adhesives. The nitrogen bonds that it contains tend to be very strong, and can really help strengthen a
number of glues and tapes. Manufacturers often activate these bonds by dissolving the crystals in
formaldehyde. The resulting mixture can be used as an industrial adhesive, as in the production of
cardboard boxes; it also features as an ingredient in many poured plastics. In some cases it could also
be used as a coating for materials like textiles and paper.

Fig. 2 Urea Formaldehyde fused

plugs

Fig. 2.1 Urea Formaldehyde Resin

Powder

Consumer Products
A number of consumer-oriented and cosmetics products also incorporate this substance. Hair
conditioners or tooth-whitening products often use it, for instance, usually as a way to help the product
stay thick in the tube or bottle. Dish soaps sometimes also include it in at least in trace amounts to help
keep emulsified ingredients from separating.
Facial cleaners sometimes incorporate the substance, too, since it can help in hydrating the skin.
Certain makeup products blend it in to help achieve a creamier, glossier finish once applied. Some
cigarette brands have, from time to time, added it as a flavor enhancer. Environmental activists in
many places are often quick to point out that it can be used in an eco-friendly way to reduce fuel
emissions from power plants and diesel engines, too.
Livestock Feed
Urea is sometimes also used in cattle and livestock feed, particularly in the developing world. It is
usually considered to be an effective feed since it contains high concentrations of nitrogen, which can
generally aid animal growth. The relatively cheap price of urea-based products also makes this feed a
popular choice for many farmers. The compound is relatively inexpensive to make and doesnt cost
much to transport, two factors that boost its popularity in many parts of the world. It isnt always the
best choice for a given set of circumstances, but it will work in a great many different ways.

3.2 Industrial Purposes

For the Manufacture of Resins for Marine Plywood Production

Plywood is made of three or more thin layers of wood bonded together with an adhesive. Each layer of
wood, or ply, is usually oriented with its grain running at right angles to the adjacent layer in order to
reduce the shrinkage and improve the strength of the finished piece. Most plywood is pressed into
large, flat sheets used in building construction.
Raw Materials
The outer layers of plywood are known respectively as the face and the back. The face is the surface
that is to be used or seen, while the back remains unused or hidden. The center layer is known as the
core. In plywoods with five or more plies, the inter-mediate layers are known as the crossbands.
Plywood may be made from hardwoods, softwoods, or a combination of the two. Some common
hardwoods include ash, maple, mahogany, oak, and teak. The most common softwood used to make
plywood in the United States is Douglas fir, although several varieties of pine, cedar, spruce, and
redwood are also used.
Composite plywood has a core made of particleboard or solid lumber pieces joined edge to edge. It is
finished with a plywood veneer face and back. Composite plywood is used where very thick sheets are
needed.
The type of adhesive used to bond the layers of wood together depends on the specific application for
the finished plywood. Softwood plywood sheets designed for installation on the exterior of a structure
usually use a phenol-formaldehyde resin as an adhesive because of its excellent strength and resistance
to moisture. Softwood plywood sheets designed for installation on the interior of a structure may use a
blood protein or a soybean protein adhesive, although most softwood interior sheets are now made
with the same phenol-formaldehyde resin used for exterior sheets. Hardwood plywood used for interior
applications and in the construction of furniture usually is made with a urea-formaldehyde resin.
Some applications require plywood sheets that have a thin layer of plastic, metal, or resin-impregnated
paper or fabric bonded to either the face or back (or both) to give the outer surface additional resistance
to moisture and abrasion or to improve its paint-holding properties. Such plywood is called overlaid
plywood and is commonly used in the construction, transportation, and agricultural industries.
Other plywood sheets may be coated with a liquid stain to give the surfaces a finished appearance, or
may be treated with various chemicals to improve the plywood's flame resistance or resistance to
decay.

For explosives
Urea Nitrate

Urea Nitrate is a high explosive produced by combining dissolved urea fertilizer with nitric acid. Urea
nitrate is formed as odorless crystals that are colorless to off-white, although additives and or metal
from the mixing container may alter the compounds appearance. Urea nitrate is used as a secondary
explosive/main charge

Automobile systems
Urea
is
used
in SNCR and SCR reactions
to
reduce
the NOx pollutants in exhaust
gases from combustion from Diesel, dual fuel, and lean-burn natural gas engines. The BlueTecsystem,
for example, injects a water-based urea solution into the exhaust system. The ammonia produced by
the hydrolysis of the urea reacts with the nitrogen oxide emissions and is converted into nitrogen and
water within the catalytic converter. Trucks and cars using these catalytic converters need to carry a
supply of diesel exhaust fluid (DEF, also known as AdBlue), a mixture of urea and water.

IV.

DETAILED MANUFACTURING PROCESS or PROCESS OPERATION

IV.1.

Urea Plant Installation

IV.1.1. Urea Plant Layout Description

Figure 2 : Detailed plant layout model of process plant used for production of ammonia and
urea from natural gas, along with utilities and treatment sections.
A simple plant layout model explains how to design a process plant effectively with all the facilities
required for smooth running of production of desired product, for example to produce ammonia from

natural gas and air and then urea by ammonia and carbon dioxide, a prefect design can be made so that
it operates with high performance and less maintenance with negligible shut downs. Start up of plant
after periodic maintenance should not be much difficult to handle and it should come in line as quickly
as possible with appropriate controlling system.
Coming to the description of plant layout designing a process plant requires enough area so that it can
adjust some of the sections like:

Process unit

Off-sites

Cooling towers

Electrical stations

Effluent treatment plant

Demineralisation plant

Pre-treatment plant

Raw material and product storage facility

Power generator unit

Boiler section

Control room, administration block and canteen

Transport station

Maintenance and workshop section

The above are some of the main section to present in any process plant by default and of course based
on product and chemical reaction mechanism some of other section can be included for example in
case of pharmaceutical product separate quarantine and packing section are included. As per know let
see what are the operation of each section and their role in industry would be. By design a plant layout
before construction of the plant will help to place the section in available are so that plant can operate
economically and obtain profits. During the design some of the factors really help a design engineer to
give his best output.

IV.1.2. Factors which Influence the Plant Layout:

Integration of section
Minimum man and material movements
Smooth running of process
Safe and secured system
Flexibility

IV.2.

Step by Step or Stage by Stage Detailed Process Description:

IV.2.1. Urea Process Description:

The commercial synthesis of urea involves the combination of ammonia and carbon dioxide
at high pressure to form ammonium carbamate which is subsequently dehydrated by the
application of heat to form urea and water.

Reaction 1 is fast and exothermic and essentially goes to completion under the reaction
conditions used industrially. Reaction 2 is slower and endothermic and does not go to completion.
The conversion (on a CO2 basis) is usually in the order of 50-80%. The conversion
increases with increasing temperature and NH3/CO2 ratio and decreases with increasing
H2O/CO2 ratio.
The design of commercial processes has involved the consideration of how to separate the
urea from the other constituents, how to recover excess NH3 and decompose the carbamate
for recycle. Attention was also devoted to developing materials to withstand the corrosive
carbamate solution and to optimise the heat and energy balances. The simplest way to decompose the
carbamate to CO2 and NH3 requires the reactor effluent to be depressurised and heated. The earliest
urea plants operated on a Once Through principle where the off-gases were used as feedstocks for
other products.
Subsequently Partial Recycle techniques were developed to recover and recycle some of
the NH3 and CO2 to the process. It was essential to recover all of the gases for recycle to the
synthesis to optimise raw material utilisation and since recompression was too expensive an
alternative method was developed. This involved cooling the gases and re-combining them to
form carbamate liquor which was pumped back to the synthesis. A series of loops involving
carbamate decomposers at progressively lower pressures and carbamate condensers were

used. This was known as the Total Recycle Process. A basic consequence of recycling the
gases was that the NH3/CO2 molar ratio in the reactor increased thereby increasing the urea
yield.
Significant improvements were subsequently achieved by decomposing the carbamate in
the reactor effluent without reducing the system pressure. This Stripping Process dominated
synthesis technology and provided capital/energy savings. Two commercial stripping systems
were developed, one using CO2 and the other using NH3 as the stripping gases.
Since the base patents on stripping technology have expired, other processes have emerged
which combine the best features of Total Recycle and Stripping Technologies. For convenience
total recycle processes were identified as either conventional or stripping processes.
The urea solution arising from the synthesis/recycle stages of the process is subsequently
concentrated to a urea melt for conversion to a solid prilled or granular product.
Improvements in process technology have concentrated on reducing production costs and
minimising the environmental impact. These included boosting CO2 conversion efficiency,
increasing heat recovery, reducing utilities consumption and recovering residual NH3 and
urea from plant effluents. Simultaneously the size limitation of prills and concern about the
prill tower off-gas effluent were responsible for increased interest in melt granulation processes
and prill tower emission abatement. Some or all of these improvements have been used in
updating existing plants and some plants have added computerised systems for process control.
New urea installations vary in size from 800 to 2,000t.d-1 and typically would be
1,500t.d-1 units.
IV.2.2. The Variables That Affect The Autoclave Reactions

IV.2.2.1.

Temperature

Process temperature (185 oC) favours equilibrium yield at a given pressure

(180
atm). The conversion of ammonium carbamate to urea gradually increases
as the
temperature increases. However, after a particular temperature, depending
upon
the pressure, the conversion suddenly drops with further increase in
temperature.
The pressure corresponding to this temperature which is usually in the
range of
175-185oC, is known as the decomposition pressure which is about 180
atm.
IV.2.2.2.

Pressure

The main reaction is sufficiently slow at atmospheric pressure. However, it

starts

almost instantaneously at pressure of the order of 100 atm and

temperature of 150
oC. There is reduction in volume in the overall reaction and so high pressure
favors the forward reaction. This pressure is selected according to the
temperature
to be maintained & NH3:CO2 ratio.
IV.2.2.3.

Concentration

Higher the concentration of the reactants, higher will be the forward

reaction
according to the law of mass action. CO2 being the limitimg reagent higher
NH3:CO2 ratio favors conversion. Since, dehydration of carbamate results in
urea
production, lesser H2O:CO2 ratio favors conversion. Water intake to the
reactor
should therefore be minimum.
IV.2.2.4.

Residence time

Since, urea reaction is slow and takes about 20 mins to attain equilibrium,
sufficient time is to be provided to get higher conversion. Reactor is
designed to
accommodate this with respect to the other parameters of temperature,
pressure
and concentration.

IV.2.3. First Process: Production Of Feed For Urea Plant

IV.2.3.1.
Production Of Ammonia
IV.2.3.1.1. Haber Process Schematic Representation (Ammonia Synthesis )

IV.2.3.1.2. Hydrogen Production

Hydrogen is produced by the reaction of methane with water. However, before this can be
carried out, all sulfurous compounds must be removed from the natural gas to prevent
catalyst poisoning. These are removed by heating the gas to 400oC and reacting it with zinc
oxide:

Following this, the gas is sent to the primary reformer for steam reforming, where superheated
steam is fed into the reformer with the methane. The gas mixture heated with natural
gas and purge gas to 770oC in the presence of a nickel catalyst. At this temperature the
following equilibrium reactions are driven to the right, converting the methane to hydrogen,
carbon dioxide and small quantities of carbon monoxide:

This gaseous mixture is known as synthesis gas.

IV.2.3.1.3. Nitrogen Addition
The synthesis gas is cooled slightly to 735oC. It then flows to the secondary reformer where
it is mixed with a calculated amount of air. The highly exothermic reaction between oxygen
and methane produces more hydrogen. Important reactions are:

1Air is approximately 78% nitrogen, 21% oxygen and 1% argon with traces of other gases.
In addition, the necessary nitrogen is added in the secondary reformer.
As the catalyst that is used to form the ammonia is pure iron, water, carbon dioxide and
carbon monoxide must be removed from the gas stream to prevent oxidation of the iron. This
is carried out in the next three steps.

IV.2.3.1.4. Removal Of Carbon Monoxide

Here the carbon monoxide is converted to carbon dioxide (which is used later in the synthesis
of urea) in a reaction known as the water gas shift reaction:

This is achieved in two steps. Firstly, the gas stream is passed over a Cr/Fe3O4 catalyst at
360oC and then over a Cu/ZnO/Cr catalyst at 210oC. The same reaction occurs in both steps,
but using the two steps maximizes conversion.

IV.2.3.1.5. Water Removal

The gas mixture is further cooled to 40oC, at which temperature the water condenses out and
is removed.
IV.2.3.1.6. Removal Of Carbon Oxides
The gases are then pumped up through a counter-current of UCARSOL solution (an
MDEA solution, see article). Carbon dioxide is highly soluble in UCARSOL, and more than
99.9% of the CO2 in the mixture dissolves in it. The remaining CO2 (as well as any CO that
was not converted to CO2 in Step 3) is converted to methane (methanation) using a Ni/Al2O3
catalyst at 325oC: 2

The water which is produced in these reactions is removed by condensation at 40oC as above.
The carbon dioxide is stripped from the UCARSOL and used in urea manufacture. The
UCARSOL is cooled and reused for carbon dioxide removal.
IV.2.3.1.7. Synthesis Of Ammonia
The gas mixture is now cooled, compressed and fed into the ammonia synthesis loop (see
Figure 1). A mixture of ammonia and unreacted gases which have already been around the
loop are mixed with the incoming gas stream and cooled to 5oC. The ammonia present is
removed and the unreacted gases heated to 400oC at a pressure of 330 barg and passed over
an iron catalyst. Under these conditions 26% of the hydrogen and nitrogen are converted to
ammonia. The outlet gas from the ammonia converter is cooled from 220oC to 30oC. This
cooling process condenses more the half the ammonia, which is then separated out. The
2These reactions are the reverse of the primary reformer reactions seen in Step 1. Thecatalyst in both
cases

is nickel, illustrating the fact that a catalyst accelerates both the forward and back reactions of an
equilibrium system.
At reforming temperatures (~850oC) the methane is almost completely converted to carbon oxides and
hydrogen as the reaction is endothermic and favoured by the high temperature. However, at the
much lower temperature used for methanation (~325oC), the equilibrium lies to the right and
practically complete conversion of the carbon oxides to methane is obtained.
remaining gas is mixed with more cooled, compressed incoming gas. The reaction occuring
in the ammonia converter is:

The ammonia is rapidly decompressed to 24 barg. At this pressure, impurities such as

methane and hydrogen become gases. The gas mixture above the liquid ammonia (which
also contains significant levels of ammonia) is removed and sent to the ammonia recovery
unit. This is an absorber-stripper system using water as solvent. The remaining gas (purge
gas) is used as fuel for the heating of the primary reformer. The pure ammonia remaining is
mixed with the pure ammonia from the initial condensation above and is ready for use in urea
production, for storage or for direct sale. Ammonia product specifications are given in
Table 2.

Water is not listed among the gases considered because its levels are highly variable. All water is
eliminated
after step 4.
All figures are given in mol % (i.e. the percentage of the total number of moles of gas present that are
due to
this gas).

*The gaseous composition after Step 4 is the same as that after Step 3 as Step 4 is simply the removal
of water.

IV.2.3.1.8. Material Balance

IV.2.3.1.9. Energy Balance
IV.2.3.2.

Recycling Carbon Dioxide from Ammonia Production Plant

4.2.4. Second Process: Storage and Transfer Equipment

DESCRIPTION OF STORAGE AND TRANSFER EQUIPMENT
Liquefied ammonia from production plants is either used directly in downstream plants or transferred
to storage tanks. From these the ammonia can be transferred to road tankers, rail tank cars or ships.
Ammonia is usually stored by using one or other of three methods:
Fully refrigerated storage in large tanks with a typical capacity of 10,000 to 30,000 tonnes (up to
50,000)
Pressurised storage spheres or cylinders up to about 1,700 tonnes
Semi-refrigerated tanks Emissions during normal operation are negligible. Major leaks of ammonia
from storage tanks are almost unknown with most of the leaks which do occur being during transport
or transfer. A well designed, constructed, operated and maintained installation has a very low

probability of an ammonia leak of hazardous proportions. However, even though the residual risk is
small, the effects of a major leak on areas of high population density could be very serious. It is
therefore good practice to build ammonia storage and handling installations at a sufficient distance
from domestic housing, schools, hospitals or any area where substantial numbers of people may
assemble. In some countries there are planning procedures or regulations which control the siting of
ammonia storage installations and similar establishments. Where there are no formal controls, the
siting of ammonia storage facilities should be given serious consideration at the design stage. It is
undesirable for ammonia storage tanks to be sited close to installations where there is a risk of fire or
explosion, since these could increase the possibility of a release of ammonia.
Storage Tanks Anhydrous ammonia is stored in three types of tank as outlined above:
Fully refrigerated at a temperature of about 33C, these tanks are provided with refrigeration
equipment Non-refrigerated tanks in which the ammonia is stored at ambient emperature Semirefrigerated spheres Refrigerated storage is preferred for storage of large quantities of liquid ammonia.
The initial release of ammonia in the case of a line or tank failure is much slower than with pressurized
ammonia. There are several construction types for the storage of refrigerated liquid products. The most
important types are:
Single containment: a single-wall insulated tank, normally with a containment bund around it
Double containment: this type of storage tank has two vertical walls, both of which are designed to
contain the stored amount of liquid and withstand the hydrostatic pressure of the liquid. The roof rests
on the inner wall
Full containment: the two walls of this closed storage tank are also designed to contain the stored
amount of liquid, but in this case the roof rests on the outer wall. The tank must be constructed in
conformity with an agreed code for the construction of pressure vessels or storage tanks and taking
account of its pressure and operating temperature.
The design and materials of construction of the tank should be checked by consulting an appropriate
national, or recognised international, standard. These could make demands on the blast resistance of
storage tanks in some cases. The storage tank must be safeguarded against high pressure and in the
case of refrigerated liquid ammonia also against a pressure below the minimum design pressure.
The ingress of warm ammonia into cold ammonia must be avoided to eliminate risk of excessive
evaporation and the roll-over phenomenon. All storage tanks should be equipped with two
independent level indicators, each having a high level alarm. An automatic cut-off valve, operated by a
very high level alarm instrument, should be installed on the feeding line. In cases of refrigerated liquid
ammonia, storage tanks must be equipped with a recompression installation to liquefy the boil-off.
There should be at least two refrigeration units to allow proper maintenance and to prevent the
emission of ammonia via the relief valves. Furthermore, an installed alternative power supply may be
necessary. An automatic discharge system to a flare may be provided in case of failure of the

refrigeration equipment. The flare must be located at a suitable distance from the tanks. Relief valves
should be provided, appropriate for the duty using an adequate margin between operating and relief
pressure.
Urea (NH2CONH2) is of great importance to the agriculture industry as a nitrogen-rich
fertiliser. In Kapuni, Petrochem manufacture ammonia and then convert the majority of it
into urea. The remainder is sold for industrial use.
Storage and Transfer Equipment in the Plant
a.) Ammonia
NH3 is pumped to the urea plant at 25bar pressure and 27C. It is then supplied to a
high pressure reciprocating pump for discharge to the urea synthesis section of the
plant and the flow is regulated by a speed controller at a discharge pressure of 150200bar depending on the process applied
b.) Carbon Dioxide
CO2 is supplied to the CO2 compressor and discharged at high pressure to the
synthesis section of the urea plant.
c.) Conditioning Agent
An aqueous solution of urea-formaldehyde resin containing 50-60%wt
formaldehyde and 20-25%wt urea is supplied by tanker and off-loaded to a buffer
storage tank. It is injected by pump into the urea melt prior to prilling or
granulation. In some modern urea granulation plants continuous urea-formaldehyde
resin production units are an integral part of the granulation technology.
Feedstocks are aqueous formaldehyde, molten urea and ammonia.
The liquid ammonia coming directly from battery limits is collected in the ammonia receiver tank from
where it is drawn to & compessed at about 23 ata pressure by means of centrifugal pump. Part of this
ammonia is sent to medium pressure absorber & remaining part enters the high pressure synthesis
loop . The NH3 of this synthesis loop is compressed to a pressure of about 240 ata . Before entering the
reactor it is used as a driving fluid in the carbamate ejector, where the carbamate coming from
carbamate separator is compressed upto synthesis pressure . The liquid mixture of ammonia &
carbamate enters the reactor where it reacts with compressed CO2.

4.2.5) Third Process: Urea Synthesis in Synthesis Tower

4.2.5.1) Urea Synthesis

Urea synthesis
Urea is made from ammonia and carbon dioxide. The ammonia and carbon dioxide
are
fed into the reactor at high pressure and temperature, and the urea is formed in a two
step
reaction
2NH3 + CO2 NH2COONH4 (ammonium carbamate)
NH2COONH4H2O + NH2CONH2 (urea)
The urea contains unreacted NH3 and CO2 and ammonium carbamate.
As the pressure is reduced and heat applied the NH2COONH4 decomposes to NH3
and CO2. The ammonia and carbon dioxide are recycled.
The urea solution is then concentrated to give 99.6% w/w molten urea, and
granulated for use as fertiliser and chemical feedstock.
In the reactor the NH3& gaseous CO2 react to form amm. Carbamate , a portion of which
dehydrates to form urea & water . The fraction of carbamate that dehydrates is determined by
the ratios of various reactants , operating temp , the residence time in the reactor & reaction
pressure . The mole ratio of NH3 / CO2 is around 2:1 , the mole ratio of water to CO2 is
around 0.67 : 1 .

In the synthesis conditions ( T= 190C , P= 154 atm) , the 1st reaction occurs rapidly & is
completed . The 2nd reaction occurs slowly & determines the reactor volume . Urea reactor is a
plug flow type with 10 no.s of sieve trays to avoid back mixing & to avoid escape of gaseous
CO2 which must react in the lower part of the reactor . Stagewise decomposition is carried out
to reduce water carry over to the reactor which could adversely affect conversion .

4.2.5.2.) Material Balance at Reactor

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

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

Figure: Material Balance at Reactor in Urea Plant

Table: Flow of Materials across Reactor

INLET STREAM
Material specific heat at 40 C
NH3
0.53 cal/gm C = 2.219 Kj/KgC
CO2
0.22 cal/gm C = 0.9211 Kj/Kg C
specific heat at 180 C
Carbamate 0.62 cal/gm C = 2.596 Kj/Kg C
Heat input
mCpt
NH3 :
CO2 :
Carbamate:

3.6968 x 104 x 2.219 x 40 = 0.328 x 107 Kj/hr

4.7843 x 104 x 0.9211 x 40=0.176 x 107 Kj/hr
9.5336 x 104 x 2.24 x 180= 4.455 x 107 Kj/hr

Heat input = 4.959 x 107 Kj/hr

OUTLET STREAM
Material
specific heat at 180oC
NH3
0.55 cal/gm oC
CO2
0.23 cal/gm oC
Carbamate
0.62 cal/gm oC
Urea
0.4828 cal/gm oC
Water
1 cal/gm oC
Biuret 183.8 Kj/KmoloC 0.002 6.07
Total = 3,451.3

mol fractions (x)

Flow rate
(Kmol/hr)
39.15 Kj/KmoloC 0.033 114.76
42.37 Kj/Kmol oC0.0158 54.36
202.49 Kj/KmoloC 0.354 1222.3
121.32 Kj/KmoloC0.296 1020.83
75.37 Kj/KmoloC 0.299 1032.94

4.2.5.3. Energy Balance at Reactor

Figure: Energy Balance at Reactor in Urea Plant

4.2.6) Fourth Process: Stripping

4.2.6.1. Options
a.) Carbon dioxide Stripping Process

NH3 and CO2 are converted to urea via ammonium carbamate at a pressure of
approximately 140bar and a temperature of 180-185C. The molar NH3 /CO2
ratio applied in the reactor is 2.95. This results in a CO2 conversion of about
60% and an NH3 conversion of 41%. The reactor effluent, containing
unconverted NH3 and CO2 is subjected to a stripping operation at essentially
reactor pressure, using CO2 as stripping agent. The stripped-off NH3and CO2
are then partially condensed and recycled to the reactor. The heat evolving from
this condensation is used to produce 4.5bar steam some of which can be used for
heating purposes in the downstream sections of the plant. Surplus 4.5bar steam
is sent to the turbine of the CO2 compressor.The NH3 and CO2 in the stripper
effluent are vaporised in a 4bar decomposition stage and subsequently
condensed to form a carbamate solution, which is recycled to the 140bar
synthesis section. Further concentration of the urea solution leaving the 4bar
decomposition stage takes place in the evaporation section, where a 99.7% urea
melt is produced.

Figure: Block
DiagramStripping
of a Total
Recycle CO2 Stripping Urea
b.) Ammonia
Process
Process.

NH3 and CO2 are converted to urea via ammonium carbamate at a

pressure of 150bar and a temperature of 180C. A molar ratio of 3.5 is
used in the reactor giving a CO2 conversion of 65%. The reactor

effluent enters the stripper where a large part of the unconverted

carbamate is decomposed by the stripping action of the excess NH 3.
Residual carbamate
and CO2 are recovered downstream of the stripper in two successive
stages operating at 17 and 3.5bar respectively. NH3 and CO2 vapours
from the stripper top are mixed with the recovered carbamate solution
from the High Pressure (HP)/Low Pressure (LP) sections, condensed in
the HP carbamate condenser and fed to the reactor. The heat of
condensation is used to produce LP steam.The urea solution leaving the
LP decomposition stage is concentrated in the evaporation section to a
urea melt.

Figure: Block Diagram of a Total Recycle NH3 Stripping Urea

Process.
c.) Advance Cost and Energy Saving (ACES ) Process

In this process the synthesis section operates at 175bar with an NH 3 /

CO2 molar ratio of 4
and a temperature of 185 to 190C.13. The reactor effluent is stripped
at essentially reactor pressure using CO 2 as the stripping agent. The
overhead gas mixture from the stripper is fed to two carbamate
condensers in parallel where the gases are condensed and recycled
under gravity to the reactor along with absorbent solutions from the HP
scrubber and absorber. The heat generated in the first carbamate
condenser is used to generate 5bar steam and the heat formed in the
second condenser is used to heat the solution leaving the stripper
bottom after pressure reduction.The inerts in the synthesis section are
purged to the scrubber from the reactor top for recovery and recycle of
NH3 and CO2 . The urea solution leaving the bottom of the stripper is
further purified in HP and LP decomposers operating at approx. 17.5bar
and 2.5bar respectively. The separated NH3 and CO2 are recovered to
the synthesis via HP and LP absorbers. The aqueous urea solution is
first concentrated to 88.7%wt in a vacuum concentrator and then to the
required concentration for prilling or granulating.

d.) Isobaric Double Recycle ( IDR ) Process

In this process the urea synthesis takes place at 180-200bar and 185190C. The NH3 / CO2 ratio is approximately 3.5-4, giving about 70%
CO2 conversion per pass. Most of the unconverted material in the urea
solution leaving the reactor is separated by heating and stripping at
synthesis pressure using two strippers, heated by 25bar steam, arranged
in series. In the first stripper, carbamate is decomposed/stripped by
ammonia and the remaining ammonia is removed in the second stripper
using carbon dioxides as stripping agent.
Whereas all the carbon dioxide is fed to the plant through the second
stripper, only 40%
of the ammonia is fed to the first stripper. The remainder goes directly
to the reactor for temperature control. The ammonia-rich vapours from
the first stripper are fed directly to the urea reactor. The carbon dioxide
rich vapours from the second stripper are recycled to the reactor via the
carbamate condenser, irrigated with carbamate solution recycled from
the lower-pressure section of the plant.

The heat of condensation is recovered as 7bar steam which is used

down-stream in the
process. Urea solution leaving the IDR loop contains unconverted
ammonia, carbon dioxide and carbamate. These residuals are decomposed and vaporised in
two successive distillers, heated with low pressure recovered steam. After this, the
vapours are condensed to
carbamate solution and recycled to the synthesis loop.
The urea solution leaving the LP decomposition for further
concentration, is fed to two
vacuum evaporators in series, producing the urea melt for prilling and
granulation.
4.2.6.2. Selection Of the Process
Snamprogetti ammonia-stripping urea process is selected because it involves a high
NH3 to CO2 ratio in the reactor, ensuring the high conversion of carbamate to urea .
The highly efficient ammonia stripping operation drastically reduces the recycling
of carbamate and the size of equipment in the carbamate decomposition .
Snamprogetti technology differs from competitors in being based on the use of
excess ammonia to avoid corrosion as well as promote the decomposition of
unconverted carbamate into urea. Formation of urea from ammonia & carbon di
oxide takes place through
reversible reactions with formation of ammonium Carbamate as intermediateproduct
. Now, success of any urea mfg process depends on how economically we can
recycle carbamate to the reactor. Snamprogetti process of urea mnufacturing
accomplishes the above task by stripping process.

This reaction involves increase in volume & absorption of heat . Thus this reaction
will be favored by decrease in pressure & increase in temp . Moreover decreasing
the partial pressure of either of the products will also favor the forward reaction .
Process based on first principle of decrease in pressure & decrease in temp is called
conventional process , whereas process based on increase/decrease of partial
pressures of NH3or CO2 is called stripping process. According to above equation
we have : K= (pNH3)2*(pCO2) [where, K =equilibrium constant]

The stripping is effected at synthesis pressure itself using CO2 or NH3 as stripping
agent . If CO2 is selected , it is to be supplied to the decomposers/stripper as in
Stamicarbon CO2 stripping process. While if NH3 is selected , it is to be obtained
from the system itself because excess NH3 is present in the reactor as in Snams
process. CO2 stripping is advantageous because introducing CO2 increases pCO2.
So pNH3 will be reduced to maintain P constant as P = pCO2+ pNH3.
At a particular temp K is constant so 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 1st stage decomposition
should be in such a way that min water evaporates because the recovered gases go
alongwith the carbamate to reactor again & if water enters reactor producti
on will be affected adversely due to hydrolysis of urea . So , stagewise
decomposition of carbamate
is done . Second consideration in favor of isobaric stripping is that higher carbamate
recycle pressure results in condensation at higher temp & that recovery in the form
of f low pressure steam. This is why stagewise reduction in pressure is practiced.
4.2.6.3. Material Balance at Stripper

Since, no reaction takes place in the stripper & only carbamate gets recycled back to
Figure:
Materialthe
Balance
Urea Plant ,water & biuret in
the reactor.
Therefore,
amountatofStripper
ammoniain
,carbon-di-oxide
the outlet stream of stripper will be same as it was in the inlet stream.

Table: Flow of Materials across Stripper

4.2.6.4. Energy Balance at Stripper

Figure: Energy Balance at Stripper in Urea Plant

4.2.7) Fifth Process: Decomposition / Purification and Recovery

4.2.7.1. Stages Of Purification
Urea purification takes place in two stages at decreasing pressure as follows :

1st stage at 18 ata pressure, i.e, MP decomposer

2nd stage at 4.5 ata pressure ,i.e, LP decomposer

a.) First Stage:

1st stage purification & recovery stage at 18 ata:
It is falling film type MP decomposer . It is divided into 2 parts : Top separator,
where the released flash gases , the solution enters the tube bundle &
decomposition section where the residual carbamate is decomposed & required
heat is supplied by means of 24 ata steam condensate flowing out of the stripper.
b.) Seond Stage:
2nd purification & recovery stage at 4.5 ata:
The solution leaving the bottom of MP decomposer is expanded at 4.5 ata
pressure& enters the LP decomposer (falling film type). This is again divided
into two parts : top separator where the released flash gases are removed before
the solution enters the tube bundle . Decomposition section where the last
residual carbamate is decomposed & the required heat is supplied by means of
steam saturated at 4.5 ata.
4.2.7.2. Material Balance

a.) Material Balance at Medium Pressure Decomposer

The amount of ammonia ,carbon-di-oxide ,water & biuret will remain constant as no
reaction is taking place. 50 % of ammonia & carbon-di-oxide are assumed to escape
from the top of the separator & rest goes with the bottom product. Amount of water &
biuret remains constant as no reaction takes place.

c.) Material Balane at Low Pressure Decomposer

Remaining ammonia & carbon-di-oxide are assumed to escape from the top.

4.2.7.3. Energy Balance

a.) Energy Balance at Medium Pressure Decomposer

b.) Energy Balane at Low Pressure Decomposer

Heat input = 2.921 x 107 Kj/hr

4.2.8) Sixth Process: Urea Concentration

4.2.8.1. Evaporation
Next section is urea concentration & objective is to reduce water content of urea to
as low as 1 % . For the purpose a vacuum concentrator in two stages is provided .
The solution leaving the LP decomposer bottom with about 72% urea is sent to the
1st vacuum concentrator operating at a pressure of 0.23 ata .The mixed phase
coming out enters the gas liquid separator, wherefrom the vapours are extracted by
the 1st vacuum system, while the solution enters the 2nd vacuum concentrator
operating at a pressure of 0.03 ata . The two concentrators are fed by saturated steam
at 4.5 ata . The mixed phase coming out enters the gas liquid separator , wherefrom
the vapours are extracted by the 2nd vacuum system .

4.2.8.2. Material Balance

4.2.8.3. Energy Balance

4.2.9) Seventh Process: Final Processing

4.2.9.1. For UreaProduction:
4.2.9.1.1. Option for Final Product:

In urea fertilizer production operations, the final product is in either prilled or granular form.
Production of either form from urea melt requires the use of a large volume of cooling air
which is subsequently discharged to the atmosphere

Figure: Block diagram for Urea Granullation and Prilling Process

a.) Prilling
The concentrated (99.7%) urea melt is fed to the prilling device (e.g. rotating
bucket/shower type spray head) located at the top of the prilling tower. Liquid
droplets are formed which solidify and cool on free fall through the tower
against a forced or natural up-draft of ambient air. The product is removed from
the tower base to a conveyor belt using a rotating rake, a fluidised bed or a
conical hopper. Cooling to ambient temperature and screening may be used
before the product is finally transferred to storage.The design/operation of the
prilling device exerts a major influence on product size.
Collision of the molten droplets with the tower wall as well as inter-droplet
contact causing agglomeration must be prevented. Normally mean prill
diameters range from 1.6-2.0mm for prilling operations. Conditioning of the
urea melt and crystal seeding of the melt, may be used to enhance the anticaking and mechanical properties of the prilled product during storage/handling.
b.) Granullating
Depending on the process a 95-99.7% urea feedstock is used. The lower feedstock
concentration allows the second step of the evaporation process to be omitted and
also simplifies the process condensate treatment step. The basic principle of the
process involves the spraying of the melt onto recycled seed particles or prills

circulating in the granulator. A slow increase in granule size and drying of the
product takes place simultaneously. Air passing through the granulator solidifies the
melt deposited on the seed material. Processes using low concentration feedstock
require less cooling air since the evaporation of the additional water dissipates part
of the heat which is released when the urea crystallizes from liquid to solid. All the
commercial processes available are characterised by product recycle, and the ratio
of recycled to final product varies between 0.5 and 2.5. Prill granulation or fattening
systems have a very small recycle, typically 2 to 4%. Usually the product leaving
the granulator is cooled and screened prior to transfer to storage. Conditioning of the
urea melt prior to spraying may also be used to enhance the storage/handling
characteristics of the granular product.
4.2.9.1.2. Material Balance

4.2.9.1.3. Energy Balance