The Production of Urea Chemical Process

Chemical Process Principle Mini Project The Production of Urea
THE PRODUCTION OF UREA
CHEMICAL PROCESS PRINCIPLE MINI PROJECT
Bachelor of Chemical Engineering Technology (Hons)
By
Reyhana Binti Noorsham 55213116163

Siti Syazana Binti Mohd Saberi 55217116092
Nurul Farzana Binti Abd Mustaffa 55216116208
Nur Amirah Binti Mohamad Pahmi 55213116150
Section L02-T2
Supervised by Dr Amin Safwan Bin Alikasturi
Universiti Kuala Lumpur Malaysian Institute of Chemical
And Bioengineering Technology
(UniKL MICET)
Taboh Naning
Malacca
THE PRODUCTION OF UREA
CHEMICAL PROCESS PRINCIPLE MINI PROJECT
WORK DISTRIBUTION FORM
Name Id number Student No.

Reyhana Binti Noorsham 55213116163 3
Siti Syazana Binti Mohd Saberi 55217116092 4
Nurul Farzana Binti Abd Mustaffa 55216116208 1
Nur Amirah Binti Mohamad Pahmi 55213116150 2
PROJECT TASK
NO TASK TASK STUDENT NO.
1 Cover Page and Table of Contents All
2 Executive Summary All
3 Introduction All
4 Process selection All
5 Process Flow Diagram (PFD) All
6 Process Equipment Student 3 and 4
7 Material Balances Student 1 and 2
8 Energy Balances Student 3 and 4
9 Process and Design Improvement Student 1 and 2
10 References and Appendices All
EXECUTIVE SUMMARY
This mini project of urea production involved the understanding and application of the
chemical process principles’ study. To fully apprehend the production of urea, together, the
project team has done thorough literature on the process background involved, including the
demand product of 200,000 metric tons per year, along with its recent production technologies.
Further literature appears to show multiple processes for the production of urea. After detailed
discussion and consideration, the selected process was the Snamprogetti Urea Technology by
Saipem Co. From the selected process, this mini project henceforth refers to its processes and
technologies for the production of urea.
Initially, the project team together researched, discussed and brainstormed the requirements in
urea production. The manufacturing of urea involves the below reaction:
1. CO2 + 2NH3 NH2COONH4
2. NH2COONH4 NH2CONH2 + H2O
The first two reactions above are the basis of reaction involved in any urea plant. The project
team succeeds in ascertain the most applied urea technology patent; the Snamprogetti Urea
Technology by Saipem Co., Mitsui Toatsu or Toyo Koatsu Process (Japan), Once- through
Urea Process and Stamicarbon (Holland). In the process selection section, the project team
provided detailed processes involved in these four urea technology patents. To select the ideal
process for this mini project, the project team decided to hold five focus criteria; maximize heat
recovery, minimize impurities, minimize power requirement, lowering operating cost and
lastly pollution control. the project team’s members each hold one of those four processes,
delivering each minute details of the processes, plus, their strengths and weaknesses in order
to properly compare them. In table 1, it provided a full comparison of the processes according
with the five focus criteria and concludingly, the selected process was the Snamprogetti Urea
Technology. From the Snamprogetti’s patent provided by the Saipem Co.., a process flow
diagram (PFD) is generated, detailed with the requirements pressure and temperature of each
process equipment. The requirements further discussed in the process equipment section, done
by the mini project’s members of student 3 and student 4.
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From the PFD, the project proceeds with the calculation material balance, finding the overall
balance of each unit in the process, with the target product of 200,000 metric tons per year
(daily production: 547.95 metric tons). The calculation was done together by the project
members of student 1 and student 2. While student 1 and student 2 occupied with the material
balance’s calculation, the other two project’s members of student 3 and 4 proceeds with the
energy balance calculations, finding the required heat input and output of each equipment. The
results of each equipment’s required heat are; 5113.563 kJ/hr for the reactor, 1361313.86 for
the stripper, -1454842.63 kJ/hr for the carbamate condenser, -1543032.55 kJ/hr for the medium
pressure decomposer, -1150434.5 kJ/hr for the low pressure decomposer, for the vacuum
−931349.58 kJ/mol evaporator and lastly, -37544.994 kJ/hr for the prilling tower.
Finally, the mini project ended with a section of process and design equipment in which a
number of possible suggestions to improve the energy economy of the selected process. Several
suggestions were the installation of technologies; applicable to enhance the Snamprogetti
process equipment. One of the few significant technologies that are believe to give a great
impact are the Vortex Mixer and Variable Frequency Drive (VFD).5757
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Table of Contents
1.0 Executive Summary……………………………………………………………………...1
2.0 Introduction………………………………………………………………………………5
2.1 Introduction to urea……………………………………………………………………….5
2.2 History of urea……………………………………………………………………………5
2.3 Properties of urea…………………………………………………………………………6
2.4 The synthesis of urea…………………….……………………………………………......7
2.5 Production of urea………………………….…………………………………………….7
2.6 Usage of urea……………………………………………………………………………..9
2.7 Major Hazards of urea Production…………………………………….……….………..10
3.0 Process Selection….…………………………………………………………………….13
3.1 Snamprogetti Urea Technology…………………………………………………………14
3.2 MITSUI TOATSU or TOYO KOATSU PROCESS (Japan) ……………………………17
3.3 Once- through Process…………………………………………………………………..20
3.4 Stamicarbon (Holland) ………………………………………………………………….24
3.5 Full Comparison of Urea Processes……………………………………………………...27
3.6 Selected process: The Snamprogetti Urea Technology………………………………….29
4.0 Process Flow Diagram of urea…………………………………………………………32
5.0 Process Equipment ………………………………………………………………….….33
5.1 Reactor……………………………………………………………………………….….33
5.2 The Stripper…………………………………………………………………………......34
5.3 Carbamate Condenser………………………………………………………………...…35
5.4 Medium Pressure Decomposer (MP Decomposer) …………………………………….36
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5.5 Low Pressure Decomposer (LP Decomposer) …………………………………………37
5.6 Vacuum Evaporator…………………………………………………………………….37
5.7 Prilling Tower…………………………………………………………………………..38
6.0 Material Balances………………………………………………………………………39
7.0 Energy Balances………………………………………………………………………...45
8.0 Process & Design Improvement…….…………………………………………………53
9.0 References………………………………………………………………………………55
10.0 Appendices…………………………………………………………………………….57
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2.0 Introduction
The objective of this mini project is to learn and apply the chemical process principle for
production of urea. This report presents the background of urea; it’s origin, the synthesis and
analysis involved, and finally the chemical processes generated, with the target production rate
of 200,000 MT/ year. A more recent and advanced technologies also will be applied in the
chemical processes in order to obtain a chemical process that benefits in any way as possible.
2.1 Introduction to urea
Urea, an organic compound that alternatively known as carbamide, has the chemical formula
of CO(NH2)2. Urea classified in amide functional group as it has two –NH2 groups, joining
with (C=O) carbonyl functional group. Urea is one of the most notable organic compound in
daily life. In biological view, the human’s body involves urine significantly in the nitrogen
excretion; combining two ammonia molecules (NH3) with carbon dioxide (CO2) molecule in
urea cycle. In agriculture view, urea is widely used in fertilizers as plant’s nitrogen source while
for chemical industry, it acts as raw material for most other chemical production.
2.2 History of urea
In the early 17th century, a Dutch scientist named Herman Boerhaave was first to discover urea
in urine. The discovery was done thru a series of step to isolate the urea, but Boerhaave simply
evaporated them from human’s urine, which took more than a year and through crystallization
process, crystals of urea was obtained. This discovery then was further ado by Friedrich
Wohler, a German chemist whose first synthesis urea (Fairall. 1996). He is accounted as the
pioneer in organic chemistry as he accidentally succeeded in synthesised urea from ammonium
cyanate from his Wohler synthesis in the year of 1828. His discovery refuted the hypothesis of
vitalism, a hypothesis from another chemist, Jons Jacob Berzellius, that stated living things are
alive because of some special “vital force” (Fairall, 1996). Berzellius hypothesised that organic
compounds could be made only by living things which entirely dissent today’s chemistry world
as organic compound is being made every day in any laboratory.
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2.3 Properties of urea
2.3.1 Computed Properties
Property Name Property Value
Molecular weight 60.056 g/mole
Hydrogen Bond Donor Count 2
Hydrogen Bond Acceptor Count 1
Rotatable Bond Count 0
Complexity 29
Topological Polar Surface Area 69.1 A2
Monoisotopic Mass 60.032 g/mole
Exact Mass 60.032 g/mole
XLogP3- AA -1.4
Compound is Canonicalized true
Formal Charge 0
Heavy Atom Count 4
Defined Atom Stereocenter Count 0
Undefined Atom Stereocenter Count 0
Defined Bond Stereocenter Count 0
Undefined Bond Stereocenter Count 0
Isotope Atom Count 0
Covalently- Bonded Unit Count 1
Table 1: Computed properties of urea.
Note: Data deposited in or computed by PubChem [table 1]
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2.3.2 Physical properties of urea
Odourless, colourless solid, practically non- toxic and hygroscopic (tendency to attract water).
2.3.3 Chemical properties of urea
Chemical name (Common name): Urea, Carbamide, Iso- urea, Carbonyldiamide
Molecular formula: NH2CONH2
Molecular weight: 60.056 g/mol
Density: 1.32 g/cm3
Melting point: 132.7 °C
2.4 The Synthesis of urea
In any process involving urea production, the underlying principle remains the same with these
two reactions below:
𝐾𝑐𝑎𝑙
1) CO2 + 2NH3 NH2COONH4 ∆𝐻 = −37.4 𝑚𝑜𝑙
𝑔𝑚
𝐾𝑐𝑎𝑙
2) NH2COONH4 NH2CONH2 + H2O ∆𝐻 = +6.3 𝑚𝑜𝑙
𝑔𝑚
Undesirable side reaction:
1) 2NH2CONH2 NH2CONHCONH2 + NH3

(biuret)
In the first two reactions above are both equilibrium reaction. Under 185℃ -190℃ and 180-
200 atms, the first reaction undergoes almost towards completion. The first reaction carbamate
formation is highly exothermic, releasing heat. The reaction immediately continues to be
endothermic with the formation of urea. The undesirable side reaction shown is the formation
of dimer known as biuret, NH2CONHCONH2, resulted from the condensation of urea. This
biuret is a troublesome product that will harmfully affect the growth of some plants (Bhaskar.
& Das. 2007).
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2.5 Production of urea
2.5.1 Production of Urea in Malaysia
Petronas Chemicals Group (PetChem), a subsidiary of PETRONAS is the second largest urea
producer in South East Asia. In February 2012, PetChem had broken ground for the Sabah
Ammonia Urea (SAMUR) to build up the plant. SAMUR was located in Sipitang Oil & Gas
Industrial Park (SOGIP), Sabah which was about 145 km Southwest of Kota Kinabalu, Sabah.
SOGIP is the second largest urea producer in South East Asia. The main targets of this company
are to strength the PERTRONAS Chemicals Group’s (PCG) as PCG is the key regional
fertiliser player and to support Malaysia’s Economic Transformation Programme as the
agriculture sector is one of the National Key Economic Areas. Petronas Gas Resource Offshore
Sabah is the supplier of the natural gas for the feedstock of SAMUR Plant. SAMUR plants has
three branch of plants which are urea plant, ammonia plant and granulation plant. Urea plant
produce 1.2 million metric tons per annum (mtpa), ammonia pant produce 0.74 million metric
tons per annum (mtpa) and granulation plant produce 1.4 million metric tons per annum (mtpa).
2.5.2 Urea Production in India (The largest producer and the second largest consumer of
urea)
Based on the data that had been recorded in 2015-2016, India has produced a record about 24.5
million metric tons per annum (mtpa) of urea which make this country to become the largest
producer of urea. But, aside from that India also become the second largest consumer of this
urea as this country consumed 32 million metric tons per annum (mtpa) which had been
imported form Oman, China and Iran. India oil imported more than a quarter from what it
exported from these countries.
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Table 2: Most Fertilizer Dependent Countries of the World (2013)
Rank Country Fertilizer Consumption (kg/hectare of arable land)
1 Qatar 6, 898.70
2 Singapore 2,759.60
3 Seychelles 1,750.00
4 Malaysia 1,726.60
5 New Zealand 1,578.90
6 Kuwait 1,097.80
7 Bahrain 1,031.30
8 Oman 887.70
9 United Arab Emirates 855.50
10 Hong Kong SAR, China 841.00
Sheth. K. (2017, March 13) Most Fertilizer Dependent Countries of the World in 2013. Worldfacts. Retrieved from
http://www.worldatlas.com/articles/most-fertilizer-dependent-countries-in-the-world.html
2.5.3 Agreement Project Between Malaysia and India
Malaysia and India are expected to sign about 15 memorandum of understanding (MoUs)
and several agreements on infrastructure development projects worth RM30 billion. This
agreement was held between our Prime Minister, Datuk Seri Najib Razak and India’s Prime
Minister, Narendra Modi. This agreement was involving infrastructure development, will be
on urea and ammonia projects, liquefied natural gas supply and the construction of a technology
park. It had been said that one of the projects would be implemented in Malaysia. The project
that will be develop in Malaysia is the development of urea and ammonia manufacturing plant.
This product will be supply to the Republic of India. This project will be going to be a huge
deal to Malaysia as before this only Oman had a similar dedicated deal to supply urea and
ammonia to India. This B2B agreement will see the involvement of a Malaysian consortium
and India government linked companies for the supply of urea and ammonia. It was expected
that Malaysia will supply around one million tonnes of urea and ammonia annually to India.
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2.6 Usage of urea
Urea or carbamide is product produced from ammonia and carbon dioxide is a very important
chemical in agricultural and polymer industries. The main usage of urea, mainly worldwide
90% used it as nitrogen fertilizer and indeed, more urea manufactured by mass than any other
organic chemical Urea also important as it is in reducing from diesel engines in cars, buses and
lorries. Diesel engines run at high temperatures and nitrogen and oxygen from the air are able
to react together under these conditions to produce high concentrations of nitric acid. Another
way to remove pollutant is to allow it to react with ammonia to form nitrogen.
Urea also is an industrial product that is used as feed additive for live stocks. Urea is the most
nonprotein nitrogen (NPN) compound used as feed ingredients for ruminant animals. It serves
as source of nitrogen for the biosynthesis of protein with the mediation of bacteria and other
microorganisms. However, it uses as such must consider among other as its lack of energy and
its deficiency in minerals including sulphur. It is readily converted to ammonia in the rumen.
When fed excessive doses, it can result to fatal toxicity due to ammonia accumulation in the
rumen which will in turn led to a rise in the level of blood ammonia.
It is also industrial production of synthetic resins. Urea also used in the manufacture of
synthetic resins with various applications such as plastic, adhesives, mouldings, laminated,
plywood, particleboard, textile and coatings. With formaldehyde, it produces a hard,
electrically non-conducting plastic. It is also an industrial product used in the production of
pharmaceutical products. In 1864 the German chemist Adolph von Baeyer first synthesized
acid from diethyl malonate and urea. Certain derivatives of barbituric acid (barbiturates), such
as pentothal, pentobarbital and secobarbital are used as sedatives(tranquilizer) or sleep inducer.
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2.7 Major Hazards of Urea Production
2.7.1 To Human
1. Fire
Gases in the burning process. If the human inhale the fume, it can cause a minor corrosion
in lungs. If this happened in surrounding, all kinds of fire extinguishing agents are allowed
to use. (DOT, UN 1357 & UN 0220, Safety Data Sheet)
2. Inhalation
Once human inhale the odour of this compound, it may cause cough, shortness of breath
and sore throat since this compound can be evaporate at 20°c. As prevention, human must
wear a mask every time you get nearer to this compound. If it still happens to human, make
sure get the fresh air and rest well. (DOT, UN 1357 & UN 0220, Safety Data Sheet)
3. Skin and Eyes

As this carbamide touched the skin, it can cause the redness to this part. So, before entering
industry or laboratory, human must wear personal protection equipment which are
protective gloves, safety spectacles and the boots. If this still happened, make sure to rinse
and wash this part with a plenty of water for a several minutes and take to the doctor for
other treatment. However, repeated contact with skin may cause dermatitis.
(DOT, UN 1357 & UN 0220, Safety Data Sheet)
4. Ingestion
This compound may cause convulsions, headache, nausea and vomiting if human keep
exposing with this compound. Make sure do not drink, eat or smoke during do this work
since it is easily to evaporate and can get to your food. As prevention, make sure to drink a
lot of water every day outside your workplace. (DOT, UN 1357 & UN 0220, Safety Data
Sheet)
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2.7.2 To the Environment
The production of urea gives a major effect of aquatic toxicity. When the urea reached the
ground, it also can cause the water pollution at a certain place. This is due to the toxic that came
from the urea. When it absorbs in the soil, then it goes to the pond or river, it may cause the
death of the aquatic organism. (Ave. E van Nieuwenhuyse 4, 2000, Production of Urea booklet
no.5 of 8)
2.7.3 Industrial Hazard
1. Equipment or piping failure due to corrosion

The corrosiveness is determined by the temperature, the process components, the
concentration of dissolved oxygen and the presence of contaminant. To avoid this, happen,
make sure to use the stainless steel with lined of carbon steel vessel for economic reasons
plus it can avoid a potentially hazardous situation. (Ave. E van Nieuwenhuyse 4, 2000,
Production of Urea booklet no.5 of 8)
2. Explosion hazard due to the formation of an explosive gas mixture

Explosive gas mixtures can be form in the inert scrubber, the off-gases which is consists of
oxygen, hydrogen, nitrogen and possibility of some non-condensed carbon dioxide. Make
sure the process operates in well controlled to avoid any explosion form the gases mixture.
For a better operation, hydrogen which is present in carbon dioxide feedstock is reduced
by catalytic combustion to minimize the risk of forming the explosion. (Ave. E van
Nieuwenhuyse 4, 2000, Production of Urea booklet no.5 of 8)
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3.0 Process Selection
After several research and discussion, four different processes in production of urea were found
and deeper analysed. Upon determining the best out of those four processes, a detailed study
has been done based on particular criteria which are crucial for urea production. The studied
criteria focus on these requirements;
I. Maximize heat recovery

II. Minimize impurities
III. Minimize power requirement
IV. Lowering operating cost
V. Pollution control
This section will discuss the processes of urea along with its pros and cons. The processes
discussed are:
1. Snamprogetti Urea Technology (Italy)

2. Mitsui Toatsu or Toyo Koatsu Process (Japan)
3. Once- through Urea Process
4. Stamicarbon (Holland)
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3.1 SNAMPROGETTI UREA TECHNOLOGY
3.1.1 Introduction to Snamprogetti Urea Technology
The Snamprogetti Urea Technology grasps the total recycle stripping operational which
upholds ammonia as self-stripping agent. In most urea production or in any other type of
production, a 100% conversion; or complete total reaction will never occur. In urea production,
the synthesis of urea will leave significant amount of excess ammonia; unconverted, in the
output stream. The Snamprogetti process brilliantly utilises these excess ammonia, to strip CO2
in a process section of the stripper; which recombining them to become ammonium carbamate
(in a carbamate condensers) which then return back to the reactor to be converted to urea.
The overall result of the Snamprogetti’s process scheme shows that it succeeds in established
an internal recycle of the fundamental reactants; ammonia and carbon dioxide, without any
need to pump them again, substantially saving power usage. Additional to the necessary of
reducing pumping, Snamprogetti operational also allows another valuable saving in steam
requirement, since the operating temperature level of the ammonium carbamate condenser by
utilizing the heat released by the condensing vapour. (Saipem.2014)
3.1.2 Process Description
From the reactor, the urea synthesis is approximately done under the temperature of 180-190℃,
together with the pressure of 130 atms. Excess ammonia then undergoes stripping process, in
a stripper, which operates about 190℃ and 130atms. The stripper-off gas then condensed in a
vertical shell and tube condenser, operating at about 130 atms and 148-160℃ (Bhaskar. & Das.,
Manufacture of Urea, p.20). The condensate then combines to form ammonium carbamate in
a carbamate condenser; a steam producing high pressure condenser, recycling the carbamate
back into the reactor. The urea product solution that leaves the reactor, the stripper will further
degas in medium-low pressure decomposition system as it may still contain 2-3% of residual
unreacted carbamate. The residual unreacted carbamate ammoniacal solution will then
recovered and pumped back to the reactor (Bhaskar. & Das., Manufacture of Urea, p.20).
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3.1.3 Strengths and weaknesses of Snamprogetti’s Process
Although The Snamprogetti urea technology comes with high end functionality of multiple
equipment and machineries, like in any production processes, there must be several down sides
to it. The first complex aspect of this technology is it is governed by an equilibrium requiring
of removal and recycle of the reactants not transformed to urea. This part of aspect shows that
the upmost significant part in production of urea, its reaction; requires a lot of analysis;
regarding its input, output, its conversation rate and other more., to be in equilibrium state.
Next, the processes requirement of pressure and temperature are significantly high. On top of
that, the solutions involve are really corrosive (e.g. ammonia). Furthermore, environmentally
opposing, any urea plant is a main contributor towards air and water pollution (Saipem- The
Snamprogetti Urea Technology Booklet, 2014, p.8).
Focusing on the weaknesses, Snamprogetti has completely solved them by providing high
quality of solutions of its advanced technology. From Saipem- The Snamprogetti Urea
Technology Booklet, page 9-12, describes the below:
I. High process regulation – low raw material consumption and low energy requirement
II. Sustainable environmental pollution
III. Recovery in process condensate - BFW (Boiler Feed Water)
IV. The Stripper
V. High reliability
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Figure 1: Snamprogetti Process Flow Diagram (Saipem- The Snamprogetti Urea Technology Booklet, 2014)
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3.2 MITSUI TOATSU OR TOYO KOATSU PROCESS (JAPAN)
3.2.1 Introduction to Mitsui Toatsu or Toyo Koatsu Process (Japan)
Mitsui Toatsu Total recycle was designed by Toyo Engineering Corporation in 1968. Retrieved
May 29, 2017 from www.mitsui.chem.corporate, The name of Mitsui Toatsu came from the
collaboration between two company in Japan which are Mitsui Chemical Industry and Toyo
Koatsu Industries. Toyo Engineering Corporation (TEC), a worldwide engineering contractor
and one of three major urea process licensers. TEC has engineered and constructed, as of the
end of 2000, 93 urea plants and 10 urea granulation plants based on TEC technologies, giving
a quarter of the world’s total production capacity by the three major urea processes licensers.
3.2.2 PROS of Mitsui Toatsu or Toyo Koatsu Process (Japan)
1. High CO2 Conversion
This process has three different stages of pressures. This different pressures will lead to the
high conversion of CO2.
3.2.3 CONS of Mitsui Toatsu or Toyo Koatsu Process (Japan)
1.Formation of Biuret
Due to the removal of unconverted carbamate, the urea solution needs to be concentrated before
converting to the final solid form. After the third decomposer, the removal of water about 25%
of the solution creates a big problem as it will form biuret. This because of the presence of free
ammonia, heating the solution will promote the decomposition and will form biuret.
2.Large Amount of Energy
This process required three decomposers to converted the unconverted carbamate to urea. As
each of the decomposers has different amount of pressure and temperature, this will require a
high amount of energy.
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3.High Cost
As this process use a large amount of energy, the operating cost will be high. This will make
the company to spend a lot for this urea production.
3.2.3 Process Description
This process is the total recycle urea process which do the recycling of carbamate solution
with three different pressures stage. During this process, the carbamate will be decomposing
and recover back to the system. Firstly, the liquid ammonia (NH3) from the storage, carbamate
and compressed carbon dioxide (CO2) will be mix together in the reactor. The reactor is
operated at about 195 ℃ and 240 atm with a NH3 to CO2 molar ratio of about 4 to 3 (4:3).
During this process, about 67 % of the total ammonium carbamate present in the reactor is
converted to urea. The unconverted carbamate is decomposed and stripped from the urea
solution together with excess NH3 in a series of three pressure-stage decomposers. These three
decomposers have three different pressures and temperatures. This carbamate will firstly go
into the decomposer with the lowest pressure and temperature which is at atmospheric
temperature (1 atm) and 120 ℃. Then this carbamate will continue to the second decomposer
which operates with 3.06 atm and 130 ℃. Lastly to make sure the carbamate will convert into
more urea, this solution will flow into the highest pressure decomposer that operates with 18
atm & 150 ℃. This process is works when the off-gas from each decomposition stage is
condensed to solution in its respective water cooled condenser and the solution thus obtained
is pumped to the next high pressure
staged condenser. The results from this process will produce about 67% of urea that had been
converted from the total ammonium carbamate that present in the reactor. The main feature of
the Mitsui Toatsu process is the fact that the gaseous phase in each decomposition stage is
contacted in counter current flow with the urea product solution issuing from the preceding
decomposition stage. Either a packed section or a sieve tray section is used for this purpose.
Excess NH3 is separated from the aqueous solution of carbamate & scrubbed from the last
traces of CO2 in counter current flow with reflux liquid, NH3, fed to the top of the high pressure
absorber. The pure excess NH3 thus obtained is condensed to liquid with cooling water &
recycled to the reactor. The carbamate solution is recycled back to the reactor for total recovery.
(Bhaskar. & Das., Manufacture of Urea, p.24)
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Figure 2: Mitsui- Toatsu ACES Synthesis Section. (Sakata. & Yanagawa. 2001. Latest Urea Technology for Improving Performance and
Product Quality Booklet)
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4.3 ONCE-THROUGH UREA PROCESS
3.3.1 Introduction and Process Description of Once-through Urea Process
In production of urea, ammonia and carbon dioxide were involved in commercial synthesis of
urea at high pressure to form ammonium carbamate which is subsequently dehydrated by the
application of heat to form water and urea. (Lloyd. M. Elkin, October 1969, Urea)
Once-through process is the simplest way to decompose the carbamate to carbon dioxide and
ammonia where the feature of this process limit the corrosion by using the special construction
material. (Jay SHM. August 1970, Module 9-Urea)
Basically, this principle ensure that the off-gases were used as a feedstock for other products
but this principle are not recovered for recycle process. (Jay SHM. August 1970, Module 9-
Urea)
Generally, it is conventional process where the unconverted carbamate will be decomposed to

NH3, and CO2, gas at very low pressure by heating the urea synthesis reactant effluent mixture.
These gases will be separated from urea solution and will be utilized to produce amount of
ammonium salts by absorbing the ammonia in sulphuric acid or nitric acid. (Bhaskar. & Das.,
Manufacture of Urea, p.18).
In this process, liquid of ammonia is pumped through the plunger pump at high pressure which
is 200atm while the carbon dioxide gases is compressing through the compressor up to the urea
synthesis reactor. (googlebook. 9.4- Urea Processes. Pg.269) The mole ratios that have feed
into the processes for these two compounds, which are carbon dioxide and ammonia is 2:1 or
it also can be 3:1. (Bhaskar. & Das., Manufacture of Urea, p.18).
Normally, the temperature of the reactor will operate at the range from 175°C to 190°C but
regularly the temperature will maintain at 185°C by regulating the amount of excess ammonia
which in percentage, when 100% excess ammonia required, there will be around 35% will
converted into urea which is about 75% carbon dioxide are converted at the same time.
(Bhaskar. & Das., Manufacture of Urea, p.18)
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In the reactor effluent solution, it produced around 80% of urea after stripping process of
decomposed carbamate was made. Stripping process was made in the steam heated shell and
tube heat exchanger. Those unconverted ammonia and carbon dioxide goes to steam heating at
moderate pressure at 2atm in the carbamate stripper. Since this process produce large amount
of off-gases, it is a must for this process be in conjunction in coproduction of other material as
recovery. (Heba Ramadan. August 15. Manufacture Of Urea)
At the end of the process, it has been found that around 60% of urea was attained after the
conversion of the carbamate has been done. Any excess hear from the reactor was removed by
means of low-pressure steam-producing coil and lastly a large amount of urea was produced.
(Bhaskar. & Das., Manufacture of Urea, p.19).
3.3.2 Strengths of Once-through Urea Process
1. Simplest process to produce urea

This process happened in short period of time and do not need any extras work on it. It just
goes once-through as the substance entered the reactor.
2. Least expensive for operating cost and capital investment
This process used small amount of cost and it will be held at low temperature and low
pressure plus, this process is suitable used for a small scale of product needed.
3. Least flexible
This process is easy to handle and it is capable to create another product at one time in same
process operated such as ammonium nitrate.
Cannot be operated unless some prevision is made to utilize large amount of ammonia
and off- gas (Heba Ramadan. August 15. Manufacture of Urea)
3.3.3 Weaknesses of Once-through Urea Process
1. Large quantity of ammonia salt formed as a coproduct

The ammonia salt should be in flow of producing the main product which is urea. So, since
it goes to coproduct, it will decrease the amount of target urea needed. (Heba Ramadan.
August 15. Manufacture of Urea)
21
2. Overall carbon dioxide conversion is low

It causes less CO2 converted to the urea, so it directly makes the urea produced is low.
(Heba Ramadan. August 15. Manufacture of Urea)
3. High environmental pollution

Since the production of carbon dioxide is high, it can cause the air pollution, the larger
amount of carbon dioxide release to the air, the higher the air pollution in the industrial
area. (Heba Ramadan. August 15. Manufacture of Urea)
4. Non-recycle process
Which may cause the side product to be wasted because this product actually can be
recycles to produce another batch of urea. (Heba Ramadan. August 15. Manufacture of
Urea)
22
Figure 3: Once- through urea process flow diagram. (Bhaskar. & Das. 2007. Manufacture of urea. Rourkela, India.)
23
3.4 STAMICARBON PROCESS (HOLLAND)
For this process, the carbon dioxide, CO2, stripping process are based on the reactor
effluent/waste will not been brought to lower pressure as the typical conventional liquid recycle
urea process, but stripped at synthesis pressure by gaseous CO2 reactor feed stream in a heated
vertical heat exchanger.
The high pressure stripper will operate on 140 atm at 190°C. The stripped urea solution
contained 15% of unconverted carbamate and let down for about 3 atm for degassing in steam
heated low pressure decomposer at 120°C. The off gas recovered were condensed with cooling
water in low pressure condenser working on 65°C and 3 atm. The solution obtained then
pumped to the high pressure condenser by means of high pressure carbamate pump. The off
gas recovered form high pressure stripper is condensed in high pressure condenser which
operates at 170°C and 140 atm. The heat of condensation is removed on the shell side of the
condenser by vaporising the equivalent amount of condensate. The 3.4atm steam then produced
can be reused in another section of the plant.
Mixture of gas and liquid issuing from high pressure condenser is fed to reactor for total CO 2
condensation to carbamate and subsequent conversion to urea. The inerts were vented from
reactor through a water coolant vent condenser. The reactor effluent at 185°C and 140 atm is
fed to high pressure stripper. [Bhaskar, K., & Das, P. C. (n.d.). Manufacture of urea. Retrieved
May 12, 2017, from http://ethesis.nitrkl.ac.in/4237/1/Manufacture_of_Urea.pdf].
24
3.4.1 Strengths of Stamicarbon Process
The pros of this process are the stripper used in this process were using high temperature and
pressure for the process, that will produce such efficient product in desired time. This will also
cut down the time for the product to be produced. Stamicarbon uses high pressure CO2 stripper
to separate ammonium carbamate from urea and water at synthesis pressure, and the
unconverted ammonium carbamate could be recycled so no extra water needed to be added to
recycle the carbamate. (The Comparison of Stamicarbon and Saipem Urea Technology, 2016).
3.4.2 Weaknesses of Stamicarbon Process
The cons for this process are it did not involve high ratio between NH3 to CO2 in the reactor,
which will make produce lower rate conversion of carbamate to urea. This will make the cost
of for production of urea spike as the product produce will consume more time and money.
25
Figure 4: Process scheme of the synthesis section of the Stamicarbon process. (Brouwer. & Baboo. 2016. The Comparison of Stamicarbon and Saipem Urea Technology, ResearchGate)
26
3.5 FULL COMPARISON OF UREA PROCESSES
Table 3 provides an overview of the weaknesses of the processes of urea discussed and the solution provided in overcoming them.
Urea process Weakness Solution and Strength Criteria Focus
Snamprogetti 1) Acquire complex aspect 1) High process efficiency- low raw Maximization Minimization Minimization Minimization Pollution
Urea of equilibrium of material and low energy heat recovery of impurities of power of operational control
Technology removal and recycle of requirement requirement cost
(Italy) unconverted reactants 2) Process condensate recovery-
2) Requirement of essential BFW     
high pressure and 3) The stripper- accommodate
temperature of its ammonia as stripper agent
equipment 4) Sustainable environmental
3) Corrosive solution pollution – guarantee low urea
involved- e.g. ammonia dust emission, low urea and
4) Environmentally ammonia contamination in the
opposing process water (contain 1ppm of
urea and 1ppm of ammonia)
Mitsui Toatsu 1) Formation of biuret High CO2 conversion from three  
or Toyo 2) Large energy different decomposers
Koatsu requirement – three
Process decomposers for urea
(Japan) conversion
3) High cost
Once- 1) Large quantity of 5) Simplest urea process – require  
through Urea ammonia salt formed as short period of time and less
27
Process coproduct – decrease the energy requirement (once feed

amount of target urea through to reactor)
2) Overall low CO2 6) Less cost for operating and
conversation – low urea capital investment – held low
produced temperature, low pressure as only
3) High environmental for small scale of production
pollution – low CO2 7) Flexible – easy to handle as only
conversation causes air able to produce one product at a
pollution (high CO2 time
concentration in air)
4) Non- recycle process –
causes side product to be
wasted
Stamicarbon 1) Low rate conversion of 1) Recycle carbamate  
(Holland) carbamate to urea – 2) Can produce desired product in
consume more time and time
money
28
3.6 SELECTED PROCESS – THE SNAMPROGETTI UREA TECHNOLOGY
After further consideration and comparison, it is determined that the Snamprogetti Urea
Technology to be the best urea process, compared with the other discussed urea processes;
Mitsui Toatsu or Toyo Koatsu Process (Japan), Once- through Urea Process and Stamicarbon
(Holland). This is entirely in regards to the efficiency of the Snamprogetti tenchnology,
tackling and handling the issues at hand in processing of urea. Below are the few solutions
brilliantly provided and managed by Snamprogetti technology, making it to be best urea
process. Below, are the few solutions provided by Snamprogetti, taken from the Saipem- The
Snamprogetti Urea Technology Booklet, 2014, from page 8 till 12.
3.6.1 High process regulation
In Snamprogetti’s, it is ensured that both raw material consumption and energy requirements
are efficiently managed. Up to 99.8% of raw material namely ammonia and carbon dioxide
will be converted to urea; delivering low utilization of raw material, substantially providing the
effect of sustainable environmental pollution (ammonia; pollutant can be reduced). Also, with
the high ratio of NH3 and CO2 in the reactor confirms a high conversation of ammonium
carbamate (an intermediate) to urea. Together with the ammonia-stripping operation; the
stripper, this significantly diminish the recycle of unconverted carbamate. Along- side with the
heat recoveries technology, high conversion, high stripping efficiency and heat recoveries
minimise the energy requirement, i.e. steam, electric power and cooling water consumption.
(Saipem.2014)
3.6.2 Sustainable environmental pollution
The proprietary design of Snamprogetti’s natural- draught prilling tower guarantees urea dust
emission lower than 40mg/Nm3 in air. Also, its technology of the process water discharged
from the plant to contain only 1ppm of urea and 1ppm of ammonia significantly reduces water
pollution.
29
3.6.3 Recovery in process condensate
As the discharged process water contain 1ppm of urea and 1ppm of ammonia, Snamprogetti
succeeds in brilliantly use the negligible values of pollutants water discharge to three targets
contribution; environmental pollution reduced, specific consumption of urea also reduced and
lastly the process water for technical purpose of BFW (boiler feed water). BFW uses for the
steam production at pressures, possible of extend as high as 110 bar.
3.6.4 The Stripper
In the Snamprogetti technology, the NH3 and CO2 separation is done in the usage of ammonia
acting as stripping agent along with the imperative heat, which the condensing steam supplies.
The stripper consists of a tube, made by bimetallic, consisting of two coaxial tubes, an external
tube made of 25-22-2 Cr-Ni-Mo and an external tube made of zirconium. According to the
Snamprogetti’s technologists, the tubes are produced separately, according to its specification,
which the assembled to obtain a proper mechanical bonding. Recently, the stripper design has
been developed and implemented for the stripper designs of Full Zirconium Stripper and
OMEGABOND® Stripper. These strippers can withstand severe conditions i.e. high
temperature; allowing long life of equipment, optimisation of plant operating conditions and
minimisation of required maintenance. The Full Zirconium Stripper can resist erosion and
corrosion.
3.6.5 High reliability
Snamprogetti’s high reliability covers an easy and safe operation. One of the technology
includes is the Medium Pressure section in the Snamprogetti’s, acts as detector for any
technical faulty in the synthesis loop of high pressure, which secure better pliability. Also in
the high pressure synthesis loop, the blocking-in likelihood during emergency shutdowns
simplifies upon the plant to restart. Focusing to a more alarming issue, explosive mixtures are
much more serious as any event of explosion resulted in life losses and damage in plant. In
urea plant, the abundant presence of flammable compounds of CH4, C2H6 and H2 combined
with passivation air (O2 and NH3) are released to the atmosphere. Also, any excess NH3 are
then act as stripping agent in the stripper, minimises O2 for passivation, thus avoiding the
formation of explosive mixture. Although through all the years, no explosion has ever occurred
30
in plants based on the Snamprogetti’s technology. On top of that, there is no mechanical failures
have ever occurred. All of the special features account to Snamprogetti show their fully
reliability which is extremely crucial for urea plant.
31
Figure 5: Process Flow Diagram of the Snamprogetti Urea Technology. Made by Nurul Farzana Binti Abd Mustaffa & Reyhana Binti Noorsham. E-draw. 2017. May 29.
32
5.0 Process Equipment
5.1 Reactor
In the process, inside the reactor, when liquid ammonia was compressed with CO2 at high
temperature and pressure will produce urea in two forms;
2NH3 + CO2  NH2COONH4
NH2COONH4  NH2CONH2 + H2O
Both reactions are reversible as only partial conversion occurs in the reactor. In the reactor, the
NH3 & gaseous CO2 react to form ammonia Carbamate which a portion of which dehydrates to
form urea & water. The fraction of Carbamate that dehydrates is determine by the ratio of
various reactants, operating temperature, the residence time in the reactor and reaction pressure.
NH 3
The mole reaction of is around 2 : 1 . The mole ration to CO2 is around 0.67: 1.
CO2
In the synthesis conditions (T=180°C, P=188 atms), the first reaction occur rapidly and is
completed. The second reaction occurs slowly and determined the reactor volume. Urea reactor
is a plug flow type with 10 no.s sieve trays to avoid back mixing and to avoid escape where
stripping occur of NH3 favours decomposition of carbamate, and 80% of carbamate is
decomposed here. The pressure inside the stripper is the same as the reactor.
Kcal
NH2COONH4 (s) 2NH3 (g) + CO2 (g) Δ H = +37.4
gm  mole
This reaction involves increase in volume and absorption of heat, this this reaction will be
favoured by decrease in pressure and increase in temperature. Plus, decreasing the partial
pressure of either of the products will also favour the forward reaction. (Bhaskar. & Das.,
Manufacture of Urea). The process based on first principle of decrease in pressure and decrease
in temperature is called conventional process whereas process based on increase/decrease of
partial pressure of NH3 or CO2 is called stripping process. According the above equation, we
have;
K = (pNH3)2*(pCO2) [ where, K= equilibrium constant
33
5.2 The Stripper
The stripping is affected at synthesis pressure itself using CO2 or NH3 as stripping agent. If CO2
is selected, it is to supplied to the decomposer or stripper. While if NH3 is selected it is to be
obtained from the system itself because excess NH3 is present in the reactor as in
Snamprogetti’s process. CO2 stripping is advantageous because introducing CO2 increase p
CO2. So, pNH3 will be reduced to maintain P constant as
P = pCO2 + pNH3.
At a particular temp K is constant so when pNH3 is reduced to keep K constant, carbamate will
be reduced faster by decomposition as pNH3 appears in the equilibrium equation with a power
of two. Selection of 1st stage decomposition should be in such was that minimizes water from
evaporates because the recovered gases go along with the carbamate to reactor again and if
water enters reactor again, the production will be affected adversely due to hydrolysis of urea.
(Saipem- The Snamprogetti Urea Technology, 2014, p.5).
34
5.3 Carbamate Condenser
The main usage of Carbamate Condenser is to cool ammonia feed and the gases from the
stripper that mainly CO2. Their ammonia and carbon dioxide combined again to from
ammonium carbamate, which then will be passed again to the reactor to convert it to urea.
The traditional high pressure carbamate condenser is a vertical shell and tube exchanger with
process medium on the tube idea. Ammonium carbamate wash solution from the scrubber,
which recover residual ammonia and carbon dioxide from the inert gas purge from synthesis
loop. The overhead gases from stripper and the recovered solution from medium pressure
absorber all then flow to the high pressure carbamate condenser through mixer where total
mixture except for a few inerts is condensed and recycled back to the reactor by carbamate
ejector. Condensing the gases at high temperature and pressure permits the recovery of
condensation heat in the production of steam at 4.5 atms in high pressure carbamate
condenser. From top of carbamate separator, the incondensable gases come out consisting of
inerts and little quantity of NH3 and CO2 unreacted in the condenser. The unreacted reactants
then are sent to the bottom of Medium Pressure Decomposer (MP Decomposer).
35
5.4 Medium Pressure Decomposer (MP Decomposer)
In this section, the main target is to partially strip out the reactants (ammonia and carbon
dioxide) from the urea solution. The removal is done by condensation in water, recycled them
back to the reactor, together with ammonia and carbon dioxide aqueous solution collected from
the downstream section of the plant. A distillation column is prepared in this section to separate
excess ammonia and recycled back to the reactor separately. This column operates at about 17
bar. Snamprogetti added a particular feature of another partial condensation of the removal
ammonia and carbon dioxide in a shell of preheater within vacuum section, recovering some
energy in the form of 200 kg of steam per ton of urea. Aside from the feature, another advance
technology of inerts washing. Inerts such as CO, H2 and CH4, contained mainly in the carbon
dioxide and passivation air, though quantity of passivation air resulted is considered little
compared to other type of plants. Here, the washing inerts defines as recovering ammonia in
the inerts. For the complete abatement of the ammonia contained in the inerts, in completely
safe conditions with regard to explosions, Snamprogetti has patented a washing method that
has already been applied in some plants. This consists of washing the inerts with water after
the addition of a quantity of flammable gas, as for example natural gas, in such an amount that
after the ammonia has been eliminated, the composition of the inerts is out of the explosive
field due to the excess of flammable gas. The washed inerts are sent to a burner together with
the natural gas (Saipem- The Snamprogetti Urea Technology, 2014, p.5).
Image 1: Safe Ammonia Washing from “Inerts” [Process of inerts washing- ammonia recoveration]. (2014). Retrieved May
4, 2017, from http://www.saipem.com/static/documents/spm_UREAri_L02_14_01_10.pdf
36
5.5 Low Pressure Decomposer (LP Decomposer)
From Saipem’s booklet of The Snamprogetti Urea Technology, it is summarised that the low
pressure decomposer, falling film type of decomposer, has the main purpose of to further purify
and recover undesired product in the urea solution flowing from previous process of MP
decomposer. Before entering LP decomposer, the flowing urea solution is first expanded at 4.5
atms. Flowing into the LP decomposer, the solution passes through two parts of top separator
and decomposition section. Similarly, in the MP decomposer, the top separator function as to
remove any released flash gases (gas- form refrigerant; spontaneously produced when
condensed liquid subjected to boiling), from entering the tube bundle. Passes through the top
separator, the decomposition section then performs the decomposition of any residual
carbamate, and also the condensation of residual carbon dioxide and ammonia, to be removed
and recycle back to the reactor (Saipem- The Snamprogetti Urea Technology, 2014, p.5).
5. 6 Vacuum Concentration (Evaporator)
Upon leaving the LP section, the urea solution then enters this section with the target process
of concentrating, again, removing any residual of carbon dioxide, ammonia, although their
presence is small in quantities. This final concentration process is made under vacuum in two
steps at 0.3 and 0.03 atms respectively, for the formation of prilled product and granular
product, according to the granulation technology used. The necessary heat has been provided
thru partial condensation of the vapours from the MP section. This section also provides the
solution of lump formation problem that occur during second vacuum separator. The
prevention of lump formation is by wetting the internal walls of the separator, a small recycling
of molten urea process. Water condensation also introduced in this section where Snamprogetti
succeed in discharging large amount of process water with 1 ppm of urea and 1 ppm of
ammonia and simultaneously, reutilize the process water as BFW, in order to minimise energy
consumption (Saipem- The Snamprogetti Urea Technology, 2014, p.5).
37
5.7 Prilling (Finishing section)
In this final section, the final product of 98% molten urea will be converted to pellets. Prilling
is the method of producing reasonably uniform spherical particles from molten solids, strong
solutions or slurries, (Walters. J. K. 2011, February) which in this case, pellets. Molten urea
(99.8% b.w.) is sprayed at the top of the prilling tower, at a height of 55-80 m, according to
climatic conditions; at the bottom, essentially spheroidal urea particles, namely prills, are
collected and sufficiently cooled in order to be sent to storage or directly to the bagging section
without screening, coating or any other treatment. Certain plant owners have requested the
additional of formaldehyde (an organic compound- aldehyde) to the molten urea just before
entering this section. The purpose is to improve the free-flowing characteristics of the prilled
urea and to achieve a slight increase in hardness. Additionally, a cooling medium is formed
upon the rising draught of air inside the prilling which removes the solidification heat and cools
the prills. Unfortunately, the prilling tower top’s design has come up with environmental hazard
of too much air entrain too much of urea dust. This represents a serious pollution problem.
With regard to this issue, Snamprogetti has patented a dedusting system, which manage to
reduce urea dust from 40 to 15 mg/Nm3of air. Aside from urea dust, the presence of ammonia
entertains the similar issue. Hence to abate ammonia, Snamprogetti came up with the solution
of washing the air with slight acidified acid which is done just before the prilling tower. The
addition of an inorganic acid to the urea melt (solution) drastically reduces ammonia quantity
in the air from the prilling tower. The values obtained are 20-70 mg/Nm3. Fortunately, side
result from this process is that ammonia quantity in the prills is greatly reduced and also drastic
reduction in the presence of ammonia in the work environment (conveyor belt chutes, storage)
(Saipem- The Snamprogetti Urea Technology, 2014, p.6).
38
6.0 Material Balance
REACTOR
NH3 = 364.97 Kg/Hr

CARBAMATE = 35.312.74
CO2 = 338.84 Kg/Hr
Kg/Hr
Urea = 22,374.63 Kg/Hr
NH3 = 13,091.51 Kg/Hr
Carbamate = 35,312.74 Kg/Hr
CO2 = 16,941.96 Kg/Hr REACTOR Water = 6792.19 Kg/Hr
Biuret = 624.90 Kg/Hr
INPUT OUTPUT
FLOWRATE FLOWRATE
MATERIALS % MATERIALS %
(Kg/Hr) (Kg/Hr)
FEED UNREACTED
NH3 13,091.51 43.59 NH3 364.97 0.55
CO2 16,941.96 56.41
CO2 338.84 0.52
TOTAL 30,033.47 100
RECYCLE PRODUCTS
Carbamate 35,312.74 100 Urea 22,374.63 34
Carbamate 35,312.74 53.66
Water 6792.19 10.32
Biuret 624.90 0.95
TOTAL 65,345.41 100 TOTAL 65,808.27 100
39
STRIPPER
Carbamate = 35,312.74
kg/hr
NH3 = 364.97 Kg/Hr
CO2 = 338.84 Kg/Hr NH3 = 364.97 Kg/Hr
Urea = 22,374.63 Kg/Hr CO2 = 338.84 Kg/Hr
Water = 6792.19 Kg/Hr STRIPPER Urea = 22,374.63 Kg/Hr
Biuret = 624.90 Kg/Hr Water = 6792.19 Kg/Hr
Carbamate = 35,312.74 Kg/Hr Biuret =624.38 Kg/Hr
INPUT OUTPUT
FLOWRATE FLOWRATE
(Kg/Hr) (Kg/Hr)
BOTTOM PRODUCT
NH3 364.97 0.55 NH3 364.97 1.20
CO2 338.84 0.52 CO2 338.84 1.11
Urea 22,374.63 34 Urea 22,374.63 73.37
Carbamate 35,312.74 53.66 Water 6792.19 1.11
Water 6792.19 10.32 Biuret 624.38 1.20
Biuret 624.90 0.95
TOTAL 30495.01 100
TOP PRODUCT
Carbamate 35,312.74 100

TOTAL 65,808.27 100
40
MEDIUM-PRESSURE SEPARATOR
NH3 = 182.49 Kg/Hr

CO2 = 169.42 Kg/Hr
MEDIUM- NH3 = 182.49 Kg/Hr

NH3 = 364.47 Kg/Hr CO2 = 169.42 Kg/Hr
PRESSURE
CO2 = 338.84 Kg/Hr Urea = 22,374.63 Kg/Hr
SEPARATOR
Urea = 23,374,63 Kg/Hr Water = 6792.19 Kg/Hr
Water = 6792.19 Kg/Hr Biuret = 624.38 Kg/Hr
Biuret = 624,38 Kg/Hr
INPUT OUTPUT
FLOWRATE FLOWRATE
(Kg/Hr) (Kg/Hr)
NH3 364.47 1.20 NH3 182.49 0.61

CO2 338.84 1.11 CO2 169.42 0.56
Urea 23,374.63 73.37 Urea 22,374.63 74.23
Water 6792.19 22.27 Water 6792.19 22.53
Biuret 624.38 2.05 Biuret 624.38 2.07
TOTAL 30,143,11 100
LOSES
NH3 182.49 51.86

CO2 169.42 48.14
TOTAL 30,495.01 100 TOTAL 851.91 100
41
LOW-PRESSURE SEPARATOR
NH3 = 182.49 Kg/Hr

CO2 = 169.42 Kg/Hr
NH3 = 182.49 Kg/Hr

CO2 = 169.42 Kg/Hr Urea = 22,374.63 Kg/Hr
LOW-PRESSURE
Urea = 22,374.63 Kg/Hr Water = 6792.19 Kg/Hr
SEPARATOR
Water = 6792.19 Kg/Hr Biuret = 624.38 Kg/Hr
INPUT OUTPUT
FLOWRATE FLOWRATE
(Kg/Hr) (Kg/Hr)
NH3 182.49 0.61 Urea 22,374.63 75.10

CO2 169.42 0.57 Water 6792.19 22.80
Urea 22,374.63 74.23 Biuret 624.38 2.10
Water 6792.19 22.53
TOTAL 29,791.20 100
Biuret 624.38 2.07
LOSSES
NH3 182.49 51.86

CO2 169.42 48.14
TOTAL 30,143.11 100 TOTAL 351.91 100
42
EVAPORATOR
H2O = 6485.79 Kg/Hr
Urea = 22,374.63 Kg/Hr Urea = 22,374.63 Kg/Hr

Water = 6792.19 Kg/Hr Water = 306.4 Kg/Hr
Biuret = 624.38 Kg/Hr EVAPORATOR Biuret = 624.38 Kg/Hr
X = 0.7510 (75.10%)
Y = 0.96 (96%)
Fx = Py
(29,791.20 Kg/Hr) x (0.7510) = P (0.96)
P = 23,305.41 Kg/Hr
OVERALL BALANCE:
F=P+E
29,791.20 = 23,305.41 + E
E = 6485.79 Kg/Hr
INPUT OUTPUT
FLOWRATE FLOWRATE
(Kg/Hr) (Kg/Hr)
Urea 22,374.63 74.76 Urea 22,374.63 96

Water 6792.19 23.16 Water 306.4 1.32
Biuret 624.38 2.09 Biuret 624.38 2.68
TOTAL 23,305.41
LOSES
Water 6485.79 100

TOTAL 29,791.20 100
43
PRILLING TOWER Air

Water = 287.72 Kg/Hr
Urea = 22,374.63 Kg/Hr

Urea = 22,374.63 Kg/Hr
Prilling Tower Water = 18.68 Kg/Hr
Water = 306.4 Kg/Hr
X = 0.96 (96%) Air
Y = 0.972 (97.2%)
Fx = Py
(23,305.41 Kg/Hr) x (0.96) = P (0.972)
P = 23,017.69 Kg/Hr
INPUT OUTPUT
FLOWRATE FLOWRATE
(Kg/Hr) (Kg/Hr)
Urea 22,374.63 96 Urea 22,374.63 97.2

Water 306.4 1.32 Water 18.68 0.081
Biuret 624.38 2.68 Biuret 624.68 2.71
TOTAL 23,017.64 100
LOSES
Water 287.72 100

TOTAL 23,305.41 100
44
7.0 Energy Balance
1. At reactor:
CO2 (g, 40℃,1.6 atms) CO2 (g, 180℃,188 atms)
Reactor NH3 (g, 180℃,188 atms)
40℃
NH3 (l, 40℃, 23 atms)
(180℃,188 atms) NH2CONH2 (urea) (g, 180℃,188 atms)
NHCONHCONH2 (biuret) g, 180℃,188 atms)
NH2COONH4 (carbamate) (v, 180℃,188 atms)

NH2COONH4 (carbamate), H2O (v, 180℃,188 atms)
(l, 155℃, 150atms)
Inlet stream:
Component 𝑛̇ (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
ℎ𝑟 𝑘𝑚𝑜𝑙 ̂(
𝑛̇ ∆𝐻 )
ℎ𝑟
CO2 (g, 40℃, 1.6 atms) 385.04 -392.94 -151297.62
NH3 (l, 40℃, 23 atms) 770.09 -66.66 -51334.2
NH2COONH4 (l, 155℃, 1.6 atms) 588.55 - 2471.91 -1454842.63
𝑘𝐽 -1657474.45
∑ 𝑛̇ ∆𝐻 ( )
ℎ𝑟
Outlet stream:
Component 𝑛̇ (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
ℎ𝑟 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ ∆𝐻
ℎ𝑟
CO2 (g, 180℃,188 atms) 7.7 −387.28 -2982.056
NH3 (l, 180℃,188 atms) 21.47 -61.276 -1315.60
NH2CONH2 (urea) (s, 180℃,188 atms) 372.54 7555.52 2814733.421
NHCONHCONH2 (biuret) (g,180℃,188 atms) 6.06 1235.330 7486.10
NH2COONH4 (carbamate) (v, 180℃,188 atms) 588.55 1235.945 727415.43
H2O (v, 180℃,188 atms) 377.34 -236.52 -89248.46
𝑘𝐽 3456088.84
∑ 𝑛̇ ∆𝐻 ( )
ℎ𝑟
𝑘𝐽
̂ ( ) = 𝑄𝑜𝑢𝑡𝑙𝑒𝑡 − 𝑄𝑖𝑛𝑙𝑒𝑡
𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
𝑄 = 3456088.84 − (−1657474.45) = 𝟓𝟏𝟏𝟑. 𝟓𝟔𝟑
𝒉𝒓
45
NH2COONH4
(carbamate vapours),
2. At stripper:
(v, 205℃,150 atms)
CO2 (g, 180℃,188 atms)
𝑛̇ 𝑡 CO2 (g, 205℃,150 atms)
NH3 (g, 180℃,188 atms)
NH3 (g, 205℃,150 atms)
NH2CONH2 (urea) (s, 180℃,188 atms)
NH2CONH2 (urea) (s, 205℃,150 atms)
NHCONHCONH2 (biuret) g, 180℃,188 atms) Stripper
NHCONHCONH2 (biuret) g, 205℃,150 atms)
NH2COONH4 (carbamate) (v, 180℃,188 (205℃,150 atms
atms) H2O (v, 205℃,150 atms)
H2O (v, 180℃,188 atms)

𝑛̇ 𝑏
Inlet stream: all reactants as reference states. Hence:
Component 𝑘𝑚𝑜𝑙 𝑘𝐽
𝑛̇ ( ) ̂(
∆𝐻 )
ℎ𝑟 𝑘𝑚𝑜𝑙
CO2 (g, 180℃,188 atms) 7.7 0
NH3 (g, 180℃,188 atms) 21.47 0
NH2CONH2 (urea) (s, 180℃,188 atms) 372.54 0
NHCONHCONH2 (biuret) g, 180℃,188 atms) 6.06 0
NH2COONH4 (carbamate) (v, 180℃,188 atms) 588.55 0
H2O (v, 180℃,188 atms) 377.34 0
Outlet stream:
Component 𝑛̇ 𝑡 (𝑘𝑚𝑜𝑙 ) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽 𝑛̇ 𝑏 (𝑘𝑚𝑜𝑙 ) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
𝑛̇ 𝑡 ∆𝐻 ) ℎ𝑟 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ 𝑏 ∆𝐻
ℎ𝑟 ℎ𝑟
CO2 (g, 205 ℃, 150 atms) - - - 7.7 1.081 8.324
NH3 (g, 205 ℃, 150 atms) - - - 21.47 1.024 21.99
NH2CONH2 (urea) (s, 205 ℃, 150 atms) 372.54 1700.25 633411.14 - - -
NHCONHCONH2 (biuret) (g, 205 ℃, - - - 6.06 19.892 120.55

150 atms)
NH2COONH4 (carbamate) (v, 205 ℃, - - - 588.55 1235.955 727421.32
150 atms)
H2O (v, 205 ℃, 150 atms) - - - 377.34 0.876 330.55
𝑘𝐽 633411.14 𝑘𝐽 727902.72
Total =∑ 𝑛̇ 𝑡 ∆𝐻 ( ) Total =∑ 𝑛̇ 𝑏 ∆𝐻 ( )
ℎ𝑟 ℎ𝑟
𝑘𝐽
𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
𝑄 = (633411.14 + 727902.72) − 0 = 𝟏𝟑𝟔𝟏𝟑𝟏𝟑. 𝟖𝟔
𝒉𝒓
46
3. At carbamate condenser:
NH2COONH4 (carbamate)
(v, 205℃,150atms) Water

Carbamate 25℃
Condenser
Steam
(155℃,150 atms)
4.5 atms,130℃
NH2COONH4
(carbamate)
(l, 155℃, 150atms)
∆𝐻
NH2COONH4 (carbamate) NH2COONH4 (carbamate)
(v, 205℃, 150atms) (l, 155℃, 150atms℃)
𝑛̇ ( ) ̂(
∆𝐻 )
NH2COONH4 (carbamate) 588.55 − 2471.91
𝑘𝐽
Q =𝑛̇ ∆𝐻 (ℎ𝑟)
𝑚𝑜𝑙 𝑘𝐽 𝒌𝑱
𝑄 = 588.55 × (−2471.91 ) = −𝟏𝟒𝟓𝟒𝟖𝟒𝟐. 𝟔𝟑
ℎ𝑟 𝑚𝑜𝑙 𝒉𝒓
47
4. At medium pressure separator (MPS)

CO2 (g, 140℃,17 atms)
𝑛̇ 𝑡 3 (g, 140℃,17 atms)
NH CO2 (g, 140℃,17 atms)
CO2 (g, 205℃,150 atms)
NH3 (g, 205℃,150 atms) NH3 (g, 140℃,17 atms)
NH2CONH2 (urea) (s, 205℃,150 atms) MPS NH2CONH2 (urea) (s, 140℃,17 atms)
NHCONHCONH2 (biuret) g, 205℃,150 atms) (140℃,17 atms) NHCONHCONH2 (biuret) g, 140℃,17 atms)
H2O (v, 205℃,150 atms) H2O (v, 140℃,17 atms)
𝑛̇ 𝑏
𝑘𝑚𝑜𝑙
Component 𝑛̇ ( ) ̂ ( 𝑘𝐽 )
∆𝐻
CO2 (g, 205℃,150 atms) 7.7 0
NH3 (g, 205℃,150 atms) 21.47 0
NH2CONH2 (urea) (s, 205℃,150 atms) 372.54 0
NHCONHCONH2 (biuret) (g, 205℃,150 atms) 6.06 0
H2O (v, 205℃,150 atms) 377.34 0
Outlet stream:
Component 𝑛̇ 𝑡 (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽 𝑛̇ 𝑏 (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
ℎ𝑟 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ 𝑡 ∆𝐻 ℎ𝑟 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ 𝑏 ∆𝐻
ℎ𝑟 ℎ𝑟
CO2 (g, 140℃,17 atms) ) 3.85 -2.7679 -10.66 3.85 -2.7679 -10.66
NH3 (g, 140℃,17 atms) 10.73 -2.6223 -28.137 10.73 -2.6223 -28.137
NH2CONH2 (urea) (s, - - - 372.54 -4138.58 -1541786.59

140℃,17 atms)
NHCONHCONH2 (biuret) (g, - - - 6.06 -51.72 -313.423
140℃,17 atms)
H2O (v, 140℃,17 atms) - - - 385.05 -2.2657 -872.4
𝑘𝐽 -38.797 𝑘𝐽 -1542993.75
∑ 𝑛̇ 𝑡 ∆𝐻 ( ) ∑ 𝑛̇ 𝑏 ∆𝐻 ( )
ℎ𝑟 ℎ𝑟
𝑘𝐽
𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
𝑄 = (−38.797 + (−1542993.75)) − 0 = −𝟏𝟓𝟒𝟑𝟎𝟑𝟐. 𝟓𝟓
𝒉𝒓
48
5. Low Pressure Separator (LPS) 𝑛̇ 𝑡

CO2 (g, 80℃,4.5 atms)
NH3 (g, 80℃,4.5 atms)

6. CO2 (g, 140℃,17 atms)
NH3 (g, 140℃,17 atms)

7.
NH2CONH2 (urea) (s, 140℃,17 atms) LPS NH2CONH2 (urea) (s, 80℃,4.5 atms)
8.
NHCONHCONH2 (biuret) g, 140℃,17 atms) NHCONHCONH2 (biuret) g, 80℃,4.5 atms)
(80℃, 4.5 atms)
9.
H2O (v, 140℃,17 atms) H2O (v, 80℃,4.5
𝑛̇ 𝑏 atms)
𝑘𝑚𝑜𝑙
Component 𝑛̇ ( ) ̂ ( 𝑘𝐽 )
∆𝐻
CO2 (g, 140℃,17 atms) 3.85 0
NH3 (g, 140℃,17 atms) 10.73 0
NH2CONH2 (urea) (g, 140℃,17 atms) 372.54 0
NHCONHCONH2 (biuret) (s, 140℃,17 atms) 6.06 0
H2O (v, 140℃,17 atms) 377.34 0
Outlet stream:
Component 𝑛̇ 𝑡 (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽 𝑛̇ 𝑏 ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
𝑛̇ 𝑡 ∆𝐻 ) 𝑘𝑚𝑜𝑙 ̂(
𝑛̇ 𝑏 ∆𝐻 )
ℎ𝑟 𝑘𝑚𝑜𝑙 ℎ𝑟
( )
ℎ𝑟
CO2 (g, 140℃,17 atms) ) 3.85 −2.4251 -9.337 - - -
NH3 (g, 140℃,17 atms) 10.73 -2.3067 -24.75 - - -
NH2CONH2 (urea) (s, - - - 372.54 -3085.13 -1149334.33

140℃,17 atms)
140℃,17 atms)
H2O (v, 140℃,17 atms) - - - 377.34 -2.0584 -776.717
𝑘𝐽 -34.09 𝑘𝐽 -1150400.431
∑ 𝑛̇ 𝑡 ∆𝐻 ( ) ∑ 𝑛̇ 𝑏 ∆𝐻 ( )
ℎ𝑟 ℎ𝑟
𝑘𝐽
∑ 𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
∑ 𝑄 = (−34.09 + (−1150400.351)) − 0 = −𝟏𝟏𝟓𝟎𝟒𝟑𝟒. 𝟓
𝒉𝒓
49
6. Vacuum Evaporator
Evaporator 1
𝑛̇ 1𝑡 𝑛̇ 2𝑡
H2O (v, 85℃,0.3 atms) H2O (v, 27.5℃,0.03 atms)
NH2CONH2 (urea) (s, 80℃,4.5 atms) NH2CONH2

(urea) (s, 85℃,0.3
NHCONHCONH2 (biuret) g, 80℃,4.5 atms)
atms)
NHCONHCONH2
NH2CONH2 (urea) (s,
H2O (v, 80℃,4.5 atms) (biuret) g,
27.5℃,0.03 atms)
63.1 ℃ 85℃,0.3 atms) 23.77℃
0.3 atm 0.03 atm
NHCONHCONH2 (biuret)
H2O (v, 85℃,0.3
(g, 27.5℃,0.03 atms)
atms)
𝑛̇ 1𝑏 H2O (v, 27.5℃,0.03 atms)
𝑛̇ 2𝑏
Evaporator 2
At evaporator 1:

𝑛̇ ( ) ̂(
∆𝐻 )
NH2CONH2 (urea) (s, 80℃,4.5 atms) 372.54 0

NHCONHCONH2 (biuret) (g, 80℃,4.5 atms) 6.06 0
H2O (v, 80℃,4.5 atms) 377.34 0
Outlet stream:
Component 𝑛̇ 1𝑡 ̂
∆𝐻 𝑘𝐽 𝑛̇ 1𝑏 ̂ ( 𝑘𝐽 )
∆𝐻 𝑘𝐽
̂( )
𝑛̇ 1𝑡 ∆𝐻 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ 1𝑏 ∆𝐻
𝑘𝑚𝑜𝑙 𝑘𝐽 ℎ𝑟 𝑘𝑚𝑜𝑙 ℎ𝑟
( ℎ𝑟
) (𝑘𝑚𝑜𝑙) ( ℎ𝑟
)
NH2CONH2 (urea) (s, - - - 372.54 234.27 87274.946

85℃,0.3 atms)
NHCONHCONH2 (biuret) - - - 6.06 3.978 24.107
(g, 85℃,0.3atms)
H2O (v, 85℃,0.3 atms) 0.1704 30.7 197.18 0.1704 33.6
𝑘𝐽 180.16 30.7 𝑘𝐽 87332.65
Total =∑ 𝑛̇ 2𝑡 ∆𝐻 (ℎ𝑟) Total =∑ 𝑛̇ 1𝑏 ∆𝐻 (ℎ𝑟)
50
𝑘𝐽
∑ 𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
∑ 𝑄 = (30.7 + 87332.65) − 0 = 𝟖𝟕𝟑𝟔𝟑. 𝟑𝟓
𝒉𝒓
At evaporator 2:
𝑛̇ ( ) ̂(
∆𝐻 )
NH2CONH2 (urea) (s, 85℃,0.3 atms) 372.54 0
NHCONHCONH2 (biuret) (g, 85℃,0.3 atms) 6.06 0
H2O (v, 85℃,0.3 atms) 197.18 0
Outlet stream:
Component 𝑛̇ 2𝑡 ̂(
∆𝐻
𝑘𝐽
) ̂ (𝑘𝐽 )
= 𝑛̇ 2𝑡 ∆𝐻 𝑛̇ 2𝑏 (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
𝑘𝑚𝑜𝑙 ℎ𝑟 ℎ𝑟 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ 2𝑏 ∆𝐻
𝑘𝑚𝑜𝑙 ℎ𝑟
( )
ℎ𝑟
NH2CONH2 (urea) (s, 27.5℃,0.03 - - - 372.54 -2499.12 -931022.16

atms)
27.5℃,0.03 atms)
H2O (v, 27.5℃,0.03 atms) 180.16 −1.9477 -350.9 17.02 −1.9477 -33.15
𝑘𝐽 -17.02 𝑘𝐽 -931332.56
Total =∑ 𝑛̇ 2𝑡 ∆𝐻 ( ) Total =∑ 𝑛̇ 2𝑏 ∆𝐻 ( )
ℎ𝑟 ℎ𝑟
𝑘𝐽
∑ 𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
∑ 𝑄 = (−17.02 + (−931332.55)) − 0 = −𝟗𝟑𝟏𝟑𝟒𝟗. 𝟓𝟖
𝒉𝒓
(total heat required for vacuum evaporator.)
51
7. Prilling Tower air

Water vapour 25℃
NH2CONH2 (urea) (s, 27.5℃,0.03 atms)

Prilling Tower air
NHCONHCONH2 (biuret) (g, 27.5℃,0.03 25℃
(25℃, 1atm)
atms)
H2O (v, 27.5℃,0.03 atms)
NH2CONH2 (urea) (s, 25.0 ℃,1 atms)
NHCONHCONH2 (biuret) (g, 25.0 ℃,1

atms)
H2O (v, 25.0 ℃,1 atms)
𝑛̇ ( ) ̂(
∆𝐻 )
NH2CONH2 (urea) (s, 27.5℃,0.03 atms) 372.54 0
NHCONHCONH2 (biuret) (g, 27.5℃,0.03 atms) 6.06 0
H2O (v, 27.5℃,0.03 atms) 17.02 0
Outlet stream:
Component 𝑘𝑚𝑜𝑙
𝑛̇ 𝑡 ( ) ̂(
∆𝐻
𝑘𝐽
) ̂( )
Q = 𝑛̇ ∆𝐻
𝑘𝐽
𝑛̇ 𝑏 (
𝑘𝑚𝑜𝑙
) ̂(
∆𝐻
𝑘𝐽
) 𝑘𝐽
ℎ𝑟 𝑘𝑚𝑜𝑙 ℎ𝑟 ℎ𝑟 𝑘𝑚𝑜𝑙 ̂( )
𝑛̇ ∆𝐻
ℎ𝑟
NH2CONH2 (urea) (s, 25℃,1 atms) - - 372.54 −100.51 -37444
NHCONHCONH2 (biuret) (g, - - 6.06 -2.01 -12.18

25℃,1 atms)
H2O (v, 25℃,1 atms) 15.98 -0.08411 -1.344 1.04 -0.08411 -87.47
𝑘𝐽 -1.344 𝑘𝐽 -37543.65
Total =∑ 𝑛̇ 𝑡 ∆𝐻 ( ) Total =∑ 𝑛̇ 𝑏 ∆𝐻 ( )
ℎ𝑟 ℎ𝑟
𝑘𝐽
∑ 𝑄 = ∑ 𝑛̇ ∆𝐻
ℎ𝑟
𝒌𝑱
∑ 𝑄 = (−1.344 + (−37543.65) − 0 = −𝟑𝟕𝟓𝟒𝟒. 𝟗𝟗𝟒
𝒉𝒓
52
8.0 Process Design and Improvement
In the production of urea, it is usually done in a big scale such in industrial field. The plant
itself and the system involves are so many that each might have flaws and errors after it was
place there. Big process such as Snamprogetti and Stamicarbon (Holland) that were done by
its respective company, years by years will improve the machinery that they used. This is
because, the process that they already had is good and efficient at its best, but improvement
and precautions for every machinery involved and system done will always have room for
reconstruction and make the whole process better; besides cut off the money and produce more
product. The production of urea can be increase by making a few improvements in the flow of
the process. Usually, the engineers while focus on two things on how to increase the efficiency
which is temperature and pressure. But, there are a few problems that will affect the
manufacturing of urea which is the formation biuret and the unstable temperature and pressure
during the reaction. However, these two thing can be overcome by so many ways as we own
Carbamate Condenser regarding the biuret part.
First thing first, the main idea to increase the maximum product of Urea are by controlling the
pressure and temperature. This could be done easily by adjusting the control panel. The
production of urea will increase as the pressure and temperature increase. The temperature
should be increase to maximum at 175-180℃, then falls of sharply. However, for every
changes that will be done either in Reactor, Stripper, Medium or Low Pressure Condenser,
there will be consequences because the pressure and temperature used usually are different and
changes can give such defect. The maximum temperature and pressure should not be operating
without excess ammonia as the increasing of temperature and pressure will enhance the
corrosion rates to machinery. And in this problem, it will be hard because we are operating on
producing Urea at the finest, and Ammonia is one of the crucial reactant needed to produce
Urea. Without the presences of Ammonia might could have save the machinery involved but,
the product will become close to degenerate. When the temperature increases, urea will be
decomposed to biuret which is detrimental to germinating seeds and toxic to animals.
Moreover, when the pressure increase, operating cost of compression and reaction equipment
will also increase.
53
To avoid the corrosion rates to machinery, a few steps can be taken during the manufacturing
of urea. When operating the reaction, the temperature and pressure should be make sure to be
at the minimum. This is to make sure that every machinery can operate at the optimum
temperature and pressure but still produce the best amount of Urea as the product. Besides,
corrosion resistant metals and maintaining the proper reaction conditions also can be applied.
For example, by regular check ins on machinery and also oil up the gear, basically extra on the
maintenance. This can longer the life of the machine itself and also cut down any extra money
needed to repair the machinery in case it goes down. Things like this can be done by keeping
the maintenance good and regular.
One of the improvement that can be make is by installing Vortex Mixer and Conversion
Booster at the bottom of the reactor. By installing this devices, the conversion efficiency can
be increase. Moreover, energy and steam consumption also can be reduced. Both Vorter Mixer
and Conversion Booster will not disturb the temperature and pressure because these two
devices act as a catalyst if it is a reaction. It will not mix into the product or anything instead it
will produce higher product faster and more than the usual. This addition on the devices can
consume less time, which can lead to less energy and electrical supply needed. This can make
a company that own the plant to cut off expenses on Urea but did not produce less product.
Last but not least, the other improvement is by installing Variable Frequency Drive (VFD).
This device is a type of motor controller that drives an electric motor by varying the frequency
and voltage supplied to the electric motor. This device should be install for Reverse Osmosis
(RO) feed water pumps of RO Reject Recycle Plant. This device can help reducing the
electrical power consumption of RO Reject Recycle Plant. This can also help in cut off some
cost and energy used in system of any plant. Next, the usage of anhydrous ammonia also can
help avoiding the biuret formation. Anhydrous ammonia will form liquid urea-ammonia
solution that will remains liquid at reduced temperatures. This will be helpful because if there
is no formation of biuret, this will help in produce more Urea in less time because no recycle
reaction will occur and it will be done it less time.
54
9.0 References
1. Baboo. P. & Brouwer. M. (2016. October). The comparison of Stamicarbon and Saipem
Urea Technology. ResearchGate.
2. Baboo. P., Brouwer. M., Eijkenboom. J., Mohammadian. M., Notten. G. & Prakash.
G. (2016). The Comparison of Stamicarbon and Saipem Urea Technology. The
Comparison of Stamicarbon and Saipem Urea Technology, Part 1. Retrieved June 6,
2017, from
https://www.researchgate.net/publication/309385422_The_Comparison_of_Stamicarb
on_and_Saipem_Urea_Technology.].
3. Bera. S. (2016. April 1). Record urea production at 24.5 million tonnes in 2015.
Livemint. Retrieved from
4. Bhaskar. K & Das. C. P. (2007). Manufacture of urea (Degree’s thesis). Deemed
University, National Institute of Technology, Rourkela, India.
5. Fairall. J. S. (1996). Molecules of the month- Urea. School of Applied Science,
DeMontfort University, Leicester, United Kingdom.
http://www.livemint.com/Politics/12T4yVMZew6D6SrS6myeXM/Record-urea-
production-at-245-million-tonnes-in-201516.html
6. Mitsui Chemical Timeline. (2017) In Our History. Retrieved May 29,2017, from
http://www.mitsuichem.com/corporate/history/chronology/index.htm
7. Nawaz. M. (2014, April). Design Project: Design of a fertiliser plant producing Urea
and Ammonium Sulphate from Ammonia. School of Science and Technology.
8. Ram. S. B. (2017, March 23) Malaysia, India Agreements on projects worth RM30
billions to be signed. New Straits Time. Retrieved from
https://www.pressreader.com/malaysia/new-straitstimes/20170328/281908772977393
9. Sabah Ammonia Urea (SAMUR). (2017) In Petronas. Retrieved May 1,2017, from
http://www.petronas.com.my/our-business/downstream/OKP/Pages/SAMUR.aspx
10. Saipem- Snamprogetti. (2014). The snamprogetti urea technology.
11. Sheth. K. (2017, May 13). Most Fertilizer Dependent Countries in The World.
Worldatlas. Retrieved from http://www.worldatlas.com/articles/most-fertilizer-
dependent-countries-in-the-world.html
55
12. SPa, S. (2014). SnamProgetti Urea Technology. The SnamProgetti Urea Technology.
Retrieved June 4, 2017, from
http://www.saipem.com/en_IT/static/documents/spm_UREAri_L02_14_01_10.pdf
13. Walters. J. K. (2011. February 2). Prilling. Thermopedia. Retrieved from
http://www.thermopedia.com/content/1059/
14. Satish. C. (2016, June). Innovations in fertiliser production. Indian Journal of
Fertilisers. Pp12-13.
15. Hartman. C. (2014, March 20). What is a variable frequency drive? VFDs. Retrieved
from http://www.vfds.com/blog/what-is-a-vfd
16. Best Practices of in Energy Efficiency in RFC, Trombay Unit. Knowledge Exchange
Platform. Retrieved from http://knowledgeplatform.in/wp-
content/uploads/2016/02/10.-RCF-Trombay-1st-KEP-Jagdishpur.pdf
17. Yanagawa. T. & Sakata. E. (n. d.) Latest urea technology for improving performance
and product quality. Toyo Engineering Cooperation. Tokyo, Japan.
18. Manee. V. B., Ranveer. C. A. & Suryawanshi. M. (2016, January 1). Improvement
reactor efficiency of urea. International Journal of Science Technology and
Management, (5.1). IJSTM. Shivaji University. Kolhapur, India.
56
10. 0 Appendices
Appendix A
Calculation for material balance
MT
Production Rate: 200,000
year
No of Working Days: 365 Days
MT 1year MT
Daily Production: 200,000 × = 547.95
year 365days day
MT 1kg 1day kg
Urea: 547.95 × × = 22831.25
day 0.001MT 24 hr hr
Composition of the Final product:
kg
Urea : 98% = 22,374.63
hr
kg
Biuret : 1% = 228.31
hr
kg
Water : 1% = 228.31
hr
Main Reactions:
CO2 + 2NH3 → NH2COONH4
NH2COONH4 → NH2CONH2 + H2O
CO2 + 2NH3 → NH2CONH2 + H2O (overall reaction)
57
Side Reaction:
2NH2CONH2 → NH2CONHCONH2 + NH3
(Reaction 4)
kg 120kg / kmol kg kg
228.31 Biuret produced by = × 228.31 = 265.99 Urea
hr 103kg / kmol hr hr
(Reaction 2)
kg kg kg
Urea produced = 22,374.63 + 265.99 = 22,640.62
hr hr hr
kg 34kg / kmol kg
22,640.62 Urea produced by = × 22,640.62
hr 60kg / kmol hr
kg
= 12, 829.68 NH3
hr
(Reaction 1)
44kg / kmol kg
CO2 reacted = × 22,640.62
60kg / kmol hr
kg
= 16,603.12 CO2
hr
For 98% conversion:
kg kg
NH3 = 12, 829.68 / 0.98 = 13,091.51
hr hr
kg kg
CO2 = 16,603.12 / 0.98 = 16,941.96
hr hr
58
If (Reaction 3) is 100% complete,
kg kg
Urea produced = 60kg / kmol × 16,941.96 = 23,102.67
hr hr
44kg / kmol
For 98% conversion:
kg kg
Urea produced = (0.98) (23,102.67 ) = 22,640.62
hr hr
Therefore, Urea converted to Biuret and NH3
kg kg
= 23,102.67 - 22,374.63
hr hr
kg
= 728.04
hr
(Reaction 4)
103kg / kmol kg
Biuret produced = × 728.04
120kg / kmol hr
kg
= 624.90
hr
(Reaction 2)
18kg / kmol kg
Water produced = × 22,640.62
60kg / kmol hr
kg
= 6792.19
hr
Reactor (Urea= 34%)
59
kg kg
Flow rate of stream = 22,374.63 / 0.34 = 65,807.74
hr hr
(Reaction 1)
34kg / kmol kg kg
NH3 reacted = × 22,640.62 = 12,829.68
60kg / kmol hr hr
(Reaction 4)
17kg / kmol kg kg
NH3 produced = × 728.04 = 103.14
120kg / kmol hr hr
kg kg kg
NH3 unreacted = 13,091.51 - 12,829.68 + 103.14
hr hr hr
kg
= 364.97
hr
(Reaction 1)
44kg / kmol kg kg
CO2 reacted = × 22,640.62 = 16,603.12
60kg / kmol hr hr
kg kg kg
CO2 unreacted = 16,941.96 - 16,603.12 = 338.84
hr hr hr
Flow Rate Carbamate = Flow rate of stream at reactor’s exit - (flow rate of urea +
CO2 + NH3 + water + biuret)
60
kg kg kg
= 65,807.74 - (22,374.63 + 338.84 + 364.97
hr hr hr
kg kg kg
+ 6792.19 + 624.90 )
hr hr hr
kg
= 35,312.74
hr
61
Appendix B
Calculation for energy balance
Reference: C (s), N2 (g), H2 (g), O2 (g) at 25℃ at 1 atm
∆H= ∆𝐻𝑓 + ∆𝐻𝑏
At reactor: reactions involved;
CO2 (g) + 2NH3(l) NH2COONH4 (v)
NH2COONH4 (v) NH2CONH2 (g) + H2O
2NH2CONH2 (g) NH2CONHCONH2 (g) + NH3 (l)
Input stream:
𝐾𝐽 40
∆HCO2 =−393.5 𝑚𝑜𝑙 + ∫25 36.11 × 10−3 + 4.233 × 10−5 𝑇 − 2.887 × 10−8 𝑇 2 + 7.464 ×
10−12 𝑇 3
𝐾𝐽
= -392.94 𝑚𝑜𝑙
𝐾𝐽 40
∆HNH3 = −67.2 𝑚𝑜𝑙 + ∫25 35.15 × 10−3 + 2.954 × 10−5 𝑇 + 0.4421 × 10−8 𝑇 2 − 6.686 ×
10−12 𝑇 3
𝐾𝐽
= -66.66 𝑚𝑜𝑙
𝐾𝐽
∆HNH2COONH4 = - 2471.91 𝑚𝑜𝑙
(taken from energy balance calculation from carbamate condenser sec.)
62
Outlet stream:
𝐾𝐽 180
∆HCO2= =−393.5 𝑚𝑜𝑙 + ∫25 36.11 × 10−3 + 4.233 × 10−5 𝑇 − 2.887 × 10−8 𝑇 2 + 7.464 ×
10−12 𝑇 3
𝐾𝐽
= −387.28 𝑚𝑜𝑙
𝐾𝐽 180
∆HNH3 = −67.2 𝑚𝑜𝑙 + ∫25 35.15 × 10−3 + 2.954 × 10−5 𝑇 + 0.4421 × 10−8 𝑇 2 − 6.686 ×
10−12 𝑇 3
𝐾𝐽
= -61.276 𝑚𝑜𝑙
𝐾𝐽 180
∆𝑯𝑯𝟐 𝑶=−241.83 𝑚𝑜𝑙 + ∫25 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 −
3.593 × 10−12 𝑇 3
𝐾𝐽
= -236.52 𝑚𝑜𝑙
𝐾𝐽 180
∆𝑯𝒖𝒓𝒆𝒂=−333.3 𝑚𝑜𝑙 + ∫25 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= 7555.52 𝑚𝑜𝑙
∆𝑯𝒃𝒊𝒖𝒓𝒆𝒕 = 𝑛̇𝐶∆𝑇
𝑚𝑜𝑙 𝐽
= 6.06 131.3𝐾 𝑚𝑜𝑙 × (453.15 𝐾 − 428.15𝐾)
ℎ𝑟
𝐾𝐽
= 1235.330 𝑚𝑜𝑙
∆HNH2COONH4= ̇ 𝑛𝐶∆𝑇
𝑚𝑜𝑙 𝐽
=588. 55 ℎ𝑟 × 84.0 𝐾 𝑚𝑜𝑙 × (453.15 𝐾 − 428.15𝐾)
𝐾𝐽
= 1235.945 𝑚𝑜𝑙
63
At Stripper:
Inlet stream: All reactants as reference states.

Outlet stream:
205
∆HCO2= ∫180 36.11 × 10−3 + 4.233 × 10−5 𝑇 − 2.887 × 10−8 𝑇 2 + 7.464 × 10−12 𝑇 3
𝐾𝐽
= 1.081 𝑚𝑜𝑙
205
∆HNH3 = ∫180 35.15 × 10−3 + 2.954 × 10−5 𝑇 + 0.4421 × 10−8 𝑇 2 − 6.686 × 10−12 𝑇 3
𝐾𝐽
= 1.024 𝑚𝑜𝑙
205
∆𝑯𝑯𝟐 𝑶=∫180 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3
𝐾𝐽
= 0.876 𝑚𝑜𝑙
205
∆𝑯𝒖𝒓𝒆𝒂= ∫180 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= 1700.25 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
= 6.06 × 131.3𝐾 𝑚𝑜𝑙 × (453.15 𝐾 − 428.15𝐾)
ℎ𝑟
𝐾𝐽
= 19.892 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
=588. 55 ℎ𝑟 × 84.0 𝐾 𝑚𝑜𝑙 × (478.15 𝐾 − 453.15𝐾)
𝐾𝐽
= 1235.96 𝑚𝑜𝑙
64
At carbamate condenser:
NH2COONH4 (carbamate) NH2COONH4 (carbamate)

(v, 205℃, 150atms) (l, 155℃, 150 atms)
𝑚𝑜𝑙 𝐽
=588. 55 ℎ𝑟 × 84.0 𝐾 𝑚𝑜𝑙 × (428.15 𝐾 − 478.15𝐾)
𝐾𝐽
= - 2471.91 𝑚𝑜𝑙
65
At MPS:
Outlet stream:
140
∆HCO2= ∫205 36.11 × 10−3 + 4.233 × 10−5 𝑇 − 2.887 × 10−8 𝑇 2 + 7.464 × 10−12 𝑇 3
𝐾𝐽
= −2.7679 𝑚𝑜𝑙
140
∆HNH3 = ∫205 35.15 × 10−3 + 2.954 × 10−5 𝑇 + 0.4421 × 10−8 𝑇 2 − 6.686 × 10−12 𝑇 3
𝐾𝐽
= -2.6223 𝑚𝑜𝑙
140
∆𝑯𝑯𝟐 𝑶=∫205 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3
𝐾𝐽
= -2.2657 𝑚𝑜𝑙
140
∆𝑯𝒖𝒓𝒆𝒂=∫205 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= -4138 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
= 6.06 ℎ𝑟
× 131.3𝐾 𝑚𝑜𝑙 × (413.15𝐾 − 478.15𝐾)
𝐾𝐽
= -51.72
𝑚𝑜𝑙
66
At LPS:
Outlet stream:
80
∆HCO2= ∫140 36.11 × 10−3 + 4.233 × 10−5 𝑇 − 2.887 × 10−8 𝑇 2 + 7.464 × 10−12 𝑇 3
𝐾𝐽
= −2.4251 𝑚𝑜𝑙
80
∆HNH3 = ∫140 35.15 × 10−3 + 2.954 × 10−5 𝑇 + 0.4421 × 10−8 𝑇 2 − 6.686 × 10−12 𝑇 3
𝐾𝐽
= -2.3067 𝑚𝑜𝑙
80
∆𝑯𝑯𝟐 𝑶=∫140 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3
𝐾𝐽
= -2.0584 𝑚𝑜𝑙
80
∆𝑯𝒖𝒓𝒆𝒂=∫140 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= -3085.13 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
= 6.06 × 131.3𝐾 𝑚𝑜𝑙 × (353.15𝐾 − 413.15𝐾)
ℎ𝑟
𝐾𝐽
= -47.74 𝑚𝑜𝑙
67
At Evaporator:
Evaporator 1
Outlet stream:
85
∆𝑯𝑯𝟐 𝑶=∫80 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3
𝐾𝐽
= 0.1704 𝑚𝑜𝑙
85
∆𝑯𝒖𝒓𝒆𝒂=∫80 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= 234.27 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
= 6.06 × 131.3𝐾 𝑚𝑜𝑙 × (358.15𝐾 − 353.15𝐾)
ℎ𝑟
𝐾𝐽
= 3.978 𝑚𝑜𝑙
Evaporator 2
Outlet stream:
27.5
∆𝑯𝑯𝟐 𝑶=∫85 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3
𝐾𝐽
= -1.9477𝑚𝑜𝑙
27.5
∆𝑯𝒖𝒓𝒆𝒂=∫85 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= −2499.12 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
= 6.06 × 131.3𝐾 𝑚𝑜𝑙 × (300.65𝐾 − 358.15𝐾)
ℎ𝑟
𝐾𝐽
= −45.75 𝑚𝑜𝑙
68
At Prilling tower:
Outlet stream:
25
∆𝑯𝑯𝟐 𝑶=∫27.5 33.46 × 10−3 + 0.6880 × 10−5 𝑇 + 0.7604 × 10−8 𝑇 2 − 3.593 × 10−12 𝑇 3
𝐾𝐽
= -0.08411𝑚𝑜𝑙
25
∆𝑯𝒖𝒓𝒆𝒂=∫27.5 38.43 + 4.98 × 10−2 𝑇 + 7.05 × 10−4 𝑇 2 − 8.61 × 10−7 𝑇 3
𝐾𝐽
= −100.51 𝑚𝑜𝑙
𝑚𝑜𝑙 𝐽
= 6.06 × 131.3𝐾 𝑚𝑜𝑙 × (298.15𝐾 − 300.68𝐾)
ℎ𝑟
𝐾𝐽
= −2.01 𝑚𝑜𝑙
69
Appendix C
Calculation Data
Appendix C.1: Heat of formation of carbon dioxide from Physical Property Tables.
Appendix C.2: Heat of formation of ammonia from Physical Property Tables.
Appendix C.3: CpdT calculation of water from Physical Property Tables.
70
Appendix C.4: CpdT calculation for carbon dioxide and ammonia from Physical Property Tables.
Appendix C.5: Heat of formation of water from Physical Property Tables.
71
Specific heat capacity of

carbamate
Appendix C.6: Nawaz. (2014). Specific heat of capacity of carbamate. Design Project: Design of fertiliser plant producing plant and
ammonium sulphate from ammonia.
Appendix C.7: U.S. Secretary of Commerce on behalf of the United States of America. (2016). National Institute of Standards and
Technology.
72
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Chemical Process Principle Mini Project The Production of Urea

THE PRODUCTION OF UREA

CHEMICAL PROCESS PRINCIPLE MINI PROJECT

Bachelor of Chemical Engineering Technology (Hons)

Reyhana Binti Noorsham 55213116163

Supervised by Dr Amin Safwan Bin Alikasturi

Universiti Kuala Lumpur Malaysian Institute of Chemical

And Bioengineering Technology

THE PRODUCTION OF UREA

CHEMICAL PROCESS PRINCIPLE MINI PROJECT

WORK DISTRIBUTION FORM

Name Id number Student No.

Siti Syazana Binti Mohd Saberi 55217116092 4

Nurul Farzana Binti Abd Mustaffa 55216116208 1

Nur Amirah Binti Mohamad Pahmi 55213116150 2

1. CO2 + 2NH3 NH2COONH4

2. NH2COONH4 NH2CONH2 + H2O

1.0 Executive Summary……………………………………………………………………...1

2.1 Introduction to urea……………………………………………………………………….5

2.2 History of urea……………………………………………………………………………5

2.3 Properties of urea…………………………………………………………………………6

2.4 The synthesis of urea…………………….……………………………………………......7

2.5 Production of urea………………………….…………………………………………….7

2.6 Usage of urea……………………………………………………………………………..9

2.7 Major Hazards of urea Production…………………………………….……….………..10

3.0 Process Selection….…………………………………………………………………….13

3.1 Snamprogetti Urea Technology…………………………………………………………14

3.2 MITSUI TOATSU or TOYO KOATSU PROCESS (Japan) ……………………………17

3.3 Once- through Process…………………………………………………………………..20

3.4 Stamicarbon (Holland) ………………………………………………………………….24

3.5 Full Comparison of Urea Processes……………………………………………………...27

3.6 Selected process: The Snamprogetti Urea Technology………………………………….29

4.0 Process Flow Diagram of urea…………………………………………………………32

5.0 Process Equipment ………………………………………………………………….….33

5.2 The Stripper…………………………………………………………………………......34

5.3 Carbamate Condenser………………………………………………………………...…35

5.4 Medium Pressure Decomposer (MP Decomposer) …………………………………….36

5.5 Low Pressure Decomposer (LP Decomposer) …………………………………………37

5.6 Vacuum Evaporator…………………………………………………………………….37

5.7 Prilling Tower…………………………………………………………………………..38

6.0 Material Balances………………………………………………………………………39

7.0 Energy Balances………………………………………………………………………...45

8.0 Process & Design Improvement…….…………………………………………………53

2.1 Introduction to urea

2.2 History of urea

2.3 Properties of urea

2.3.1 Computed Properties

Property Name Property Value

Molecular weight 60.056 g/mole

Hydrogen Bond Donor Count 2

Hydrogen Bond Acceptor Count 1

Rotatable Bond Count 0

Topological Polar Surface Area 69.1 A2

Monoisotopic Mass 60.032 g/mole

Exact Mass 60.032 g/mole

Compound is Canonicalized true

Heavy Atom Count 4

Defined Atom Stereocenter Count 0

Undefined Atom Stereocenter Count 0

Defined Bond Stereocenter Count 0

Undefined Bond Stereocenter Count 0

Isotope Atom Count 0

Covalently- Bonded Unit Count 1