CH4015: Comprehensive Design Project I

Group Report
Plant for Production of Urea

Group members: 140038K - Anuththara J.G.M

140046H - Arunasiri R.A.D.S

140055J - Attanayake D.D.S

140057R - Bandara A.M.H.S

140070B - Bandara Y.W

Date of submission: 13.07.2018

Supervisor: Prof. (Mrs.) Amarasinghe B.M.W.P.K

Department of Chemical and Process Engineering

University of Moratuwa
 ABSTRACT

Urea is one of the major chemicals which is mass produced in industry. With the rising
population the demand for urea increases annually. About 90% of world’s produced urea is
used as fertilizer. Production of urea-formaldehyde and melamine-methanal resins are other
major uses of urea. In this report, a literature review, production process and process
technologies of manufacturing urea including the material and energy balances are presented.
The report discusses mainly four types of commercialized processes used in urea production
industry; Straight through process, Snampogetti ammonia stripping process, Stamicarbon and
Mitsui-Toatsu process. For the development of this urea manufacturing process, Snampogetti
ammonia stripping process has been selected considering its efficiency, ease of material storage
and issues of corrosion that arises in the process.

The process is based on the reaction of ammonia and carbon dioxide producing ammonium
carbamate and subsequent decomposition of ammonium carbamate into urea. The two
reactions primarily occur in the reactor and for further conversion ammonium carbamate is
decomposed at two pressure stages in decomposers. For separation processes a high-pressure
stripper, two phase separators, evaporators are used. A prilling tower is utilized to produce urea
prills for end requirement.

The output for the plant has been decided as 1,500,000 MT per annum using analysis of global,
regional and local demands. As raw materials, ammonia is imported since there are no
ammonia production plant in Sri Lanka and the requirement for carbon dioxide is supplied
using decomposition of limestone. The hourly flow rate of product is 174 MT which consumes
191 MT/hr ammonia and 150 MT/hr of carbon dioxide. The report also includes a concise
evaluation on health, safety and environmental aspects.

i
 ACKNOWLEDGEMENT

Our sincere gratitude goes out to the Head of the Department of Chemical and Process
Engineering, Dr. (Mrs) S.H.P. Gunawardena, Module coordinator of Comprehensive Design
Project I (CH 4014), Dr. (Mrs.) Olga Gunapala for the valuable support.

We would like to extend our gratefulness to our supervisor, Pro.(Mrs)B.M.W.P.K.

Amarasinghe, for the valuable guidance and the encouragement throughout the period
whenever needed. We are thankful to Dr. (Mrs.) Maneesha, Dr.(Mr.) Shantha Amarasinghe
and Dr. (Mr.) P.G.Rathnasiri for sharing her valuable knowledge with us.

We must also thank all the fellow staff members, instructors for being a valuable helping hand
to accomplish tasks which otherwise wouldn’t have been achievable. In addition, our gratitude
goes to all the non-academic staff members in the department, especially the technical officers
and all staff members in the CAPD center who non-tiringly helped us to do project work in the
computer laboratory.

Finally, we should express our heartfelt gratitude to all our fellow batch mates for sharing their
knowledge and expertise among us to ensure a successful outcome from the project.

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 Table of Contents
1 INTRODUCTION ............................................................................................................ 1

2 LITERATURE REVIEW AND PROCESS SELECTION ........................................................... 3

2.1 LITERATURE SURVEY ........................................................................................................ 3

2.1.1 What is Urea?............................................................................................................................ 3

2.1.2 Composition and the Structure .................................................................................................. 3

2.1.3 Physical properties .................................................................................................................... 4

2.1.4 Uses of Urea.............................................................................................................................. 4

2.1.5 Production history of Urea......................................................................................................... 6

2.1.6 Health effect of Urea ................................................................................................................. 8

2.2 RAW MATERIAL AVAILABILITY ......................................................................................... 9

2.2.1 Ammonia (NH3) ......................................................................................................................... 9

2.2.2 Carbon Dioxide (CO2) .............................................................................................................. 10

2.3 PROCESS SELECTION ....................................................................................................... 13

2.3.1 Once through urea manufacturing method .............................................................................. 13

2.3.2 Snamprogetti ammonia stripping process ................................................................................ 14

2.3.3 Stamicarbon process ............................................................................................................... 15

2.3.4 Mitsui Toatsu process .............................................................................................................. 16

2.3.5 Process Comparison and Selection........................................................................................... 17

3 FEASIBILITY REPORT AND PROCESS CHEMISTRY ESTABLISHMENT ............................. 19

3.1 RAW MATERIAL COST AND PRODUCT VALUES ............................................................... 19

3.1.1 Ammonia ................................................................................................................................ 19

3.2 LOCAL, REGIONAL & GLOBAL MARKETS FOR UREA AND PRICE ANALYSIS ...................... 20

3.2.1 Global Demand........................................................................................................................ 20

3.2.2 Regional Demand .................................................................................................................... 20

3.2.3 Local Demand.......................................................................................................................... 21

3.3 HEALTH, SAFETY AND ENVIRONMENT ............................................................................ 23

3.3.1 Health ..................................................................................................................................... 23

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 3.3.2 Safety ...................................................................................................................................... 24

3.3.3 Environmental Impact Assessment .......................................................................................... 25

3.4 ECONOMIC EVALUATION ............................................................................................... 28

3.5 PROCESS CHEMISTRY...................................................................................................... 30

3.5.1 Process Technology ................................................................................................................. 30

3.5.2 Operating variables ................................................................................................................. 31

3.5.3 Optimum conditions ................................................................................................................ 33

4 HEAT AND MASS BALANCE AND PROCESS FLOWSHEET DEVELOPMENT .................... 35

4.1 DEVELOPMENT OF PROCESS FLOW DIAGRAM ............................................................... 35

4.1.1 Process Flow Diagram.............................................................................................................. 36

4.1.2 Process Streams ...................................................................................................................... 37

4.2 MATERIAL BALANCE ....................................................................................................... 37

4.2.1 Material Balance for Reactor ................................................................................................... 38

4.2.2 Material Balance for High Pressure Stripping Column............................................................... 39

4.2.3 Material Balance for Medium-Pressure Decomposer and Low-Pressure Decomposer ............... 41

4.2.4 Material Balance for Vacuum Evaporators ............................................................................... 43

4.2.5 Material Balance for Prilling Tower .......................................................................................... 44

4.2.6 Material Balance for Carbon Dioxide Absorber......................................................................... 45

4.2.7 Material Balance for Pool Condenser ....................................................................................... 46

4.2.8 Material Balance for Separator 1 and Separator 2 .................................................................... 47

4.3 ENERGY BALANCE ........................................................................................................... 48

4.3.1 Reactor ................................................................................................................................... 50

4.3.2 High Pressure Stripping Column............................................................................................... 51

4.3.3 Medium Pressure Decomposer ................................................................................................ 52

4.3.4 Low Pressure Decomposer....................................................................................................... 53

4.3.5 Low Vacuum Evaporator .......................................................................................................... 54

4.3.6 High Vacuum Evaporator ......................................................................................................... 55

4.3.7 Prilling Tower .......................................................................................................................... 56

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 4.3.8 Carbon Dioxide Absorber ......................................................................................................... 57

4.3.9 Pool Condenser ....................................................................................................................... 58

4.3.10 Separator 1 ......................................................................................................................... 59

4.3.11 Separator 2 ......................................................................................................................... 60

5 CONCLUSION .............................................................................................................. 61

6 REFERENCES ................................................................................................................ 63

7 APPENDIX ................................................................................................................... 66

7.1 MATERIAL BALANCE CALCULATIONS .............................................................................. 66

7.1.1 Reactor ................................................................................................................................... 66

7.1.2 MP and LP Decomposers ......................................................................................................... 67

7.1.3 Vacuum Evaporators ............................................................................................................... 68

7.2 Utility Calculations ......................................................................................................... 70

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 LIST OF TABLES

Table 2-1- Physical properties of Urea (Urea) ...................................................................... 4

Table 2-2- Potential health effects of Urea and First aid measures (Urea, 2015)................... 8

Table 2-3 - Physical properties of Ammonia (Ammonia, n.d.)............................................... 9

Table 2-4- Physical Properties of CO2 (Physical Properties for Carbon Dioxide) ................ 10

Table 2-5 - Process Comparison .......................................................................................... 17

Table 3-1 - Urea Fertilizer Consumption in Sri Lanka ......................................................... 21

Table 3-2 - Demand Forecast for Sri Lanka ......................................................................... 22

Table 3-3 - Summary of Occupational Health and Issues .................................................... 23

Table 3-4 - Undesired Environmental Impacts .................................................................... 26

Table 3-5 - Permissible Discharge Levels ........................................................................... 27

Table 3-6 - Preventive Measures ......................................................................................... 28

Table 3-7 – Cost Factors ..................................................................................................... 29

Table 3-8 – Cost Breakdown ............................................................................................... 29

Table 4-1 - Process Streams ................................................................................................ 37

Table 4-2 - Ractor Stream Flow Rates ................................................................................. 39

Table 4-3 - HP Stripper Material Flow Rates....................................................................... 41

Table 4-4 – MP Decomposer Material Flow Rates .............................................................. 42

Table 4-5 - LP Decomposer Material Flow Rates ................................................................ 42

Table 4-6 - Low Vacuum Evaporator Flow Rates ................................................................ 43

Table 4-7 - High Vacuum Evaporator Flow Rates ............................................................... 43

Table 4-8 - Prilling Tower Material Flow Rates .................................................................. 45

Table 4-9 Carbon Dioxide Absorber Flow Rates ................................................................. 46

Table 4-10 - Pool Condenser Flow Rates ............................................................................ 47

Table 4-11 - Seperator 1 Flow Rates ................................................................................... 47

Table 4-12 - Seperator 2 Flow Rates ................................................................................... 48

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 LIST OF FIGURES

Figure 2.1 - Lewis Structure of Urea ..................................................................................... 3

Figure 2.2 - Physical appearance of Urea as a fertilizer........................................................ 4

Figure 2.3 - Urea using as a fertilizer.................................................................................... 5

Figure 2.4- Carbon Capturing methods (Ozcan, 2014) ....................................................... 11

Figure 2.5- Limestone deposits in Sri Lanka (L.J.D.FERNANDO, 1986) ............................ 12

Figure 2.6 - Once through Urea Production Process (Das & Bhaskar, 2007)........................ 13

Figure 2.7 - Snampogetti Ammonia Stripping Process (Das & Bhaskar, 2007) .................... 15

Figure 2.8 - Stamicarbon Process (Das & Bhaskar, 2007) ................................................... 16

Figure 3.1 - Conversion % vs Temperature for Urea ............. Error! Bookmark not defined.

Figure 3.2 - Conversion vs Pressure for Urea ...................................................................... 33

Figure 4.1 - Process Flow Diagram ..................................................................................... 36

Figure 4.2 - Reactor streams................................................................................................ 39

Figure 4.3 - HP Stripper Streams......................................................................................... 40

Figure 4.4 -MP and LP Decomposers Flow Streams............................................................ 42

Figure 4.5 - Evaporator Flow Streams ................................................................................. 43

Figure 4.6 - Prilling Tower Streams .................................................................................... 44

Figure 4.7 - Carbon Dioxide Absorber ................................................................................ 46

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 NOMENCLATURE

abs - Absolute

bw - By weight

H - Enthalpy

HP - High Pressure

INR - Indian Rupee

LKR - Sri Lankan Rupees

LOTO -Lock Out Tag Out

LP - Low Pressure

m - Mass flow rate

MP - Medium Pressure

P - Pressure

RH - Relative Humidity

SCR - Selective Catalytic reduction

SNCR - Selective non-catalytic reduction

T - Temperature

USD - United States Dollar

viii
 1 INTRODUCTION

Urea is one of the chemicals which is produced mostly in the world. With the rising population,
the demand for urea increases annually because it can be used as a nitrogen rich fertilizer to
increase the yield of plants per acre. This is a non-toxic material; However, the raw materials
and production process is hazardous.

The main raw materials for the production of urea are ammonia and carbon dioxide. In most of
the plants in the world, this process is integrated with natural gas production facilities because
the raw materials should be kept in high pressure in pressure vessel so that the transportation
become highly cost intensive process. Specially, when handling high pressure process, special
safety precautions needed to be taken. With natural gas production requirement to
transportation with gases are minimized.

For the production of urea from ammonia and carbon dioxide there are mainly four processes
are commercialized. Once through process, Snampogetti ammonia stripping process,
Stamicarbon process and Mitsui Toatsu process. These all four processes use the same principle
for synthesis, but the can be contrasted on recycle process of raw materials. Corrosion is a
major issue in developing a process and process equipment, therefore to minimized corrosion
relatively low pressure and low temperatures are used with aid of stainless steel and titanium
for equipment fabrication. Snampogetti ammonia stripping process was least

South Asian region is one of the region which has high demand for urea. India alone imports 8
million MT of urea per annum. However, in Sri Lanka the demand is limited to approximately
500,000 MT per annum, thus, production of surplus urea than the Sri Lankan demand provide
an opportunity to export to regional countries. A throughput of 1,500,000 MT per annum has
been decided for the plant with aid of analysis with demand and price variations. Cost of
anhydrous ammonia has the significant effect in cost calculation which 726 USD per MT. The
selling price for urea is estimated at 1777 USD per MT. Estimated capital cost for the plant is
1683 million USD. Annual projected profit is 183.54 USD with a payback period of 9.17 years.

With urea being an essential chemical for agricultural purposes Sri Lanka requires a
considerable supply of urea. Since there is no plant currently operating in the country a
production facility will be of high use since it will eliminate the requirement to import urea.
As the objective is to export urea after fulfilling the local demand there will be revenue
generated from overseas. With imports being reduced and exports being increased this will
result in net positive trade balance.

Development if the process flow sheet has been done with the influence of Snampogetti
ammonia stripping process. This is the most cost effective, less corrosive and mild temperature
and pressures utilization process. The pressures are temperatures are relatively lower so that in
the perspective of safety, intently safe process could be able to develop. Temperatures and
pressures that are utilized in equipment are obtained by literature.

This report contains the material balance for production of 1,500,000 MT of urea. The hourly
flow rate of product is 174 MT which consumes 191 MT/hr ammonia and 150 MT/hr of
carbon dioxide. Material balance for each equipment has been done based on the information
obtained from the literature. The assumptions made during calculations are stated on respective
sections of material balance. With integration to the material balance energy balance for each
equipment is calculated. The utility requirement is also estimated based on endothermic or
exothermic based on the process. The process includes, reaction, stripping, decomposing,
evaporating and separation.
 2 LITERATURE REVIEW AND PROCESS SELECTION

2.1 LITERATURE SURVEY

2.1.1 What is Urea?

Urea is a white crystalline colorless, odorless solid organic compound with chemical formula
CO(NH2)2. Urea, also known as carbamide and it was the first organic compound ever
synthesized by chemists (Australia).

Urea is the world's most commonly used nitrogen fertilizer and indeed more urea is
manufactured than any other organic chemical. Other than as a nitrogen fertilizer and feed
supplement, it is also a starting material for the manufacture of plastics and drugs. Containing
46.7 % N, it is the most concentrated nitrogen fertilizer, and is readily available as prills
(granules). Since it is the cheapest form of nitrogen fertilizer to transport favored in developing
countries. And also, it is naturally occurring, non-protein nitrogenous compound human urine
since it is a waste product of many living organisms. This is because it is at the end of chain of
reactions which break down the amino acids that make up proteins.

2.1.2 Composition and the Structure

Urea is an organic compound formed by carbon, oxygen, nitrogen and hydrogen molecules
with the chemical formula CO(NH2)2. This amide has two –NH2 groups joined by a carbonyl
(C=O) functional group. Urea contains 46.7% nitrogen by weight.

Figure 2.1 - Lewis Structure of Urea

The urea molecule is planar in the crystal structure, but the geometry around the nitrogen atom
is pyramidal in the gas-phase which is the minimum-energy structure. In solid urea, the oxygen
center is engaged in two N-H-O hydrogen bonds. Here the C-N bonds have significant double
bond characters.
2.1.3 Physical properties

Following Table 2-1 represents the physical properties of Urea.

Table 2-1- Physical properties of Urea (Urea)

Physical appearance Urea appears to be a cloudy white or light yellow. It is normally

translucent and comes in the form of a liquid or solid (pellets).
Odor The smell of urea is almost non-existent. If a sample of urea is not
odorless, it will have a slight ammonia scent.
Density 1.33 g/cm3 at 1.34oF
Melting Point 132 °C to 135 °C
Solubility Urea is soluble in water. Its solubility ratio is 119 grams per 100
grams water at a temperature of 77oF or 25oC.
Molecular Weight 60.06 g/mole.
pH 7.2 (10% solution)
Decomposition Urea decomposes at 270.8 oF (132.7 oC.) it decomposes into
ammonia and carbon dioxide. If burned, it emits small amounts of
nitrogen oxides.

Figure 2.2 - Physical appearance of Urea as a fertilizer

2.1.4 Uses of Urea

a.) Agricultural Uses

More than 90% of world industrial production of urea is used as a nitrogen-release fertilizer.
Urea has the highest nitrogen content of all solid nitrogenous fertilizers in common use.
Therefore, it has the lowest transportation costs per unit of nitrogen nutrient.Urea hydrolyses
back to ammonia and carbon dioxide in the soil. The ammonia is oxidized to nitrate by the
bacteria in the soil. Nitrate can be absorbed by the plants.

Urea is also used in many multi-component solid fertilizer formulations. Urea is highly soluble
in water and therefore, very suitable for use in fertilizer solutions (in combination with
ammonium nitrate-UAN) (ex- in ‘foliar feed’ fertilizers). For fertilizer use, granules are
preferred because of their narrower particle size distribution. The most common impurity of
synthetic urea is biuret because it is a byproduct of synthesis urea production. It must be present
at less than 2 percent of the time as it impairs plant growth.

Figure 2.3 - Urea using as a fertilizer

b.) Pharmaceutical

Urea and malonic acid react to form barbituric acid which is one of main for ingredients used
to make riboflavin (vitamin B2). Urea is also used in the production of various acylureas and
urethanes for use as sedatives and hypnotics. It is also used as a reactant in some ready-to-use
cold compresses for first-aid use, due to the endothermic reaction it creates when mixed with
water.

Urea-containing creams are used as topical dermatological products to promote rehydration of

the skin. It is also used as an ingredient in some hair conditioners, facial cleansers, bath oils
and lotions. Urea is a main ingredient in hair removers such as Nair or Veet. Urea is an
ingredient in many tooth whitening products also.

c.) Chemical Industry

Melamine is formed by the dehydration of urea. Melamine is primarily used in the production
of melamine-formaldehyde resins which have much greater hardness and stain resistance than
urea-formaldehyde resins which is also a resin formed by urea. Urea-melamine-formaldehyde
is waterproof glue and it is used for marine plywood.

Urea is an agent in the dyeing and printing of textiles. It provides solubility to the bath and
retains some moisture, which is required for the dyeing or printing process. As well as urea can
be used to make urea nitrate which is a high explosive that is used industrially and as part of
some improvised explosive devices (Bareja, 2013).

d.) Automobile Industry

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. As an example, in
BlueTec systems, water-based urea solution is injected into the exhaust system. The ammonia
produced by the hydrolysis of the urea reacts with the nitrogen oxide emissions and is converted
into N2 and water within the catalytic converter. Trucks and cars using these catalytic
converters need to carry a supply of diesel exhaust fluid which is a mixture of urea and water
(Urea).

2.1.5 Production history of Urea

French chemist Hillaire Rouelle discovered urea in 1773. 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 Wöhler obtained urea by treating silver isocyanate with
ammonium chloride in a failed attempt to prepare ammonium cyanate.

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 various and therefore production is high. Approximately one million
pounds of urea is manufactured in the United States alone each year and most of them are used
in production of fertilizers.

Following shows the timeline of evolution of Urea production (SANDERSON, 1959).

Before 1732 Herman Boerhaave did experiments to produce urea from urine.

1773 French chemist Hillaire Rouelle discovered urea from urine.

1798 Fourcroy and Vauquelin obtained that Urea was referred to as "the special urinary
constituent," present in greatest abundance, which causes urine, evaporated to syrup,
to crystallize, and yield crystals on addition of nitric acid.

1799 Fourcroy and Vauquelin proposed the name of “urea”.

1808 Fourcroy and Vauquelin identified the properties of much purer urea

1822 Prevost and Dumas demonstrated the presence of urea in blood. By a comparison of
the composition of the blood of dogs, eats, and rabbits before and after nephrectomy.

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 Wöhler
obtained urea by treating silver isocyanate with ammonium chloride in a failed
attempt to prepare ammonium cyanate.

1870 The process of dehydrating ammonium carbamate under conditions of high heat and
pressure to produce urea was first implemented which is still used in today (History
of urea, 2018).

1873 Bassarov that it can be produced by heating ammonium carbamate at high

temperature of 130-140°C in sealed glass tubes.

1920 The company I.G. Farbenindustrie in Germany first engaged in commercialized

production of synthetic urea from ammonium carbamate in 1920.

1922 United States Patent Office approved the patent application of Carl Bosch and
Wilhelm Meiser for an improved method of producing synthetic urea. The method
 involved the forced mixing of NH3 and CO2. It also included the use of a container
that was capable of withstanding high pressure and heat.

1923 Subsequently, the Bosch-Meiser process (also called BASF process, for Badische
Anilin & Soda Fabrik of Germany) was applied in the large-scale production of
synthetic urea starting 1922.

2.1.6 Health effect of Urea

Although urea is not a lethal substance at low concentration, that is considered as a hazard in
industrial use.

Table 2-2- Potential health effects of Urea and First aid measures (Urea, 2015)
Potential Description First aid measures
health
effect
Inhalation Causes irritation to the respiratory Remove to fresh air. If not breathing,
tract. Symptoms may include give artificial respiration. If breathing
coughing, shortness of breath. May be is difficult, give oxygen. Get medical
absorbed into the bloodstream with attention.
symptoms similar to ingestion.
Ingestion Causes irritation to the gastrointestinal Induce vomiting immediately as
tract. Symptoms may include nausea, directed by medical personnel. Never
vomiting and diarrhea. May also cause give anything by mouth to an
headache, confusion and electrolyte unconscious person. Get medical
depletion. attention.
Skin contact Causes irritation to skin. Symptoms Immediately flush skin with plenty of
include redness, itching, and pain. water for at least 15 minutes while
removing contaminated clothing and
shoes. Wash clothing before reuse.
Thoroughly clean shoes before reuse.
Get medical attention if symptoms
occur.
Eye contact Causes irritation, redness, and pain. Immediately flush eyes with plenty of
water for at least 15 minutes, lifting
lower and upper eyelids occasionally.
Get medical attention immediately.
Chronic A study of 67 workers in an
exposure environment with high airborne
concentrations of urea found a high
incidence of protein metabolism
 disturbances, moderate emphysema,
and chronic weight loss.
Aggravation Supersensitive individuals with skin or
of Pre- eye problems, kidney impairment or
existing asthmatic condition should have
Conditions physician's approval before exposure to
urea dust.

Urea is not conserved as a fire hazard. But reactions with incompatibles may pose an explosion
hazard. Urea is kept in tightly closed container, stored in a cool, dry, ventilated area protected
against physical damage. Also, it should be isolated from incompatible substances.

2.2 RAW MATERIAL AVAILABILITY

2.2.1 Ammonia (NH3)

Ammonia (NH3) is a colorless inorganic compound, usually in gaseous form with a

characteristic pungent odor. It is one of the most commonly produced industrial chemicals in
the world. In the environment, ammonia is part of the nitrogen cycle and is produced in soil
from bacterial processes. Ammonia is also produced naturally from decomposition of organic
matter, including plants, animals and animal wastes.

Physical properties of Ammonia

Table 2-3 - Physical properties of Ammonia (Ammonia, n.d.)

Formula NH3
Molecular Weight (g/mol) 17.031
Boiling Point (°C) -33.35
Melting Point (°C) -77.7
Liquid density (kg/m3) at −33.3 °C 681.9
Gas Density 1.013 bar at 15 °C (kg/m3) 0.73

Ammonia is used in refrigeration plants of ice making machines, and at boiling point it gives
a white crystalline solid. It has a high heat of vaporization (23.3 kilojoules per mole at its
boiling point) and can be handled as a liquid in thermally insulated containers.
Ammonia can be highly toxic to a wide range of organisms. In humans, the greatest risk is
from inhalation of ammonia vapor, with effects including irritation and corrosive damage to
skin, eyes and respiratory tracts. At very high levels, inhalation of ammonia vapor can be fatal.
When it is dissolved in water, elevated levels of ammonia are also toxic to a wide range of
aquatic organisms.

Ammonia is one of the most abundantly-produced inorganic chemicals. The worldwide

production in 2016 was 146,000,000 metric tons. China produced 32.9% of the worldwide
production. (Suzette M. Kimball, 2016). But in Sri Lanka, large scale ammonia production
plants which are sufficient enough to supply raw material for a large-scale urea production
plant, are not available. Therefore, most appropriate and lowest cost method for supplying raw
material for a urea production plant which is going to be located in Sri Lanka, is importing
ammonia from another country.

2.2.2 Carbon Dioxide (CO2)

Carbon dioxide (CO2) is a colorless gas having a faint, sharp odor and a sour taste and it is a
minor component of Earth’s atmosphere (about 3 volumes in 10,000). CO2 formed in
combustion of carbon-containing materials, in fermentation, and in respiration of animals and
employed by plants in the photosynthesis of carbohydrates. The presence of the gas in the
atmosphere keeps some of the radiant energy received by Earth from being returned to space,
thus producing the so-called greenhouse effect.

Physical and Chemical Properties and uses of carbon dioxide

Table 2-4- Physical Properties of CO2 (Physical Properties for Carbon Dioxide)

Chemical Formula CO2

Molecular Weight (g/mol) 44.01
Boiling Point (°C) −78.5
Melting Point (°C) −56.6
Liquid Density -370C (kg/m3) 1101
Gas Density 0oC 1 atm (kg/m3) 1.977

It is an acidic oxide and reacts with water to give carbonic acid. Carbon Dioxide has many
industrial applications. Frozen carbon dioxide is known as “dry ice” which is useful as a
cooling agent and can save the frozen food in a freezer during a power failure. In manufacturing
and construction, carbon dioxide is used as a shield gas in welding and in the oil industry and
also used to simplify extraction from wells.

Carbon dioxide (CO2) as a raw material

Even though the current concentration is about 0.04% by volume and it is a minor component
in atmosphere, it cannot be easily captured to use as a raw material for a production processes
such as urea production. Here we considered about 2 methods of carbon dioxide formation to
take as a raw material for the urea production plant and most suitable method is going to be
used.

1. Carbon capturing method

The objective of the carbon capturing methods is to capture emitting CO2 due to biomass and
fuel combustion from the effluents discharged by industrial infrastructures. As shown in Figure
2-4, one of three methods are post-combustion process. It is the capturing of CO2 diluted in
combustion fumes and the entrapment is carried out using a liquid solvent (usually amines).
Here 3 to 15% CO2 is captured by volume. In pre-combustion process, carbon is captured
before combustion during the fuel fabrication process. Here 15 to 60% of CO2 is captured in
dry volume. In oxy-combustion process, concentrated smoke at 90% CO2 is generated by
producing pure oxygen combustion. Here more than 80% of CO2 by volume is captured.

Figure 2.4- Carbon Capturing methods (Ozcan, 2014)

2. Thermal decomposition of Calcium Carbonate (CaCO3)

 Limestone is mainly calcium carbonate, CaCO3. When it is heated, it breaks down to
form calcium oxide and carbon dioxide. Here are the equations for the thermal decomposition
of calcium carbonate:

CaCO3(s) CaO(s) + CO2(g)

In Sri Lanka limestone deposits are available (Figure 2-5). The sedimentary limestones of
Miocene age are best developed in the Jaffna peninsula, where they occur as hard, compact
rocks with a CaCO3, content of well over 95%. These same limestones extend along the north-
west coastal belt to Puttalam on the west coast (L.J.D.FERNANDO, 1986).

Figure 2.5- Limestone deposits in Sri Lanka (L.J.D.FERNANDO, 1986)

Even though the third method of carbon capturing is more efficient, all those carbon dioxides
capturing methods are more energy intensive. There for from the above 2 methods, most
economical method for supplying carbon dioxide for the urea plant is using thermal
decomposition of CaCO3 since limestone is available in Sri Lanka.
2.3 PROCESS SELECTION

In industry there are mainly four commercialized urea production processes can be identified;
Once through process, Snampogetti ammonia stripping process, Stamicarbon process and
Mitsui Toatsu process. A detail description on each process is stated below.

2.3.1 Once through urea manufacturing method

Ammonia is pumped through a high-pressure plunger pump and carbon dioxide through a
compressor into the reactor. The ammonia to carbon dioxide feed mole ratio is kept at
NH3/CO2=2/1 or NH3/CO2=3/1. The reactor is operated at about 200 atm pressure and
temperature range 175 0C-190 0C

The effluent from the reactor is reduced to a pressure of 2 atm and carbamate is decomposed
and stripped from the urea solution. This is done by sending the reactants through a heat
exchanger where heat is supplied by steam. The gas separated from the urea solution will
contain the excess ammonia and ammonia produced by the unfavorable decomposition of
carbamate. The ammonia in the waste stream to urea produced in weight ratio is about 0.6.
Average carbamate conversion to urea is about 60%. The ammonia present in the waste stream
will be absorbed by nitric or sulphuric acids to produce ammonium salts.

Figure 2.6 - Once through Urea Production Process (Das & Bhaskar, 2007)
2.3.2 Snamprogetti ammonia stripping process

Snamprogetti process established at Milan, Italy in 1956. First industrial urea plant based on
this process was came into effect in 1971. The process is based internal carbamate recycle
technique which also known as Snam NH3 stripping process.

In this process unconverted carbamate in the reactor effluent solution is stripped and recovered
from the reactor solution at the pressure of the reactor. Then the solution is condensed in a
high-pressure steam condenser to an aqueous solution and recycled back to the reactor. A part
of liquid NH3 in the feed is vaporized and used as a stripping agent to strip ammonium
carbamate.

The operating temperature of the reactor is 188oC and the operating pressure is about 150 bar.
The stripper also operates at same conditions. The high-pressure condenser that condenses
ammonium carbamate vapors operates at the same pressure conditions and the temperature
155oC. In this process the reactor has high ammonia-carbon dioxide ratio (NH3/CO2=3.2-3.4
molar). The whole process consists, (The Snamprogetti Urea Technology, 2005)

High pressure synthesis loop

This section consists the urea synthesis reactor and the stripper necessary to recycle NH3 and
CO2 not converted to urea in the reactor.

Medium pressure recovery section

In this section the purpose is to strip out the remaining ammonia and carbon dioxide from the
urea solution and after condensation recycle it back to the reactor along with the ammonia and
carbon dioxide aqueous solution result in the downstream section of the plant. Through
distillation column ammonia excess is separated and recycled to the reactor. The operating
pressure is 17 barg.

Low pressure recovery section

Further stripping of ammonia and carbon dioxide occur in this section. The operation pressure
is at 3.5 barg. the vapors of ammonia and carbon dioxide condensed and recycled back to the
reactor via medium pressure section.

Vacuum evaporation section

Urea solution that leaves the low-pressure section contains 70% urea by weight. In vacuum
concentration section the concentration of urea solution is increased to 98.1% by weight. This
operation happens in two steps at 0.23 and 0.03 bar abs.

Process condensate section

All possible heat recoveries are introduced into this section. And there is a possibility to
reutilize process water as boiler feed water. This helps to minimize the energy consumption.

Prilling section

98.5% b.w concentrated molten urea is sprayed at the top of the prilling tower. The height of
the prilling can be varied from 55 to 80 meters, according to climatic conditions. Spherical
particles of urea collected at the bottom of the tower. These spherical particles are called prills.

Figure 2.7 - Snampogetti Ammonia Stripping Process (Das & Bhaskar, 2007)

2.3.3 Stamicarbon process

In 1947 Stamicarbon in Netherlands introduced CO2 stripping-based process for Urea

production. In this process the unconverted ammonium carbamate in the reactor effluent
solution is stripped at the same pressure of the reactor using gaseous CO2 from the reactor feed
stream. The operating temperature and pressure of the reactor is 185-190oC and 140bar. The
stripper also operates at the same pressure and the temperature. After stripping the solution still
contains 15% of unconverted ammonium carbamate. This solution goes into a low-pressure
decomposer for further degassing. The stripped ammonium carbamate is partially condensed
and recycled back to the reactor. The heat generated from this condensation is used to produces
3.4atm steam that can be used for heating purposes in another section of the plant. In this
process the reactor has ammonia-carbon dioxide ratio 2.95-3 molar. Further concentration of
urea takes place in the evaporation section where 99.7% urea melt is produced (Stmicarbon,
2009).

Figure 2.8 - Stamicarbon Process (Das & Bhaskar, 2007)

2.3.4 Mitsui Toatsu process

This is a total recycle process. The unreacted ammonia and carbon dioxide are completely
recycled in this process. The reactor is operated at 1950C and 240 atm. NH3/CO2=2.8 in molar
ratio. The conversion of ammonium carbamate to urea is about 67%.

The unconverted carbamate is decomposed. Then ammonia and carbon dioxide are stripped
from the urea solution. The decomposition and stripping are done in three steps at three
equilibrium stages respectively 18 atm & 150 0C, 3.06 atm & 130 0C, & 1 atm & 120 0C. The
gases stripped from each stage is contacted in a counter current flow with the urea solution of
the preceding step. This done to minimize the amount of water vapor that will be recycled back
to the reactor. The reduced concentration of water in the recycle stream will favor the
decomposition of carbamate into urea. The excess ammonia is separated from the carbamate
solution and all the CO2 present will be scrubbed with counter current flow with the reflux
liquid. Here the ammonia is fed to the top of the high-pressure absorber. The obtained pure
ammonia is cooled using cooling water and condensed. The condensed ammonia is recycled
back to the reactor. The carbamate solution is also recycled back to the reactor for complete
recovery (Ono, Fujii, & Inoue, 1982).

2.3.5 Process Comparison and Selection

In order to select the most suitable process for urea production comparison between the four
processes needed. However once through process is least efficient of with lower yield and high
raw material consumption. Therefore, once through process is eliminated. Conditions for
remaining three processes are tabulated as in Table 2-5 - Process Comparison. Most favorable
conditions are bold in the table.

Table 2-5 - Process Comparison

Description Mitsu Toatsu Stamicarbon Snamprogetti

Feed NH3+CO2 NH3+CO2 NH3+CO2
Reactor 185-190oC 188oC
Temperature 195oC
Reactor Pressure 240atm 140bar 150bar
Stripper pressure 18atm 140bar 150bar
Stripper 150oC 167-187oC 190-208oC
temperature range
(top – bottom)
CO2 conversion in 64%
reactor 87% 60%
NH3 conversion in 36% 41%
reactor 70%
CO2 conversion in 79% 84%
synthesis NA
NH3 conversion in 79% 47%
synthesis NA
Recirculation stages 1 1 2
Price NA NA NA
Molar NH3/CO2 ratio 2.80 2.95 3.3-3.6
Molar H2O/CO2 0.39 0.5-0.6
ratio 0.50
NH3 Consumption 568 kg/mt 567 kg/mt 566 kg/mt
 CO2 Consumption 740 kg/mt 733 kg/mt 735 kg/mt
785 kg/mt (23 730 kg/mt (110 bar,
Steam Consumption 800 kg/mt bar,330oC) 510oC) Including
Excluding CO2 CO2 Compressor
compressor turbine turbine and
plus 50kg/mt LP hydrolyser
steam export (4.5 bar,
saturated)
Power Consumption 15 kWh/mt 20 kWh/mt 21 kWh/mt
Cooling water 71m3/mt 80m3/mt
Consumption 81m3/mt
Urea from 84% CO2 converts
The reactor recirculation stage into urea.
Urea Yield effluent contains contains 75 wt%
80% of urea urea. After
decompositions
recovery,
evaporation 99%
urea melt is
produced.

*NA – No information available

In order to ensure an inherently safer design, temperature and pressure are the vital
parameters. Therefore, even though Mitsu Toatsu process has a higher conversion rate; 87%
of CO2 conversion, due to the very high operating pressure the equipment cost would be much
higher and will pose much more hazardous conditions. Therefore, it was eliminated as a viable
method for manufacturing of urea.

In Stamicarbon process a lower ratio of NH3: CO2 is used, and CO2 is used in the scrubbing
process. This results in higher corrosion rates and therefore the equipment will have to be
replaced frequently which will disrupt production and incur higher maintenance cost.

Snampogetti process utilizes less steam; 730kg/MT, and lower ammonia consumption per
metric ton of Urea. The cooling load is comparatively reasonable with acceptable level of total
conversion. Since the process utilizes lower pressure compared with other two processes this
is safer to design. Therefore, after considering all parameters and scenarios it was decided that
the most suitable process for manufacturing of urea was Snamprogetti process in which the
conversion, capital expenditure, maintenance cost and risk are at acceptable levels.
 3 FEASIBILITY REPORT AND PROCESS CHEMISTRY
ESTABLISHMENT

3.1 RAW MATERIAL COST AND PRODUCT VALUES

3.1.1 Ammonia

Importing Ammonia à Ammonia is frequently imported to Sri Lanka from large scale
manufacturer countries such as India, China mostly in the forms of anhydrous liquid ammonia
(without water) packed in IMO tanks, ammonia in aqueous solution, and liquid ammonia
(liquid ammonia) 23-25%. Since ammonia with high concentration results high yield of
products, here we decide to import anhydrous liquid ammonia. And also, ammonia is going
to be imported from India because of the low transportation cost and can be buy at low cost
rates.

Anhydrous liquid ammonia is predominantly used in fertilizers supplying usable nitrogen for
agricultural productivity and it is usually stored as a liquid in refrigerated tanks at –33.3°C and
atmospheric pressure, often in doubled-walled tanks with the capacity for hundreds or
thousands of tones.From Ammonia shipment from India to Sri Lanka data sheet for March of
2017 (Info Drive India, 2017) average cost of 1 kg of anhydrous ammonia is 0.583 USD.

Following shows the tariff charges gazetteted by Sri Lanka Custom Authority for importing
anhydrous ammonia (Inorganic chemicals- organic or inorganic compounds, 2017).

VAT (Value added tax) = 15%

PAL (Port and Airport Development Levy) = 7.5%

NBT (Nation Building Tax) = 2%

Then the cost for 1kg of anhydrous ammonia importing

)* ,.* -
= 0.583 + (0.583 × )++ + 0.583 × )++ + 0.583 × )++ )

=0.726 USD
3.2 LOCAL, REGIONAL & GLOBAL MARKETS FOR UREA AND PRICE
ANALYSIS

3.2.1 Global Demand

Urea is one of most widely used chemical in the world. With the rising population the
demand for food increases. Adding urea as a fertilizer, increases crop yield per acre.
Therefore, the importance of this chemical rises annually.

Agriculture based countries are major consumers of urea. 90% of global urea production is
used for the manufacture of fertilizer. China, India, United States and Brazil are the major
importers of urea. Asia-pacific region caters almost two thirds of the current global demand of
Urea, which is approximately 184 million tons per year. India is the main Urea producer while
China and Russia are the main Urea exporter in the world as per the current situation. Asia-
pacific countries like Indonesia, Russia and Pakistan also produce Urea in large quantities.
Even the Middle East plays a critical role in catering the Urea export market, with the aid of
countries like Qatar, Saudi Arabia, Egypt, Oman, Iran etc. The availability of natural gas
resources in the Middle East countries offers ideal conditions for production.

The global consumption of urea has grown over the past decade. This is mainly due to increase
in consumption of fertilizer for production of food. India and China accounts for the largest
consumption of urea in the world. The total demand of India for the year ended March 2016
was 32 million MT and out of the quantity, 7.5 million MT has been imported (Chakraborty &
Singh, 2017).

3.2.2 Regional Demand

In South Asian Subcontinent, India, Pakistan and Bangladesh are the largest consumers for
urea. Since India is a larger consumer globally, there is an opportunity to export urea to India
in larger Quantities. In 2014 the total urea import to India was 8,749,000 MT and its growing
annually (India: Urea, production (tonnes), 2014). The total demand in Pakistan is 5.59
million metric tons; 696,034 MT was imported in 2014 (Pakistan: Urea, production (tonnes),
2014). 2.581million MT was the total demand of Bangladesh in 2014 and 1.742 million MT
was imported (Bangladesh: Urea, production (tonnes), 2014). Sri Lanka has opportunity to
cater the demand on the Indian subcontinent because country is situated in strategically
competent location. Since the demand for fertilizer is increasing with the rising population,
we can anticipate future growth in urea demand of above countries.

3.2.3 Local Demand

Sri Lanka has produced urea during 1980 to 1985 era, abled to cater the own demand and
export. The peak production was 96,981 MT in the year 1982. However due to prevailing
conditions in the country the manufacturing facility had to be closed down in 1985. In Sri
Lanka, majority of urea used as fertilizer. The total demand in 2014 was 453,691 MT (Sri
Lanka: Urea, production (tonnes, 2014); all imported. The consumption of urea fertilizer
under subsidized scheme can be shown as in Table 3-1 - Urea Fertilizer Consumption in Sri
Lanka.

Table 3-1 - Urea Fertilizer Consumption in Sri Lanka

District Urea fertilizer consumption (MT)

Ampara 3789
Anuradhapura 1809
Badulla 1203
Baticoloa 1054
Colombo 44
Galle 122
Gampaha 236
Hambanthota 1719
Kaluthara 223
Kandy 205
Kegalla 107
Kilinochchi 80
Kurunegala 3910
Mannar 361
Matale 433
Mathara 348
Monaragala 1175
Mulathive 71
Nuwara Eliya 295
Polonnaruwa 1999
Puttalam 1088
Rathnapura 660
Trincomalee 1398
Vawnia 474
Total 22800
According above table most of the demand for urea emerge from Eastern and Uva provinces.
This information is vital when determining a location for the plant to minimize the
transportation cost and time lag. The total demand for urea in Sri Lanka is about 450,000 MT
according to 2014 data. If we anticipate 4.2% (Sri Lanka Agriculture Value added Annual
Percent Growth, 2018) per annum growth which is the growth rate of agriculture value
addition, the demand for next years can be predicted as inTable 3-2 - Demand Forecast for Sri
Lanka,

Table 3-2 - Demand Forecast for Sri Lanka

Year Demand (MT)

2015 468,900

2016 488,593

2017 509,114

2018 530,497

2019 552,778

2020 575,995

2021 600,186

2022 625,394

The total regional demand, which is based on India, Pakistan and Bangladesh, is about 11.187
million MT. When compared with Sri Lankan demand, this is 25 times higher value. The major
objective of designing this plant should be to cater Sri Lankan urea demand. However, since
the regional demand is significant, it is economically beneficial to export some quantity of
urea. Thus, as the initial phase it is more feasible to design 1,500,000 MT/annum (which is
about 3 times the local demand) plant to reduce the risk of failure. The output of decided based
on the payback period where it can be recovered on 9 years (see ECONOMIC EVALUATION
section). From this option ⅓ of output from the facility able to cater domestic demand while
remaining ⅔ can be exported depending on the regional demand.
3.3 HEALTH, SAFETY AND ENVIRONMENT

3.3.1 Health

Heath hazards can be categorized mainly into two categories. Occupational health and the heath
of residents in the vicinity of the production facility. Since CO2 and NH3 are used as the raw
materials in Urea production plant, proper handling of these two substances is crucial.
Although CO2 is not sheer toxic, inhalation in great amounts can cause health issues. Situations
as such may arise due to leakages in inventory, vessels and piping system. Exposure to
anhydrous ammonia may happen via skin contact basically. Therefore, careful handling is
required. Inhalation of gaseous ammonia is also possible in case of a leakage in vessels.

Urea, the end product is produced as prills. Formation of prills may also cause the formation
of particulate matters, which workers will easily expose to. This scenario can even happen in
a daily basis and could critically affect health. Ammonium carbamate can be distinguished as
the intermediate product while Biuret is the unfavorable product in the urea production plant.
Since the production runs in a closed loop, chance of exposure to these two components is less.
But in a case like a leakage or during cleaning and maintenance, such substances could get
exposed to workers. As both of these are fairly toxic, workers will have to be really attentive
to avoid any undesirable consequence.

Prior to the production of Urea, CO2 is also generated within the same plant via thermal
decomposition of Calcium carbonate. And coal is more likely to be used as a fuel source in the
mentioned process and also for the generation of process steam. Workers will have to be careful
when manipulating both Calcium carbonate and coal since particulate matters generated from
those can easily migrate into the respiratory systems. In summary, occupational health issues
can be identified as in Table 3-3 - Summary of Occupational Health and Issues,

Table 3-3 - Summary of Occupational Health and Issues

Carbon dioxide In high concentrations breathing difficulties, suffocation,

death
Toxic

Ammonia Inhalation of high concentration breathing difficulties,

inability to distinguish smells, dizziness, suffocation, death
 Urea Particulate matter results cough in inhalation and suffocation
and
respiratory diseases
Ammonium Skin and eye irritant
carbamate
Biuret Hazardous in case of skin contact, of eye contact, of ingestion,
of inhalation (irritant).
Coal Flammable, particles could cause respiratory issues
Calcium carbonate Particles could cause respiratory issues
Noise Temporary hearing deficiencies, permeant hearing
deficiencies, Increase of mental stress.
Temperature Thermal burns, Heat strokes
Vibrations Vibration syndrome
Ergonomics Physical disorders, joint pains, increase of mental stress,
problems in vision in eyes.

If the emission limits not complied with the standards the community living nearby the facility
will be affected. Exposure to ammonia gas, particulate matter from calcium carbonate and urea
prills could cause respiratory health issues. Failure to treat the effluent water could cause
drinking water issues and pollution of water bodies and mainly leads to chronic diseases among
the community. Noise has to be kept at permissible levels in order to prevent the disturbances
to neighborhoods. There is also a possibility fire and explosion hazards that cause damage up
to several kilometer because the process demands high pressure and temperature with
involvement of toxic gases.

To overcome the such issues, emission control system in the plant needed to be maintained and
operated properly including the wastewater treatment plant. The nearby community should be
educated on hazards and train them to react in an emergency situation. Establishment of Fire
and safety department inside the facility is a must due to its magnitude of intense operations.
Pipelines, tanks should be inspected regularly to prevent leaks and ruptures, and also needs to
construct wind barriers to prevent the fly over of particulate materials from dumping yards.

3.3.2 Safety

Safety should be a major concern when developing the plant. Consideration of inherent safety
at the design stage itself minimizes the cost for operational safety activities thus minimizes the
vulnerabilities. The process operates at high temperatures and pressure and the materials used
in the process is relatively hazardous. When designing the plant, the wind direction, rainfall,
placements of process area and storage facilities, contingency plans should be critically
evaluated in order to actively engage for the safety.

Operation areas that has high temperatures, such as reactor, furnaces, kiln and heat exchangers,
a safety region should be marked how far the operators could reach during its operations.
Moreover, safety of rotating equipment is also vital and safety railings should be constructed
around the moving parts of equipment to prevent accidently contact of body parts. During a
maintenance process, LOTO concept can be adopted to prevent accidently startup of
maintaining equipment so that the technician could conduct his work safety.

Proper personal protective equipment should be worn when handling chemicals. This includes
safety gears, respiratory masks, safety goggles, high visibility jackets, gloves etc. It is also vital
that proper training should be given for workers of plant regularly to ensure the robust safety
awareness. The chemicals that used in the facility has to be stored properly. This requires
knowledge on chemical handling and storage which has to be obtained from chemical
manufactures and material safety data sheets.

Moreover, compliance with occupational standards such as National Institute of Occupational

Safety and Health act of Sri Lanka, Office and Shop Act and OSHA standards are important
guideline to govern the safety culture in the facility.

3.3.3 Environmental Impact Assessment

In a building of process plant, the environmental impact has to be assessed. The assessment
should be done to determine the impact for the surrounding due to the building plant. Facilities
should be provided for the effective disposal of the effluent without any public nuisance. When
selecting a plant location, permissible tolerance levels for discharging various effluents must
be considered and potential requirements for additional waste treatment facilities should be
considered. The disposal of harmful and toxic effluents will be covered by legal regulations,
and appropriate authorities must be consulted to determine the standards which must be met.
Since there is enough land space with low population in selected Gomarankadawala area,
required waste treatment processes can be installed without any barriers.

Possible emissions; - Snamprogetti ammonia stripping process, the manufacturing method of

producing Urea allows only a limited amount of gas emissions as it’s predominantly a closed
loop. The only possible emission during the process can take place in the vacuum evaporator
when Urea is concentrated by evaporating water from the solution. Even though both NH3 and
CO2 are stripped via numerous units prior to this stage, there may still contain slight amounts
of these gases; and may emit to the atmosphere with the water vapor. Apart from that, emissions
can happen during the production of CO2 and process steam. Flue gas is expected to transmit
from the furnace and the boiler respectively. Also, there is a possibility of particulate matter
emissions as fly ash and bottom ash due to the use of bio mass or coal in the heat supplying
units. Since Urea is produced as prills, there is a possibility of generating more particulate
matter in the process. Further, the leakages during storage, carriage and production (in vessels)
could lead raw materials, end product and even the intermediate products get transferred to the
environment.

Elevated temperatures; - In this selected process of ammonia production, we encounter a

furnace, a boiler and a reactor that operate in intense heat. These elevated temperatures are
bound to have adverse effects towards the surrounding, i.e., the environment.

Excessive noise; - In the aforementioned process, there is a requirement for equipment like
pumps and compressors and also in some cases the pressure difference between two units is
significant. In such scenarios these pumps and compressors could generate an excessive noise
leading to environmental effects.

Energy wastage; - In Snamprogetti ammonia stripping process the reactor operates at an

elevated pressure of 155 bar. And CO2, which is used as a reactant has to be compressed up to
that level before introducing to the reactor. As a matter of fact, the compressor efficiencies are
significantly low (below 40%) and due to that the energy wastage could be critical.

A summary of undesirable impact for environment is tabulated in Table 3-4 - Undesired

Environmental Impacts

Table 3-4 - Undesired Environmental Impacts

Incident Effects

• Unpleasant odor (even at low concentrations)

• Hazardous to aquatic organisms
emissions
Possible

NH3 • Can harm vegetation under high concentrations

• May encourage acidification of ground & water bodies over
time
 CO2 • Can contribute to greenhouse effect, hence global warming

• Cause visibility impairment

Particulate • Can acidify water bodies
matter • Cause acid rains
• Damage farm crops and sensitive forests

Can result in
Flue gas • Global warming
• Smog
• Acid rains – can be harmful to vegetation and water life

Elevated temperatures • Can have adverse effects on the wild life (i.e. Birds)

• Can cause annoyance to nearby residents

Excessive noise
• May effect on the existing pattern of the nature

Each form of electricity generation has an adverse effect on the

Energy wastage environment. Hence any wastage of energy has an indirect, but a
definite consequence to the environment.

Environmental impact monitoring; - Environmental legislation requires responsible parties

for operations that effect the environment to execute environmental impact monitoring. In the
case of this plant, the monitoring should align with the rules and regulations governed by the
Central Environmental Authority. In the aforementioned process, the possible emissions are
broadly the emissions to atmosphere; yet the acts & regulations from the CEA don’t cover for
CO2 or NH3; which are the major emissions. Further if we consider CO as the most
predominant hazardous constituent of flue gas, a permissible level could be determined. And
in scenarios like cleaning and maintenance, there may raise a need of discharging the effluent
to an inland water body closed by. Therefore, monitoring for possible hazardous substances in
such cases could be vital too. When considering the permissible noise levels, the determined
plant location, Gomarankadawala is treated as a rural residential area. Discharge standards
according to Central Environmental Authority (CEA) as in Table 3-5 - Permissible Discharge
Levels

Table 3-5 - Permissible Discharge Levels

 Permissible level as per
Mode of discharge Unit measured
CEA
Carbon monoxide From flue gas to the
ppm 50
(CO) atmosphere
From the effluent to inland
Ammoniacal Nitrogen mg/l 50
water bodies
Day time Night time
Noise - dB
55 45

Preventive measures; - For the mitigation of environmental impacts, preventive measures can
be taken as in Table 3-6 - Preventive Measures

Table 3-6 - Preventive Measures

CO2 & NH3 emissions from the By means of a wet scrubber at the evaporator outlet, Discharge
vacuum evaporator gas then directed to stack where standby incinerator is present if
scrubber fails or overloads.
Flue gas from the furnace & the Strike a balance between minimum acid dew point and
boiler maximum thermal air discharge to atmosphere. Regular
maintenance of boilers and furnaces and tuning the flames.
Particulate matters By means of bag filters and electrostatic precipitators.

Vessel & container leakages Construction of dikes around the tanks, wind barriers, proper
drainage system which direct to wastewater system.
Elevated temperatures By maintaining a proper ventilation system and optimum
insulation of process vessels
Excessive noise Regular maintenance of pumps and compressors, Acoustic
insulation at gas throttling and expanding area of pipelines and
vessels

3.4 ECONOMIC EVALUATION

Economic evaluation is carried out based on limited cost data and design details. The value
derived in preliminary evaluation could have ±30% variance. To arrive at a more realistic
capital cost estimation for the plant following equation can be used (Sinnott, 1999).
 𝑆- +.4
𝐶- = 𝐶) × 1 3
𝑆)

This equation is also known as the six- tenth rule. C2 and C1 demonstrate capital cost of plant
which has the capacities S2 and S1 respectively. A study conducted on urea fertilizer complex
project in Mozambique shows the capital and operational costs that are anticipated with
development of urea production facility. The capacity of plant in Mozambique is 1725 MT/day.
The capital cost associated with project was 1000 Million USD; 505m USD for urea plant and
495m USD for utilities, offsite facilities (Toyo Engineering Corporation, Sumitomo
Corporation, 2012)The plant that that is developed in this project has a capacity of 1.5 million
MT per year; 4110 MT per day. According to above equation, capital cost for plant can be
derived as 1.683 billon USD. For calculation of operational costs, following breakdown has
been considered in table Table 3-7 – Cost Factors (Sinnott, 1999).

Table 3-7 – Cost Factors

Fixed Operational Cost Variable Operational Cost

Maintenance 5% of Capital Raw material - 726 USD/MT
cost/year Ammonia
Labor 1000 workers at Raw material - 20 USD/MT
60000 LKR average Limestone (Young's Sand &
salary Gravel, 2018)
Laboratory cost 3% of production Shipping and 20% of selling price
cost Packaging
Plant Overheads 50% of labor cost Processing cost 35% of selling price
Taxes 2% of Capital
cost/year
Insurance fees 2% of capital
cost/year
Licensing and 5% of sales price
Royalty fees

Selling price of Urea is 120 INR/kg (Zauba Technologies & Data, 2014). Conversion of USD
to INR is taken as 1 USD = 67.52 INR and Conversion of USD to LKR is taken as 1 USD =
160 LKR. Thus, the selling price of urea is about 1777 USD/MT. From above factors the cost
breakdown for the plant is as in Table 3-8 – Cost Breakdown

Table 3-8 – Cost Breakdown

Million USD Million USD

Revenue 2665.5
Operational Costs Ammonia 616.4
 Limestone 50
Shipping and 533.1
Packaging
Processing 932.925 (2132.4)
Fixed Costs Maintenance 168.3
Labor 0.5625
Laboratory and R&D 58.8
Plant Overheads 0.2812
Taxes 33.66
Insurance 33.66
Licensing and 133.275 (428.5395)
Royalty
Profit per annum 183.54

The payback period for the facility can be calculated as follows,

𝑇𝑜𝑡𝑎𝑙 𝐶𝑎𝑝𝑖𝑡𝑎𝑙 𝑐𝑜𝑠𝑡 𝑓𝑜𝑟 𝑝𝑙𝑎𝑛𝑡

𝑃𝑎𝑦𝑏𝑎𝑐𝑘 𝑃𝑒𝑟𝑖𝑜𝑑 (𝑖𝑛 𝑦𝑒𝑎𝑟𝑠) =
𝑃𝑟𝑜𝑓𝑖𝑡 𝑝𝑒𝑟 𝐴𝑛𝑛𝑢𝑚

1683 𝑀𝑖𝑙𝑙𝑖𝑜𝑛 𝑈𝑆𝐷

𝑃𝑎𝑦𝑏𝑎𝑐𝑘 𝑃𝑒𝑟𝑖𝑜𝑑 (𝑖𝑛 𝑦𝑒𝑎𝑟𝑠) =
183.54 𝑀𝑖𝑙𝑙𝑖𝑜𝑛 𝑈𝑆𝐷 𝑝𝑒𝑟 𝑎𝑛𝑛𝑢𝑚

𝑷𝒂𝒚𝒃𝒂𝒄𝒌 𝑷𝒆𝒓𝒊𝒐𝒅 (𝒊𝒏 𝒚𝒆𝒂𝒓𝒔) ≈ 𝟗. 𝟏𝟕 𝒚𝒆𝒂𝒓𝒔

Since this is a large-scale manufacturing facility the payback period can be expected within 5-
10 years (LeanManufacturing, 2009). According to above calculations the plant can earn
183.54 million USD per annum and cover its capital cost in 9.17 years. Thus, this is a viable
option to be invested on.

3.5 PROCESS CHEMISTRY

3.5.1 Process Technology

Many methods are being used to produce urea. However, for all the processes the underlying
principle is the same. Urea is produced by the following reactions

𝐾𝑐𝑎𝑙
𝐶𝑂- + 2𝑁𝐻f ↔ 𝑁𝐻- 𝐶𝑂𝑂𝑁𝐻h ∆𝐻 = −37.4
𝑚𝑜𝑙

𝑘𝑐𝑎𝑙
𝑁𝐻- 𝐶𝑂𝑂𝑁𝐻h ↔ 𝑁𝐻- 𝐶𝑂𝑁𝐻- + 𝐻- 𝑂 ∆𝐻 = +6.3
𝑚𝑜𝑙
Ammonia (liquid) and carbon dioxide (gas) are pumped at high pressure (140-250 atm) into
the reactor at high temperature (1700C-2000C). This is an exothermic reversible reaction
producing carbamate. Then the carbamate is decomposed to produce urea. This is also an
equilibrium reaction. The energy output by the initial reaction provides the heat required for
the second reaction.

The second reaction is the slower of the two reactions and will be the rate limiting step. In the
decomposition of carbamate, the following reaction should be avoided as Biuret will affect the
growth of some plants.

2𝑁𝐻- 𝐶𝑂𝑁𝐻- ↔ 𝑁𝐻- 𝐶𝑂𝑁𝐻𝐶𝑂𝑁𝐻- + 𝑁𝐻f

3.5.2 Operating variables

Temperature à The conversion of ammonium carbamate to urea increases with the

temperature. It is about 50% at 170oC-190oC when the pressure is high enough keep the
reactants in liquid state. The rate of reaction increases with the temperature. At the range of
170oC – 200oC we can obtain an acceptable equilibrium in 0.3-1 hours or at lower temperatures
with excess ammonia. Corrosion difficulties increase with the temperature. Because of this
180oC-210oC can be accepted as the optimum range for most processes (Chapter XI Urea,
1982). The change in conversion with temperature is varied as in Error! Reference source
not found. at 180 atm pressure.
 Error! Reference source not found.

Pressure à The conversion increases with pressure at constant temperature if the reactants are
in the liquid phase. If reactants are in the vapor phase further increase of pressure is not
beneficial. Pressure must be determined considering the rate of reaction and stoichiometric
NH3: CO2 ratio. Pressure range of 140-250 atm is commonly used for 180oC-210oC
temperature range (Chapter XI Urea, 1982). Conversion of urea changes as in Figure 3.1 -
Conversion vs Pressure for Urea with pressure at 1750C.
 Figure 3.1 - Conversion vs Pressure for Urea

Mole ratio of NH3: CO2 àAmmonia – carbon dioxide mole ratio above two have better rate
of reaction. This increases the percentage of CO2 converted to urea but decreases the percentage
of NH3 converted to urea. Recycling of excess NH3 is easier compared to CO2. Because of
this most processes use 50% or more excess ammonia in the reactor. So, the mole ratio of
ammonia and carbon dioxide is 3:1 or more (Chapter XI Urea, 1982).

Residence time à It takes somewhere around 20 minutes to attain equilibrium for the urea
reaction. For higher conversion of urea, sufficient time must be provided in the reactor.

3.5.3 Optimum conditions

Maximizing the percentage of conversion of urea in the reactor is not economical, because that
would require an excessive retention time. the main goal is to get maximum amount of urea
production per unit time. but the cost of recycling unreacted CO2 and NH3 as well as the cost
of increased reactor size and corrosion difficulties which increase with temperature must
consider when deciding the operating conditions. Typical operating conditions are:
temperature, 180oC-210oC; pressure, 140-250 atm; NH3: CO2 mole ratio, 3:1 - 4:1; and
retention time, 20-30 minutes.
Biuret formation à One of the problems that occur during the production of urea is biuret
formation. Biuret adversely affect the growth of some plants. Biuret content in urea should not
exceed 1.5% by weight.

2NH2CONH2 NH2CONHCONH2 + NH3

 4 HEAT AND MASS BALANCE AND PROCESS
FLOWSHEET DEVELOPMENT

4.1 DEVELOPMENT OF PROCESS FLOW DIAGRAM

The selected process for the production of urea is Snampogetti ammonia stripping process.
According to the Figure 2.7 - Snampogetti Ammonia Stripping Process (Das & Bhaskar, 2007)
Process contains a Reactor, Stripping column, Pool condenser, Medium and low-pressure
Decomposers, Evaporator and a prilling tower. However, to recover the effluent gases leaving
from MP and LP Decomposers a separate system needed to be developed.

To recover the gases the effluent gases from decomposers are condensed and directed into two
separator vessels. In these separator vessels, water is removed in liquid form, from the stream
and ammonia and carbon dioxide leaves as gas. The water is then send to the wastewater
treatment plant. The separated ammonia and carbon dioxide gases then send through a carbon
dioxide absorber to recover the ammonia. Calcium hydroxide is used to absorb carbon dioxide.
The recovered ammonia is then compressed and pump to the process.

For removal of water from Urea two evaporators are used as different pressures. This is because
to increase the efficiency of evaporation of water and maintain the temperature of the system
just above the melting temperature of urea to prevent decomposition and formation of biuret.
To supply the vacuum conditions for evaporators steam jet ejectors are used and the evaporated
water is then send for treatment.
4.1.1 Process Flow Diagram

Figure 4.1 - Process Flow Diagram

4.1.2 Process Streams

Table 4-1 - Process Streams

Stream Stream Description Stream Stream Description
No. No.
1 Ammonia feed to reactor 13 Evaporated water vapor
2 CO2 Feed to reactor 14 Concentrated urea
3 Ammonia carbamate recycle 15 Evaporated water vapor
4 Reactor Effluent 16 Air inlet to the prilling tower
5 Ammonia stripping gas to stripper 17 Air outlet
6 Stripping Column bottom product 18 Urea prills – Final product
7 Stripping Column top product 19 Un-condensed gases from pool
condenser
8 MP decomposer bottom product 20 Separator 1 effluent
9 MP decomposer top product 21 Absorber feed
9a Condensed MP decom. top product 22 Separator 1 effluent
10 LP decomposer bottom product 23 Absorber feed
11 LP decomposer top product 24 Ammonia gas recycle
11a Condensed LP decom. Top product 25 Calcium hydroxide feed
12 Concentrated urea 26 Calcium carbamate outlet

4.2 MATERIAL BALANCE

Following Data has been considered for the calculation of material balance

Final product from prilling tower only contains urea and biuret 98.5% and 1.5% weight basis
respectively. Daily production of urea is 4110 MT/day which approximately equals to 172 MT
of urea per hour.

Since biuret in the final product is 1.5% (w/w)

172
𝐵𝑖𝑢𝑟𝑒𝑡 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑝𝑒𝑟 ℎ𝑜𝑢𝑟 = × 1.5 = 2.6193 𝑀𝑇/ℎ𝑟
98.5

Which is 0.02543 Mmol/hr

Molecular weights of components,

NH3 à 17 CO2 à 44 Urea à 60 Biuret à 103

Ammonium Carbamate à 78
Data for Ammonia, CO2 and water liquid vapor behaviors for respective temperatures and
pressure are taken using ASPEN PLUS V9 under the “IDEAL” Property method. These data
are mentioned in respective sections.

4.2.1 Material Balance for Reactor

Following assumptions are made for calculation of material balance for the reactor.

1. Biuret and Urea are only produced in the reactor.

2. Carbamate recycle stream only contains ammonium carbamate and the all the
carbamate from the recycle stream converted into urea
3. Conversion of CO2 Ammonium Carbamate is 30%

Data

1. Overall Conversion of CO2 to urea in the synthesis is 84% mole basis.

2. CO2 to Ammonium Carbamate conversion is 30%
3. Ammonia to CO2 feed ratio is 3.3 mole basis
4. Biuret concentration in final product is taken as 1.5% weight basis of urea. Therefore,
by calculations biuret formation in the reactor should be maintained below
2.6193 Mt/ℎ𝑟

172 𝑀𝑡/ℎ𝑟
𝐵𝑖𝑢𝑟𝑒𝑡 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑝𝑒𝑟 ℎ𝑟 = × 1.5 = 2.6193 Mt/ℎ𝑟
98.5

Equations,

𝐶𝑂- + 2𝑁𝐻f − −→ 𝑁𝐻- 𝐶𝑂𝑂𝑁𝐻h

𝑁𝐻- 𝐶𝑂𝑂𝑁𝐻h − −→ 𝑁𝐻- 𝐶𝑂𝑁𝐻- + 𝐻- 𝑂

2𝑁𝐻- 𝐶𝑂𝑁𝐻- − −→ 𝑁𝐻- 𝐶𝑂𝑁𝐻𝐶𝑂𝑁𝐻- + 𝑁𝐻f

For calculation of Material Balance for reactor see APPENDIX Reactor.

Material flow through the reactor can be shown as follows,

Figure 4.2 - Reactor streams

Table 4-2 - Ractor Stream Flow Rates

Stream Component Molar flow Mass flow Total Inflow
No. rate rate (MT/hr) (Total
(Mmole/hr) Outflow)
Inlet 1 NH3 11.263 191.471 394.92
2 CO2 3.4131 150.1764
3 Ammonium 0.683 53.274
Carbamate
Outlet 4 NH3 4.69296 79.78032 (394.92)
CO2 0.15386 6.75752
Ammonium 1.024 79.872
Carbamate
Urea 2.867 172.02
Water 2.867 51.61
Biuret 0.02543 2.6162

4.2.2 Material Balance for High Pressure Stripping Column

Assumptions,

1. No ammonium Carbamate decompose in the stripper

2. Water, Ammonia and Carbon dioxide vapor liquid behavior does not affect by urea,
Ammonium carbamate or biuret, Thus, they behave independently
 3. 66.7% of Ammonium carbamate is stripped out to the vapor stream and rest flows
with the bottom

Data,

1. Input flow rate and composition is equal to reactor effluent stream (stream 4)
2. Stripping ammonia (stream 5) for the column is chosen as 10% of ammonia input
flow rate to the reactor. Which is 1.1263 Mmole/hr.
3. For Ammonia, CO2 and Water flow rates for vapor stream and Bottom stream
obtained from APEN PLUS V9 and shown below

Components Moles on vapor Moles in liquid

stream (7) stream (6)
Water 0.139623 2.72738
NH3 2.24581 2.25749
CO2 0.0993061 0.0358938

Material flow through the High-Pressure Stripper can be shown as follows,

Figure 4.3 - HP Stripper Streams

 Table 4-3 - HP Stripper Material Flow Rates
Component Molar Flow Rates (Mmole/hr)
Inlet Outlet
Stream 4 Stream 5 Stream 6 Stream 7
Urea 2.867 0 2.867 0
Biuret 0.02543 0 0.02543 0
Ammonium 1.024 0 0.341 0.683
Carbamate
Water 2.867 0 2.72738 0.13962
NH3 4.69296 1.1263 2.25749 2.24581
CO2 0.15386 0 0.0358938 0.0993061
Total 10.34199 1.1263 8.25419 3.1677361
Total 11.4 (11.4)
Inflow/(Outflow)

4.2.3 Material Balance for Medium-Pressure Decomposer and Low-Pressure

Decomposer

Assumptions,

1. Decompose of Ammonium carbamate only produces NH3 and CO2 not urea.
2. 50% of ammonium carbamate is decomposed in MP decomposer and rest is
decomposed at LP decomposer.
3. Bottom liquid leaves from the LP condenser contains trace amounts of NH3 and CO2
thus considered zero.

Data,

1. Input to the MP decomposer is the bottom from High pressure separator (Stream 6).
2. Operating pressures for MP and LP Decomposers are 17 barg and 3.5 barg
respectively.
3. Operating Temperatures for MP and LP Decomposers are 1550C and 1200C
respectively.

Decomposition reaction;

NH2 COONH4--→CO2+2NH3

For Calculations for MP and LP decomposers see APPENDIX MP and LP Decomposers

Material flow through the MP and LP Decomposers can be shown as follows,

 Figure 4.4 -MP and LP Decomposers Flow Streams

Table 4-4 – MP Decomposer Material Flow Rates

Mass Flow Rates (MT/hr)
Component Inlet Outlet
Stream 6 Stream 9/9A Stream 8
Urea 172.02 0 172.02
Biuret 2.6162 0 2.6162
Ammonium Carbamate 26.598 0 13.299

Water 47.637378 18.223524 29.413872

NH3 37.773983 41.34536 2.230723
CO2 1.2281192 8.5946388 0.14208304
Total 287.8736802 68.1635228 219.721878
Total Inflow/Outflow 287.87 (287.88)

Table 4-5 - LP Decomposer Material Flow Rates

Molar Flow Rates (MT/hr)
Component Inlet Outlet
Stream 8 Stream 11/11A Stream 10
Urea 172.02 0 172.02
Biuret 2.6162 0 2.6162
Ammonium Carbamate 13.299 0 0

Water 29.413872 8.3918034 21.022056

NH3 2.230723 7.6166341 0
 CO2 0.14208304 7.5418596 0
Total 219.721878 23.5502971 195.658256
Total Inflow/(Outflow) 219.72 (219.72)

4.2.4 Material Balance for Vacuum Evaporators

Assumptions: - Only water evaporates in both evaporators

For Calculations see APPENDIX

Material flow through the high vacuum and low vacuum evaporators can be shown as follows,

Figure 4.5 - Evaporator Flow Streams

Table 4-6 - Low Vacuum Evaporator Flow Rates

Stream 10 Stream 12 Stream 13
Component
F (MT/hr) L1 (MT/hr) V1 (MT/hr)
Inlet Outlet
Urea 172.02 172.02 0
Biuret 2.6162 2.6162 0
Water 21.022056 14.5896 6.43247
Total 𝟏𝟗𝟓. 𝟔𝟓𝟖 𝟏𝟖𝟗. 𝟐𝟐56 𝟔. 𝟒𝟑𝟐𝟒𝟕
Total Inflow/(Outflow) 195.658 (195.66)

Table 4-7 - High Vacuum Evaporator Flow Rates

Component Stream 12 Stream 14 Stream 15
 L1 (MT/hr) L2 (MT/hr) V2 (MT/hr)
Inlet Outlet
Urea 172.02 172.02 0
Biuret 2.6162 2.6162 0
Water 14.5896 0.7285753 13.861
Total 𝟏𝟖𝟗. 𝟐𝟐𝟓𝟔 𝟏𝟕𝟓. 𝟑𝟔𝟒𝟕𝟖 𝟏𝟑. 𝟖𝟔𝟏
Total Inflow/(Outflow) 189.2256 (189.2257)

4.2.5 Material Balance for Prilling Tower

Assumptions:

1. All water evaporates

2. Exit air is saturated in water.

Data

1. Relative humidity (RH) in Trincomalee district ~ 70%(AVERAGE HUMIDITY IN

TRINCOMALEE, n.d.)
2. Dry bulb temperature in Trincomalee ~ 300C
(Trincomalee Wether Forcast, n.d.)

For Calculations see APPENDIX

Material flow through Prilling tower can be shown as follows,

Figure 4.6 - Prilling Tower Streams

 Table 4-8 - Prilling Tower Material Flow Rates
Mass Flow rates (MT/h)
Component Inlet Outlet
Stream 14 Stream 16 Stream 17 Stream 18
Urea 172.02 0 0 172.02
Biuret 2.6162 0 0 2.6162
Water 0.7285753 1.45715 2.18572588 0
Dry air 0 80.9528 80.95281036 0
Total 175.3647753 82.41 83.13853624 174.6362
Total Inflow/(Outflow) 257.77 (257.77)

4.2.6 Material Balance for Carbon Dioxide Absorber

Assumptions:

• Ca(OH)2 is continuously supplied.

• NH3 do not react with Ca(OH)2.
• No Excess Ca(OH)2 is supplied.

Reaction,
𝐶𝑂- + 𝐶𝑎(𝑂𝐻)- → 𝐶𝑎𝐶𝑂f + 𝐻- 𝑂

CO2 mass flow rate in to the absorber = 21.318 MT/h

-).f){
CO2 mole flow rate in to the absorber = hh
= 0.4845 Mmol/hr

Required Ca(OH)2 mole flow rate = 0.4845 Mmol/hr

Required Ca(OH)2 mass flow rate = 0.4845 * 74 = 35.853 MT/hr

 Figure 4.7 - Carbon Dioxide Absorber

Table 4-9 Carbon Dioxide Absorber Flow Rates

Mass Flow rates (MT/h)
Component Inlet Outlet
Stream 19+21+23 Stream 25 Stream 24 Stream 26
CO2 21.318 0 0 0
NH3 104.590 0 104.590 0
Ca(OH)2 0 35.853 0 0
CaCO3 0 0 0 48.45078
H2O 17.4689 0 0 26.6689
Total 143.377 35.853 104.59 75.1197
Total inflow
179.23 (179.23)
/(Outflow)

4.2.7 Material Balance for Pool Condenser

Assumptions,

• All Carbamate condenses

• NH3, CO2 and water leaves from the vapor stream.
• No reaction take place inside the pool condenser
 Table 4-10 - Pool Condenser Flow Rates
Mass Flow Rates (MT/hr)
Component Inlet Outlet
Stream 7 Stream 3 Stream 19
Ammonia Carbamate 53.274 53.274 0
NH3 61.1534 0 61.1534
CO2 5.5294 0 55294
Water 3.96862 0 3.96862
Total 123.92545 53.274 70.65145
Total Inflow/(Outflow) 123.92 (123.92)

4.2.8 Material Balance for Separator 1 and Separator 2

Assumptions,

• Water, NH3 and CO2 are in Equilibrium in given temperature and pressure

Data

• Seperator 1 à Operating Temperature = 1000C

à Operating Pressure = 17 barg
• Seperator 2 à Operating Temperature = 1000C
à Operating Pressure = 3.5 barg

From ASPEN PLUS V9 the vapor and liquid flow rates for the separator 1 and Separator 2 as
follows.

Table 4-11 - Seperator 1 Flow Rates

Components Mass Flow Rates (MT/hr)
Inlet Outlet
Stream 9 Stream 21 Stream 20
Water 18.223524 1.8060876 16.4174346
NH3 41.34536 36.038606 5.3067574
CO2 8.5946388 8.3003272 0.29431248
Total 68.1635228 46.1450208 22.01850448
Total Inflow/(Outflow) 68.1635 (68.1635)
 Table 4-12 - Seperator 2 Flow Rates
Components Mass Flow Rates (MT/hr)
Inlet Outlet
Stream 11/11A Stream 23 Stream 22
Water 8.3918034 2.9730636 5.4187416
NH3 7.6166341 7.3982028 7.3982028
CO2 7.5418596 7.4886196 0.05324044
Total 23.5502971 17.859886 5.69041334
Total Inflow/(Outflow) 23.55 (23.55)

4.3 ENERGY BALANCE

Energy balance, heating cooling required for equipment is calculated using formation
Enthalpies of components in respective temperature and pressures. The data is acquired by
ASPEN PLUS V9 software. The difference between flow enthalpies in and flow enthalpies out
has been taken as the equipment duty. The assumption is made that no work done by the system
inside the process equipment. 𝐻|}~•€• (Enthalpy of formation of the stream) can be represented
by following formula

𝐻|}~•€• = ‚ 𝑚ƒ 𝐻ƒ

m – Mass flow rate of ith component

H – Enthalpy of Formation of ith component

For the energy balance of equipment sign convention is taken as plus for heat input to the
equipment and minus for heat removal from the equipment.

Utility Requirement

Steam used is saturated at 170oC. Steam at this temperature is used due to the heat recovery
from the reactor, stripper and pool condenser will be used to generate saturated steam. The
reactor is operating at the minimum temperature at 188oC. Allowing a temperature difference
of 18oC saturated steam at 170oC is generated. Assume all steam is converted to saturated water
at the same pressure.

Steam pressure 7 barg

Latent heat of steam 2.048684 MJ/kg

specific enthalpy of saturated steam 2.76789 MJ/kg

specific enthalpy of saturated water 0.719206 MJ/kg

Cooling water at 25oC is supplied. The exit temperature is 40oC. However, in steam generation
outlet is 170 oC steam.

Temperature Difference 15oC

Specific Heat Capacity of Water 0.004186 MJ/kgK

Specific Enthalpy of Water At 25oC 0.10068 MJ/kg

Specific Enthalpy of Water At 40oC 0.16754 MJ/kg

Requirement of utility for each equipement is calculated in APPENDIX Utility Calculations

 4.3.1 Reactor

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Stream 1 Stream 2
Component Stream 3(liq.)
F(liq.) F(vap.) Stream 4(liq.)
P=155 bar &
P=155bar & T=188 P=150 bar & T=188 P=155bar & T=1880C
0 0 T=2000C
C C
H m H m H m H m
NH3 -2329.8 191.471 - - -2329.8 79.78032
CO2 - -8790.52 150.1764 - -8790.52 6.75752
Urea - - - -5238.55 172.02
Ammonium
- - -213.136 53.274 -237.032 79.872
Carbamate
Biuret - - - -5219.42 2.6162
Water - - - -15098.1 51.61
Total
Enthalpy -446089.136 -1320128.648 -11354.607 -1958185.47
(MJ/h)

Energy Inflow from process streams = +1777572.965 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = −180612.507 𝑀𝐽/ℎ

Energy Outflow from process streams = −1958185.47 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Cooling needed for the reactor = 50.17 MW

Cooling Water Required to produce 170oC Saturated steam= 67715.8931 Kg/hr

 4.3.2 High Pressure Stripping Column

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Component Stream 4(liq.) Stream 5(vap.) Stream 6(liq.)
Stream 7(vap.)
P=155bar & T=188 P=150 bar & P=150 bar &
0 P=150bar & T=2000C
C T=188 0C T=2000C
H m H m H m H m
-
NH3 -2329.8 79.78032 21.2772 -2300.86 37.773983 -2300.86 61.153437
2329.8
CO2 -8790.52 6.75752 - -8778.58 1.2281992 -8778.58 5.5293964
Urea -5238.55 172.02 - -5209.27 172.02 - -
Ammonium
-237.032 79.8954 - -213.136 26.598 -9.89172 53.274
Carbamate
Biuret -5219.42 2.6162 - -5197.97 2.6162 - -
Water -15098.1 51.608 - -15029 47637378 -13091 3.9686166
Total
Enthalpy -1958185.47 -4955.8584 -1729002.49 -241725.877
(MJ/h)

Energy Inflow from process streams = +1963141.328 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = +36412.9648 MJ/hr

Energy Outflow from process streams = −1970728.367 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Amount of heat supply to the HP stripper = 10.11 MW

Cooling Water Required to produce 170oC Saturated steam= 2844.559896 Kg/hr

4.3.3 Medium Pressure Decomposer

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Component Stream 6(liq.) Stream 8(liq.) Stream 9(vap.)
P=150bar & T=2000C P=17 barg & T=155 0C P=17 barg & T=1550C
H m H m H m
NH3 -2300.86 37.773983 -2407.95 2.316114 -2407.95 41.85825
CO2 -8778.58 1.2281992 -8822.85 0.1513996 -8822.85 8.929932
Urea -5209.27 172.02 -5313.16 172.02 - -
Ammonium
-213.136 26.598 13.299 -
Carbamate -286.903 -
Biuret -5197.97 2.6162 -5276.19 2.6162 - -
Water -15029 47637378 -15275.7 30.60432 -13177.7 18.48852
Total Enthalpy
-1729002.489 -1387531.406 -415530.9008
(MJ/h)

Energy Inflow from process streams = +1729002.489 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = −74059.8176 𝑀𝐽/ℎ

Energy Outflow from process streams = −1803062.307 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Cooling load required for MP decomposer = 20.572 MW

Cooling Water Required = 1107685.028 Kg/hr
 4.3.4 Low Pressure Decomposer

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Component Stream 8(liq.) Stream 10(liq.) Stream 11(vap.)
P=17barg & T=1550C P=3.5 barg & T=120 0C P=3.5 barg & T=1200C
H m H m H m
NH3 -2407.95 2.316114 - - -2488.49 7.6166341
CO2 -8822.85 0.1513996 - - -8856.27 7.5418596
Urea -5313.16 172.02 -5385.63 172.02 - -
Ammonium
13.299 - -
Carbamate -286.903 - -
Biuret -5276.19 2.6162 -5332.83 2.6162 - -
Water -15275.7 30.60432 -15448.3 21.022056 -13244.7 8.43918034
Total Enthalpy
-1387531.41 -1265142.85 -196891.064
(MJ/h)

Energy Inflow from process streams = +1387531.41 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = −74502.508 𝑀𝐽/ℎ

Energy Outflow from process streams = −1462033.914 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Cooling Load for the LP decomposer = 20.695 MW

Cooling water required = 1114306.133 Kg/hr

 4.3.5 Low Vacuum Evaporator

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Stream 13
Component Stream 10 Stream 12
V1(vap.)
F(liq.) L1(liq.)
P=0.23 bar &
P=4.5bar & T=120 0C P=0.23 bar & T=135 0C
T=1350C
H M H m H m
Urea -5385.63 172.02 -5355.77 172.02 - -
Biuret -5332.83 2.6162 -5309.01 2.6162 - -
Water -15448.3 21.022056 -15376 14.589585 -13215.9 6.4324708
Total Enthalpy
-1265142.85 -1159518.45 -85010.8914
(MJ/h)

Energy Inflow from process streams = +1265142.85 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = +20613.51 MJ /h

Energy Outflow from process streams = −1244529.341 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Heating load for the Low vacuum Evaporator = 5.726 MW

Steam Required = 10061.82994 Kg/hr

 4.3.6 High Vacuum Evaporator

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Component Stream 12 Stream 14 Stream 15
L1(liq.) L2(liq.) V2(vap.)
P=0.23bar & T=135 0C P=0.03 bar & T=135 0C P=0.03 bar & T=1350C
H m H m H m
Urea -5355.77 172.02 -5355.77 172.02 -
Biuret -5309.01 2.6162 -5309.01 2.6162 -
Water -15376 14.589585 -15376 0.7285753 -13215.9 13.86101
Total Enthalpy
(MJ/h)
-1159518.45 -946391.561 -183185.72

Energy Inflow from process streams = +1159518.45 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = +29941.1674 MJ/h

Energy Outflow from process streams = −1129577.281 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Heating load for the high vacuum evaporator = 8.317 MW

Steam Required = 14614.82952 Kg/hr

 4.3.7 Prilling Tower

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Component Stream 14(liq.) Stream 16(vap.) Stream 17(vap.) Stream 18(solid)
P=1atm & T=135 0C P=1atm & T=25 0C P=1atm & T=25 0C P=1atm & T=25 0C
H m H m H m H m
NH3 - - - - -
CO2 - - - - -
Urea -5355.77 172.02 - - -5555.5 172.02
Ammonium
- - - -
Carbamate -
Biuret -5309.01 2.6162 - - -5468 2.6162
-
Water 0.7285753 -13422.9 1.457156 -13422.9 2.1857259 -
-15376 16259.5
Air - 1.29E-13 80.95281 1.29E-13 80.95281 -
Total
Enthalpy -946391.561 -19559.1866 -29338.7799 -969962.492
(MJ/h)

Energy Inflow from process streams = +965950.7476 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = −33350.5238 𝑀𝐽/ℎ𝑟

Energy Outflow from process streams = −999301.2719 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Cooling load to the prilling tower = 9.264 MW

Cooling Water Required = 498811.3047 kg/hr

 4.3.8 Carbon Dioxide Absorber

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Stream Stream 25 Stream 24 Stream 26
Stream 19(vap.)
Stream 21(vap.) 23(vap.) (liq.) (liq.) (liq.)
P=150bar & T=200
0 P=18bar & T=100 0C P=4.5bar & P=1 bar & T=40 P=1 bar & T=40 P=1 bar & T=40
C
T=100 0C
Componen H m H m H m H m
H m H m
t
- 7.3982 - - 104.5902 -
61.15343 36.0386
NH3 - -2533.41 2533. 028 2663. 458
7 06
2300.86 41 53
- 7.4886 - - -
5.529396 8.30032
CO2 - -8877.91 8874. 196
4 72
8778.58 91
- - 35.8535 - -
Ca(OH)2 - - 8620. 772
43
- - - - 48.450
CaCO3 - - 12050. 78
8
- 2.9730 - - - 26.67
3.968616 1.80608
Water -13282.3 1328 636 15802.
6 76
-13091 2.3 1
Total -124692.6286 -309073.2525 -278579.2574 -1009552.4
Enthalpy -241198.9056 -188979.12
(MJ/h)

Energy Inflow from process streams = +863943.9067 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = −15096794.83𝑀𝑗/ℎ

Energy Outflow from process streams = −1285431.657 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Cooling load to the Carbon Dioxide Absorber = 4193.55 MW

Cooling water required = 225797101 kg/hr

4.3.9 Pool Condenser

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Inlet Outlet
Stream 7(vap.) Stream 19(vap.) Stream 3(liq.)
P=150bar & T=2000C P=150bar & T=200 0C P=150 bar & T=2000C
Component H m H m H m
NH3 -2300.86 61.153437 -2300.86 61.153437 -
CO2 -8778.58 5.5293964 -8778.58 5.5293964 -
Urea - - -
Ammonium
-9.89172 53.274 - -213.136 53.274
Carbamate
Biuret - - -
Water -13091 3.9686166 -13091 3.9686166 -
Total Enthalpy
-241725.8771 -241198.9056 -11354.60726
(MJ/h)

Energy Inflow from process streams = +241725.8771 𝑀𝐽/ℎ

Energy Addition / Removal to/from equipment = −10827.63577𝑀𝐽/ℎ

Energy Outflow from process streams = −252553.5129 𝑀𝐽/ℎ

Energy Balance = 0

Utility Requirement

Cooling Load to the pool condenser = 3 MW

Cooling Water Required to produce 170oC Saturated steam= 4059.536284 Kg/hr

4.3.10 Separator 1

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Outlet Inlet
Stream 9A
Stream 21(vap.) Stream 20(liq.)
(vap.)
P=17barg & T=1000C P=17barg & T=100 0C
P=17 barg & T=1550C
Component H m H m H m
NH3 -2533.41 36.038606 -3249.49 5.3688244 41.34536
CO2 -8877.91 8.3003272 -8877.9 0.29431248 8.5946388
Urea - - -
Ammonium
- - -
Carbamate
Biuret - - -
Water -13282.3 1.8060876 -15541.2 16.4174346 18.223524
Total Enthalpy
-188979.12 -275003.7665 -463982.8865
(MJ/h)

Enthalpy of stream 9A equals to the sum of the stream 20 and 21 enthalpies because there is
no work done in separator 1.
𝐻‰Š = -463982.8865 MJ/h
Enthalpy difference heat exchanger 1 = 𝐻‰Š − 𝐻‰
between stream 9A and stream 9A = −48451.98572𝑀𝐽/ℎ

Utility Requirement

Cooling Load to the heat exchanger 1 = 13.459 MW

Cooling water required = 724678.2187 Kg/hr
4.3.11 Separator 2

Enthalpies- H(kj/kg) and Flow rates -m(Mt/h)

Outlet Inlet
Stream 23(outlet) Stream 11(inlet)
Stream 22(outlet)(liq.)
(vap.) (vap.)
P=3.5barg & T=100 0C
P=3.5barg & T=1000C P=3.5 barg & T=1200C
Component H m H m H m
NH3 -2533.41 7.3982028 -3249.49 0.2184313 7.6166341
CO2 -8874.91 7.4886196 -8877.91 0.05324044 7.5418596
Urea - - -
Ammonium
- - -
Carbamate
Biuret - - -
Water -13282.3 2.9730636 -15541.2 5.4187416 8.3918034
Total -124692.6286 -85396.20111 -210088.8297

Enthalpy of stream 11A equals to the sum of the stream 22 and 23 enthalpies because there is
no work done in separator 2.
𝐻))Š = -210088.8297MJ/h
Enthalpy difference heat exchanger 2 = 𝐻))Š − 𝐻))
between stream 9A and stream 9A = −13197.76604𝑀𝐽/ℎ

Utility Requirement

Cooling Load to the Heat Exchanger 2 = 3.66MW

Cooling water Required = 197394.0478 Kg/hr
 5 CONCLUSION

Urea has a higher global and regional demand. India, Bangladesh and Pakistan annually import
8.7 million, 1.7 million and 0.7 million metric tons respectively, thus, the production capacity
for the urea production plant has been decided by evaluating mainly on Regional and Local
demands. The annual urea production from the plant is stated at 1,500,000 MT per year, which
1/3 of it is for domestic consumption and remaining 2/3 will be exported to neighboring
countries such as India, Bangladesh and Pakistan.

The Preliminary economic evaluation stated, capital cost for the plant is 1,683 million USD,
which derived by using one-tenth rule. As reference plant, a urea production plant which was
built in Mozambique was taken. Major operating cost include the import cost of urea which is
726 USD per metric ton. The analysis of price fluctuations, supply and demand patterns for
urea, ammonia and carbon dioxide is used to derive at reasonable prices. According to the
calculations, plant could be able to yield 183.54 million USD worth of profit per year. The
average payback period for the facility is 9.17 years which is reasonable compared with
magnitude of this project.

The process involves high pressures and temperatures which could susceptible for many risks
and hazards. At the process selection stage, comparatively, inherently safer design has been
selected in order to minimize risks. The raw materials, ammonia and carbon dioxides are kept
at high pressure vessels which needs special attention. It has been stated that regular inspection
of vessels, pipelines should be conducted as well as gas detectors should be fixed in tank farm
and process area. Direction of wind, also has been critically concerned during the HSE analysis
for the placement of tank farm and process area.

Heath related issues which affect to employers and residents nearby is also focused in the report
and necessary actions and procedures are developed. Chemical which are susceptible for
leaking, noise levels, vibrations, gaseous wastes are identified and mitigatory measures also
been considered.

The development of the process flow diagram is done with the aid of Snampogetti ammonia
stripping process. Process includes a reactor which converts ammonia and carbon dioxide into
ammonium carbamate and then to urea. Biuret is an undesired side reaction which happens
inside the reactor. High pressure stripping column evaporates much of ammonium carbamate
into vapor phase then recycled into the reactor. Bottom from the High-pressure stripping
column then decomposed at two pressure stages, which converts remaining ammonium
carbamate into ammonia and carbon dioxide. The effluent from decomposers then concentrated
using evaporators and then sent to the prilling tower to produce urea prills.

The production rate for urea is 174.64 MT/hr. According to the material balance the feed rate
of ammonia is 191.47 MT/hr and 150.18 MT/hr of carbon dioxide. The overall conversion of
carbon dioxide to urea is 84%. Unreacted ammonia and carbon dioxide is separated by
absorbing carbon dioxide by calcium hydroxide and ammonia is then recycled into the process.

The Process can be further optimized to recover CO2 and improve the conversion of raw
materials to urea. A process integration is highly feasible for this process because the process
involves high temperatures, which demands high loads of utilities. Integrating the process
could significantly reduce the utility needs for the plant. Distillation can be used to recover the
remaining trace amount of ammonia and CO2 in effluent water for effective utilization of raw
materials and improve the discharge wastewater quality.
 6 REFERENCES

Anon., 1982. Chapter XI Urea. [Online]

Available at:
https://open.unido.org/api/documents/4819812/download/FERTILIZER%20MANUAL.%20
UREA.%20A%20DRAFT%20REPORT%20(19837.en)
[Accessed 15 05 2018].

Anon., 2005. The Snamprogetti Urea Technology. [Online]

Available at: http://www.saipem.com/static/documents/spm_UREAri_L02_14_01_10.pdf
[Accessed 17 05 2018].

Anon., 2009. Stmicarbon. [Online]

Available at: https://teamecho.wikispaces.com/file/view/Stamicarbon-
+Urea+Production+Process.pdf
[Accessed 18 05 2018].

Anon., 2015. Urea. [Online]

Available at: https://www.cdc.gov/niosh/ipcsneng/neng0595.html

Anon., 2017. Inorganic chemicals- organic or inorganic compounds. In: Sri Lanka Customs
National Imports Tariff Guide. Sri Lanka: Sri Lanka Custom , pp. Chapter 28-page-6.

Anon., 2018. History of urea. [Online]

Available at: https://thechemco.com/chemical/urea/

Anon., 2018. Sri Lanka Agriculture Value added Annual Percent Growth. [Online]
Available at: https://tradingeconomics.com/sri-lanka/agriculture-valueadded-
[Accessed 18 May 2018].

Anon., n.d. AVERAGE HUMIDITY IN TRINCOMALEE. [Online]

Available at: https://weather-and-climate.com/average-monthly-Humidity-
perc,Trincomalee,Sri-Lanka
[Accessed 29 June 2018].

Anon., n.d. Physical Properties for Carbon Dioxide. [Online]

Available at: http://www.airproducts.com/products/Gases/gas-facts/physical-
properties/physical-properties-carbon-dioxide.aspx
[Accessed 24 MAY 2018].

Anon., n.d. Trincomalee Wether Forcast. [Online]

Available at: https://www.worldweatheronline.com/trincomalee-weather/eastern-
province/lk.aspx
[Accessed 29 June 2018].
Anon., n.d. Urea. [Online]
Available at: https://pubchem.ncbi.nlm.nih.gov/compound/urea#section=Melting-Point

Anon., n.d. Urea. [Online]

Available at: http://www.newworldencyclopedia.org/entry/Urea
[Accessed 9 July 2018].

Australia, S., n.d. What is Urea?. [Online]

Available at: http://sesl.com.au/blog/what-is-urea/

Bareja, B. G., 2013. What is Urea? Fertilizer Yes, But There are More. [Online]
Available at: https://www.cropsreview.com/what-is-urea.html

Info Drive India, 2017. Ammonia Export from India to Sri Lanka. [Online]
Available at: https://www.infodriveindia.com/india-export-data/ammonia-export/fc-
sri_lanka-report.aspx
[Accessed 16 May 2018].

L.J.D.FERNANDO, 1986. SCIENCE EDUCATION SERIES. cOLOMBO 7: NATURAL

RESOURCES, ENERGY AND SCIENCE AUTHORITY.

LeanManufacturing, 2009. Payback Period. [Online]

Available at: http://www.leanmanufacture.net/kpi/paybackperiod.aspx
[Accessed 2 June 2018].

Ono, H., Fujii, H. & Inoue, S., 1982. Synthesis of urea. [Online]
Available at: http://www.freepatentsonline.com:
http://www.freepatentsonline.com/4365089.pdf
[Accessed 17 05 2018].

Ozcan, D. C., 2014. Techno-Economic Study of the Calcium Looping Process for CO2
Capture from Cement and Biomass Power Plants. s.l.:The School of Engineering, The
University of Edinburgh.

SANDERSON, F. K. a. P. M., 1959. UREA IN THE HISTORY OF ORGANIC

CHEMISTRY. JOURNAL OF CHEMICAL EDUCATION , 9 Septemer.

Silva, G., 2017. Fertilizer price trends in 2017. [Online]

Available at: http://msue.anr.msu.edu/news/fertilizer_price_trends_in_2017
[Accessed 2 June 2018].

Sinnott, R. K., 1999. Coulson & Richardson's Chemical Engineering. 3rd Edition ed. Oxford:
Butterworth Heinemann.

Suzette M. Kimball, U. G. S., 2016. MINERAL COMMODITY SUMMARIES 2016. Virginia:

U.S. Department of the Interior.
Toyo Engineering Corporation, Sumitomo Corporation, 2012. STUDY ON THE UREA
FERTILIZER COMPLEX PROJECT IN THE REPUBLIC OF MOZAMBIQUE. [Online]
Available at:
https://www.jetro.go.jp/ext_images/jetro/activities/contribution/oda/model_study/earth_infra/
pdf/h23_saitaku_23e.pdf
[Accessed 2 June 2018].

Young's Sand & Gravel, 2018. http://www.youngssandandgravel.com/. [Online]

Available at: http://www.youngssandandgravel.com/pricelist.htm
[Accessed 2 June 2018].

Zauba Technologies & Data, 2014. Detailed Export Data of anhydrous ammonia. [Online]
Available at: https://www.zauba.com/export-anhydrous+ammonia-hs-code.html
[Accessed 9 June 2018].
 7 APPENDIX

7.1 MATERIAL BALANCE CALCULATIONS

7.1.1 Reactor

The flow rate of urea and biuret in reactor effluent stream can be identified as below.

MT/hr Mmol/hr
Urea 172 2.867
Biuret 2.6193 0.02543

Stream 2 àSince the overall conversion of CO2 is 84%, the required feed rate of CO2 to the
reactor (Since the CO2 enters to the system only from the reactor)

2.867
𝐶𝑂2 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = = 3.4131 𝑀𝑚𝑜𝑙/ℎ𝑟
0.84

Stream 1 àAmmonia is feed into the reactor is based on the molar ration of NH3 to CO2 is
3.3. Therefore, NH3 flow rate to the reactor

𝑁𝐻3 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑡𝑜 𝑡ℎ𝑒 𝑟𝑎𝑐𝑡𝑜𝑟 = 3.3 × 3.4131 = 11.263 𝑀𝑚𝑜𝑙/ℎ𝑟

The conversion of CO2 to Ammonium Carbamate is assumed to be 30%. Since overall

conversion of CO2 is 84% and one pass conversion through the reactor is 64%, It can be
assumed that 66.67% of formed Ammonium carbamate enters to the reactor through the recycle
stream.

Stream 3 à 𝐴𝑚𝑚𝑜𝑛𝑖𝑢𝑚 𝐶𝑎𝑟𝑏𝑎𝑚𝑎𝑡𝑒 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 𝑇𝑜𝑡𝑎𝑙 𝐶𝑂2 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 × 30% ×
66.67%

𝑀𝑚𝑜𝑙𝑒
𝐴𝑚𝑚𝑜𝑛𝑖𝑢𝑚 𝐶𝑎𝑟𝑏𝑎𝑚𝑎𝑡𝑒 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 3.4131 × 30% × 66.67% = 0.683
ℎ𝑟

Stream 4 à The stream 4 is the reactor effluent stream which contains Urea, Water,
Ammonium Carbamate, Biuret, Unreacted NH3 and CO2.

Biuret is 0.02543 Mmol/hr, Urea 2.867 Mmol/hr

𝐴𝑚𝑚𝑜𝑛𝑖𝑢𝑚 𝐶𝑎𝑟𝑏𝑎𝑚𝑎𝑡𝑒 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 𝐶𝑂2 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 × 30%

𝐴𝑚𝑚𝑜𝑛𝑖𝑢𝑚 𝐶𝑎𝑟𝑏𝑎𝑚𝑎𝑡𝑒 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = 3.4131 × 30% = 1.024 Mmol/hr

From stoichiometry the water flow rate is equal to urea flow rate which is 2.867 Mmole/hr

𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝐶𝑂2
= 𝐶𝑂2 𝑖𝑛𝑝𝑢𝑡 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 − 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑡𝑜 𝑈𝑟𝑒𝑎 − 𝐶𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑡𝑜 𝑏𝑖𝑢𝑟𝑒𝑡
− 𝑐𝑜𝑛𝑣𝑒𝑟𝑡𝑒𝑑 𝑡𝑜 𝑎𝑚𝑚𝑜𝑛𝑖𝑢𝑚 𝑐𝑎𝑟𝑏𝑎𝑚𝑎𝑡𝑒

𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝐶𝑂2 = 3.4131 − 3.4131 × 64% − 2 × 0.02543 − 1.024

= 0.15386 𝑀𝑚𝑜𝑙𝑒/ℎ𝑟

𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑁𝐻3
= 𝑁𝐻3 𝑖𝑛𝑝𝑢𝑡 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 − 𝐶𝑜𝑛𝑣𝑒𝑟𝑡𝑖𝑜𝑛 𝑡𝑜 𝑈𝑟𝑒𝑎 𝑖𝑛 𝑓𝑖𝑟𝑠𝑡 𝑝𝑎𝑠𝑠
− 𝐶𝑜𝑛𝑣𝑒𝑟𝑡𝑖𝑜𝑛 𝑡𝑜 𝐵𝑖𝑢𝑟𝑒𝑡 − 𝐶𝑜𝑛𝑣𝑒𝑟𝑡𝑖𝑜𝑛 𝑡𝑜 𝐴𝑚𝑚𝑜𝑛𝑖𝑢𝑚 𝐶𝑎𝑟𝑏𝑎𝑚𝑎𝑡𝑒

𝑈𝑛𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑁𝐻3 = 11.263 − 2 × (2.867 − 0.683) − 3 × 0.02543 − 2 × 1.024

= 4.69296 𝑀𝑚𝑜𝑙/ℎ𝑟

7.1.2 MP and LP Decomposers

Ammonium Carbamate inflow to MP Decomposer is 0.341 Mmol/hr

If 50% decomposers at MP decomposer, 0.1705 Mmol/hr decomposes in MP condenser and

same amount decomposes at LP Decomposer

From stoichiometry this produces 0.1705 Mmole/hr CO2 and 0.341 Mmol/hr NH3 additionally

Equilibrium vapor-liquid data for water NH3 and CO2 system in MP Decomposer calculated
using ASPEN PLUS and shown below

Components Moles on vapor Moles in liquid

stream (9) stream (8)
Water 1.02714 1.70024
NH3 2.46225 0.136242
CO2 0.202953 0.0034409

Equilibrium vapor-liquid data for water NH3 and CO2 system in LP Decomposer calculated
using ASPEN PLUS and shown below,
 Components Moles on vapor Moles in liquid
stream (11) stream (10)
Water 0.468647 1.23159
NH3 0.451369 0.0258738 ~ 0
CO2 0.171347 0.00259372 ~ 0

7.1.3 Vacuum Evaporators

Low vacuum evaporator

Feed stream for vaccum evaporator is as follows

Stream 10 (F)
Component Mass frac.–X(w/w %) Mass flow rate(Mt/h)
Urea 0.8792 172.02
Biuret 0.01337 2.6162
Water 0.10744 21.022056
Total (F) = 195.658

Applying material balance for urea in evaporator 1,

𝐹. 𝑋’,”~•€ = 𝑉1. 𝑌—),”~•€ + 𝐿1. 𝑋™),”~•€

Since evaporator effluent only contains water,

𝑌—),”~•€ = 0

𝑭. 𝑿𝒇,𝒖𝒓𝒆𝒂 = 𝑳𝟏. 𝑿𝑳𝟏,𝒖𝒓𝒆𝒂

X ),¡¢£¤ = 0.9091,

𝐹. 𝑋’,”~•€ 172.02
𝐿1 = =
𝑋™),”~•€ 0.9091

𝐿1 = 189. 22 𝑀𝑇/ℎ𝑟

Applying the overall material balance for evaporator 1,

𝐹 + 𝑆1 = 𝑉1 + 𝐿1 + 𝐶1

Since all steam condenses,

𝑆1 = 𝐶1

𝑭 = 𝑽𝟏 + 𝑳𝟏
 𝑉1 = 𝐹 − 𝐿1

𝑉1 = 195.658 − 189. 22 = 6.43247 MT/hr

Water = 𝐹. 𝑋’,§€}~ − 𝑉1 = 21.022056 − 6.43247 = 14.5896 MT/hr

Prilling Tower

Material balance calculations for prilling tower,

From Psychometric Charts,

• H1= Absolute Humidity @ RH=70% & DBT=300C = 0.018 kg/kg of Dry Air
• HSat. = Absolute Humidity @ RH=100% (Sat.) & DBT=300C = 0.027 kg/kg of Dry Air sat.
• Dry air flow rate = 𝐴ƒ¨,©~ª ,

Appling the material balance for water,

𝐹ƒ¨,§€}•~ + 𝐴ƒ¨,©~ª × 𝐻1 = 𝐹«”},§€}•~ + 𝐴«”},©~ª × 𝐻|€}.

Fout,water = 0 (Assume that all water is evaporated)

𝐴ƒ¨,©~ª = 𝐴«”},©~ª

𝐹ƒ¨,§€}•~ = 𝐴ƒ¨,©~ª (𝐻|€}. − 𝐻1)

𝐹ƒ¨,§€}•~
𝐴ƒ¨,©~ª =
(𝐻|€}. − 𝐻1)

0.7285753
𝐴ƒ¨,©~ª = = 80.9528 𝑀𝑇/ℎ𝑟
(0.027 − 0.018)

Water content in air inlet,

𝐴ƒ¨,§€}•~ = 𝐴ƒ¨,©~ª × 𝐻1 = 80.9528 × 0.018 = 1.45715 𝑀𝑇/ℎ𝑟

Water content in air outlet,

𝐴«”},§€}•~ = 𝐴ƒ¨,§€}•~ + 𝐹ƒ¨,§€}•~ = 1.45715 + 0.7285753 = 2.85726 𝑀𝑇/ℎ𝑟

 7.2 Utility Calculations

Residual Heat Steam flow Cooling Inlet Stream Outlet Stream

rate(kg/hr) water flow Stream Enthalpy(MJ/hr) Stream Enthalpy(MJ/hr)
MJ/hr MW
rate(kg/hr)
Reactor -180613 -50.1701 67715.8931 1 -446089.1358 4 -1958185.47
2 -1320128.648
3 -11354.60726
Cooling 6817.636117 steam 187430.1434
water
Total -1770754.755 total -1770755.327
Enthalpy enthalpy
Stripper -7587.04 -2.10751 2844.559896 4 -1958185.47 6 -1729002.49
5 -4955.8584 7 -241725.877

Cooling 286.3902903 steam 7873.42889

water
total -1962854.938 total -1962854.938
enthalpy enthalpy

MP 160079 44.46639 78137.48602 6 -1963141.328 8 -1387531.41

decomposer
9 -415530.901
steam 216275.9662 steam 56196.94877
condensate
total -1746865.362 total -1746865.362
enthalpy enthalpy

LP -74502.5 -20.6951 1114306.133 8 -1387531.41 10 -1265142.85

decomposer
11 -196891.064
Cooling 112188.3414 Cooling 186690.8495
water water
total -1275343.069 total -1275343.065
enthalpy enthalpy

Low 20613.51 5.725975 10061.82994 10 -1265142.85 12 -1159518.45

vacuum
Evaporator
13 -85010.8914
steam 27850.03847 steam 7236.528462
condensate
total -1237292.812 total -1237292.813
enthalpy enthalpy

High 29941.17 8.316991 14614.82952 12 -1159518.45 14 -946391.56

Vacuum
Evaporator
15 -183185.72
steam 40452.24048 steam 10511.07308
condensate
total -1119066.21 total -1119066.207
enthalpy enthalpy

Prilling -33350.5 -9.26403 498811.3047 14 -946391.56 17 -29338.7799

Tower
 16 -19559.1866 18 -969962.492
Cooling 50220.32216 Cooling 83570.84599
water water
total -915730.4244 total -915730.4259
enthalpy enthalpy

CO2 - - 225797101 19 -241198.9056 24 -278578.6027

Absorber 15096794.176 4193.553938
21 -188979.12 26 -
15682159.48

23 -124692.6286
25 -309073.2525
Cooling 22733252.133 Cooling 37830046.31
water water
total 21869308.227 total 21869308.227
enthalpy enthalpy

Pool -10827.6 -3.00768 4059.536284 7 -241725.877 3 -11354.60726

condenser
19 -241198.9056
Cooling 408.7141131 steam 11236.34989
water condensate
total -241317.1629 total -241317.163
enthalpy enthalpy

Separator 1 -48452 -13.4589 724678.2187 9 -415530.9008 20 -275003.7665

21 -188979.12
Cooling 72960.60306 Cooling 121412.5888
water water
total -342570.2977 total -342570.2977
enthalpy enthalpy

Separator 2 -13197.8 -3.66605 197394.0478 11 -196891.0637 22 -85396.20111

23 -124692.6286
Cooling 19873.63273 Cooling 33071.39877
water water
total -177017.431 total -177017.4309
enthalpy enthalpy