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
Chemical Process Principle Mini Project The Production of Urea

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
N TASK TASK STUDENT NO.
O
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
Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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

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Chemical Process Principle Mini Project The Production of Urea

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

9.0 References………………………………………………………………………………55

10.0 Appendices…………………………………………………………………………….57

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Chemical Process Principle Mini Project The Production of Urea

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 –NH 2 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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Chemical Process Principle Mini Project The Production 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
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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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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Chemical Process Principle Mini Project The Production of Urea

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 (NH 3)
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, NH 3, fed to the top of the high
pressure absorber. The pure excess NH3 thus obtained is condensed to liquid with cooling

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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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Chemical Process Principle Mini Project The Production of Urea

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)

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Chemical Process Principle Mini Project The Production of Urea

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)

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Chemical Process Principle Mini Project The Production of Urea

Figure 3: Once- through urea process flow diagram. (Bhaskar. & Das. 2007. Manufacture of urea. Rourkela, India.)

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Chemical Process Principle Mini Project The Production of Urea

3.4 STAMICARBON PROCESS (HOLLAND)

For this process, the carbon dioxide, CO 2, 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].

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Chemical Process Principle Mini Project The Production of Urea

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 CO 2
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 NH 3 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.

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Chemical Process Principle Mini Project The Production of Urea

Figure 4: Process scheme of the synthesis section of the Stamicarbon process. (Brouwer. & Baboo. 2016. The Comparison of Stamicarbon and Saipem Urea Technology, ResearchGate)

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 Chemical Process Principle Mini Project The Production of Urea

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 BFW     
essential high pressure 3) The stripper- accommodate
and 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
Process coproduct – decrease energy requirement (once feed

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 Chemical Process Principle Mini Project The Production of Urea

the amount of target through to reactor)

urea 6) Less cost for operating and
2) Overall low CO2 capital investment – held low
conversation – low urea temperature, low pressure as
produced only for small scale of
3) High environmental 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

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Chemical Process Principle Mini Project The Production of Urea

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 NH 3 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.

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Chemical Process Principle Mini Project The Production of Urea

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 NH 3 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

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Chemical Process Principle Mini Project The Production of Urea

occurred 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.

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Chemical Process Principle Mini Project The Production of Urea

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.

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Chemical Process Principle Mini Project The Production of Urea

5.0 Process Equipment

5.1 Reactor

In the process, inside the reactor, when liquid ammonia was compressed with CO 2 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

NH 3
reaction pressure. The mole reaction of CO 2 is around 2 : 1 . The mole ration to CO is
2

around 0.67: 1.

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;

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Chemical Process Principle Mini Project The Production of Urea

K = (pNH3)2*(pCO2) [ where, K= equilibrium constant

5.2 The Stripper

The stripping is affected at synthesis pressure itself using CO 2 or NH3 as stripping agent. If
CO2 is selected, it is to supplied to the decomposer or stripper. While if NH 3 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 pNH 3 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 1 st 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).

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Chemical Process Principle Mini Project The Production of Urea

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).

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Chemical Process Principle Mini Project The Production of Urea

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, H 2 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).

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Chemical Process Principle Mini Project The Production of Urea

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

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
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Chemical Process Principle Mini Project The Production of Urea

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).

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

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Chemical Process Principle Mini Project The Production of Urea

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).

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Chemical Process Principle Mini Project The Production of Urea

6.0 Material Balance

REACTOR
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

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

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Chemical Process Principle Mini Project The Production of Urea

STRIPPER
INPUT OUTPUT

MATERIAL FLOWRATE MATERIAL FLOWRATE

% %
S (Kg/Hr) S (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

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

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Chemical Process Principle Mini Project The Production of Urea

MEDIUM-PRESSURE SEPARATOR
INPUT OUTPUT
NH3 = 182.49 Kg/Hr
MATERIAL FLOWRATE CO 2 = 169.42 Kg/Hr
MATERIAL FLOWRATE
% %
S (Kg/Hr) S (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

MEDIUM- NH3 = 182.49 Kg/Hr

NH3 = 364.47 Kg/Hr PRESSURE CO2 = 169.42 Kg/Hr
CO2 = 338.84 Kg/Hr SEPARATOR Urea = 22,374.63 Kg/Hr
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

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 Chemical Process Principle Mini Project The Production of Urea

LOW-PRESSURE SEPARATOR
INPUT OUTPUT

MATERIAL FLOWRATE MATERIAL FLOWRATE

% %
S (Kg/Hr) S (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

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
Biuret = 624.38 Kg/Hr

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 Chemical Process Principle Mini Project The Production of Urea

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
EVAPORATOR Biuret = 624.38 Kg/Hr
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
INPUT OUTPUT

MATERIAL FLOWRATE MATERIAL FLOWRATE

% %
S (Kg/Hr) S (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
29,791.20 = 23,305.41 + E
E = 6485.79 Kg/Hr

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Chemical Process Principle Mini Project The Production of Urea

PRILLING TOWER
Air
Water = 287.72 Kg/Hr

Urea = 22,374.63 Kg/Hr

Urea = 22,374.63 Kg/Hr Water = 18.68 Kg/Hr
Prilling Tower
Water = 306.4 Kg/Hr Biuret = 624.38 Kg/Hr
Biuret = 624.38 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

MATERIAL FLOWRATE MATERIAL FLOWRATE

% %
S (Kg/Hr) S (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

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 Chemical Process Principle Mini Project The Production of Urea

7.0 Energy Balance

1. At reactor:
CO2 (g, 180℃ ,188 atms)
CO2 (g, 40℃ ,1.6 atms)
Reactor NH3 (g, 180℃ ,188 atms)
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)
Inlet stream:
(l, 155℃ , 150atms)

Component kmol kJ kJ
ṅ ( ¿ ^(
∆H ¿ ṅ ∆ H
^( )
hr kmol 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 ( ^(
∆H kJ
ṅ ∆ H
^( )
hr
kmol kJ
¿ ¿
hr kmol
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
Q=∑ ṅ ∆ ^
H
hr ( )
=¿ Q −Qinlet ¿
outlet

kJ
Q=3456088.84−(−1657474.45 ) =5113.563
hr

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 Chemical Process Principle Mini Project The Production of Urea
NH2COONH4 (carbamate
vapours),
2. At stripper:
(v, 205℃ ,150 atms)
CO2 (g, 180℃ ,188 atms)
ṅt 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)
Stripper
NHCONHCONH2 (biuret) g, 180℃ ,188 atms)
NHCONHCONH2 (biuret) g, 205℃ ,150 atms)
(205℃,150 atms
NH2COONH4 (carbamate) (v, 180℃ ,188 atms)
H2O (v, 205℃ ,150 atms)
H2O (v, 180℃ ,188 atms) ṅ b
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

Inlet stream: all reactants as reference states. Hence:

Outlet stream:

Component ṅt ( ^(
∆H kJ ṅ ( ^(
∆H ^ ( kJ )
ṅt ∆ ^
H( ) b ṅ b ∆ H
kmol hr kmol hr
¿ kJ ¿ kJ
hr ¿ hr ¿
kmol kmol
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
∑ ṅt ∆ H ( hr )
Total = Total = ∑ ṅb ∆ H ( hr )
kJ
Q=∑ ṅ ∆ ^
H ( )
hr
=¿ Q outlet −Qinlet ¿

50
Chemical Process Principle Mini Project The Production of Urea

kJ
Q= ( 633411.14+727902.72 )−0=1361313.86
hr
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℃)

Component kmol kJ
ṅ ( ¿ ^(
∆H ¿
hr kmol
NH2COONH4 (carbamate) 588.55 − 2471.91

kJ
Q =ṅ ∆ H ( )
hr
mol kJ kJ
Q=588.55
hr (
× −2471.91
mol )
=−1454842.63
hr

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 Chemical Process Principle Mini Project The Production of Urea

4. At medium pressure separator (MPS)

CO2 (g, 140℃ ,17 atms)

ṅNH 3 (g, 140℃ ,17 atms)

t
CO2 (g, 205℃ ,150 atms) CO2 (g, 140℃ ,17 atms)

NH3 (g, 205℃ ,150 atms) NH3 (g, 140℃ ,17 atms)
MPS
NH2CONH2 (urea) (s, 205℃ ,150 atms) NH2CONH2 (urea) (s, 140℃ ,17 atms)
(140℃ ,17 atms)
NHCONHCONH2 (biuret) g, 205℃ ,150 atms) NHCONHCONH2 (biuret) g, 140℃ ,17 atms)

H2O (v, 205℃ ,150 atms) H2O (v, 140℃ ,17 atms)
ṅ b

Inlet stream: all reactants as reference states. Hence:

Component ṅ ( ^( kJ
∆H ¿
kmol
kmol
¿
hr
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 kmol kJ kJ kmol ^(

∆H ^ ( kJ )
ṅt ( ¿ ^(
∆H ¿ ṅt ∆ ^
H( ) ṅ b ( ¿ ṅ b ∆ H
hr kmol hr hr hr
kJ
¿
kmol
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
∑ ṅt ∆ H ( hr ) ∑ ṅb ∆ H ( hr )

Q=∑ ṅ ∆ ^
H ( kJhr )=¿ Q outlet −Qinlet ¿

52
Chemical Process Principle Mini Project The Production of Urea

kJ
Q=(−38.797+(−1542993.75))−0=−1543032.55
hr
5.

53
 Chemical Process Principle Mini Project The Production of Urea

Low Pressure Separator (LPS) ṅt

CO2 (g, 80℃ ,4.5 atms)

NH3 (g, 80℃ ,4.5 atms)

6. CO2 (g, 140℃ ,17 atms)
7. NH3 (g, 140℃ ,17 atms)
8. LPS NH2CONH2 (urea) (s, 80℃ ,4.5 atms)
NH2CONH2 (urea) (s, 140℃ ,17 atms)
9. (80℃ ,4.5 atms) NHCONHCONH2 (biuret) g, 80℃ ,4.5 atms)
NHCONHCONH2 (biuret) g, 140℃ ,17 atms)
ṅ b,4.5 atms)
H2O (v, 80℃
H2O (v, 140℃ ,17 atms)

Inlet stream: all reactants as reference states. Hence:

Component ṅ ( ^( kJ
∆H ¿
kmol
kmol
¿
hr
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
Component ṅt ( ^(
∆H kJ ṅ b ( ^ ( kJ0 ¿ ^ ( kJ )
H2O (v, 140℃,17 atms) ṅt ∆ ^
H( ) 377.34 ∆ H ṅ b ∆ H
hr kmol hr
kmol kJ kmol
¿ ¿ ¿
hr kmol 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)

NHCONHCONH2 (biuret) - - - 6.06 -47.74 -289.304

(g, 140℃,17 atms)

H2O (v, 140℃,17 atms) - - - 377.34 -2.0584 -776.717

kJ -34.09 kJ -1150400.431
∑ ṅt ∆ H ( hr ) ∑ ṅb ∆ H ( hr )
Outlet stream:

∑ Q=∑ ṅ ∆ H^ ( kJ
hr )
=¿Q outlet−Q inlet ¿

54
 Chemical Process Principle Mini Project The Production of Urea

kJ
∑ Q=(−34.09+(−1150400.351))−0=−1150434.5 hr
6. Vacuum Evaporator

Evaporator 1
ṅ1 t ṅ2 t

H2O (v, 85℃ ,0.3 atms) H2O (v, 27.5℃ ,0.03 atms)

NH2CONH2 (urea)
NH2CONH2 (urea) (s, 80℃ ,4.5 atms)
(s, 85℃ ,0.3 atms)
NHCONHCONH2 (biuret) g, 80℃ ,4.5
NHCONHCONH2
atms)
(biuret) g, 85℃ ,0.3
NH2CONH2 (urea) (s, 27.5℃
H2O (v, 80℃ ,4.5 atms) atms)
63.1 ℃ 23.77℃ ,0.03 atms)
0.3 atm H2O (v, 85℃ ,0.3 0.03 atm NHCONHCONH2 (biuret) (g,
atms) 27.5℃ ,0.03 atms)
ṅ1 b H2O (v, 27.5℃ ,0.03 atms)
ṅ2 b

Evaporator 2
At evaporator 1:

Inlet stream: all reactants as reference states. Hence:

Component ṅ ( ^( kJ
∆H ¿
kmol
kmol
¿
hr
NH2CONH2 (urea) (s, 80℃,4.5 atms) 372.54 0
NHCONHCONH 6.06 ^0 (
ṅ1 t2 (biuret) (g,
^ 80℃,4.5 atms) kJ
Component ( ∆H ( ṅ1 b ( ∆H kJ
ṅ1 t ∆ H
^( ) ṅ1 b ∆ ^
H( )
H2O (v, 80℃,4.5 atms) hr 377.34 0 hr
kmol kJ kmol kJ
¿ ¿ ¿ ¿
hr kmol hr kmol
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 Total = 87332.65
Total =∑ ṅ2 t ∆ H ( )
hr

55
 Chemical Process Principle Mini Project The Production of Urea

kJ
∑ ṅ1 b ∆ H ( hr )

Outlet stream:

∑ Q=∑ ṅ ∆ H^ ( kJ
hr )
=¿Q −Q inlet ¿
outlet

kJ
∑ Q=(30.7+ 87332.65)−0=87363.35 hr

At evaporator 2:
Inlet stream: all reactants as reference states. Hence:

Component ṅ ( ^( kJ
∆H ¿
kmol
kmol
¿
hr
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 ṅ2 t ( ^(
∆H kJ ṅ2 b ( ^(
∆H ^ ( kJ )
=ṅ2 t ∆ H
^( ) ṅ2 b ∆ H
hr hr
kmol kJ kmol kJ
¿ ¿ ¿ ¿
hr kmol hr kmol
NH2CONH2 (urea) (s, 27.5℃,0.03 - - - 372.54 -2499.12 -931022.16
atms)

NHCONHCONH2 (biuret) (g, - - - 6.06 -45.75 -277.245

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 Total = -931332.56

Total = ∑ ṅ2 t ∆ H ( hr )
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Chemical Process Principle Mini Project The Production of Urea

kJ
∑ ṅ2 b ∆ H ( hr )

∑ Q=∑ ṅ ∆ H^ ( kJ
hr )
=¿Q outlet−Q inlet ¿

kJ
∑ Q=(−17.02+ (−931332.55 ) ) −0=−931349.58 hr
(total heat required for vacuum evaporator.)

7. Prilling Tower air

Water vapour
25℃

NH2CONH2 (urea) (s, 27.5℃ ,0.03 atms) air

Prilling Tower
25
NHCONHCONH2 (biuret) (g, 27.5℃ ,0.03 atms) (25℃ , 1atm)
℃
H2O (v, 27.5℃ ,0.03 atms)

NH2CONH2 (urea) (s, 25.0 ℃ ,1 atms)

NHCONHCONH2 (biuret) (g, 25.0 ℃ ,1 atms)

Inlet stream: all reactants as reference states. Hence: H2O (v, 25.0 ℃ ,1 atms)

Component ṅ ( ^( kJ
∆H ¿
kmol
kmol
¿
hr
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:

57
 Chemical Process Principle Mini Project The Production of Urea

Component kmol ^(
∆H kJ ṅ b ( ^(
∆H ^ ( kJ )
ṅt ( ¿ Q =ṅ ∆ H
^( ) ṅ ∆ H
hr hr hr
kJ kmol kJ
¿ ¿ ¿
kmol hr kmol
NH2CONH2 (urea) (s, 25℃,1 - - 372.54 −100.51 -37444
atms)

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 = ∑ ṅt ∆ H ( hr ) Total = ∑ ṅb ∆ H ( hr )

∑ Q=∑ ṅ ∆ H^ ( kJ
hr )
=¿Q −Q inlet ¿
outlet

∑ Q=¿
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

58
Chemical Process Principle Mini Project The Production of Urea

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.

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.

59
Chemical Process Principle Mini Project The Production of Urea

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.

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.

60
Chemical Process Principle Mini Project The Production of Urea

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
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.

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Chemical Process Principle Mini Project The Production of Urea

10. 0 Appendices
Appendix A
Calculation for material balance

MT
Production Rate: 200,000 year

No of Working Days: 365 Days

MT 1 year MT
Daily Production: 200,000 year × 365 days = 547.95 day

MT 1 kg 1 day kg
Urea: 547.95 day × 0. 001 MT × 24 hr = 22831.25 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)

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Chemical Process Principle Mini Project The Production of Urea

Side Reaction:

2NH2CONH2 → NH2CONHCONH2 + NH3

(Reaction 4)

kg 120 kg/kmol kg kg
228.31 hr Biuret produced by = 103 kg/kmol × 228.31 hr = 265.99 hr Urea

(Reaction 2)

kg kg kg
Urea produced = 22,374.63 hr + 265.99 hr = 22,640.62 hr

kg 34 kg/kmol kg
22,640.62 hr Urea produced by = 60 kg/kmol × 22,640.62 hr
kg
= 12, 829.68 hr NH3
(Reaction 1)

44 kg/kmol kg
CO2 reacted = 60 kg/kmol × 22,640.62 hr
kg
= 16,603.12 hr CO2

For 98% conversion:

kg kg
NH3 = 12, 829.68 hr / 0.98 = 13,091.51 hr

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Chemical Process Principle Mini Project The Production of Urea

kg kg
CO2 = 16,603.12 hr / 0.98 = 16,941.96 hr

If (Reaction 3) is 100% complete,

60 kg/kmol kg kg
Urea produced = 44 kg/kmol × 16,941.96 hr = 23,102.67 hr
For 98% conversion:

kg kg
Urea produced = (0.98) (23,102.67 hr ) = 22,640.62 hr

Therefore, Urea converted to Biuret and NH3

kg kg
= 23,102.67 hr - 22,374.63 hr
kg
= 728.04 hr

(Reaction 4)

103 kg/kmol kg
Biuret produced = 120 kg/kmol × 728.04 hr
kg
= 624.90 hr

(Reaction 2)

18 kg /kmol kg
Water produced = 60 kg /kmol × 22,640.62 hr
kg
= 6792.19 hr

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Chemical Process Principle Mini Project The Production of Urea

Reactor (Urea= 34%)

kg kg
Flow rate of stream = 22,374.63 hr / 0.34 = 65,807.74 hr

(Reaction 1)

34 kg/kmol kg kg
NH3 reacted = 60 kg/kmol × 22,640.62 hr = 12,829.68 hr

(Reaction 4)

17 kg/kmol kg kg
NH3 produced = 120 kg/kmol × 728.04 hr = 103.14 hr

kg kg kg
NH3 unreacted = 13,091.51 hr - 12,829.68 hr + 103.14 hr
kg
= 364.97 hr

(Reaction 1)

44 kg/kmol kg kg
CO2 reacted = 60 kg/kmol × 22,640.62 hr = 16,603.12 hr

kg kg kg
CO2 unreacted = 16,941.96 hr - 16,603.12 hr = 338.84 hr

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Chemical Process Principle Mini Project The Production of Urea

Flow Rate Carbamate = Flow rate of stream at reactor’s exit - (flow rate of urea +
CO2 + NH3 + water + biuret)
kg kg kg
= 65,807.74 hr - (22,374.63 hr + 338.84 hr + 364.97
kg kg kg
hr + 6792.19 hr + 624.90 hr )

kg
= 35,312.74 hr

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Chemical Process Principle Mini Project The Production of Urea

Appendix B
Calculation for energy balance

Reference: C (s) , N 2(g), H 2(g) , O2(g) at 25℃ at 1 atm

∆H= ∆ H f +∆ H b

At reactor: reactions involved;

CO2 (g) + 2NH3(l) NH2COONH4 (v)

NH2COONH4 (v) NH2CONH2 (g) + H2O

2NH2CONH2 (g) NH2CONHCONH2 (g) + NH3 (l)

Input stream:

40
KJ −3 −5 −8 2 −12 3
∆HCO2 =−393.5 + ∫ 36.11× 10 +4.233 ×10 T −2.887 × 10 T +7.464 × 10 T
mol 25

KJ
= -392.94
mol

40
KJ
∆HNH3 = −67.2 +∫ 35.15 ×10−3 +2.954 ×10−5 T +0.4421× 10−8 T 2 −6.686 ×10−12 T 3
mol 25

KJ
= -66.66
mol

KJ
∆HNH2COONH4 = - 2471.91
mol
(taken from energy balance calculation from carbamate condenser sec.)

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Chemical Process Principle Mini Project The Production of Urea

Outlet stream:

180
KJ
∆HCO2= =−393.5 + ∫ 36.11 ×10−3 +4.233 ×10−5 T −2.887 × 10−8 T 2 +7.464 ×10−12 T 3
mol 25

KJ
= −387.28
mol

180
KJ
∆HNH3 = −67.2 + ∫ 35.15 ×10−3+ 2.954 ×10−5 T + 0.4421× 10−8 T 2−6.686 × 10−12 T 3
mol 25

= -61.276
KJ
mol
180
∆ H H O=−241.83 KJ + ∫ 33.46 ×10−3 +0.6880 ×10−5 T + 0.7604 ×10−8 T 2−3.593 ×10−12 T 3
2
mol 25

= -236.52
KJ
mol

180
∆ H urea =−333.3 KJ + ∫ 38.43+ 4.98 ×10−2 T +7.05 ×10−4 T 2 −8.61× 10−7 T 3
mol 25
KJ
= 7555.52
mol

∆ H biuret =ṅ C ∆T
mol J
= 6.06 131.3 × ( 453.15 K−428.15 K )
hr K mol
KJ
= 1235.330
mol

∆HNH2COONH4¿˙n C ∆T
mol J
=588. 55 × 84.0 × ( 453.15 K−428.15 K )
hr K mol

KJ
= 1235.945
mol
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Chemical Process Principle Mini Project The Production of Urea

At Stripper:

Inlet stream: All reactants as reference states.

Outlet stream:

205
∆HCO2= ∫ 36.11 ×10−3 + 4.233× 10−5 T −2.887 ×10−8 T 2+7.464 ×10−12 T 3
180
KJ
= 1.081
mol

205
∆HNH3 ¿ ∫ 35.15× 10−3 +2.954 ×10−5 T +0.4421 ×10−8 T 2−6.686 ×10−12 T 3
180

KJ
= 1.024
mol

205
∆ H H O=∫ 33.46 ×10−3 +0.6880 ×10−5 T +0.7604 × 10−8 T 2−3.593 ×10−12 T 3
2
180

KJ
= 0.876
mol

205
∆ H urea =∫ 38.43+4.98 ×10−2 T +7.05 ×10− 4 T 2−8.61 ×10−7 T 3
180
KJ
= 1700.25
mol

∆ H biuret =ṅ C ∆T

mol J
= 6.06 ×131.3 × ( 453.15 K−428.15 K )
hr K mol
KJ
= 19.892
mol

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Chemical Process Principle Mini Project The Production of Urea

∆HNH2COONH4¿˙n C ∆T
mol J
=588. 55 × 84.0 × ( 478.15 K−453.15 K )
hr K mol

KJ
= 1235.96
At carbamate condenser: mol

NH2COONH4 (carbamate) NH2COONH4 (carbamate)

(v, 205℃, 150atms) (l, 155℃, 150 atms)

∆HNH2COONH4¿˙n C ∆T
mol J
=588. 55 × 84.0 × ( 428.15 K−478.15 K )
hr K mol

KJ
= - 2471.91
mol

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Chemical Process Principle Mini Project The Production of Urea

At MPS:
Inlet stream: All reactants as reference states.
Outlet stream:

140
∆HCO2= ∫ 36.11 ×10−3 + 4.233× 10−5 T −2.887 ×10−8 T 2+7.464 ×10−12 T 3
205
KJ
= −2.7679
mol

140
∆HNH3 ¿ ∫ 35.15× 10−3 +2.954 ×10−5 T +0.4421 ×10−8 T 2−6.686 ×10−12 T 3
205

= -2.6223
KJ
mol
140
∆ H H O=∫ 33.46 ×10−3 +0.6880 ×10−5 T +0.7604 × 10−8 T 2−3.593 ×10−12 T 3
2
205

= -2.2657
KJ
mol

140
∆ H urea =∫ 38.43+4.98 ×10−2 T +7.05 ×10− 4 T 2−8.61 ×10−7 T 3
205
KJ
= -4138
mol

∆ H biuret =ṅ C ∆T

mol J
= 6.06 ×131.3 × ( 413.15 K−478.15 K )
hr K mol

KJ
= -51.72
mol

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Chemical Process Principle Mini Project The Production of Urea

At LPS:
Inlet stream: All reactants as reference states.
Outlet stream:

80
∆HCO2= ∫ 36.11 ×10−3 + 4.233× 10−5 T −2.887 ×10−8 T 2+7.464 ×10−12 T 3
140
KJ
= −2.4251
mol

80
∆HNH3 ¿ ∫ 35.15× 10−3 +2.954 ×10−5 T +0.4421 ×10−8 T 2−6.686 ×10−12 T 3
140

= -2.3067
KJ
mol

80
∆ H H O=∫ 33.46 ×10−3 +0.6880 ×10−5 T +0.7604 × 10−8 T 2−3.593 ×10−12 T 3
2
140

= -2.0584
KJ
mol

80
∆ H urea =∫ 38.43+4.98 ×10−2 T +7.05× 10− 4 T 2−8.61 ×10−7 T 3
140

KJ
= -3085.13
mol

∆ H biuret =ṅ C ∆T

mol J
= 6.06 ×131.3 × ( 353.15 K −413.15 K )
hr K mol
KJ
= -47.74
mol

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Chemical Process Principle Mini Project The Production of Urea

At Evaporator:
Evaporator 1
Inlet stream: All reactants as reference states.
Outlet stream:

85
∆ H H O=∫ 33.46 × 10−3 +0.6880 ×10−5 T + 0.7604 ×10−8 T 2−3.593 ×10−12 T 3
2
80
KJ
= 0.1704
mol

85
∆ H urea =∫ 38.43+ 4.98 ×10−2 T +7.05 × 10−4 T 2−8.61× 10−7 T 3
80

KJ
= 234.27
mol

∆ H biuret =ṅ C ∆T

mol J
= 6.06 ×131.3 × ( 358.15 K −353.15 K )
hr K mol
KJ
= 3.978
mol

Evaporator 2
Inlet stream: All reactants as reference states.
Outlet stream:

27.5
∆ H H O= ∫ 33.46 ×10−3+ 0.6880× 10−5 T + 0.7604 ×10−8 T 2−3.593 ×10−12 T 3
2
85
KJ
= -1.9477
mol

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Chemical Process Principle Mini Project The Production of Urea

27.5
∆ H urea = ∫ 38.43+ 4.98× 10−2 T +7.05 ×10−4 T 2−8.61× 10−7 T 3
85

KJ
= −2499.12
mol

∆ H biuret =ṅ C ∆T

mol J
= 6.06 ×131.3 × ( 300.65 K −358.15 K )
hr K mol
KJ
= −45.75
mol

At Prilling tower:

Inlet stream: All reactants as reference states.

Outlet stream:

25
∆ H H O= ∫ 33.46 ×10−3+ 0.6880× 10−5 T + 0.7604 ×10−8 T 2−3.593 ×10−12 T 3
2
27.5
= -0.08411
KJ
mol
25
∆ H urea = ∫ 38.43+ 4.98× 10−2 T +7.05 ×10−4 T 2−8.61× 10−7 T 3
27.5

KJ
= −100.51
mol

∆ H biuret =ṅ C ∆T

mol J
= 6.06 ×131.3 × ( 298.15 K −300.68 K )
hr K mol

KJ
= −2.01
mol

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Chemical Process Principle Mini Project The Production of Urea

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.

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Chemical Process Principle Mini Project The Production of Urea

76

Appendix C.4: CpdT calculation for carbon dioxide and ammonia from Physical Property Tables.
 Chemical Process Principle Mini Project The Production of Urea

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.

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Chemical Process Principle Mini Project The Production of Urea

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