Contents

CHAPTER 01:
Introduction
Summary..................................................................................................................................7
1.1 Background of fertilizer......................................................................................................7
1.2. Properties of Urea..............................................................................................................8
1.2.2. Stability and Reactivity...................................................................................................9
1.2.3. Ecological Information.................................................................................................10
1.3 Raw material resources.....................................................................................................10
1.4 Disposal Considerations....................................................................................................11
1.5 Transport Information.......................................................................................................11
1.6 Advantages of Fertilizer Urea...........................................................................................11
1.7 Uses of Urea.....................................................................................................................11
1.8 Product and Consumption.................................................................................................13
1.9 Urea production in Pakistan..............................................................................................14
Reference................................................................................................................................16
CHAPTER 02
Process Selection
2.1 Types of process for the manufacturing of UREA............................................................17
2.1.1. Once through urea process...........................................................................................17
2.1.2. Partial Recycle Urea Process........................................................................................18
2.1.3. Internal Carbamate Total Recycle Urea Process:..........................................................19
2.1.3.1. Stamicarbon Process (Carbon Dioxide Stripping)......................................................20
2.1.3.2. Snamprogetti Process (Ammonia Stripping)..............................................................21
2.1.3.4 ACES process.............................................................................................................23
2.1.4. Manufacturing process of process selected..................................................................26
2.1.5. Urea synthesis..............................................................................................................26
2.1.5.1 Effect of various parameters.......................................................................................27
2.2. Selection of process........................................................................................................28
2.3. Process description..........................................................................................................29
2.3.1. Synthesis and high pressure (hp) recovery....................................................................29
2.3.2 Medium pressure (MP) purification and recovery..........................................................30
2.3.3 Low pressure (LP) purification and recovery.................................................................31
2.3.4 Vacuum concentration...................................................................................................31
2.3.5 Process condensate treatment.........................................................................................31
2.3.6. Prilling..........................................................................................................................32
2.4. Block Diagram Of Snamprogetti Process.........................................................................33
2.5 Process flow diagram........................................................................................................34
References..............................................................................................................................35
CHAPTER 03:
Material and Energy balance
3.1 Material balance................................................................................................................36
3.1.1. Reactor..........................................................................................................................37
3.1.2. Stripper.........................................................................................................................38
3.1.3. Medium pressure separator...........................................................................................39
3.1.4. Low Pressure Separator................................................................................................39
3.1.5. Vacuum evaporator.......................................................................................................40
3.1.6. Prilling tower................................................................................................................40
3.2 Energy balance..................................................................................................................41
3.2.1. Energy Balance across Reactor.....................................................................................41
3.2.3. Carbamate Condenser...................................................................................................42
3.2.4. Medium Pressure Separator..........................................................................................44
3.2.5. Low Pressure Separator................................................................................................45
3.2.6. Evaporator.....................................................................................................................46
3.2.7. Prilling Tower..............................................................................................................47
CHAPTER NO.4:
EQUIPMENT DESIGN
4.1 Reactor..............................................................................................................................49
4.1.1 Thickness of Shell..........................................................................................................50
4.1.2 Head Design...................................................................................................................51
4.1.3 Diameter of Pipes...........................................................................................................51
4.2 Evaporator Design............................................................................................................52
4.2.1Design Assuming............................................................................................................55
4.2.2 Wall Thickness Calculation...........................................................................................56
4.2 Prilling Tower...................................................................................................................57
4.3 Ammonia Feed Pump.......................................................................................................58
4.4 Waste water distillation tower C-2....................................................................................60
4.5 Distillation Tower Reboiler E-16......................................................................................60
4.6 Distillation Tower Overhead Condenser E-17..................................................................61
4.7 Distillation Tower Preheater E-18.....................................................................................61
4.8 Hydrolizer Preheater E-19................................................................................................61
4.9 Process Condensate Cooler E-20......................................................................................62
4.10 Hydrolizer R-2................................................................................................................62
4.11 Reflux Accumulator V-8.................................................................................................62
4.12 Distillation Tower Reflux Pump P-15A/B......................................................................62
4.13 Hydrolizer Feed Pump P-16A/B.....................................................................................63
4.14 Carbonate Closed Drain Tank T-4..................................................................................63
4.15 Closed Drain Recovery Pump P-18A/B..........................................................................63
Chapter no.5:
Instruementation
Instrument...............................................................................................................................64
5.1 Instruments and Control Objectives..................................................................................64
5.2.1 Safe Plant Operation......................................................................................................64
5.2.2 Production Rate..............................................................................................................64
5.2.3 Product Quantity............................................................................................................64
5.3 Typical Control Systems...................................................................................................65
5.3.1 Level Control.................................................................................................................65
5.3.1 Pressure Control.............................................................................................................65
5.3.2 Flow Control..................................................................................................................65
5.3 P&ID of Stripper..............................................................................................................66
5.4 P&ID of Condenser..........................................................................................................66
5.5 P&ID of Reactor...............................................................................................................67
5.6 P&ID of Compressor........................................................................................................68
5.7 Process control and Instrumentation Diagram...................................................................69
5.8 P&ID for Urea Reactor after HAZOP...............................................................................69
5.9 Control process.................................................................................................................71
5.10 Start - up Procedure........................................................................................................72
5.11 Normal Shut Down.........................................................................................................73
5.12 Emergency Shut down................................................................................................73
5.13 List of alarms & their settings.........................................................................................74
Reference:...............................................................................................................................75
CHAPTER NO.6:
COST ESTIMATION
6.1 Cost Estimation.................................................................................................................76
6.2 Direct Cost........................................................................................................................76
6.3 Indirect cost......................................................................................................................76
6.2.1 Costs usually allocated indirectly...................................................................................77
6.3 Index.................................................................................................................................77
6.4 Fixed Capital Investment..................................................................................................77
6.5 Working Capital................................................................................................................77
6.6 Depreciation......................................................................................................................78
6.7 Internal Rate of Return (IRR)...........................................................................................78
6.8 Payback Period.................................................................................................................78
6.9 Cost Estimation.................................................................................................................78
6.10 Equipment List................................................................................................................79
6.11 Direct Cost......................................................................................................................80
6.12 Indirect Cost....................................................................................................................81
Reference:...............................................................................................................................84
CHAPTER NO.7:
ENVIRONMENT, HAZOP STUDY AND SITE SELECTION
7.1 Site Selection....................................................................................................................85
7.2 Site Characteristics...........................................................................................................86
7.3 Safety and Environmental Measures.................................................................................86
7.4 Site Selection for Project...................................................................................................87
7.5 Plant Layout......................................................................................................................88
7.6 Importance........................................................................................................................89
7.7 Safety of Urea Plant..........................................................................................................90
7.7.1 Safety Factors Relevant To Urea...................................................................................90
7.8 Hazard identification.........................................................................................................90
7.9 First Aid (Emergency procedure)......................................................................................91
7.10 Handling and Storage......................................................................................................92
7.10.1 Safe Handling..............................................................................................................92
7.11 Exposure Controls & Personal Protection.......................................................................92
7.12 Engineering Controls Ventilation....................................................................................93
7.13 Environmental Impact Assessment (EIA).......................................................................93
7.14 EIA Objective.................................................................................................................93
7.15 Environmental Impact of Urea Plant...............................................................................93
7.16 Urea Plant Effluent.........................................................................................................94
7.17 Air Quality and Emissions..............................................................................................94
7.18 Water..............................................................................................................................94
7.19 Emissions to Air..............................................................................................................94
7.20 Emissions to Water.........................................................................................................94
7.21 Emissions to Land...........................................................................................................95
7.22 Emission Estimation Techniques....................................................................................95
7.23 Pollution Prevention........................................................................................................95
7.23.1 Snamprogetti Urea process..........................................................................................95
7.24 HAZOP Study.................................................................................................................96
7.24.1 Basic Concept..............................................................................................................96
7.24.2 Objective......................................................................................................................97
7.24.3 Key Words...................................................................................................................97
7.24.4 HAZOP Study Methodology........................................................................................98
7.24.5 HAZOP Study Steps...............................................................................................99
7.24.6 HAZOP Study of Different Equipment Heat Exchanger..............................................99
Appendix 1...........................................................................................................................107
References............................................................................................................................110
 List of Figurers
Figurer 1. 1 consumption and production of urea world-wide................................................14
YFigurer 2. 1 once through urea process................................................................................17
Figurer 2. 2 partial recycle process.........................................................................................19
Figurer 2. 3 block diagram of urea synthesis..........................................................................20
Figurer 2. 4 Stamicarbon process for urea production............................................................20
Figurer 2. 5 snamprogetti process for urea production............................................................22
Figurer 2. 6 Toyo koatsu process for urea production.............................................................22
Figurer 2. 7 ACES process for urea production......................................................................24
Figurer 2. 8 block diagram of snamprogetti processblock diagram of snamprogetti process. .33
Figurer 2. 9 Process flow diagram of urea using snamprogetti process...................................34
YFigurer 3. 1 material balance across reactor.........................................................................38
Figurer 3. 2 material balance across stripper...........................................................................38
Figurer 3. 3 material balance across medium pressure separator............................................39
Figurer 3. 4 material balance across low pressure separator...................................................39
Figurer 3. 5 material balance across vacuum evaporator.........................................................40
Figurer 3. 6 material balance across prilling tower.................................................................40
Figurer 3. 7 energy balance across reactor..............................................................................41
Figurer 3. 8 energy balance across carbamate condenser........................................................42
Figurer 3. 9 energy balance across low pressure separator......................................................45
Figurer 3. 10 energy balance across evaporator......................................................................46
Figurer 3. 11 energy balance across prilling tower.................................................................47
YFigurer 4. 1 Reactor.............................................................................................................50
Figurer 4. 2 Energy Balance across Evaporator......................................................................54
YFigurer 7. 1 Site Selection....................................................................................................88
Figurer 7. 2 Plant Layout........................................................................................................90
Figurer 7. 3 HAZOP study of heat exchanger.......................................................................100
Figurer 7. 4 HAZOP Study of Reflux Accumulator..............................................................102
Figurer 7. 5 HAZOP Study of Pump.....................................................................................103
Figurer 7. 6 HAZOP Study of Reactor..................................................................................104
Figurer 7. 7 HAZOP Study of Compressor...........................................................................106
 List of Tables
YTable 1. 1 Chemical properties of urea..................................................................................9
Table 1. 2 Specific heat of urea.................................................................................................9
Table 1. 3 Annual production of urea.....................................................................................14
Table 1. 4 Urea plant in Pakistan............................................................................................15
YTable 2. 1 urea process operating conditions and requirements...........................................25
YTable 4. 1 Evaportor Design................................................................................................52
Table 4. 2 Evaporator..............................................................................................................54
Table 4. 3 Graph to find out heat transfer co-efficient............................................................55
YTable 5. 1 Alarms.................................................................................................................74
YTable 6. 1 Equipment...........................................................................................................80
Table 6. 2 Direct Cost.............................................................................................................81
Table 6. 3 Indirect Cost...........................................................................................................82
YTable 7. 1 Plant Layout.......................................................................................................98
Table 7. 2 HAZOP Study of Different Equipment Heat Exchanger.....................................101
Table 7. 3 Relfux Accumulator............................................................................................102
Table 7. 4 HAZOP Study of Reflux Accumulator...............................................................103
Table 7. 5HAZOP Study of Reactor....................................................................................105
Table 7. 6 HAZOP Study of Compressor.............................................................................107
 CHAPTER 01:
Introduction

Summary
In this chapter, we will cover the aspects of urea fertilizer and how it is
handled. The use of manure and composts as fertilizers is probably almost as old as
agriculture. Modern chemical fertilizers include one or more of the three elements that
are most important in plant nutrition: nitrogen, phosphorus, and potassium. Of
secondary importance are the elements sulfur, magnesium, and calcium. Most
nitrogen fertilizers are obtained from synthetic ammonia; this chemical compound
(NH3) is used either as a gas or in a water solution, or it is converted into salts such as
ammonium sulfate, ammonium nitrate, and ammonium phosphate, but packinghouse
wastes, treated garbage, sewage, and manure are also common sources of it.
Phosphorus fertilizers include calcium phosphate derived from phosphate rock or
bones. The more soluble superphosphate and triple superphosphate preparations are
obtained by the treatment of calcium phosphate with sulfuric and phosphoric acid,
respectively. Under this section, the transportation and handling of urea fertilizer is
discussed.
1.1 Background of fertilizer
Pure urea was first isolated from urine in 1727 by the Dutch scientist Herman
Boerhaave, and he extracted urea from urine by working with the concentrated-by-
boiling residue. But if only not considering the purity of urea, the discovery of urea
should be attributed to the French chemist Hilaire Rouelle, and he prepared urea (or
its addition compound with sodium chloride).
In 1828, just 55 years after its discovery, urea became the first organic compound to
be synthetically formulated, this time by a German chemist named Friedrich Wohler,
one of the pioneers of organic chemistry. It was found when Wohler attempted to
synthesis ammonium cyanate, to continue a study of cyanates which he had been
carrying out for several years. On treating silver cyanate with ammonium chloride
solution he obtained a white crystalline material which proved identical to urea
obtained from urine.[1]
AgNCO + NH4Cl → (NH2)2CO + AgCl
 Synthetic urea is created from synthetic ammonia and carbon dioxide and can
be produced as a liquid or a solid. The process of dehydrating ammonium carbamate
under conditions of high heat and pressure to produce urea was first implemented in
1870 and is still in use today. Uses of synthetic urea are numerous and therefore
production is high. Approximately one million pounds of urea is manufactured in the
United States alone each year, most of it used in fertilizers. Nitrogen in urea makes it
water soluble, a highly desired property in this application.
Chemical Name: Urea
Chemical Family: Amides
Synonyms and Common Trade Names
 Carbamide
 Carbonyldiamine
 Carbonyl Diamide
Urea is an important nitrogenous fertilizer. Its utilization is increasing steadily,
it being the preferred nitrogen fertilizer worldwide. It is used in solid fertilizer, liquid
fertilizer, formaldehyde resins and adhesives .

1.2. Properties of Urea

Physical Properties of Urea
Urea is a
 White
 Odorless
 hygroscopic solid
 It is non-corrosive.
 Table 1. Chemical properties of urea.

Chemical properties Values

Molecular weight 60.05
Relative humidity 60%
Boiling point not applicable
Melting point 270.8°F (132.7°C)
Maximum Nitrogen content 46.6 %
Specific gravity 1.335
Heat of fusion 60 Cal/gm (endothermic)
Heat of solution, in water 58 Cal/gm (endothermic)
Bulk density 0.74
pH 7.2 (10% water solution)

Table 1. Specific heat of urea

Temperature, oC Specific heat, KJ/kgoC

0 1.398
50 1.66
100 1.89
150 2.11

1.2.2. Stability and Reactivity

 Stability (thermal, light, etc.): Stable under normal conditions of storage and
handling.
 Incompatibility (materials to avoid): Nitric acid, sodium nitrite, nitrosyl
perchlorate, gallium perchlorate, hypochlorites, phosphorus pentachloride.
 Hazardous Decomposition Products: When heated above melting point,
decomposes to ammonia and carbon dioxide. If burned, emits small amounts of
nitrogen oxides.
 Hazardous Polymerization: Will not occur
 Conditions to Avoid: Decomposes when heated above melting point.
1.2.3. Ecological Information
Urea can be toxic to domestic animals and has caused poisonings when it was
applied unevenly on pastures as a fertilizer. Large amounts of urea can damage plant
seedlings and inhibit germination.
At high concentrations, urea can be toxic to aquatic life. As a readily available
source of nitrogen, urea can also foster excessive growth of algae or microorganisms
in water systems. Notify local health and wildlife officials and operators of nearby
water intakes upon contamination.
Ecotoxicity Information:
The cell multiplication toxicity threshold values for bacteria, green algae, and
protozoa are >10,000, >10,000, and 29 mg/L, respectively. The critical range for the
creek chub is 16,000 to 30,000 mg/L in Detroit river water.
Environmental Fate Information:
Particulate-phase urea is physically washed out of the atmosphere by dry and
wet deposition. In the soil, urea degrades rapidly, usually within 24 hours; however,
degradation may be slower depending on soil type, moisture content, and urea
formulation.
The ultimate degradation products are carbon dioxide and ammonia. The soil
mobility is high based on an organic carbon partition coefficient of 8. In water,
biodegradation to carbon dioxide and ammonia is the major fate pathway. The
biodegradation rate increases with increasing temperature and presence of
phytoplankton. Oxidation of urea by nitrifying bacteria can increase biological
oxygen demand. Bioaccumulation of urea is very low. The 72-hour bioconcentration
factor (BCF) for carp is reported to be 1.

1.3 Raw material resources

The raw material for urea is anhydrous ammonia, which is manufactured from
air and natural gas by Haber-Bosch process. The nitrogen is taken from air and
hydrogen is taken from natural gas and CO2 is stripped from natural gas.
The main raw materials of Urea are:
 Nitrogen from Air
 Natural Gas
1.4 Disposal Considerations
Urea is not considered a hazardous waste under Federal Hazardous Waste
Regulations 40 CFR 261. Consult local or state environmental regulatory agencies for
acceptable disposal procedures and locations. Follow standard disposal procedures.

1.5 Transport Information

Urea is not listed as a hazardous material by the U.S. Department of
Transportation (DOT), Transport Canada (TC), International Maritime Organization
(IMO), and the United Nations (UN).

1.6 Advantages of Fertilizer Urea

 Urea can be applied to soil as a solid or solution or to certain crops as a foliar
spray.
 Urea usage involves little or no fire or explosion hazard.
 Urea's high analysis, 46% N, helps reduce handling, storage and transportation
costs over other dry N forms.
 Urea manufacture releases few pollutants to the environment.
 Urea, when properly applied, results in crop yield increases equal to other
forms of nitrogen.

1.7 Uses of Urea

Urea is used for soil and leaf fertilization (more than 90% of the total use); in
the manufacture of urea–formaldehyde resins; in melamine production; as a nutrient
for ruminants (cattle feed); as a reducing agent in SCR(selective catalytic reduction)
technology for NOx reduction in off-gases from combustion processes; and in
miscellaneous applications.
 About 56 % of Urea manufactured is used in solid fertilizer.
 About 31 % of Urea manufactured is used in liquid fertilizer.
 Urea-formaldehyde resins have large use as a plywood adhesive.
 Melamine-formaldehyde resins are used as dinnerware & for making extra
hard surfaces [2].
1. Soil and Leaf Fertilization.
Urea contains 46% of nitrogen. Nitrogen is the most important plant nutrient
for crop production. It is an important building block in almost all plant structures.
Nitrogen occupies a unique position as a plant nutrient because rather high amounts
are required compared to the other essential nutrients. It stimulates root growth and
crop development as well as the uptake of the other nutrients. Therefore, plants
usually respond quickly to nitrogen addition to the soil.
Worldwide, urea has become the most important nitrogenous fertilizer. Urea
has the highest nitrogen content of all solid nitrogenous fertilizers; therefore, its
transportation costs per ton of nitrogen nutrient are lowest. Being one of the world’s
most important fertilizers, urea plays an important role in securing the worldwide
food supply.
In the application of nitrogenous fertilizers, like urea, the efficiency of
nitrogen usage by crops is limited. Typical values in the 30–60% range are reported
for the amount of nitrogen taken up by the crops. The remainder of the applied
nitrogen is lost through processes as leaching and volatilization. Not only does this
reduce the efficiency of the farming process; it also may significantly influence the
bioenvironment of waters and soils. For instance, excess nitrogen may result in
troublesome algal blooms with depletion of oxygen in natural rivers, lakes, and seas
[3].
2. Urea–Formaldehyde Resins
A significant proportion of urea production is used in the preparation of urea–
formaldehyde resins. These synthetic resins are employed in the manufacture of
 adhesives molding powders
 Varnishes
 Foams
They are also used to impregnate paper, textiles, and leather.
3. Melamine Production
At present, nearly all melamine production is based on urea as a feedstock
(Melamine and Guan amines). Since ammonia is formed as a coproduct in melamine
production from urea, integration of the urea and melamine production processes is
beneficial.
4. Feed for Cattle and other Ruminants
Because of the activity of microorganisms in their cud, ruminants can
metabolize certain nitrogen- containing compounds, such as urea, as protein
substitutes. In the United States this capability is exploited on a large scale. In
Western Europe, by contrast, not much urea is used in cattle feed.
5. Reducing Agent in SCR Technology
The use of urea as a reducing agent in SCR technologies\ to reduce the amount
of NOx in off-gases from combustion processes forms a rapidly growing market [4].

Other Uses
On a smaller scale, urea is employed as a raw material or auxiliary in
 the pharmaceutical industry
 the fermenting
 brewing industries
 the petroleum industry
 It is also used as an ingredient in printer ink formulations
 urea is used as a solubilizing agent for proteins and starches
 As a deicing agent for airport runways.

1.8 Product and Consumption

Almost 150 million tons of urea fertilizer is consumed worldwide per year.
 The Americas represent 17% of the global consumption but produce only
10%.
 The Americas import approximately 14 million tons per year to meet their
needs, split roughly 7 million tons to North America and 7 million tons to
Central and South America.
 Urea production is estimated at 149.6 million tons in 2010, up 1.4% from
2009. During the years 2001-2010, urea production grew on average at 3.8%
per year. The largest producers are also the largest consumers, namely China
and India. China is self sufficient on nitrogen fertilizer but India’s imports
requirement is growing.
 Table 1. Annual production of urea

World 151 million tones

Europe 10 million tones
North America 10 million tones
Asia 94 million tones
FSU 11 million tones

Figurer 1. consumption and production of urea world-wide

Most of the new nitrogen capacity in the world is urea, so it is natural that
production/consumption growth rates are higher for urea than for ammonia/total
nitrogen. Lately, the difference has been quite large, since urea has taken market
share, particularly from ammonium bicarbonate in China. In addition, a major share
of the capacity shutdowns in high energy cost regions has been stand-alone ammonia
plants.
As urea has high nitrogen content (46%), transport is relatively cheap. In
addition, demand growth is to a large extent taking place in climates which favor urea
use .

1.9 Urea production in Pakistan

Ten Urea plants are producing 4.8 Million Metric Tons urea per annum in
Pakistan, whereas its total demand is 5.6 million metric tons.70% of total
consumption of Urea is in Punjab. Therefore annual shortage of urea is around
800000 metric tons. Currently Urea price in Pakistan is RS 1800 per 50 kg and
imported price is Rs 2200 per 50kg. Urea is imported to meet its deficiency and
government has to give subsidy at a rate of Rs 400 per bag.
 Table 1. Urea plant in Pakistan

S.no Name Technology Capacity

(MTPD)
1 PAFL, Mianwali TEC, japan 1050
2 Pak-Arab fertilizer, Multan Snamprogetti, Italy 300
3 Engro Chemicals P1, Sdq TEC Japan 810
4 Engro Chemicals P2, Sdq TEC Japan 1750
5 FFC-1 Goth Machi Snamprogetti, Italy 2105
6 FFC-2 Goth Machi Snamprogetti, Italy 1940
7 FFC-3, Mirpur Mathelo Snamprogetti, Italy 1750
8 DH chemicals Mitsui-Toatsu Japan 1350
Sheikhupura
9 FFBL, Karachi Stami,Netherland 1670
10 Fatima Fertilizer Stamicarbon 1500
Reference
[1] Gresham, E. L., James, E. J., Raye, J. R., Battaglia, F. C., Makowski, E. L., &
Meschia, G. (1972). Production and excretion of urea by the fetal lamb. Pediatrics, 50(3), 372-
379.
[2] Singh, V. D. (2010). U.S. Patent No. 7,687,041. Washington, DC: U.S. Patent and
Trademark Office.
[3] ULLMANN'S Encyclopedia of Industrial Chemistry/urea
[4] Santora, V., Askew, B., Ghose, A., Hague, A., Kim, T., Laber, E., ... & Smith, L.
(2002). U.S. Patent Application No. 09/930,753.
 CHAPTER 02
Process Selection

2.1 Types of process for the manufacturing of UREA

Several processes are used to urea manufacturing. Some of them are used
conventional technologies and others use modern technologies to achieve high
efficiency. These processes have several comparable advantages and disadvantages
based on capital cost, energy cost, efficiency and product quality. Some of the widely
used urea production processes are[1]:
 Once through urea process
 Partial recycle urea process
 Internal carbamate urea process
 Stamicarbon process
 Snamprogetti process
 Mitsui Toatsu process
 ACES process

2.1.1. Once through urea process

Figurer 2. once through urea process

In this process liquid NH3 is pumped through a high pressure plunger pump
and gaseous CO2 is compressed through a compressor up to the urea synthesis reactor
pressure at an NH3 to CO2 feed mole ratio of 2/1 or 3/1. The reactor usually operates
in a temperature range from 175 to 190 oC. The reactor effluent is let down in pressure
to about 2 atm and the carbamate decomposed and stripped from the urea-product
solution in a steam heated shell & tube heat exchanger. The moist gas, separated from
the 85-90 % urea product solution, & containing about 0.6 tons of gaseous NH 3 per
ton of urea produced is usually sent to an adjacent ammonium nitrate or ammonium
sulfate producing plant for recovery. An average conversion of carbamate to urea of
about 60 % is attained. The NH 3 & CO2 gas is separated from the urea solution and
utilized to produce ammonium salts by absorbing NH3, either in sulfuric or nitric acid.
The once –through process is simplest and least expensive (both capital and operating
cost) among the three process. Least flexible and cannot be operated unless some
provision is made to utilize large amount of ammonia and off-gas. The disadvantage
of this process is the large amount of ammonia salt formed as co product and limited
amount of carbon dioxide conversion [2].

2.1.2. Partial Recycle Urea Process

Ammonia and carbon dioxide react in the urea reactor for the urea synthesis.
In this process all unconverted ammonia and carbon dioxide were recycled to the urea
reactor. The recirculation occurs in two stages. The first recirculation was operated at
high pressure separator and second at the high pressure stripper. The first recirculation
comprises at a separator which separate the excess ammonia which evaporates, the off
gas from the first step was subjected to high pressure absorber from which relatively
pure ammonia at the top and bottom product of aqueous ammonium carbamate
solution were obtained, both recycled to urea reactor separately. In high pressure
stripper carbamate is stripped to give top product of ammonia gas which is sent to
absorber and bottom product to low pressure stripper where urea solution is obtained.
Part of the off–gas is recycled back to the reactor. The amount of ammonia is reduced
to 15% to that of once through that must be used in other processes. Investment cost
is somewhat lower than the total recycle process, this advantage apparently does not
compensate the inflexibility arising from the necessity to operate a co-product plant
with mutual interdependency problems. However, it finds application in UAN co-
product plants.
 Figurer 2. partial recycle process

2.1.3. Internal Carbamate Total Recycle Urea Process:

The unreacted carbamate & the excess ammonia are stripped from the urea
synthesis reactor effluent by means of gaseous hot CO2 or NH3 at the reactor pressure,
instead of letting the reactor effluent down to a much lower pressure. The NH 3 & CO2
gas, thus recovered at reactor pressure, is condensed and returned to the reactor by
gravity flow for recovery so basically the general objectives are to maximize the heat
recovery, Minimize the amount of carbamate solution recycled (smaller pumps and
less power) and amount of water returned to the reactor (better conversion), Minimize
power requirement, Maximize ammonia recovery (lowering operating cost and less,
Maximize ammonia recovery (lowering operating cost and less pollution) , Other
important requirement is of-course minimizing investment. The problem is finding the
best balance between the utility consumption and maintenance on one hand and
investment on the other hand.
 Figurer 2. block diagram of urea synthesis

2.1.3.1. Stamicarbon Process (Carbon Dioxide Stripping)

Figurer 2. Stamicarbon process for urea production

In 1966 Stamicarbon of Netherland introduced CO2 stripping. NH3 and CO2

are converted to urea via ammonium carbamate at a pressure of approximately 140
bar and a temperature of 180-185° C. The molar NH 3/CO2 ratio applied in the reactor
is 2.95. This results in a CO 2 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 NH3 and CO2 are then partially condensed and recycled to the reactor.
The heat evolving from this condensation is utilized to produce 4.5 bar steam, some of
which can be used for heating purposes in the downstream sections of the plant.
Surplus 4.5 bar steam is sent to the turbine of the CO 2 compressor. The NH3 and CO2
in the stripper effluent are vaporized in a 4 bar decomposition stage and subsequently
condensed to form a carbamate solution, which is recycled to the 140 bar synthesis
section. Further concentration of the urea solution leaving the 4 bar decomposition
stage takes place in the evaporation section, where a 99.7% urea melt is produced.

2.1.3.2. Snamprogetti Process (Ammonia Stripping)

This process is based on the principle of the internal carbamate recycle
technique and is commonly called the Snam NH 3 stripping process. NH3 and CO2 are
converted to urea via ammonium carbamate at a pressure of 150 bar and a temperature
of 180° C. A molar ratio of 3.5 is used in the reactor giving a CO 2 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 NH3. Residual
carbamate and CO2 are recovered downstream of the stripper in two successive stages
operating at 17 and 3.5 bar respectively. NH3 and CO2 vapors 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, the operating parameters for six sections are Synthesis and high pressure
(HP) recovery (160 bar), Medium pressure (MP) purification and recovery (17 bar),
Low pressure (LP) purification and recovery (3.5 bar), Vacuum concentration (2
steps: 0.3 and 0.03 bar abs), Process condensate treatment, Finishing: prilling and
granulation [3].
 Figurer 2. snamprogetti process for urea production

2.1.3.3. Mitsui Toatsu or Toyo Koatsu process

Figurer 2. Toyo koatsu process for urea production

This total recycle urea process is a carbamate solution recycle process with
three pressure-staged carbamate decomposition & recovery systems. The reactor is
operated at about 195 C, 240 atm, & with a NH 3 to CO2 molar ratio of about 4.3.
About 67 % of the total ammonium carbamate present in the reactor is converted to
urea. The unconverted carbamate is decomposed and stripped from the urea solution
together with excess NH3 in a series of three pressure-stage decomposers, operating
respectively at about 18 atm & 1500C, 3.06 atm & 1300C, & atmospheric pressure &
1200C. The main feature of the Mitsui Toatsu process is the fact that the gaseous
phase in each decomposition stage is contacted in counter current flow with the urea
product solution issuing from the preceding decomposition stage. Either a packed
section or a sieve tray section is used for this purpose. The effect is that the NH 3 &
CO2 gaseous mixture obtained from the decomposition of carbamate is considerably
reduced in vapor content. Thus the amount of water recycled to the reactor is
maintained at a relatively low level and a relatively high conversion in the reactor is
attained. The off-gas from each decomposition stage is condensed to solution in its
respective water-cooled condenser and the solution thus obtained is pumped to the
next high pressure staged condenser. Excess NH3 is separated from the aqueous
solution of carbamate & scrubbed from the last traces of CO 2 in counter current flow
with reflux liquid, NH3, fed to the top of the high-pressure absorber. The pure excess
NH3 thus obtained is condensed to liquid with cooling water & recycled to the reactor.
The carbamate solution is recycled back to the reactor for total recovery.

2.1.3.4 ACES process

Advanced process for cost and energy process consist of reactor,stripper,
carbamate condenser and scrubber. All equipment are operated at 175 bar. The reactor
is operated at 1900C and an ammonia to carbon dioxide ratio of 4:1. Liquid ammonia
is feed to the reactor where carbon dioxide after compression is introduced into the
stripper for stripping aid. The synthesis mixture from reactor consist of urea,
unconverted ammonium carbamate, excess ammonia and water s fed to top of
stripper. Stripper separate the ammonia gas which is evaporated and carbon dioxide
separated from carbamate solution in bottom part. The overhead gas is introduced into
carbamate condenser, here mixture is condensed and absorbed by carbamate solution
coming from medium pressure recovery stage. The gas and liquid from condenser
then recycled to reactor. The urea solution from stripper with almost 15% ammonia is
purified further in medium (17.5 bars) and low (2.5 bars) pressure decomposer.
Ammonia and carbon dioxide recovered through absorption in low and medium
pressure absorber. The purified urea solution is further concentrated by two stage
evaporation up to 99.7% for urea pril production then it is passed through prilling
tower or urea granulator [4].
Figurer 2. ACES process for urea production
 Table 2. urea process operating conditions and requirements

Snamprogetti Stamicarbon TEC ACES

Thermal CO2 Stripping Process
Stripping
Reactor Pressure, atm 156 140 175
Reactor temp 0C 188 183 190
Molar NH3 /CO2 ratio 3.3-3.6 2.95 4.0
Molar H2 O/CO2 ratio 0.5-0.6 0.39 0.6
CO2 conversion in reactor, % 64 60 6.8

NH3 conversion in reactor,% 41 36 34

CO2 conversion in synthesis, % 84 79 NA

NH3 Conversion in synthesis,% 47 79 NA

No. of High-pressure vessel- 5 4 5

synthesis
Recirculation-stages 2 1 2
NH3 consumption ,t/t 0.566* 0.566* O.568
CO2 Consumption,t/t 0.735* 0.733 0.735/0.740
Import steam,t/tb 0.950 0.920 0.80
Cooling water, t/tb 75 70 80
Electricity,kWh/tb 21-23 15 15
Liquid effluent
Free NH3 ,ppmw 2 1 5
Urea, ppmw 2 1 5
Hydrolyzer steam pressure, bar 38 25 25

Note: NA = Not available

A. Based on final product area granules containing +4.5 or -4.5 kg formaldehyde/ton
product, using UF85 (urea+ biuret 25%, formaldehyde 60%,water 15%)
B. Depending on plant location and available utilities, these figures can vary greatly.
The plants can easily be designed for minimum stream or minimum electric power:
the decision is on a cost basis
2.1.4. Manufacturing process of process selected
In the reactor, when liquid ammonia reacts with compressed CO2 ( at 162 ata)
at high temperature & pressure gives urea according to the following reactions:
2NH3 + CO2 ======= NH2COONH4 exothermic
NH2COONH4 ======= NH2CONH2 + H2O endothermic
As the reactions are reversible in nature only partial conversion occurs in the
reactor. Urea solution consisting of urea ,carbamate, wet unconverted CO2 & NH3 are
fed into the stripper where stripping action of NH 3 favors decomposition of
carbamate, and hence 80% of carbamate is decomposed here. Pressure in the stripper
is same as that of the reactor. Urea solution from the stripper is sent to medium
pressure decomposer where Urea purification takes place by the dehydration of the
carbamate. urea solution is further purified in Low pressure decomposer. Off gases
from the MP decomposer & LP decomposer are sent to the medium pressure
condenser & medium pressure absorber for the recovery of unconverted Ammonia. In
this way 71.12% of Urea solution resulting from LP decomposer is sent to Vacuum
concentrators operating in two stages: 1) 1st Vacuum evaporator. 2) 2nd vacuum
evaporator Finally, 99.8 % molten urea is sent to the prilling towers where urea prills
are formed by passing a current of cold air in the tower from the bottom. Proper size
Urea prills are sent to bagging section through belt conveyors. In bagging section,
coating of Urea prills may be done if required. Oversized Urea prills or lumps are sent
to lump dissolving tank.

2.1.5. Urea synthesis

NH3 & CO2 react under specific concentration, temperature & pressure
conditions to form Urea as per the following reactions:
1) CO2 (g) + 2NH3 ( g) ===== NH2COONH4 (s) ; H = -37.64 kcal/gm mol
2) NH2COONH4 (s) ===== NH2CONH2 (s) + H2O (l) ; H=6.32 kcal/gm mol
------------------------------------------------------------------------------------------------
CO2 (g) + 2NH3 (g) ===== NH2CONH2 (s) + H2O (l); H = -31.32 kcal/gm mol
So, overall urea synthesis is exothermic, releasing heat of 31.32 kcal/gm mol at
standard conditions of 1 atm pressure & 25°C. But actual heat available in a urea
synthesis reaction will be only 5.74 kcal/gm mol because of the heat lost in
evaporation of liquid NH3, evaporation of water & melting of urea. This is based on
the actual plant data. Further energy is consumed in feeding CO 2 & NH3 at high
temperature & pressure, in recycling of carbamate, in vacuum concentration of urea,
for operating different pumps & compressors etc. which altogether makes the urea
production energy consuming.

2.1.5.1 Effect of various parameters

Temperature
In above reactions 1st reaction is exothermic & 2nd one is endothermic. So,
according to Le-chatelier’s Principle 1st reaction is favoured at low temp & 2nd one
at high temp. Further , reaction no. 1 is fast & reaches to completion but reaction no. 2
is slow & determines the overall rate of urea production. For sufficient completion of
reaction no.2 optimum temp is maintained. It is observed that max equilibrium
conversion occurs between 190 to 200°C. If temp is increased beyond 200°C
corrosion rate increases.
NH2COONH4 (s) ===== 2NH3 (g) + CO2 (g) ; H= -ve (K1)
NH2COONH4 (s) ===== NH2CONH2 (s) + H2O (l) ; H = -ve (K2)
Both the reactions are favored at high temp but our objective is to maximize
2nd reaction as 1st reaction is undesirable in the reactor. So, our operating zone
should be in the region where K2 > K1.

Pressure
Overall urea synthesis reaction is given below:
CO2 (g) + 2NH3 (g) ====== NH2CONH2 (s) + H2O (l)
There is reduction in volume in the overall reaction & so high pressure favors
the forward reaction. This pressure is selected according to the temp to be maintained
& NH3:CO2 ratio.

Concentration
Higher the concentration of the reactants , higher will be the forward reaction
according to the law of mass action. CO2 being limiting reagent higher NH 3:CO2 ratio
favors conversion . Since, dehydration of carbamate results in urea production, lesser
H2O:CO2 ratio favors conversion , water intake to the reactor should be therefore min.
Residence time
Since, urea conversion reaction is slow, 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 & concentration.

2.2. Selection of process

Snam NH3 stripping process
Formation of urea from ammonia & carbon-di-oxide takes place through
reversible reactions with formation of ammonium carbamate as intermediate product.
Now, success of any urea manufacturing process depends on how economically we
can recycle carbamate to the reactor. Snamprogetti process of urea manufacturing
accomplishes the above task by stripping process.
NH2COONH4 (s) ====== 2NH3 (g) + CO2 (g) ∆ H = + 37.4 Kcal/gm-mole
This reaction involves increase in volume & absorption of heat . Thus this
reaction will be favored by decrease in pressure & increase in temperature. 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 NH3 or CO2 is called stripping process. According to above equation, we
have
K = (pNH3)2*(pCO2) [where, K= equilibrium constant]
The stripping is affected 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 Snam’s process.
CO2 stripping is advantageous because introducing CO2 increase pCO2. So pNH3 will
be reduced to maintain P constant as P = pCO 2 + 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 along with the carbamate to reactor
again & if water enters reactor, production 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 recycles pressure
results in condensation at higher temp & that recovery in the form of low pressure
steam. This is why stagewise reduction in pressure is practiced.

2.3. Process description

The process is divided into six sections:
 Synthesis and high pressure (HP) recovery
 Medium pressure (MP) purification and recovery
 Low pressure (LP) purification and recovery
 Vacuum concentration
 Process condensate treatment
 Finishing: prilling
2.3.1. Synthesis and high pressure (hp) recovery
This section includes: the reactor where urea is formed; the stripper necessary
to strip out as vapors, from the urea solution leaving the reactor, a large amount of
ammonia and carbon dioxide not converted to urea in the reactor; the carbamate
condenser that condenses these vapors ; the ejector that recycles the ammonium
carbamate solution to the reactor. In this equipment the pressures are of a similar
level, 150 bar, while the temperatures of the outlet solutions are 188, 205 and 155°C
for the reactor, the stripper and the carbamate condenser, respectively. The urea
reactor is characterised by a high ammonia- carbon dioxide ratio (NH 3/CO2 = 3.2 - 3.4
molar) and a low water carbon dioxide ratio (0.4 - 0.6 molar). Inside the reactor a
matching number of trays of a very simple design are installed to improve the
conversion. Under these conditions 62-64% (conversion) of the total CO 2 entering the
reactor is converted to urea. The total carbon dioxide conversion in the HP section (or
loop) is 85-90%. All the equipment in this section, the heaviest of the urea plant, is
installed at ground level, thus providing a horizontal layout with all the relevant
benefits. The stripper and the hydrolyzer in the waste water section are the only two
items of equipment in the plant that consume medium pressure steam. The amount of
steam consumed in the stripper is practically completely recovered in the carbamate
condenser: its pressure is lower but still sufficient to be used in the urea plant itself.
Even under severe conditions, all the equipment in this section has a safe life of more
than 20 years. The quantity of oxygen introduced into the plant as air is 0.25% vol of
the fresh feeding carbon dioxide. This minimum amount guarantees, at the same time,
excellent equipment passivation and the absence of explosive mixtures where the
“inert” are released from the plant into the atmosphere after practically all the
ammonia contained therein has been washed. In this way obvious pollution and start-
up problems are completely averted. All kinds of machinery (reciprocating and
centrifugal) is utilized according to local conditions or client requests.

2.3.2 Medium pressure (MP) purification and recovery

The purpose of this section is to partially strip out the reactants, ammonia and
carbon dioxide from the urea solution and, after their condensation in water, to
recycle the obtained solution to the reactor, together with the ammonia and carbon
dioxide aqueous solution resulting from the downstream sections of the plant. The
ammonia excess is separated in this section and recycled to the reactor separately. A
distillation column is provided for this purpose. The operating pressure is 17 bar . A
particular feature is included in this section. Ammonia and carbon dioxide are
partially condensed in the shell of a preheater within the vacuum section, thus
recovering some energy in the form of 200 kg of steam per ton of urea, with an
investment cost that, even in existing plants, has a pay-back time of less than two
years. Another particular characteristic of the MP section is the washing of the so-
called inert (CO, H2 and CH4 contained mainly in the carbon dioxide and the
passivation air). As already emphasized, the quantity of passivation air in the is very
small (one third compared with other technologies). It is therefore easy to recover
ammonia from the inert without the risk of explosion mainly due to H2/O2 mixtures.
No hydrogen removal from carbon dioxide is required. Upon special requests,
different washing systems have been designed and have already been installed in
industrial plants. For the complete abatement of the ammonia contained in the inert, in
completely safe conditions with regard to explosions, it has patented a washing
method that has already been applied in some plants. This consists of washing the
inert with water after the addition of a quantity of flammable gas, as for example
natural gas, in such an amount that after the ammonia has been eliminated, the
composition of the inert is out of the explosive field due to the excess of flammable
gas. The washed inert are sent to a burner together with the natural gas. It should be
emphasized that the presence of the MP section provides great plant flexibility, which
can be operated over a wide range of NH3/CO2 ratios, with excess ammonia present in
the urea stream from the stripper being recovered and condensed by the MP section.
Furthermore, although in principle the control of the NH 3/CO2 ratio in the synthesis
loop is important, in practice, owing to the presence of the MP section, some
fluctuations are acceptable and there is no need for strict control of the NH 3/CO2 ratio
in the Snamprogetti process.

2.3.3 Low pressure (LP) purification and recovery

Further stripping of ammonia and carbon dioxide is made in the LP section,
operating at 3.5 bar. The vapors, containing ammonia and carbon dioxide, are
condensed and recycled to the reactor via the MP section. An appropriately sized tank
is provided in this section to collect all the solutions from the plant when it is shut
down for long time. Therefore, in no circumstances are solutions discharged from the
plant.

2.3.4 Vacuum concentration

The urea solution leaving the LP section is about 70% b.w. and contains small
quantities of ammonia and carbon dioxide. The final concentration of the urea
solution (99.8% b.w.) is made under vacuum in two steps at 0.3 and 0.03 bar abs. for
the prilled product, and in one or two steps for the granular product, according to the
granulation technology chosen. An important feature of this section is the
preconcentration of the urea solution to about 86% b.w. The necessary heat is
provided by partial condensation of the vapors (ammonia and carbon dioxide
essentially) from the MP section evaporator. Particular care is taken in the design of
this section to minimize temperatures and residence times so as to keep the biuret at
minimum values. A simple solution has been found to the problem of lump formation
in the second vacuum separator: lump formation is prevented by wetting the internal
walls of the separator by means of a small recycle of molten urea.

2.3.5 Process condensate treatment

The excellent result achieved in the treatment of waste water from urea plants
has received worldwide recognition. Its success in discharging the large amount of
process water with 1 ppm of urea and 1 ppm of ammonia shows it is possible to
reduce pollution while obtaining urea at a lower cost (lower specific consumption of
ammonia and reutilization of process water as BFW). All possible and convenient
heat recoveries have been introduced into this section in order to minimize energy
consumption. It contains distillation tower and pre heater and hydrolyser and its
preheater.

2.3.6. Prilling
Prilling is the easiest technology to manufacture solid urea with commercially
valid chemical and physical characteristics. Molten urea (99.8% b.w.) is sprayed at
the top of the prilling tower, at a height of 55-80 m, according to climatic conditions;
at the bottom, essentially spheroidal urea particles, namely prills, are collected and
sufficiently cooled in order to be sent to storage or directly to the bagging section
without screening, coating or any other treatment. In a few plants, plant owners have
requested that formaldehyde (0.2-0.3% b.w.) be added to the molten urea just before
the prilling section in order to improve the free- flowing characteristics of the prilled
urea and to achieve a slight increase in hardness [5].

High process efficiency

The process is extremely efficient as regards both raw material consumption
and energy requirements. Almost the entire quantity of raw materials, namely
ammonia and carbon dioxide, is transformed into urea. This means low consumption
of raw materials, as close as possible to the theoretical value and, at the same time,
sustainable environmental pollution (more than 99.8% of the ammonia is transformed
into urea). The high NH3/CO2 ratio in the reactor ensures a high conversion of
ammonium carbamate, an intermediate compound in the reaction, to urea (up to 64%).
This result, together with the highly efficient ammonia-stripping operation, drastically
reduces the recycle of unconverted carbamate and the size of equipment in carbamate
decomposition and recovery sections. Some important heat recoveries have been
introduced, with a pay-back time of less than two years. High conversion, high
stripping efficiency and heat recoveries minimize the energy requirement, i.e. steam,
electric power and cooling water consumption.
2.4. Block Diagram Of Snamprogetti Process
NH3 CO2