‫بسم هللا الرحمن الرحيم‬

University of Khartoum

Faculty of engineering

Chemical engineering

Manufacturing OF UERA

ROAA MOHAMED SHARF ELDEEN 152022

FATIMA ABD ELBAGE OMER 152046

SOLAFA ABD ELHADI MOHAMED 152034

Supervisor: PROF KAMIL WAGIALLAH

Table of Contents
Chapter one:-................................................................................................................... 5
1.1 Introduction....................................................................................................... 1
1.2PROPERTIES OF UREA : ..................................................................................... 1
1.2.1PHYSICAL PROPERTIES OF UREA:- ........................................................... 2
1.2.2 CHEMICAL PROPERTIES OF UREA:-......................................................... 2
1.3 Uses of urea:- ......................................................................................................... 2
1.4 Urea as fertilizer- ................................................................................................ 3
1.4.1 Fertilizers: ....................................................................................................... 3
1.4.2 Types of Fertilizers: ......................................................................................... 3
1.5 Benefits of Urea: .................................................................................................... 4
1.5.1 Agricultural: .................................................................................................... 4
1.5.2 Cosmetic: ........................................................................................................ 4
1.5.3 Environmental: ................................................................................................ 4
1.6 Production of Urea: ................................................................................................ 4
1.6.1 Production of urea in body: .............................................................................. 4
1.6.2 Production of urea industrially: ........................................................................ 5
1.7 Raw Materials:-...................................................................................................... 5
1.7.1 Ammonia:- ...................................................................................................... 5
Chapter (2): ..................................................................................................................... 1
2.1 History ................................................................................................................... 2
2.2 Methods of Manufacturing: .................................................................................... 2
2.3 The Principal Raw Materials Required for This Purpose Are NH3 & CO2:[20] ...... 2
2.4 Process Technology: .............................................................................................. 3
2.5Various Processes for The Manufacture of Urea: ..................................................... 3
1)Once-Through Urea Process:................................................................................. 3
2) Solution Recycle Urea Process: ............................................................................ 5
3) Internal Carbamate Recycle Urea Process: ........................................................... 5
Chapter 3:...................................................................................................................... 10
Process description ...................................................... Error! Bookmark not defined.
3.1 Selection of the Process: ...................................................................................... 11
 3.2 Parameters that effect on this process: .................................................................. 13
3.2.1Temperature: .................................................................................................. 13
3.2.2 Pressure: ........................................................................................................ 13
3.2.3Concentration: ................................................................................................ 13
3.2.4 Residence time: ............................................................................................. 14
3.3 The Snamprogetti urea process is divided into five sections: ................................ 14
3.3.1 Urea Synthesis & High-Pressure Recovery: ................................................... 14
3.3.2 Medium pressure section (18 atm): ................................................................ 15
3.3.3Low pressure section (4.5): ............................................................................. 16
3.3.4 Urea Concentration: ....................................................................................... 16
3.3.5 Urea Prilling: ................................................................................................. 16
Chapter 4:...................................................................................................................... 17
material blance ................................................................ Error! Bookmark not defined.
4.1 Introduction ......................................................................................................... 18
4.2 General Assumptions for Calculation ................................................................... 18
4.3 REACTOR .......................................................................................................... 21
4.4 STRIPPER: .......................................................................................................... 22
4.5 MEDIUM PRESSURE SEPARATOR: ................................................................ 23
4.6 LOW PRESSURE SEPARATOR: ....................................................................... 24
4.7 VACUUM EVAPORATOR: .............................................................................. 25
4.8 PRILLING TOWER: .......................................................................................... 27
Chapter 5....................................................................................................................... 29
ENERGY BLANCE ........................................................ Error! Bookmark not defined.
5.1 Introduction ......................................................................................................... 30
5.2 REACTOR: ......................................................................................................... 31
5.3 STRIPPER: ............................................................................................. 34
5.4 CARBAMATE CONDENSER ............................................................................ 35
5.4 CARBAMATE CONDENSER ............................................................................ 36
5.5 MEDIUM PRESSURE SEPARATOR ................................................................. 37
5.6 LOW PRESSURE SEPARATOR ........................................................................ 39
5.71st EVAPORATOR: ............................................................................................. 42
5.8 2end EVAPORATOR: ........................................................................................ 44
5.9 PRILLING TOWER: ........................................................................................... 46
CHAPTER 1
INTRODUCTION
CHAPTER 5:Energy Balance

1.1Introduction

Urea is an organic white compound manufactured worldwide, in various shapes and

sizes, from ammonia and carbon dioxide.
Urea, also called carbamide, the diamide of carbonic acid. Its formula isH2NCONH2.
Urea has important uses as a fertilizer and feed supplement, as well as a starting material
for the manufacture of plastics and drugs. It is a colorless, crystalline substance that melts
at 132.7° C (271° F) and decomposes before boiling.
Urea was first isolated from urine in 1773 by the French chemist Hilaire-Marin Rouelle.
Its preparation by the German chemist Friedrich Wöhler from ammonium cyanate in
1828 was the first generally accepted laboratory synthesis of a naturally
occurring organiccompound from inorganic materials[1].

Urea is the chief nitrogenous end product of the metabolic breakdown of proteins in all
mammals and some fishes. The material occurs not only in theurine of all mammals but
also in their blood, bile, milk, and perspiration. In the course of the breakdown of
proteins, amino groups (NH2) are removed from the amino acids that
partly comprise proteins. These amino groups are converted to ammonia (NH3), which is
toxic to the body and thus must be converted to urea by the liver. The urea then passes to
the kidneys and is eventually excreted in the urine[2].

Nitrogen as an animal feed additive and fertilizer. Here, we'll focus on its role as a
nitrogen fertilizer. In the past decade, urea has surpassed and nearly replaced ammonium
The agricultural industry widely uses urea, a white crystalline solid containing 46 percent
nitrate as a fertilizer. It being the preferred nitrogen fertilizer worldwide,it used in solid
and liquidfertilizer, formaldehyde resins and adhesives.

Figure 1.1 urea Chemical Structure and shape

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CHAPTER 5:Energy Balance

1.2PROPERTIES OF UREA :
1.2.1PHYSICAL PROPERTIES OF UREA:-
Urea is a white, odorless, hygroscopic solid. It is non-corrosive.

It is highly soluble in water but less soluble in alcohol .It is insoluble in ether[3].

1.2.2CHEMICAL PROPERTIES OF UREA:-

Urea be haves as a mono acid base .It reacts with acids to form salts.

Melting Point 132.70 °C [4]

Boiling Point 332.48°C

Decomposes 132.2°C

Density 1.33 g/cm3 [5]

Molecular Wt 60.06 g/mol

Vapor Pressure 1.2 x 10-5 mmHg [6]

Viscosity 1.78 mPa.-s [7]

pH 7.2 [8]

Specific gravity 1.335

1.3Uses of urea:-
Urea is a raw material used in the manufacture of many chemicals, such as various
plastics, urea-formaldehyde resins and adhesives. It is also essential for making
feedstock, glue, fertilizer, commercial products, and in resin production.

There are several uses ofurea such as:

 It is used as a nitrogen-release fertilizer.

 It is used in lanthanide chemistry as an important reagent.
 It is used in the manufacturing of high explosive like urea nitrate.
 It used in creams or ointments to rehydrate skin.
 It is used in the urea breath test to detect the presence of bacteria in the stomach.

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CHAPTER 5:Energy Balance

 It is used as an ingredient in dish soap.

 It is used in hair removal creams.
 It is used in making pretzels as a browning agent.
 It is used in the manufacture of melamine.

1.4Urea as fertilizer-

The agricultural industry widely uses urea, a white crystalline solid containing 46
percent nitrogen as an animal feed additive and fertilizer, While over 90%
of urea produced is used as a fertilizer[9].

 About 56 % of Urea manufactured is used in solid fertilizer.

 About 31 % of Urea manufactured is used in liquid fertilizer.

1.4.1Fertilizers:
Fertilizers are any material or mixture used to supply one or more of the essential plant
nutrient elements. Sixteen nutrients are essential for plant growth and development. Of
the major nutrients, nitrogen, phosphorus, and potassium are required in relatively large
amount. Calcium, Magnesium, and Sulfur are also required in relative large amounts, but
are less likely to be deficient in the soil system. Micro-nutrients are essential to plants in
relatively small amounts.

1.4.2Types of Fertilizers:

Fertilizers are often divided into two main groups, organic and inorganic, depending on
the source of the material.

1.4.2.1Organic Fertilizers:

Organic fertilizers are derived from plant or animal material. Raw materials commonly
used in their production include:
• Animal manure.
• Post-harvest plant material.
• Organic waste.
• Bio solids / sludge (human waste)

1.4.2.2Inorzganic Fertilizers:
Inorganic fertilizers are obtained via commercial chemical process like N-P-K
fertilizers(N nitrogen, P phosphorus, K potassium).

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CHAPTER 5:Energy Balance

1.5 Benefits of Urea:

1.5.1Agricultural:

Due to its high nitrogen content, most of Urea is used to make fertilizer. Nitrogen helps
plants grow quickly and aids in the production of a healthy and abundant crop. In
addition to providing ample nitrogen, Urea is also useful because it can be used as either
a solid or a solution. In addition, there are very few hazards associated with the use of
Urea, and it does not release as many pollutants into the air as other nitrogen sources.
Urea is also found in cattle feed, because it provides the animals with a good source of
nitrogen[9].

1.5.2Cosmetic:

Urea is used to treat dryskin conditions (e.g., eczema, psoriasis, corns, callus) and some nail
problems (e.g., ingrown nails). It may also be used to help remove dead tissue in some
wounds to help wound healing. Urea is known as a keratolytic. It increases moisture in
the skin by softening the horny substance (keratin) holding the top layer of skin cells
together. This effect helps the dead skin cells fall off and helps the skin keep more water
in[10].

1.5.3Environmental:

Urea is also used to help improve the environment. In addition to its use as a fertilizer,
which does not pollute the air, Urea also lowers NOx emissions in vehicles. NOx refers
to a group of "highly reactive gasses" according to the Environmental Protection Agency.
These gasses can cause respiratory problems and assist in the formation of ozone.

The Institute of Clean Air Companies notes that Urea and similar agents have been found
to lower NOx emissions by up to 75%.

1.6Production of Urea:
1.6.1Production of urea in body:
Urea (commonly referred to as carbamide) is a waste product that is produced in most
living organisms. This compound is human urine’s main organic component. The liver
transforms the ammonia to a non-toxic compound, urea, which can then be transferred
safely into the kidneys in the blood, where it is extracted in urine[11].

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CHAPTER 5:Energy Balance

1.6.2Production of urea industrially:

Urea was first produced industrially by the hydration of calcium Cyanamid but the easy
availability of ammonia led to the development of ammonia/carbon dioxide technology.
This is a two step process where the ammonia and carbon dioxide react to form
ammonium carbamate which is then dehydrated to urea.

Urea is now prepared commercially in vast amounts from liquid ammonia and liquid
carbon dioxide. These two materials are combined under high pressures and elevated
temperatures to form ammonium carbamate, which then decomposes at much lower
pressures to yield urea and water[12].

1.7Raw Materials:-
1.7.1Ammonia:-
Ammonia, a colorless gas with a distinct odor composed of nitrogen and hydrogen atoms,
is a building-block chemical and a key component in the manufacture of many products
people use every day. It occurs naturally throughout the environment in the air, soil and
water and in plants and animals, including humans. The human body makes ammonia
when the body breaks down foods containing protein into amino acids and ammonia, then
converting the ammonia into urea.

Ammonia NH3 is a comparatively stable, colorless gas at ordinary temperature, with

boiling point -33°C. Ammonia gas is lighter than air with a density of approximately 0.6
times that of air at the same temperature[13]. Ammonia can be highly toxic to a wide
range of organisms. In human the greatest risk is from inhalation of Ammonia vapor,
with effects including irritation and corrosive damage to skin, eye and respiratory tracks
at very high levels inhalation of Ammonia can be fatal. When dissolved in water,
elevated levels of Ammonia are also toxic to a wide range of aquatic organisms[14].
Ammonia is highly soluble in water, although the solubility decreases rabidly with
increased temperature. Ammonia reacts with water in a reversible reaction to produce
Ammonium NH4+ and hydroxide OH- ions. Ammonia is a weak base. The formations of
hydroxide ions in this reaction increase the pH of the water, forming an alkaline solution.
If the hydroxide Ammonia ions react further with other components in the water, more
Ammonia with react to reestablish the equilibrium.
NH3 + H2O → (NH4)++ OH-

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CHAPTER 5:Energy Balance

Ammonia storage:-
Anhydrous Ammonia is usually stored as liquid in refrigerated tanks at -33.3°C and
atmospheric pressure, often in doubled-walled tanks with capacity for hundreds or
thousands of tones. The low temperature is usually maintained by venting of Ammonia
gas. The vented gas is re-liquefied for recycling, or absorbed in water to make aqueous
Ammonia. Relatively small quantities and anhydrous Ammonia are sometimes stored
under pressure in spherical vessel at ambient temperature. Ammonia is corrosive to alloys
of copper and zinc and these materials must never be used in Ammonia services. Iron and
steel are usually the only metals used in Ammonia storage tanks, piping and fittings.

1.7.2Carbon dioxide:

Carbon dioxide appears as a colorless odorless gas at atmospheric temperatures and

pressures[15], relatively nontoxic and noncombustible. Heavier than air[16] and may
asphyxiate by the displacement of air, soluble in water. Forms carbonic acid, a mild acid,
under prolonged exposure to heat or fire the container may rupture violently and rocket.
Used to freeze food, to control chemical reactions, and as a fire extinguishing agent[17].

6
 Chapter 2
Literature Review

1
2
1
CHAPTER 2: Literature review

2.1 History
Urea has a long and interesting history. It was first discovered in 1727 by the Dutch
scientist Herman Boerhaave[18], when he was able to isolate the compound from urine.
A century later, in 1828, urea was synthesized in a chemical lab for the first time[19].he
reaction, which was discovered by Friedrich Wöhler, was a milestone in chemistry, since
it was now possible to make an organic compound from two inorganic substrates without
the participation of living organisms. The reaction discovered by Wöhler is as follows:

(NH2)2CO + AgCl↔ AgNCO + NH4Eq(2.1)

Friedrich Woehler reaction

Research on the synthesis of urea has continuously progressed since it was first
discovered. In the beginning of the 20th century, urea was commercially synthesized by
the hydration of Cyanamid obtained from calcium Cyanamid

CaCO3 + CNNH2↔ CaCN2 + H2O + CO2 Eq(2.2)

CO(NH2)2↔ CNNH2 + H2O Eq(2.3)

First commercial synthesis of urea

After the invention of the Haber-Bosch process in 1913, where ammonia is synthesized
from hydrogen and atmospheric nitrogen on an industrial scale, both ammonia and
carbon dioxide were easier to obtain. This made it possible to develop a new synthesis
route for urea. The new route, invented in 1922, is known as the Bosch-Meiser process.

2.2Methods of Manufacturing:
1) From ammonia, carbon monoxide & sulfur in methanol.
2) Liquid ammonia and liquid carbon dioxide at 1750 - 3000 psi & 160 - 200 ⁰C reacts to
form ammonium carbamate NH4CO2NH2 which decomposes at lower pressure about 80
psi to Urea & water.

2.3The Principal Raw Materials Required for This Purpose

Are NH3 & CO2:[20]
1) Snamprogetti ammonia stripping process
2) Stamicarbon CO2 stripping process
3) Once through Urea process
4) Mitsui Toatsu total recycle Urea process

2
CHAPTER 2: Literature review

We selected the Snamprogetti ammonia stripping process for the manufacture of Urea,
because it involves a high NH3 to CO2 ratio in the reactor, ensuring the high conversion
of carbamate to Urea[21].
In this process ammonia & CO2 are compressed & fed to the reactor. The unconverted
carbamate is stripped and recovered from the Urea synthesis reactor effluent solution at
reactor pressure, condensed to an aqueous solution in a steam producing high pressure
condenser & recycled back to the reactor by gravity. Part of the liquid NH3 reactor feed,
vaporized in a steam heated exchange, is used as inert gas to decompose & strip
ammonium carbamate in the steam heated high pressure stripper.

2.4Process Technology:
Although there are several processes currently used for the manufacture of Urea, the
underlying principle for all the processes is same. The two main reactions involved are:

1) CO2 + 2NH3 ↔ NH2 COONH4 ΔH= -37.4 Kcal/gm molEq(2.4)

2) NH2COONH4 ↔ NH2CONH2 + H2O ΔH= + 6.3 Kcal/gm molEq(2.5)

Undesirable side reaction taking place is:

3) 2NH2CONH2 ↔ NH2CONHCONH2 + NH3Eq(2.6)

Both 1st & 2nd reactions are equilibrium reactions. The 1st reaction almost goes to
completion at 185-190 °C & 180 - 200 atm. The 2nd reaction (decomposition reaction) is
slow and determines the rate of the reaction. Unconverted CO2 & NH3, along with
undecomposed carbamate, must be recovered and re-used. This is a troublesome step.
The synthesis is further complicated by the formation of a dimer called biuret,
NH2CONHCONH2, which must be kept low because it adversely affects the growth of
some plant.

2.5Various Processes for The Manufacture of Urea:

The Urea synthesis reactor always contains unreacted Carbamate & more or less excess
Ammonia, depending upon the composition of the feeds. This poses the practical problem
of separating the unreacted material from the Urea solution & of reutilizing this unreacted
material. Depending upon the method of reutilization of the uncreated material, the
commercial Urea synthesis processes are divided into the following main categories:

1)Once-Through Urea Process:

The unconverted Carbamate is decomposed to NH3 & CO2 gas by heating the Urea
synthesis reactor effluent mixture at low pressure. The NH3 & CO2 gas is separated from
the Urea solution and utilized to produce Ammonium salts by absorbing NH3, either in
sulfuric or nitric acid[20].

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CHAPTER 2: Literature review

Once Through Urea Process [Fig-2.1]:

In this process liquid NH3 is pumped through a high-pressure plunger pump and gaseous
CO2 is compressed through a compressor up to the Urea synthesis reactor pressure at
NH3 to CO2 feed mole ratio of 2/1 or 3/1. The reactor usually operates in a temperature
range from 175 to 190 °C. The reactor effluent is let down in pressure to about 2 atm and
the Carbamate decomposed and stripped from the Urea-product solution in a steam
heated shell & tube heat exchanger. The moist gas, separated from the 85-90 % Urea
product solution, & containing about 0.6 tons of gaseous NH3 per ton of Urea produced
is usually sent to an adjacent Ammonium nitrate or Ammonium sulfate producing plant
for recovery. An average conversion of Carbamate to Urea of about 60 % is attained.
Excess heat is removed from the reactor by means of a low-pressure steam-producing
coil in an amount of about 280,000 Cal/Kg Urea produced.

Figure 2.1 Once Through Urea Process

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CHAPTER 2: Literature review

2) Solution Recycle Urea Process:

The NH3 & CO2 gas recovered from the reactor effluent mixture either in one or in
several pressures staged decomposition sections is absorbed in water and recycled back to
the reactor in the form of an Ammoniacal aqueous solution of Ammonium
Carbamate[20]

3) Internal Carbamate Recycle Urea Process:

The uncreated Carbamate & the excess Ammonia are stripped from the Urea synthesis
reactor effluent by means of gaseous hot CO2 or NH3 at the reactor pressure, instead of
letting the reactor effluent down to a much lower pressure. The NH3 & CO2 gas, thus
recovered at reactor pressure, is condensed and returned to the reactor by gravity flow for
recovery[20].

A) SnamProgetti (Italy) [Fig-2.2]

This process is based on the principle of the internal Carbamate recycle technique and is
commonly called the Snam NH3 stripping process. The basic difference between the
Snam process & the conventional Carbamate solution recycle Urea processes is the fact
that in this case the unconverted Carbamate is stripped and recovered from the Urea
synthesis reactor effluent solution at reactor pressure, condensed to an aqueous solution
in a steam producing high pressure condenser, & recycle back to the reactor by gravity.
Part of the liquid NH3 reactor feed, vaporized in a steam heated exchanger, is used as
inert gas to decompose & strip Ammonium Carbamate in the steam heated high pressure
stripper. The reactor operates at about 162 atm & 180-190 °C. The stripper operates at
about 162 atm & 190 °C. The stripper off-gas is condensed in a vertical shell & tube
condenser, operating at about 130 atm & 148-160 °C. Low pressure steam is produced in
the high-pressure Carbamate condenser. The Urea product solution, leaving the stripper
& still containing 2-3 % of residual uncreated Carbamate, is further degassed in a low-
pressure decomposition-absorption system. The recovered Ammoniacal solution of
Ammonium Carbamate is pumped back to the reactor[20].

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CHAPTER 2: Literature review

Figure 2.2 Snamprogetti Process

B) Stamicarbon (Holland)[Fig-2.3]

The novelty of the CO2 stripping process consists of the fact that the reactor effluent is
not let down to a lower pressure as in the conventional liquid recycle Urea process, but is
stripped at synthesis pressure by the gaseous CO2 reactor feed stream in a steam heated
vertical heat exchanger. The high-pressure stripper operates at about 140 atm & 190 °C.
The stripped Urea solution still contains about 15% of the unconverted Carbamate, & it is
let down to about 3 atm for further degassing in the steam heated low pressure
decomposer at about 120 °C. The off gas recovered is condensed with cooling water in
the low-pressure condenser, operating at about 65 °C & 3 atm. The solution thus obtained
is pumped to the high-pressure condenser by means of high pressure Carbamate pump.
The off gas recovered from the high-pressure stripper is condensed in the high-pressure
condenser, which operates at about 170 °C & 140 atm. The heat of condensation is
removed on the shell side of the condenser by vaporizing the equivalent amount of
condensate. The 3.4 atm steam thus produced can be reused in another section of the
plant.

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CHAPTER 2: Literature review

The mixture of gas & liquid issuing from the high-pressure condenser is fed to the reactor
for total CO2 condensation to Carbamate & subsequent conversion to Urea. The inert are
vented from the reactor through a water-cooled vent condenser. The reactor effluent, at
about 185 o C & 140 atm, is fed to the high-pressure stripper as described above[20].

Figure 2.3 Stamicarbon Process

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CHAPTER 2: Literature review

C) Mitsui Toatsu or Toyo Koatsu Process (Japan) [Fig-2.4]

This total recycle Urea process is conventional Carbamate solutions recycle process with
three pressure-staged Carbamate decomposition & recovery systems. The reactor is
operated at about 195°C, 240 atm, & with a NH3 to CO2 molar ratio of about 4.3. About
67 % of the total Ammonium Carbamate present in the reactor is converted to Urea.
The unconverted carbamate is decomposed and stripped from the Urea solution together
with excess NH3 in a series of three pressure-stage decomposers, operating respectively
at about 18 atm & 150 °C, 3.06 atm & 130 °C, & atmospheric pressure & 120 °C. The
main feature of the Mitsui Toatsu process is the fact that the gaseous phase in each
decomposition stage is contacted in counter current flow with the Urea product solution
issuing from the preceding decomposition stage. Either a packed section or a sieve tray
section is used for this purpose. The effect is that the NH3 & CO2 gaseous mixture
obtained from the decomposition of Carbamate is considerably reduced in vapor content.
Thus, the amount of water recycled to the reactor is maintained at a relatively low level
and a relatively high conversion in the reactor is attained. The off-gas from each
decomposition stage is condensed to solution in its respective water-cooled condenser
and the solution thus obtained is pumped to the next high pressure staged condenser.
Excess NH3 is separated from the aqueous solution of Carbamate & scrubbed from the
last traces of 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[20].

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CHAPTER 2: Literature review

Figure 2.4 Mitsui Toatsu Total Recycle Urea Process

9
 CHAPTER 3
Process Description

10
CHAPTER 5:Energy Balance

3.1 Selection of the Process:

Snamprogetti Ammonia-stripping Urea process is selected because it involves a high
NH3 to CO2 ratio in the reactor, ensuring the high conversion of Carbamate to Urea. The
highly efficient Ammonia stripping operation drastically reduces the recycling of
Carbamate and the size of equipment in the Carbamate decomposition. Snamprogetti
technology differs from competitors in being based on the use of excess Ammonia to
avoid corrosion as well as promote the decomposition of unconverted Carbamate into
Urea. Formation of Urea from Ammonia & carbon di oxide takes place through
reversible reactions with formation of Ammonium Carbamate as intermediate product.
Now, success of any Urea mfg. process depends on how economically we can recycle
Carbamate to the reactor. Snamprogetti process of Urea manufacturing accomplishes the
above task by stripping process.

It would be more accurate to talk about the cost of urea, which is affected by several
parameters (including steam consumption). The diagram below shows all these
parameters, i.e. the advantages of the Snamprogetti urea technology and their impact on
the cost of the product together with high plant reliability (low energyrequirement ,low
investment, and operational cost ,high reliability and lowpollution).

The Snamprogetti Urea Process is basically a total recycle stripping process

using ammonia as a self-stripping agent. The Snamprogetti process used the
excess ammonia present in the urea solution leaving the reactor to strip CO 2 from urea
solution in a falling film steam heated heat exchanger operated at the urea reactor
pressure. The separated CO2 and NH3 are recombined as ammonium carbamate in the
carbamate condensers, also operating at urea reactor pressure and then returned to the
reactor for conversion to urea.

NH2COONH4 (s) ===== 2NH3 (g) + CO2 (g) Δ H = + 37.4 Kcal/gm-mole

Eq(3.1)
This reaction involves increase in volume & absorption of heat. Thus, this reaction will
be favored by decrease in pressure & increase in temp. Moreover, decreasing the partial
pressure of either of the products will also favor the forward reaction. Process based on
first principle of decrease in pressure & decrease in temp is called conventional process,
whereas process based on increase/decrease of partial pressures of NH3 or CO2 is called
stripping process. According to above equation we have:

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

The stripping is affected at synthesis pressure itself using CO2 or NH3 as stripping agent.
If CO2 is selected, it is to be supplied to the decomposers/stripper as in Stamicarbon CO2
stripping process. While if NH3 is selected, it is to be obtained from the system itself
because excess NH3 is present in the reactor as in Snam’s process. CO2 stripping is

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CHAPTER 5:Energy Balance

advantageous because introducing CO2 increases pCO2. So pNH3 will be reduced to

maintain P constant as P = pCO2 + pNH3.
At a temp K is constant so when pNH3 is reduced to keep K constant, Carbamate will be
reduced much faster by decomposition as pNH3 appears in the equilibrium equation with
a power of two. Selection of 1st stage decomposition should be in such a way that min
water evaporates because the recovered gases go along with the Carbamate to reactor
again & if water enters reactor production will be affected adversely due to hydrolysis of
Urea. So, stage wise decomposition of Carbamate is done. Second consideration in favor
of isobaric stripping is that higher Carbamate recycle pressure results in condensation at
higher temp & that recovery in the form of low pressure steam. Therefore, stage wise
reduction in pressure is pactised[20].

Figure 3.1 Snamprogetti Urea Process

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CHAPTER 5:Energy Balance

3.2Parameters that effect on this process:

3.2.1Temperature:

1) CO2 + 2NH3 ↔ NH2 COONH4 ΔH= -37.4 Kcal/gm molEq(3.2)

2) NH2COONH4 ↔ NH2CONH2 + H2O ΔH= + 6.3 Kcal/gm molEq(3.3)

In above reactions 1st reaction is exothermic & 2nd one is endothermic. So, according to
Le chatelier’sPrinciple 1st reaction is favored at low temp & 2nd one at high temp.
Further, reaction no. 1 is fast & reaches to completion but reaction no. 2 is slow &
determines the overall rate of Urea production. For sufficient completion of reaction no.2
optimum temp is maintained. It is observed that max equilibrium conversion occurs
between 190 to 200°C. If temp is increased beyond 200°C corrosion rate increases.

NH2COONH4 (s) ===== 2NH3 (g) + CO2 (g); H= -ve (K1) Eq(3.4)[22]
NH2COONH4 (s) ===== NH2CONH2 (s) + H2O (l); H = -ve (K2) Eq(3.5)[22]

Both the reactions are favored at high temp but our objective is to maximize 2nd reaction
as 1st reaction is undesirable in the reactor. So, our operating zone should be in the region
where K2 > K1.[20]

3.2.2 Pressure:

Overall Urea synthesis reaction is given below:

CO2 (g) + 2NH3 (g) ====== NH2CONH2 (s) + H2O Eq(3.6)

There is reduction in volume in the overall reaction & so high pressure favors the forward
reaction. This pressure is selected according to the temp to be maintained & NH3:CO2
ratio[20].

3.2.3Concentration:

Higher the concentration of the reactants, higher will be the forward reaction according to
the law of mass action. CO2 being limiting reagent higher NH3:CO2 ratio favors
conversion. Since, dehydration of Carbamate results in Urea production, lesser H2O:CO2
ratio favors conversion, water intake to the reactor should be therefore min[20].

13
CHAPTER 5:Energy Balance

3.2.4Residence time:

Since, Urea conversion reaction is slow, sufficient time is to be provided to get higher
conversion. Reactor is designed to accommodate this with respect to the other parameters
of temperature, pressure &concentration[20].

3.3The Snamprogetti urea process is divided into five sections:

• Synthesis and high pressure (HP) recovery.
• Medium pressure (MP) purification and recovery.
• Low pressure (LP) purification and recovery.
•Urea concentration.
• Urea prilling.

3.3.1Urea Synthesis & High-Pressure Recovery:

Urea is synthesized from liquid Ammonia & gaseous carbon-dioxide. The carbon dioxide
drawn from battery limits at about 1.6 atm pressure & about 40°C temp is compressed in
a centrifugal compressor up to 162 atm. A small quantity of air is added to the CO2
compressor suction to passivate the stainless-steel surfaces. Thus, protecting them from
corrosion due both to the reagent & the reaction product.
The liquid Ammonia coming directly from battery limits is collected in the Ammonia
receiver tank from where it is drawn to & compressed at about 23 atm pressure by means
of centrifugal pump. Part of this Ammonia is sent to medium pressure absorber &
remaining part enters the high-pressure synthesis loop. The NH3 of this synthesis loop is
compressed to a pressure of about 240 atm. Before entering the reactor, it is used as a
driving fluid in the Carbamate ejector, where the Carbamate coming from Carbamate
separator is compressed up to synthesis pressure. The liquid mixture of Ammonia &
Carbamate enters the reactor where it reacts with compressed CO2.
In the reactor the NH3 & gaseous CO2 react to form Ammonia. Carbamate, a Portion of
which dehydrates to form Urea & water. The fraction of Carbamate that dehydrates is
determined by the ratios of various reactants, operating temp, the residence time in the
reactor & reaction pressure. The mole ratio of NH3 / CO2 is around 2:1, the mole ratio of
water to CO2 is around 0.67:1.

2NH3 (g) + CO2 (g) ===== NH2COONH4 (s); Exothermic Eq(3.7)

NH2COONH4 (s) ===== NH2CONH2 (s) + H2O (l); Endothermic Eq(3.8)

In the synthesis conditions (T= 180°C, P= 162 atm), the 1st reaction occurs rapidly & is
completed. The 2nd reaction occurs slowly & determines the reactor volume. Urea
reactor is a plug flow type with 10 no’s of sieve trays to avoid back mixing & to avoid

14
CHAPTER 5:Energy Balance

escape of gaseous CO2 which must react in the lower part of the reactor. Stage wise
decomposition is carried out to reduce water carry over to the reactor which could
adversely affect conversion.
Urea solution containing Urea, Carbamate, H2O & unconverted CO2 & NH3 enters the
high-pressure stripper where the pressure is same as that of the reactor. The mixture is
heated as it flows down the falling film exchangers. The CO2 content of the solution is
reduced by the stripping action of NH3 as it boils out of the solution. The Carbamate
decomposition heat is supplied by 24 atm steam.

The stream leaving the reactor contains 34 wt% urea and the rest comprises ammonium
carbamate, water and ammonia. To obtain a product that meets purity specifications,
purification steps are needed, the first of these is the stripper.

The stripper is a falling film heat exchanger which facilitates the decomposition of
ammonium carbamate into ammonia and CO2. These gasses help strip additional
ammonia from the liquid thereby purifying the product stream to the point where it
contains 72.98wt% urea. The off-gasses from the stripper are sent to the high pressure
carbamate receiver, where they are condensed to form ammonium carbamate, which in
turn is fed back into the carbamate separator and subsequently to the reactor. The urea
solution coming from the stripper makes its way to the medium pressure section of the
process[23].

3.3.2Medium pressure section (18 atm):

Medium pressure section of the process contains only one unit for the purification of the
urea solution, this unit being the medium pressure decomposer. However, it is a vital part
of the plant since it ensures that pure ammonia and carbamate solution are recovered and
fed back to the high pressure synthesis section. As mentioned above, the only purification
step occurs in the medium pressure decomposer, which purifies the urea solution to
74.5wt% urea. The purified urea liquor then makes its way to the low pressure
decomposer and the resulting off-gases are transferred to the shell of the preheated,
where they are absorbed and react, thereby heating the endothermic reaction occurring
within the unit. This procedure helps to increase the energy efficiency of the plant.

The MP section also receives the fresh ammonia feed for the entire plant, the carbamate
solution coming from the shell of the preheater and subsequently the MP carbamate
condenser is fed into the bottom of the column of the reactor[23].

15
CHAPTER 5:Energy Balance

3.3.3Low pressure section (4.5):

The LP section is the last section that is aimed at the decomposition of ammonium
carbamate to purify the product. This purification occurs within in the low pressure
decomposer, where the urea liquor is purified to 76.12wt%[23].

3.3.4Urea Concentration:

The vacuum evaporation section is, as the name suggests, aimed at concentrating the urea
solution through evaporation of any remaining water as low as 1%.For the purpose a
vacuum concentrator in two stages is provided. The solution leaving the LP decomposer
bottom with about 76.12% Urea is sent to the 1st vacuum concentrator operating at a
pressure of 0.23 atm. The mixed phase coming out enters the gas liquid separator,
wherefrom the vapors are extracted by the 1st vacuum system, while the solution enters
the 2nd vacuum concentrator operating at a pressure of 0.03 atm. The two concentrators
are fed by saturated steam at 4.5 atm. The mixed phase coming out enters the gas liquid
separator, wherefrom the vapors are extracted by the 2nd vacuum system[23].

3.3.5Urea Prilling:

The molten Urea leaving the 2nd vacuum separator is sent to the prilling bucket by means
of a centrifugal pump. The Urea coming out of the bucket in the form of drops fall along
the prilling tower & encounters a cold air flow which causes its solidification. The solid
prills falling to the bottom of the prilling tower are sent through the screeners to retain
lumps only, & then to belt conveyor which carries the product to the automatic weighing
machine & to the Urea storage sections. Urea lumps by the means of belt conveyor are
recycled to the underground tank, where they are dissolved[23].

16
 CHAPTER 4
Material Balance

17
CHAPTER 5:Energy Balance

4.1Introduction
Material quantities as they pass through processing operations can be described by
material balances. Material balances are the basis of process design. A material balance
taken over the complete process will determine the quantities of raw materials required
and products produced. Balances over individual process units set the process stream
flows and compositions[24]. Such balances are statements on the conservation of mass.
Similarly, energy quantities can be described by energy balances, which are statements
on the conservation of energy[25]. If there is no accumulation, what goes into a process
mustcome out. It is true for continuous operation over any chosen time interval.
Material balances are fundamental to the control of processing, particularly in the control
of yields of the products. The increasing cost of energy has caused the industries to
examine means of reducing energy consumption in processing. Energy balances are used
in the examination of the various stages of a process, over the whole process and even
extending over the total production system from the raw material to the finished product.

The general conservation equation for any process system can be written as:

Material out = Material in + Generation - Consumption – Accumulation

For a steady-state process the accumulation term will be zero. If there is no chemical
reaction the steady-state balance reduces:
Material out = Material in

Time basis might be chosen as a basis for calculation when results are to be presented in
tone/y .

4.2General Assumptions for Calculation

• No reaction occurs at in the separation.
• 300 working days in the year.
• Basis for calculation is one hour.

18
CHAPTER 5:Energy Balance

Selected capacity : 250,000 tons/year

No. of working days: 300

Daily production :250,000/300 = 833.3tons/day

Urea 34722.2 Kg/hr of 98 % purity

Composition of the final product :

Urea : 98 % (34027.756Kg/hr)
Biuret : 1 % (347.2 Kg/hr)
Water : 1 % (347.2Kg/hr)

Assumption :

Overall conversion to urea is assumed to be 96 %.

MAIN REACTIONS:

CO2 + 2NH3 -------- NH2COONH4 (1)

NH2COONH4 -------- NH2CONH2 + H2O (2)

CO2 + 2NH3 -------- NH2CONH2 + H2O (overall reaction) (3)

Side reaction:

2NH2CONH2 ------- NH2CONHCONH2 + NH3 (4)

347.2 Kg/hr of Biuret produced by = (120/103)*347.2= 404.5Kg/hr of urea (reaction 4)

So, urea produced by reaction (2) = 34027.756+ 404.5 = 34432.256 Kg/hr
34432.256 Kg/hr of urea produced by = (34/60)*34432.256 = 19511.6Kg/hr NH3
Similarly, CO2 reacted in reaction (3) = (44/60)*34432.256 = 25250.32Kg/hr
Assuming 96 % conversion we get

NH3 actually required = 19511.6/0.96 = 20324.58 Kg/hr

CO2 actually required = 25250.32/0.96 = 26302.42Kg/hr

Now, considering reaction (4) :

If reaction (3) is 100 % complete then,
Urea produced = (60/44)*26302.42 = 35866.9 Kg/hr
But, for 96 % conversion
Urea produced = 0.96*35866.9= 34432.224 Kg/hr

19
CHAPTER 5:Energy Balance

Therefore, Urea converted to Biuret & NH3 = 34432.224 – 34027.756 = 404.468 Kg/hr
So, from reaction (4)
Biuret produced = (103/120)*404.468 = 437.168 Kg/hr
Water produced in reaction (3) = (18/60)*34432.256 = 10329.6768Kg/hr
At reactor’s exit (Urea = 34 %)
Flow rate of stream = 34027.756/0.34 = 100081.6353 Kg/hr
NH3 reacted in reaction (3) = (34/60)*34432.224 = 19511.5936 Kg/hr
NH3 produced in reaction (4) = (17/120)*404.468= 57.2996 Kg/hr
So, NH3 unreacted = 20324.58 – 19511.5936 + 57.2996 = 870.286 Kg/hr
CO2 reacted in reaction (1) = (44/60)*34432.224= 25250.2976 Kg/hr
Therefore, CO2 unreacted = 26302.42 – 25250.2976 = 1052.1224 Kg/hr
Now,
Flow rate of stream at reactor’s exit – (flow rate of urea+CO2+NH3+water+biuret) =
Flow rate of carbamate
100081.6353- (34027.756 + 10329.6768 + 347.168 +1052.1224 + 870.286) =
53454.626Kg/hr

20
CHAPTER 5:Energy Balance

4.3REACTOR

Figure 4.1 Flow of material across urea reactor

Table 4.1 Flow of material across urea reactor

In 0ut
Material Flow rate % Material Flow rate %
kg/hr kg/hr

Feed UNREACTED

CO2 26302.42 56.41 CO2 1052.097 1.05

NH3 20324.58 43.59 NH3 870.2722 0.883
TOTAL 46627 100 PRODUCTS
UERA 34027.75 34
RECYCLE WATRE 10329.68 10.32
CARBMATE 53454.61 100 CARBMATE 53454.61 53.4
BIURET 347.2046 0.347

TOTAL 100081.61 100 TOTAL 100081.6 100

21
CHAPTER 5:Energy Balance

4.4 STRIPPER:

Figure 4.2 Flow of material across urea stripper

Since, no reaction takes place in the stripper & only carbamate gets recycled back to the
reactor. Therefore, the amount of ammonia, carbon-di-oxide, water & biuret in the outlet
stream of stripper will be same as it was in the inlet stream.

Table 4.2 Flow of material across urea stripper:

INPUT OUTPUT

MATREIAL FLOWRATE % MATREIAL FLOWRATE %

Kg/hr Kg/hr

Bottom product

CO2 1052.097 1.05 CO2 1052.097 2.256

NH3 870.2722 0.883 NH3 870.2722 1.866

UREA 34027.75 34 UREA 34027.75 72.98

WATER 10329.68 10.32 WATER 10329.68 22.15

CARBMATE 53454.61 53.4 BIURET 347.2046 0.748

BIURET 347.2046 0.347 TOPPRODUCT

CARBMATE 53454.61 100

TOTAL 100081.61 100 TOTAL 100081.6 100

22
CHAPTER 5:Energy Balance

4.5 MEDIUM PRESSURE SEPARATOR:

Figure 4.3 Flow of material across urea medium pressure separator

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

Table 4.3 Flow of material across urea medium pressure separator:

INPUT OUTPUT

MATERIAL Flowrate % MATERIAL Flowrate kg/hr %

kg/hr

CO2 1052.097 2.256 CO2 526.0484 1.15

NH3 870.2722 1.866 NH3 435.1361 0.95

UREA 34027.75 72.98 UREA 34027.75 74.5

WATRE 10329.68 22.15 WATER 10329.68 22.62

BIURET 347.2046 0.748 BIURET 347.2046 0.78

LOSSES

CO2 526.0484 54.73

NH3 435.1361 45.27

TOTAL 46627 100 TOTAL 46627 100

23
CHAPTER 5:Energy Balance

4.6LOW PRESSURE SEPARATOR:

Figure 4.4 Flow of material across urea low pressure separator

Remaining Ammonia and carbon Dioxide are assumed to escape from the top.

Table 4.4 Flow of material across urea low pressure separator:

INPUT OUTPUT

MATERIAL FLOW % MATERIAL FLOW RATE %

RATE Kg/hr Kg/hr

CO2 526.0484 1.15 UREA 34027.75 76.12

NH3 435.1361 0.95 WATRE 10329.68 23.1

UREA 34027.75 74.5 BIURET 347.2046 0.78

WATER 10329.68 22.62 TOTAL 44704.63

BIURET 347.2046 0.78 LOOSES

CO2 526.0484 54.73

NH3 345.1361 45.27

TOTAL 45665.82 100 TOTAL 45665.82 100

24
CHAPTER 5:Energy Balance

4.7VACUUM EVAPORATOR:

Figure 4.5 Flow of material across urea evaporator

The fraction of Urea in feed stream (9) = 76.12%

The fraction of Urea in product stream (11) = 97.88%
Making Urea balance:
N9 = N11
0.7612 * 44704.63 = 0.9788 * X
N10 = 34766.21 Kg/hr
Overall Material Balance:
S9 = S10 + S11
S10= 9938.422 Kg/hr

25
CHAPTER 5:Energy Balance

Table 4.5 Flow of material across urea evaporator:

INPUT OUTPUT

MATERIAL FLOWRATE % MATERIAL FLOWRATE %

Kg/hr
Kg/hr

UREA 34027.75 76.12 UREA 34027.75 97.88

WATRE 10329.68 23.1 WATRE 391.2554 1.13

BIURET 347.2046 0.78 BIURET 347.2046 0.99

TOTAL 34766.21 100

LOSSES

WATER 9938.422 100

TOTAL 44704.630 100 TOTAL 44704.63 100

26
CHAPTER 5:Energy Balance

4.8 PRILLING TOWER:

Figure 4.6 Flow of material across urea prilling tower

The fraction of Urea in feed stream (11) = 97.88 %

The fraction of Urea in product stream (13) = 98 %

Making Urea balance:
S11 = S13
0.9788 * 34766.21 = 0.98 * N13
N13 = 34723.64 Kg/hr
Overall material balance:
N11 = N12 + N13
N12 = 42.57Kg/hr

27
CHAPTER 5:Energy Balance

Table 4.6 Flow of material across urea prilling tower:

INPUT OUTPUT

MATERIAL FLOW % MATERIAL FLOW RATE %

RATE Kg/hr Kg/hr

UREA 34027.75 98

UREA 34027.75 97.88 WATER 348.6846 1

WATER 391.2554 1.13 BIURET 347.2046 1

BIURET 347.2046 0.99 TOTAL 34723.64 100

LOSSES

WATER 42.57 100

TOTAL 34766.208 100 TOTAL 34766.21 100

28
 CHAPTER 5
Energy Balance

29
CHAPTER 5:Energy Balance

5.1 Introduction
In process design, energy balances are made to determine the energy requirements of the
Process, the heating, cooling and power required. In plant operation, an energy balance
(Energy audit) on the plant will show the pattern of energy usage, and suggest areas for
conservation and saving. Energy can exist in several forms: heat, mechanical energy,
electrical energy, and it is the total energy that is conserved. The total enthalpy of the
outlet streams will not equal that of the inlet streams if energy is generated or consumed
in the processes; such as that due to heat of reaction. A general equation can be written
for the conservation of energy

Energy out = Energy in — generation — consumption — accumulation[26]

This is a statement of the first law of thermodynamics.

An energy balance can be written for any process step. Chemical reaction will involve
energy (exothermic) or consume energy (endothermic).
For steady-state processes the accumulation of both mass and energy will be zero.
Reference temperature for all calculation was taken 25 o C

30
CHAPTER 5:Energy Balance

Assumption : Reference temperature = 0°C

5.2REACTOR:

Figure 5.1 Energy flow across reactor

General form of energy balance around reactor:

Q = ΣΔ𝑯𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏+ ΣΔ𝑯𝒐𝒖𝒕– ΣΔ[26]Eq. (5.1)

INLET STREAM (ΣΔ𝑯) 𝒊𝒏:

Material Specific heat at 40°C

NH3 0.53 cal/gm°C = 37.723Kj/kmol°C

CO2 0.22 cal/gm°C = 40.5284 Kj/kmol°C

Specific heat at 180°C

Carbamate 0.62 cal/gm°C = 202.488 Kj/kmo°C

31
CHAPTER 5:Energy Balance

Heat input mCpΔT

NH3 37.723 x 1195.563529 x 40 = 1804009.721Kj/hr

CO2 40.5284x 597.7822727x 40 = 969086.3625Kj/hr

Carbamate 202.488 x 685.315553 x 180 =24978271.99Kj/hr

ΣΔ𝐻𝑖𝑛= 27751368.07Kj/hr

ΔHR = - 31.32 Kcal/gm mol

= - 0.013 x 107 Kj/Kmol of Urea formed.

Amount of Urea formed during the reaction = 567.1291Kmol/hr

ΔHR = 567.1291 x 0.013 x 107 Kj/hr
= 73726791.67Kj/hr

OUTLET STREAM

Material Specific heat at 180°C [27] Flow rate

NH3 0.55 cal/gm°C = 39.15 Kj/Kmol°C 51.19248

CO2 0.23 cal/gm°C = 42.37 Kj/Kmol°C 23.91129

Carbamate 0.62 cal/gm°C = 202.49 Kj/Kmol°C 685.3156

Urea 0.4828 cal/gm°C =121.32 Kj/Kmol°C 567.1291

Water = 79.416Kj/Kmol°C 573.871

Biure = 183.8 Kj/Kmol°C 3.370918

Total =1904.79

M Cp
m Cp = 51.19248 x 39.15 + 23.91129x 42.37 + 685.3156 x 202.49 + 567.1291 x 121.32
+573.871 x 79.416 + 3.370918 x 183.8
= 256785.0793

Heat output = mCpΔtEq. (5.2)

= 256785.0793x 180
= 46221313.7Kj/hr

32
CHAPTER 5:Energy Balance

Heat Input + ΔHR - Heat Output = Rate of accumulation Eq. (5.3)

27751368.07+ 73726791.67–46221313.7 = Rate of accumulation

Rate of accumulation = 55256843.3Kj/hr

Assumption:

Cooling water at 25°C is used to remove heat from the reactor. The outlet is steam at an
absolute pressure of 4.5 bar (Ts = 147.9°C).

Heat gained by cooling water = 552568483.3Kj/hr

mCpΔt + mλ= 552568483.3Kj/hr

Or, m (CpΔt + λ) = 552568483.3

m [4.3046 x (147.9 - 25) + 2120.684] = 552568483.3Kj/hr

Here λ = 2120.684Kj/kg

&Cp = 4.3046Kj/kg°C

M = 20853.8476 Kg/hr

33
CHAPTER 5:Energy Balance

5.3STRIPPER:

Figure 5.10 Energy flow across stripper

Total inlet heat = 462213131.69Kj/hr

OUTLET STREAM

1) Liquid
Material Specific heat at 180°C Flow rate

NH3 0.58 cal/gm°C = 41.31 Kj/Kmol°C 51.19248392

CO 0.24 cal/gm°C = 44.22 Kj/Kmol°C 23.91129091

Urea 0.5385 cal/gm°C = 135.3 Kj/Kmol°C 567.1291455

Water = 79.776 Kj/Kmol°C 573.8709818

Biuret = 183.8 Kj/Kmol°C 3.370918147

Total = 1219.47482

34
CHAPTER 5:Energy Balance

M Cp =

M Cp = 51.19248392 x 41.31 + 23.91129091 x 44.22 + 567.1291455 x 135.3 +

573.8709818 x 79.776 + 3.370918147 x183.8

= 126305.4Kj/Kmol°C

Heat output = mCpΔt

= 126305.4 x 185

= 23366498.7Kj/hr

2) Vapor: Ammonium carbamate

Material Specific heat at 185°C Flow rate (Kmol/hr)

Carbamate 0.62 cal/gm°C = 202.49 Kj/Kmol°C 685.315563

For carbamate λ = 210 Kj/Kg

Heat carried by carbamate = m CpΔt + m λ

= 685.315563 x202.49x 185 + 685.315563 x 210

= 36897835Kj/hr

Here, Steam at 24 atm is used (Ts = 221.8°C)

λ of steam = 1850.454 Kj/kg

Heat Supplied by Steam = Heat Output – Heat Input

= (23366498.7+ 36897835–462213131.69)

m λ=14043020Kj/hr

m = 14043020/1850.454

m = 7588.959Kg/hr

35
CHAPTER 5:Energy Balance

5.4 CARBAMATE CONDENSER

Figure 5.11 Energy flow across carbamate condenser

Energy balance:

mv λv= ms Cp (Ts - 25) + ms λs Eq. (5.4)

Putting the values, we get:

685.315563 x 210 = ms [4.187 x (147.9 - 25) + 2120.684] [Where λs = 2120.6 84Kj/kg]

ms = 4236.47691 Kg/hr

36
CHAPTER 5:Energy Balance

5.5MEDIUMPRESSURESEPARATOR

Figure 5.4 Energy flow across medium pressure separator

Heat Input = 4.157 x 107 Kj/hr

1) Liquid

OUTLET STREAM

Material Specific heat at 180°C Flow rate

NH3 0.54 cal/gm°C = 38.4 Kj/Kmol°C 25.59624196

CO2 0.23 cal/gm°C = 42.37 Kj/Kmol°C 11.95564545

Urea 0.493 cal/gm°C = 123.84 Kj/Kmol°C 567.1291455

Water 1 = 77.1336Kj/Kmol°C 573.8709818

Biuret 170.92 Kj/Kmol°C 3.370918147

Total = 1181.922933

37
CHAPTER 5:Energy Balance

M Cp =Σ m Cpi

M Cp = 25.59624196 x 38.4 + 11.95564545 x 42.37 + 567.1291455x 123.84 +

573.8709818x 77.1336 +3.370918147 x 170.92Kj/Kmol°C

= 116563.6219 Kj/hr.°C

Heat output = 116563.6219x 140

= 16318907.06Kj/hr

2) For Gases Escaping from the Top

λ at 140°C

Material latent heat 180°C Flow rate

NH 320 cal/gm°C = 22.777 x 10^3Kj/Kmol°C 25.59624

CO 110 cal/gm°C = 20.265 x 10^3 Kj/Kmol°C 11.95565

Total = 37.55189

λ m = Σ mλi Eq. (5.5)

λ m = (25.59624 x 22.777 x10^3+ 11.95565x 20.265x10^3)

= 825286.8Kj/Kmol

Material Specific heat at 140°C Flow rate

NH3 0.54 cal/gm°C = 38.4 Kj/Kmol°C 25.59624

CO2 0.23 cal/gm°C = 42.37 Kj/Kmol°C 11.95565

Total = 37.55189

M Cp = Σ mCpi

M Cp = 25.59624 x 38.4 + 11.95565x 42.37

= 1489.456389Kj/Kmol°C

Heat escaping from the top = m (CpΔt + λ) Eq. (5.6)

= (825286.8 + 21.969 x1489.456389x140)
= 1033810.653 Kj/hr

38
CHAPTER 5:Energy Balance

Assumption:

Cooling water enters at 25°C & leaves at 50°C.

Heat gained by cooling water = Heat Input - Heat Output Eq. (5.7)

= (23366498.7– 16318907.06 – 1033810.653 )

mCpΔt= 6013780.988 Kj/hr

m =6013780.988 / (4.1812x 25)

m = 35957266.98 Kg/hr

5.6 LOW PRESSURE SEPARATOR

Figure 5.5Energy flow across low pressure separator

Heat Input = 16318907.06

39
CHAPTER 5:Energy Balance

1) Liquid

OUTLET STREAM

Material Specific heat at 80° C Flow rate

Urea 0.429 cal/gm°C = 107.76 Kj/Kmol°C 567.1291455

Water = 75.5532Kj/Kmol°C 573.8709818

Biuret 149 Kj/Kmol°C 3.307918147

Total 1144.371045

M Cp = Σ mi Cpi
M Cp = 567.1291455 x 107.76 + 573.8709818 x 75.55 + 3.370918147 x149
= 104973.8926 Kj/Kmol°C
Heat Output = 104973.8926 x 80
= 8397911.407Kj/hr

2) For Gases Escaping from the Top

λ at 80°C

Material latent heat at 80°C Flow rate

NH3 260 cal/gm°C = 18.51 x 10^3 Kj/Kmol°C 25.59624

CO2 85 cal/gm°C = 15.66 x 10^3 Kj/Kmol°C 11.95565

Total = 37.55189

λ m= Σ mi λi
λm = (25.59624x 18.51x10^3 + 11.95565 x 15.66x10^3) Kj/Kmol°C
= 661011.8Kj/hr
Material Specific heat at 140°C Flow rate

NH3 0.52 cal/gm°C = 37.013 Kj/Kmol°C 25.59624

CO2 0.21 cal/gm°C = 38.69 Kj/Kmol°C 11.95565

Total = 37.55189

40
CHAPTER 5:Energy Balance

M Cp = Σ mi Cpi

M Cp = 25.59624 x 37.013 + 11.95565 x 38.69

= 1409.057626 Kj/hr.°C

Heat escaping from the top = m (CpΔt + λ)

= (1409.057626 x80+661011.8)

= 773808.4566Kj/hr

Assumption:

Cooling water enters at 25°C & leaves at 50°C.

Heat gained by cooling water = Heat Input - Heat Output

= (16318907.06 - 8397911.407 - 773808.4566)

mCpΔt= 7147187.197Kj/hr

m =7147187.197/ (4.1812x25)

m = 68374.50681 Kg/hr

41
CHAPTER 5:Energy Balance

5.71stEVAPORATOR:

Figure 5.6 Energy flow across evaporator

Heat input =8397911.407 kj/hr

1) Liquid

Out let stream

For product stream coming out of 1st evaporator:

Material Specific heat at 85°C Flow rate

Urea 0.435cal/gm°C = 109.28 Kj/Kmol°C 567.1291667

Water = 75.6252Kj/Kmol°C 185.4918278

Biuret 149 Kj/Kmol°C 3.370918447

Total = 755.9919129

42
CHAPTER 5:Energy Balance

M Cp = Σ mi Cpi
M Cp = 567.1291667 x 109.28 + 185.4918278 x 75.6252 + 3.307918447x 149
= 76506 Kj/hr°C
mCpΔt = 76506 x 85

= 6503010Kj/hr

2) Water evaporated

H = m cp t

=(388.3793 x 75.355 x 63.1)

=1846704.849 kj /hr

Hout = 6503010 + 1846704.849

= 8349714.849 kj /hr

Q = Hin – Hout

= 8397911.407 – 8349714.849

= 48196.66436 kj/hr

Heat Balance 1st Evaporator:

Heat Input (Feed) + Heat Input by Steam

=
Heat Carried by Water Vapor + Energy of the Bottom Product Eq. (5.7)

Heat Input (feed) + S1 λs1 = E1 HE1 + Energy of the Bottom Product

8397911.407+ S1 x 2122.9184= 6990.8271x 2614.97 + 6503010

S1 = 7718.573514 kg /hr

43
CHAPTER 5:Energy Balance

5.82endEVAPORATOR:

Figure 5.7Energy flow across evaporator

Heat input =6503010 kj/hr

1) Liquid

Out let stream

For product stream coming out of 2 evaporator:

Material Specific heat at 27 °C Flow rate

Urea 0.435cal/gm°C = 101.9628Kj/Kmol°C 567.1291667

Water = 75.22 Kj/Kmol°C 21.7364

Biuret 143.6616 Kj/Kmol°C 3.370918447

Total = 592.2364851

44
CHAPTER 5:Energy Balance

M Cp = Σ mi Cpi

M Cp = 567.1291667 x 101.9628 + 21.7364 x 75.22 + 3.307918447x 143.6616

= 59945.36133Kj/hr°C
mCpΔt = 59945.36133 x 27

= 1618524.756Kj/hr

2)Water evaporated at 24.1c

Cp =75.25728 kj/koml.c

M =163.7554kmol/hr

H = m cp t

=(163.7554x 75.25728x 24.1)

=29700 3.3kj /hr

Hout = 1618524.756 + 297003.3

= 1915528.056kj /hr

Q = Hin – Hout

= 6503010 – 1915528.056

= 4587481.865kj/hr

Heat Balance 2end Evaporator:

Heat Input (Feed) + Heat Input by Steam

=
Heat Carried by Water Vapor + Energy of the Bottom Product Eq. (5.8)

Heat Input (feed) + S2λs2 = E2 HE2+ Energy of the Bottom Product

6503010+ S2 x 2122.9184= 2927.598x 2545.7 + 1618524.756

S2 = 1233.777222 kg/hr

45
CHAPTER 5:Energy Balance

5.9 PRILLING TOWER:

Figure 5.8 Energy flow through evaporator

Heat Input = 1618524.756 kj/hr

OUTLET STREAM

Material Specific heat at 25°C Flow rate

Urea 0.3758 cal/gm°C = 94.41 Kj/Kmol°C 567.1291455

Water = 75.37 Kj/Kmol°C 19.37136408

Biuret = 133.02 Kj/Kmol°C 3.370918147

Total = 589.8714277

46
CHAPTER 5:Energy Balance

M cp = Σ mi Cpi

M Cp = 567.1291455 x 94.41 + 19.37136408x 75.37 + 3.370918147 x 133.02

= 55451.08188 Kj/hr.°C

H1 = Heat output = 55451.08188 x 25 = 1386277.047Kj/hr

H2 = Heat of water (in the top) = m cp t

= 2.365 x75.2291x26

=4625.837 kj/hr

Heat output = H1+H2

= 1386277.047 + 4625.837

=1390902.877 kj /hr

Assuming, humidity of air at 25°C = 0.01

Heat carried away by air = Heat Input - Heat Output

(mCpΔt) dry air = (1618524.756 - 1390902.877)

= 227621.8721 kj/hr

m =227621.8721/ (1.00496 x 1)

m = 226498.4398 Kg/hr

So, flow rate of air = 226498.4398 Kg/hrs-

47
References

References

48
References

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50