Final Report Group 11 Finalize Toc, Hazop, Reference, Code PDF

CAB 4023
PLANT DESIGN II
Semester: May 2011
FINAL REPORT
PRODUCTION OF 396, 000 TONNE OF AMMONIA PER YEAR
GROUP 11
MUHAMMAD FAIZ MOHD FUDZAILI 10821
MUHAMMAD FAUZI KHAMIS 10826
MUHAMMAD NUR AZIZI ABDUL AZIZ 10853
NUR IZZATI BOHER @ BUJANG AMRI 10935
SOFIA KEETASOPON 10564
CHEMICAL ENGINEERING PROGRAMME

UNIVERSITI TEKNOLOGI PETRONAS
Bandar Sri Iskandar, 31750 Tronoh, Perak Darul Ridzuan
CERTIFICATION OF APPROVAL
CAB 4023
PLANT DESIGN II
Semester: May 2011
PRODUCTION OF 396, 000 TONNE OF AMMONIA PER YEAR
GROUP 11
MUHAMMAD FAIZ MOHD FUDZAILI 10821

MUHAMMAD FAUZI KHAMIS 10826
MUHAMMAD NUR AZIZI ABDUL AZIZ 10853
NUR IZZATI BOHER @ BUJANG AMRI 10935
SOFIA KEETASOPON 10564
APPROVED BY,
___________________________________
(DR. MOHANAD EL-HARBAWI)
CHEMICAL ENGINEERING PROGRAMME

UNIVERSITI TEKNOLOGI PETRONAS
TABLE OF CONTENT PAGE
LIST OF TABLES................................................................................................... 1
LIST OF FIGURES................................................................................................... 2
LIST OF APPENDICES........................................................................................... 3
ACKNOWLEDGEMENT......................................................................................... 4
EXECUTIVE SUMMARY........................................................................................ 5
CHAPTER 1 INTRODUCTION............................................................................. 6
1.1 BACKGROUND STUDIES.......................................................................... 6
1.2 PROBLEM STATEMENT............................................................................ 7
1.3 OBJECTIVES................................................................................................ 7
1.4 SCOPE OF WORK........................................................................................ 8
CHAPTER 2 LITERATURE REVIEW................................................................. 10
2.1 AMMONIA DESCRIPTION......................................................................... 10
2.1.1 Ammonia Definition...................................................................................... 10
2.1.2 Ammonia Properties....................................................................................... 11
2.2 FEED DESCRIPTION................................................................................... 12
2.2.1 Natural Gas – Methane................................................................................... 12
2.2.2 Hydrogen........................................................................................................ 13
2.2.3 Nitrogen.......................................................................................................... 13
2.3 ECONOMIC POTENTIAL............................................................................ 16
2.3.1 World Ammonia Consumption as of 2010.................................................... 16
2.3.2 Ammonia Market Price as of 2010................................................................ 18
2.3.3 Ammonia Production as of November 2010.................................................. 19
2.4 ALTERNATIVE PROCESS ROUTE........................................................... 20
2.4.1 Synthesis Gas Production............................................................................... 21
2.4.2 Carbon Dioxide Removal............................................................................... 24
2.4.3 Ammonia Synthesis........................................................................................ 25
2.5 SITE LOCATION.......................................................................................... 32
2.5.1 Site Consideration.......................................................................................... 32
2.5.2 The Selection Criteria..................................................................................... 32
2.5.3 Overview of Site Location............................................................................. 34
CHAPTER 3 DESIGN CONCEPT AND SYNTHESIS........................................ 37
3.1 INTRODUCTION.......................................................................................... 37
3.1.1 Batch VS Continuous..................................................................................... 38
3.2 INPUT AND OUTPUT STRUCTURE......................................................... 39
3.2.1 General input-output structure....................................................................... 39
3.2.2 Ammonia Processes Involved........................................................................ 42
3.3 REACTOR DESIGN AND REACTOR NETWORK SYNTHESIS........... 45
3.3.1 Reaction Information...................................................................................... 46
3.3.2 Reactor Type.................................................................................................. 47
3.3.3 Operating Conditions..................................................................................... 52
3.4 SEPARATION AND RECYCLE SYSTEM SYNTHESIS........................... 53
3.4.1 Separation prior to Ammonia Synthesis......................................................... 54
3.4.2 Separation in Ammonia Synthesis................................................................. 54
3.4.3 CO2 removal................................................................................................... 55
3.4.4 Recycle Structure System and Purge System................................................. 56
CHAPTER 4 INSTRUMENTATION AND CONTROL...................................... 59
4.1 INTRODUCTION.......................................................................................... 59
4.2 AMMONIA PLANT CONTROL SYSTEM................................................. 60
4.3 DEVELOPING PROECSS & INSTRUMENTATION SYSTEM................ 60
4.3.1 Reforming Unit.............................................................................................. 61
4.3.2 CO Conversion Unit....................................................................................... 64
4.3.3 CO2 Removal Unit......................................................................................... 64
4.3.4 Methanation Unit............................................................................................ 65
4.3.5 Compressor House Unit................................................................................. 66
4.3.6 Ammonia Synthesis Unit............................................................................... 66
CHAPTER 5 SAFETY AND LOST PREVENTION............................................ 68
5.1 HAZARD AND OPERABILITY STUDY (HAZOP)................................... 68
5.1.1 Basic Principles of HAZOP........................................................................... 68
5.1.2 HAZOP Guide Words and Parameters........................................................... 70
5.1.3 HAZOP Procedures........................................................................................ 71
5.1.4 Advantages of HAZOP.................................................................................. 73
5.2 HAZOP ANALYSIS...................................................................................... 73
5.2.1 HAZOP Study Nodes..................................................................................... 73
5.3 SITE LAYOUT.............................................................................................. 74
5.4 PLANT LAYOUT CONSIDERATION........................................................ 74
5.6 AMMONIA PLANT LAYOUT..................................................................... 77
5.6.1 Non-Process Area........................................................................................... 77
5.6.2 Process Area................................................................................................... 78
5.6.3 Assembly Point.............................................................................................. 80
5.6.4 Bund Walls and Dike Area............................................................................. 80
CHAPTER 6 WASTE TREATMENT.................................................................... 82
6.1 INTRODUCTION.......................................................................................... 82
6.1.1 Wastewater Treatment Methods..................................................................... 82
6.1.2 Wastewater Treatment Process Overview...................................................... 83
6.2 LAWS AND REGULATIONS ON INDUSTRIAL WASTE
(MALAYSIA)................................................................................................ 84
6.2.1 Introduction.................................................................................................... 84
6.2.2 Solid Waste.................................................................................................... 85
6.2.3 Liquid Waste.................................................................................................. 86
6.2.4 Gaseous Waste............................................................................................... 87
6.3 WASTE IDENTIFICATION......................................................................... 88
6.4 WASTE CHARACTERIZATION................................................................. 89
6.5 EFFLUENT FLOW RATE TO THE PLANT............................................... 90
6.6 WASTE TREATMENT STRATEGIES........................................................ 91
6.6.1 Wastewater Treatment.................................................................................... 91
6.6.2 Solid Waste Handling..................................................................................... 92
6.6.3 Air Pollution Control...................................................................................... 93
6.7 DESIGN OF UNIT PROCESSES AND EQUIPMENT................................ 94
6.7.1 Design of Receiving Chamber....................................................................... 94
6.7.2 Design of Equalization Basin......................................................................... 94
6.7.3 Design of Aeration Basin............................................................................... 95
6.7.4 Design of Clarifier.......................................................................................... 96
6.8 OVERALL PLANT SIZE.............................................................................. 96
CHAPTER 7 PROCESS ECONOMIC AND COST ESTIMATION.................. 98
7.1 INTRODUCTION.......................................................................................... 98
7.2 TOTAL CAPITAL INVESTMENT.............................................................. 98
7.2.1 Capital Investment.......................................................................................... 98
7.2.2 Fixed Capital Investment............................................................................... 99
7.2.3 Working Capital............................................................................................. 101
7.2.4 Land Cost....................................................................................................... 101
7.3 TOTAL OPERATION (PRODUCTION) COST.......................................... 102
7.3.1 Variable Operating Cost................................................................................. 103
7.3.2 Fixed Operating Cost..................................................................................... 104
7.2.3 General Expenses........................................................................................... 107
7.4 ESTIMATION OF TOTAL REVENUE........................................................ 109
7.5 PROFITABILITY ANALYSIS..................................................................... 109
7.5.1 Start-Up Period............................................................................................... 110
7.5.2 Depreciation................................................................................................... 110
7.5.3 Cumulative Cash Flow................................................................................... 111
7.5.7 Discounted Cash Flow Rate of Return (DCFRR).......................................... 111
CHAPTER 8 CONCLUSION AND RECOMMENDATION............................... 112
REFERENCES........................................................................................................... 114
APPENDICES............................................................................................................ 116
PFD Size A1................................................................................................................
P&ID Size A1..............................................................................................................
Plant Layout Size A3..................................................................................................
LIST OF TABLES PAGE
Table 2.1: Physical Properties of Ammonia........................................................ 12

Table 2.2: Physical Properties of Methane.......................................................... 13
Table 2.3: Physical Properties of Hydrogen........................................................ 14
Table 2.4: Physical Properties of Nitrogen.......................................................... 16
Table 2.5: Summary of Ammonia Prices............................................................. 19
Table 2.6: Advantaged and Disadvantages of Carbon Removal Process......... 25
Table 2.7: Comparison of Ammonia Synthesis Systems..................................... 31
Table 2.8: Comparison of Three Selected Location (Sources: MIDA 2010).... 34
Table 2.9: Weight Method to Choose the Site for the Plant................................ 36
Table 3.1: Comparison between Batch and Continuous Process....................... 39
Table 3.2: Specifications of the Natural Gas....................................................... 40
Table 3.3: Reactions of Ammonia Production..................................................... 41
Table 3.4: Component Destinations..................................................................... 42
Table 3.5: The Detail of Nickel Catalyst (Primary Reformer)............................ 49
Table 3.6: The Detail of Nickel Catalyst (Secondary Reformer)........................ 50
Table 3.7: The Details Iron-Oxide Catalyst (HTS).............................................. 50
Table 3.8: The Details Copper-Zink Catalyst (LTS)............................................ 51
Table 3.9: The Details Nickel Oxide Catalyst (Methanation)............................. 51
Table 3.10: The Details of Iron-Oxide Catalyst (Ammonia Converter)............... 52
Table 3.11: The Properties of Main Feedstock and Product................................ 52
Table 4.1: Control Specifications of Steam Mixing Station for
Reforming............................................................................................ 61
Table 4.2: Control Specifications of Primary Reformer..................................... 62
Table 4.3: Control Specifications of Air Mixing Station for Reformer.............. 63
Table 4.4: Control Specifications of Secondary Reformer.................................. 63
Table 4.5: Control Specifications of CO Conversion Unit.................................. 64
Table 4.6: Control Specifications of CO2 Removal Unit..................................... 65
Table 4.7: Control Specifications of Methanation Unit...................................... 65
Table 4.8: Control Specifications of Compressor Unit........................................ 66
Table 4.9: Control Specifications of Ammonia Reactor Temperature............... 66
Table 5.1: Basic Guide Words in HAZOP........................................................... 71
Table 5.2: HAZOP Study Nodes........................................................................... 73
Table 6.1: Summary of Treatment Methods........................................................ 83
Table 6.2: Summary of Wastewater Treatment Stages........................................ 84
Table 6.3: Parameter Limits of Effluents of Standard A and Standard B......... 86
Table 6.4: Malaysian Clean Air Standards for Dark Smoke and Solid
Particles............................................................................................... 87
Table 6.5: Potential Waste Streams Generated from Ammonia Plant............... 88
Table 6.6: Influent Flow Rate.............................................................................. 90
Table 6.7: Typical Design Information for Clarifiers for the Activated Sludge
Process................................................................................................. 96
Table 6.8: The Summary of Projected Area for the Main Zones........................ 96
Table 7.1: Estimation of Equipment Cost for the Project................................... 100
Table 7.2: Typical Factors for Direct Cost........................................................... 100
Table 7.3: Typical Factors for Indirect Cost........................................................ 101
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Table 7.4: Raw Material Costs............................................................................. 103
Table 7.5: Summary of the Variable Operating Cost for the Project................. 104
Table 7.6: Summary of the Total Labour Cost.................................................... 105
Table 7.7: Summary of Fixed Operating Cost..................................................... 107
Table 7.8: Summary of the General Expenses..................................................... 108
Table 7.9: Total Annual Operating Cost.............................................................. 108
Table 7.10: Timing of the Capital Investment....................................................... 110
LIST OF FIGURES PAGE
Figure 2.1: Prototypical Structure of Ammonia................................................... 10

Figure 2.2: World Consumption of Ammonia Based on 2010............................ 17
Figure 2.3: Diagram for Steam Reforming Process............................................ 22
Figure 2.4: Partial Oxidation Process Diagram................................................... 23
Figure 2.5: Haber - Bosch Process....................................................................... 27
Figure 2.6: Diagram of Claude Process............................................................... 28
Figure 2.7: Casale Synthesis Loop – High Pressure............................................ 29
Figure 2.8: Fauser Synthesis Unit........................................................................ 30
Figure 3.1: Onion Model Approach...................................................................... 38
Figure 3.2: Input-Output Structure...................................................................... 40
Figure 3.3: Catalytic Fixed-bed Reactor.............................................................. 49
Figure 3.4: Separation System for Reactor Exit is Vapor and Liquid................ 54
Figure 3.5: Two-phase Separator......................................................................... 55
Figure 3.6: The General Recycle Structure of Ammonia Synthesis Process...... 58
Figure 5.1: The HAZOP Procedure...................................................................... 72
Figure 6.1: The Proposed Wastewater Treatment System................................... 91
Figure 7.1: Classification of Operating Cost........................................................ 103
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LIST OF APPENDICES PAGE
APPENDIX 2.1: Summary of Synthesis Gas Production Process................ 118

APPENDIX 2.2: Gebeng Industrial Estate.................................................... 120
APPENDIX 3.1: The Comparisons between Batch Stirred Reactor,
Continuous Stirred Tank Reactor (CSTR) and Tubular
Reactor................................................................................ 121
APPENDIX 3.2: The Comparisons between Fixed-bed Catalytic Reactor
andFluidized-bed Catalytic Reactor................................... 123
APPENDIX 4.1: Steam Mixing Station Control Strategy Diagram............. 124
APPENDIX 4.2: Primary Reformer Control Strategy Diagram................... 125
APPENDIX 4.3: Primary Reformer Control Strategy Diagram................... 126
APPENDIX 4.4: Secondary Reformer Control Strategy............................... 127
APPENDIX 4.5: CO Shift Converters Unit Control Strategy Diagram........ 128
APPENDIX 4.6: CO2 Removal Unit Control Strategy Diagram................... 129
APPENDIX 4.7: Methanation Unit Control Strategy Diagram.................... 130
APPENDIX 4.8: Compressor House Control Strategy Diagram.................. 131
APPENDIX 4.9: Ammonia Synthesis Unit Control Strategy Diagram........ 132
APPENDIX 5.1: HAZOP Analysis: Node 1................................................... 133
APPENDIX 6.1: Design or Receiving Chamber............................................ 140
APPENDIX 6.2: Design of Equalization Basin............................................. 142
APPENDIX 6.3: Design of Aeration Basin.................................................... 143
APPENDIX 6.4: Design of Clarifier.............................................................. 144
APPENDIX 7.1: Tabulation of Net Cash Flow and Cumulative Cash
Flow..................................................................................... 145
APPENDIX 7.2: Discounted Cash Flow Analysis to Obtain DCFRR.......... 147
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ACKNOWLEDGEMENT
First of all, we would like to express our gratitude to our Lord for giving us the strength to
complete the Plant Design 2 course successfully. We would like to thanks our Supervisor,
Dr Mohanad El- Herbawi for his guidance and support throughout the semester, which led
us to the design of our plant. Our gratitude is extended to PDP II coordinator, Dr. Risza bt
Rusli and Dr. Rajashekhar Pendyala for arranging various seminars to provide support and
knowledge in assisting the group. Our appreciation is also extended to family members and
fellow friends who gave moral support to motivate us to pursue to greater heights in our
project. We appreciate the opportunity given to us to work in a team while designing our
plant.
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EXECUTIVE SUMMARY
The objective of the project is to find the best way of setting up an Ammonia producing
plant. Our team need to consider and determine which process is the most feasible to
produce Ammonia and then proceed with the steps to design an Ammonia plant.
Chapter 1 elaborates project background, history, problem statement, objectives and scope
of work. Chapter 2 gives details of process background, properties of chemicals, Ammonia
market demands, alternative process route and site feasibility study. The location chosen for
the plant is Gebeng Industrial Estate because of the availability of raw material utilities and
transportation. Chapter 3 analyzes conceptual process design and synthesis. Plant would be
operated in continuous mode. Tubular plug flow reactor is selected for the two reactions,
which are Water – gas shift and Ammonia synthesis. Separation units needed for the process
route is Carbon Dioxide removal. Unconverted Ammonia is recycled. The instrumentation
and control system for our ammonia plant will be discussed in detail in Chapter 4 whereas
Chapter 5 will focus on the hazard and operability study (HAZOP), elaborating more the
HAZOP that have been done associated with three study nodes. Furthermore, this chapter
will describe the ammonia plant layout that has been designed.
Next, Chapter 6 will cover on the waste treatment which mainly focuses on water discharge
effluent from the ammonia plant. This chapter also provides design specification which
regards to each equipment involves in wastewater treatment plant system. Most of the
process economic and cost estimation aspect will be discussed particularly in Chapter 7. At
the last part of this chapter, it covers the cumulative cash that resulted from our plant
production. At the end of the chapters, Chapter 12 will elaborate the conclusion and
recommendation which can be made to improve the efficiency of our plant production and
profit.
Indeed, production rate of our plant is 1,200 tonne/day, and 396,000 tonne per annum. The
proposed plant design is economically justified based on economic potential of the process
which shows revenue of RM 328,722,995.30 yearly. The project is proven to be technically
feasible and economically attractive.
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CHAPTER 1
INTRODUCTION
1.1 BACKGROUND STUDIES
Ammonia or commercially known as anhydrous ammonia is a molecule consisting of one
nitrogen atom and three hydrogen atoms. The nitrogen can easily gain a proton and therefore
ammonia is base. The formula for ammonia is NH3. Ammonia which exists in gas form in
room temperature possesses a strong pungent smell, and it is a starting material for the
production of many important nitrogen compounds. Another characteristic of ammonia is it
dissolves easily in water, because the hydrogen and nitrogen atoms can form hydrogen
bonds with water. In water the electrons around the nitrogen atom can easily capture
a proton, forming an alkaline solution called ammonium hydroxide which is highly reactive
and easily combines with many other chemicals.
Ammonia is also obtained as a by-product of coke ovens. Ammonia can be turned from a
gas into a liquid by compression or by cooling to about -33°C (-27.4°F). In returning to the
gaseous state, it absorbs substantial amounts of heat from its surroundings. Because of this it
is often used as a coolant in refrigerating and air-conditioning equipment.
The heart of ammonia manufacture is the Haber process where nitrogen and hydrogen are
reacted together under high pressure and temperature. The Haber process combines nitrogen
from air with the hydrogen derived mainly from natural gas (methane) into ammonia.
Hydrogen is usually produced by the steam reforming of hydrocarbons, with natural gas the
dominant feedstock. It can also be produced by the partial oxidation of naphtha or residual
oil using air or oxygen and from coal gasification. Nitrogen can be obtained by the
liquefaction of air or from producer gas.
The purified hydrogen-nitrogen mixture is compressed to 150-350 bar, mixed with recycle
feed and fed into a tubular or multi-bed reactor. The reaction takes place at 450-600°C over
a catalyst. The ammonia is condensed out by refrigeration and unreacted gases are
compressed and recycled.The reaction involves to produce ammonia is reversible and
exothermic.
6
Ammonia is the basic building block of the world nitrogen industry and is the intermediate
product from which a wide variety of nitrogen-based fertilizers and industrial products are
produced. Fertilizer use accounts for over 80% of ammonia demand. Ammonia is generally
processed into a variety of fertilizer products before being applied to the soil. These products
include urea, ammonium nitrates, ammonium sulfate and ammonium phosphates. Other
commercial usages of ammonia are:
 To manufacture synthetic fibers such as nylon and rayon
 To neutralize acidic by-products of petroleum refining
 In the rubber industry it prevents the coagulation of raw latex during transportation
 The Ostwald process is a method for converting ammonia into nitric acid
 To provide atomic hydrogen for welding
 As a household cleansing agent
Designs have been developed integrating ammonia and methanol production, and the first
grassroots plant to coproduce methanol with ammonia using Haldor Topsoe technology was
started up in 1999 for Petronas Fertilizer in Malaysia.
1.2 PROBLEM STATEMENT

Besides extensively used to manufacture fertilizer, ammonia nowadays is also used to
produce a wide variety of nitrogen-containing chemicals such as nitric acid, nitrates, and
intermediate for dyes and pharmaceuticals. There are also various technologies available for
the manufacture of nitrogen and hydrogen; the main needs for manufacturing of ammonia.
From this point of view, there is the need for industry to produce more ammonia parallel to
global market demand. The process selected shall take into account the economic factors,
capacity of production as well as safety and environmental considerations.
1.3 OBJECTIVES
The main objective of Final Year Design Project is to apply into practical and integrate the
knowledge and skills of Chemical Engineering that has been learnt and practiced so far. The
team needs to recommend the best possible design for ammonia production from nitrogen
and hydrogen.
7
To get the best possible design for ammonia production, the objectives below are fulfilled:
1. Identify the path for ammonia manufacturing and develop the flow sheet.
2. Maximize conversion of hydrogen and nitrogen to produce ammonia.
3. Produce high purity ammonia.
4. Minimize utility consumption to be cost-effective.
5. Determine the economically feasible production capacity.
6. Develop energy and material balances.
7. Design reactor, separator, heat exhanger, pumps and storage tanks.
8. Develop appropriate control strategy.
9. Attend issues on environmental and safety.
10. Determine the ideal plant location and
11. Provide a proper planning for waste management system.
1.4 SCOPE OF WORK

In order to ensure the works progress is in accordance with the timeline of proposed
activities, milestones and deadlines, details and proper scope of work need to be established
and well-planned. Below are the details of our scope of work in order to reach our objectives
in this course:
 Search, study and makes review on the journals, books, and any other reliable studies
regarding the raw materials, chemical and physical properties of the intermediate
product, product and by-product, economic evaluations for the production of
product, usage of the desirable product, main and alternative routes for desired
product‘s production, safety and environmental considerations and any other related
issues.
 Study, determine and develop the best process route and the process flow diagram
for the design project.
 Determine the location of plant based on several factors such as costs, transportation,
accessibility, utilities tariff, raw materials supply and local legal requirements.
 Makes necessary predictions, decisions and assumptions in solving the design
problems.
8
 Complete the material and energy balance for selected process.
 Apply related computer-aided design and engineering software such as iCON,
Microsoft Office Visio and Autocad as tools for designing task.
 Prepare the preliminary and interim report as well as the slides to be submitted and
present to the respective supervisor and assigned evaluators.
9
CHAPTER 2
LITERATURE REVIEW
2.1 AMMONIA DESCRIPTION
2.1.1 Ammonia Definition
Ammonia is one of the most important inorganic chemicals, consisting of one nitrogen atom
and three hydrogen atoms tightly bonded. It is designated in chemical notation as NH3. It‘s
one of the most familiar compounds of nitrogen and hydrogen as well as one of the world's
most valuable agricultural chemicals and the industrial.
Ammonia is being used throughout the industrial world as a valuable fertilizer. Ammonia
and its compounds, mostly ammonium nitrate and other ammonium salts are used for
replenish nitrogen in depleted soils. Which result in greatly increases yields of agricultural
crops, especially those that cannot obtain nitrogen from the atmosphere. Some farmers apply
anhydrous (dry) ammonia directly to their fields from pressurized tanks.
Figure 2.1: Prototypical Structure of Ammonia
The commercial of ammonia synthesis takes place in large steel reactors that are designed to
withstand very high pressures (up to one thousand atmospheres) and high temperatures
(about 700°C or 1300°F). The reactors designed also resist attacking by hydrogen gases
which can corrode many metals, especially for high temperature and pressure. When the
process begins, the hydrogen gas converts the catalyst to pure iron. Gradually, as the iron
catalyst is poisoned by carbon and sulfur compounds, it becomes less effective and must be
replaced. Nitrogen gas for the synthesis process comes from the atmosphere, while most of
the hydrogen needed is extracted from natural gas sources. Once ammonia gas has been
10
formed, it is liquefied by cooling it with water. Nitrogen and hydrogen that have not yet
been converted to ammonia are recycled through the system.
2.1.2 Ammonia Properties

2.1.2.1 Physical Properties
Under the normal conditions, ammonia is a colorless gas which is lighter than air. It has a
sharp odor which stings the nostrils and it‘s also can cause suffocation if inhaled in high
enough concentrations. Ammonia could be easily liquefied under pressure (liquid ammonia).
The liquefied ammonia has been widely used as a refrigerant. Due to its physical properties,
when the liquid vaporizes, it will absorb a large amount of heat from the surroundings. The
ammonia molecule has a trigonal pyramidal shape with the three hydrogen atoms and an
unshared pair of electrons attached to the nitrogen atom. It is a polar molecule and is highly
associated because of strong intermolecular hydrogen bonding. Table 2.1 below shows the
physical properties of ammonia.
2.1.2.2 Chemical Properties

Ammonia is compound which extremely soluble in water because the hydrogen and the
nitrogen can form hydrogen bonds with water and it is frequently used as a water solution
called aqua ammonia or ammonium hydroxide. Ammonia is a flammable gas, and reacts
with oxygen to form nitrogen and water, or nitrogen (II) oxide and water. Oxidation of
ammonia in solution leads to hydrazine, a corrosive and volatile ingredient in fuels.
Ammonia will combine with mercury to form a fulminate which is an unstable explosive
compound. Ammonia, especially in the presence of moisture, reacts with and corrodes
copper, zinc, and many alloys. Only iron, steel, certain rubbers and plastics, and specific
nonferrous alloys resistant to ammonia should be used for fabrications of anhydrous
ammonia containers, fittings, and piping. Anhydrous ammonia is a fertilizer by direct
application to the soil.
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Table 2.1: Physical Properties of Ammonia
Properties Values
Molecular weight 17.03 g/mol
Boiling Point(1.013 bar) -28°F (-33.5 °C)
Latent heat of vaporization (1.013 bar at
1371.2 kJ/kg
boiling point)
Vapor pressure (at 21 °C or 70 °F) 8.8 bar
Weight per gallon of liquid at -28°F 5.69 pounds
Weight per gallon of liquid at 60°F 5.15 pounds
Specific gravity of the liquid (water=1) 0.619
Specific gravity of the gas (air=1) 0.588
Vapor pressure at 0°F 1.1 bar
Critical temperature 270.32 °F (132.3 °C)
Critical pressure 112.8 bar
One cubic foot of liquid at 60°F expands to 850 cubic foot of gas
Ignition temperature 1204°F (651.1111 °C)
Flammable limits in air 16-25%
Odor It has a characteristic pungent odor
Taste It is bitter to taste
At 0oC and 760 mm of Hg pressure, a
Solubility volume of water can dissolve nearly 1200
volumes of ammonia.
When cooled under pressure ammonia
condenses to a colorless liquid, which
Liquefaction boils at -33.4oC. When further cooled, it
freezes to a white crystalline snow-like
solid, which melts at -77.7oC.
Its vapor density is 8.5. Hence it is lighter
Vapor Density
than air (vapor density of air = 14.4).
2.2 FEED DESCRIPTION

2.2.1 Natural Gas – Methane
2.2.1.1 Physical Properties of Natural Gas – Methane
Methane from natural gas is the major source of hydrogen required for the Haber process. It
is a chemical compound which is lighter than air with the molecular formula CH4. It is the
simplest alkane, and the principal component of natural gas. Methane's bond angles are
109.5 degrees. The relative abundance of methane and its clean burning process makes it a
very attractive fuel. However, because it is a gas at normal temperature and pressure,
methane is difficult to transport from its source. In its natural gas form, it is generally
12
transported in bulk by pipeline or LNG carriers and few countries still transport it by truck.
Table 2.2 below shows the physical properties of methane.
Table 2.2: Physical Properties of Methane
Properties Values
Chemical Formula CH4
Molecular Weight (g/mol) 16.0425
Density (Kg/m3) 0.717
Normal Boiling Point -161.6 °C
Normal Melting Point -182.4 °C
Critical Temperature -115.8°F
Critical Pressure 673.1 psia
Odor Odorless
Taste Tasteless
It dissolves in non-polar solvents like
Solubility
alcohol, carbon tetrachloride
2.2.1.2 Chemical Properties of Natural Gas – Methane

Natural gas is a gas consisting primarily of methane, naturally with 0-20% higher
hydrocarbons. It is an important fuel source and a major feedstock for the production
of ammonia, via the Haber process, for use in fertilizer production. Burning methane in the
presence of oxygen produces carbon dioxide and water. It‘s a non-polar molecule and is
insoluble in water. It‘s dissolve in non-polar solvents like alcohol, carbontetrachloride, etc.
Methane is quite unreactive, except with fluorine, chlorine, etc. With these it undergoes
substitution reactions. It is also undergoes oxidative pyrolysis to form carbon monoxide. It is
formed by reaction of methane with methyl radical which further reacts to formaldehyde.
Then formaldehyde reacts to formal radical to form carbon monoxide. The strength of
carbon hydrogen covalent bonds in strongest among all hydrocarbons. Methane also
undergoes the halogenations reaction.
2.2.2 Hydrogen
2.2.2.1Physical Properties of Hydrogen
Hydrogen is the chemical element with atomic number 1. It is represented by the symbol H.
At standard temperature and pressure, hydrogen is a colorless, odorless, insipid, nonmetallic,
highly flammable diatomic gas, formed by diatomic molecules; H2 with an atomic weight of
1.00794, hydrogen is the lightest chemical element. It‘s one of the main compounds of water
13
and of all organic matter, and it‘s widely spread not only in the Earth but also in the entire
Universe. Table 2.3 below shows the physical properties of hydrogen.
2.2.2.2 Chemical Properties of Hydrogen

At normal temperature hydrogen is a not very reactive substance, unless it has been
activated by appropriate catalyses and at high temperatures it‘s highly reactive. Hydrogen
reacts with oxygen to form water and this reaction is extraordinarily slow at ambient
temperature but if it‘s accelerated by a catalyst like platinum or an electric spark, it‘s made
with explosive violence. The use of hydrogen is the most important in the ammonia
synthesis. It is extending quickly in fuel refinement, like the breaking down by hydrogen
(hydrocracking), and in sulphur elimination. Huge quantities of hydrogen are consumed in
the catalytic hydrogenation of unsaturated vegetable oils to obtain solid fat. Hydrogenation
is used in the manufacture of organic chemical products. Huge quantities of hydrogen are
used as rocket fuels in combination with oxygen or flour and as a rocket propellent propelled
by nuclear energy.
Table 2.3: Physical Properties of Hydrogen
Properties Values
Chemical Formula H2
Normal Boiling Point, °C -252.87
Normal Melting Point, °C -259.14
Odor Odorless
Taste Tasteless
Solubility of H2 is very low. Only 2 volumes
Solubility of hydrogen dissolve per 100 volumes of
water under ordinary conditions
Its vapour density is 1. (Vapour density of air
= 14.4). Thus it is much lighter than air.
Vapor density Passing hydrogen through soap solution can
easily prove this. The bubbles formed will rise
into the air
Hydrogen can undergo liquefaction. Cooling
hydrogen to below -240oC, under a pressure
Liquefaction of 20 atmospheres or more, can liquefy it.
Liquid hydrogen is a colorless liquid, which
boils at -253oC.
14
2.2.3 Nitrogen
2.2.3.1 Physical Properties of Nitrogen
Nitrogen is one of the most interesting of all chemical elements. Nitrogen is a colorless,
odorless and tasteless gas that makes up 78.09% (by volume) of the air we breathe.
Naturally occurring nitrogen contains two isotopes, 14N and 15N, with a relative abundance
of 99.62% and 0.38%, respectively. It‘s a relatively inert gas. The liquid nitrogen is also
colorless, odorless and also similar in appearance to water. Table 4 below shows the
physical properties of nitrogen.
2.2.3.2 Chemical Properties of Nitrogen

Nitrogen is not a very active element. This evidenced by the fact that free nitrogen is
abundant in the atmosphere, where the composition of nitrogen is the air makes up to
78.084%. It‘s slightly soluble in water. Nitrogen will combine with oxygen in the presence
of lightening or spark, the product of the reaction being nitric oxide. This reaction occurs
commonly in the atmosphere and is the mechanism by which elemental nitrogen is
converted to a compound. Nitrogen oxides (NOx) is mainly produced by motor vehicles and
internal combustion of engines, they are one of the main contributors of the acid rain. They
will react with water molecules in the atmosphere to form nitric acid. Nitrogen can be used
for protecting raw materials or finished products in liquid form from the formation of
peroxides and/or gum, and from contamination by oxygenated components, regeneration of
purification beds (alumina and molecular sieve), medium for the exhaust of emitted heat in
fluid bed reactors as well as temperature control in reactors.
15
Table 2.4: Physical Properties of Nitrogen
Properties Values
Chemical Formula N2
Normal Boiling Point -195.8 °C
Normal Melting Point -210 °C
Odor It has no odor
Taste It is a tasteless gas
Nitrogen is slightly soluble in water. 1 liter of
Solubility water dissolves about 22 ml of nitrogen at
0oC
The vapor density of nitrogen is 14 (Vapor
Vapor density density of air = 14.4). Hence it is slightly
lighter than air
When cooled and compressed nitrogen
liquefies to a colorless liquid, which boils at -
Liquefaction
196oC. When further cooled, it freezes to a
white snow like solid, which melts at -210oC
2.3 ECONOMIC POTENTIAL

2.3.1 World Ammonia Consumption as of 2010
Nitrogen fertilizer consumption accounts for more than 80% of the world ammonia market,
and with the population continuing to grow and no new arable land being developed, a
renewed growth trend is projected during the forecast period. Increased usage of nitrogen
fertilizers, and in particular, urea, will be needed to meet the growing need for food. On a
country-by-country basis, nitrogen fertilizer use is closely related to the health and level of
maturity of the agricultural economy, disposable income and dietary changes.
World consumption of ammonia was increased by 12.0% or 2.3% annually during 2005–
2010, although it was slowed during the latter part of 2008 and 2009. Growth is forecast at
2.7% annually during 2010–2015. Some regions will grow faster, in particular Africa, led
primarily by increased urea production.
Ammonia consumption is driven primarily by the production of downstream fertilizer

products, such as urea, ammonium nitrates, ammonium phosphates, ammonium sulfates and
nitrogen solutions. In addition, China is the only country to use ammonium bicarbonate to
16
any degree, while the United States is the leading country for direct application of anhydrous
ammonia, and, to a lesser extent, aqueous ammonia. The growth of biofuels, and in
particular, bioethanol, is having a major impact on nitrogen fertilizer demand. The following
pie chart shows world consumption of ammonia:
Production of urea accounted for about 54% of total world ammonia consumption.
Ammonium nitrate (directly and through nitric acid) accounted for about 14%, of which an
estimated 75% is consumed in fertilizer applications and the remainder in explosives and
blasting agents. Ammonium phosphates accounted for 5.8%, ammonium bicarbonate for
4.3% (primarily China) and ammonium sulfate for 2.7%. Direct application is at least 2.7%,
most of which is consumed in the United States. Direct application is believed to be larger,
but is accounted for in the "Other" category. In addition, a small quantity of aqueous
ammonia is also consumed in direct application.
Figure 2.2: World Consumption of Ammonia Based on 2010
During the next several decades, the requirement for fertilizers is forecast to grow because
of two trends. The amount of arable land is declining while the population is growing. The
world population is forecast to reach 8.5 billion people by 2030 and 9.2 billion by 2050. At
that rate, the FAO estimates that agricultural demand will be 50–80% higher than the level
17
of production today. Conversely, the amount of productive arable land is declining as a
result of urbanization, soil erosion, and nutrient exhaustion. In addition, the amount of
usable water is declining, and could become more strained with climate change.
2.3.2 Ammonia Market Price as of 2010

2.3.2.1 Asia
Prices in the Asian ammonia market picked up momentum in the last couple of months of
2010, driven by tight supply and healthy demand in the region. Robust conditions in
the US and Europe offered additional support to Asian pricing, and high numbers for other
nitrogen products also helped buoy ammonia levels. Prices rose from $445-475/tonne CFR
(cost and freight) Asia in mid-November to $465-500/tonne CFR Asia in early February
2011. Ammonia values were anticipated to remain high throughout the first quarter of the
year. A scheduled turnaround at an ammonia facility in Indonesia in December and a
turnaround at a Malaysian plant in late February were expected to result in snug supplies
within Asia and support firm price ideas. A higher February contract price in Tampa,
together with climbing indications in Yuzhny and the Middle East, offered additional
support to ammonia values in Asia.
2.3.2.2 Europe
Ammonia prices in Europe were firm in the $390s/tonne FOB (free on board) in mid-
November. Expectations of a normal seasonal decline were diminishing amid production
problems at Gorlovka in Ukraine which were impacting Yuzhny availability and continued
strong demand from the US, as some suppliers looked to keep systems from running empty.
Despite bids from traders at lower levels there was little pressure for lower prices. Through
December prices remained in the $390-400/tonne FOB range as sentiment was still firm.
Although production at Gorlovka restarted, demand, particularly from the US, was sufficient
to absorb the extra availability. At the same time, production curtailments in Trinidad took
any slack out of the market and supported prices. At the end of the year the ammonia market
was in a bullish mood. January business was reported at $400/tonne FOB and offers moved
higher. Early in the New Year business was reported at $430/tonne FOB as limited supply
and strong demand combined to push prices up. Deals quickly followed at $450/tonne and
18
$460/tonne FOB as production problems in Trinidad and Algeria persisted, while US,
European and North African demand remained strong. At mid-February, the short term
prospects for ammonia prices remain strong. Demand from the US andEurope is still strong
and supply limited. Yuzhny prices have risen to $470/tonne FOB and could move higher
with suppliers reporting bids from traders at $480/tonne FOB Yuzhny.
2.3.2.3 US
US ammonia prices moved higher in the three months to mid-February as strong demand for
spring application stretched the limits of the supply pipeline. Supply was tightened by
production and loading difficulties at the Black Sea port of Yuzhny, Ukraine, and a late-
December shutdown at Yara‘s Tringen 1 plant in Trinidad that has a production capacity of
525,000 tonne/year. The plant was restarted on 31 January. The February contract price
settled at $515/tonne CFR Tampa, up $40/tonne from January. Looking forward, market
sources indicated that ammonia prices would be higher in February and March ahead of
spring planting in North America.
Table 2.5: Summary of ammonia prices
Region Price per tonne (USD) Logistics type
Asia 445 - 500 Cost and freight (CFR)
Europe 390 - 480 Free on board (FOB)
US 465 - 515 Cost and freight (CFR)
Based on the currency conversion of 1 USD = 3.0450 MYR as of 2/17/2011 from

(Exchange.Rates.org), selling price of ammonia is MYR 1,354.56 - 1,567.64, where the
median of MYR 1461.10 per metric tonne CFR will be applied throughout the planning.
2.3.3 Ammonia Production as of November 2010

Global ammonia capacity was 153m tonne/year NH3 in 2009, with the main additions
occurring in China,Trinidad, Indonesia, Oman, India and Egypt. According to the (Patrick
Heffer and Michel Prud‘homme, 2010) world capacity survey, global ammonia capacity will
increase by 20% to 224m tonne/year NH3 by 2014. The bulk of the growth will be in China,
Middle East, Latin America and Africa. IFA estimated global seaborne ammonia availability
will be close to 19m tonnes in 2014, a net increase of 1.7m tonnes over 2009.
19
In the medium term, China‘s ammonia capacity is projected by the IFA to increase from
62m tonne/year NH3 in 2009 to 71m tonne/year in 2013. India is ranked as the world‘s third
largest producer and importers of ammonia. Imports which are estimated at 1.9m tonnes in
2009 are used for phosphate fertilizers since domestic ammonia production is mostly
integrated with urea production. Excluding any plant restarts, IFA expected India‘s ammonia
capacity to reach 20m tonne/year in 2014.
In the Middle East, new merchant ammonia capacity is expected in Iran and Saudi Arabia.
The IFA estimated the potential for seaborne ammonia exports to grow from 3.1m tonnes in
2009 to 4.2m tonnes in 2014.
According to the IFA, no major change in merchant ammonia capacity is expected

in Europe. It is believed that Europe will remain the net importer of seaborne ammonia for
the short term. IFA predicts an average import requirement of around 3m tonne/year.
2.4 ALTERNATIVE PROCESS ROUTE

The first breakthrough in large scale synthesis of ammonia resulted from the work of Fritz
Haber who found that ammonia can be produced by direct combination of two elements,
nitrogen and hydrogen with ratio 3:1 in the present of catalyst (iron oxide with small
quantities of cerium and chromium) at relatively high temperature and under a pressure of
about 200 atm. There are three process steps of industrial ammonia production which may
be subdivided into the following sections:
1) Synthesis gas production
2) Gas purification
3) Synthesis of ammonia
Synthesis gas production is the generation of hydrogen as well as the introduction of

nitrogen. Gas purification involves the removal of CO2 and CO. Synthesis of ammonia
covers the catalyst fixation of nitrogen at elevated temperature and pressure and the recovery
of the ammonia product.
20
2.4.1 Synthesis Gas Production
An important part of ammonia synthesis is to prepare nitrogen and hydrogen in a
stoichiometric ratio of 1:3. The preparation of this will need raw materials like water, air,
carbon-containing reducing medium that may contain hydrogen (natural gas, naphta and
petroleum) and nitrogen. It is widely regarded that only the carbon-containing materials and
hydrogen from other sources are considered as raw materials as the fact the abundance of air
that provides all of the nitrogen, while water generally supplies most of the hydrogen. The
feedstock term is referred to the consumption of fossil fuel to be used as feed.
Initially the processes of manufacturing synthesis gas were originally based on the
gasification of coke from hard coal and low temperature coke from brown coal by the means
of air and steam. After World War II, gaseous fossil fuels – oil and natural gas – were
employed as feedstock. This is due to the high hydrogen content that produces higher molar
ratios of hydrogen (H2) to carbon monoxide (CO) in the synthesis gas.
In essence there are a few processes which can produce hydrogen such as:
1. Steam reforming of natural gas
2. Partial oxidation of natural gas or oil with pure oxygen
3. Gasification of coal or coke with air (or oxygen) and steam
4. Water electrolysis
Steam reforming has become the most widely used process for producing hydrogen
commercially while partial oxidation process is the second widely used process.
2.4.1.1 Steam Reforming Process

Reforming is a general name for the reaction of a hydrocarbon, such as methane, with water
and/or carbon dioxide, to produce a mixture of carbon monoxide and hydrogen. The general
overall reaction for the steam reforming can be described by the following equations:
CnH(2n+2) + n H2O ⇌ n CO + (2 n + 1)H2
21
Or more specifically for methane, usually the major constituent of natural gas, as:
CH4 + H2O ⇌ CO + 3H2 Δ H0298 = + 206 kJ/mol
Taking place at the same time is the water gas shift reaction:
CO + H2O ⇌ CO2 + H2 Δ H0298 = - 41 kJ/mol
And later arriving at the formal overall reaction:

CH4 + 2 H2O ⇌ CO + 4H2 Δ H0298 = + 165 kJ/mol
Other than natural gas (consists mainly of methane), refinery gas (mixture of hydrocarbon
gases such as methane, propane, butane and other hydrocarbons) can also be used in steam
reforming. This process is the most important method for the production of hydrogen
containing gases.
steam
to CO2
D-9 removal air
flue gas to
air preheater
18 17
1
M-10 Waste heat boiler D-11 heat exchanger

D-8
heat exchanger primary reformer CO converter
secondary reformer
sulfur purifier
Figure 2.3: Diagram for Steam Reforming Process
2.4.1.2 Partial Oxidation Process

In partial oxidation, the methane and other hydrocarbons in natural gas are reacted with a
insufficient amount of oxygen that is not enough to completely oxidize the hydrocarbons to
carbon dioxide. With less than the stoichiometric amount of oxygen available for the
reaction, the reaction products contain primarily hydrogen (48%), carbon monoxide (3%),
and a relatively small amount of carbon dioxide (o.2%) and other impurities.
22
Partial oxidation is an exothermic process—it gives off heat. The process is, typically, much
faster than steam reforming and requires a smaller reactor vessel.. Some examples of
reaction using partial oxidation process:
Methane:
CH4 + ½O2 → CO + 2H2 ΔH150/1260 = +71.2 kJ/mol
Naphta:
CH2 + ½O2 → CO + H2 ΔH150/1260 = -16.7 kJ/mol
Heavy fuel oil:

CH + ½O2 → CO + ½H2 ΔH150/1260 = -48.1 kJ/mol
This process demands careful control of the feed rates to the combustion chamber. Heat
resisting materials are needed for the construction of the reaction vessels. These are made of
steel with a lining of many layers of firebricks.
2.4.1.3 Electrolysis Process

In water electrolysis electrical energy is applied to water resulting in the production of
hydrogen and oxygen:
2 H2O + Energy → 2 H2 + O2
Gas, steam
or electricity
Natural
gas
Oxygen Nitrogen
Steam Compresion Off gas
Steam
Drier Ammonia synthesis

Partial combustion
Nitrogen scrubbing
CO + steam
conversion to CO2 removal NH3
CO2 + H2
Figure 2.4: Partial Oxidation Process Diagram

Ammonia synthesis via partial combustion of natural gas
23
Hydrogen production by electrolysis has many advantages. It produces the highest hydrogen
purity (up to 99.999%), benefits from wide-spread raw materials availability (electricity and
water), boasts simple system architecture and can be scaled economically to serve
applications ranging from the smallest hydrogen uses to the larger-volume uses. However
the main disadvantage of water electrolysis is that electricity is an expensive source of
energy or ―fuel‖. As a result the technology generally is practical only for systems with
hydrogen requirements of approximately 2,000 SCF per hour or less.
Worldwide ammonia plants based on water electrolysis for hydrogen production are less
than 0.5 % and as mentioned above is a very uneconomic option. One metric ton of
ammonia requires theoretically 1976 m3 H2 (STP). A conventional alkaline water
electrolysis needs an electric energy supply of 4.6 MWh/1000 m3 H2 (STP) which will
correspond to 9.2 MWh. The theoretical heat equivalent of 3600 kJ/kWh (hydroelectric
power supply assumed) the hydrogen production for 1 t NH, consumes 32.7 GJ. When
generating the electric power from fossil feedstocks a conversion factor of 10 900 kJ/kWh
has to be used to give a figure of 99 GJ, which is more than three times the total energy
consumption of a modern natural-gas-based ammonia plant. The summary of all these three
options are presented in APPENDIX 2.1.
2.4.2 Carbon Dioxide Removal

The next step in synthesis of ammonia is to remove its carbon dioxide content. This may be
done by several methods as follow:
1. Water scrubbing process
2. Amine process
3. Hot carbonate process
The carbon dioxide is removed in a chemical or by physical absorption process. The

solvents used in chemical absorption processes are mainly aqueous amine solutions as Mono
Ethanolamine (MEA), Activated Methyl Diethanolamine (AMDEA) or hot potassium
carbonate solutions such as Benfield LoHeat system. Physical solvents are glycol
dimethylethers (Selexol), propylene carbonate and others.
24
The summary of all these three methods are presented in Table 6.
Table 2.6: Advantaged and Disadvantages of Carbon Removal Process
Process Advantages Disadvantages
Water  Simple plant  Excessive loss of hydrogen
scrubbing  No heat load  Very high pumping load
 Solvent availability at  Poor CO2 removal efficiency
minimal cost
Amine  Rapid absorption  High heat consumption on reactivation
 Excellent stability  Less economical at high concentration of
 Easy regeneration CO2
Hot  Inexpensive absorbent  Less economical at low CO2 concentrations
carbonate  Rapid absorption  Usually followed by a second absorber to
 Reactivation up to reach low CO2 concentrations in gas
100%
2.4.3 Ammonia Synthesis

Ammonia is synthesised from hydrogen and nitrogen. Natural gas contains some sulphurous
compounds which damage the catalysts used in this process. These are removed by reacting
them with zinc oxide:
ZnO + H2S → ZnS + H2O
The methane from the natural gas is then converted to hydrogen:

CH4 + H2O ↔ 3H2 + CO
CH4 + 2H2O ↔ 4H2 + CO2
CO + H2O ↔ H2 + CO2
Air is mixed in with the gas stream to give hydrogen: nitrogen ratio of 3:1. Water, carbon
monoxide and carbon dioxide (all of which poison the iron catalyst used in the ammonia
synthesis) are removed. The carbon monoxide is converted to carbon dioxide for use in urea
production, and the carbon dioxide removed:
CO + H2O ↔ CO2 + H2
25
The remaining traces of CO and CO2 are converted to methane and then the gases cooled
until the water becomes liquid and can be easily removed. The nitrogen and hydrogen are
then reacted at high temperature and pressure using an iron catalyst to form ammonia:
N2 + 3H2 ↔ 2NH3
Many variations of the original Haber process for the synthesis of ammonia are now being
used in commercial practice, some varying to such an extent that they are identified by a
name, often that of the group of men developing them. Important among these are Haber-
Bosch, Claude, Casale and Fauser processes. All of them are fundamentally the same in that
nitrogen is fixed with hydrogen as ammonia in the presence of a catalyst, but have variations
in arrangement and construction of equipment, composition of catalyst and temperature and
pressure used.
2.4.3.1 Haber - Bosch process

Main concept of Haber-Bosch process is combining hydrogen and nitrogen with ratio 3:1 by
combining process of higher temperature, higher pressure and with help of catalyst to
increase the process reaction. This process produces an ammonia, NH3 (g), yield of
approximately 25-35%. The Haber synthesis was developed into an industrial process by
Carl Bosch. The reaction between nitrogen gas and hydrogen gas to produce ammonia gas is
an exothermic equilibrium reaction, releasing 92.4kJ/mol of energy at 298K (25oC).
N2 + 3H2 ↔ 2NH3 ∆H = -92.4 kJ mol-1
Le Chatelier‘s principle states that by increasing the pressure causes the equilibrium position
to move to the right resulting in a higher yield of ammonia since there are more gas
molecules on the left hand side of the equation than there are on the right hand side of the
equation. Increasing the pressure means the system adjusts to reduce the effect of the
change, that is, to reduce the pressure by having fewer gas molecules.
It also stated that by decreasing the temperature causes the equilibrium position to move to
the right resulting in a higher yield of ammonia since the reaction is exothermic. Reducing
the temperature means the system will adjust to minimise the effect of the change, that is, it
26
will produce more heat since energy is a product of the reaction, and will therefore produce
more ammonia gas as well. However, the rate of the reaction at lower temperatures is
extremely slow, so a higher temperature must be used to speed up the reaction which results
in a lower yield of ammonia.
The Nitrogen Engineering Corporation system is typical of plants using this process. Similar
plants have been built in many countries. The ammonia concentration in the circulating gas
leaving the catalyst is 10-14 mole %. In the condenser the ammonia concentration is reduced
by condensation to equilibrium at the exit temperature of the condenser. The condensed
ammonia is separated from the circulating gas, and the gas is boosted in pressure by a
circulating compressor to overcome the pressure drop in the synthesis loop.
Natural
gas
Steam to turbines Steam
4 38
Air
Vent
CO2
24
BFW
Primary BFW Shift Methanation
Secondary Converter
reformer reformer
9 32
8 Ammonia synthesis
Desulfurizer NH3
CO2 Removal
Figure: Ammonia synthesis via natural gas reforming

Figure 2.5: Haber - Bosch process
Reference: Kent, J. A. (1983). "Riegel's Handbook of Industrial Chemistry." 8th Edition. Van Nostrand Reinhold Company.
2.4.3.2 The Claude Process

This process departs from the Haber process more than any of the other ammonia synthesis
processes. After the last ammonia receiver, the residual gas is wasted to the atmosphere or
utilized for its heat content. The large amount of heat evolved in operating at space
velocities of 100 000 with as much as 40 % of the hydrogen-nitrogen mixture converted to
ammonia in one pass, called for a special converter design. In his original process, Claude
27
used hydrogen purified by fractional distillation of coke oven gas, and nitrogen from the
liquefaction of air. Among advantages claimed for the Claude process are the following:
1. Greater compactness, simplicity and ease of construction of the converter since
under the high pressure used the gases have smaller volume;
2. Elimination of the expensive heat exchangers required in processes operated at lower
pressure
3. Removal of ammonia with water cooling alone, rather than by ammonia refrigerators
or scrubbing processes.
The disadvantages however are the shorted lives of the converter, high equipment
maintenance due to high-pressure operation and efficiency loss in wasting approximately 20
% of the makeup gas, which is unconverted. Modifications of the Claude process include
recycling of the gas through the synthesis converters.
Conv erters
Protec tor furnac e 10

R-1
Heat ex c hangers
Condens ers
Res idual gas
Oil filter
Ammonia rec eiv ers

Water c7ollec tor
3 parts H2 and 1 part Finis hed ammonia out

N2 at 1000 atm
Ammonia synthesis, Claude process.

Figure 2.6: Diagram of Claude Process
Reference: Standen, A. (1963). "Kirk-Othmer Encyclopedia of Chemical Technolog y." 2nd Edition. USA
2.4.3.3 The Casale Process

Pressures of 500-900 atm are used in this process, which is otherwise distinguished by the
method used for controlling catalyst temperature in the specially designed converter. A
method involving recirculating gas around a synthesis loop, similar to the Haber process is
28
used. As in the Claude process, the higher pressures allow liquefaction of the ammonia at
temperature that can be attained by water-cooling. The basis for heat control of the catalyst
is to leave 2 or 3% ammonia in the gas to the converter, thereby slowing down the rate of
formation of ammonia and eliminating excessive heating of the catalyst.
2.4.3.4 The Fauser Process

This process incorporates some features which are not previously mentioned. Electrolytic
hydrogen from Fauser cells and nitrogen from liquid air units or from a purification unit
utilizing tail gases from absorption towers in the ammonia oxidation plant are used. The
mixture of hydrogen and nitrogen is compressed to 200-300 atm and after passing through
oil separator goes to an oxygen burner.
Synthesis gas feed
Ejector
Oil filter
Purge gas to recover
Ammonia condenser
Ammonia converter
High pressure separator
H.P. liquid ammonia

to let down
Fig ure: Casale synthesis loop (hig h pressure)

Figure 2.7: Casale Synthesis Loop – High Pressure
Reference: Slack, A. B.(1977). "Ammonia Part III." New York: Marcel Dekker, Inc.
29
In the oxygen burner any oxygen contained in the gas mixture combines with hydrogen in
the presence of a copper catalyst; the water formed is condensed out in a cooler and
removed in a water separator.
water water
Oil filter Oxygen burner Cooler Water separatorcoolerCondenser Circulating compressor

Oil separator
Refrigerator Ammonia converter
condenser
and heat exchanger
Water
Steam
Oil separator Cooler
Pressure letdown vessel Ammonia compressor Condenser Storage evaporator
Hydrous ammonia tank Gas holder Anhydrous
ammonia
Absorption tower storage
Ammonia synthesis,Figure 2.8: Fauser Synthesis Unit

Fauser process.
Reference: Standen, A (1963). "Kirk-Othmer Encyclopedia of Chemical Technology." 2nd Edition. USA.
30
The following table shows the comparison between four options of Ammonia synthesis process:
Table 2.7: Comparison of Ammonia Synthesis Systems
Designation Pressure, Temperature, Catalyst Recirculation Conversion, Bleed to remove
atm °C % inert
Haber- 200-350 550 Doubly promoted Yes 10-30 Yes
Bosch iron
Claude 900-1000 500-650 Promoted iron No 40-85 No

Casale 600 500 Promoted iron Yes 15-18 No
Fauser 200 500 Promoted iron Yes 12-23 Yes
*40 % conversion of the gas upon passage through a single converter and 85 % conversion after passage through a series of
converters. Gas is vented after one passes through the converters.
31
2.5 SITE LOCATION
2.5.1 Site Consideration
Generally, geographical factor, raw material supplies, utilities support, logistics and land
price are among the important criteria used to select a suitable site location for chemical
process plant. Based on location rating procedures, the complete selection criteria for site
location are shown below. Three existing industrial estates have been evaluated to choose
the most suitable location for the construction of the new plant in Malaysia. The specified
industrial zones are as follow:
i) Gebeng Industrial Estates, Kuantan, Pahang.
ii) Kerteh Petrochemical Integrated Complex (KPIC), Kerteh, Terengganu
iii) Pasir Gudang Industrial Area, Johor
2.5.2 The Selection Criteria

The selections of the site location are based on the following criteria including:
i) Sources of raw materials
ii) Transportation
iii) Market prospective
iv) Utilities and infrastructures
v) Area for expansion possibility
vi) Land price
vii) Type of industry at each locations
2.5.2.1 Source of Raw Materials

One of the major factors in finalizing the selection of chemical plant site is the source of raw
materials. In order to produce large quantity of product which is Ammonia in this case, a
large volume of raw materials is required. Therefore the nearer plant site to the source of
raw material, the lower transportation and storage cost for raw materials. Besides, another
factor such as supply, freight or transportation expenses, availability and reliability of
supply, purify of raw materials and storage requirement also been considered.
32
2.5.2.2 Transportation
The future site should be closed to these three forms of major transportation facilities
available which are road network, seaport and airport. These three facilities will increase the
import and export activities. Raw materials via tankers are most well received from seaport
facilities. And as for personnel and equipment supplies, it can be transport via airport
facilities.
2.5.2.3 Market Prospective

This chosen site should be the intermediate of the distribution center. This is because the
cost of product distribution and required for cargo is influenced by this factor. It is a very
crucial consideration of the proximity to the major markets in locating suitable area for plant
development.
2.5.2.4 Utilities and Infrastructures

Ports, airports, railways, roadways, storage facilities, water supply and also waste facilities
are part of utilities and infrastructures for a plant. If there is any commercial plant as
neighbor plant, the utilities and infrastructure may shared. The main factor of smooth
running productivity of a designed plant is by ensuring availability of power supply plants
and adequate local water supply.
2.5.2.5 Area for Expansion Possibility

The plant has a probability to expand after several years of operation, so the selected
location should take into consideration about the vacant land beside the location.
2.5.2.6 Land Price

The cost of land price plays a significant factor in developing a plant at a suitable area. It is
indeed important to select the lowest land price since construction of a new plant is essential
to gain highest economic value.
33
2.5.2.7 Type of Industry at Each Location
The types of industry surrounding the places chosen also give effluent to the plant‘s growth.
If the plant is located beside an existing plant, it will help the plant to develop easily. There
would also be infrastructures that could be used by the plant when its operation starts.
2.5.3 Overview of Site Location

Below are the comparisons of selection between the three potential areas:
Table 2.8: Comparison of Three Selected Location (Sources: MIDA 2010)
Gebeng Industrial Kerteh
Pasir Gudang
Selection Criteria Estate Petrochemical
Industrial Estate
Phase IV Integrated Complex
 30 km from
Kuantan City  36 km from  33 km from
Location
 5 km from Johor Bharu Kemaman Port
Kuantan Port
 Pasir Gudang
Port  Kuantan Port  Kemaman Port
Port
 Senai
International
 Sultan Ahmad Airport, Johor  Kuala
Airport Shah Airport,  Changi Terengganu
Kuantan International Airport
Facilities and Airport,
infrastructures Singapore
 Linking
 Linking Kuala
Kerteh-  Linking Kerteh-
Railways Lumpur–Port
Gebeng- Gebeng-Kuantan
Dickson
Kuantan
 East Coast  North-South  East Coast
Roadways
Highway Highway Highway
 Petrochemical
 Heavy
 Petrochemicals
industries
 Chemicals  Gas Processing
Type of industry  Palm Oil
 Petrochemicals Plant
Preferred Processing
 Plastics  Chemicals and
 Shipbuilding
Plastics
 Transportation
and Logistics
Area available  1618.78 acres  44.16 acres  2000 acres
34
Land price  RM32.30 to  RM88.10 to  RM2.00 to
(per m2) RM118.40 RM 236.80 RM60.30
 Gas Malaysia  Gas Malaysia  Gas Malaysia
Sources of raw materials
Sdn Bhd, Sdn Bhd, Pasir Sdn Bhd,
Gebeng. Gudang. Kerteh.
 Tenaga  Tasik Kenyir
Nasional Hydroelectric
Berhad  Sultan Iskandar Dam (400 MW)
(1200MW), Power Station  IPP YTL (600
Power Supply
Tanjung (644 MW) MW)
Gelang  Paka Power plant
 CUF Gebeng (900 MW)
(42MW)  CUF Kerteh
 Loji Air  Bukit Sah
Semambu  Syarikat Air  Sungai Cherol
Water Supply
 CUF Johor  Sungai Kemasik
Gebeng  CUF Kerteh
 Special land
 Research
Premium.
 Pioneer Status incentives
 Discounts in
 ITA  High
assessment rates
 Infrastructure technology
during first 3
Allowance. incentive.
years of
 Five-year  Minimal
Incentives operation.
exemption on customs
 Deferred land
import duty. formalities and
Premium
 5 % discount duty free import
payment.
on monthly  Minimal
 Discount of 25-
electricity bills. formalities in
38% on water
export
rates.
Weight method has been used in order to find the most feasible location for the plant. The
ranking between 5 (highest) to 1 (lowest) has been assigned to each selected criteria. After
doing the comparison, Gebeng Industrial Estate, Kuantan, Pahang is selected as the most
suitable site for constructing the plant based on the characteristics below:
35
Table 2.9: Weight Method to Choose the Site for the Plant
Selected Site Gebeng Industrial Pasir Gudang Kerteh Petrochemical

Estate Industrial Estate Integrated Complex
Phase IV
Types of Industrial 5 5 5
Price and Land Areas 4 3 5
Raw Material Sources 5 5 5
Transportation 4 4 3
Utilities 5 4 4
TOTAL MARKS 23/25 21/25 22/25
PERCENTAGES (%) 88 76 80
RANKING 1 (selected) 3 2
i) The suppliers can meet demand for raw materials, which is located near to
the proposed plant. Channeling the raw materials to the plant using pipelines
can help to reduce the land transportation cost.
ii) Existence of all major transportation networks to the proposed plant location
offers wider range of marketability options, locally or internationally.
iii) Strategically located in the heart of South East Asia, one of the world‘s
fastest growing economic regions, where Kuantan Port allows for ease of
transportation all over the world with all year round deep-water seaport.
iv) Economical local work force due to the existence of several training centre
institutions.
v) Ready built industrial land for heavy industries reduce cost for site
preparation
vi) Inexpensive cost of land and availability of vacant site for construction and
expansion.
The map of Gebeng is shown in APPENDIX 2.2.
36
CHAPTER 3
DESIGN CONCEPT AND SYNTHESIS
3.1 INTRODUCTION
In designing a plant, process design and optimization is the most important part that must be
taken into consideration. The main objective of conceptual design is to determine the most
efficient and economical process plant. The process decision hierarchy proposed by Douglas
is the main approach used for conceptual design and process flow sheeting in this project.
As a result, estimation of costs along with equipments size can be calculated while
proceeding through the levels in the hierarchy to design a plant with high profitability. There
are five levels in Hierarchy of Decisions based on (Douglas, 1988):
i. Level 1: Batch versus continuous
ii. Level 2: Input-output structure of the flow sheet
iii. Level 3: Reactor design and structure of the flow sheet
iv. Level 4: General structure of separation system
v. Level 5: Heat exchanger network
The minimum design knowledge required is based on these heuristics. Thus, the base case is
not intended to be a final or detailed design. Importantly, numbers of decisions will be
made in the hierarchy that can be re-considered in order to identify alternative process
options.
Onion model has also been used as our guidelines in designing the Ammonia production
plant. Basically, Onion model is a layered approach used to achieve high quality process.
The Onion diagram as shows in Figure 4.1 emphasizes the sequential, or hierarchical, nature
of process design. For example, a reactor is needed before the separation and recycle system
can be designed and so on (Smith, 2005). In order to optimize selectivity and conversion in
the reaction system, process conditions are often frozen. Thus, it can minimize the process
development time.
37
Figure 3.1: Onion Model Approach
3.1.1 Batch VS Continuous

Batch process generally contains several units that designed to be started and stopped
frequently. During a normal operating cycle, (Douglas, 1988) mentioned that the units are
filled with materials and perform desired function for specific period. Then, the units are
shut down and drained, before it is finally cleaned before repeating the cycle again. Batch
process usually consists of one or more units that operate continuously and can accomplish
several operations in single batch vessel.
As for continuous process, (Douglas, 1988) stated that it needs individual vessel for each
operations. Every unit of this process operate 24 hours per day, 7 days per week for a year at
almost constant conditions prior to plant shut down for maintenance purposes. (Douglas,
1988) also had proposed few guidelines that need to be taken into considerations prior to
select the process operation mode to be used. Based on these guidelines, continuous process
is more preferable to be applied in our design. Table 3.1 summarized the selection criteria of
our design.
38
3.2 INPUT AND OUTPUT STRUCTURE
3.2.1 General input-output structure
Table 3.1: Comparison between Batch and Continuous Process
Selection Criteria Batch Continuous
Production Capacity In general, batch process is Continuous process
suitable for production generally suitable for
capacity that less than production capacity that
10×106 lb/yr. more than 10×106 lb/yr. For
our design, the estimated
production capacity is
397980 ton/yr which is
equivalent to 795,960,000
lb/yr.
Thus, continuous process
is preferable.
General Market Demand Batch process basically This process is preferable
preferable for seasonal for continuous production
demand and short lifetime throughout a year. Since
products. The plant is used our plant is expected to be
to produce another product operating 330 days per
during the period of no year, continuous process is
demand. more preferable.
Operational Problems This process is usually ideal The reaction rate of all
when handling slow units in our design are
reaction since it is basically fast due to usage
periodically started and of catalysts in numbers of
stopped. The possibility of sections such as nickel-
slurry formation is also low based catalyst in both
since the equipment is primary reformer and
periodically clean after secondary reformer and
each process. iron oxide in ammonia
converter. In lieu to this,
there will be low possibility
of slurry formation. Hence,
continuous process is
preferable.
In general, input information normally available at the initial stage of a design problem.
Based on (Douglas, 1988) in order to fix the input-output structure of a flowsheet, a box is
drawn around the total process. Then the raw materials that need to be fed to the process,
products and by-products that have to be removed will be known.
39
Figure 3.2: Input-Output Structure
In order to fix the input-output structure of the flowsheet, there are few parameters that need
to be discussed as per below:
i. Should we purify the feed streams before they enter the process?
The main of raw material for Ammonia production is natural gas. This reactant can be
obtained all year round as there are local suppliers. Table 3.2 below shows the specifications
of the raw materials.
Table 3.2: Specifications of the Natural Gas
Chemical Name Portion
Methane 92.73 %
Ethane 4.07 %
Other hydrocarbons 3.20 %
The feed streams entering the reactor do not require purification such as Carbon dioxide,
removal unit, Mercury removal unit or Sulfur removal unit. This is because; there is no
carbon dioxide, mercury, sulfur containment in the feed stream as per gas specification from
the Table 3.2. Plus, it would be more economical that purification unit is not required.
Furthermore, the feed is not expected to contain significant amount of impurities and
catalyst poison. Hence, feed purification is unnecessary.
ii. Should we remove or recycle a reversible by-product?

The reactions involve in the ammonia production; Primary reformer unit, Secondary
reformer unit, Shift conversion unit, Methanation unit and Ammonia synthesis unit are
reversible reactions as shown in the Table 3.3 below.
40
Table 3.3: Reactions of Ammonia Production
Name of Unit Reaction
Primary Reformer CH4 + H2O ⇌ CO + 3H2
C2H6 + 2H2O ⇌ 2CO + 5H2
C3H8 + 3H2O ⇌ 3CO + 7H2
C4H10 + 4H2O ⇌ 4CO + 9H2
CO + H2O ⇌ CO2 + H2
Secondary Reformer CH4 + H20 ⇌ CO + 3H2
CH4 + 2CO +3O2 ⇌ 3CO2 + 2H2
High Temperature Shift Conversion CO + H2O ⇌ CO2 + H2
Low Temperature Shift Conversion CO + H2O ⇌ CO2 + H2
Methanation CO + 3H2 → CH4 + H20
CO2 + 4H2 → CH4 + 2H20
Ammonia Synthesis N2 + 3H2 ⇌ 2NH3
According to the reaction in Methanation process, by-product produced from reactions is

H2O. H2O will be recycled back into Primary reformer unit as a steam, shift conversion unit
and also in the utility part. For CO2 gas which produced as by product from Shift Conversion
unit will be removed from the process in the CO2 removal unit since CO2 is poison the
ammonia catalyst and sell.
iii. Should we use a gas recycle and purge stream?

Since the percentage conversion of ammonia synthesis is only 30%, therefore recycle stream
is required in order to get more products. The purge stream is also need in order to release a
bit of ammonia gas to prevent increasing of pressure and accumulate while process keep
running continuously.
iv. Should we not bother to recover and recycle some reactants?

According to our design guidelines, it is stated that we should all valuable materials. Since
some materials, such as water, are much less valuable than organic ones, we do not bother to
recover and recycle unconverted amounts of these components. We feed them to the process
so that they would be converted, but often we feed them as an excess to let some other
valuable reactant will achieve a complete conversion.
41
v. How many product streams will there be?
In order to determine the number of product streams that will leave the process, all the
components that are expected to leave reactor are listed. The components and their
destinations are as shown in Table 3.4.
Table 3.4: Component Destinations
No Components Destination
1 H2 Recycle
2 N2 Recycle
3 CH4 Recycle
4 CO2 By product
5 CO By product
6 NH3 Product / Purge
7 H2O Recycle
3.2.2 Ammonia Processes Involved

The Requirements for ammonia productions are to create suitable feedstock to synthesis
ammonia. Below is the purpose of the steps before ammonia synthesis:
 To synthesize H2 and N2
 To remove CO and CO2 (poison to NH3 synthesis reaction)
Natural gas is used as the main feed for ammonia production in order to produce hydrogen
gas (H2) and N2 is produced from air. Below are the selected processes used to produces the
ammonia.
3.2.2.1 Primary Reformer

The function of this process is to synthesis the hydrocarbons in the natural gas into hydrogen
(H2), carbon monoxide (CO), carbon dioxide (CO2) and traces of high hydrocarbon into
methane by adding high pressure steam together in inlet stream. This mixture will react in
side two stages of reformer. The main reaction in primary reformer is to be expected to
reach conversion of 75%. Catalyst used in these reactions is 15% Nickel alloy as catalyst
support. Operation parameter inside primary reformer, temperature is 760-840°C and
pressure is in the range of 27 - 39 bar (M.Boumaza, 2007).
42
Main reaction:
CH4+ H 2O ⇌ CO + 3H2
Excess of reactant = CH4
Conversion = 75%.
By-product reaction:
CO + H2O ⇌ CO2 + H2
Excess of reactant = CO
Conversion = 75%.
3.2.2.2 Secondary Reformer

The function of this process is to further reform hydrocarbons natural gas into steam (H2O)
and CO2 by combustion with process air, oxygen (O2). Other component such as nitrogen
(N2) and inert gases in process air is eventually will be carried over with process gas flow as
inert throughout the reactors till it reaches synthesis ammonia gas. Catalyst used in these
reactions is nickel as catalyst support. Operation parameter inside secondary reformer,
temperature is 800-1000oC and pressure is approximately 30 bars (Appl D. , 1999).
Combustion reaction:
CH4 + 2CO + 3O2 ⇌ 3CO2 + 2H2O
Conversion = 100%.
Main reaction:
CH4 + 2H2O ⇌ CO2 + 4H2
Conversion = 85%.
43
3.2.2.3 Shift Conversion
The function of this process is to convert traces of CO into CO2 and increase H2 yield by
reaction with steam. Here the same reaction occurs twice. CO converter is divided into two
stages which are in high (HT) and low (LT) temperature. For high temperature CO shift
converter, catalyst used is Cr-Fe oxide. Operation parameter inside high temperature CO
shift converter, temperature is 300oC -500oC and pressure is in the range of 32 - 35 bars
(Appl D. , 1999). For low temperature CO shift converter, catalysts used are Cu-Zn oxide
and alumina. Operation parameter inside high temperature CO shift converter, temperature
is 200oC -210oC and pressure is in the range of 33 - 35 bars.
Main reaction:
CO + H2O ⇌ CO2 + H2
Conversion at high temperature-shift converter = 90%.
Conversion at low temperature-shift converter = 90%.
3.2.2.4 CO2 Removal

The function of this process is the remove carbon dioxide (CO2) as it poisons to catalyst in
the ammonia synthesis unit. The type of separation technique selected is the absorption
process using MDEA. CO2 will be introduced in the absorber at the bottom and goes up
through contractor plates in the column. It contacts lean amine solution (high concentration
amine solution with no presence of CO2) which fed at the top of the column. CO2 is
absorbed by the amine solution and leaves the absorber to stripper for removing the
absorbed CO2. Then the stripped or lean amine will be sent back to the absorber. The
absorption column operates at high pressure while the stripper is operated at closer to
atmospheric pressure. The temperature at the absorption column is close to the ambient
temperature (30-40 oC) (oilandgas, 2008).
3.2.2.5 Methanation
The Function of this unit is to ensure that traces of CO and CO2 are not present inside
ammonia synthesis gas, because CO and CO2 will be poisonous to ammonia synthesis
44
reactor catalyst. Catalyst used in these reactions is Nickel Oxide. Operation parameter inside
secondary reformer, temperature is 250 - 350oC and pressure is in the range of 25-30 bars
(Appl D. , 1999).
Main reaction:
1. CO + 3H2 → CH4 + H2O
Conversion = 100%.
2. CO2 + 4H2 → CH4 + 2H2O

Excess of reactant = CO2
Conversion = 100%.
3.2.2.6 Ammonia Synthesis Reactor (Haber process)

The feeds, hydrogen will be obtained from the steam methane reforming while nitrogen
produced from process air feed from secondary reforming. Reaction between these two
components will undergo Haber process to produce ammonia in gas form. The reaction is
carried out at pressure of 150 - 250 bar and temperature of 400 - 550 °C. The excess reactant
is hydrogen. A conversion of 30% weight percent can be obtained at the start of the reaction
cycle (Appl D. , 1999). To increase reaction conversion recycle of synthesis gas reactor must
be done. Ammonia synthesis favors reaction at high pressure and low temperature. The
reaction that occur to synthesize ammonia is shown as below:
3H2 + N2 ⇌ 2NH3
Excess of reactant = H2
3.3 REACTOR DESIGN AND REACTOR NETWORK SYNTHESIS

The reactor is the heart of most processes; developments in process technology often centre
on improvements in the design and operation of the reactor (Johnston, Martyn S. Ray and
David W., 1989). Since most of the process design starts with the reactor, the first decisions
45
are those that lead to the choice of reactor. These decisions are amongst the most important
in the whole process design.
Good reactor performance is of paramount importance in determining the economic viability

of the overall design and fundamentally important to the environmental impact of the
process. In addition to the desired products, reactors produce unwanted byproducts. These
unwanted byproducts not only lead to a loss of revenue but can also create environmental
problems (Smith, 2005).
The issue that need to be addressed here are basically reactor type, catalyst, size, operating
conditions (temperature and pressure), phase and feed conditions (concentration and
temperature).
3.3.1 Reaction Information

Generally, there are two exothermic reactions in ammonia synthesis which are,
Water – gas shift: CO + H2O ⇌ CO2 + H2 (1)
Ammonia synthesis: N2 + 3H2 ⇌ 2NH3 (2)
In these reactions, high temperatures correspond to small reactor volumes, but for these
reactions the equilibrium conversion decreases as the reactor temperature increases. Hence,
these reactions are often carried out in a series of adiabatic beds with either intermediate
heat exchangers to cool the gases or a bypass of cold feed to decrease the temperatures
between the beds.
The main reaction in path of producing ammonia is ammonia synthesis reaction (2). This
reaction basically covers the catalyst fixation of nitrogen at elevated temperature and
pressure and the recovery of the ammonia product.
46
3.3.2 Reactor Type
3.3.2.1 Flow Pattern Models of Reactor
Basically, selection of reactor is kind of crucial since it is important in order to ensure the
feed operates at its maximum. There are variety of reactors exist in current industries, but in
general, all of them can classified under these three major types of reactors (Ullman, 2004).
There are batch stirred-tank reactor, continuous stirred-tank reactor and tubular reactor.
APPENDIX 3.1 summarized all the details consisting of principal application, residence
time, flow patterns, advantages and disadvantages of these three types of reactors.
Selection Justification:
The reactor type chosen is tubular reactor. The main reason of choosing this reactor is
mainly because the reaction involves is homogenous gas phase reaction. In this synthesis
process, reactor operates at high pressure and temperature. It also approaches the
equilibrium conversion of about 20 to 30 percent in each pass. The ammonia is separated
from unreacted H2 and N2, and these are recycled back to the reactor.
In ammonia synthesis, high temperatures correspond to small reactor volumes. For

exothermic reactions, the equilibrium conversion decreases as the temperature increases and
thus, a good temperature control is needed. Therefore, these reactions are often carried out in
a series of adiabatic beds with either intermediate heat exchangers to cool the gases or
bypass the cold feed to decrease the temperatures between the beds. Some compromise can
be achieved between high temperatures involving small reactor volumes and high
equilibrium conversions. In addition, tubular plug flow reactor is relatively easy to maintain
with no moving parts, and it usually produces the highest conversion per reactor volume of
any of the flow reactors.
CSTR are not chosen due to its lower final conversion than in other basic reactor types
because of complete mixing. As for batch stirred reactor, it has a limited temperature control
capabilities, especially with highly endothermic or exothermic reactions like the conversion
of H2 and N2 to NH3. Plus, no agitation is needed for this reaction.
47
3.3.2.2 Reactor Configurations
There are eight configuration of reactors based on (Smith, 2005). However, since the
reaction in our plant is using catalyst, only two types of catalytic reactors will be taken into
considerations under this topic which are fixed-bed catalytic reactors and fluidized-bed
catalytic reactors. APPENDIX 3.2 summarized the comparisons between these two catalytic
reactors.
Selection justification:
The configuration of reactor chosen is fixed-bed catalytic reactor. The mainly reason of
choosing this reactor is due to its highest conversion per weight of catalyst as compared to
any catalytic reactor. Thus, it allows high catalyst activity in small catalyst particles. In
addition, fixed bed reactor which behaves as plug flow allows efficient contacting between
reactants and catalyst. The catalyst of the reactor also may be placed in one or more fixed
beds (i.e., layers across the reactor) or may be distributed in a series of parallel long tubes.
Thus, it allows careful control of residence time which is essential to discourage the
formation of byproducts, and also to control contact times between reactants and catalyst. As
for fluidized bed, the reactor is complex with considerable by-passing. Such behavior is
unsatisfactory for effective contacting, which requires much more catalyst for high gas
conversion, and greatly depresses the amount of intermediate which can be formed in series
reactions.
In summary, fixed bed reactors are commonly used in industrial catalytic industries due to
their flexibility, efficiency and are generally low-cost and maintenance reactors. According
to (Coker, 2001) also, the latter type of fixed-bed reactor is widely used in industry (e.g.,
ammonia synthesis) and offers several advantages such as gives less chance for back
mixing.
48
Figure 3.3: Catalytic Fixed-bed Reactor
3.3.2.3 Catalysts
The ammonia synthesis catalyst basically can be viewed as the heart of an ammonia plant.
Although the proportionate cost of catalysts compared to the total cost of a modern ammonia
synthesis plant is negligible, the economics of the total process are determined considerably
by the performance of the ammonia catalyst (Appl M. , 1999). Generally, there are five
sections of our plant that will be using catalysts:
i. Primary reformer
The table below summarized the details of catalyst that will be used for this section
which is nickel catalyst.
Table 3.5: The Detail of Nickel Catalyst (Primary Reformer)
Bulk Density 950 kg / m3
Description Over time, physical deterioration of the catalyst can lead to increased
pressure drop and reduced activity. Pure alumina can be brittle and
vulnerable to the effects of thermal shocks. The addition of calcium to the
alumina carrier increases thermoshock resistance and mechanical strength
while inhibiting side reactions.
Composition  NiO: 16.5%  Al2O3: 74.5%
(wt %)  CaO: 6.0%  Si: <0.1%
 REO (Rare Earth): 3.0%
49
ii. Secondary reformer
This section basically used nickel as catalyst but in different composition and
support. The details of the catalyst used for this section is summarized as follow:
Table 3.6: The Detail of Nickel Catalyst (Secondary Reformer)
Bulk Density  1000 kg / m3 (Active Heat Shield)
 950 kg / m3 (Main Catalyst)
Description Over time, thermal and physical deterioration of the catalyst can
lead to reduced activity and increased pressure drop. In order to
overcome this, stable ring shape and high crush strength resist
attrition while the addition of calcium to its alumina base adds
excellent thermal durability and thermoshock resistance.
Composition In general, this catalyst can be divided into two main groups
(wt %) which are the active heat shield and main catalyst. The
compositions of these two groups are as follow:
Active Heat Shield: Main Catalyst:
 NiO: 5.1%  NiO: 15.2%
 CaO: 5.5%  CaO: 6.0%
 Al2O3: 89.4%  Al2O3: 78.8%
 SiO: <0.1%  SiO: <0.1%
iii. Shift Converter

There are two types of converters under this section which are high temperature shift
converter and low temperature shift converter. Both these converters basically using
different type of catalysts; high temperature shift converter is using iron oxide
catalyst while low temperature shift converter is using copper zink catalyst. The
tables below summarized the details of these two catalysts.
Table 3.7: The Details Iron-Oxide Catalyst (HTS)
Bulk Density  1250-1450 kg / m3
Description Using ferrous (Fe2+) nitrate as raw material, major components are
Fe2O3 and Cr2O3, and also contain a small quantity of promoter. It
has high strength in reducing phase and the strength doesn't lower
subject to reduction. No brittle failure or crush during long
operation period.
Composition  Fe2O3: 78.0% - 82.0%
(wt %)  Cr2O3: 9.0% - 10.0%
 CuO: 1.5% - 2.5%
 Sulphur: 0.025% max
50
However, as for low temperature shift converter, the catalyst used is copper-zink
catalyst. The table below summarized the details of this catalyst.
Table 3.8: The Details Copper-Zink Catalyst (LTS)
Bulk Density  1500 kg / m3
Description Due to copper‘s high affinity for sulfur, even trace amounts, whether
due to insufficient feedstock purification or plant upset, can poison
the low temperature shift catalyst. However, this catalyst provides
increased poison resistance due to its high zinc oxide content which
allows it to effectively act as its own guard bed.
Composition  CuO: 37.0%
(wt %)  ZnO: 37.0%
 Al2O3: 26%
iv. Methanator
The catalyst that is nickel oxide used for this section mainly consists of nickel
crystallite. The table below summarized the details of this catalyst.
Table 3.9: The Details Nickel Oxide Catalyst (Methanation)
Bulk Density  1100 kg / m3
Description The active species consists of nickel crystallites which can
sinter and aggregate over time reducing both surface area and
catalytic activity. Temporary overheating due to plant upset
can accelerate this aging process.
Composition  NiO: >25.4%
(wt %)  REO: >7.0%
 Al2O3: 67.6%
51
v. Ammonia Converter
For Ammonia Synthesis, the most suitable catalyst is triply promoted iron oxide catalyst.
The table below summarized the details of this catalyst:
Table 3.10: The Details of Iron-Oxide Catalyst (Ammonia Converter)
Bulk Density  2650 kg/m3
Description The activity is expected to be loss in service by 30-50% in three years
depending on severity of operating conditions and presence of poisons.
Catalyst is slowly deactivated at operating temperatures above 530oC.
This catalyst however can be poisoned by hydrocarbons such as
lubricating oils and olefins which can crack and plug pores.
Composition  FeO: 32.6%
(wt %)  Al2O3: 4.1%
 K2O: 0.9%
 CaO:1.4%
 SiO2: 0.7
 TiO2: 0.7
Generally, longer catalyst life and higher activity should be important goals for economical
purposes. Higher conversions reduce power requirements by lowering the amount of
recycle. A catalyst active at lower temperature would be most attractive for exothermic
reaction (Rase, 1977).
3.3.3 Operating Conditions

3.3.3.1 Temperature and Pressure
The table below summarized the heat and temperature properties of both feedstock and
product.
Table 3.11: The Properties of Main Feedstock and Product
Component Natural Gas Ammonia
(Feedstock) (Product)
Latent Heat of Vaporization, ∆Hv 510 1371.2
(kJ/kg)
Boiling Point, BP (°C) -162 -33.5
From the table, we can see that the main feedstock in ammonia production is natural gas.
Although synthesis of ammonia is an exothermic reaction, obtaining the raw-materials is an
energy consuming step, especially for hydrogen, if water is use as resource. If part of the
hydrogen is supplied by hydrocarbons, energy requirements are less. This makes natural gas
52
the most attractive side resource, because only this way about 50 % of hydrogen can be
obtained from water.
3.3.3.2 Phase and Feed Condition

The synthesis gas entering the synthesis loop contains 1.0-1.5% Ar + CH4 which do not
react, acting as inerts which build up to significant levels which could inhibit reaction. In
order to keep the Ar and CH4 at an acceptable level a purge is taken off the loop which
represents 4-6% of the total synthesis gas supplied into the unit (the flash gas flow above is
too small to purge off large amounts of argon and methane).
Generally, the natural gas is admitted to the primary reformer, where part of it is used as
feedstock, together with steam to make hydrogen. The remainder of it is used as fuel gas to
fire the reformer. Air is added to the secondary reformer where further reactions take place
involving oxygen. Nitrogen is introduced into the secondary reformer with the air and this
flow is controlled so that the synthesis gas ultimately entering the synthesis contains a ratio
of 3:1 [H:N].
3.4 SEPARATION AND RECYCLE SYSTEM SYNTHESIS

Separation is an important phase in almost all chemical engineering processes. According to
(Douglas, 1988), prior to determine the general structure of the separation system, firstly we
need to determine the phase of the reactor effluent stream. There are three possibilities for
vapor-liquid process, but as for our project which is production of ammonia, we just
consider the possibility as stated below, where the reactant effluent is a two-phase mixture:
 If the reactor effluent is a two-phase mixture, we can use the reactor as a phase
splitter (or put a flash drum after the reactor). We send the liquids to a liquid to a
separation system. If the reactor is operating above cooling-water temperature, we
usually cool the reactor vapor stream to 100oF and phase-split this stream as in figure
below. If the low-temperature flash liquid we obtain contains mostly reactants (and
no product components that are formed as intermediates in a consecutive reaction
scheme), then we recycle them to the reactor (we have the equivalent of a reflux
condenser). However, if the low-temperature flash liquid contains mostly products,
we send this stream to liquid recovery system. The low-temperature flash vapor is
53
usually sent to a vapor recovery system. But, if the reactor effluent stream contains
only a small amount of vapor, we often send the reactor effluent directly to a liquid
separation system (i.e. distillation train).
Figure 3.4: Separation System for Reactor Exit is Vapor and Liquid
3.4.1 Separation prior to Ammonia Synthesis

Prior to ammonia synthesis takes place, there are four series of separation process. The main
purpose of this separation process is basically to remove the water from the effluent of the
methanation process and purify the gas needed for ammonia synthesis. The liquid which is
the water will be removed by using two-phase separator (flash drum) in order to separate the
liquid and gas phase. The gas which are mainly N2 and H2 will rise to the top of the
separator prior to entering the mixer before proceed with ammonia synthesis process inside
the reactor. The reasons of choosing this two-phase separator are:
i. To recover valuable product: N2 and H2.
ii. Improve product purity by ensuring only pure N2 and H2 gas that will be mixed prior
to ammonia synthesis reaction.
iii. The gas-liquid ratio is high for all desired products: N2, H2 and water.
3.4.2 Separation in Ammonia Synthesis

The effluent from the ammonia reactor will be in two phases; liquid and gas. The effluent is
cooled and mixed with fresh synthesis gas, then compressed before ammonia separation.
Basically, the general features of two-phase separator are:
i. Separate two phase (gas and liquid) in the inlet stream.
ii. Retention time is short since only need to separate liquid from gas.
54
iii. Purging time is short due to negligible dead volume.
In two-phase separator, the gas within the process stream continues to rise as the heavier
liquids separate, attach and coalesce into droplets within the matrix. As the droplets within
the matrix increase, so does their weight. Consequently, the heavier droplets travel toward
the bottom of the separator due to gravity.
Figure 3.5: Two-phase Separator
3.4.3 CO2 removal

Carbon dioxide needs to be removed prior to methanation process since it is a poison to the
catalyst in that process inside the absorber. For this purpose, methyldiethanolamine or
MDEA is chosen to be used as the absorption solution since it is well known for its
relatively slow reaction rate for CO2. However, MDEA is not usually associated with
situations where the removal of large amounts of CO2 is desired (Jerry A. Bullin, John C.
Polasek, and Stephen T. Donnely, 2006).
MDEA has a number of properties which make it attractive for CO2 removal:
i. High solution concentration (up to 50-55 wt%).
ii. High acid gas loading.
iii. Low corrosion even at high solution loadings.
55
iv. Slow degradation rates.
v. Lower heats of reaction.
vi. Low vapor pressure and solution losses.
The primary disadvantages are:

i. Slow reaction rate with CO2.
ii. Tendency to foam at high concentration.
iii. Higher cost.
However, the slow reaction rate can usually be overcome by proper operating temperatures
and the design of the trays in the absorber to give adequate liquid residence time. The slow
reaction rate can also be overcome to a significant degree by adding one or two of the more
reactive primary or secondary amines to form a mixture of amines in water. The primary or
secondary amines are added in the amount of 5-10% of the total amine present.
In most applications, considerably less MDEA is consumed or lost which assists in
mitigating the higher costs. Thus the disadvantages associated with the use of MDEA and
MDEA based mixtures of amines can usually be overcome to an acceptable level.
3.4.4 Recycle Structure System and Purge System

3.4.4.1 Recycle Structure System
A common feature of many chemical processes is the presence of recycle. One example of
mass recycle is a reactor, separator with recycle of unreacted reactant. This configuration is
very common in industry, and includes both liquid phase and gas phase systems. Some
examples of gas phase systems are ammonia and methanol plants (T. Larsson, S. Skogestad
and Cheng-Ching Yu, 1999).
(Nicola Nikacevic, Mina Jovanovic and Menka Petkovska, 2010) also mentioned that
removal of the product from the system would shift equilibrium towards more production of
ammonia, as the driving force for the forward reaction would remain high in the reactor.
Higher conversions would result in minimization of the recycle loop which would lead to
energy and investments savings.
56
The main factors that dictate the recycle structure of a process are basically:
i. Reactor conversion: In order to achieve complete conversion of the reaction, the
reactor might require extremely long residence time, which is normally uneconomic.
If it is incomplete conversion, whereby the unreacted gases are valuable to be
disposed. Therefore, the reactor requires a recycle for unconverted feed material to
improve the conversion.
ii. By product formation: The unreacted feed is normally recycled but the byproduct
must be removed to maintain the overall material balance. Instead using two
separators to remove by product, a purge can be used and save the cost of separator.
However, in our production, the main purpose of purging is to remove the inert such
as methane, argon and helium. Because they are inert, they tend to concentrate in the
synthesis loop and must be removed to maintain the material balance.
iii. Improve selectivity: In systems of multiple reactions, by products are sometimes
formed in the reversible reaction. The formation of by product can be inhibited by
recycling and suppress the byproduct formation in the reversible reaction.
In our design, ammonia is separated from the unreacted gas by condensation in the two-
phase separator, which requires relatively low temperatures for reasonable efficiency. The
unconverted gas is supplemented with fresh synthesis gas and recycled to the converter.
After the gas leaves the synthesis converter, ammonia is condensed by cooling and the
recycle gas is referred to the recycle compressor. The main purpose of this recycling is
basically to recover the hydrogen and other unreacted gases such as nitrogen and inert gases.
Figure 14 shows the general recycle structure of the process.
From the figure, gases (H2 and N2) that are not reacted will be recycled back to the reactor
for further reaction as conversion of ammonia synthesis is only 30%. The continual recycle
can increase the conversion to as higher as 98%.
57
Figure 3.6: The General Recycle Structure of Ammonia Synthesis Process
3.4.4.2 Purge System

Conventional reforming with methanation as the final purification step produces a synthesis
gas containing inerts (methane and argon) in quantities that do not dissolve in the condensed
ammonia. Thus, these inerts need to be removed by taking out a purge stream from the loop.
The concentration of the inert gases (methane and argon) in the synthesis loop is controlled
by withdrawing a small continuous purge gas stream since they tend to decrease the specific
converter performance by reducing the hydrogen and nitrogen partial pressure.
The size of this purge stream controls the level of inerts in the loop to about 10-15%. The
remaining gas (purge gas) is used as fuel for the heating of the primary reformer. The pure
ammonia remaining is mixed with the pure ammonia from the initial condensation above
and is ready for use in urea production, for storage or for direct sale.
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CHAPTER 4
INSTRUMENTATION AND CONTROL
4.1 INTRODUCTION
Plant instrumentation and control is a very important aspect of any operating plant. This
is because that it is required that the plant operates within the safety limit specified, it is
profitable, maximizes resources available while minimizing wastage as well minimizing
any environmental impacts. This is done by having good control of the process variables
ensuring the plant quality standards are met.
There are three important points that makes plant instrumentation and control important
which are:
1. Safe Plant Operation

 To keep the process variables within known safe operation limits.
 To make sure the temperature and pressure are at the desired levels.
 To detect any possible dangers as they develop and provide alarms and
automatic shutdown systems.
2. Production Rate and Quality

 To achieve the desired product output quality which means meeting to
its composition specifications for outlet stream of reactors according to
the literature specification.
3. Cost Operation
 Tooperate at the lowest production cost, while maintaining quality.
 To minimize the usage of heating and cooling utility, and thus reducing
the utility cost.
 Maximize plant capacity reducing any wastage of resources.
The types of basic control strategies that are implemented are:

 Feedback control
 Feedforward control
 Cascade control
 Ratio control
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4.2 AMMONIA PLANT CONTROL SYSTEM
The control loop system consists of the variables we need to control (controlled), in order
to control other variablesthat can cause the controlled variable do deviate from desired
values (disturbance). This is done through alteringvariables that can control/affect the
disturbances which are manipulated variables.
The main identified key variables that need to be controlled in the ammonia plant are:
i. Steam to carbon ratio at the mixing point before entering the primary
reformer.
ii. Fuel-air ratio for the combustion process in primary reformer.
iii. H/N ratio entering the ammonia reactor.
iv. HTS and LTS temperature control to prevent its catalyst from
degradation.
v. CO2 content in process gas leaving the CO2removal section.
vi. Control the temperature of the ammonia converter beds.
vii. Control the amounts of inert purged.
Besides the key controlled variables, there are some auxiliary control systems repeated
throughout the plant for:
 Heat exchangers/heaters/coolers
 Separators
 Compressors
4.3 DEVELOPING PROCESS & INSTRUMENTATION DIAGRAM

After identifying the key controlled variables in the plant, we proceed with developing
the P&ID. We divided our ammonia plant into the following stage units:
1. Reforming unit
2. CO conversion unit
3. CO2 removal unit
4. Methanation unit
5. Compressor house unit
6. Ammonia Synthesis unit
60
At this point we will proceed unit by unit developing its control strategy
4.3.1 Reforming Unit

The reforming unit can be divided into four sections:
- Steam mixing station.
- Primary reformer.
- Air mixing station.
- Secondary reformer.
a) Steam mixing station

The purpose of this section is to introduce steam into the process gas for the reforming
reaction that uses steam as reactant to produce Hydrogen. Based on the mass balance and
literature it is found that a steam to carbon ratio of about 3:1 is required here. This means
a control strategy controlling the ratio will be required. APPENDIX 4.1 shows the
diagram of steam mixing station control strategy.
Table 4.1: Control Specifications of Steam Mixing Station for Reforming
Control Strategy Ratio Control
Selected
Control Objective To maintain steam to carbon flows at a ratio
of 3:1.
Controlled - Steam to Carbon ratio
Variable
Measured - NG flow rate.
Variables - Steam flow rate.
Manipulated - Steam flow rate.
Variable
Disturbances - NG flow rate considered the disturbance
since it‘s not controlled.
Set Points - Desired Ratio= around 3:1
b) Primary Reformer
The purpose of this section is to produce hydrogen from methane and steam. The process
is endothermic, so heat is needed for the reaction to occur. In this section we have a
desired conversion of methane (our limiting reactant is methane as it is more expensive),
a control strategy to control the temperature of the primary reformer to be at the optimum
temperature must be implemented. A fuel-air ratio control strategy is also needed to
optimize the combustion process. Thus we need to tackle two significant disturbances
that are fuel gas supply flow rate (pressure) and fuel gas composition. Fuel gas supply
61
flow rate affects the pressure for a given control valve opening whereas fuel gas
composition will affect the desired fuel-air ratio. APPENDIX 4.2 shows the diagram of
primary reformer control strategy.
Table 4.2: Control Specifications of Primary Reformer
Control Strategy - Ratio control (fuel-air)
Selected - Cascade (for fuel gas pressure)
Control Objective To maximize the conversion of methane in the
primary reformer section.
Controlled - Temperature of the primary reformer.
Variables - Fuel gas flow rate.
- Fuel-air ratio for the combustion heating
process.
Measured - Process gas temperature outlet of primary
Variables reformer.
- Fuel gas inlet flow rate.
- Fuel gas inlet flow rate.
- Air inlet flow rate.
Manipulated - Fuel gas inlet flow rate (pressure).
Variable - Air inlet flow rate.
Disturbances - Fuel gas supply pressure.
- Fuel gas composition.
Set Points - Outlet temperature = 815.6oC
c) Air mixing station

The purpose of this section is the introduction of air which is to introduce nitrogen
needed for ammonia synthesis later. The important variable to control is the air flow rate,
because it depends on how much methane (or NG) flow rate in the feed. The target is to
inject enough air to supply the desired amount of nitrogen to react with the hydrogen
produced and a little more to force hydrogen to react more as the limiting and more
expensive product. The desired H/N ratio is usually specified at 3:1. At the same time we
do not want to inject too much air which will increase the amount of inerts and excess
nitrogen that will affect the equilibrium of the ammonia synthesis reaction. A
feedforward controller gets its measurement from the natural gas feed, computes the air
flow rate required and sends its output signal to affect the compressor speed through the
steam flow rate running the turbine. APPENDIX 4.3 shows the diagram of air mixing
control strategy.
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Table 4.3: Control Specifications of Air Mixing Station for Reformer
Control Strategy - Feedforward control.
Selected - Feedback control.
Control Objective To maintain the H/N ratio at its desired
stoichiometric ratio.
Controlled - Air flow rate (indirectly).
Variables - Steam flow rate (directly).
Measured Variables - Air flow rate.
- Process gas (NG) flow rate.
Variable
Disturbances - Process gas (NG) feed flow rate.
- H/N ratio at inlet of ammonia converter.
Set Points - Desired H/N ratio = 3:1.
d) Secondary Reformer
The purpose of the secondary reformer to further produce hydrogen from the available
methane in the process gas and at the same time is the point where nitrogen is introduced
into the process through air. Reaction in the secondary reformer may go as high as
1000oC, therefore cooling jacket is used to cool down any hotspots in the reactor. The air
flow is controlled by the ratio determined from air mixing station to the natural gas feed.
The inlet temperature and methane introduction are being controlled by the primary
reformer outlets. The control strategy implemented in the secondary reformer is to cool
down any hotspot detected in the reactor. APPENDIX 4.4 shows the diagram of
secondary reformer control strategy.
Table 4.4: Control Specifications of Secondary Reformer
Control Strategy - Cascade control.
Selected
Control To cool down any hotspots detected in the reactor
Objective to prevent undesirable safety occurrence as well
as unwanted operating conditions.
Controlled - Temperature of the secondary reformer bed.
Variables - Water level in the cooling jacket.
Measured - Temperature of the secondary reformer bed.
Variables - Water level in the cooling jacket.
Manipulated - Cooling water flow.
Variable
Disturbance - Process gas inlet temperature.
Set Points - Set point for level is determined temperature.
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4.3.2 CO Conversion Unit
The purpose of this unit is to convert all CO to CO2 to be removed later in CO2 removal
unit as CO2 is poison to catalysts in the ammonia converter. The control requirement for
the shift converters is the inlet temperatures of both HTS and LTS, to maintain the
performance of their catalysts and the conversion of CO. APPENDIX 4.5 shows the
diagram of CO shift converters unit control strategy.
Table 4.5: Control Specifications of CO Conversion Unit
Control Strategy - Feedback control.
Selected
Control Objective To control the inlet temperatures of the shift
converters.
Controlled - HTS, LTSinlet temperature.
Variable
Measured Variable - HTS, LTS inlet temperature.
Manipulated - Cooling water flow rate.
Variable
Disturbance - Cooling water temperature and inlet
temperature
Set Point - Desired inlet temperature = 350oC for HTS
and 220oC for LTS
4.3.3 CO2 Removal Unit

The purpose of this unit is to remove CO2 from the process gas stream. The main
controlled variable is the CO2 content in the outlet process gas stream as well as in the
regenerated amine solution. Both control systems have the same basic structure of
cascade control. The CO2 composition in the inlet stream is measured, compared with the
set point, and the required extra amine flow is calculated to adjust the set point on the
flow controller of the amine flow. Absorption requires high pressure whereas desorption
requires low pressure. Therefore pressure controllers for both columns are also used to
regulate the pressure. APPENDIX 4.6 shows the diagram of CO2 removal unit control
strategy.
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Table 4.6: Control Specifications of CO2 Removal Unit
Selected - Feedforward control.
- Cascade control.
Control Objective To maintain CO2 slippage in the process gas
below a minimum level.
Controlled - Absorber top CO2 composition.
Variables - Regenerated amine solution CO2
composition.
- Absorber bottom level.
Measured - Amine solution inlet flow rate.
Variables - Heating medium flow rate.
- Absorber bottom level.
- CO2 composition in process gas inlet.
- CO2 composition in regenerated amine
solution.
Variables - Amine solution inlet flow rate.
- Absorber top flow rate.
- Desorber top flow rate.
- Absorber bottom flow rate.
Disturbance - Process gas inlet CO2composition.
Set Point - Desired outlet CO2 composition = <0.18%
4.3.4 Methanation Unit

The purpose of this unit is to get rid of remaining CO and CO2 in the process gas by
converting them into methane. The required control strategy is to maintain the reactor
inlet temperature, which is taken care of by controlling the flow of a bypass line to the
heat exchanger E-017 that is mixed with the heated line. APPENDIX 4.7 shows the
diagram of methanation unit control strategy.
Table 4.7: Control Specifications of Methanation Unit
Selected
Control Objective To control the inlet temperature of the
methanator.
Controlled Variable - Inlet temperature to methantor.
Measured Variable - Inlet temperature line to methantor.
Manipulated - By-pass line flow rate.
Variable
Disturbance - Temperature of process gas outlet of
absorber column.
Set Point - Desired inlet temperature = 180oC.
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4.3.5 Compressor House Unit
The purpose of this unit is to raise the process gas pressure to the desired reaction
pressure in the ammonia converter isaround157barg. The compressor house comprises of
equipment‘slike compressors, coolers and separators. Therefore, the process control
scheme for the compressor house is mainly dealt with the outlet pressure desired.
Usually, even if there is more than one compressor in series, only the outlet of the last
compressor line is controlled for pressure. APPENDIX 4.8 shows the diagram of
compressor house control strategy.
Table 4.8: Control Specifications of Compressor Unit
Selected
Control Objective To control the outlet pressure of a
compressor.
Controlled Variable - Compressor outlet pressure.
Measured Variable - Compressor outlet pressure.
Manipulated - Turbine steam flow rate.
Variable
Disturbance - Inlet pressure of process gas.
Set Point - Desired outlet of 3rd compressor
temperature = 157barg.
4.3.6 Ammonia Synthesis Unit

The purpose of this unit is the production of our ammonia product, and thus could be
considered the most essential unit. There are two control strategies involved in this unit:
a) Reactor temperature control

The reactor converter bed temperatures need to be controlled because the reaction is
highly exothermic that may lead to high temperatures in the bed running away from the
optimum reaction temperature and ultimately causes less production. The strategy is
inserting by-pass lines from the main inlet synthesis gas to cool the bed temperatures.
Table 4.9: Control Specifications of Ammonia Reactor Temperature
Control Strategy Selected - Feedback control.
Control Objective To control the reactor bed temperatures for
optimum production.
Controlled Variable - Bed temperatures.
Measured Variable - Bed temperatures.
Manipulated Variable - Cooler by-pass line flow rate.
Disturbance - Composition of synthesis gas that may
lead to more heat released.
Set Point - Each bed has its set point temperature.
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b) H/N ratio control
The H/N ratio has been dealt with in previous stages. APPENDIX 4.9 shows the diagram
of ammonia synthesis unit control strategy.
67
CHAPTER 5
SAFETY & LOSS PREVENTION
5.1 HAZARD AND OPERABILITY STUDY (HAZOP)
HAZOP was developed by Imperial Chemical Industries (ICI) in Britain in 1964. This
technique is one of the most powerful techniques to indicate potential hazards that may arise
from deviations of design intent. HAZOP was intended for apply in new facilities but it has
its usefulness to use in the existing plant especially for modifications as well. The HAZOP is
carried out by a multi-disciplinary team in which people from different disciplines, from
inside and also sometimes from outside the company or plant. HAZOP is based on the
principle that several experts with different backgrounds can interact and identify more
problems when working than working separately and combining the results.
Initially the HAZOP technique was developed in order to analyze chemical process system
but later on, it has been extended to others system types as well as to the complex operations
and software systems.
5.1.1 Basic Principles of HAZOP

Hazards and Operability (HAZOP) is the structured and systematic technique for identify
and evaluate problems that may represent risk to personnel or equipment of a planned or
existing process or operation, or prevent operation efficiency. The value of HAZOP study is
highly depends on wide knowledge and experience within the HAZOP team and also their
ability for identifying all plant or equipment hazards and operability problems. Where each
segment such as pipeline, piece of equipment, instrument and etc. is carefully examined and
all possible deviations from intent operating conditions are identified. A meaningful
deviation is physically possible one, for example, more flow, low pressure or reverse
reaction. Deviations such as no temperature or reverse viscosity have no reasonable,
physical meaning and are not considered. HAZOP studies are usually applied during:
 Normal operation
 Foreseeable change in operation, e.g. upgrading, reduced output, plant start-
up and shut-down.
 Suitability of plant materials, equipment and instrumentation
68
 Provision for failure of plant services such as steam, electricity, cooling
water.
 Provision for maintenance.
HAZOP is conducted using a brainstorming approach by a team. It is a most effective

method in identifying potential hazards, failures and operability problems as a team effort
which consists of process engineer, mechanical engineer, instrument engineer, plant and
prices designer, operating personnel etc. The study will focus on particularly section call
―study nodes‖ throughout the process The process operating and design parameters such as
temperature, pressure, flow rate, etc are identified at each node. The potential of deviations
in these parameters to happen and the consequences result are studied and evaluated.
For a basis of HAZOP study the following information should be available:
 Process flow diagrams (PFDs)
 Piping and instrument diagrams (P&IDs)
 Layout diagrams
 Material safety data sheets
 Provisional operating instructions
 Heat and material balance
 Equipment data sheets Star-up and emergency shut-down procedures
The review process is systematic and some of the terminologies being used in HAZOP
include:
 Study nodes
A specific location in the process in which the design or process are intent to
evaluated. Typically comprise of one major equipment (Reactor, etc.) associated
with minor equipment (valve, pump, etc.) and other additional equipment.
 Intentions
Intentions define of how the process is expected to behave at the node. This can take
a number of forms and can either be descriptive or diagrammatic as examples as
examples are flow sheets, line diagram and P&IDs.
 Parameters
69
The relevant parameters for the condition of the process which are commonly used
such as pressure, temperature, flow, level and etc.
 Guide Words
A short words or phrases used to create the imagination of a deviation of the design
or process intent. The commonly used guide words include No, More, Less, Reverse,
As well as, part of and Other than. Each guide word will be applied to the process
parameters at the study which is being examined.
 Deviations
Deviations are created by assigning the guide word to each applicable parameter
such as No Flow, Less Pressure.
 Causes
Causes define the reasons why the deviation could occur. Several causes may be
determined for one deviation.
 Consequences
These are the result of the deviation in case they occur. Several consequences may
come from one cause and in turn, one consequence may have several causes
 Safe Guards
Safe guard is the facilities that provide to reduce the occurrence frequency of the
deviation or to mitigate its consequence.
5.1.2 HAZOP Guide Words and Parameters

In each segment of HAZOP study; pipeline, instrument, equipment will be carefully
examined by fully defining the intent of each segment and then applying the guide words.
The guide word as illustrated in Table 5.1 is used to ensure that design is explored in every
conceivable way.
70
Table 5.1: Basic Guide Words in HAZOP
Guide Words Meaning Examples
NO None of design intent is achieved No flow
MORE Quantitative increases in parameter More flow, More temperature
LESS Quantitative decreases in parameter Less flow, Less temperature
Reverse flow, Reverse order of
REVERSE The logical opposite of the design intent
reaction
AS WELL AS An addition activity occur Other valves closed at the time
Only part of the system is
PART OF Only some of design intent is achieved.
shutdown
OTHER Complete substitution – another activity
Liquid in the gas piping
THAN takes place
5.1.3 HAZOP Procedure
A HAZOP study examines the process, equipment by equipment and line by line using the
guidewords to detect any hazards and identify causes for operational problems, or quality
problems (Rausand, 2005). Figure 1 below shows the method on how the HAZOP study is
carried out.
71
Yes
Yes
Figure 5.1: The HAZOP Procedure
Based on Figure 5.1, the HAZOP procedure is further elaborated in these following steps :
1. Divide the system into sections such as reactor (i.e., storage, reactor, etc.)
2. Choose a study node
3. Describe the design intent as well as operating conditions of the node.
4. Select a process parameter (flow, pressure, temperature, etc.)
5. Apply a guide word (No, More, Less, etc.) to the parameter and determine causes
6. Identify consequence associated with cause.
72
7. Specify predominate safeguards/actions against each consequence.
8. Make recommendation to mitigate the consequence if the severity and/or probability
are unacceptable by company risk acceptable level.
9. Repeat for other guide word and process parameter.
10. Repeat all procedure for other nodes.
5.1.4 Advantages of HAZOP

 HAZOP is systematic, reasonable comprehensive and flexible examination.
 It is covers safety as well as operational aspects.
 It is a multidisciplinary study that utilizes operational experience and
considers operational procedure.
 It is an excellent well – proven method for studying large plant in a specific
manner.
5.2 HAZOP ANALYSIS

5.2.1 HAZOP Study Nodes
A complete HAZOP study is covered process by process, equipment by equipment and line
by line as the procedure which stated earlier. For this HAZOP study, 3 nodes have been
chosen. The chosen nodes are stated in Table 5.2. The HAZOP Analysis for each node is
discussed in detail in APPENDIX 5.1, APPENDIX 5.2 and APPENDIX 5.3 respectively.
Table 5.2: HAZOP Study Nodes
Node Description
1 Methanator (R005) including incoming line discharge from heat exchanger (E016).
Ammonia Converter (R006) including incoming line discharge from heat exchanger
2
(E005).
3 Ammonia Separator (V006) including incoming line discharge from cooler (E019)
5.3 SITE LAYOUT

The location of a plant can have a turning effect on the overall feasibility of a process plant
and indeed the capacity for future expansion. Many factors must be considered when
selecting a suitable plant site. The most important factors are as follows:
 Location with respect to the marketing area
73
 Raw material supply
 Transport facilities
 Availability of labor
 Availability of suitable land
 Environmental impact and effluent disposal
 Local community consideration
 Climate
In addition to main plant, we also have to consider the associated services which have to be
merged within a particular plant site. Canteens, parks, general utilities, emergency medical
services and places for storage must also be taken into consideration while deciding on a
particular site.
5.4 PLANT LAYOUT CONSIDERATION

Plant layout refers to the arrangement of physical facilities such as machines, equipment,
tools, furniture and others in such a manner so as to have the quickest flow of material at the
lowest cost and with the least amount of handling in processing the product from the receipt
of raw material to the delivery of the final product.
Before constructing a plant layout, several factors have to be taken into account as to ensure
that all process units and buildings are arranged to give the most economical and efficient
flow of materials and personnel around the site. A well designed plant layout is the one that
can be beneficial in achieving the following objectives:
 Proper and efficient utilization of available floor space
 Transportation of work from one point to another without delay
 Proper utilization of production capacity
 Reduce the material handling cost
 Utilize labour efficiently
 Reduce accidents
 Allow easy maintenance of machines and plant
74
 Improve productivity
As referred to Coulson & Richardson (1994), the principal factors to be considered in
producing a plan layout are:
 Economic consideration, construction and operating cost
 The process requirement
 Convenience of operation
 Convenience of maintenance
 Safety
 Future expansion
 Modular construction
i. Costs
The cost of construction can be minimized by adopting a layout that gives the
shortest run of connecting pipe between equipment, and the least amount of
structural steel works.
ii. Process requirements
All the required equipments have to be placed properly within process. Even the
installation of the auxiliaries should be done in such a way that it will occupy the
least space. An example of the need to take into account process requirements is the
need to elevate the base of a column or vessel to provide the necessary head pressure
to a pump or the operating head for a reboiler.
iii. Convenience of operation
Equipment that needs to have frequent operator attention should be located
convenient to the control room. Valves, sample points and instruments should be
located at convenient positions and heights. Sufficient working space and headroom
must be provided to allow easy access to equipments.
iv. Convenience of maintenance
Considerations which regard to the maintenance work are taken into account when
the plant is laid out. Some of them are:
 Reactors which use catalysts are located in open space for easiness of
removing or replacing the catalysts.
75
 Enough space is allocated for heat exchanger for withdrawing the bundles
purposes.
 Compressors and pumps are located under cover since they require
dismantling for maintenance.
v. Safety
Safety and protection of human lives must be the superior concern in the layout
preparation. The following considerations are some of the precautions that will give
significant impact if they are excluded in the plant layout:
 For fire protection, any part of the plant should be accessible from at least
two directions.
 Process unit handling flammables should be separated to minimize possible
spread of fires.
 All areas protected with sprinkler or deluge systems must be contained with
provisions for rapid drainage to large remote reservoirs.
 Process vessels with substantial inventories of flammable liquids must be
located at grade.
 Flammable materials must be stored outside dike areas and away from
process units and others active areas, control room office change rooms, etc.
 Equipment subject to explosion hazard must beset away from occupied
buildings and areas.
 Blast walls may be needed to isolate potentially hazardous equipment, and
contain the effect of explosion.
 At least to escape routes for operators must be provided from each level in
process buildings. Meanwhile on elevated areas, at least one should be a
stairway.
vi. Plant expansion
Equipments should be located so that it can be conveniently tied in with future
expansion of the process.
vii. Modular construction
In recent years there has been a move to assemble sections of plant at the plant
manufacturer‘s site. These modules will include the equipment, structural steel,
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piping and instrumentation. The modules are then transported to the plant site, by
road or sea. The advantages of modular construction are improve quality control,
reduced construction cost, less need for skilled labor on sites and less need for skilled
personnel on overseas.
viii. General consideration
Open, structural, steelwork, building are normally used for process equipment,
whereby closed buildings are only used for process operations that require protection
from the weather.
5.5 AMMONIA PLANT LAYOUT

In the project, the ammonia plant will be constructed at Gebeng industrial zone in Pahang.
The layout includes the arrangement of production site, storages for ammonia product,
workshops, laboratories, waste water treatment plant, utility facilities, administration
buildings, medical facilities and amenities. The plant layout also comprises the important
safety structures such as fire station and assembly points. The estimated overall area of this
plant is about 1.5 km2. In the plant area, there are 2 main areas which are process area and
non-process area.
5.5.1 Non-Process Area

As discussed by Kirk-Othmer (1997), non-process area should be located at a distance of at
least 60 meters from processing area. The reason is to provide a sufficient safe range as well
as to avoid any incident due to fire or explosion from the process zone. The buildings which
are located in the non-process area are:
i. Security post
 Guard posts are located at the entrance of the site. The function of
security gates is to ensure unauthorized access into the plant. There are 4
security posts in the ammonia plant:
– Main entrance guard post – to monitor the access of personnel or
cars between the site and public area. Security check will be
performed to ensure that there is no intruder come across the plant
area.
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– 2 Process area guard posts – to perform a security check to
ensure that there are no hazardous or undesired materials being
brought into the process area. To enter the process area, each
personnel should indicate a ―safety briefing‖ card.
– Truck main entrance guard post – heavy transports such as
trucks and cranes should enter the process area at a different route
which is located at the back side of the ammonia plant.
ii. Administration complex
Administration complex consists of administration buildings, HSE
department, laboratories, training center, technical service department and in
house contractor office. This complex is located at a remote distance from the
process area to avoid any explosion and fire hazard since the population of
personnel is focused in this area. Facilities which are situated in the complex
are the parking lot, cafeteria, surau, clinic, fire station and workshop. Fire
station is located in between the administration building and the process area.
5.5.2 Process Area

Process area is the crucial area where the production operation takes place. This area
contains most of the hazardous chemicals that are used in the operation unit to produce
ammonia. Thus, the arrangement of the process site including all of the equipments involved
as well as auxiliary buildings has to be done carefully. Listed below are the process units
and buildings which are located in the process area;
 Primary and Secondary Reformer Units
These units receive natural gas and steam for steam reforming process. The
reforming process converts the mixture of natural gas and steam into the main
substance to produce ammonia which is H2 and N2. Other than H2 and N2, CO2 is
also produced and the process occurs in a very high temperature which is up to
1000˚C. Thus, this area is segregated slightly away from the next process unit
which is high temperature shift converter (HTS) and low temperature shift
converter (LTS). The equipments in this area consist of primary reformer,
secondary reformer, compressor, heater and mixer.
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 Syngas Production Unit
These units receive raw from reformer units. The trace of CO which is partially
converted from reformer units is reduced to produce more CO2. The flow of H2,
N2 and CO2 will undergo a series of separator to remove water and CO2 from the
syngas before it enters the reaction unit. This unit will consist of a methanator, a
series of syngas compressor and coolers.
 Reaction unit
This unit converts the H2 and N2 into ammonia at high temperature and pressure.
It is the main process where the conversion of ammonia occurs. A series of heat
exchanger and coolers is located in front of this unit to further cool the ammonia
a reasonable temperature. The flow of ammonia will enter a separator to separate
unconverted syngas and pure ammonia.
 Ammonia Storage
This is the place where the ammonia product is stored in anhydrous form. A
refrigeration system is provided to maintain the temperature of ammonia at
suitable pressure.
 Utilities
This unit will supply cooling water, high, medium and low pressure steam,
instrument air to the main process unit. It is located near to the reaction and
syngas production area to ease the flow of the utilities inside the pipe.
 Central Control Room
Ammonia production processes consist of material flow, level, pressure,
temperature as well as valves control, will be monitored from the central control
room. Central control room is located inside the process zone which it is
constructed with explosion proof doors and thick concrete walls to ensure the
safety of the personnel. In case of emergency occurs in the plant, central control
room will be the assembly point in the process area.
 Analysis Lab
Quality of waste water should be inspected before it is discharged into the
discharge river. If uncertainty occurs which regard to the waste water quality, a
sample will be tested and analyzed to determine whether it meets the
79
specifications or not. All the result will be sent to the control room and some
adjustments in controlling will be made, if necessary. Thus, the laboratory and
control building is situated adjacent to each other.
 Chemical Storage
This unit stores vessels containing chemical substance used for the process.
 Flare Area
Flare is used to burn all excess gas that is emitted from the process units as well
as to burn some of the waste gas from waste treatment area. According to
statement from Kirk-Othmer (1997), which stated that the minimum safety range
from flare to unit operation and storage farm is in radius of 60 meters, the flare is
located far from the process area and administration complex.
 Mechanical Warehouse and Workshop
Warehouse stores all the equipment‘s spare parts and the workshop for
maintenance job. It is situated adjacent to the in-house contractors‘ workshop.
 Expansion Site
There are some free areas allocated for the future plant expansion. They occupy
enough space for further expansion, whether for process reaction or producing
the plant‘s own utility such as cooling water and steam.
5.5.3 Assembly Point

In the ammonia plant, several locations have been identified as suitable places for assembly
area which is show in the layout in Appendix. In case of emergency, personnel associated
with the nearest area will be gathered in the assembly point. For the non process area, the
assembly points are determined to be in front of the car park, between the buildings in the
administration complex. For the process area, the assembly points are in front of the
expansion ground near to the process area main entrance and in the utilities control building.
5.5.4 Bund Walls and Dike Area

The storage tank area will be used to store ammonia products. The walls are generally
constructed of concrete, brick, steel or other suitable impermeable and fire resistant material
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whereas the dike area is an area bounded by contours of land or a physical barrier that
retains a fuel to a dept greater than 1". Its main purpose is for it to confine any chemical
spillage, prevent spreading of fire and to protect fire fighters.
Note that the plant layout has been attached together in A3 size with other PFD and PNID in
this file.
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CHAPTER 6
WASTE TREATMENT
6.1 INTRODUCTION
In general, waste can be defined as anything that has no value to the person who is
responsible for it. As for wastewater, it can be defined as a combination of liquid- or water-
carried wastes removed from residence, institutions, and commercial and industrial
establishment, together with such groundwater, surface water, and stormwater as may be
present (Metcalf & Eddy, 1991). Wastewater mostly consists of pure water (more than
95%), and there are numerous processes that can be used to clean up waste waters
depending on the type and extent of contamination.
Waste can be divided into different types. It can be classified according to their physical,
chemical and biological characteristics. Another way to classify the types of wastes is
according to their consistency. By consistency means, wastes with less than 70% water are
considered as solid wastes while liquid wastes are those with less than 1% solids. Liquid
waste is also usually known as wastewater. Sludge is type of waste that can be classified as
in between of liquid and solid waste.
The wastewater can be classified as sanitary, commercial, industrial, agricultural or surface
runoff based on its origin. However, as compared to other wastewater, industrial wastewater
contains different pollutants and is often more variable, concentrated and toxic. The term
wastewater itself somehow need to be separated from the term sewage, since sewage is
subset of wastewater that is contaminated with feces or urine though many people use term
sewage referring to any waste water.
6.1.1 WASTEWATER TREATMENT METHODS

The wastewater treatment is a process of receiving, neutralizing and treating various waste
effluents and making it meeting the requirement as set by the government under Department
of Environment. It can be characterized into three subdivisions; namely physical, chemical
and biological. The table below summarized the wastewater treatment methods as
mentioned in previous statement.
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Table 6.1: Summary of Treatment Methods
METHODS DESCRIPTION
Physical  Apply physical forces in treatment process.
 Form the basis of most process flow diagram.
 Process depends on physical properties of the
impurities like size of particles, specific gravity and
viscosity.
 Usually used for the removal of coarse solids, grease
and volatile organic compounds.
 Typical unit operations under this method are
screening, mixing, flocculation, sedimentation,
flotation, filtration and gas transfer.
Chemical  Removal or conversion of contaminants is brought
about by the addition of chemicals or by other
chemical reactions.
 Used for the precipitation of suspended and colloidal
solids, disinfection of wastewater, and control of
odors.
 Most commonly wastewater treatments being used
are precipitation, adsorption and disinfection.
Biological  Removal of contaminants is brought about by
biological activity.
 Used primarily to remove the biodegradable organic
substances (colloidal or dissolved) in wastewater and
also used to remove nutrient (nitrogen and
phosphorus) in wastewater.
 This method aims to coagulate and remove the
nonsettleable colloidal solids and to stabilize the
organic matter.
 Most commonly used biological processes are
activated-sludge process, aerated lagoons,
stabilization ponds and extended aeration system.
6.1.2 WASTEWATER TREATMENT PROCESS OVERVIEW

In general, there are four stages of wastewater treatment process; preliminary, primary,
secondary and tertiary/advance. Historically, the term ―preliminary‖ and ―primary‖ referred
to physical unit operations; ―secondary‖ referred to chemical and biological unit processes;
and ―tertiary‖ or ―advance‖ referred to combination of all three (Metcalf & Eddy, 1991).
The table below summarized the description of general stages in wastewater treatment
process.
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Table 6.2: Summary of Wastewater Treatment Stages
STAGE DESCRIPTION
Preliminary Treatment  Defined as the removal of wastewater constituents that
may cause maintenance or operational problems with the
treatment operations, processes, and ancillary systems.
 Preliminary treatment includes screening and
comminution for the removal of debris and rags, grit
removal for the elimination of coarse suspended matter
that may cause wear or clogging of equipment, and
flotation for the removal of large quantities of oil and
grease.
Primary Treatment  Portion of the suspended solids and organic matter is
removed from the wastewater.
 Effluent ordinarily contains considerable organic matter
and will have a relatively high BOD.
 Principal function is usually as a precursor to secondary
treatment.
Secondary Treatment  Directed principally toward the removal of biodegradable
organics and suspended solids.
 By conventional means, secondary treatment is defined as
the combination of processes customarily used for the
removal of these constituents and includes biological
treatment by activated sludge, fixed-film reactors, or
lagoon system and sedimentation.
Tertiary/Advance  Defined as level of treatment required beyond
Treatment conventional secondary treatment to remove constituents
of concern including nutrients, toxic compounds, and
increased amount of organic materials and suspended
solids.
 Used in a variety of reuse application where a high
quality of water is required such as for industrial cooling
water and groundwater recharge.
6.2 LAWS AND REGULATIONS ON INDUSTRIAL WASTE

(MALAYSIA)
6.2.1 INTRODUCTION
Basically, the statutory requirement that needs to be complied with is the Environmental
Quality Act 1974 (EQA 1974). EQA is an enabling piece of legislation for preventing,
abating and controlling pollution, and enhancing the environment, or for other related
purposes. Under this act, all industries in Malaysia are required to comply with the stated
regulations and any failure to do so will results in penalty. Numbers of 23 related regulations
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have been gazette (including the Environmental Quality (Prescribed Premises)
(Environmental Impact Assessment) Order 1987) since the introduction of Environment
Quality Act in 1974. This act provides a profound regulatory framework in the shaping of
the environmental protection and conservation landscape of Malaysia. In general, there are
several closely regulations that related to Ammonia plant, namely:
i. Environmental Quality (Clean Air) Regulation 1978
ii. Environmental Quality (Sewage and Industrial Effluent) Regulation 1979
iii. Environmental Quality (Scheduled Waste) Regulation 1989.
iv. Other closely related regulations
a) Environmental Quality (Compounding of Offences) Rules 1978
b) Environmental Quality (Licensing) Regulations 1977.
v. Occupational Safety and Health (Use and Standards of Exposure of Chemical
Hazardous to Health) Regulations 1977.
Apart from this, the Department of Environment (DOE) also been established in order to
administer and enforce the act. The following paragraphs discuss the regulations limit
regarding the solid, liquid and gaseous was emitted from Ammonia plant.
6.2.2 SOLID WASTE

According to Environmental Quality (Scheduled Wastes) Regulations 1989, scheduled
waste must be treated and disposed of at facilities approved by Department of Environment
(DOE). In industrial activities, most of the solid wastes are being sent to Kualiti Alam Sdn.
Bhd and they will be responsible in handling scheduled waste and waste disposal. The
scheduled wastes are categorized into two parts under this regulation, namely:
i. Part I: Scheduled Wastes from Non-Specific Sources
ii. Part II: Scheduled Wastes from Specific Sources
In the production of ammonia, the solid wastes are fall under Part II, and they are generated
from the catalysts used in the processing sections namely primary reformer, secondary
reformer, shift converter, methanator, CO2 removal and ammonia converter. In this
85
regulation, the catalysts can be categorized under S231: Spent industrial catalysts from
chemical plant and plant manufacturing detergent or soap or toiletries.
However, these catalysts will not be treated on-site. In lieu to this, the only possible way is
to treat them at an off-site treatment facility. At the moment, the government has restricted
the scheduled wastes that could not be treated on-site must be sent to Kualiti Alam Sdn.
Bhd. for further treatment and disposal.
6.2.3 LIQUID WASTE

The effluent that to be released to Malaysian water needs to comply with Environmental
Quality (Sewage and Industrial Effluents) Regulations, (Regulation 8(1) Third Schedule,
Standard A, EQA 1979). This is due to the release of the effluent is to the Sungai Balok,
Gebeng, that serve as a water catchments area for the housing area of the surroundings.
Basically, the main consideration in wastewater treatment system is the COD and BOD
value. According to this regulation, no person shall discharge effluent which contains
substances in concentrations greater than those specified as parameter limits of:
i. Standard A, as shown in the third column of the Third Schedule
ii. Standard B, as shown in the fourth column of the Third Schedule
Table 6.3: Parameter Limits of Effluents of Standard A and Standard B

Source: Third Schedule, EQA 1974
Standard
Parameter Unit
A B
Temperature °C 40 40
pH Value - 6.0 – 9.0 5.5 – 9.0
BOD at 20°C mg/L 20 50
COD mg/L 50 100
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6.2.4 GASEOUS WASTE
With reference to the Environmental Quality (Clean Air) Regulations 1978, there is no
emission limits provided for the air pollutants listed in Table 6.4.
Table 6.4: Malaysian Clean Air Standards for Dark Smoke and Solid Particles
Substance Emitted Source of Standards
Emission
Dark Smoke Equipment using Ringelmann Chart
non-solid fuel No. 1
Solid Particles Industry Std A: 0.6
Std B: 0.5
Std C: 0.4
(in each normal m3
of effluent gases)
Note:
1. Every new facility should comply with Standard C.
2. Every existing facility should comply with Standard A within two years and
comply with Standard B within three years, from the date these regulations
come into force.
The emission of VOCs (Volatile Organic Compounds) to the atmosphere will cause hazard
to nature. The VOC level has to be maintained at 0.16 mg/ m3 to ensure that the
surrounding is not affected by VOCs depending on the height of stack. All vessels having
their own air control system, each of them is provided with high pressure relieve valve that
open if the pressure inside the vessel exceeding the safety operating limit. The over pressure
gaseous will be directed to knock out drum before goes to flaring system. Permission from
DOE is essential for installing this facility (i.e. flare) as stated in the Clean Air Act, 1978.
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6.3 WASTE IDENTIFICATION
The potential wastes generated from the plant are identified in the following streams.
Table 6.5: Potential Waste Streams Generated from Ammonia Plant
Stream No. Component Composition Flow rate Phase
(based on iCON) (kg/hour)
W6 Hydrogen 0.00008% 0.04 Liquid
Nitrogen 0.00558% 2.89 Liquid
Carbon dioxide 0.33557% 173.78 Liquid
Water 99.65878% 51610.48 Liquid
54 Hydrogen 17.34567% 2087.35 Gas
Nitrogen 78.74078% 9475.54 Gas
Methane 2.44785% 294.57 Gas
Ammonia 1.46570% 176.38 Gas
Other than the wastes as described in the table above, solid wastes are principally spent
catalysts that originate in ammonia production. From our research, the catalysts that have
been identified to be used in this Ammonia plant are:
i. Nickel Catalyst (Primary Reformer Section).
ii. Nickel Catalyst (Secondary Reformer Section).
iii. Iron-Oxide Catalyst (High Temperature Shift Conversion Section).
iv. Copper-Zink Catalyst (Low Temperature Shift Conversion Section).
v. Nickel Oxide Catalyst (Methanation Section).
vi. Iron-Oxide Catalyst (Ammonia Converter Section).
Generally, these catalysts can last for about three years. As time goes by, the efficiency of
the catalysts will be decreasing and need to be replaced and this task is the responsibility of
the vendor or the service provider who provide the catalysts. The efficiency of the catalysts
is decreasing due to the certain formation on the surface of the catalyst itself such as carbon
and sulfur that can be poisonous to the catalysts.
Other than wastes as mentioned in previous paragraph, lubricant oil used by equipments
along the process in manufacturing of the ammonia might be part of the contaminants in the
discharged effluent.
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6.4 WASTE CHARACTERIZATION
Considering the nature of generated wastewater is a must prior to design the wastewater
treatment system since the quality of effluent is depending on the characteristics of the
influent. Two tests that may give a good indication on the effect of the effluent to the
environment are Biological Oxygen Demand (BOD) and Chemical Oxygen Demand (COD).
As for this Ammonia plant, there are two waste streams have been identified according to
iCON. The first stream is in liquid form, namely stream W6. This stream is basically a
combination stream of wastewater from separation process between liquid which is water
and gas that contains approximately 99.93% of nitrogen, hydrogen and methane.
From iCON, the temperature of discharge effluent is about 40.0457oC. According to

Parameter Limits of Effluents of Standard A and Standard B in Environmental Quality
(Sewage and Industrial Effluents) Regulations, (Regulation 8(1) Third Schedule, Standard
A, EQA 1979), the maximum allowable of discharge effluent temperature is 40oC. Hence,
by considering the temperature factor, there is no need for cooling down of the effluent prior
to discharge. However, there is a possibility that the stream is also contaminated with other
contaminants from:
i. Cooling water including blowdown water.
ii. Filter washing drainwater (methyldiethanolamine (MDEA) solution filter).
iii. Rainwater of the limited contaminated area.
iv. Floor washing water including oily water.
v. Off-spec condensate from ammonia unit.
Wastewater is also may contaminated with traces of ammonia and oils from compressing
gas unit. Emissions to water may also occur due to the scrubbing of waste gases containing
ammonia if gases are not recovered in a closed loop so that no aqueous ammonia emissions
occur.
The second stream (S54) is in gas form and that stream is basically located near to purge gas
section. From iCON, the major contaminant inside the stream is nitrogen, followed by
hydrogen, methane and ammonia. The main purpose of this small continuous purge gas
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stream is basically to control the concentration of inert gas (methane) since it tends to
decrease the specific converter performance by reducing the hydrogen and nitrogen partial
pressure.
Apart from this purge gas section, there is another potential emission to the atmosphere from
ammonia plant. The activity from reforming section may release sulfur dioxide in a low
concentration since natural gas is used. The ammonia from the process itself can release to
the environment in the range of less than 0.04 to 2 kg/tonne of ammonia produced.
According to (Group, 2007), process emissions from ammonia plants consist mainly of
natural gas, hydrogen (H2), carbon dioxide (CO2), ammonia (NH3), and carbon monoxide
(CO). Hydrogen sulfide (H2S) may be present depending on the fuel used. Fugitive
emissions of NH3 from storage tanks, valves, flanges, and tubing may also occur, especially
during transportation or transfer. Non-routine emissions associated with process upsets or
accidents may contain natural gas, carbon monoxide (CO), hydrogen (H2), carbon dioxide
(CO2), volatile organic compounds (VOCs), nitrogen oxide (NOX), and NH3.
6.5 EFFLUENT FLOW RATE TO THE PLANT

The table below summarized the influent flow rate to the plant.
Table 6.6: Influent Flow Rate
Stream Component Flow rate Mass Flow Mass Flow
No. (kg/hour) (*mgd) (m3/sec)
W6 Hydrogen 0.04 0.000023 0.000001
Nitrogen 2.89 0.014653 0.000642
Carbon dioxide 173.78 0.001438 0.000063
Water 51610.48 0.327209 0.014336
* mgd = mil gal per day
From the table, it can be seen that the average discharge of water is 0.014336 m3/sec.
In order to determine the maximum discharge from this stream,
Maximum discharge = 3 × average discharge
m3
= 3 × 0.014336
sec
3
m
= 0.043008
sec
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6.6 WASTE TREATMENT STRATEGIES
6.6.1 WASTE WATER TREATMENT
As mentioned in Section 6.5, it can be predicted that most of the potential contaminants in
the generated wastewater falls under organic type. Figure 6.1 shows the proposed design of
the wastewater treatment plant.
Generally, the wastewater treatment strategy must comply with the specified parameter limit
of Standard A in the regulation stated above. The details explanations of the proposed
wastewater treatment system are as follow.
 Equalization Basin
The equalization tank helps to provide the sure capacity for flow equalization and
retention time for equalization of pH, temperature and concentration of contaminants
before further treatment. This tank acts as a buffer to any surge in the inflow of
wastewater. This is because a steady flow is vital to ensure the next equipment
producing desired performance results.
Figure 6.1: The Proposed Wastewater Treatment System
 Corrugated Plate Interceptor (CPI) Separator

From the equalization tank, the waste water will flow into the CPI package. This
section provides an environment that is suitable for the gravity separation of oil and
solids from the wastewater. Oil separated from the water is then collected in the
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Skimmed Oil Tank. Solids deposited from the CPI are collected in the sludge
compartment where they are periodically discharged by gravity flow to the Sludge
Sump. The advantage of using CPI is it can remove oil and grease and thus, there is
no need for flotation to be used in the next step of treatment.
 Biological Treatment
i. Aeration Basin
In this section, wastewater is treated either on a flow-through basis or with
solids recycle. Waste conversion is the essential function of this treatment
process. The biological treatment section has been designed to provide
maximum BOD reduction at minimum sludge production rates. The BOD can
be reduced by aerobic decomposition in the aeration basin that will assimilate
the organic material in the wastewater. The basin shall equipped with
aeration devices and these devices will provide the oxygen necessary for the
biological activity and provide sufficient stirring action in the basins to keep
the mixed liquor suspended solids (MLSS) in suspension.
ii. Clarifier
The waste water containing MLSS flows by gravity into this section from
aeration basin. The MLSS settles on the bottom of the clarifier and the
clarified effluent overflows the notch overflow weir fitted at the periphery of
the clarifier. The MLSS is re-circulated to the aeration tank using the return
pumps which run continuously in order to maintain the concentration in the
basin. The clear water will be transferred to the Waste Water Filters.
iii. Wastewater Filter
The solids will be separated further from liquid in this section. The suspended
solids will clogged in the filter media layer and water will flows downwards
through the bed.
6.6.2 SOLID WASTE HANDLING

The solid separated from water in the CPI is then collected in the sludge sump. Basically,
all solid wastes from the Ammonia Plant will not be treated on-site. The solid wastes will be
handled and processes by the third party, which is the Kualiti Alam Sdn Bhd. The wastes
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must be packaged and labeled accordingly to the guidelines provided before sending it to
Kualiti Alam. This is to ensure that the wastes is handled and transported to the treatment
facility appropriately. The followings are the standard aspects that need to be taken into
consideration during packaging and labeling the wastes.
i. Criteria of appropriate packaging
(a) Packaging must be robust, i.e. can withstand normal chemical reaction, and
capable of withstanding transportation by lorry.
(b) Packaging must be leak-proof.
(c) Container must not be weakened by bulging, corrosion or tear.
ii. Rule of thumb of appropriate packing selection
(a) Liquid organic/inorganic waste: bunghole drums (steel/plastic).
(b) Solid waste: open top drum (steel/plastic) with cover and clamp.
(c) Dry solid waste and contaminated rags: One tonne PP bags.
iii. Standard packaging
(a) Bunghole Drum: maximum dimensions: Height = 90cm, diameter = 60cm,
drum not to be filled more than 90% and weighs not more than 200kg.
(b) Clamped open top drum: Maximum dimensions same as bunghole drum,
filled not more than 10cm from the top.
(c) PP bags: must be double-lined, not to be filled more than 10cm from top.
iv. Labeling of packaging
(a) Must adhere to 3rd Schedule (Regulation 8) of Environmental Quality
(Scheduled Wastes) Regulations 1989.
(b) All obsolete marks, labels, etc must be removed or erased.
(c) All labels shall be able to withstand open weather exposure.
(d) Hazards associated to the waste must be clearly identified and labeled
accordingly.
(e) All markings must be clear and easy to identify.
6.6.3 AIR POLLUTION CONTROL

The following methods are suggested in order to control the emissions from Ammonia Plant:
 Use synthesis NH3 purge gas treatment to recover NH3 and H2 before combustion of
93
the remainder in the primary reformer.
 The residence time for off-gas in the high temperature zone of the primary reformer
need to be increased.
 Ammonia emissions should be collected from relief valves or pressure control
devices from vessels or storages and sent to a flare or to wet scrubber.
 Install leak detection methods to detect fugitive emissions of ammonia from process
and storage.
 Implement maintenance programs, particularly in stuffing boxes on valve stems and
seals on relief valves, to reduce or eliminate releases.
 Use hot process gas from the secondary reformer to heat the primary reformer tubes
(the exchanger-reformer concept), thus reducing the need for natural gas.
6.7 DESIGN OF UNIT PROCESSES AND EQUIPMENTS

Basically, in order to make a proper estimation of wastewater treatment plant cost, it is
necessary to know the size of the wastewater treatment plant. Prior to determine the size or
area of the wastewater treatment plant, the sizes or areas of major equipments need to be
estimated first.
From our proposed design of wastewater treatment plant, there are four major equipments
needed; receiving chamber, equalization basin, aeration basin and clarifier. The calculations
prior to determine the size of these four major equipments are been described in details in
APPENDIX 6.1, APPENDIX 6.2, APPENDIX 6.3 and APPENDIX 6.4.
6.7.1 Design of Receiving Chamber

Based on the calculations performed in APPENDIX 6.1, the Receiving chamber will be
designed with the size of 0.81 m × 1.61 m × 2 m.
6.7.2 Design of Equalization Basin

Based on (Metcalf & Eddy, 1991), the depth of equalization basin is varied from 1.5 to 2 m
in the event of floating aerator is used inside the basin. The normal detention time for
equalization basin is usually 2 to 12 hours, depending on types of equalization unit. As for
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this plant, the detention time is assumed to be 4 hours, equal to 14, 400 seconds since the
equalization basin is not proposed to be design in the form of facultative aerated lagoon.
Assuming the water cumulative flows for all the hourly time period is the same as stated in
Table 6.6, the area of equalization tank is estimated to be 310 m2 . The details calculation are
as attached in APPENDIX 6.2.
6.7.3 Design of Aeration Basin

Factors that need to be considered in designing an aeration basin are basically:
1. BOD removal.
2. Effluent characteristics.
3. Oxygen requirements.
4. Temperature effects.
5. Energy requirement for mixing.
6. Solids separation.
However, in order to estimate the surface area of the aeration basin, only volume of effluent
is taken into consideration. Here, the volume of water is estimated using the water mass flow
from stream W6.
In order to estimate the surface area, the mean cell-residence time is use as the basis of the
design. The mean cell-residence time should be selected in order to ensure:
i. The suspended microorganisms will bioflocculate for easy removal by
sedimentation.
ii. An adequate safety factor is provided when compared to the mean cell-
residence time washout.
By taking into considerations all of these factors and making some assumptions as stated in
APPENDIX 6.3, the area of aeration basin is 1652 m2 .
95
6.7.4 Design of Clarifier
There are several approaches being used in the design of clarification process. The approach
that is most commonly used is to base the design on a consideration of the surface overflow
rate and the solids loading rate. Typical surface overflow rates and depth for clarifier are
given in Table 6.7.
Table 6.7: Typical Design Information for Clarifiers for the Activated Sludge Process
Source: (Metcalf & Eddy, 1991)
Type of Overflow Rate, m3/m2.d
Depth, m
Treatment Average Peak
Settling after air-
16 - 28 40 – 64 3.5 – 6
activated sludge
Settling after
oxygen-activated 16 - 28 40 - 64 3.5 – 6
sludge
Settling after
8 - 16 24 - 32 3.5 - 6
extended aeration
Based on calculation in APPENDIX 6.4, the surface area of the clarifier is 45 m2 .
6.8 OVERALL PLANT SIZE

In order to estimate the overall wastewater treatment plant size, there are numbers of
assumptions have been made:
1. The projected surfaces are for concrete wall clarifier.
2. Compartments divider walls for aeration tanks are minor and can be neglected.
3. Only major equipments individual compartment volumes are been considered.
4. Plant inside diameter is estimated by using theoretical equation.
Total area per plant required:

Table 6.8: The Summary of Projected Area for the Main Zones
Zone Projected Area, m2
Receiving Chamber 1.3
Equalization Basin 310
Aeration Tank 1652
Clarifier 45
Total 2008.3 ≈ 2010
96
4 ×A
Plant inside diameter =
π
4 × 2010
=
π
Thus, total projected area for wastewater treatment plant is 2010 m2 with 53 m
plant inside diameter.
97
CHAPTER 7
PROCESS ECONOMIC AND COST ESTIMATION
7.1 INTRODUCTION
To evaluate the economic performance of the plant, economic analysis was done to
determine the costs of equipments, fixed capital, working capital and its annual operation
(production cost). These were done by using the correlations obtained from Coulson &
Richardson‘s Chemical Engineering Design: Volume 6 by Sinnot (2003).
After evaluating those costs, the profitability of the project were accessed by constructing
the cash flow and discounted cash flow diagram. All the necessary calculations for this
chapter are shown in the Appendix.
7.2 TOTAL CAPITAL INVESTMENT

7.2.1 Capital Investment
Capital investment is the amount of investment needed to construct the plant as well as
putting it into operation. Allocation of expenses must be available for equipment purchasing
and installation. Suitable land must be obtained, taking into account all the transportation
efficiency and the capability of the selected location. Proper plant facilities must be
available for instance piping systems, control systems and other services to ensure smooth
plant operation for a long term period. Apart from that, additional expenses must also
available for the plant operation before the sales revenue is available.
The capital needed to build and supply the required manufacturing and plant facilities is
called fixed capital investment (FCI) while that necessary for the operation of plant is
termed the working capital (WC). The sum of the fixed capital investment, working capital
and the land cost is known as the total capital investment (TCI).
Total Capital Investment = Fixed Capital Investment + Working capital + Land cost
98
7.2.2 Fixed Capital Investment
Fixed capital is the total cost of the plant to be ready for start-up. It can be categorized into
two main parts, which are manufacturing costs (direct cost) and non-manufacturing fixed
capital investment (indirect cost).
Direct cost is for completing the process operation (equipment, piping, instrumentations,
electrical, etc) while components that are not directly related to the process operation (land,
supervision, contingency, contractor‘s fees, etc) are considered as indirect cost. Several
types of direct and indirect costs are described as follows:
i. Piping
ii. Instrumentation
iii. Electrical
iv. Buildings
v. Utilities
vi. Site development
vii. Design and engineering
viii. Contingency
Though all the capital cannot be precisely determined without the actual full specifications
about the plant and processes, it can however be estimated using the factorial method of cost
estimation or more known as the ‗Lang factor‘. This method utilizes the equipment purchase
cost to calculate the other components (both direct and indirect costs) in the fixed capital
investment. The equipment cost is obtained by referring to the size and amount of
equipments in the process flow diagram. The equipment purchase costs are shown in the
following table:
99
Table 7.1: Estimation of Equipment Cost for the Project
Cost
Cost Index USD/unit Total Cost
Equipment Quantity USD/unit Index (2011) (2011) (USD)
Cooler 12 75,000.00 1404.7 1519.8 81,145.44 973,745.28
Heater 3 79,060.00 1104.2 1519.8 108,816.69 326,450.07
Heat Exchanger 4 905,212.00 1104.2 1519.8 1,245,916.68 4,983,666.72
Compressor 5 2,330,000.00 1104.2 1519.8 3,206,967.94 16,034,839.70
Separator 5 180,050.00 1104.2 1519.8 247,817.42 1,239,087.08
Primary Reformer 1 388,000.00 1104.2 1519.8 534,035.86 534,035.86
Absorption
1 350,000.00 481,733.38
Column 1104.2 1519.8 481,733.38
Ammonia
1 400,000.00 432,775.68
Converter Reactor 1404.7 1519.8 432,775.68
Vessel Tank 1 90,000.00 1519.8 1519.8 90,000.00 90,000.00
Pump 3 120,000.00 1104.2 1519.8 165,165.73 495,497.19
Total Equipment Purchase Cost (RM) 76,890,675.08
From the calculations, the total equipment purchase cost is RM 76,890,675.08.

Once the total equipment cost is obtained, the factorial method of cost estimation is used to
calculate the fixed capital investment. The factors are as shown in Table 7.2 and Table 7.3:
Table 7.2: Typical Factors for Direct Cost

Direct cost Factors
f1 Equipment erection 0.40
f2 Piping 0.70
f3 Instrumentation 0.20
f4 Electrical 0.10
f5 Buildings, process 0.15
f6 Utilities 0.50
f7 Storages 0.15
f8 Site development 0.05
f9 Ancillary buildings 0.15
Total direct cost = Equipment purchase cost x (1 + f1 + f2 + f3 + f4 + f5 + f6 + f7 + f8 + f9)

= RM 76,890,675.08 x (1 + 0.40 + 0.70 + 0.20 + 0.10 + 0.15 + 0.50 + 0.15 + 0.05 + 0.15)
= RM 261,428,295.27
100
Table 7.3: Typical Factors for Indirect Cost
Indirect cost Factors
f10 Design and Engineering 0.30
f11 Contractor‘s fee 0.05
f12 Contingency 0.10
Fixed Capital Investment (FCI) = Total direct cost x (1 + f10 + f11 + f12)
= RM 261,428,295.27 x (1+ 0.30 + 0.05 + 0.10)
= RM 379,071,028.14
7.2.3 Working Capital

The working capital is the additional investment needed to start the plant up and operate it to
the point when income is earned. It includes the cost of:
1. Start-up
2. Initial catalyst charges
3. Raw materials and intermediates in the process
4. Finished product inventories
5. Funds to cover outstanding accounts from customers
Typically, Sinnot (2003) proposes that the estimated value of working capital is simply five
percent of the fixed capital investment.
Working capital = 0.05 x Fixed Capital Investment
= 0.05 x RM 379,071,028
= RM 18,953,551.41
7.2.4 Land Cost

The cost for land and its accompanying surveys and fees depend on the location of the
property. Timmerhaus (2003) uses a value of 8 percent of the equipment purchase cost:
Land cost = 0.08 x Equipment Purchase Cost
= 0.08 x RM 76,890,675.08
= RM 6,151,254.01
101
Thus, as mentioned earlier:
Total Capital Investment = Fixed Capital Investment + Working Capital + Land Cost
= RM 379,071,028 + RM 18,953,551 + RM 6,151,254
= RM 404,175,834.56
7.3 TOTAL OPERATION (PRODUCTION) COST

An estimate of the annual operating cost to manufacture the product is needed to judge the
viability of a project as well as to make choices between possible alternative processing
schemes. Similar as the fixed capital investment, the operation cost is also divided into two;
direct and indirect operating cost.
Direct cost, which is also known as the manufacturing cost can be further classified into two
categories; variable operating cost and fixed operating cost. Variable production costs
include expenses for raw materials, catalysts and all the utilities throughout the plant
operation while fixed costs mainly consists of maintenance, operating labor, laboratory
costs, supervision, plant overhead, capital charges, insurances and local taxes. The variable
cost depends on the product amount, contrary to fixed cost which does not vary much with
the production rate and must be paid regardless of the quantity produced.
On the other hand, indirect operating cost refers to the other general expenses involved in
the operation of the company. These include administrative, marketing as well as research
and development costs.
Total Operating Cost = Variable Operating Cost + Fixed Operating Cost + General
Expenses
102
Figure 7.1: Classification of Operating Cost
7.3.1 Variable Operating Cost

7.3.1.1 Raw Material Cost
For the production of Ammonia, the raw materials used are Natural Gas and Steam. In this
raw material cost estimation, the price Natural Gas obtained from PGB and Steam obtained
from CUF Gebeng. In order to calculate the annual cost, the plant is assumed to operate for
7920 hours per year. The overall raw material cost is shown in Table 7.4 on the next pages:
Table 7.4: Raw Material Costs
Raw materials Current Price (RM / Mass Flowrate Total Price (RM /
tonne) (tonne / year) hour)
Natural Gas 371.25 284,096.10 105,470,678.02

Steam 21.09 852,289.34 17,974,782.11
Total Raw Material Cost (RM/hour) 123,445,460.13
Thus, the annual raw material cost = RM 123,445,460.13
103
7.3.1.2 Utilities Cost
The costs of utilities include the steam, cooling water and electricity cost are estimated as
15% of Fixed Capital Investment:
Utilities = 0.15 x Fixed Capital Investment
= 0.15 x RM 379,071,028.14
= RM 56,860,654.22
The variable cost for the project is summarized as shown in Table 65:
Table 7.5: Summary of the Variable Operating Cost for the Project
Item Cost (RM/year)
Raw materials 123,445,460.13
Utilities 56,860,654.22
Total Variable Operating Cost (RM/year) 180,306,114.35
Thus, the total variable cost is RM 180,306,114.35/year.
7.3.2 Fixed Operating Cost

7.3.2.1 Operating Labour Cost
Operating labor is the manpower needed to operate the plant; that is directly involved with
running the process.
The operation of the plant shall be as follows:

a. Operation of the plant shall be in two shifts a day, rotated between four groups.
b. Each group will have 3 technicians, 3 operation engineer and 1 supervisor.
c. Salary for technician is RM 1800.00/month, supervisor is RM 2000.00/month and
operation engineer is RM 2500.00/month.
104
Table 7.6: Summary of the Total Labour Cost
Salary Working period
Item Person Group Subtotal
(RM/month) (months)
Technician 3 4 1,800.00 12 259,200.00
Supervisors 1 4 2,000.00 12 96,000.00

Operation
3 4 2,500.00 12 360,000.00
Engineers
Total Labor Cost (RM/year) 715,200.00
Thus, total operating labor cost = RM 259,200/year + RM 96,000/year + RM 360,000/year

= RM 715,200/year
7.3.2.2 Maintenance Cost

This item will include the cost of maintenance labor and the materials (including equipment
spares) needed for the maintenance of the plant. The annual maintenance cost for chemical
plants are high, and is estimated to be 5 percent of the fixed capital investment. This cost
can be considered to be divided evenly between labor and materials.
Maintenance Cost = 0.05 x Fixed Capital Investment
= 0.05 x RM 379,071,028.14
= RM 18,953,551.41/year
7.3.2.3 Miscellaneous Materials Cost (Plant supplies)

Miscellaneous materials include materials that are required to operate the plant but that are
not covered under raw materials and maintenance. These will include safety clothing, hard
hats, safety glasses, instrument charts, pipe gaskets and cleaning materials. The cost of
miscellaneous materials is 10 percent of the maintenance cost.
Miscellaneous Materials Cost = 0.10 x Maintenance Cost
= 0.10 x RM 18,953,551.41
= RM 1,895,355.14/year
105
7.3.2.4 Plant Overhead Cost
Included under plant overhead costs are all the general costs associated with operating the
plant not included under the other headings; such as general management, plant security,
medical, canteen, general clerical staff and safety. It would also normally include the plant
technical personnel not directly associated with and charged to a particular operating area.
This expense is about 50 percent of the operating labor cost.
Overhead Cost = 0.50 x Operating Labor Cost
= 0.50 x RM 715,200
= RM 357,600/year
7.3.2.5 Laboratory Cost

Laboratory expenses are required for process monitoring and quality control. The laboratory
cost is taken to be as 30 percent of the operating labor costs.
Laboratory Expenses = 0.30 x Operating Labor Cost
= 0.30 x RM 715,200
= RM 214,560/year
7.3.2.6 Capital Charges

Capital Charges = 0.10 x Fixed Capital Investment
= 0.10 x RM 379,071,028.14
= RM 37,907,102.81/year
7.3.2.7 Insurance
This involves the site and plant insurance, which is paid premiumly to the insurers every
year. Insurance is usually 1 percent of the fixed capital investment.
Insurance = 0.01 x Fixed Capital Investment
= 0.01 x RM 379,071,028.14
= RM 3,790,710.28/year
106
7.3.2.8 Local Taxes
The magnitude of the local property taxes depends on particular locality of the plant and the
regional laws. It is taken to be 1 percent of the fixed capital investment.
Local Taxes = 0.01 x Fixed Capital Investment
= 0.01 x RM 379,071,028.14
= RM 3,790,710.28/year
7.3.2.9 Royalties
If the process used has not been developed exclusively by the operating company, royalties
and license fees need to be paid. A value of 1 percent from the fixed capital investment is
used.
Royalties = 0.01 x Fixed Capital Investment
= 0.01 x RM 379,071,028.14
= RM 3,790,710.28/year
All the fixed operating costs are summarized in following table:

Table 7.7: Summary of Fixed Operating Cost
Type of fixed operating cost Percentage Cost (RM/year)
Operating labor cost (OLC) - 715,200.00
Maintenance(5% FCI) 0.05 18,953,551.41
Miscellaneous (10% Maintenance Cost) 0.1 1,895,355.14
Plant overhead (50% OLC) 0.5 357,600.00
Laboratory (30% OLC) 0.3 214,560.00
Capital charges (10% FCI) 0.1 37,907,102.81
Insurance (1% FCI) 0.01 3,790,710.28
Local taxes (1% FCI) 0.01 3,790,710.28
Royalties (1% FCI) 0.01 3,790,710.28
Total Fixed Operating Cost (RM/year) 71,415,500.21
7.2.3 General Expenses

7.2.3.1 Administrative cost
This heading includes the salaries and wages for the administrative personnel (secretaries,
accountants, computer support staff, etc) along with the costs for overhead items related to
administrative activities. It is approximated as 1 percent of the fixed capital investment.
107
Administrative Cost = 0.01 x Fixed Capital Investment
= 0.01 x RM 379,071,028.14
= RM 3,790,710.28/year
7.2.3.2 Distribution and marketing

These types of general expenses are incurred in the process of selling and distributing the
product. It includes expenses for the sales office, shipping expenses, cost of containers as
well as technical sales service. This is also taken to be 1 percent of the fixed capital
investment.
Distribution & Marketing = 0.01 x Fixed Capital Investment
= 0.01 x RM 379,071,028.14
= RM 3,790,710.28/year
The total general expense is summarized in the following table:

Table 7.8: Summary of the General Expenses
Type of general expenses Cost (RM/year)
Administrative 3,790,710.28
Distribution and marketing 3,790,710.28
Total General Expenses (RM/year) 7,581,420.56
After estimating the variable operating cost, fixed operating cost and general expenses, we
can calculate the annual operating cost to manufacture the product.
Total Operating Cost = Variable Operating Cost + Fixed Operating Cost + General
Expenses
Table 7.9: Total Annual Operating Cost

Type of Operating Cost Cost (RM/year)
Variable operating cost 180,306,114.35
Fixed operating cost 71,415,500.21
General expenses 7,581,420.56
Total Operating Cost (RM/year) 259,303,035.12
Thus, as shown in table, the total operating cost for the project is estimated to be RM
259,303,035.12/year.
108
7.4 ESTIMATION OF TOTAL REVENUE
The revenue generated by plant operation comes from the product sales. The total annual
revenue from product sales is the sum of the unit price for the product multiplied by its rate
of sales.
Annual sales revenue, (RM/year) = Total sale product (tonne/year) x Product sales price
(RM/tonne)
Based on ICIS pricing, the price for our product, Ammonia is RM 1502.25/tonne. Using
7920 hours per year as the annual operating hours, the total revenue is calculated as below:
Price of Ammonia = RM 1502.25/tonne
Plant production rate = 395,876.21 tonne/year
Total annual revenue = RM 1502.25/tonne x 395,876.21 tonne/year
= RM 598,168,953.91/year
7.5 PROFITABILITY ANALYSIS

In the process of making an investment decisions, the profit anticipated from the investment
must be judged relative to some profitability analysis. A profitability analysis is a
quantitative measure of profit with respect to the investment required. In determining the
economic performance of a project, it is important to base the decision on these economic
parameters:
i) Rate of Return (ROR)
ii) Net Present Worth (NPW)
iii) Payback period
iv) Discounted cash flow rate of return (DCFRR)
Several assumptions are made in the profitability analysis for this project. The assumptions
are as follows:
i) The plant has a project plant life of 20 years.
ii) The plant construction period is 3 years before commencing production. Hence, the
total investment cost is distributed evenly between the 3 years.
iii) The plant operates for 7920 hours per year.
109
iv) Local taxes are assumed to be at 10% from the profit annually.
v) It is assumed that operating cost, sale income and cost of raw materials beginning
from the fourth operating year to the end of project plant life are constant throughout
the years.
vi) The minimum attractive rate of return (MARR) for the project is assumed to be 15
%.
7.5.1 Start-Up Period

The plant will commence operation in year 4, following the assumption made earlier. Since
the estimated total investment is RM 404,175,833.56, the timing of the investment will be:
Table 7.10: Timing of the Capital Investment
Year Item Cost (RM)
1 Equipment purchasing cost 76,890,675.08
2 Construction progress 154,165,803.54
3 Construction progress 154,165,803.54
4 Working capital 18,953,551.41
Total Capital Investment (RM) 404,175,833.56
7.5.2 Depreciation
Depreciation is a charge to the revenue resulting from an investment in real property. The
depreciation rates depend on government policy and on accounting practices of the
particular company. For this project, the depreciation is calculated by using the following
equation:
Depreciation, D = (B - SV) / n
= [B - (0.03 x Fixed Capital Investment)] / n
Where B = total capital investment

SV = salvage value, 3% from the fixed capital investment
n = total plant life
Therefore, D = [RM 404,175,833.56 - RM 11,372,130.84] / 20
110
= RM 19,640,185.14/year
7.5.3 Cumulative Cash Flow

A cash flow diagram shows the forecast cumulative net cash flow over the life of a project.
It gives a clear picture of the resources required for a project and the timing of the earnings.
The net cash flow for each year is tabulated in APPENDIX 7.1.
7.5.4 Discounted Cash Flow Rate of Return (DCFRR)

Discounted Cash Flow Rate of Return (DCFRR) or also known as Internal Rate of Return
(IRR) analysis is a measure of the maximum rate that the project could pay and still break
even by the end of the project life. It is determined by calculating the net present worth
(NPW) at various interest rates. The interest rate at which the cumulative NPW at the end of
the project is zero is the DCFRR. The more profitable the project is, the higher the
percentage of DCFRR that the project can afford. The following formula is used to calculate
DCFRR:
n t
NFW
 (1  r
n 1
' n
)
0
where,
NFW  estimated net cash flow in year n
r'  discounted cash flow rate of return per cent/100
t  life of projects, years
The value of r‘ is found by trial-and-error calculations. The r values that were chosen to
calculate DCFRR are 20%, 25%, 30%, 35% and 40%. Detailed tabulation of results can be
obtained from APPENDIX 7.2.
111
CHAPTER 8
CONCLUSION AND RECOMMEDATION
It has been proven conceptually that the establishment of new production plant in Malaysia
is feasible. Based on the feasibility study conducted, Gebeng Industrial Estate, Kuantan,
Pahang is identified to be the best location for a new ammonia production plant. In essence,
this is due to the combination of attractive features, incentives and availability of raw
materials and basic utilities.
The plant is to be operated in a continuous mode, which involves the reaction between
hydrogen and nitrogen to produce ammonia. The reactor selected for this process is the
catalytic fixed-bed reactor. The proposed plant design is economically justified and is said to
be viable for investment based on the economic potential of the process. The plant is
designed in such a way that it is environmentally friendly and safe to operate with optimum
production. Hence, the project is proven to be technically feasible and economically
attractive.
At the end of Plant Design Project 2 (PDP 2) it can be concluded that the team has managed
to meet all the objectives of the project. This project has been extremely helpful in
cultivating and enhancing the knowledge and skills at hand. As final year students, the
experience gained throughout the project has given the opportunity in designing a real
processing plant, which has improved our understanding in the chemical engineering field.
Not only that, other skills are also developed in the process, which includes communication
skills, management skills, and most importantly, teamwork.
In order to achieve a better plant, the design and detail of the equipment should be
introduced. The design which includes the detailed mechanical design of equipments along
with their specifications would help in determination the equipment that will be given to the
manufacturer later. Discussion on the detailed design will include the process design,
mechanical design and the drawings of major equipments. The process design comprises of
basis of selection, sample calculations, design methodology, start-up and shut-down
procedures. The mechanical design part will include the material selection, pressure vessel
112
thickness calculations, flanges, nozzles etc. The drawings of the major equipments will
contain the dimensions as well as standards. The best material use for the equipment must be
also included. Optimization of design must be done.
According to the current design, some improvement might be add to achieve a better
economical such as integrate ammonia plant together with urea plan since we can sell more
expensive product. Besides, ammonia recovery unit (ARU) to recover and hydrogen
recovery unit (HRU) might be added to maximize to both product and reactant.
113
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116
APPENDICES
117
CHAPTER 2
APPENDICES
APPENDIX 2.1: Summary of Synthesis Gas Production Process
Process Reaction Process description Remarks
Steam CH4 + H2O →  Natural gas consists mainly of methane and  About 65% of the world‘s hydrogen
Reforming CO + 3 H2 refinery gas is a mixture of hydrocarbon comes from natural gas and refinery
Process gases such as methane, propane, butane and gas.
CO + H2O → other gases.  Advantages:
CO2 + H2  These gases are treated with steam at a 1. Produced more hydrogen if compare
temperature 700-800C in the presence of to other process.
CH4 + 2 H2O → nickel supported on an inert material. 2. Less energy requirement.
CO2 + 4 H2  The resulting gas mixture contains by 3. Economically competitive due to the
volume about 57% hydrogen, 21% low price of the feedstock.
nitrogen, 10% carbon dioxide 11% carbon 4. Less carbon monoxide produced.
monoxide and some impurities.
 It is used in countries where natural gas has
been found such as the United States, Italy,
France, Pakistan and Yugoslavia.
 Used for carbonaceous material  Disadvantages:
Partial CnH(2n + 2) + ½  This process is adapted to the partial 1. Demands careful control of the feed
Oxidation nO2 → nCO + (n oxidation of coal and fuel oil rates to the combustion chamber.
Process + 1)H2  The carbonaceous materials are burned with 2. Heat resisting materials are needed
a limited quantity of oxygen in the presence for the construction of the reaction
of steam at a temperature of about 1300- vessels bricks.
1500C 3. Not economically competitive due to
 Oxygen is used instead of air for the the high price of the oxygen.
reaction 4. More carbon monoxide produced.
 The gas obtained from this process contains 5. Less hydrogen produced.
about 48% hydrogen, 48% carbon
monoxide,
118
 3% carbon dioxide, 0.2% hydrogen and
some impurities.
 Two electrodes are placed in a vessel full of  Has been utilized commercially where
Electrolysis water. The cathode is an iron plate and the low-cost electricity is available, such as
Process H2O ↔ H2 + O2 anode is a nickel iron plate. Canada and Norway.
 A diaphragm of asbestos is placed between  The energy required amounts to 32.7
the electrodes. GJ(hydro electric) or 99 GJ (electricity
 Water decomposed at a voltage difference by fossil fuel) for a metric ton of
of from 2.0 to 2.3 V between the electrodes, ammonia.
giving rise to hydrogen at the cathode and  Advantage: yields very pure hydrogen.
oxygen at the anode.  Disadvantage: high cost of electricity in
Malaysia.
119
APPENDIX 2.2: Gebeng Industrial Estate
120
CHAPTER 3
APPENDICES
APPENDIX 3.1: The Comparisons between Batch Stirred Reactor, Continuous Stirred Tank Reactor (CSTR) and Tubular
Reactor
Reactor Principal Residence Kinetics/Flow Pattern Advantages Disadvantages
Type Application Time
Batch  Liquid-phase  Same for  Batch flow:  Use for substance produce  Relatively high operating
Stirred reactions all fluid Reactants are charged on a small scale cost due to long
Reactor  Liquid-solid elements at the beginning of  Better process control downtimes and high
reactions operation. The than in continuous manpower requirements
contents or reactor are operation when solid or  Limited temperature
subjected to perfect highly viscous phase form control capabilities,
mixing for a certain  Well-defined residence especially with highly
period of time, after time endothermic or
which the products are exothermic reactions
discharged.
Continuous  Liquid-phase  Varies  Mixed flow:  Consistent product quality  Final conversions lower
Stirred reactions according Feed and product due to reproducible than in other basic
Tank  Gas liquid to takeoff are both process control reactor types because of
Reactor reaction individual continuous. Reactor  Low operating costs complete mixing
(CSTR)  Gas liquid fluid content is assumed to especially at high (unreacted starting
reaction over elements be perfectly mixed and throughputs material can get into the
suspended have uniform  Wide range of throughput product stream)
catalyst composition and  Unfavorable if the
temperature reaction must take place
throughout reactor. at high pressure.
Tubular  Homogenous  Same for  Plug flow:  Favorable conditions for  Very high degree of
Reactor gas-phase all fluid A steady uniform temperature control by specialization, often with
reactions elements. movement of reactants heat supply or heat complicated design and
 Liquid-phase in one direction. removal high investment
reactions  No moving mechanical  Relatively large pressure
121
 Gas and parts, hence especially drop
liquid phase suitable for high pressure  Allowed high ratio of
reaction over service heat transfer
solid catalyst  Close temperature control
 Gas-Liquid  High throughput with
reactions little or no back mixing.
122
APPENDIX 3.2: The Comparisons between Fixed-bed Catalytic Reactor and Fluidized-
bed Catalytic Reactor
Reactor Fixed-bed Catalytic Reactor Fluidized-bed Catalytic Reactor
General The fixed-bed (packed-bed) reactor In fluidized-bed reactors, solid
Features is a tubular reactor that is packed material in the form of fine particles
with solid catalyst particles. The is held in suspension by the upward
catalyst of the reactor may be flow of the reacting fluid. The fluid
placed in one or more fixed beds stream is passed up through the
(i.e., layers across the reactor) or particles at a rate strong enough for
may be distributed in a series of them to lift and not fall back into
parallel long tubes. Most designs the fluidized phase above its free
approximate to plug-flow behavior. surface by carryover in the fluid
The simplest form of fixed-bed stream. Overall, the performance of
catalytic reactor uses an adiabatic a fluidized-bed reactor often lies
arrangement. somewhere between the mixed-flow
and plug flow models.
Advantages • For most reactions, it gives the • Savings in operating expenses due
highest conversion per weight of to heat recovery in the reaction
catalyst of any catalytic reactor. regeneration steps.
• Provides large volumes of • Rapid mixing of reactants-solids
processed reactants. and high heat transfer rates.
• Gives less chance for back • Easy to control both the heat
mixing. transfer and the fluid flow system.
• No catalyst or product separation • Useful in situations where catalyst
problems. particles need frequent
• Practical and economical choice at regeneration.
very high pressures.
Disadvantages • The catalysts are highly prone to • Attrition of the catalyst can cause
deactivation. the generation of catalyst fines,
• The catalysts often require which are then carried over from
regeneration after a relatively short the bed and lost from the system.
period of operation. This may incur • For continuous system,
additional cost. complicated systems like multiple
• It is difficult to control the reactors, extensive valving and
temperature and heat-transfer in the piping are required.
catalyst bed. • High cost of the reactor and
• Some part of the catalyst surface catalyst regeneration equipment.
remains unused as a result of the
reaction system and the rate-
controlling step.
123
CHAPTER 4
APPENDICES
APPENDIX 4.1: Steam Mixing Station Control Strategy Diagram
124
APPENDIX 4.2: Primary Reformer Control Strategy Diagram
125
APPENDIX 4.3: Primary Reformer Control Strategy Diagram
126
APPENDIX 4.4: Secondary Reformer Control Strategy Diagram
127
APPENDIX 4.5: CO Shift Converters Unit Control Strategy Diagram
128
APPENDIX 4.6: CO2 Removal Unit Control Strategy Diagram
129
APPENDIX 4.7: Methanation Unit Control Strategy Diagram
130
APPENDIX 4.8: Compressor House Control Strategy Diagram
131
APPENDIX 4.9: Ammonia Synthesis Unit Control Strategy Diagram
132
CHAPTER 5
APPENDICES
APPENDIX 5.1: HAZOP Analysis: Node 1
HAZOP
Methanator (R005) including incoming line discharge from heat exchanger (E016)
Study :
Node : 1
Intention : To transport process gas from Heat exchanger to methanator.
Guide
Parameter Deviation Possible Causes Consequences Safeguards Recommendations
Word
1. Line (S22) 1. No process gas into 1. Flow indicator is 1. Install gas detection
leakage. the reactor. provided. system.
2. Loss of feed 2. Release of toxic 2. Perform regular 2. Install no flow
NO No Flow supply. material. schedule inspection alarm.
3. Blockage inside on process line.
pipeline (S22).
1. Partially plug 1. Pressure drop 1. Flow indicator is 1. Install gas detection

line. inside the reactor provided. system.
2. Control valve (R005). 2. Perform regular
LESS Less Flow failure. 2. Less process gas schedule inspection
FLOW 3. Line (S22) into reactor (R005). on process line.
leakage. 3. Release of toxic
material.
1. Control valve 1. Over pressure 1. Flow indicator is 1. Install high flow
failure. inside the reactor. provided. alarm.
2. May lead to reactor 2. Perform regular
MORE More Flow
explosion. schedule inspection
3. Undesired product on process line.
quality.
1. Back pressure. 1. Reverse flow from 1. Perform regular 1. Install non-
Reverse
REVERSE 2. Failure of reactor (R005). schedule inspection return/check valve.
Flow
pressure controller. 2. Less of product on pressure
133
3. Compressor yield. controller.
trips.
1. Malfunction of 1. Temperature 1. Install low
Low 1. Rate of reaction is
heat exchanger indicator is provided temperature alarm.
LOW Tempera- reduced.
(E016) to notify the
ture
TEMPERA- operator.
TURE 1. Failure of cooler. 1. Temperature build 1. Temperature 1. Install high
High
2. Poor heat up inside the reactor. indicator is provided temperature alarm.
HIGH Tempera-
transfer in the heat 2. May lead to reactor to notify the
ture
exchanger (E016) explosion. operator.
1. Compressor 1. May lead to 1. Pressure indicator 1. Install Low pressure
Low
LOW failure. reverse flow. is provided to notify alarm.
Pressure
2. Pipe leakage. operator.
1. Failure of 1. Pipe vibration. 1. Pressure indicator 1. Install high pressure
PRESSURE pressure safety 2. May lead to reactor is provided to notify alarm.
High valve. explosion. operator. 2. Install emergency
HIGH
Pressure 2. More process shutdown system.
gas into the reactor.
3. Pipe blockage.
1. No feed supply 1. Product does not 1. Temperature
into the reactor. meet specification. indicator is
2. Temperature & provided.
No
NO pressure are not at 2. Pressure indicator -
Reaction
desired condition. is provided.
3. Flow indicator
alarm is provided
REACTION
1. Less feed flow at 1. Undesired product 1. Temperature
the pipeline. purity. indicator is
2. Temperature & provided.
Less
LESS pressure are not at 2. Pressure indicator -
Reaction
desired condition. is provided.
3. Flow indicator
alarm is provided
134
1. More than limit 1. More heats build 1. Temperature
of material flow up that may lead to indicator is
into the reactor. reactor explosion. provided.
More 2. Occurrence of 2. Pressure indicator
MORE -
Reaction hotspot. is provided.
3. Flow indicator
alarm is provided.
135
HAZOP Study : Ammonia Converter (R006) including incoming line discharge from heat exchanger (E005).
Node : 2
Intention : To transport process gas from Heat exchanger to ammonia converter.
Guide
Word
1. Line rupture 1. No process gas into the 1. Flow indicator is 1. Install gas
2. Loss of feed supply reactor (R006). provided. detection system.
NO No Flow 3. Line (S42) leakage 2. Release of toxic 2. Perform regular 2. Install no flow
material. schedule inspection on alarm.
process line.
1. Partially plug line. 1. Pressure drop inside the 1. Flow indicator is 1. Install gas
2. Control valve reactor (R006). provided. detection system.
failure. 2. Less process gas into 2. Perform regular 2. Install low flow
LESS Less Flow
3. Line (S42) leakage. reactor (R006). schedule inspection on alarm.
3. Release of toxic process line.
FLOW material.
1. Control valve 1. Over pressure inside the 1. Flow indicator is 1. Install high flow
failure. reactor. provided. alarm.
More 2. May lead to reactor 2. Perform regular
MORE
Flow explosion. schedule inspection on
3. Undesired product process line.
quality.
1. Failure of pressure 1. Reverse flow from 1. Perform regular 1. Install non-
Reverse controller. reactor (R006) schedule inspection on return/check valve.
REVERSE
Flow 2. Compressor trips. 2. Less of product yield. pressure controller.
Low 1. Malfunction of heat 1. Desired reaction could 1. Temperature indicator 1. Install low
LOW Tempera- exchanger (E005). not be achieved. is provided to notify the temperature alarm.
TEMPERA- ture operator.
TURE High 1. Failure of cooler. 1. Temperature builds up 1. Temperature indicator 1. Install high
HIGH Tempera- 2. Poor heat transfer in inside the reactor. is provided to notify the temperature alarm.
ture the heat exchanger 2. May lead to reactor operator. 2. Install proper
136
(E005). explosion. cooling system and
insulator.
1. Compressor failure. 1. May lead to reverse 1. Install Low
Low
LOW 2. Pipe leakage. flow. pressure alarm.
Pressure
1. Failure of pressure 1. Pipe vibration. 1. Pressure indicator is 1. Install high
PRESSURE safety valve. 2. May lead to reactor provided to notify pressure alarm.
High 2. More process gas explosion. operator. 2. Install emergency
HIGH
Pressure into the reactor. 2. Pressure safety valve shutdown system.
3. Pipe blockage. (PSV) is provided.
1. No feed supply into 1. Product does not meet 1. Temperature indicator

the reactor. specification. is provided.
No 2. Temperature & 2. Pressure indicator is
NO -
Reaction pressure are not at provided.
desired condition. 3. Flow indicator alarm is
provided
1. Less feed flow at 1. Low product yield. 1. Temperature indicator
the pipeline. 2. Undesired product is provided.
Less 2. Temperature & purity. 2. Pressure indicator is
REACTION LESS -
Reaction pressure are not at provided.
desired condition. 3. Flow indicator alarm is
provided
1. More than limit of 1. More heats build up that 1. Temperature indicator
material flow into the may lead to reactor is provided.
More reactor. explosion. 2. Pressure indicator is
MORE -
Reaction 2. Occurrence of hotspot. provided.
3. Flow indicator alarm is
provided.
137
HAZOP Study : Ammonia Separator (V006) including incoming line discharge from cooler (E019)
Node : 3
Intention : To transport process gas from cooler to ammonia converter.
Guide
Word
1. Line rupture. 1. No process product into 1. Flow indicator is 1. Install gas
2. Line (S49) leakage. the separator (V006). provided. detection system.
NO No Flow 3. Control valve 2. Release of toxic 2. Perform regular 2. Install no flow
failure. material. schedule inspection on alarm.
process line.
1. Partially plug line. 1. Pressure drop inside the 1. Flow indicator is 1. Install gas
2. Control valve separator (V006). provided. detection system.
failure. 2. Less product gas into 2. Perform regular 2. Install low flow
LESS Less Flow
3. Line (S49) leakage. separator. schedule inspection on alarm.
3. Release of toxic process line.
FLOW material.
1. Control valve 1. Over pressure inside the 1. Flow indicator is 1. Install high flow
failure. separator. provided. alarm.
2. May lead to reactor 2. Level indicator is
More
MORE explosion provided.
Flow
3. Undesired product 3. Perform regular
quality schedule inspection on
process line.
1. Failure of pressure 1. Reverse flow from 1. Perform regular 1. Install non-
Reverse
REVERSE controller. reactor (R006) schedule inspection on return/check valve.
Flow
2. Compressor trips. 2. Less of product yield. pressure controller.
Low 1. Malfunction of heat 1. Desired reaction could 1. Temperature indicator 1. Install low
LOW Tempera- exchanger (E019) not be achieved. is provided to notify the temperature alarm.
TEMPERA- ture operator.
TURE High 1. Failure of cooler. 1. Temperature builds up 1. Temperature indicator 1. Install high
HIGH Tempera- 2. Poor heat transfer in inside the separator. is provided to notify the temperature alarm.
ture the heat exchanger 2. May lead to reactor operator. 2. Install proper
138
(E019) explosion cooling system and
insulator.
1. Compressor failure. 1. May lead to reverse - 1. Install Low
Low
LOW 2. Pipe leakage. flow. pressure alarm.
Pressure
1. Failure of pressure 1. Pipe vibration. 1. Pressure indicator is 1. Install high
PRESSURE
safety valve. 2. May lead to explosion. provided to notify pressure alarm.
High
HIGH 2. More product gas operator. 2. Install emergency
Pressure
into the reactor. 2. Pressure safety valve shutdown system.
3. Pipe blockage. (PSV) is provided.
139
CHAPTER 6
APPENDICES
APPENDIX 6.1: Design or Receiving Chamber
m3
Design flow = 0.043008 sec
Detention time = 60 sec
Volume required = flow ×detention time

m3
= 0.043008 sec
× 60 sec
= 2.58084 m3
Provide depth = 2m
Volume
Area =
Depth
2.58084 m3
=
2m
=1.29024 m2
≅ 1.3 m2
L=2B
Assume that the ratio of length to breadth is 2:1,
L ×B = 2B ×B = 2B2 = 1.3 m2
B = 0.806 m ≅ 0.81 m
L = 1.612 m ≅ 1.61 m
140
To check,
Volume designed = B ×L ×depth

= 0.81 m × 1.61 m ×2 m
= 2.6082 m3
Volume designed > volume required!

Receiving chamber will be designed with the size of 0.81 m × 1.61 m × 2 m.
141
APPENDIX 6.2: Design of Equalization Basin
m3
Design flow = 0.043008
sec
Detention time = 14,400 sec
Volume required = flow ×detention time

m3
= 0.043008 sec
× 14,400 sec
= 619.315 m3
Assuming the depth of the equalization basin is the same as receiving chamber which is 2m,
Volume
Area =
Depth
619.315 m3
=
2m
=309.658 m2
≅ 310 m2
142
APPENDIX 6.3: Design of Aeration Basin
Generally, the typical design value of mean cell-residence time for aeration basin is varies
from 3 to 6 days. For design purpose, the mean cell-residence time is taken as 4 days and the
lagoon depth is assumed to be 3 m.
Volume required = flow × mean cell-residence time

gal m3
= 327209 day
× 4 days × 264.17 gal
= 4954.52 m3
Volume
Area =
Depth
4954.52 m3
=
3m
=1651.507 m2
≅1652 m2
143
APPENDIX 6.4: Design of Clarifier
The hydraulic equation below can be used to approximate the area needed for the clarifier:
Q
SAC =
OR
Where:
SAC = Clarifier surface area, m2
Q = Maximum effluent flow, m3/day =1238.6304 m3/day
OR = Overflow rate (refer Table 8), m3/m2.day = 28 m3/m2.day
3
1238.63 m day
Clarifier Surface Area, SAC = 3
28 m
m2 .day
= 44.24 m2
≅ 45 m2
144
CHAPTER 7
APPENDICES
APPENDIX 7.1: Tabulation of Net Cash Flow and Cumulative Cash Flow
Year Annual Sales Depreciation Total Cash Income Net Profit Federal Net Profit Net Cash Accumulation
Capital Income A(S) A(BD) Expenses A(CI)=A(S)- ANP Income After Taxes, Income of ANNP
Investment A(TE)-A(BD) (TE)+A(BD) =A(CI)-A(BD) Taxes (30%) ANNP A(NCI)
A(I) A(IT) =ANP-A(IT)
1 40,417,583.36 -40,417,583.36 -40,417,583.36

-
2 101,043,958.39 101,043,958.39 -141,461,541.74
-
3 282,923,083.49 282,923,083.49 -424,384,625.23
4 418,718,267.74 19,640,185.14 259,303,035.12 159,415,232.62 139,775,047.48 41,932,514.25 97,842,533.24 117,482,718.37 -306,901,906.86
5 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 -63,803,708.16
6 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 179,294,490.53
7 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 422,392,689.23
8 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 665,490,887.93
9 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 908,589,086.62
10 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 1,151,687,285.32
11 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 1,394,785,484.02
12 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 1,637,883,682.71
13 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 1,880,981,881.41
14 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 2,124,080,080.11
15 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 2,367,178,278.80
16 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 2,610,276,477.50
17 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 2,853,374,676.20
18 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 3,096,472,874.89
19 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 3,339,571,073.59
20 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 3,582,669,272.29
145
21 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 3,825,767,470.98
22 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 4,068,865,669.68
23 598,168,953.91 19,640,185.14 259,303,035.12 338,865,918.79 319,225,733.66 95,767,720.10 223,458,013.56 243,098,198.70 4,311,963,868.38
146
APPENDIX 7.2: Discounted Cash Flow Analysis to Obtain DCFRR
Year of Net Cash Discount Discounted Discounted Cash Discount Discounted Discounted Discount Discounted Discounted Discount Discounted Discounted
Completion Income Factor, Cash Flow for 10% Factor, Cash Cash Factor, Cash Cash Factor, Cash Cash
A(NCI) fd (i = Flow for 10% Cummulative fd (i = Flow for 15% Flow for 15% fd (i = Flow for 20% Flow for 20% fd (i = Flow for 30% Flow for 30%
10%) sum[A(NCI)*fd] 15%) sum[A(NCI)*fd] Cummulative 20%) sum[A(NCI)*fd] Cummulative 30%) sum[A(NCI)*fd] Cummulative
1 -40,417,583.36 0.91 -36,743,257.60 -36,743,257.60 0.87 -35,145,724.66 -35,145,724.66 0.83 -33,681,319.46 -33,681,319.46 0.77 -31,090,448.74 -31,090,448.74
- - -
2 101,043,958.39 0.83 -83,507,403.63 -120,250,661.22 0.76 -76,403,749.25 111,549,473.91 0.69 -70,169,415.55 103,850,735.01 0.59 -59,789,324.49 -90,879,773.23
- - - -
3 282,923,083.49 0.75 -212,564,300.14 -332,814,961.37 0.66 -186,026,519.92 297,575,993.84 0.58 -163,728,636.28 267,579,371.29 0.46 -128,777,006.60 219,656,779.82
- - -
4 117,482,718.37 0.68 80,242,277.42 -252,572,683.94 0.57 67,171,125.53 230,404,868.30 0.48 56,656,403.54 210,922,967.75 0.35 41,133,965.33 178,522,814.49
- - -
5 243,098,198.70 0.62 150,944,855.17 -101,627,828.78 0.50 120,862,768.78 109,542,099.52 0.40 97,695,713.85 113,227,253.90 0.27 65,473,412.83 113,049,401.66
6 243,098,198.70 0.56 137,222,595.61 35,594,766.83 0.43 105,098,059.81 -4,444,039.71 0.33 81,413,094.88 -31,814,159.02 0.21 50,364,163.71 -62,685,237.95
7 243,098,198.70 0.51 124,747,814.19 160,342,581.02 0.38 91,389,617.23 86,945,577.52 0.28 67,844,245.73 36,030,086.71 0.16 38,741,664.40 -23,943,573.55
8 243,098,198.70 0.47 113,407,103.81 273,749,684.83 0.33 79,469,232.37 166,414,809.90 0.23 56,536,871.44 92,566,958.15 0.12 29,801,280.30 5,857,706.75
9 243,098,198.70 0.42 103,097,367.10 376,847,051.93 0.28 69,103,680.32 235,518,490.22 0.19 47,114,059.54 139,681,017.69 0.09 22,924,061.77 28,781,768.53
10 243,098,198.70 0.39 93,724,879.18 470,571,931.11 0.25 60,090,156.80 295,608,647.02 0.16 39,261,716.28 178,942,733.97 0.07 17,633,893.67 46,415,662.20
11 243,098,198.70 0.35 85,204,435.62 555,776,366.72 0.21 52,252,310.26 347,860,957.29 0.13 32,718,096.90 211,660,830.87 0.06 13,564,533.59 59,980,195.79
12 243,098,198.70 0.32 77,458,577.83 633,234,944.56 0.19 45,436,791.53 393,297,748.82 0.11 27,265,080.75 238,925,911.62 0.04 10,434,256.61 70,414,452.40
13 243,098,198.70 0.29 70,416,888.94 703,651,833.50 0.16 39,510,253.51 432,808,002.33 0.09 22,720,900.62 261,646,812.25 0.03 8,026,351.24 78,440,803.64
14 243,098,198.70 0.26 64,015,353.58 767,667,187.08 0.14 34,356,742.18 467,164,744.51 0.08 18,934,083.85 280,580,896.10 0.03 6,174,116.34 84,614,919.98
15 243,098,198.70 0.24 58,195,775.98 825,862,963.07 0.12 29,875,427.98 497,040,172.49 0.06 15,778,403.21 296,359,299.31 0.02 4,749,320.26 89,364,240.24
16 243,098,198.70 0.22 52,905,250.89 878,768,213.96 0.11 25,978,633.03 523,018,805.52 0.05 13,148,669.34 309,507,968.65 0.02 3,653,323.28 93,017,563.51
17 243,098,198.70 0.20 48,095,682.63 926,863,896.59 0.09 22,590,115.68 545,608,921.20 0.05 10,957,224.45 320,465,193.11 0.01 2,810,248.67 95,827,812.19
18 243,098,198.70 0.18 43,723,347.85 970,587,244.44 0.08 19,643,578.85 565,252,500.05 0.04 9,131,020.38 329,596,213.48 0.01 2,161,729.75 97,989,541.94
19 243,098,198.70 0.16 39,748,498.04 1,010,335,742.48 0.07 17,081,372.91 582,333,872.96 0.03 7,609,183.65 337,205,397.13 0.01 1,662,869.04 99,652,410.97
20 243,098,198.70 0.15 36,134,998.22 1,046,470,740.70 0.06 14,853,367.75 597,187,240.71 0.03 6,340,986.37 343,546,383.50 0.01 1,279,130.03 100,931,541.00
21 243,098,198.70 0.14 32,849,998.38 1,079,320,739.08 0.05 12,915,971.96 610,103,212.67 0.02 5,284,155.31 348,830,538.82 0.00 983,946.18 101,915,487.18
22 243,098,198.70 0.12 29,863,634.89 1,109,184,373.98 0.05 11,231,279.96 621,334,492.63 0.02 4,403,462.76 353,234,001.57 0.00 756,881.67 102,672,368.85
23 243,098,198.70 0.11 27,148,758.99 1,136,333,132.97 0.04 9,766,330.40 631,100,823.03 0.02 3,669,552.30 356,903,553.87 0.00 582,216.67 103,254,585.53
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CAB 4023

Semester: May 2011

CHEMICAL ENGINEERING PROGRAMME

Semester: May 2011

PRODUCTION OF 396, 000 TONNE OF AMMONIA PER YEAR

MUHAMMAD FAIZ MOHD FUDZAILI 10821

CHEMICAL ENGINEERING PROGRAMME

Table 2.1: Physical Properties of Ammonia........................................................ 12

LIST OF FIGURES PAGE

Figure 2.1: Prototypical Structure of Ammonia................................................... 10

APPENDIX 2.1: Summary of Synthesis Gas Production Process................ 118

1.2 PROBLEM STATEMENT

1.4 SCOPE OF WORK

Figure 2.1: Prototypical Structure of Ammonia

2.1.2 Ammonia Properties

2.1.2.2 Chemical Properties

2.2 FEED DESCRIPTION

2.2.1.2 Chemical Properties of Natural Gas – Methane

2.2.2.2 Chemical Properties of Hydrogen

2.2.3.2 Chemical Properties of Nitrogen

2.3 ECONOMIC POTENTIAL

Ammonia consumption is driven primarily by the production of downstream fertilizer

Figure 2.2: World Consumption of Ammonia Based on 2010

2.3.2 Ammonia Market Price as of 2010

Based on the currency conversion of 1 USD = 3.0450 MYR as of 2/17/2011 from

2.3.3 Ammonia Production as of November 2010

According to the IFA, no major change in merchant ammonia capacity is expected

2.4 ALTERNATIVE PROCESS ROUTE

Synthesis gas production is the generation of hydrogen as well as the introduction of

2.4.1.1 Steam Reforming Process

And later arriving at the formal overall reaction:

M-10 Waste heat boiler D-11 heat exchanger

Figure 2.3: Diagram for Steam Reforming Process

2.4.1.2 Partial Oxidation Process

Heavy fuel oil:

2.4.1.3 Electrolysis Process

Steam Compresion Off gas

Drier Ammonia synthesis

Figure 2.4: Partial Oxidation Process Diagram

2.4.2 Carbon Dioxide Removal

The carbon dioxide is removed in a chemical or by physical absorption process. The

2.4.3 Ammonia Synthesis

The methane from the natural gas is then converted to hydrogen:

CH4 + 2H2O ↔ 4H2 + CO2

2.4.3.1 Haber - Bosch process

Steam to turbines Steam

Figure: Ammonia synthesis via natural gas reforming

2.4.3.2 The Claude Process

Protec tor furnac e 10

Ammonia rec eiv ers

3 parts H2 and 1 part Finis hed ammonia out

Ammonia synthesis, Claude process.

2.4.3.3 The Casale Process

2.4.3.4 The Fauser Process

Synthesis gas feed

Purge gas to recover

High pressure separator

H.P. liquid ammonia

Fig ure: Casale synthesis loop (hig h pressure)

Oil filter Oxygen burner Cooler Water separatorcoolerCondenser Circulating compressor

Ammonia synthesis,Figure 2.8: Fauser Synthesis Unit

Claude 900-1000 500-650 Promoted iron No 40-85 No