CHAPTER II

PROCESS MODELING AND FLOWSHEETING

2.1 Process Description

Recirculation 18 D-13
19

13
11 12
F-10
9
X-8
F-7 E-9 14
3 4 5 6 7 8
1
2 Waste treatment
X-3 X-6 16
M-1 C-2 E-5 15
R-4 10 F-12
Ammonia synthesis
M-11 17 20
Storage
Ammonia purification X-14

Figure 2.1 : Flow Diagram for Ammonia Production Plant

Generally:
1. Feedstock of Nitrogen (99.99% purity) and Hydrogen (99.99% purity).
2. Nitrogen mixed with Hydrogen (ratio H2 to N2 3:1) in presence of promoted
iron as catalyst to produce Ammonia.
3. Reactor condition : Pressure ~ 170 atm, Temperature ~ 450°C
 4. Product obtains from separation system which is form by 3 flashes in order to
obtain above 99.95% purity.

The objective of this project is to design a plant produce 100,000 MT

Ammonia / year. After we consider all the six processes (Haber-Bosch, Modified
Haber-Bosch, Claude, Casale, Fauser and Mont Cenis) with its’ operating condition,
we choose Fauser Process with some modifications. Those modifications are:
1. The source of Hydrogen is supplied by supplier, not produced by Electrolytic
hydrogen from Fauser cells.
2. The source of Nitrogen is supplied by supplier, not obtain from liquid air
units or from a purification unit utilizing tail gases from absorption towers.
3. The condition in Ammonia Converter: ~ 170 °C and 450 atm.

The plant is basically consists of three major operating parts as follow:

1. Ammonia synthesis
2. Ammonia Purification
3. Recirculation

2.1.1 Ammonia synthesis

18
3 4 5 6 7
1
2
X-3 X
M-1 C-2 E-5
Ammonia synthesis R-4

Figure 2.2 : Ammonia Synthesis

This is the main stage of the process producing Ammonia. In this stage,
Hydrogen and Nitrogen are mixed thru ratio 3 to 1 for stoichiometry reaction,
compress to 172.74 atm, preheat to 450°C, and the reaction will be occurred in
reactor via Haber route:
N 2  3H 2  2 NH 3 ΔH298 = -46000 kJ/kmole

43
 Pressure in the reactor (also call Ammonia Converter) is around 170 atm and
temperature is set around 450°C. Promoted iron is used as a catalyst for this process.
Only 30% of Hydrogen is reacted per pass in the converter due to the unfavourable
equilibrium conditions. Because of this reaction is exothermic, temperature control is
required inside the reactor to maintain the optimum temperature of reaction.

2.1.2 Ammonia Purification

18 D-13
19

13

11 12
F-10
9
X-8
E-9
14
4 5 6 7 8
F-7
Waste treatm ent
X-3 X-6 16
C-2 E-5
R-4
15
10 F-12

M -11 17
20
Storage

Ammonia purification X-14

Figure 2.3 : Ammonia Purification

The products from the reactor contain Ammonia, unreacted Nitrogen and
unreacted Hydrogen. The product stream then expanded to 90 atm and cooled to
37°C. After that the stream is fed to the separation system which forms by 3 flashes.
The 1st flash (F-7) will separate most of the Nitrogen and Hydrogen to upper stream
(gas phase) and fed into the 2nd flash (F-10). The main function of 2nd flash is to
separate most of the Nitrogen and Hydrogen for recycle stream. Residual Nitrogen,
Hydrogen and Ammonia from flash 1 and flash 2 will feed to the 3rd flash (F-12).
The upper stream (gas phase) from the 3rd flash contain small amount of Ammonia,
Nitrogen and Hydrogen. Our product, Ammonia will obtain from the lower stream of
the 3rd flash.

44
2.1.3 Recirculation

Recirculation 18 D-13
19

13
11 12
F-10
9
X-8
F-7 E-9 14
3 4 5 6 7 8
1
2 Waste treatment
X-3 X-6 16
M-1 C-2 E-5 15
R-4 10 F-12
Figure 2.4 : Recirculation M-11
17 20
Storage
X-14
Recirculation or recycle is form by upper stream from flash 2 and mix with
fresh feeds before fed into compressor. Recycle stream contain large amount of
Nitrogen Hydrogen. A purge system is added between the 2nd flash and the recycle
stream in order to avoid accumulation of product in the plant of synthesis Ammonia.

45
46
2.2 Basis Equipment Selection

As shown in the flow diagram above, five types of equipment are used for the
production of Ammonia such as reactor, heat exchangers, compressors, expander and
flash. Each type of equipment consists of different categories. For example, stirred
tank reactor, tubular reactor, packed bed reactor and fluidised bed reactor are the
category for reactor. The selection of each unit operation is made based on their
advantage. The following discussion briefly carries out the objective and operation
condition of each unit.

2.2.1 Compressor

Function of compressor is to compress a gas phase stream to a specified

outlet pressure or to a pressure limited by a specified work available. In this plant,
one compressor has been used, it placed after the mixed stream of recycle and fresh
feed, and before the exchanger fed to reactor. This compressor compress stream inlet
from 59.97 atm to 172.74 atm. The stream temperature will increase from -22.28°C
to 114.31°C. Compressor C-2 is placed in front of exchanger in the flow diagram
because compress a stream to a certain pressure will automatically increase its
temperature.

Compressor can be divided into two major categories: continuous-flow

compressor (centrifugal compressor and axial flow compressor) and positive
displacement compressor (rotary compressor and reciprocating compressor). After
consider the advantages and disadvantages of each compressor, we have decided to
use centrifugal compressor. The reasons are:
1. It is the cheapest compare with the other types of compressor.
2. It can operate at a wide range of flow rates and pressures.
3. The flow is easier to control.
4. It offers a smooth flow.
5. It operates at low noise and need little maintenance.

47
2.2.2 Heat Exchanger

There are 4 exchangers in this plant, which 2 of them are used for cooling and
another 2 are used in order to heat the stream to desired temperature. Although by
increasing or reducing the pressure of the stream, the temperature of that stream will
also be slightly increase or decrease. However, it is not enough to achieve the desired
condition. So heat exchanger is used in hopes to control the temperature of the
streams.

There are many types of heat exchanger that can be used. Here, internal
floating head with clamp ring heat exchanger with one shell pass and 2 tubes passes
has been selected because they are suitable for high-temperature differentials.
Besides, it is easier to clean as the tubes can be rodded from end to end and the
bundle removed.

2.2.3 Reactor

For gas phase reaction, there are 3 type of reactor that can be used. There are
tubular plug-flow reactor, tubular packed-bed (also called a fixed-bed) reactor and
fluidized-bed reactor. In this plant, tubular packed-bed reactor has been chosen. The
reasons are:

1. It gives the highest conversion per weight of catalyst of any catalytic reactor.
2. Some modification has been done in order to control the temperature inside
the reactor.

Catalyst we used for this reaction is promoted iron. The catalyst is obtained
by reduction of iron oxide, often of a composition close to Fe 3O4, promoted with
various nonreducible oxides. The most important promoters are AL2O3, K2O, and
CaO.

48
2.2.4 Expander

Expander has the identical performance as valve but differ only in the phase
involves. Valve is dealing only with liquid phase while expander is only valid for gas
phase. The expander is needed to decrease the pressure of gas phase stream to certain
pressure that we need. Two expanders have been used in this plant. One of them
place after reactor to decrease the pressure from 172.68 atm to 90 atm. The second
expander used to expand the pressure for upper stream from 1st flash. The pressure is
decrease from 89.91 atm to 60 atm.

2.2.5 Flash

Flash can be considered as a simple and economic separation system because

it separate the components in the streams base on its liquid and vapor equilibrium.
Flash is not an ideal separation equipment, it can only separate by roughly and the
purity of the desired product always be low. But in our plant, Ammonia can be
obtained for flash system with purity 99.8%. There are 2 reasons:
1. The difference of boiling point between product (Ammonia) and raw
materials (Nitrogen and Hydrogen) is very large, it is easily to separate.
2. There are 3 flashes in the plant. 1st flash used to separate product (Ammonia)
and unreacted raw materials (Nitrogen and Hydrogen) with purity of
Ammonia in liquid stream 88.7%. Function of 2nd flash is separate the feed
stream so that the purge can be taken after the flash, where the concentration
of ammonia is the lowest and the inert concentration is highest, so less
product will be lost in the purge. The 3rd flash is used to increase the purity of
Ammonia to 99.8%.

2.3 Manual Material Balance

The procedure of doing manual material balance, for reactor can refer to
Elementary Principles of Chemical Processes, page 121-124 and for flash
calculation, the method can be refer to Systematic Methods of Chemical Process

49
Design, page 61-67. Some assumptions have been constructed to make the
calculation easier. The design-based assumptions are:
1. No leakage in the pipes and vessels in the system.
2. Catalyst used in reactor does not contribute in mass.
3. All the components in the system behave as ideal condition.
4. The total input of any substance to compressor, pump, valve, mixer or heat
exchanger is assumed equal to the total output of the substance where no
reaction occurs.
5. All calculations are done in kmole/hr.

Antoine constants of the materials that involve in calculation are tabulated in

the following table.
Table 2.1 : Antoine Constants of Materials

Antoine Constant
Item Formula M.W
A B C

Ammonia NH3 17.031 16.9481 2132.50 -32.98

Nitrogen N2 28.013 14.9542 588.72 -6.60
Hydrogen H2 2.016 13.6333 164.90 3.19
Methane CH4 16.043 15.2243 597.84 -7.16

2.3.1 Pre-calculation

In order to get the initial estimation of raw materials’ flowrates to be fed into
the reactors, an overall mass calculation involved recycled stream is performed.

Working days per year = 330 days

Working hours per day = 24 hours
Production requirement
= 100,000 Metric tone Ammonia per year
= 1 108 kg Ammonia per year
100,000 MT NH3 1000 kg 1 kmole 1 year 1 Day
=
year 1 MT 17.031 kg 330 Days 24 Hours

50
 = 741.3694 kmole/hr
= 742 kmole/hr
Detail of calculations are shown in Appendix B.1.

2.3.2 Summary of Mass Balance Calculation

Table 2.2 : Summary of Mass Balance Calculation

Component Flowrate (kmole/hr) Total Flowrate
Stream
NH3 N2 H2 (kmole/hr)
1 0.0000 403.7751 0.0000 403.7751
2 0.0000 0.0000 1185.5873 1185.5873
3 39.1053 1251.5000 3754.5002 5045.1055
4 39.1053 1251.5000 3754.5002 5045.1055
5 39.1053 1251.5000 3754.5002 5045.1055
6 790.0053 876.0500 2628.1501 4294.2055
7 790.0053 876.0500 2628.1501 4294.2055
8 790.0053 876.0500 2628.1501 4294.2055
9 79.0005 858.1349 2597.9460 3535.0814
10 711.0048 1.0881 0.7130 712.8059
11 79.0005 858.1349 2597.9460 3535.0814
12 79.0005 858.1349 2597.9460 3535.0814
13 39.5003 856.2878 2594.8615 3490.6496
14 39.5003 1.8471 3.0845 44.4319
15 750.5051 2.9352 3.7975 757.2378
16 7.5051 2.0401 2.9658 12.5110
17 743.0000 0.8951 0.8317 744.7268
18 39.1053 847.7249 2568.9129 3455.7431
19 0.3950 8.5629 25.9486 34.9065
20 743.0000 0.8951 0.8317 744.7268
= Product stream

2.4 Manual Energy Balance

In process design, energy balances are important to determine the energy

requirements of the process: the heating, cooling and power required. The procedure
for doing the manual energy balance can refer to Elementary Principles Of Chemical

51
Processes, page 312-315. The calculation is based the first law of thermodynamics
where kinetic energy differences, potential energy differences and work done on the
system by its surroundings are zero. So, the law become
Q = ΔH = ΣnoĤo - ΣniĤi
where reference conditions: the elements that constitute the reactants and products at
25ºC and the non-reactive molecular species at any convenient temperature.

Each enthalpy calculation is difference depends on the phase for that stream.
If the phase is in vapour form, specific enthalpy is calculated by

H v (T, y)  H f  H T   y k H f , k (T1 )   y k  Cp k (T)dT

T2

T1
k k

If the phase is in liquid form, the specific enthalpy can be calculated by using:
T
H L (T, x )   x k ( H f , k   Cp k ( )d  H kvap (T))
T0
k

Where:
(Tck  T ) 0.38
H kvap (T )  H kvap (Tb )[ ]
(Tck  Tb )
If the stream is in the liquid-vapour mixture form, the specific enthalpy can be
calculated by using Equation 2.5:
H(T, z )  H V (T, y)  (1  )H L (T, x )

Here, some assumptions have been made also. There are:

1. The process system is an open system.
2. Adiabatic process where no heat loss to the environment.
3. All the liquid and gas heat capacities are constant at certain temperature.
4. All the enthalpies calculated are taken at 25ºC at 1 atm as reference whereas for
non-reactive molecular species, the reference state is taken at any convenient
condition.
5. For component Hydrogen (H2) and Nitrogen (N2), heat of vaporization at
operating temperature is assumed 0 kJ/hr because Toperating > Tc.
6. Estimated η = 0.38 (for calculate heat of vaporization at Toperate.

52
 Heat capacities of the gas and liquid phase are the same for the entire
component and will be tabulated in the following table.

Table 2.3 : Heat Capacity Coefficients of Materials.

Cp Constant Hvap Hf

Comp. Tb (K) Tc (K)
A B C D (kJ/kmol) (kJ/kmol)
NH3 27.315 2.38E-2 1.71E-5 -1.18E-8 239.65 405.6 23.3620 -45900
N2 31.150 -1.36E-2 2.68E-5 -1.17E-8 63.25 126.2 5.5810 0
H2 27.143 9.27E-3 -1.38E-5 7.65E-9 20.35 33.2 0.9040 0

2.4.1 Summary of Energy Balance Calculation

Table 2.4 : Summary of Stream Energy Calculation

Temperature Pressure Enthalpy

Stream Phase
(°C) (atm) (kJ/hr)
1 Vapor 25.00 60.00 0
2 Vapor 25.00 60.00 0
3 Vapor -22.81 59.97 -9020872
4 Vapor 108.15 172.74 9965208.8
5 Vapor 450.00 172.71 60469833
6 Vapor 450.00 172.68 21198489
7 Vapor 372.22 90.00 10257827
8 Mixture -23.00 89.97 -42326673
9 Vapor -23.00 89.94 -8936896
10 Liquid -23.00 89.94 -33390030
11 Mixture -27.50 89.91 -9399058
12 Mixture -41.85 60.00 -10871850
13 Vapor -41.86 59.97 -8915427
14 Liquid -41.86 59.97 -1956628
15 Mixture -23.29 59.97 -35328058
16 Vapor -23.29 59.94 -1066.563
17 Liquid -23.29 59.94 -35326978
18 Vapor -41.86 59.97 -8826861
19 Vapor -41.86 59.97 -89154.27
20 Liquid -15.00 59.91 -35115497
= Product stream
2.4.2 Summary of Equipments Energy Balance

53
 Table 2.5 : Equipment Energy Balance

Heat duty
Proses Equipment
(kJ/hr)
Mixer, M-1 -194010.9661
Compressor, C-2 18986080.8258
Exchanger, X-3 50504624.3208
Reactor, R-4 -39271343.7024
Expander, E-5 -10940662.8237
Exchanger, X-6 -52584499.4025
Flash, F-7 -253.4740
Exchanger, X-8 -462162.5045
Expander, E-9 -1472791.3182
Flash, F-10 -246.0794
Mixer, M-11 18600.3926
Flash, F-12 13.4499
Exchanger, X-14 211480.1761

Detail of calculations are shown in Appendix B.2.

2.5 Computer Simulation

In order to verify the manual mass balance calculation result and manual
energy balance calculation result, simulation for plant was run on Design II
simulator. The simulation is carried out after perform the manual material and
manual energy balance. The purpose of this procedure is to confirm the results
between calculated results and simulated results can be compare. The results of
simulation are shown in Appendix B.3.

2.5.1 Comparison Result of Manual Calculation and Result of Simulation

54
 Table 2.6 : Comparison Result of Manual Calculation and Result of Simulation
Manual calculation Simulation Error
Stream
(kmole/hr) (kmole/hr) (%)
1 403.7751 380.1200 5.86
2 1185.5873 1140.3000 3.82
3 5045.1055 4988.9400 1.11
4 5045.1055 4988.9400 1.11
5 5045.1055 4988.9400 1.11
6 4294.2055 4246.4300 1.11
7 4294.2055 4246.4300 1.11
8 4294.2055 4246.4300 1.11
9 3535.0814 3543.2720 0.23
10 712.8059 703.1006 1.36
11 3535.0814 3543.2720 0.23
12 3535.0814 3543.2720 0.23
13 3490.6496 3502.6820 0.34
14 44.4319 40.6020 8.62
15 757.2378 743.7017 1.79
16 12.5110 0.3615 97.11
17 744.7268 743.3423 0.19
18 3455.7431 3467.6370 0.34
19 34.9065 35.0268 0.34
20 744.7268 743.3423 0.19
= Product stream
Note : Calculation for error is base on manual calculation
value of  manual calculation  value of  simulation
Error (%) =  100
value of  manual calculation
(value) = negative value

2.6 Optimization

2.6.1 Introduction

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 operating without compromising that are predetermined. The reason for
optimization is reduced capital cost and operating cost without violating the
constraints that are predetermined.

55
 At a practical level, optimization is defined as “Given a system or process,
fined the best solution to this process within constraints”. To quantify the ‘best
solution’ we first need an objective that serves as quantitative indicator of
“goodness” for a particular solution. Typical objectives for process design include
capital and operating cost, product yield, overall profit and so on.

The value of the objective function is determined by manipulation of the

problem variable. These variables can physical represent equipment sizes and
operating conditions (e.g. pressures, temperatures 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.

2.6.2 Parameter Optimization for Individual Equipment

The objective of this part is to discover the best condition or solution to the
problems. The best solution usually results in economic or technical incentives.
Examples of economic incentives are maximum profit and maximum costs, where as
technical incentives are increased yield and reactor conversion. The optimization has
been limited to parameter optimization of individual (stand-alone) equipment only,
which means that the equipment to be optimized is firstly disconnected from other
plant structure. Then, some objective function is set and the objective function is
evaluated altering the operating conditions of the specific equipment. Optimization
of an ammonia process is always involved its economic performance and trade-off.
That why we are always trying to minimize the waste, bounded by the constraints of
operation feasibility. In a plant process optimization, trade-off between capital cost
and operating costs is usually involved.

2.6.3 General Procedure

56
 When setting out to optimize any system, the first step is clearly to identify
the objective: the criterion to use to judge the system performance. For a chemical
process, the overall objectives for the operating company will be optimize to
maximize profits. These main sub-objectives, which the designer will work to
achieve. The main sub-objective will usually be to minimize operating cost. Other
sub-objective may be to reduce investment, maximize yield, reduce labour
requirements, reduce maintenance, and operates safety.

The second step is to determine the objective function: the system of equation
and other relationship, which relate the objective with the variables to be
manipulated to optimize the function. If the objective is economic, it will be
necessary to express the objective function in economic term (cost). Difficulties will
rise in expressing functions that depend on a value judgment. For example, the social
benefits and the social costs that arise from pollution.

The third step is to find the value of the variable that gives the optimum value
of the objective function (maximum or minimum). The best technique to be used for
this step will depend on the complexity of the system and on the particular
mathematical model used to represent the system.

2.6.4 Economic Tradeoffs

Economic will always be the major objective of plant optimization. Two

types of economic trade-off involved when optimizing the design the equipment. The
optimization that can be done independently on single equipment is call local trade-
off. By contrast, in global trade-off, any changes in the design of certain equipment
will effect operations through the flow sheet. Optimizing a reactor will cause global
trade-off. If the reactor conversion is changed so as to optimize its setting, then not
only is the reactor affected in size of recycle also will affect the utilities used and the
heat exchanger work.

2.6.5 Brief Description

57
 In order to obtain the optimum operating parameter for the plant, an
optimization is done on the following equipment using the DESIGN II version 8.35
simulator. The purpose of rearrangement of the flow sheet is to:
i) Ensure the suitable equipment will be used for the process.
ii) Utilize the heat properly by exchanging the heat between the cold and hot
streams.
iii) Minimize the operating or equipment cost and maximize the profit.

In our optimizing work for this process flow diagram, we will only concentrate on
the most critical unit in our plant as below:
i) Reactor, R-4
ii) Flash column, F-7, F-10, F-12

2.6.5.1 Optimization of Reactor System

Optimization of reactor system is the most important task in process

optimization because it is global factor that will influence all the downstream
processes and equipment. Hence, the optimum operating conditions for the reactor
must be determined prior to a detail downstream process design. Once the optimum
operating conditions for reactor has been decided, the optimization of other down
stream equipment can be done without affecting the operating condition of the
reactor.

The reactor optimization was done by changing the conversion of the selected
component in each reactor. As the conversion decrease, the unreacted limiting
reactant increase, yet, however, the reactor duty decreases. In other words,
conversion is proportional to reactor duty and inverse proportional to unreacted
reactant. The objective of reactor optimization is to discover the optimum point
where the lost of reactant and reactor duty is the less. (Assumption: conversion
changing does not affect the size of the reactor and hence the capital cost for the
reactor vessel remains constant. The reactor duty determines the major consideration
in the optimization. )

58
 The optimization of reactor involved the following aspects:
i) type of reactor
ii) catalyst
iii) reactor conversion
iv) reactor temperature

i) Type of Reactor
There are two types of reactor suitable for this plant, the packed-bed reactor
and fluidized bed reactor (plug flow reactor). Packed-bed reactors are used for gas
and gas-liquid reaction. In fluidized bed reactor, fluid material (catalyst) in the form
of fine particle is held in suspension by the upward flow of the reacting fluid. In this
design project, pack bed reactor has been chosen to carry out the reaction between
gas hydrogen and gas nitrogen to reform gas ammonia with the conversion value
30% which produce gas ammonia 743 kmol/hr. This reaction is highly exothermic
and the pressure maintains as 172.17 atm in the reactor.

ii) Catalyst
A catalyst is a substance that affects the rate of a reaction but emerges form
the process unchanged. Chemically, a catalyst usually changes a reaction rate by
promoting a different molecular path for the reaction. The choice of catalyst is
crucially important. Catalysts increase the rate of reaction but are unchanged in
quantity and chemical composition at the end of the reaction. If the catalyst is used to
accelerate a reversible reaction, it does not by itself alter the position of the
equilibrium. When systems of multiple reactions are involved, the catalyst may have
different effects on the rates of the different reactions. This allows catalysts to be
undesired reactions. Hence the choice of catalyst can have a major influence on
selectivity.

iii) Reactor Conversion

The conversion of the reactor can be defined as reactant consumed in the
reactor per reactant fed to reactor. The conversion of the reaction is one of the crucial
factors in the processing plant. It is a global factor that will affect the down stream
processes as will as the reactor itself. The conversion of the reactor will also have
trade-off both locally and globally:

59
  Local trade-off of the reactor conversion and reactor size.
Higher reactor conversion means larger reactor will be required.
Therefore, decision has to be made between having a high conversion
process with large reactor or a low conversion process with smaller
reactor volume.
 Global trade-off between reactor conversion and separation duty.
The higher the conversion of the reactor, the amount of unreacted reactant
will be small and separation duty also small, but with higher reactor cost.
On the other hand, low reactor conversion can minimize the reactor cost
but increases the separation duty.

The operating condition of the reactor is 450C and 172.71 atm. The total
conversion of the ammonia can reach over 30%. The reaction of ammonia is highly
exothermic; this is the reason why this reactor has been chosen instead of another
reactor. In this section, the effects of the total conversion of ammonia towards the
reactor duty and final product purity will be studied, in order to choose the optimum
operating parameters for the reactor. The optimum parameters are economically
saving, for example, with the highest purity but low reactor duty. The effects of the
total conversion of the Ammonia towards the reactor duty and final product purity

Using the mass and energy hand calculation, the conversion of the total
conversion of ammonia will be varied from 0.1 to 0.7. The effect towards the reactor
duty whether increased or decreased will be observed. The final product purity is
related to the economy aspect, where the purest the product, the better market price
for it, so it is better to obtain the highest purity of the final product from the plant.
But in order to choose the best operating parameter for the reactor, integrity between
these two aspects must be considered, where the best operating parameter should be
based on the following priority: high purity and low utility cost to cool down reactor
and its effluent stream.

Table 2.7 : Reactor Duty and Final Product Purity at Different Total Ammonia
Conversion

60
 Reactor Duty Final Product Purity
Total Ammonia conversion
(kJ/hr) ( mole % )
0.1 -13238905.7 99.3696
0.2 -26477811.3 99.6610
0.3 -39716718.2 99.7681
0.4 -52955626.7 99.8238
0.5 -66194532.4 99.8579
0.6 -79433438.0 99.8810
0.7 -92672343.7 99.8976

Prepared by : Mohd. Ridzuan b Wahab

Mohd Ariff Husni b Hussain

Total ammonia conversion

0.1 0.2 0.3 0.4 0.5 0.6 0.7
0.E+00 100
-1.E+07 99.9

Final product purity (mole%)

-2.E+07 99.8
-3.E+07
Reactor duty (kJ/hr)

99.7
-4.E+07
99.6
-5.E+07
99.5
-6.E+07
99.4
-7.E+07
-8.E+07 99.3

-9.E+07 99.2

-1.E+08 99.1
Reactor Duty Final Product Purity

Figure 2.5 : Result of Optimization for Reactor, R-4

From the graph, it shows that final product purity and reactor duty is
proportional to the total ammonia conversion. From the literature survey, the total
conversion of Ammonia is 0.3 and from the graph, it shows that 0.26 conversion of
Hydrogen is the optimum conversion to obtain final product purity. The highest final
product purity with this total conversion is almost 99.9%. But with this purity and
conversion (0.6), reactor heat duty will become higher. So, to reduce the reactor
duty, conversion 0.26 has been choose. At this conversion, reactor duty is around
-35000000 kJ/hr and purity is 99.68%.

61
 iv) Reactor Temperature
The choice of reactor temperature depends on many factors. Generally, the
higher the rate of reaction, the smaller reactor volume needed safety consideration,
materials of construction limitations, or maximum operating temperature for the
catalyst set practical upper limits. The temperature for the converter reactor is 4500C.
The catalyst gives a maximum conversion at this temperature.

2.6.5.2 Optimization of Flash Column

The main purpose of the flash drums is to get rid of most of the inert gases
and impurities in the reactor effluents. Thus, this will ease the separation for the final
step and recycle stream in order to get the product/reactants specifications. The
objective of the flash drum optimization is to obtain an optimum point or reasonable
value for certain selected parameters. For this, liquid ammonia product should be
maintained as high as possible in their amount after the flash distillation.

Nevertheless, gases at the top stream in flash drum such as gas nitrogen and
gas hydrogen need to be separate as much as possible through flash distillations to
obtain high purity of ammonia. All of the gas produce from top stream at flash drum
will be at recycle stream and reheat to 250C before enter into the mixer at stream 1.

There are a few design or operating parameters involved in the process of

optimizing the flash drum efficiency. Drum temperature is taken as the main
parameter for the optimization purpose. Trial and error method is used to determine
the required temperatures to get optimum product of liquid ammonia.

As we know, the main objective of flash column in this plant is to obtain

desire purity of liquid ammonia and flow rates of top stream. To fulfill the objective,
we need to flash out the nitrogen and hydrogen liquid by three flash drum to achieve
purity above 99.7681% of ammonia. Meanwhile the temperature to flash out
ammonia is about -230C in the first flash drum, -41.850C at second flash drum and
-23.290C at third flash drum, so that condensers are needed to success the flash

62
separator. Two condensers were added before enter the flash drum at stream 7 and
stream 9 in this design plant. Due to the temperature drop in the condensers, that
mean a slightly drop in temperature too. But it does not affect much in terms of the
flash drum optimization.

Therefore, in the following section, the effects of temperature in the flash

drum towards the purity of ammonia and the heat duty are used in optimize the flash
drum. And again the heat duty and purity were obtained from hand calculation with
help of program Microsoft Excel.

For Flash Column 1, the inlet stream is a mixture phase. At fixed pressure of
89.97 atm (equal to 0.03atm pressure drop from condenser, X-6); we would like to
know the temperature that most of the light components come up on top stream. The
optimization result is shown in table below. It’s clear from figure below that the
optimum temperature of 22.5 °C should be used.

Table 2.8 : Flash Duty and Ammonia Purity at Different Temperature (Flash,

F-7)

Flash Duty Final Product Purity

Temperature (ºC)
(kJ/hr) ( mole % )
-20 115883.2633 99.7497
-21 77594.7232 99.7554
-22 38927.59643 99.7611
-23 -12484.9961 99.7667
-24 -39224.3609 99.7721
-25 -78673.493 99.7775
-26 -118249.604 99.7828

Prepared by : Yeap Fuey Fen

63
 1.5E+05 99.79

1.0E+05 99.78

Final product purity (mole%)

5.0E+04 99.77
Flash duty (kJ/hr)

0.0E+00 99.76
-20 -21 -22 -23 -24 -25 -26
-5.0E+04 99.75

-1.0E+05 99.74

-1.5E+05 99.73
o
Temperature ( C)

Flash Duty Final Product Purity

Figure 2.6 : Result of Otimization for Flash, F-7

For Flash Column 2, the inlet stream is a vapor phase. At fixed pressure of 60
atm, we would like to know the temperature that most of the light components come
up on top stream. The optimization result is shown in table below. The optimum
temperature of flash column 2 is 39.3°C as shown in figure below.

Table 2.9 : Flash Duty and Ammonia Purity at Different Temperature (Flash,

F-10)

Flash Duty Final Product Purity

Temperature (ºC)
(kJ/hr) ( mole % )
-38.00 -24386.7371 99.8882
-39.00 -2894.7484 99.8911
-40.00 -32788.6576 99.8943
-41.85 -41144.9185 99.8990
-42.00 -41843.0397 99.8994
-43.00 -46579.2643 99.9019
-44.00 -51446.9000 99.9047

Prepared by : Pang Zhen Tao

64
 o
Temperature ( C)
-38.00 -39.00 -40.00 -41.85 -42.00 -43.00 -44.00
0 99.91

-10000 99.91

Final product purity (mole%)

99.90
-20000
Flash duty (kJ/hr)

99.90
-30000
99.89
-40000
99.89

-50000 99.88

-60000 99.88
Flash Duty Final Product Purity

Figure 2.7 : Result of Optimization for Flash, F-10

For Flash Column 3, the inlet stream is a mixture phase. At fixed pressure of
59.97 atm, we would like to know the temperature that most of the light components
come up on top stream. The optimization result is shown in table below. The
optimum temperature of flash column 3 is 22.90°C as shown in figure below.

Table 2.10 : Flash Duty and Ammonia Purity at Different Temperature (Flash,

F-12)

Temperature Flash Duty Final Product Purity

(ºC) (kJ/hr) ( mole % )
-20.00 173788.9756 99.8105
-21.00 127480.3171 99.8137
-22.00 91197.9728 99.8166
-23.29 38275.4940 99.8205
-24.00 9208.5262 99.8227
-25.00 -31539.2474 99.8256
-26.00 -72124.7362 99.8286

Prepared by : Rohaiza bt Abdul Rahim

65
 2.E+05 99.84

99.83
2.E+05

Final product purity (mole%)

99.83
1.E+05
Flash duty (kJ/hr)

99.82
5.E+04
99.82

0.E+00
-20.00 -21.00 -22.00 -23.29 -24.00 -25.00 -26.0099.81

-5.E+04
99.81

-1.E+05 99.80
o
Temperature ( C)
Flash Duty Final Product Purity

Figure 2.8 : Result of Optimization for Flash, F-12

66