Chapter 2

CHAPTER II
PROCESS MODELING AND FLOWSHEETING
2.1
INTRODUCTION
The process flow diagram (Figure 2.1) illustrates the urea plant process design.
This diagram is a layout of all units operation, which are needed in proper sequence to
convert the raw material to desired product, urea.
The plant is to produce a total amount of 200,000 metric ton urea per annum. The
operating day for this plant is 315 days per year and 24 hours a day. The minimum purity
of the urea in the market is 99% with not more than 1% biuret (Ullmanns Encyclopedia
of Industrial Chemistry, Volome, A27).
In this urea plant design, the urea is produced by interaction between ammonia
and carbon dioxide. The process can be represented schematically as essentially
constituting four sections, which are:
o Urea synthesis
o Urea purification
o Unconverted ammonia and carbon dioxide recovery and recycle
o Urea crystallization
Process Modeling & Flowsheeting
2- 2
-1352. kj/hr (condenser)
NH3 & CO2 Recovery

29
26
25
26
28
14
M-11
C-18
3
1
C-21
2
M-1
C-2
X-3
10
R-4
C-16
12
R-
17
13
M-1
26
X-3
C-2
C-16
X-8
F-7
15
E-6
6 C-18
16
C-22
X-15
X-10
18
8
F-9
323
X-1
5
R-4
C-2
M-1
C-19
C-16
T-5
10
X-3
6
21
11
F-14
C-19
X-15
24
M-12
19
20
29
T-5
31
22
X-20
T-13
Urea
purification
Figure 2.1: Urea Production Process Flow Diagram
C-19
27
11
X-20
Vacuum
Crystallizer
Urea
Synthesis
X-17
30
Urea
Crystallization
Storage Tank

2.2
2- 3
PROCESS DESCRIPTION
Referring to Figure 2.1, a great part of the carbamate [SC=Eff. (H2O + NH3 +
CO2] included in the urea solution coming out of the reactor (R-4) and part of the
free ammonia, NH3 present are stripped and recycled into the reactor, while a urea
solution leaves the stripper having a relatively low content of residual carbon
dioxide, CO2. This solution is treated in a purification column (T-13). And, the
obtained vapors from stripper (T-5) and purification column (T-13) are sent to a
series of flash column (F-7, F-9, F-14) to be treated and recycled to further reactions.
Finally, the urea-product solution is solidified based on crystallization concept. Such
a process, as are most of the urea processes used actually on industrial scale, is of the
total recycling type, which means that unreacted NH3 and CO2 coming out of the
reactor are recycled to the reactor.
2.2.1
Urea Synthesis
2.2.1.1 Pre Synthesis: Mixer, M-1; Compressor, C-2 and C-16; Heat Exchanger,
X-3
The fresh ammonia gas through line 1 is compressed and mixed with the
carbamate recycle stream (line 26) in the mixer, M-1. The recycle stream mainly
consists of ammonia, carbon dioxide and water vapor. Urea only occurs in this
recycle stream in minute quantities. The mixture is then compressed using
compressor, C-2 to a very high synthesis pressure at 175 bar. The feed to the reactor
are mainly cooled by heat exchanger, X-3 to synthesis temperature at 190C.
2.2.1.2 Urea Synthesis Reactor, R-4
The manufacture of urea which based on reaction of ammonia with carbon
dioxide occurs in a reactor, R-4 at elevated temperature (190C) and pressure of 175
bar. The outlet temperature of the reactor is same as the feed inlet temperature as the
reactor is isothermal type reactor.
Apparently the reaction takes place in two steps, the first is

2NH3 (l)
Ammonia
2- 4
CO2 (l)
NH2COONH4 (l)
Carbon
Dioxide
Ammonium
Carbamate
H = -117KJ/mol
And the second step in the reaction is

NH2COONH4 (l)
NH2CONH2 (aq) + H2O (l)
Ammonium
Carbamate
Urea
H + +15.5KJ/mol
Water
In the first reaction, carbon dioxide and ammonia are converted to

ammonium carbamate: the reaction is fast and exothermic. In the second reaction,
which is slow and endothermic, ammonium carbamate dehydrates to produce urea
and water. Since more heat is produced in the first reaction than consumed in the
second, the overall reaction is exothermic (Ullmanns Encyclopedia of Industrial
Chemistry, Vol. A27).
The rate of formation of carbamate is highly dependent upon the pressure.
When all other factors are constant the rate of formation increases proportionally to
the square root of the pressure. The rate of formation also increase with temperature,
until a maximum is reached, at which point the rate decreases sharply to zero at a
temperature where the dissociation pressure is equal to the reaction pressure
(www.keele.ac.uk/depts/ch/resources/urea/ureahome.html). The dissociation pressure
of pure carbamate has been investigated quite extensively and the average value of
all the investigations is shown in Table 2.1.
Table 2.1: Dissociation Pressure of Pure Carbamate
Temperature, C
Ammonium
Carbamate Vapor
Pressure, atm absolute
40
60
80
100
120
140 160
0.31
1.05
3.1
8.5
21
46
98
180
200
150,190*
200,360*
Source: Encyclopedia of Chemical Technology, vol. 21

*
Obtained from extrapolation. Above 170C the rate of reaction 2 rapidly increases and exact
carbamate vapor pressure determinations are very difficult to perform due to the formation of water
and urea and the consequent lowering of the carbamate partial pressure.
2- 5
From this information, therefore, it is advisable in industrial urea production

to operate at the highest pressure and at the highest temperature compatible with this
pressure. As the synthesis temperature and pressure have been chosen at 190C and
175 bar respectively, the effluent from the reactor, R-4 contains no ammonium
carbamate instead of carbamate included in the urea solution which consists H2O,
NH3, CO2 and urea.
The synthesis reaction in the reaction space, R-4 is carried out in accordance
with the following process parameters:
NH3/CO2mol
3.5
H2O/CO2mol
0.5
CO2 conversion yield
75%
Urea processes differ mainly in the conditions (composition, temperature and

pressure) at which these reactions are carried out. Traditionally, excess NH3 is used to
react with CO2. This is to minimize the biruet formation in the reaction space.
Biuret formation from urea:
2CO(NH2)2
NH2CONHCONH2 + NH3
Biuret is impurity which has been shown to be toxic to crops, thus the levels of this
must be kept low in the marketed urea product. The high NH3 concentration in the
reactor shifts the biuret formation reaction to the left, such that only a small amount
of, or no biuret is formed in the reactor. In downstream sections of the plant, NH3is
removed from the urea solution, thereby creating a driving force for biuret formation.
The effluent from reactor, R-4 which consists of carbamate included in urea
solution is then cooled down to 170C using a heat exchanger, X-15 before entering
purification section.

2.2.2
2- 6
Urea Purification
2.2.2.1 CO2 Stripping Column, T-5

The stripping equipment, T-5 is subjecting the reaction mixture leaving
reactor R-4 to a treatment of separation of the free ammonia in aqueous solution
present in the mixture. In this column, at synthesis pressure, a considerable part of
free ammonia present in the urea solution is stripped off by the effect of stripping
CO2 which rises through the column in countercurrent after being fed through line 9.
Since the CO2 feed used as stripping agent need to be in gas form, thus, the feed
through line 8 has to be compressed using compressor, C-19.
From the to of T-5, a vapor mixture is obtained composed of carbamate
mixture at temperature of 188.38C, and is fed through the line 10 to the flash drum
zone. An expander, E-6 is used to reduce the high pressure effluent from the top
column to 12 bar before entering flash drum, F-7. From the bottom of T-5, a urea
solution is obtained at a higher temperature of 349.26C, comprising low
concentrations of both NH3 and CO2, water and urea, and is mixed with the bottom
effluent from flash drum zone (line 18) before going into the second stage of urea
purification through line 20.
2.2.2.2 Mixer, M-12
Urea solution with small portion of NH3 and CO2 from line 11, and flash drum
zone (line 18) are mixed in the mixer, M-12 for further urea purification. The
solution is preheated through a heat exchanger, X-17 to 150C and the vapor and
liquid mixture is fed into the purification column, T-13 through line 20 at pressure of
5 bar.
2.2.2.3 Urea Purification Column, T-13
The main objective of this distillation column is to get rid of the NH3 and CO2
that included in the urea solution in order to obtain higher purity and concentration
urea solution.
2- 7
A negligible amount of NH3 and CO2 are present in the bottom product of T13. The urea concentration, so-called urea melt is normally set to be greater than
99%mol at this stage. This concentrate is fed through line 22 to solidification section
where crystallization takes place. The vapors produced in this purification stage are
fed through line 21 to a flash drum in order to get ammonia and carbon dioxide to be
recycled.
2.2.3
Ammonia And Carbon Dioxide Recovery And Recycle
2.2.3.1 Flash Drum: F-7, F-9, and F-14

The recovery of free ammonia begins in the stripper, T-5 where the ammonia
is stripped by fresh stream of carbon dioxide through line 9. The main objective of
this series of flash drum is to recover mainly ammonia and carbon dioxide from the
carbamate solution (SC). The feeds to the flash drums are heated (X-8, X-10) or
depressurized (E-6) before accessing the separation. The top vapors from the flash
drum zone recycled through the line 14, 17-28, and 23-29 is mixed in the mixer, M11 before going back the reactor, R-4. Compressors, C-21 and C-22 are used to raise
the outlet pressure of F-9 and F-14 in order to have same pressure of the three top
stream of the flash drums which entering mixer.
2.2.3.2 Heat Exchanger: X-8, and X-10
A total amount of four heat exchangers are used in the recovery and recycle
section. Both heat exchanger X-8 and x-10 are used to increase the temperature.
2.2.3.3 Mixer, M-11; Compressor, C-18
The multiple input streams from the flash drums through line 14, 17, and 23
are mixed before they are being sent out. The effluent from the mixer is compressed
by the compressor, C-18 before mixing with fresh feed ammonia (line 2) and
entering the reactor, R-4 for urea synthesis.

2.2.4
2- 8
Urea Crystallization
Urea is normally obtained from the synthesis section as a concentrated
solution and is usually further processed to solid urea, which is more economical for
shipping and distribution. The solid form in which urea may appear include crystals,
flake, prills and granules. Here, urea crystallization is chosen as it presents a
relatively pure and quite well suited for both agricultural and industrial uses.
The urea-product solution containing more than 99% urea from the bottom of
urea purification column, T-13 is cooled using heat exchanger, X-20 to 140C and is
then fed through line 22 to a vacuum crystallizer. Water evaporates and leaves
crystallizer as water vapor (line 31). The crystals separated from the water vapor are
then sent to storage tank (line 29) and ready for final handling.
2.2.5
The Mond Index

The Mond Index is a rapid hazard assessment method for use on chemical
plant or in plant design. It produces a numerical ranking for each section of the plant
based upon the properties of materials present, quantity, operating conditions and
type of process. Scales are provided to convert the rankings into qualitative
descriptions of the hazard potential of each unit. The index is primarily concerned
with fire and explosion problems. Toxicity is considered only as a possible
complicating factor. The method gives credits for plant safety features associated
with both the hardware and the software.
The overall aim of the index is to provide a rapid means of identifying and
assessing those sections of the plant having a significant fire or explosion potential.
Uses of the index include assessments of operational plants and the initial
examination of new designs, where it can be used as an aid to inherently safe design
and to help with plant layout.
Total Material Factor, B
Reactive combinations of materials key material in reactor has a reaction which is
more exothermic than combustion then the material factor should be based on the
2- 9
exothermicity of this reaction, B = 1.8 x Hr where Hr is the heat of reaction in

kcal/g.
Total Special Material Hazards, M
Liquefied flammable gases - this refers to materials with boiling points below 30C,
stored as liquids under pressure. A release of such a liquid gives a cooled vapour/mist
cloud due to flashing which is normally denser than air.
Total General Process Hazards, P
Reaction stages where a reactor is used for several purposes and contamination by
one product could affect a subsequent reaction. The factor selected should depend on
the extent of contamination and possible consequences.
Material transfer where flexible or removable pipe work is involved and additional
pipe connections for simultaneous venting or inert gas purging are required.
Special Process Hazards, S
High pressure, p a factor for units operating at above atm. Pressure to allow for the
enhanced fire and explosion risks. Its range between 1000 to 10000 psig.
Quantity Hazards, Q
Quantity of material should be entered in tonnes and the quantity factor, Q
determined which a minimum value of Q = 1 for quantities of less than 100 kg.
Total Acute Health Hazards, T
Skin effects - the material is rapidly harmful by skin contact, either by skin
absorptions
Inhalation effects the rate of vapour generation from the released material and the
concentration which can be tolerated for a few minutes without
causing an immediate threat to life or risk of permanent damage.
Fire Index, F
The Fire Index concentrates on the amounts of flammable material in the unit,
its energy release potential and the area unit.
2- 10
The expression is:

F = (B*K)/N
And description categories can be derived from the table below:
F
FIRE INDEX
CATEGORY
Light
Low
Moderate
High
Very high
Intensive
Extreme
Very extreme
02
25
5 10
10 20
20 50
50 100
100 - 250
> 250
Internal Explosion Index, E
This is expressed as:
E = 1 + ( M + P + S )/100
And gives a measure of the potential for explosion within the unit.
Corresponding descriptive categories are given below.
INTERNAL EXPLOSION INDEX
0 1.5
1.5 2.5
2.5 4
46
Above 6
CATEGORY
Light
Low
Moderate
High
Very high
Aerial Explosion Index, A

Important features in assessing aerial explosion risk include the quantity of
material available and its heat of combustion, the likelihood of release, the rate and
height of release and the mixing characteristics of the gas. All of these factors have
been evaluated during the Mond Index assessment and based upon study of a number
of large flammable releases, the individual terms have been combined to give an
aerial explosion index according to the expression.
A = B ( 1 + M /100 )( QHE / 1000 ) ( t + 273/300 )( 1 + p )
2- 11
Corresponding descriptive categories are given below:

AERIAL EXPLOSION INDEX
0 10
10 30
30 100
100 400
400 1700
Above 1700
CATEGORY
Light
Low
Moderate
High
Very high
Extreme
Overall Hazard Rating, R

As it is often necessary to compare units having different types of hazard, an
overall hazard index has been developed based upon the indices described above.
The combination adopted is:
OVERALL HAZARD RATING
0 20
20 100
100 500
500 1100
1100 2500
2500 12500
12500 65000
> 65000
CATEGORY
Mild
Low
Moderate
High (Group 1)
High (Group 2)
Very High
Extreme
Very Extreme
Equivalent Dow Index, D

This is calculated using the expression
D = B ( 1 + M / 100 )( 1 + P/100 )[ 1 + ( S + Q + L + T ) /100 )]
Experience of using the original Dow Index showed that units giving similar
Dow Index values could have different types of hazard potential, with fire risk
dominant in one case and explosion risk in another. To distinguish between these
cases a separate Fire Index and two explosion indices have been developed. With the
availability of these separate indices it is not necessary to convert Dow Index values
into descriptive ratings or to use it to compare units. However it is retained as a basic
element of the Overall hazard Index.
2- 12
2.2.5.1 Mond Index At Reactor

Score
Material Factor
Reactive combination of materials
Special Material Hazards
none
Mixing and Dispersion Characteristic, m
General Process Hazards
Handling and physical changes only
Reaction stages
Material transfer
Special Process Hazards
none
High Pressure, p
Category
1.5
1.5
0
30
0
60
50
110
30
Total Special Process Hazards, S

Quantity Hazards
Quantity of Material
30
Total Quantity Hazards, Q

Layout hazards
Height (H)
Normal working are (N)
Structure Design
Other features
Total layout Hazards, L
Acute Health Hazards
Skin effect
Dow Index, D = B (1+ M/100) (1 + P/100) (1 + (S + Q + L +
T)/100)
Fire Index, F = (B * K) / N
Internal Explosion Index, E = 1 + (M + P + S)/100
Aerial Explosion Index, A = B (1 + m/100) (QHE/1000)
(t+273/300) (1+p)
Overall Hazard Rating, R = D {1+ [0.2 * E * (AF)1/2]}
50
50
5
5
2
10
5
5
50
25
8.60
0.30
2.70
0.00
13.24
Light
Moderate
Light
Mild
From the table, all the Fire, Internal Explosion, Aerial Explosion and Overall
Hazard Index are presented either in LIGHT or MODERATE category. For this, the
reactor as well as the materials is conducted in the safe manner.
2- 13
2.2.5.2 Mond Index At Distillation Column
Score Category
Material Factor
0.5

none
0.5

40
High pressure, p and temperature
60

Quantity Hazards
60

Layout hazards
Height (H)
Structure Design
Other features
Skin effect
T)/100)
50

(t+273/300) (1+p)
0
50
40
50
8
14
55
75
152
5
50
50
4.33
0.04
2.50
0.00
6.49
Light
Moderat
e
Light
Mild
Refer to the table, the Fire, Internal Explosion, Aerial Explosion and Overall
Hazard Index are in the category of LIGHT/MODERATE. Materials in distillation
column are not hazardous but these materials are normally toxicity because its
inhalation effects are 50.
2- 14
2.2.5.3 Mond Index At Stripper
Score Category
Material Factor
1.8

none
Reaction stages
Material transfer
none
High Pressure, p
1.8

Quantity Hazards
40

Layout hazards
Height (H)
Structure Design
Other features
Skin effect
T)/100)
(t+273/300) (1+p)
50
0
30
0
20
20
40
40
50
5
5
5
5
20
20
20
7.53
0.36
2.10
0.00
10.70
Light
Low
Light
Mild
The table shows that materials in stripper are not hazardous material refers to
overall hazard rating, R where below HIGH category. Similarly, the stripper Fire,
2- 15
Internal Explosion, Aerial Explosion and Overall Hazard Index are within the
category of LOW or LIGHT.
2.2.5.4 Mond Index At Flash Drum
Score Category
Material Factor
1.2

none
Reaction stages
Material transfer
none
High Pressure, p
1.2

Quantity Hazards
40

Layout hazards
Height (H)
Structure Design
Other features
Skin effect
T)/100)
50

(t+273/300) (1+p)
0
50
0
30
30
60
40
50
8
8
10
10
36
10
10
6.80
0.15
Light
Moderat
2.50
e
Light
0.00
10.20
Mild
2- 16
For the condition we have chosen for the three flash drums, they are operated
in safe condition if we referred to the analysis above. All the indices are classified
below hazardous category, that is, below HIGH category.
2.2.5.5 Conclusion
The most important index is the overall hazard rating, R. Experience from
applying the full method to operating plants has shown that is uncommon for a unit,
after a complete assessment, to have an overall hazard category below MILD, and it
is reasonable to assume that a unit assessed at this level can be operated in a
satisfactory manner given full regard to the hazards indicated by the assessment. As
offsetting usually reduces the overall hazard category by one or two levels then it
could argued that there is no need to continue beyond the initial assessment when the
initial category is at or below HIGH (Group 2). However, there are important gains
from the offsetting analysis since it identifies the benefits deriving from the safety
hardware and software and indicates the relative importance of the various measures
being taken, and in most cases it should be completed.
In addition to examining the category of the overall hazard rating it is
necessary to consider the other indices, even in those cases where the overall hazard
rating is not above HIGH(2). The Fire Index relates directly to Fire Load, as set out
in the table, and so can be used to estimate fire durations. Categories up to intensive
are often found for this index, particularly for stock tanks. For the internal explosion
and aerial explosion indices a level of moderate or below should be sought after
offsetting. Hence levels of high or above in the initial assessment indicate that the
review and offsetting stages should definitely be carried out and show where
offsetting features are most needed.
From the safety assessment we have done on the units exist in our urea
production flowsheet, it is convinced that this plant fulfills the basic safety
requirements. This plant is expected to be operating in safe manner all the way since
2- 17
the overall hazard rating for all the equipments are categorized as MILD. This urea
plant will not face any explosion problem due to our non-explosive materials. It can
be assured through the results of our Mond Index analyses above. As a conclusion,
the plant is under control without any hazardous wastes which cannot give any effect
for plant operating.
2.3
EQUIPMENT SELECTION
2.3.1
Urea Synthesis Reactor

Reactor is the place where the process synthesis occurred (raw materials are
converted into products). The design of an industrial chemical reactor must satisfy
the requirement of the chemical, mass and heat transfer factors. Any catalytic reactor
(packed bed reactors, fixed bed or fluidized bed catalytic reactors) is not suitable for
the synthesis since urea synthesis is a non-catalytic reaction. The manufacture of urea
occurs in a reactor at elevated temperature and pressure and it can be considered as a
heterogeneous reaction where two phases exist: gaseous reactants (mainly NH3 and
CO2) and liquid products (mainly urea and water).
Stirred-tank reactors become unfavorable due to high temperature and
pressure needed in urea synthesis (Smith, 1995). Under high pressure conditions, a
small diameter cylinder requires a thinner wall than a large diameter cylinder. Under
high pressure conditions, use of a tubular reactor is preferred, although mixing
problems with heterogeneous reactions and other factors may prevent this. Besides,
heating has been shown to cause, by decomposition in series, the formation of
impurity in urea synthesis. Such reactors should be avoided for all systems in which
byproduct formation is via series reactions. Another important factor to the
disadvantages of the stirred-tank reactor is that for a given conversion it requires a
large inventory of material relative to tubular reactor. This is not desirable for safety
reasons if the reactants or products are particularly hazardous.
Viewing from the above pros and cons of the stirred-tank and tubular
reactors, it is wise to select tubular reactor to convert ammonia and carbon dioxide to
2- 18
urea. It consists of a cylindrical pipe and is normally operates at steady state.

Although tubular reactors often take the actual form of a tube, they can be any reactor
in which there is steady movement in one direction only. Because the characteristic
of tubular reactors approximates plug-flow, they are used if careful control of
residence time is important, as in this case where there are multiple reactions in
series. It is relatively easy to maintain (no moving part), and it usually produces the
highest conversion per reactor volume. High surface area to volume ratio is possible,
which is an advantage if high rates of heat transfer are required. It is sometimes
possible to approach isothermal conditions or a predetermined temperature profile by
careful design of the heat transfer arrangements
Tubular reactors, as previously stated, are also advantageous for high pressure
reactions where smaller diameter cylindrical vessels can be used to allow thinner
vessel walls.
2.3.2
Urea Melt Crystallizer

Crystallization is a method of purification and also serves to provide
crystalline materials in the desired size range. Crystallization cannot occur without
supersaturation. A classification of crystallizing equipment can be made based on the
methods used to bring about supersaturation as follow: (1) supersaturation produced
by cooling the solution with negligible evaporation tank and batch crystallizers; (2)
supersaturation produced by evaporation of the solvent with little or no cooling
evaporator-crystallizer and crystallizing evaporators; (3) supersaturation by
combined cooling and evaporation in adiabatic evaporator vacuum crystallizers
(Geankoplis, 1993).
In crystallizers producing supersaturation by cooling the substances must
have a solubility curve that decreases markedly with temperature. When the
solubility curve changes little with temperature, evaporation of the solvent (water in
the case of urea solution) to produce supersaturation is often used. The solubility
curve of urea (Figure 2.2) shows that it decreases but changes little with temperature.
It is clear that cooling and evaporation are needed to bring about supersaturation in
urea crystallization process, that is, using vacuum crystallizer.
-1
2- 19
In the method of cooling adiabatically in a vacuum, a hot solution (line 22) is

introduced into a vacuum, where the solvent flashes or evaporates and the solution is
cooling adiabatically. This method to produce supersaturation is the most important
Solubility in water
(g urea/100g solution)
one for large-scale production (200,000 MT/annum urea) (Geankoplis, 1993).
120
100
80
60
40
20
0
0
20
40
60
80
100
120
140
Temperature ( C)
Source: Encyclopedia of Chemical Technology, vol. 21
Figure 2.2: Solubility of Urea in Water

2.3.3
Operating Conditions Summary

25
26
Equipment
5
R-4
C-2 26
M-1
X-3
6
C-18
Operating Condition
M-11
C-18 Synthesis Reactor, R-4
Urea
Objective: To convert NH3 and14CO2 to urea
Type
: Isothermal17reactor
Catalyst
: Nil
7
Temperature
: 190C
13
10
12
25
Pressure
: 175 bar
X-15
Reactor
Fraction
Conversion
: 75%
M-11
E-6
X-8
F-7
14
15
R-4
10
C-2
X-3
6
7
X-15
C-19
9
T-5
C-19
17
CO2 Stripping Column,
T-5
Objective: To strip off free NH3
13
12
Type
E-6
X-8 Feed F-7
Vapor Fraction 18
23
Stripping
Agent16
15
X-10Pressure
F-9 (T
Temperature,
7, P7)
T-5
(T9, P9)
11
(T10, P10)
18
(T11, P11)
M-12
Urea Purity 21
X-10
Urea Purification Column, T-13

19
24
Objective: To recover >99%
urea
F-14
20
19
20
X-17
22
X-17
22
T-13
T-13
F-9
: Partial condenser
: 0.0
: Gas CO2
: 170.00C, 175 bar
21
: 463.42C,
155 bar
: 188.38C, 151 bar
: 349.26C, 152 bar
F-14
: 38.635%
11
M-12
23
16
24
15
23
16
X-10
F-9
5
2- 20
18
T-5
11
21
Type
Feed Vapor Fraction
24
Temperature,
Pressure (T20, P20)
(T21, P21)
(T22, P22)
Reflux Ratio
Urea Purity
F-14
M-12
19
20
X-17
: Partial condenser; Total

reboiler
: 0.13854
: 150.00C, 5 bar
: 118.46C, 2 bar
: 228.88C, 3 bar
: 99.5%
22
T-13
Flash Drum
Objective: To recover ammonia to be recycled
F-7
Type
Stream In
Stream Out (Top, Bottom)
Temperature, Pressure (T13, P13)
(T14, P14)
(T15, P15)
: Adiabatic
: 13
: 14, 15
: 100.00C, 12 bar
: 95.89C, 10 bar
: 95.89C, 10 bar
F-9
Type
Stream In
(T17, P17)
(T18, P18)
: Adiabatic
: 16
: 17, 18
: 145.00C, 10 bar
: 126.43C, 5 bar
: 126.43C, 5 bar
F-14
Type
Stream In
(T23, P23)
(T24, P24)
: Isothermal
: 21
: 23, 24
: 118.49C, 2 bar
: 94.00C, 1 bar
: 94.00C, 1 bar
Mixer
Objective: To mix 2 or more similar streams to form a
homogenous phase stream
M-1
Stream In
Stream Out
(T3, P3)
(T26, P26)
: 2, 26
:3
: 594.98C, 50 bar
: 596.25C, 50 bar
: 596.53C, 50 bar
M-11
Stream In
Stream Out
(T17, P17)
(T23, P23)
(T25, P25)
M-12
: 14, 17, 23
: 25
: 95.89C, 10 bar
: 126.43C, 5 bar
: 94.00C, 1 bar
: 87.52C, 1 bar
Stream In
Stream Out
(T18, P18)
(T19, P19)
2- 21
: 11, 18
: 19
: 349.26C, 152 bar
: 126.43C, 5 bar
: 191.33C, 5 bar
Compressor
Objective: (i) To increase the stream pressure
(ii) To pump the feed into the following unit
operation
C-2
Stream In
Stream Out
(T4, P4)
:3
:4
: 596.25C, 50 bar
: 822.45C, 175 bar
C-16
Stream In
Stream Out
(T2, P2)
:1
:2
: 30.00C, 1 bar
: 594.98C, 50 bar
C-18
Stream In
Stream Out
(T26, P26)
: 25
: 26
: 87.52C, 1 bar
: 596.53C, 50 bar
C-19
Stream In
Stream Out
(T26, P26)
:8
:9
: 30C, 5 bar
: 463.42C, 15.5 bar
C-21
Stream In
Stream Out
(T28, P28)
: 17
: 28
: 126.43C, 5 bar
: 218C, 10 bar
C-22
Stream In
Stream Out
(T29, P29)
: 23
: 29
: 94C, 1 bar
: 469.49C, 10 bar
Expander, E-6
Objective: To decrease the stream pressure
25
M-11
C-18
2- 22
14
17
Valve, V-7
R-4
10
13
12
X-8
7
E-6
Stream In
Stream Out
Temperature,
Pressure (T10, P10)
F-7
(T12, P12)
15
X-10
Heat Exchanger
X-15
9
T-5
X-1
11
16
: 10
: 12
: 188.38C, 151 bar
: 68.02C, 12 bar
23
F-9
Objective: To increase/decrease stream temperature

X-3
X-8
Decrease
temperature
Increase temperature
218
Stream In
:4
Stream In
: 12
Stream Out
:5
Stream Out
: 13
Temperature In : 822.45C
21
Temperature Out: 190.00C
Temperature Out: 100C
X-10
X-15
Increase temperature
Decrease temperature
F-14
Stream
In
:
15
Stream
In
:6
M-12
24 Out
Stream Out
: 16
Stream
:7
Temperature
Out:
145.00C
19
X-17
X-20
20
Decreased temperature
Decreased temperature
Stream In
: 19
Stream In
: 22
Stream Out
: 20
Stream Out
: 27
X-17
Temperature In22 : 191.33C
T-13
2.4
MASS AND ENERGY BALANCES
2.4.1
Introduction
This plant is designed to produce 200,000 metric ton per annum of urea. In
order to evaluate the conceptual flowsheet presented in the previous section, we need
to consider the detailed of mass and energy balances. This precedes the later tasks of
plant equipment sizing and economic evaluation. Using DESIGN II version 8.35
simulator has carried out the mass balance for this plant.
Mass balance is the basic of process design where the quantities of raw
material required and products produced can be determined. Also, the purpose of
developing the mass balance is to establish energy balances and opportunities for
heat integration. The design of a new process is not complete until it is established
that the inputs and outputs of the entire process and each individual unit satisfy
2- 23
balance equations applied to each process material. All the manual calculations
obtained are compared with the simulation results. A balance on a material in a
system (a single process unit, a collection of units, or an entire process) may be
written in the following general way (Rousseau, 1986):
Input
+
(enters
through
system
boundaries)
Generation - Output (leaves

(produced
through
within system)
system
boundaries)
Consumption = accumulation
(buildup
(consumed
within system)
within system)
In both manual calculation and simulation, some important assumptions are

made:
1.
The basis of the design is based on 200,000 metric ton per annum
urea production.
2.
The plant operates at 315 days per year with 24 hours a day.
3.
The system is steady state.
4.
The composition of the reactants used and the specification of the

urea product are based on what available in the market.
It is very important to know the vapor pressure and volatility for each single
component present in each stream during mass balance calculation. It is a common to
calculate vapor pressure from Antoine equation. Besides, other equations for each
particular component can also be used to predict the vapor pressure for all range of
temperatures, such as below:
Urea
*
: ln P (kPa) C1
C2
C4 ln T C5T C 6
T C3
(2.1)
where, T in Kelvin
Ammonia
P * (kPa) Pc 10 C5 * Tr 1 / Tr
(2.2)
Carbon Dioxide
: P ( kPa) Pc 10
*
C5 * Tr 1 / Tr
(2.3)
Water
C2
C
*
C 3 ln T C 4 ln T 5
: P ( Pa) exp C1
T
where, T in Kelvin; Tmin= 273.15K.
(2.4)
2- 24
The equation constants are shown in the table below:

Table 2.2: The Equation Constant
Component
C1
C2
C3
NH2CONH2* 2.13316e+1 -1.05011e+4
0
#
NH3
0
1.5714
0.48316
CO2#
0
1.732
0.56907
**
H2O
73.649
-7258.2
-7.3037
C4
9.7941e-2
0
0
4.17e-06
C5
C6
6.34741e-9 2.0
2.9562
0
3.3097
0
2.0
0
Sources:
* HYSIS Component Library Databank
** Chemical Engineering Volume 6
# DESIGN II Component Library Databank
In evaluating energy balances, we assume ideal properties for all of the

process streams. Moreover, we neglect kinetic and potential energies and consider
only enthalpy changes. The standard reference state for enthalpy, where H=0, are
set to be T=298 K and P =1 atm. And finally, for these preliminary calculations, we
assume no H of mixing or pressure effect on H (Biegler et al., 1997).
To calculate enthalpies of vapor phase mixtures, the general formula we use
is:
T2
H v (T , y ) H f H T k y k H f ,k (T1 ) y k C p , k (T )dT
k
T1
where H f , k (T1 ) is the heat of formation for component k at T1 and

temperature dependent heat capacities for the component k are represented by
C p , k (T ) ; whereas the enthalpies for liquid mixtures can be estimated by:
H L (T , x) H f H T k xk H f , k
k
C p , k ( ) d H vap
(T )
(2.6)
k
where H vap is heat of vaporization of specific component.
(2.5)
2- 25
k
k
H vap
(T ) H vap
(Tb ) Tck T / Tck Tb
(2.7)
The essential parameter used to calculate the enthalpies in both streams is

heat capacities, C p , k (J/mole.K) at specific temperature, as below:
T2
T1
C p ,k (T ) dT Ak (T T )
Bk (T 2 T ) C k (T 3 T ) Dk (T 4 T )
2
3
4
(2.8)
The enthalpy constants are tabulated as followed:

Table 2.3: Enthalpy Constant
Comp
Ak
Bk
Ck
Dk
Urea#
NH3*
CO2*
H2O*
0.287231
27.313
19.795
32.243
3.8597e-3
2.383e-2
7.343e-2
1.923e-3
1.3e-6
1.707e-5
5.601e-5
1.055e-5
-1.184e-8
1.715e-8
-3.596e-9
Hf
(kJ/mol)
-2.4559e+5
-45.72
-393.77
-242.00
Hv
(J/mol)
54574.57
23362
17166
40683
Tkc
(K)
705
405.6
304.2
647.3
Sources:
# HYSIS Component Library Databank
* Chemical Engineering Volume 6
2.4.2
Pre Calculation
Urea production
200,000 MT 1000kg
1 yr
1day
1kmol
yr
1MT
315day 24hr 60.06kg
= 440.4766kmol urea solution/hr

The detail manual mass and energy calculation are included in
Appendix Chapter 2.
Tkb
(K)
465
239.65
194.65
373.15
2- 26
Table 2.4: Manual Calculation Stream Summary
S1
S2
NH3
881.07
881.07
CO2
0.00
Urea
S3
S4
S5
S6
S7
S8
S9
S10
S11
2055.56 2055.56 2055.56 1174.59 1174.59
0.00
0.00
1172.77
1.83
1172.77 1172.77 1164.21
8.561
0.00
587.29
587.29
587.29
146.82
146.82
441.1
441.1
500.99
87.00
500.99
500.99
500.243
0.751
0.00
0.00
2.94
2.94
2.94
443.41
443.41
0.00
0.00
1.02
442.40
1.0162
1.02
3.44E-5
1.016
Water
0.00
0.00
293.65
293.65
293.65
734.12
734.12
0.00
0.00
205.06
532.00
205.06
205.06
138.05
67.01
Total
881.07
881.07
2939.44 2939.44 2939.44 2498.94 2498.94
441.1
441.1
S16
S17
S18
S19
S20
S21
S22
S23
S24
1879.84 1063.23 1879.84 1879.84 1802.51

S28
S29
S25
S26
S27
77.34
S30
S31
NH3
8.56
7.36
1.20
3.03
3.03
3.31
0.00
2.92
0.11
1174.50 1174.50
CO2
0.75
0.72
0.03
87.02
87.02
87.02
8.70E-11
86.37
0.65
587.34
Urea
1.02
9.69E-6
1.02
443.41
443.41
0.00
Water
67.01
8.99
58.02
590.03
590.03
589.19
0.84
149.95
Total
77.34
17.07
60.26
1123.49 1123.49
679.51
444.25
239.24
443.41 1.71E-24 4.43E-19
S12
0.00
587.34 8.70E-11
S13
S14
S15
7.36
2.92
0.00
0.00
0.72
86.37
0.00
8.70E-11
9.69E-6 1.71E-24 443.41
0.00
2.94
2.94
443.41
439.24
293.65
293.65
0.84
8.99
149.95
0.00
0.84
440.00
2058.42 2058.42
444.25
17.07
239.24
443.41
0.84
2- 27
Table 2.5: Comparison of Molar Flow Rate Between Manual and Simulation
Results
Stream
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
S31
*
Manual
881.065
881.065
2939.44
2939.44
2939.44
2498.941
2498.941
441.10
441.10
1879.840
1063.227
1879.840
1879.840
1802.507
77.335
77.335
17.0728
60.2636
1123.491
1123.491
679.512
444.253
239.240
440.002
2058.423
2058.423
444.253
17.0728
239.240
443.41
0.84
Simulation
888.00
888.00
2966.95
2966.95
2966.95
2526.456
2526.456
440.50
440.50
1879.852
1087.096
1879.852
1879.852
1802.151
77.6996
77.6996
17.4061
60.2929
1147.390
1147.390
704.6808
442.709
263.682
440.998
2083.239
2083.239
442.709
17.4061
263.682
-*
-
Error (%)
0.7810
0.7810
0.9273
0.9273
0.9273
1.0891
1.0891
-0.1362
-0.1362
0.0007
2.1956
0.0007
0.0007
-0.0198
0.4692
0.4692
1.9153
0.0487
2.0829
2.0829
3.5717
-0.3487
9.2696
0.2260
1.1912
1.1912
-0.3487
1.9153
9.2696
-
Note: Since there is lack of solid handling in DESIGN II version 8.35

simulator, the urea crystallization section of the urea production
process will only be calculated manually.
2- 28
2.5 INDIVIDUAL EQUIPMENT OPTIMIZATION

2.5.1
Introduction To Optimization
At a practical level, the term optimization is defined as follows:
Given a system or process, find the best solution to this process
within constraints.
The process of optimization is carried out to determine the optimum operating
condition and physical design that could achieve best process performance of each unit
operation without compromising all the constraints that are predetermined. The reason
for optimization is reduced capital cost and operating cost without violating the
constraints that are predetermined.
Firstly, we need objective function that serves as a quantitative indicator of
goodness of particular solution so that we can quantify the best solution. Capital and
operating cost, product yield and overall profit are the most typical process design
objectives.
According to Biegler (1997), the values of objective function are determine by
manipulation of the problem variables which can physically represent equipment sizes
and operating conditions such as pressure, temperature and feed flow rates.
Finally, the limits of process operation, product purity, validity of the model,
and relationships among the problem variables need to be considered as constraints in
the process. Similarly, the variable values must be adjusted to satisfy these constraints.
Robin Smith in his book, Chemical Process Design, has cited two forms of
optimization employed in chemical process design. Structural Optimization, the first
form that represent a model of our process structure is simulated and evaluated all over
again so as to compare with previous data. Alternatively, each structure can be subjected
to parameter optimization by changing operating conditions within that structure.

2.5.2
2- 29
Parameter Optimization For Individual Equipment

After designing the process flow diagram, the next important task of a designer is
to seek optimum solution to a design problem. The task of formally optimizing the
design of a complex processing plant involving several hundred variables. The main
objective of this chapter has been the optimization of the individual equipment of the
integrated urea plant to produce 200,000 MT / annum of urea. But the task can be
divided into more manageable units, identifying the key variables and concentrating
work where the effort involved will give the greatest benefit. In this case, we planned to
optimize the reactant recovery separator (flash separator), urea purification distillation
column and carbon dioxide-stripper.
In this preliminary optimization, the best solution usually results in economic or
technical incentives. Examples of economic incentives are maximum profit and
maximum costs, whereas technical incentives are increased yield and reactor conversion.
Individual equipment optimization usually has been limited to parameter optimizations
of individual (stand-alone) equipment only, which mean that the equipment to be
optimized is firstly disconnected from other plant structure. Next, we set an objective
function and the objective function is evaluated through altering the operating conditions
of the specific equipment.
Basically, optimization of urea process involves its economic performance and
trade-off. Target for optimization is to maximize the profit and minimize wastes bounded
by the constraints of operation feasibilities. But, as a balancing between engineering and
business world, it is unpractical to achieve a product purity of 100% at skyrocketing
costs, when the customer could do with a product purity of 99%. Trade-off between
operating and capital cost also an important factor in plant optimization. For example, in
order to increase the purity or higher recovery of reactant ammonia in stripper, we could
very well increase the number of trays in the stripper column. However, we should never
forget that we have to pay more for capital investment and operating cost. So, achieving
a trade-off between the question how many trays and their costs?
2- 30
In order to obtain the optimum operating parameter for the plant, an optimization
has been done on the following equipment, using simulator Design II version 8.35.
(1)
Flash Separator, F-14
(2)
CO2 Stripper Column, T-5
(3)
Urea Purification Column, T-13
We concentrating on the last flash separator (F-14) among the three flash
separators because the two previous separators (F-7 and F-9) are mainly use to moderate
the pressure drop and prevent tremendous pressure decrease. Product losses, top and
bottom products purity not so being concern in this two separators compare to F-14. By
the way, we have left out the optimization of the reactors. The reason has been the
absence and lacking of information, especially the reaction rate constant for the
reactions. The conversion that we have set in simulator is fix and cannot be vary.
The procedure of doing the optimization is by varying the selected parameters
of the equipment and observing the output value given by simulator.
2.5.3
Flash Separator (Ammonia Recovery), F-14 Optimization

The objective of this flash drum is to achieve highest recovery of the unreacted
ammonia and carbon dioxide from water and trace of urea after two reactants recovery
section. It also ensures high purity water discharge, which contains low percentage of
ammonia. The purposes of optimization are:
To reduce duty of flash column.
To increase the reactant recovery.
To reduce the products losses.

Among the few design and operating parameters for optimise the flash operating
efficiency, flash temperature and pressure has been chosen as two main optimization
parameters.
2- 31
2.5.3.1 Effect Of the Operating Pressure

In this part of optimization, ranges of pressure have been used at constant
temperature of 94oC. The Design II simulation results are shown in Table 2.6 below.
Table 2.6: The Effects of The Operating Pressure on Urea Losses and
Ammonia, Carbon Dioxide Recovery
Pressure
1.0
1.5
2.0
2.5
3.0
Duty (-kJ/hr)
x E-07
1.9036E+07
2.4770E+07
1.9036E+07
2.6302E+07
2.6550E+07
NH3 Recovery CO2 Recovery

0.865
0.9997
0.602
0.9985
0.865
0.9997
0.369
0.9961
0.3091
0.9949
Urea loss (kgmole/hr)

X E+02
0.342
0.3531
0.342
0.3553
0.3556
3.0000E+07
1.2
2.5000E+07
2.0000E+07
0.8
1.5000E+07
0.6
1.0000E+07
0.4
Reactant Recover Fraction
Duty (-kJ/hr)
Effect Of Operating Pressure On Reactant Recovery , Product

Losses & Flash Duty
Duty (-kJ/hr) x E-07

NH3 Recovery
CO2 Recovery
Urea loss (KGMOLE/HR) X E+02
5.0000E+06
0.2
0.0000E+00
0.5
1.0
1.5
2.0
Pressure (bar)
2.5
3.0
3.5
Figure 2.3: Duty of Flash and Fraction Vs Pressure

From the graph above, it is obvious that flash-operating pressure has a significant
effect on the ammonia recovery. For pressure higher than 2 bars, ammonia recovery
2- 32
fraction starts reducing. As the pressure increases, the relative volatility may be will
decrease, hence will lower the flash separation efficiency in term of ammonia recovery.
After the point at 2 bar, the flash duty also increases rapidly.
As a conclusion, we observe that the flash reaches its optimum point at pressure
= 2 bar which achieve minimize duty and high recovery fraction.
The operating pressure does not make a significant change on the carbon dioxide
recover and urea losses.
2.5.3.2 Effect Of Operating Temperature

By varying the operating temperature of flash drum at constant pressure of 2 bar,
the effect on flash duty, reactant recovery and product losses has been obtained. Table
2.7 and Figure 2.4 Show the simulated result for this optimization.
Table 2.7: The Effect of Operating Temperature on Flash Duty, Reactant Recovery
and Product Losses
0.8
2.0000E+07
0.6
1.5000E+07
0.4
1.0000E+07
NH3 Recovery
CO2 Recovery
0.2
5.0000E+06
Duty (-kJ/hr)
0
0.0000E+00
80
85
90
95
100
Tem perature (oC)
105
110
118
Duty (-kJ/hr)
Fraction
Temperature
Urea loss (kgmole/hr)
(oC)
Duty (-kJ/hr) NH3 Recovery CO2 Recovery
80
2.7451E+07
0.2934
0.997
0.003559
85
2.6963E+07
0.3450
0.9965
0.003556
90
2.6393E+07
0.4040
0.997
0.003552
95
2.5695E+07
0.4129
0.9974
0.003545
Effect Of Operating Temperature On Reactant Recover, Duty And Product
100
2.4779E+07
0.5532
0.9979
0.003534
Losses
1.2
3.0000E+07
105
2.3443E+07
0.6470
0.9984
0.003514
110
2.1133E+07
0.7590
0.999
0.00347
1
2.5000E+07
118
4.5307E+06
0.9820
0.9999
0.002296
2- 33
Figure 2.4: Effect of Operating Temperature on Reactant Recovery and Flash Duty
Urea Losses (kgmole/hr)

x E+02
Effect Of Operating Temperature On Urea Losses

0.004
0.0035
0.003
0.0025
0.002
0.0015
0.001
0.0005
0
Urea loss (KGMOLE/HR) X E+02
80
85
90
95
100
105
110
118
Temperature (oC)
Figure 2.5: Effect of Operating Temperature on Product Losses

From the graph shown above, with the increasing of operating temperature until
about the same with feed temperature at 118oC, the ammonia recovery is the highest and
at this point also given minimum urea losses. Besides, condenser duty also decreases in
this case. So, we can know that the optimum operating temperature is nearly about the
feed temperature.

2.5.4
2- 34
Distillation Column Optimization

Optimization of distillation can be practice based on many parameters,
such as pressure, temperature, reflux ratio, number of tray and location of feed.
For example, as the pressure in distillation column raised, will cause:
Relative volatility decreases effect the degree of separation, hence more number of
plates are required.
Condenser and reboiler duty decrease due to reduction in latent heat of vaporization.
Higher vapour density given smaller column diameter.
Reboiler temperature increases with a limit often set by thermal decomposition of

the material being vaporised, causing excessive fouling.
Increase in condenser temperature.

As the pressure is lowered, the effects will obviously reverse. The lower limit is
often set by desire to avoid vacuum operation and refrigerant in condenser. Both
conditions involve capital and operating cost penalties and increase the complexity of
the design.
Column optimization can be done also by varying the reflux ratio. There is a
capital energy trade-off for a stand-alone column. As the reflux ratio increase from it
minimum value, the capital cost will decrease initially as the number of tray reduced.
But, the utility costs increase as reboiling and condensation required. Generally, the
operating cost is indicated by the condenser and reboiler duty. Capital cost is showed by
the size of distillation column (size and number of trays). In order to minimize the
capital cost within operating specification, minimum columns diameter and minimum
number of tray should be used. With the help of Design-II simulator, the optimization
seems to be achieved.
2.5.4.1 Urea Purification Column, T-17 Optimization
The main purpose of this column is to concentrate the urea solution to become
urea melt and so purify the urea produced. Optimization of this column mainly to
2- 35
minimum the reboiler and condenser duty by varying different process variables like
pressure, number of tray, and location of feed, reflux ratio and temperature. The
operating costs will decreases when the reboiler and condenser duty reduce.
Optimized
parameter
Minimum number
of tray
Reflux ratio
Consequence
1. Reduce condenser
and reboiler duty
2. Reduce column
height (h)
1. Depend on feed
composition and
vapor fraction
Pressure
1. Optimum pressure
giving a best
separation
Temperature
1. Optimum
temperature giving
a best separation
Location Of Feed
1. Depend on the
vapor fraction of
feed
Gain
Loss
1. Use less energy 1. Unable to

2. Reduce cost of
achieve
column
product
specification
1. Reduce usage
of energy
2. Increase
product purity
3. Operating cost
will be
minimize
1. Reduce energy
needed
2. Give a easy
separation
1. Reduce energy
needed
2. Give a easy
separation
1. Minimize
reboiler and
condenser duty.
2.5.4.2 Effect Of The Reflux Ratio

Figure 2.6 and Table 2.8 shows the optimization results condenser and reboiler
duty within a range of reflux ratio. For this case, temperature, location of feed and
pressure become control variables to achieve the objective function minimizing the
condenser and reboiler duty, hence reduce operating costs.
2- 36
Table 2.8: Effect of Reflux Ratio on Condenser and Reboiler Duty

Reflux Ratio Condenser Duty (-kJ/hr) x E-07 Reboiler Duty (kJ/hr) x E-07
2.0
5.807
8.313
2.5
7.259
9.765
3.0
8.700
11.22
3.5
10.16
12.67
4.0
11.61
14.12
4.5
13.07
15.57
5.0
14.52
17.02
5.5
15.97
18.47
18
20
16
18
14
16
14
12
12
10
10
Condenser Duty (-kJ/hr) x E-07
6
4
Reboiler Duty (kJ/hr) x E-07
Condenser Duty (-kJ/hr) x E07
Effect of Reflux Ratio On Reboiler & Condenser Duty
0
1
10
Reflux Ratio
Figure 2.6: Effect of Reflux Ratio on Reboiler and Condenser Duty

As showed above, as reflux ratio is decreased, heat duty is also decreased, thus
minimise operating cost. The minimum reflux ratio is around 0.5. Energy consumption
will be decreased if the heat duty is decreased. From the same graph, reboiler duty
increases linearly with condenser duty. In order to minimise the total consumption of
energy, other parameter such as number of tray should be included together in order to
get the optimum condition for the operation.
This will give the reduction in total consumption of energy thus decrease the
operating cost. Low reflux ratio will increase the number of tray need for separation. The
optimum reflux ratio occurs at the point where the sum of fixed charges and operating
2- 37
cost is minimum, which is approximate 0.5. As a rough approximation, the optimum

reflux ratio falls in the range 1.1 1.3 times reflux minimum. (Max S. Peters, Kalus D.
Timmerhaus, Plant Design And Economics For Chemical Engineers, 3rd Edition).
2.5.4.3 Effect Of The Number Of Tray
During optimization using simulator, ranges of number of tray have been with
constant pressure, temperature and fixed feed tray. The purity of urea have been set at
99.5%. The result stated below in Table 2.9 and also Figure 2.7 and 2.8.
Table 2.9: Effect of Number of Tray on Reflux Ratio, Column Diameter, Reboiler
and Condenser
Condenser Duty
(-kJ/hr) x E-07
40.65
34.84
29.03
23.23
17.42
Tray Num Reflux Ratio Diameter (m)

6
6
5.790
7
8
5.392
8
10
4.961
9
12
4.487
10
14
3.955
Reboiler Duty (kJ/hr)

x E-07
43.15
37.35
31.54
25.73
19.93
1.2682
1.4
1.268
1.2
1
0.8
1.2678
1.2676
0.6
0.4
1.2674
1.2672
1.267
0.2
0
1.2668
4
4.5
5.5
6.5
7.5
8.5
Num ber of Tray
Figure 2.7: Effect of Number of Tray on Reboiler and Condenser
Duty (kJ/hr) x E-07
Urea Losses
(kgm ole/hr) x E+02
Effect Number of Tray On Reboiler & Condenser Duty
2- 38
Diameter
Reflux
Diameter (m)
Reflux
Effect of the number of tray on the reflux ratio and column diameter
0
7
10
Number of tray
Figure 2.8: Effect of The Number of Tray on The Reflux Ratio and Column Diameter
From Figure 2.7, we have seen that as the number of tray increase, the condenser
duty becomes smaller but not much significant effect on reboiler duty. At this point, the
condenser and reboiler duty is minimized and minimum losses of desired urea
production capacity obtained. These will reduce the operating cost. To ensure the
optimum point affected by the number of tray, we observe also the changes of column
diameter and reflux ratio. The results are shown in Figure 2.8. As the number of tray
increases, reflux ratio and diameter also increase but in different rate, thus increase the
capital costs. These shows inverse effect if compare to the reboiler and condenser duty.
If combining two graphs, we found that the optimum point around 7-8 number of tray to
balance the trade-off between capital and operating costs.
2- 39
2.5.4.4 Effect Of Operating Pressure

At constant reflux ratio, temperature, feed location and purity at 99.5%.
Optimization has been done within a range of column operating pressure from 1.5 bar to
9.5 bar. Changes profile of column diameter, reboiler and condenser duty has been
observed as stated below.
Table 2.10: Effect of Operating Pressure on Column Diameter, Reboiler and
Condenser Duty
Pressure
(bar)
1.5
2.5
3.5
4.5
5.5
6.5
7.5
8.5
9.5
Condenser Duty (-kJ/hr) Reboiler Duty (kJ/hr)

x E-07
x E-07
10.42
12.76
10.16
12.67
9.991
12.62
9.857
12.58
9.744
12.61
9.645
12.69
9.556
12.72
9.476
12.73
9.401
12.74
Diameter
(m)
3.369
3.161
3.032
2.941
2.880
2.838
2.801
2.771
2.744
12.8
12
12.75
10
12.7
Reboiler Duty (kJ /hr) x E-07
12.65
Condenser Duty (-kJ /hr) x

E-07
Diameter
12.6
12.55
8
6
4
Diameter (m)
Duty (kJ/hr)xE-07
Effect of Operating Pressure On Reboiler , Condenser Duty &

Column Diameter
12.5
12.45
0
1.5
2.5
3.5
4.5
5.5
6.5
7.5
8.5
9.5
Pressure (bar)
Figure 2.9: Effect of Operating Pressure on Column Diameter, Reboiler and

Condenser Duty
2- 40
The optimum operating pressure around 4.5 bar. The higher value of pressure
will make the condenser duty to increase. Optimum operating pressure will ensure the
operating costs minimized and balancing the capital costs with the reasonable column
diameter. It is unwise to operate the column at too high pressure because the pump work
will be increase too.
2.5.4.5 Effect Of Operating Temperature
Table 2.11 and Figure 2.10 represent the results in optimising the operating
temperature and its effect on product losses, reboiler and condenser duty.
Table 2.11: Effect Of Operating Temperature On Product Losses, Reboiler and
Condenser Duty
Temperature
(oC)
100
125
150
175
200
Condenser Duty
(-kJ/hr) x E-07
10.16
10.16
10.16
10.16
10.16
Reboiler Duty (kJ/hr)

x E-07
13.66
13.28
12.67
11.08
9.43
Product Loss
(kgmole/hr) x E+02
3.131
3.242
3.592
6.629
16.363
10.2
10.18
18
10.16
10.14
14
16
12
10.12
10.1
10.08
10
Product Loss (kgmole/hr) x E+02
10.06
10.04
10.02
10
Duty (kJ/hr)x E-07
Losses (kgmole/hr)
xE+02
Effect of operating Temperature On Reboiler & Condenser Duty
0
100
125
150
175
200
Temperature ( C)
Figure 2.10: Effect of Operating Temperature on Product Losses, Reboiler and

Condenser Duty
2- 41
As the operating temperature increases, the product losses increase while the
reboiler duty decreases. The optimum operating temperature is about 150C. Although
after this optimum point, the operating costs will minimized due to tremendous reduce in
reboiler duty. But, in other way, maximum product loss is occurred.
2.5.4.6 Effect Of Feed Tray Location

Normally, location of feed tray also to get the maximum product purity. In this
optimization, different location of feed tray have been tried and stated in the figure and
table below.
Table 2.12: Effect of Feed Tray Location Product Purity, Reboiler and Condenser
Duty
Feed
Tray
2
3
4
5
6

10.18
10.17
10.17
10.17
10.17
Condenser Duty (-kJ/hr) x

E-07
12.690
12.69
12.68
12.68
12.68
Product Purity (%)

99.62
99.65
99.66
99.66
99.66
Effect of Feed Tray On Product Purity, Reboiler & Condenser Duty
Duty (kJ/hr)
12.5
99.68
12
99.66
11.5
11
99.64
99.62
Product Purity
10.5
10
99.6
2
4
Feed Tray
Figure 2.11: Effect of Feed Tray Location Product Purity, Reboiler and
Condenser Duty
Product Purity
99.7
13
2- 42
Feed tray location has the negligible effect on the heat duty, but strong effect
observed on the final product purity. The suitable feed tray location will ensure the
higher quality of final product and produces high-grade urea. Start from tray 4, the
product purity achieves 99.66%.
2.5.5
CO2 Stripping Column, T-5 Optimization

The main objective of this stripping column is to strip out the unreacted ammonia
from reactor product stream which containing mixture of urea, water, ammonia and
carbon dioxide. The vapor stream from stripper recycles back to reactor to improve the
product yield. Thus, the major concern in this stripper optimization is to determine
various optimum points for several parameters to obtain highest ammonia recovery with
minimum capital costs such as reduce column diameter.
However, we have tested on several problem variables number of tray, stripping
agent flow rate, operating pressure and temperature in this optimization process. But, we
found that most of these variables do not have significant impact on the certain variables
like urea product losses. Besides, constraint of the parameters changes also occurred
because convergence for this column only limited in small variables change.
2.5.5.1 Effect Of The Number Of Tray
Table 2.13: Effect of The Number of Tray on The Urea Purity
Figure 2.12:
Tray Number
3
4
5
6
7
8
9
10
of Tray on The Urea Purity
Product Purity
0.370
0.395
0.4113
0.422
0.429
0.436
0.380
0.380
Effect of The Number
2- 43
Because of the simulator convergence factor, the variation on the column tray
number only shows significant impact on the bottom urea purity. Because this product
stream not the final product stream, the urea content is not require present in high purity.
At constant operating temperature and stripping agent flow, the product purity reaches
its optimum point at tray number 8 as shown in Figure 2.12.
2.5.5.2 Effect On Stripping Agent Flow
Stripping agent, CO2 in gases phase is needed to strip out the ammonia from the
liquid phase inlet. Hence, the flow rates of stripping agent play an important role in
determining the ammonia recovery and the design parameter of this stripper such as
diameter.
Table 2.14: Effect of The CO2 Flow Rate on The Ammonia Recovery and Column
Diameter
Carbon Dioxide Flow Rate
(kgmole/hr)
439.0
439.5
440.5
441.0
441.5
Ammonia Recovery Diameter (m)

0.9914
1.622
0.9913
1.629
0.9914
1.622
0.9915
1.625
0.9916
1.672
2- 44
Effect Of Stripping Agent Flow Rate On Ammonia Recovery And Column

Diameter
0.99165
Ammonia Recovery
Fraction
1.67
1.66
Diameter (m)
0.9916
Ammonia Recovery
0.99155
0.9915
1.65
0.99145
1.64
0.9914
1.63
0.99135
1.62
0.9913
1.61
438.5
Diameter (m)
1.68
0.99125
439.0
439.5
440.0
440.5
441.0
441.5
442.0
CO2 Flow Rate (kgmole/hr)
Figure 2.13: Effect of The CO2 Flow Rate on The Ammonia Recovery
and Column Diameter
In order to get the high ammonia recovery fraction with reasonable column
diameter and so capital costs, from the graph above, we found that the optimum CO2
flow is around 440.0 441.5 kgmole / hr. The optimization is doing at constant pressure,
temperature and number of tray.
2.5.5.3 Effect Of The Operating Temperature

Ranges of operating temperature have been used with constant pressure, CO2
flow and number of stages in this optimization. The simulation results are shown below.
Table 2.15: Effect of The Operating Temperature on The Ammonia
Recovery and Column Diameter
Temperature
(oC)
350
440
460
480
500
Ammonia
Recovery
Fraction
0.9915
0.9916
0.9914
0.9916
0.9913
Diameter (m)
1.671
1.672
1.675
1.674
1.679
2- 45
1.68
1.679
1.678
1.677
1.676
1.675
1.674
1.673
1.672
1.671
1.67
0.99165
0.9916
0.99155
0.9915
Diameter
0.99145
Ammonia Recovery
0.9914
0.99135
Diameter (m)
Ammonia Recovery
Fraction
Effect Of Operating Temperature On Ammonia Recovery And

Diameter
0.9913
0.99125
350
370
390
410
430
450
470
490
Temperature ( C)
Figure 2.14: Effect of The Operating Temperature on The Ammonia

Recovery and Column Diameter
Optimum operating temperature located between 470 480C with the highest
ammonia recovery and not too large diameter. This ensures a reduction in capital costs.

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CHAPTER II

PROCESS MODELING AND FLOWSHEETING

Process Modeling & Flowsheeting

-1352. kj/hr (condenser)

NH3 & CO2 Recovery

Figure 2.1: Urea Production Process Flow Diagram

Process Modeling & Flowsheeting

Process Modeling & Flowsheeting

And the second step in the reaction is

NH2CONH2 (aq) + H2O (l)

In the first reaction, carbon dioxide and ammonia are converted to

Source: Encyclopedia of Chemical Technology, vol. 21

Process Modeling & Flowsheeting

From this information, therefore, it is advisable in industrial urea production

CO2 conversion yield

Urea processes differ mainly in the conditions (composition, temperature and

Process Modeling & Flowsheeting

2.2.2.1 CO2 Stripping Column, T-5

Process Modeling & Flowsheeting

Ammonia And Carbon Dioxide Recovery And Recycle

2.2.3.1 Flash Drum: F-7, F-9, and F-14

Process Modeling & Flowsheeting

The Mond Index

Process Modeling & Flowsheeting

exothermicity of this reaction, B = 1.8 x Hr where Hr is the heat of reaction in

Process Modeling & Flowsheeting

The expression is:

Aerial Explosion Index, A

Process Modeling & Flowsheeting

Corresponding descriptive categories are given below:

Overall Hazard Rating, R

Equivalent Dow Index, D

Process Modeling & Flowsheeting

2.2.5.1 Mond Index At Reactor

Total Special Process Hazards, S

Total Quantity Hazards, Q

Process Modeling & Flowsheeting

2.2.5.2 Mond Index At Distillation Column

Total Material Factor, B

Total General Process Hazards, P

High pressure, p and temperature

Total Special Process Hazards, S

Total Quantity Hazards, Q

Internal Explosion Index, E = 1 + (M + P + S)/100

Process Modeling & Flowsheeting

2.2.5.3 Mond Index At Stripper

Total Material Factor, B

Total Special Process Hazards, S

Total Quantity Hazards, Q

Process Modeling & Flowsheeting

2.2.5.4 Mond Index At Flash Drum

Total Material Factor, B

Total Special Process Hazards, S

Total Quantity Hazards, Q

Internal Explosion Index, E = 1 + (M + P + S)/100

Process Modeling & Flowsheeting

Process Modeling & Flowsheeting

Urea Synthesis Reactor

Process Modeling & Flowsheeting

urea. It consists of a cylindrical pipe and is normally operates at steady state.

Urea Melt Crystallizer

Process Modeling & Flowsheeting

In the method of cooling adiabatically in a vacuum, a hot solution (line 22) is

one for large-scale production (200,000 MT/annum urea) (Geankoplis, 1993).