A PLANT DESIGN PROJECT ON

SYNTHESIS OF 1000MTPD OF AMMONIA FROM

SYNGAS THROUGH COAL GASIFICATION
PROCESS

Supervised by:
Dr. Mohammad Younas (Associate Professor)
Submitted by:
Nazish Mushtaq (11PWCHE0617)
Hasna Abeer (11PWCHE0676)
Naveed ullah (11PWCHE0627)
Muhammad Faheem (11PWCHE0614)

Internal Examiner External Examiner

_____________ ______________

Chairman

A thesis
presented to the University of Engineering and Technology, Peshawar
in partial fulfillment of the thesis requirement for the degree of
BSc in Chemical Engineering

Peshawar, Khyber Pukhtoonkhwa, Pakistan, Year

1
In the name of ALLAH who is supremely merciful, the most kind.

2
 AUTHOR ‘S DECLARATION
We hereby declare that we are the authors of this thesis. This is a true copy of the thesis,
including any required final revisions, as accepted by my examiners.
We understand that our thesis may be made electronically available to the public.

3
 ABSTRACT
Only a minor part of the world’s fertilizer production today is based upon ammonia
produced by gasification of coal. The most widespread technology for ammonia production is
the steam reforming of natural gas, naphtha or LPG. This represents 75-80% of the total
ammonia production, whereas 10-15% is made from partial oxidation of fuel oil and 5% from
coal. However, the price increase of hydrocarbons & its continuous use has resulted in a
focus interest in coal gasification technology as a basis for large scale fertilizer production.
This alternative is particularly interesting to developing countries lacking fossil fuels or
having abundant coal reservoirs. The process is environmentally friendly because of using
low rank coal lignite (25-30% C) and CO2 produced during the process could be captured and
is utilized for the urea production and part of which can be recycled to gasifier for the
production of syn gas.
The world coal resources will end up in about 147 years, whereas the world resources of
gas and oil will end up in about 63 years and 41 years respectively. Pakistan has abundant of
coal reservoirs in Baluchistan, Punjab, KPK and Azad Jammu Kashmir. According to rough
estimates, the total coal resources of Pakistan are more than 185 Billion Tonnes. Pakistan
agricultural sector contributes 21% of the GDP, absorbing 45% of total labour force so
ammonia production by coal gasification can boost up the agricultural sector for its crucial
role in Pakistan economy.
In this “FYP”, synthesis root of ammonia from coal via syn gas will be studied. In this
process the coal is converted into syn gas by means of partial oxidation with air & steam in
gasifier proceeded by sulphur removal, shift reactions, CO2 capture & ammonia synthesis.
The project is based on production of 1000 metric ton of Ammonia per day from Syngas. The
project is comprised of feasibility study followed by material and energy balances of the
process flow sheet. The design of selected equipment will be presented. Hazop study,
instrumentation of the process and economic aspects will also be described.

4
 ACKNOWLEDGEMENT
“So all the Praises and Thanks be to Allah, the Lord of the heavens and the Lord of the earth
and the Lord of the Worlds. And His (Alone) is the Majesty in the heavens and the earth, and
He is the All-Mighty, the All-Wise”.
(Al-Jathiyah: 36-37)
Thanks to ALMIGHTY ALLAH, for enabling us to complete this project.

"Acquire knowledge and impart it to the people."

(Al-Tirmidhi, Hadith 107)

All respect for OUR HOLY PHROPHET who is the perfect role model and whose
teachings are source of knowledge and guidance for whole mankind.

We are deeply indebted to our respected and honorable project supervisor Dr. MOHAMMAD
YOUNAS, Associate Professor ,Chemical Engineering Department, UET Peshawar, whose
stimulating motivation, sincere guidance and valuable knowledge not only help us in
completing this project but also make us able to face different kind of situations.

Our special thanks to our beloved parents for their all time encouragement, trust, moral and
financial support help us to get such a big achievement of our life.
.
We would like to express our gratitude towards faculty member for their kind attitude, co-
operation and encouragement which help us in completion of our project.
We humbly extend our thanks for all concerned people for being so much cooperative in our
journey.

5
 DEDICATED TO OUR

Parents, teachers, sincere friends

And all of those who gave us courage in struggle full journey of our studies.
Their support and prayers help us in making our way. Thanks for being the part
of our life.

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TABLE OF CONTENT
S.NO TOPIC DESCRIPTION PAGE
NO NO
1 Abstract 4
2 Abbreviation used 10
3 Glossary 11
4 List of Tables 12
5 List of figures 13
6 Chapter :1 15
1. Introduction 16
1.1 General introduction 16
1.2 Problem Statement 18
1.3 Objectives 19
1.4 Structure of Project Report 19
7 Chapter :2 20
Literature Review 20
2.0 Ammonia 21
2.1 Historical Background 21
2.2 Properties of Ammonia 21
Physical properties 21
Chemical properties 23
Structure of Ammonia 25
2.3
2.4 Uses and Application of Ammonia 26
Ammonia Used in Manufacturing of: 26
Ammonia Uses in Fertilizer 27
Precursor to Nitrogenous Compounds 27
Urea 28
Amino acids 28
Acrylonitrile 28
Cleaner 29
Fermentation 29
Antimicrobial agent for food products 29
Minor and Emerging Uses 29
2.5 Different Process for Ammonia Production 31
Conventional ammonia synthesis by steam reforming 31
Ammonia production by partial oxidation of heavy fuel 32
Ammonia production from syngas by coal gasification 32
Ammonia production by electrolysis of water 34
2.6 Coal 34
Coal Reserves 34
Coal Recovery 35
Drawbacks of using coal 35
Coal Formation 35
Types of Coal 36
How Coal Is Found 37
Moving Coal to Market 39
Coal Future 39
New Technologies for Coal Combustion 40
Coal Gasification Technology 41
2.7 Process Steps 42

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 Syngas Generation via Coal Gasification 42
2.8 Classification of Gasifiers 45
Up Draft Gasifier 45
Down Draft Gasifier 46
Cross Draft Gasifier 47
Other types of gasifier 48

Chapter 3: 49
Process Flowsheet 50
Material Balance 51
3.1 Definition 51
3.2 Mathematical Form
52
3.3 Material Balance for Equipment
Ammonia Reactor
53
Coal Composition 56
Balance on High Temperature and Low Temperature Shift Reactor 58
Gasifier Balance 61
Balance on High Temperature Shift Reactor 65
Balance on Low Temperature Shift Reactor 68
Balance on Desulphurization Unit 71

Chapter : 4 75
Energy Balance 75
4.1 Definition 76
4.2 Mathematical Form 76
4.3 Energy Balance for Equipments 77
Ammonia Reactor 78
Desulphurization Unit 81
Cooler 3 85
Low Temperature Shift Reactor 88
Cooler 2 92
High Temperature Shift Reactor 95
Cooler 1 99
Gasifier 102
Waste heat boiler 106
Preheater 108
Converter Effluent Exchanger 110
Heater 112

Chapter :5 114
Plant Design 114
5.1 Plug Flow Reactor 115
5.2 Retention Time 115
5.3 Rate of Reaction 115
5.4 Volume of Reactor 115
5.5 Surface Area
5.6 115
Outer Diameter 115
5.7
5.8 Volume of Material Used In Plug Flow Reactor 116
5.9 Material of Construction of Reactor 116
5.10 Ellipsoidal Head 116
5.11 Pressure Drop across the Bed 117

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 Compressor Design 118

Chapter :6 120
Cost Estimation 120
6.1 Process economics 121
6.2 Ammonia Reactor Cost 121

Chapter :7 123
Instrumentation and Process Control 123
7.1 Pressure Measurement 124
7.2 Temperature Measurement 124
7.3 Flow Controller 125
7.4 Control Element 125
7.5
Threshold value for Parameter of Ammonia Reactor 125

Chapter :8 127
HAZOP Study and Safety 127
8.1 HAZOP study 128
8.2 Fire Protection 130
8.3 Emergency Procedures 130
8.4
Personal Protective Equipment 130
8.5
Security 131

Chapter :9 132
9.1 133
Conclusion
References 134

9
 ABBERIVIATIONS USED
CB Known base cost for equipment with capacity QB
CE Equipment cost for carbon steel at moderate pressure and
temperature with capacity Q
Cp Molar heat capacity at constant pressure at 298.15 K in J/mol K
Dp Dia. Of pallet in meter
Dt =Di Dia of Reactor in metre
Do Outer Dia of Reactor in metre
fP Correction factor for design pressure
fT Correction factor for design temperature
FT Flow Transmitter
FC Flow Controller
∆Hf Standard molar enthalpy (heat) of formation at 298.15 K in kJ/mol
J=E Joint Efficiency
J Joules
M Constant depending on equipment type
m⁰ Mass/day
Mol No’s of moles
n⁰ Mol/day
Pi Design Pressure (Mpa)
P Pressure in atm
PI Pressure Indicator
PC Pressure Controller
Qnet Net Energy absorbed or released in KJ/day
Qin Heat in (KJ/day)
Qout Heat out (KJ/day)
QB Base size
Q Size in m 3
R Gas Constant = 8.314 Kj /kmol.k
T Temperature in K
TI Temperature Indicator
TC Temperature Controller
TE Temperature Element
TT Temperature Transmitter
Vo Velocity in m/sec
V Volume in m3
XA Conversion
ɛ Porosity
µ Viscosity

10
 GLOSSARY
Chemical Compounds/ Elements Molecular weight
C 12
CO 28
CH4 18
CO2 44
H2 2
H2S 34
N2 28
NH3 17
O2 32
S 32
SO2 64

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 LIST OF FIGURES
CHAPTERS FIGURE DESCRIPTION PAGE NO
NO
Chapter 1 Fig 1.1 Data is based on BP Statistical Survey of 17
World Energy 2010
Chapter 2 Fig 2.1 Structure of Ammonia. 25
Fig 2.2 Percent use of ammonia for different 26
products
Fig 2.3 Percent use of ammonia for crops 27
Fig 2.4 Updraft Gasifier 45
Fig 2.5 Downdarft Gasifier 46
Fig 2.6 Cross draft Gasifier 48

Chapter 3 Fig 3.1 Mass balance across ammonia 54

Fig 3.2 Mass balance across shift gas reactor 60
Fig 3.3 Mass balance for gasifier 62
Fig 3.4 Mass balance on HTSR. 66
Fig 3.5 Mass balance on LTSR 69
Fig 3.6 Mass balance for desulphurization unit 72
Fig 3.7
Chapter 4 Fig 4.1 Energy Balance 76
Fig 4.2 Energy balance across ammonia reactor 79
Fig 4.3 Energy balance on desulphurization unit. 82
Fig 4.4 Energy balance on cooler 3 86
Fig 4.5 Balance across LTSR 89
Fig 4.6 Energy balance across cooler 2 93
Fig 4.7 Balance across HTSR 96
Fig 4.8 Energy balance across cooler 1 100
Fig 4.9 Energy balance across gasifier 103
Fig 4.10 Mass balance across waste heat boiler. 107
Fig 4.11 Energy balance across preheater 109
Fig 4.12 Energy balance across converter effluent 111
exchanger.
Fig 4.13 Energy balance across heater 113
Chapter 5 Fig 5.1 Three stage Adiabatic Compression with 118
Intercooling.

Chapter 7 Fig 7.1 Ammonia Process instrumentation 126

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 LIST OF TABLES
CHAPTERS TABLE DESCRIPTION PAGE
NO NO
Chapter 1 1.1 Geological survey of Pakistan / Pakistan Energy 18
Book 2003

Chapter 2 2.1 Physical properties of ammonia 22

2.2 Name of reactions and chemical equations for process 42
involved in coal gasification.
Chapter 3 3.1 Mass balance across ammonia reactor 55
3.2 Thar coal data for coal 57
3.3 Mole balance across shift reactor. 60
3.4 Mass of reactant for gasifier 63
3.5 Mass of product for gasifier 64
3.6 Inlet and Outlet amount of high temperature shift 67
reactor.
3.7 Inlet and Outlet amount of low temperature shift 70
reactor.
3.8 Amount for desulphurization unit at inlet. 73
3.9 Amount for desulphurization unit at outlet. 73

Chapter 4 4.1 Energy balance across ammonia reactor 80

4.2 Reaction Temperature and Q 80
4.3 Mole fraction of components of desulphurization unit 82
4.4 Data for Oxygen. 82
4.5 Product gas data. 83
4.6 Energy absorbed 83
4.7 Sulphur Data 83
4.8 Mole fraction of component for cooler 3 86
4.9 Energy balance for cooler 87
4.10 Mole fraction at Inlet and Outlet of LTSR 89
4.11 Total Heat of formation 90
4.12 Data for syn gas 90
4.13 Data for water 90
4.14 Heat of formation 91
4.15 Data for product 91
4.16 Mole fraction 93
4.17 Streams data 94
4.18 Heat of formation 96
4.19 Energy absorbed 97
4.20 Water Data 97
4.21 Heat of formation for product. 97
4.22 Energy absorbed by product 98
4.23 Streams data 100
4.24 Mole Fraction 100
4.25 Mass of water 101
4.26 Reactant 103
4.27 Product 103
4.28 Mole Fraction 104
4.29 Mass of steam 104

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 4.30 Data to find T 105
4.31 Ammonia Data 107
4.32 Water Data 107
4.33 Hydrogen data 109
4.34 Ammonia Data 109
4.35 Ammonia data 111
4.36 Hydrogen data 111
4.37 Hydrogen data 113
4.38 Water data 113

Chapter 5 5.1 Values of different parameters for bed of reactor 117

5.2 Compressor Design Calculation. 118
6.1 Constant Values from table. 121
6.2 Cost Estimation 122

7.1 Parameters and Control elements. 126

7.2 Parameters and Threshold Values. 126

8.1 Results of HAZOP are presented in the table 128

14
 CHAPTER: 1
INTRODUCTION

15
 INTRODUCTION
1.0 General Introduction:
Ammonia is chemical compound of nitrogen and hydrogen. Nitrogen atom in ammonia
molecule is bonded with three hydrogen atoms making ammonia both a fertilizer and
hydrogen storage medium. Ammonia was first obtained in pure form in 1774 by an English
chemist Joseph Priestley [1]. He heated ammonium chloride with slack lime. The reaction
2NH4Cl + Ca(OH)2----------> NH3 + CaCl2 is still used in laboratories if required a small
quantities of this gas. Priestley collected the released ammonia over mercury. He called it
"Alkaline air" because water solution of ammonia had all attributes of alkalis [1].
At room temperature, ammonia is colorless, highly irritating gas with a pungent odor, boils at
-33.3oC at 1atm pressure. It is an excellent hydrogen carrier [2]. Ammonia is easily
condensed at ambient temperature (under 8 bar of pressure). Ammonia is produced
worldwide in large quantities which is more than 100 million ton year−1.About 80% of the
ammonia is used by fertilizer industries. It is also used as a refrigerant gas, for purification of
water supplies, and in the manufacture of plastics, explosives, textiles, pesticides, dyes and
other chemicals [3].
According to FAO report the demand for fertilizer nutrients (N+P2O5+K2O) is increasing day
by day. Total fertilizer consumption is estimated at 176.8 million ton in 2011 and is expected
with a successive growth of 1.9% per year. Nitrogen is the most important part of fertilizer,
the world nitrogen fertilizer demand increased from 108.2 million tons in 2011 to 109.9
million tons in 2012 and expected annual growth rate is 1.3%. Nitrogen is normally supplied
from ammonia. The world ammonia capacity was 161.3 million tons in 2011. Due to
successive growth in fertilizer consumption, total ammonia capacity is expected to rise to
182.2 million tons in 2015. Among the Asian countries, the bulk of the increase of world
demand for nitrogen (ammonia) is expected in India (30%) and china (7%), followed by
Pakistan (6%) between 2012 and 2016. [4].
Ammonia is made on large scale by three processes, from Ammonical liquor that is obtained
as a by-product in the manufacturing of coal gas or the carbonization of coal in recovery coke
oven, by Cyanamide process and by direct synthesis from Nitrogen and Hydrogen (Haber
Process)[1,2,5].
Gasification process is used for production of Synthesis Gas (Syngas) by using fossil fuel like
natural gas, coal, petroleum and coke. Syngas produced from coal is more feasible alternate
for ammonia production. In this process, conversion of carbonaceous(or hydrocarbon)

16
material into Syngas occurs by means of partial oxidation with air, oxygen and/or steam in
transport reactor integrated Gasifier (TRIG) which is an advanced coal gasification
technology that provides clean and particulate-free syngas for variety of industrial
applications [6] .
Generally two processes are used for coal gasification, conventional and nuclear processes. In
conventional process the raw materials are coal-water slurry and oxygen. Coal is oxidized by
partial oxidation method at high temperature. In this case the heat for gasification is supplied
by partial combustion of coal. While in the nuclear process, the steam reforming method of
coal gasification needs an external heat supply because of absence of oxygen and
endothermic nature of reaction.
In conventional process, ammonia is produced from cooled and ash free Syngas which
involves water-gas shift reaction. In water-gas shift reaction, carbon monoxide combine with
steam to form carbon dioxide and hydrogen. The gas is then passed through series of
separation processes for removal of impurities such as H2S, CO2 and waste gases. Up to 95%
of hydrogen is recovered in these separation processes. The hydrogen is then entered into
ammonia loop and is reacted with nitrogen from the air to produce ammonia [4].
Increased natural gas prices in recent years have already destroyed a significant demand for
natural gas in industrial applications. It is leading to increased interest in technologies such as
coal gasification, which convert lower value hydrocarbon feedstock’s into higher value end
products. Syngas produced by coal gasification could completely replace natural gas in many
ways such as in electricity production and in fertilizer industries .The world’s hydrocarbon
resources are finite and unevenly distributed, for many nations with declining reserves of oil
and natural gas, the only way in which energy prices are affordable and relatively stable, is to
produce chemicals, fertilizers and transportation fuels from abundant resources such as coal.

Fig 1.1 Data is based on BP Statistical Survey of World Energy 2010.

17
There are vast resources of coal in all four provinces of Pakistan and in Azad Jammu &
Kashmir. Pakistan is seventh in the list of top 20 countries of the world after the discovery of
huge lignite coal resources especially in Sindh. In Pakistan many coal resources are found in
KPK, Balochistan, Punjab and AJK, According to rough estimates, the total coal resources of
Pakistan are more than 185 Billion Tonnes[4].
Table 1.1 Geological surveys of Pakistan / Pakistan Energy Book 2003
Province Resources in million Heating value (Btu/lb)
Tonnes
Sindh 184623 5219-13555
Balochistan 217 9637-15499
Punjab 235 9472-15801
KPK 91 9386-14217
AJK 9 7336-12338

TOTAL 185,175

The high amount of coal is found in Sindh as compared to other Provinces. Pakistan did not
appear even on the list of coal-rich countries before the discovery of thar coal. Other coal
reserves in sindh are in Lakhra, Sunda-jherruck, Meting-Jhimpir, Indus east etc.In balochistan
coal is found in Dekari, Khost-Sharigh-Harni-Ziarat, Mach, Duki.In KPK it is found in
Hangu, Cherat while in Punjab it is found in Salt-Range, Makarwal[7].

1.2 Problem Statement:

As recoverable coal reserves are available in around 70 countries and for approximately 118
years. In coal gasification technology low rank, high moisture and high ash coal is used for
the production of Syngas by using Air in Transport Reactor Integrated Gasifier (TRIG).
TRIG is non-slagging gasifier which provides clean and particulate free syngas. Inside the
gasifier the coal is exposed to intense heat, oxygen and steam. The level of oxygen are tightly
controlled inside the gasifier and run as high as 99%. These high levels of oxygen help to
enable the partial oxidation process that occurs. Instead of burning, the coal is broken apart
and the result is syngas. Syngas is usually composed of carbon monoxide and hydrogen,
though other gases can occur depending on the coal composition. The hydrogen from syngas
react with nitrogen of air and produce ammonia gas (Haber process).
Overall global ammonia capacity is now forecast to rise from the 205million MT in 2010 to
nearly 239 million MT by 2020, and increase of just over 33million of MT equivalent to 16%
increase over a decade [6].

18
1.3 Objectives:
To design plant for production of 1000 MT of ammonia gas per day through syngas using
coal gasification process the particular objectives are:
• To select the appropriate raw material and compare its economics with other
resources.
• To select the most economical and environmental friendly technique for ammonia
production.
• To study the most suitable type of coal and compare it with other types.
• To study the appropriate production procedure for ammonia gas production.
• To observe overall economics of process.
• To study energy balance and mass balance.
• To study health hazards regarding project.

1.4 Structure of project report:

• Title page.
• Table of contents.
• Summary of the Project.
• Main Body of the Report(Introduction, Previous Work, Material and Energy
Balances, Discussion, Final Recommendation Design, Table Listing Equipment and
Specifications, Mechanical Design of any one Equipment, Instrumentation of any one
Equipment, Environmental and Hazop studies and Process Economics).
• Conclusion and Recommendations.
• Acknowledgement.
• References.
• Nomenclature
• Appendix.
• Recommendation.

19
 CHAPTER 2
LITERATURE REVIEW

20
2.0 Ammonia:
Ammonia is a compound of nitrogen and hydrogen with the formula NH₃. It is a colorless gas
with a characteristic pungent smell. It is the simplest stable compound and serves as a starting
material for the production of many commercially important nitrogen compounds.

2.1 Historical Background:

Ammonia was first obtained in pure form in 1774 by an English chemist Joseph Priestley [1].
He heated ammonium chloride with slack lime. The reaction is still used in laboratories if
required a small quantities of this gas. Priestley collected the released ammonia over mercury
[1]. He called it "alkaline air" because water solution of ammonia had all attributes of alkalis.
In 1784, a French chemist Claude Louis Berthollet decomposed ammonia into elements with
the help of electric discharge and thus identified the composition of this gas.

Ammonia received its official name as "ammoniac" in 1787 from the Latin name of
ammonium chloride (Sal ammoniac); because that salt was obtained near the temple of
Egyptian god Amon. This name is still retained in the majority of West-European languages
(German Ammoniak, English ammonia, and French ammoniaque); the abbreviated Russian
name "ammiak" was introduced in 1801 by Russian chemist Yakov Dmitrievich Zakharov
who was the first to develop the Russian chemical nomenclature system [8].

In the form of ammonium chloride, ammonia was important to the Muslim alchemists as
early as the 8th century, first mentioned by the Persian chemist Jābir ibn Hayyān [9] and to
the European alchemists since the 13th century, being mentioned by Albertus Magnus.[10] It
was also used by dyers in the Middle Ages in the form of fermented urine to alter the colour
of vegetable dyes. In the 15th century, Basilius Valentinus showed that ammonia could be
obtained by the action of alkalis on ammonium chloride. At a later period, when ammonium
chloride was obtained by distilling the hooves and horns of oxen and neutralizing the
resulting carbonate with hydrochloric acid, the name "spirit of hartshorn" was applied to
ammonia. [11]

The Haber-Bosch process to produce ammonia from the nitrogen in the air was developed
by Fritz Haber and Carl Bosch in 1909 and patented in 1910. It was first used on an industrial
scale in Germany during World War I, following the allied blockade that cut off the supply of
nitrates from Chile. The ammonia was used to produce explosives to sustain war efforts. [11]

2.2 Properties of Ammonia:

The physical and chemical properties of ammonia are:
2.2.1 Physical Properties:
∑ It has a characteristic pungent, penetrating odor.
∑ Ammonia forms a minute proportion of the atmosphere; it is found in volcanic gases
and as a product of decomposition of animal and vegetable matter.
∑ It is extremely soluble in water.
∑ It can easily be liquefied.
A table below describes all the physical properties of ammonia:

21
Table 2.1 Physical Properties of Ammonia

22
2.2.2 Chemical Properties:
Thermal stability:
Ammonia is highly stable. However, it can be decomposed into hydrogen and nitrogen by
passing over heated metallic catalysts or when electric discharge is passed through it.

Combustibility:
Ammonia is combustible in air. However, it will burn in an atmosphere of oxygen

Nitric oxide is obtained when a mixture of ammonia and air is passed over platinum –
rhodium catalyst at 800°C

Basic character:
Ammonia molecule has a strong tendency to donate its lone pair of electrons of nitrogen to
other molecules. Thus, it acts like a strong Lewis base. In aqueous solutions, NH3 ionizes in
accordance with the reaction.

The equilibrium constant for this reaction at 298 K is 1.8 x 10-5. Thus, ammonia ionizes to a
very small extent in aqueous solution. The aqueous solution of ammonia acts as a weak base
due to the presence of OH- ions therein. Therefore, ammonia turns red litmus blue and reacts
with acids to form salts.
For example,

With metal oxides

Ammonia gets oxidized to nitrogen, when passed over heated metal oxides.

With halogens
Ammonia reacts with halogens but the type of halogen and reaction conditions determine the
nature of products.
Chlorine:
Nitrogen and ammonium chloride are formed with a limited amount of chlorine. In the
presence of excess of chlorine, nitrogen trichloride is formed.

23
Bromine:
It gives ammonium bromide and nitrogen

Iodine:
When rubbed with solid iodine, a dark colored precipitate of nitrogen
Tri-iodide is obtained:

After drying, if NH3.NI3 is struck against a hard surface or hit with a hammer, it explodes
producing iodine vapors.

With carbon dioxide (formation of urea)

Ammonia when heated under pressure with CO2 gives urea.

With alkali metals:

When ammonia is passed over heated sodium or potassium, amides are formed and hydrogen
is set free.

Alkali metal dissolved in liquid ammonia gives a blue solution, which upon standing slowly,
liberate hydrogen. The blue color of such solutions is due to the presence of solvated
electrons (e- (NH3)n). For instance, with sodium

Action with heavy metal ions:

Ammonia forms metal hydroxides, which are insoluble and form precipitates, with the metal
ions of Al, Fe, Cr, and Zn.

24
Formation of complex compounds
Ammonia forms complex compounds with the soluble salts of copper, silver etc. With copper
sulphate solution, it gives a deep blue colored complex compound, tetramminecopper(II)
sulphate.

2.3 Structure of Ammonia:

Ammonia molecule has trigonal pyramidal shape predicted by the valence shell electron pair
repulsion theory (VSEPR theory) with a bond angle of 106.7° [12].

Fig 2.1 Structure of Ammonia

Ammonia is a covalent molecule as is shown by its dot structure. The ammonia molecule is
formed due to the overlap of three sp3 hybrid orbitals and orbitals of three hydrogens. The
fourth sp3 hybrid orbital is occupied by a lone-pair. This gives a trigonal pyramidal shape to
ammonia molecule. The H-N-H bond angle is 107.3°, which is slightly less than the
tetrahedral angle of 109°28. This is because the lone pair - bond pair repulsions tend to push
the N-H bonds slightly inwards. In liquid and solid states, ammonia is associated through
hydrogen bonds [12].

25
2.4 Uses and Application of Ammonia:
Ammonia is a very important industrial chemical, and is used widely in both its pure form
and as a feedstock for a wide variety of other chemicals. Ammonia ranks second
behind sulphuric acid in the quantity produced worldwide per year. Ammonia itself is used:

∑ As a fertilizer.
∑ In many alkaline cleansers, such as window and floor cleaners.
∑ As a refrigerant gas.

2.4.1 Ammonia Used in Manufacture of:

∑ Fertilizers, such as ammonium sulphate, ammonium nitrate, ammonium hydrogen

phosphate, and urea.
∑ Nitric acid, which is used to manufacture:

1. Ammonium nitrate fertilizer.

2. Dyes.
3. Fibers and plastics.
4. Explosives, such as ammonium nitrate, trinitrotoluene (TNT) and nitro-
glycerin.

∑ Cyanides, which are used to:

1. Manufacture synthetic polymers, such as nylon and acrylics.
2. Extract gold from ore bodies.

Percent use of Ammonia

90%
80%
80%
70%
60%
50%
Percent use

40%
27%
30%
19%
20% 14%
10% 9%
10% 5% 5%
0%
Fertilizers Ammonium Urea Fibers Ammonium Explosives others Direct
nitrate phosphate application

Fig 2.2 Percent use of ammonia for different products

26
2.4.2 Ammonia Uses in Fertilizer:
Approximately 80% of ammonia is used as fertilizers either as its salts, solutions or
anhydrously. When applied to soil, it helps provide increased yields of crops such as maize
and wheat. 30% of agricultural nitrogen applied in the USA is in the form of anhydrous
ammonia and worldwide 110 million tonnes are applied each year [13].
The total food crop production in Pakistan increased from 10 million tonnes in 1970/71 to
about 25 million tonnes in 2002/03. This was achieved due to technological developments in
varieties, water availability, and fertilizer use [14].

Total Consumption 3 Millions Tonnes

50.00% 45.50%

40.00%
Percent use by crops

30.00% 23%
20.00%
10.60%
5% 5.60% 7.40%
10.00% 2.30%
0.00%
wheat cotton Sugar cane Rice Maize vegetables others
Different crops

Fig 2.3 Percent use of ammonia for crops

2.4.3 Precursor to Nitrogenous Compounds:

Ammonia is directly or indirectly the precursor to most nitrogen-containing compounds.

Virtually all synthetic nitrogen compounds are derived from ammonia. An important
derivative is nitric acid. This key material is generated via the Ostwald
process by oxidation of ammonia with air over a platinum catalyst at 700–850 °C and
9atm.[15] Nitric acid is used for the production of fertilizers, explosives, and many organo-
nitrogen compounds.
Ammonia is also used to make the following compounds:

Hydrazine
Hydrazine is an inorganic compound with the chemical formula N2H4 colourless flammable
liquid with an ammonia-like odour. Hydrazine is mainly used as a foaming agent in
preparing polymer foams, but significant applications also include its uses as a precursor
to polymerization catalysts and pharmaceuticals. It is produced by following processes.
The Olin Raschig process is the formation of monochloroamine from ammonia and
hypochlorite and the subsequent reaction of monochloramine with ammonia towards
hydrazine. [16]

27
The Ketazine process in which ammonia is oxidized by chlorine or chloramine in the
presence of aliphatic ketones, usually acetone. The resulting ketazine is then hydrolysed to
hydrazine.

The Peroxide process is a method for the industrial production of hydrazine. In this
process hydrogen peroxide is used as an oxidant instead of sodium hypochlorite, which is
traditionally used to generate hydrazine [17].

Hydrogen cyanide
Also known as prussic acid is an inorganic compound produces on industrial scale and
precursor to many chemical compounds ranges from polymers to pharmaceuticals. [18]
Andrussow process is the industrial process for the production of hydrogen cyanide from
ammonia and methane in the presence of platinum catalyst. [19, 20]

Phenol
Phenol also known as carbolic acid is an aromatic organic compound with the molecular
formula of C6H5OH. It is a white crystalline solid that is volatile. It is mildly acidic, but
requires careful handling due to its propensity to cause chemical burns [17].
Its major uses involve its conversion to plastics or related materials. Phenol and its chemical
derivatives are key for epoxies, bakelite, nylon, detergents, herbicides such as phenoxy
herbicides, and numerous pharmaceutical drugs.
2.4.4 Urea
Urea also known as carbamide is an organic compound with the chemical formula CO(NH2)2.
Urea is widely used in fertilizers as a convenient source of nitrogen. Urea is also an
important raw material for the chemical industry [20]. Wohler synthesis is the conversion
of ammonium cyanate into urea.This chemical reaction was discovered in 1828 by Friedrich
Wohler in an attempt to synthesize ammonium cyanate.(From a combination of ammonia
with lead cyanate or cyanic acid was used to produce the intermediate).

2.4.5 Amino acids

Amino acids are biologically important organic compounds composed of amine (-NH2) and
carboxylic acid (-COOH) functional groups, along with a side-chain specific to each
amino acid. The key elements of an amino acid are carbon, hydrogen, oxygen, and nitrogen,
though other elements are found in the side-chains of certain amino acids. About 500 amino
acids are known. Because of their biological significance, amino acids are important in
nutrition and are commonly used in nutritional supplements, fertilizers, and food technology.
Industrial uses include the production of drugs, biodegradable plastics, and chiral catalysts.

2.4.6 Acrylonitrile
Acrylonitrile is a chemical compound with the formula C3H3N This colourless liquid often
appears yellow due to impurities. It is an important monomer for the manufacture of useful
plastics such as polyacrylonitrile. In terms of its molecular structure, it consists of a vinyl
group linked to a nitrile. Most industrial acrylonitrile is produced by catalytic ammoxidation
of propylene, known as the Sohio process.

28
2.4.7 Cleaner
Household ammonia is a solution of NH3 in water (i.e., ammonium hydroxide) used as a
general purpose cleaner for many surfaces. Because ammonia results in a relatively streak-
free shine, one of its most common uses is to clean glass, porcelain and stainless steel. It is
also frequently used for cleaning ovens and soaking items to loosen baked-on grime.
Household ammonia ranges in concentration by weight from 5 to 10% ammonia.
2.4.8 Fermentation
Solutions of ammonia ranging from 16% to 25% are used in the fermentation industry as a
source of nitrogen for microorganisms and to adjust pH during fermentation.
2.4.9 Antimicrobial agent for food products
As early as in 1895 it was known that ammonia was strongly antiseptic it requires 1.4grams
per litre to preserve beef tea [21].

2.4.10 Minor and Emerging Uses

As Refrigeration – R717
Because of ammonia's vaporization properties, it is a useful refrigerant. It was commonly
used prior to the popularisation of chlorofluorocarbons (Freons). Anhydrous ammonia is
widely used in industrial refrigeration applications and hockey rinks because of its
high energy efficiency and low cost. However, it suffers from the disadvantage of toxicity,
which restricts its domestic and small-scale use. Along with its use in modern vapor-
compression refrigeration it was used in a mixture along with hydrogen and water
in absorption refrigerators.
For remediation of gaseous emissions
Ammonia is used to scrub SO2 from the burning of fossil fuels, and the resulting product is
converted to ammonium sulfate for use as fertilizer. Ammonia neutralizes the nitrogen oxides
(NOx) pollutants emitted by diesel engines. This technology, called SCR (selective catalytic
reduction), relies on a vanadia-based catalyst. Ammonia may be used to mitigate gaseous
spills of phosgene.
As a fuel
Ammonia was used during World War II to power buses in Belgium, and in engine and solar
energy applications prior to 1900. Liquid ammonia also fuelled the Reaction Motors
XLR99 rocket engine that powered the X-15 hypersonic research aircraft. Although not as
powerful as other fuels, it left no soot in the reusable rocket engine and its density
approximately matches the density of the oxidizer, liquid oxygen, which simplified the
aircraft's design.
Ammonia has been proposed as a practical alternative to fossil fuel for internal combustion
engines.[38] The calorific value of ammonia is 22.5 MJ/kg (9690 BTU/lb), which is about half
that of diesel. In a normal engine, in which the water vapour is not condensed, the calorific
value of ammonia will be about 21% less than this figure.

29
Ammonia cannot be easily or efficiently used in existing Otto cycle engines because of its
very low octane rating, although with only minor modifications to carburettors/injectors and a
drastic reduction in compression ratio, which would require new pistons, a gasoline engine
could be made to work exclusively with ammonia, at a low fraction of its power output
before conversion and much higher fuel consumption.
An automobile fuel tank could store ammonia as a liquid as long as the tank was pressurized
appropriately, depending on the temperature. Ammonia's thermodynamic properties are such
that at -30 C, the tank pressure would only have to be 27.5 psi, about the same as a car tire.
At 30 °C (86 °F) the pressure in the tank would need to be 170 psi to keep the ammonia
liquid. If tank pressure was released, the liquid ammonia would turn gaseous and raise the
pressure again to that level. Common pneumatic tool air compressors operate at this pressure,
so fuel tank pressure is not a barrier to adoption of automobile fuel usage.
However, there are other barriers to widespread automobile usage. In terms of raw ammonia
supplies, plants would have to be built to increase production levels, requiring significant
capital and energy sources. Although it is the second most produced chemical, the scale of
ammonia production is a small fraction of world petroleum usage. It could be manufactured
from renewable energy sources, as well as coal or nuclear power. The 60 MW Rjukan dam
in Telemark, Norway produced ammonia via electrolysis of water for many years from 1913
producing fertilizer for much of Europe. If produced from coal, the CO2 could be
sequestered, but carbon capture and storage from coal power plants is not yet beyond
prototype stages.
In 1981, a Canadian company converted a 1981 Chevrolet Impala to operate using ammonia
as fuel.
Ammonia engines or ammonia motors, using ammonia as a working fluid, have been
proposed and occasionally used. The principle is similar to that used in a fireless locomotive,
but with ammonia as the working fluid, instead of steam or compressed air. Ammonia
engines were used experimentally in the 19th century by Goldsworthy Gurney in the UK and
in streetcars in New Orleans.
As a stimulant
Ammonia, as the vapour released by smelling salts, has found significant use as a respiratory
stimulant. Ammonia is commonly used in the illegal of methamphetamine through a Birch
reduction. The Birch method of making methamphetamine is dangerous because the alkali
metal and liquid ammonia are both extremely reactive, and the temperature of liquid
ammonia makes it susceptible to explosive boiling when reactants are added.
Textile
Liquid ammonia is used for treatment of cotton materials, giving properties
like mercerisation, using alkalis. In particular, it is used for prewashing of wool.

30
Lifting gas
At standard temperature and pressure, ammonia is less dense than atmosphere, and has
approximately 60% of the lifting power of hydrogen or helium. Ammonia has sometimes
been used to fill weather balloons as a lifting gas. Because of its relatively high boiling point
(compared to helium and hydrogen), ammonia could potentially be refrigerated and liquefied
aboard an airship to reduce lift and add ballast (and returned to a gas to add lift and reduce
ballast).
Woodworking
Ammonia has been used to darken quartersawn white oak in Arts & Crafts and Mission-style
furniture. Ammonia fumes react with the natural tannins in the wood and cause it to change
colours.
2.5 Different Process for Ammonia Production:
Techniques for ammonia production:
The most widespread technology for ammonia production is the steam reforming of natural
gas,
Naphtha or LPG (Liquid Petroleum Gases).This represents 75-80% of the total ammonia
production, whereas 10-15% is made from partial oxidation of fuel oil and only some 5%
from coal and by electrolysis of water.
Four basic steps are required to produce ammonia from any hydrocarbon feedstock:
1) Gas preparation
2) Shift conversion
3) Gas purification
4) Ammonia synthesis

Different techniques for ammonia production are as follows:

2.5.1 Conventional ammonia synthesis by steam reforming
In a conventional ammonia synthesis plant in which the steam reforming technology is
used, the gas feed is firstly desulphurized and mixed with steam to obtain a gas with
steam: carbon molecular ratio between 3.0 and 4.5. The reforming then takes place over
a nickel based catalyst contained inside the tubes in the radiant zone of a primary
reformer. The gas leaving the primary reformer at a temperature 760°-820°C is mixed
with air in a secondary reformer which it leaves at 950°-1020°C with the stoichiometric
quantity of nitrogen necessary for ammonia synthesis. When the reformed gas has
been cooled and the excess heat recovered as steam, the carbon monoxide it contains
is catalytically converted to carbon dioxide usually in two stages: one at high
Temperature and one at a lower temperature (shift conversion). After further cooling,
carbon dioxide is removed, generally by chemical absorption processes which involve
the regeneration of the solution at the expense of part of the heat from the converted
gas. Unreacted carbon monoxide and the residual carbon dioxide in the gas are then
methanated thus giving a synthesis gas containing about 1-1.2% inert.
The ammonia synthesis loop is similar to what has already been described, apart from
the fact that a small fraction of the unreacted synthesis gas has to be purged in order
to ensure that only a low level of inert compounds remains in the loop.[22]

31
2.5.2 Ammonia production by partial oxidation of heavy fuel
In the ammonia production process based upon partial oxidation of heavy fuel, the
following raw materials are used: heavy fuel, air and steam. This process has the
advantage that a number of oil qualities can be used, as well as heavy fuels with
somewhat lighter fractions. It is simpler and less sensitive than the steam reforming
process, but on the other hand the investment costs are higher partly due to the
necessity of an air fractionation unit. In principle, the process is based upon the partial
oxidation of oil under a high pressure in the presence of steam and oxygen. Oil
is fed to the reactor at a high pressure (120-150 bar) and the pressure in the process
is approx. 35 bar. Soot is taken out from the gas after the oxidizer and sulphur is
further removed before the gas passes to the CO-conversion and the CO2-removal.
Nitrogen is fed to the plant from an air fractionation unit which also provides oxygen
for the oxidizer, and the make-up gas again passes on to a conventional ammonia
synthesis section.[22]

2.5.3 Ammonia production from syn gas by coal gasification

For ammonia production, there are presently two gasifier types commercially used, the
“Entrained flow gasification” and the “moving bed gasification”. The applied pressures range
from 30 to 80 bar. The entrained flow gasification corresponds basically to the partial
oxidation concept of heavy hydrocarbons and takes place in an empty pressure vessel. The
differences from the partial oxidation route are mainly in the method of introduction of the
feedstock into the gasifier [23]. The coal is fed to the gas generator either as dry dust via lock
hoppers and rotary feeders or introduced as concentrated water/coal slurry by means of a
reciprocating pump. Flow direction and use of waste heat boilers or quench and their degree
of process integration may differ in the individual processes as well as the provisions to
collect and remove the slag at the bottom of the gasifier. The separation of entrained coal dust
from the raw gas, containing some fly ash, is very similar to carbon removal in the
gasification of heavy hydrocarbons [23]. Reaction temperatures are around 1500 °C. The raw
gas has a low methane content (0.4 %), a moderate CO2content and CO/H2 ratios larger than
1 [23].
In the moving bed process,coarse grained coal (4 to 30 mm) enters at the top of the gasifier
via a lock hopper and is evenly distributed over the cross-section of the surface of the coal
bed. The coal moves very slowly downward, and the gas leaves at the top of the gasifier at
flow rates smaller than the minimum fluidizing velocity. Ash is removed at the bottom of the
gasifier using a revolving grid with slots through which the gasifying agents, oxygen and
steam, are introduced. The temperatures are lower than in the entrained flow gasification:
1000 °C in the lower section of the bed and around 600 °C at the top where the gas leaves.
Compared to the entrained flow gasification, the raw gas contains a higher amount of
CH4and CO2and a lower CO/H2 ratio because of the higher amount of steam, which causes
the water gas reaction to proceed parallel to the partial oxidation reaction [23]:

C+½O2------------------>CO
C+H2O--------------->CO + H2
The hot reaction gas (raw gas) is first quenched with recycled gas condensates from the
subsequent waste heat boiler. Because of the lower gasification temperature (a feature which
Saves oxygen) the raw gas contains a higher amount of impurities, e.g. tars, phenols and
some higher hydrocarbons, which are normally recovered from the gas condensates [23]. The
following processes are also included in gasification process.

32
Sulphur removal
Sulphur originating from the feedstock (up to 7 %) is present in the raw gas, mainly as H2S.
Depending on the process configuration, the raw gas is cooled further under waste heat
recovery and scrubbed with a solvent, usually chilled methanol at -30 °C, whereby a
CO2/H2Sfraction is separated and fed to a Claus plant. In this unit, H2Sis converted to
elemental sulphur by combustion with air using alumina catalysts. Claus plants need an
abatement system to reduce SO2 emissions. In an alternative process, the raw gas is sent
directly to the subsequent shift conversion without prior sulphur removal. In this case, H2S is
removed after the shift conversion together with the total CO2 formed there.

Shift conversion
Depending on the gasification design, i.e. waste heat boiler or quench, additional steam has to
be supplied ahead of the shift conversion by saturation and direct injection. The conversion
takes place step-wise over iron-chromium oxide shift catalysts with intermediate heat
removal. A residual CO content of between 2 and 3 % can be attained. Over the past twenty
years, sulphur resistant catalysts containing cobalt-molybdenum have in part replaced iron-
chromium oxide catalysts. These catalysts are active at temperatures ranging from 230 to 500
°C and allow shift conversion without prior sulphur removal. In this case, the sulphur is
recovered simultaneously with the CO2 after the shift conversion. For the performance of the
cobalt-molybdenum catalyst, the presence of sulphur compounds in the gas is essential.

CO2 removal
After cooling the exit gas from the shift conversion, the process condensate is separated. The
gas is chilled and scrubbed with chilled methanol, which absorbs CO2 and H2S. Stripping
regenerates the loaded methanol. In the process version without sulphur removal ahead of the
shift conversion, two fractions are received in the regeneration: one is pure CO2, which may
be used for urea or other purposes, the other contains H2S/CO2 and is fed to a Claus plant.

Liquid nitrogen wash

For the final purification, normally liquid nitrogen at approximately -185 °C is used to
remove residual CO, CH4, and most of the argon. At the same time, nitrogen is added to the
synthesis gas. To prevent blocking of the cryogenic unit, the traces of CO2 and H2Oare
separated from the inlet gas by molecular sieve adsorption. The resulting synthesis gas is very
pure and purging in the synthesis loop is minimized. The rejected waste gas fraction serves as
a fuel.

NH3 synthesis
The synthesis of ammonia takes place on an iron catalyst at pressures usually in the range of
100 -250 bar and at temperatures of between 350 and 550 °C:

N2+3H2-------------->2NH3

Only 20-30% of the synthesis gas is converted per pass to ammonia, due to unfavourable
equilibrium conditions. The unreacted gas is recycled after removing the ammonia formed.
Fresh synthesis gas is supplemented in the loop. As the exothermic synthesis reaction
proceeds, there is a reduction in volume and so a higher pressure and lower temperature
favours the reaction. The temperature of the catalyst needs to be controlled, as the heat of
reaction at the necessary equilibrium and reaction rate produces a rise in temperature.
Subdividing the catalyst into several layers is one technique which can achieve this
temperature control. In this technique, between the layers, the gases are cooled either directly

33
by adding cooled synthesis gas or indirectly by generating steam. Various converter designs
can be utilised for this purpose.

2.5.4 Ammonia production by electrolysis of water

The synthesis of ammonia consists of making hydrogen and nitrogen in the ratio 3:1
react under high pressure and temperature in the presence of a catalyst:

3H22+N2---------------> 2NH3
The nitrogen required is based upon air liquefaction and separation, and the main
process steps are:
1) Air compression and purification;
2) Air cooling and heat exchanging;
3) Air liquefaction and separation;
4) Expansion and cooling of the residual gases.
Filtered air is compressed in a multistage compressor and then cooled to approximately
ambient temperature with condensing and separation of water during cooling. The next
step is the removal of the remaining water, CO2 and hydrocarbons from the air which is
performed in molecular sieve absorbers. The purified air is directed to a heat
exchanger ("cold box") where the temperature is lowered so as to obtain partial
liquefaction by cold product nitrogen and residual gas which is heated to approximately
ambient temperature. The final step is the separation of the air in nitrogen
and oxygen which is accomplished by means of a distillation column giving pure
nitrogen as the top product and an oxygen-rich residual as the bottom product. The
bottom product is vaporized and fed to an expansion turbine. During the expansion cooling
of the gas will occur which will cover cold losses and the refrigeration requirement
for the liquefaction of the air. Hydrogen from the water electrolysis plant and nitrogen
from the air separation plant pass to separate gas holders in order to obtain a buffer
capacity and stabilize the gas pressure. Compared with synthesis gas generated from a
hydrocarbon feedstock, water electrolysis gives an extremely pure gas, only containing a
very small amount of oxygen (0.1-0.2%), which however, will have to be removed as
oxygen is a poison to the ammonia converter catalyst. Hence, the only purification
needed is oxygen removal which is done by means of catalytic combustion where a
small amount of the hydrogen reacts with the oxygen impurities present and a
corresponding amount of water is produced. The purification takes place immediately after
the mixing of hydrogen and nitrogen, and the purified mixed gas (make-up gas) passes
to a gas holder serving as buffer for the ammonia synthesis section. Next, the synthesis
gas is compressed to the pressure of the ammonia synthesis loop (between 150-280
bars) and ammonia is synthesized over an appropriate catalyst. Product ammonia
is separated from the loop by water cooling and by means of a refrigeration circuit,
which is also commonly used to store the ammonia at atmospheric pressure. A number
of processes for the synthesis of ammonia based on make-up gas exist, having somewhat
different operating conditions and efficiencies, but all based on the same principles.[23]

2.6 Coal (Raw Material):

Coal is a product of decay from 350 million year older plants. It is an integral part of energy
production in the China, United States and India [24].
2.6.1 Coal Reserves
With many different types of coal found in different states, the U.S. remains second to Russia
in the number of estimated worldwide coal reserve [25].Between the years of 1885-1950,

34
coal was the most important fuel. One half ton of coal produced as much energy as two tons
of wood and at half the cost [26].
From low rank to high rank, the different types of coal are ordered as follows:
1. Lignite
2. Subbituminous
3. Bituminous
4. Anthracite.
Low rank coal tends to have a smoky flame and easy ignition whereas high rank coal is
known for its clean flame and difficult ignition [27]. All of these types of coals can be found
in three major United States regions known as The Appalachian Basin, The Illinois Basin,
and the northern Great Plains and Rocky Mountain region [28]. In Pakistan many coal
resources are found in KPK, Baluchistan, Punjab and AJK, According to rough estimates, the
total coal resources of Pakistan are more than 185 Billion Tons [6].

2.6.2 Coal Recovery

To recover coal from these significantly large coal reserves, workers use a process called
strip mining. By using this process, strip miners can recover all the coal in a deposit, and each
worker achieves very high productivity, recovering 30-40 tons per worker per day [30].
While strip mining was at one time a dangerous career choice, the coal mining industry is
now recognized as one of the safest, with a lower rate of injuries and illnesses per 100
employees than the agriculture, construction or retail trades [31].

2.6.3 Drawbacks of using coal

A great problem with coal, which has led to somewhat slow increases in coal production
since 1920, has been the environmental impacts involved with surface mining, the effect of
CO2 emissions on global climate, and health effects of SO2 and particulate emissions [31].
With such a dangerous emissions involved with coal production, many federal regulations
have been passed to prevent these types of problems and allow for the continuation of the
production of coal. Coal is the most used resource for electricity production as nine of every
10 tons of coal used in the United States are for electricity generation [31].

2.6.4 Coal Formation

Coal is formed when peat is altered physically and chemically. This process is called
"coalification." During coalification, peat undergoes several changes as a result of bacterial
decay, compaction, heat, and time. Peat deposits are quite varied and contain everything from
pristine plant parts (roots, bark, spores, etc.) to decayed plants, decay products, and even
charcoal if the peat caught fire during accumulation.
For the peat to become coal, it must be buried by sediment. Burial compacts the peat and,
consequently, much water is squeezed out during the first stages of burial. Continued burial
and the addition of heat and time because the complex hydrocarbon compounds in the peat to
break down and alter in a variety of ways. The gaseous alteration products (methane is one)
are typically expelled from the deposit and the deposit becomes more and more carbon-rich
as the other elements disperse. The stages of this trend proceed from plant debris through
peat, lignite, sub-bituminous coal, bituminous coal, anthracite coal, to graphite (a pure carbon
mineral).The peat to coal ratio is variable and dependent on the original type of peat the coal
came from and the rank of the coal.
Coal is called a fossil fuel because it was formed from the remains of vegetation that grew as
long as 400 million years ago. The most important element in the plant material is carbon,
which gives coal most of its energy. Most of our coal was formed about 300 million years
ago, when much of the earth was covered by steamy swamps. As plants and trees died, their

35
remains sank to the bottom of the swampy areas, accumulating layer upon layer and
eventually forming a soggy, dense material called peat.
Over long periods of time, the makeup of the earth's surface changed, and seas and great
rivers caused deposits of sand, clay and other mineral matter to accumulate, burying the peat.
Sandstone and other sedimentary rocks were formed, and the pressure caused by their weight
squeezed water from the peat. Increasingly deeper burial and the heat associated with it
gradually changed the material to coal. Scientists estimate that from 3 to 7 feet of compacted
plant matter was required to form 1 foot of bituminous coal.
Coal formation is a continuing process (some of our newest coal is a mere 1 million years
old). Today, in areas such as the Great Dismal Swamp of North Carolina and Virginia, the
Okefenokee Swamp of Georgia, and the Everglades in Florida, plant life decays and subsides,
eventually to be covered by silts and sands and other matter. Perhaps millions of years from
now, those areas will contain large coal beds.

2.6.5 Types of Coal

The term "coal” describes a variety of fossilized plant materials, but no two coals are exactly
alike. Heating value, ash melting temperature, sulfur and other impurities, mechanical
strength, and many other chemical and physical properties must be considered when
matching specific coals to a particular application.

Coal is classified into four general categories, or "ranks." They range from lignite through
subbituminous and bituminous to anthracite, reflecting the progressive response of individual
deposits of coal to increasing heat and pressure. The carbon content of coal supplies most of
its heating value, but other factors also influence the amount of energy it contains per unit of
weight. (The amount of energy in coal is expressed in British thermal units per pound. A
BTU is the amount of heat required to raise the temperature of one pound of water one degree
Fahrenheit.)

About 90 percent of the coal in this country falls in the bituminous and subbituminous
categories, which rank below anthracite and, for the most part, contain less energy per unit of
weight. Bituminous coal predominates in the Eastern and Mid-continent coal fields, while
subbituminous coal is generally found in the Western states and Alaska. Lignite ranks the
lowest and is the youngest of the coals. Most lignite is mined in Texas, but large deposits also
are found in Montana, North Dakota, and some Gulf Coast states.

Anthracite
Anthracite is coal with the highest carbon content, between 86 and 98 percent, and a heat
value of nearly 15,000 BTUs-per-pound. Most frequently associated with home heating,
anthracite is a very small segment of the U.S. coal market [32]. There are 7.3 billion tons of
anthracite reserves in the United States, found mostly in 11 northeastern counties in
Pennsylvania [32].
Bituminous
The most plentiful form of coal in the United States, bituminous coal is used primarily to
generate electricity and make coke for the steel industry. The fastest growing market for coal,
though still a small one, is supplying heat for industrial processes. Bituminous coal has a
carbon content ranging from 45 to 86 percent carbon and a heat value of 10,500 to 15,500
BTUs-per-pound.

36
Subbituminous
Ranking below bituminous is subbituminous coal with 35-45 percent carbon content and a
heat value between 8,300 and 13,000 BTU/pound. Reserves are located mainly in a half-
dozen Western states and Alaska. Although its heat value is lower, this coal generally has a
lower sulfur content than other types, which makes it attractive for use because it is cleaner
burning.
Lignite
Lignite is a geologically young coal which has the lowest carbon content, 25-35 percent, and
a heat value ranging between 4,000 and 8,300 BTUs-per-pound. Sometimes called brown
coal, it is mainly used for electric power generation.

2.6.6 How Coal Is Found

Coal found close to the surface can be uncovered and removed by large machines in a process
that is called surface mining. Surface mining techniques account for 60 percent of coal
produced in the United States 75 % in Western states, where some deposits are up to 100 feet
thick.

Only recently has surface mining played an important role in the U.S. coal industry. The
development and use of large power equipment provided the impetus that moved surface
mining into prominence, and during the 1970s it became the leading method of coal mining.

Today's surface mines are large, intensively engineered, and highly efficient mechanized
operations. When an area is to be mined, topsoil and subsoil are removed first and set aside to
be used later in reclaiming the land. Then, specially designed machines draglines, wheel
excavators, or large shovels remove the rock and other material, call overburden, to expose
the bed of coal. Smaller shovels load the coal into large trucks that remove the coal from the
pit.

Once the coal is removed, the area is reclaimed. First the overburden and then the soils are
replaced and the area is restored as nearly as possible to its original contour. Vegetation
currently suitable to the area is planted to anchor the soil and return the land to a natural,
productive state. Reclaimed lands are a valuable resource that can support farm crops,
provide new wildlife habitats, enhance recreational opportunities, and even serve as sites for
commercial development.

The complete mining operation is scheduled so that as one area is being mined, another is
being reclaimed where the coal was removed. Thus, even at the largest surface mines only a
relatively small area is disturbed by active mining at any one time. Since 1977 an estimated 2
million acres of coal mine lands have been reclaimed in this manner.

Underground mining methods are used where the coal seam is too deep or the land too hilly
for surface mining. Most underground mining takes place east of the Mississippi, especially
in the Appalachian mountain states. Coal production was once dominated by underground
mining methods, but the growth of coal mining in the West changed that. Now, only 40
percent of our coal comes from underground mines.

Underground mines differ according to how the coal seam is situated with respect to the
surface. If the coal deposit outcrops (appears at the surface) on a hillside, a drift mine can be
driven horizontally into the seam. Where the bed of coal is relatively close to the surface, yet

37
too deep to be recovered by surface mining, a slope mine can be constructed, with the mine
shaft slanting down from the surface to the coal seam. The most common type is the shaft
mine. To reach the coal, which may be as deep as 2,000 feet, vertical shafts are cut through
the overburden to the coal bed, which is excavated by machines.

In deep mines, the seam is mined in carefully engineered patterns that keep as much as half of
the coal in place to help support the roof of the active mining area. This "room and pillar"
method requires that large columns of coal remain between mined-out areas, or rooms, which
are created when the coal is mined, either by continuous mining machines or conventional
methods.

The largest amount of coal taken from underground mines is produced using continuous
miners. This machine has a large, rotating, drum-shaped cutting head studded with carbide-
tipped teeth that break up the seam of coal. Large gathering arms on the machines scoop the
coal directly onto a built-in conveyor for loading into waiting shuttle cars.

In conventional mining, a machine resembling an oversized chain saw cuts into the coal. This
gives the coal an area to expand into during blasting. Holes are drilled for explosives, which
blast loose large chunks of coal. Machines called loaders scoop the coal onto conveyors
which dump it into shuttle cars that haul the coal out through the shaft. This traditional
method of mining accounts for about 11 percent of total production.

In both continuous and conventional mining, the roof over the mined-out area is supported
for safety. The most important development in roof support both in terms of safety and cost
has been the "roof bolt." Roof bolts are long rods driven into the roof to bind several layers of
weak strata into a layer strong enough to support its own weight. Roof bolts also can anchor a
weak immediate roof to a strong, firm structure above. Machines are used to drill holes,
position the bolts and tighten them.

An increasingly popular and more efficient means of underground mining -- introduced from
Europe in the early 1950s -- is long wall mining technology. Longwall today accounts for
about one-third of total underground coal tonnage. In a continuous, smooth motion, a rotating
shear on the mining machines moves back and forth along the face -- or wall -- of a block of
coal, cutting the coal, which drops onto a conveyor and is removed from the mine. The block
of coal being mined is several hundred feet wide, thus the name longwall.

Where longwall mining machines are used, room-and-pillar arrangements are not created
throughout the entire mine (although pillars of coal are left to support the roof in haulage
ways used by people and machines moving about the mine). The longwall miner itself has a
hydraulically operated steel canopy which holds up the roof and protects miners working at
the face. As the miner cuts progressively deeper into the block of coal, the shield advances
with it, allowing the unsupported roof in the mined-out area behind it to collapse in a
controlled and safe manner.

38
2.6.7 Moving Coal to Market

Nearly 60 percent of all coal produced moves by railroad from mine to user. A large
percentage is transported in "unit trains" -- 100 or more cars that can be loaded and unloaded
automatically. Coal makes up a substantial part of the major railroads' freight business. The
fortunes of the two industries are closely linked.

The next most significant mode of transportation for coal is the nation's inland waterways
system. One in every five tons of coal mined is transported by barge, accounting for nearly a
fourth of all barge business on the nation's 25,000 miles of inland waterways. Only petroleum
products account for a larger percentage.

Smaller amounts of coal move by truck and by conveyor directly from mine to power plant.
In one case, coal from a mine in Arizona is pulverized and mixed with water to form a slurry,
then pumped 273 miles through an underground pipeline to a power plant in Nevada.

2.6.8 Coal Future

With a 250-300 year supply of coal under our feet, the picture of coal's role in the future is
bright. However, coal has a reputation to overcome: the idea that it is a dirty fuel. Modern
coal combustion facilities, such as those found at many of the nation's electric power plants,
use equipment to remove most of the polluting elements from coal smoke. In fact, so much is
removed that one can hardly see any smoke at all coming from these "smokestacks." Most of
what shows is steam. The dark, sooty material called fly ash that once went up the stack is
now removed by filters or by devices called precipitators. With precipitators, the flue gas is
passed through an electric field. The ash particles become negatively charged and are
attracted to positively charge collecting plates and later removed for disposal. This method
eliminates 99.5 percent of the offending material.

Coal contains sulfur, which combines with oxygen when the coal is burned to produce sulfur
oxides. The effect of sulfur oxides on the environment has been the topic of significant debate
for a number of years. Beginning in the 1970s, coal producers and major coal consumer
initiated a number of efforts to reduce the amount of sulfur compounds emitted into the
environment.

One was the use of "flue gas scrubbers," which can remove up to 95 percent of the sulfur
oxides from the stream of gases produced by coal combustion before they go up the
smokestack. In one process, sulfur dioxide in the flue gas reacts with a lime or limestone
water slurry to form calcium sulfite or calcium sulfate (gypsum) sludge. In another, sulfur
and sulfuric acid are produced as by-products. Still others can produce a dry by-product.

Sulfur emissions (SO2 -- sulfur dioxide) also are being reduced by greater use of inherently
low-sulfur coals. Less than two decades after the Clean Air Act was passed, the sulfur content
of coal purchased and burned by electric utilities had decreased 37 percent. Physically
washing coal after it is mined and before it is burned is another way to reduce sulfur
compound emissions. This process can remove sulfur-iron compounds (pyritic sulfur) from
raw coal, but cannot remove organic sulfur, which is part of coal's molecular structure.

39
All these techniques represent a significant investment in maintaining clean air. A single
scrubber, for example, can cost more than $100 million to construct, and many millions of
dollars a year to operate. There are more than 140 scrubbers installed and operating at U.S.
utilities, and about 50 more planned.

Electric utilities have already spent $60 billion to control sulfur emissions, and the
investment, which continues every year, has paid off. According to the U.S. Environmental
Protection Agency, sulfur dioxide emissions from electric utilities have gone down 18
percent from their 1973 peak. Taking into account that coal use by utilities has gone up
dramatically during the period makes the accomplishment all the more impressive. As new,
technologically advanced power plants replace older, less efficient ones, the trend toward
lower sulfur dioxide emissions is expected to be enhanced.

As a fossil fuel, coal also contains carbon, which combines with oxygen to form carbon
dioxide (CO2) during the combustion process. CO2 is one of five major so-called
"greenhouse" gases, which help trap radiated heat back to the earth's surface.

This "greenhouse effect" is a natural process which maintains the earth's temperature at a
level sufficient to support life. However, recent scientific and political debate has intensified
over whether human activity -- such as fossil fuel use and deforestation -- has caused an
acceleration of the natural greenhouse effect.

While most scientists agree that global atmospheric CO2 and other greenhouse gases have
risen in quantity over the past century, great disagreement remains over whether these
increases have already -- or will ever -- affect the earth's climate.

Given coal's vital present and future role in meeting the world's energy needs, solutions to
concerns over possible climate change will have to be global in nature and carefully balance
environmental objectives with viable options for continuing to fully utilize fossil fuels.

2.6.9 New Technologies for Coal Combustion

The Clean Air Act, which has been in effect since 1970, and was last amended in 1990, is the
most stringent air pollution control law in the world. Because of it, and through the combined
efforts of business and industry, citizens and government, we enjoy some of the cleanest air
to be found anywhere on the globe.

Pollution control equipment accounts for up to 40 percent of the cost of a new power plant
and 35 percent of operational costs, according to the Electric Power Research Institute. Those
costs plus operating costs currently account for about $10 billion of the nation's electric bills
each year, and will rise even higher under new Clean Air Act requirements.

Although environmental concerns about coal use center on the emission of sulfur and
nitrogen compounds and carbon dioxide, coal is not the only for the leading source of them in
our environment. However, coal combustion is a significant contributor, so as part of a
national commitment to further reduce air pollution, more than a dozen advanced
technologies for burning coal cleanly and more efficiently are being investigated. The
development and demonstration of these technologies has required a substantial investment
of more than $6 billion by government and private industry. Two of the leading technologies
are:

40
Fluidized-bed Combustion (FBC)

Crushed coal mixed with limestone is supported on a strong rising current of air. The
"fluidized" mixture acts as a boiling liquid, mixing turbulently, thus assuring efficient
combustion. The limestone reacts with and removes over 90 percent of the sulfur. As a
consequence, "scrubbers" (flue gas desulfurization) are not required for SO2 control. Because
the operating temperature is lower than in conventional boilers, the formation of nitrogen
oxides is minimized.

The FBC technology lends itself to the design of smaller boilers that can be prefabricated as
modular units at less capital cost than conventional boilers of the same generating capacity.
Because of this savings and the favorable economics of adding additional generating capacity
to a power plant only as it is needed, electric utilities and consumers both are expected to find
this technology attractive.

Coal Gasification

As an alternative to direct combustion of coal, in which the heat produced is used to develop
steam to drive generator turbines, a great deal of progress has been achieved on technologies
that depend on first gasifying the coal. The gas itself can be burned to power gas turbines,
and then the remaining heat can be harnessed to produce steam to turn turbines.

This type of arrangement, called combined cycle gasification, is extremely efficient and
clean. At one demonstration plant in California, emissions of combustion products were
comparable to those from a natural gas fired facility, allowing the plant to meet California's
clean air requirements, the strictest in the country. Another advantage of the coal gasification
process is that it can be carried on in close proximity to the mine site. Rather than shipping
the bulky coal long distances to a power plant, the power of coal can be shipped by wire from
the gasification plant.

These and other advanced clean coal technologies variously hold the promise of generating
more power with less fuel, and reduced operating and maintenance costs; greater pollution
control; some produce marketable by-products; and many utilize smaller plants that can be
modularly built. But they all speak to the same goal: making more effective and efficient use
of an abundant energy resource.

2.7 Coal Gasification Technology

Gasification is a key fundamental baseline technology for converting coal to anything other
than electrons and can potentially be competitive even there [33].
Coal gasification produces synthetic gas as the input to the Haber-Bosch process. This
process involves an exothermic reaction of coal with a mixture of oxygen and steam to
produce synthetic gas, which consists of carbon monoxide and hydrogen.

41
 2.7.1 Process Steps

Coal is first heated in a closed reaction chamber where it undergoes a pyrolysis process at
temperatures above 400°C. During pyrolysis, hydrogen-rich volatile matter is released, along
with tar, phenols, and gaseous hydrocarbons. Then, char is gasified, with the release of gases,
tar vapours and solid residues. The dominant reactions consist of partial oxidation of char,
which produces a syngas with high fractions of H2 and CO [34]. The temperature range for
this process is between 800°C and 1800°C. Specific operating conditions depend on type of
coal, properties of the resulting ash and the gasification technology [34].

The most important variable in a gasification process is the oxidant. It can be either air (with
its nitrogen component) or pure oxygen if the process includes an air separation unit (ASU)
for oxygen production [34]. The use of oxygen instead of air facilitates the partial combustion
of coal, but involves higher investment costs due to costly additional equipment. As
gasification takes place under stoichiometric shortage of oxygen,the reaction mechanism in
the gasification chamber has to be adjusted with appropriate energy balance. The direct
partial oxidation of carbon to CO, for instance, is strongly exothermic, leading to high release
of energy in form of sensible heat. However, steam gasification of coal, (forming both CO
and H2) is strongly endothermic [34].
As a consequence, a steam/oxygen mixture is commonly used.
Table 2.2 Names of reactions and chemical equations for the process involved in coal gasification.
Name of reaction Chemical equation
Water–gas (i) C + H2O ↔ CO + H2
Water–gas (ii) C + 2H2O ↔ CO2 + 2H2
Boudouard C + CO2 ↔ 2CO
Methanation C + 2H2 ↔ CH4
Oxidation (i) C + O2 ↔ CO2
Oxidation (ii) C + 0.5 O2 ↔ CO
Water–gas shift CO + H2O ↔ CO2 + H2
Methane reforming CH4 + H2O ↔ CO + 3H2

2 .7.2 Syngas Generation via Coal Gasification

Classification of Gassification Process:

The processes can be classified basically in two general ways:
(1) By the Btu content of the product gas,[3]
(2) By the type of the reactor hardware configuration, as well as by whether the reactor
system is operated under pressure or not.
The following processes for conversion of coal to gases are grouped according
to the heating value of the product gas.

42
 1) Medium- or High-Btu Gas Gasification Processes
∑ Lurgi gasifier
∑ Synthane gasifier
∑ Atgas molten iron coal gasifier

2) Low- or Medium-Btu Gas Gasification Processes

∑ Koppers-Totzek gasifier
∑ Texaco gasifier
∑ Shell gasifier
∑ Kellogg’s molten salt gasifier
∑ CO2-acceptor gasification process
∑ U-gas process

3) Low-Btu Gas Only Gasification Process

∑ Underground in situ gasification process

Based on the reactor configuration, as well as by the method of contacting gaseous and solid
streams, gasification processes can also be categorized into the following four types [35]:

1. Fixed or moving bed:

In the fixed bed reactor, coal is supported by a grate and the gasifying media (steam, air, or
oxygen) pass upward through the supported bed, whereby the product gases exit from the top
of the reactor. Only non-caking coals can be used in the fixed bed reactor. On the other hand,
in the moving bed reactor, coal and gaseous streams move counter currently, i.e., coal moves
downward by gravity while gas passes upward through the coal bed. The temperature at the
bottom of the reactor is higher than that at the top. Because of the lower temperature at the
top for coal de-volatilization, relatively large amounts of liquid hydrocarbons are also
produced in this type of gasifier. In both types of reactor, the residence time of the coal is
much longer than that in a suspension reactor, thus providing ample contact time between
reactants. Ash is removed from the bottom of the reactor as dry ash or slag. Lurgi and
Wellman-Galusha
gasifiers are examples of this type of reactor. It should be clearly understood that a moving
bed reactor is classified as a kind of fixed bed reactor, because solids in the bed stay together
regardless of the movement of the hardware that supports the bed.

Moving bed gasifiers have the following characteristics: [36]

• Low oxidant requirements;
• Relatively high methane content in the produced gas
• Production of hydrocarbon liquids, such as tars an oils
• High “cold gas” thermal efficiency when the heating value of thehydrocarbon
liquids are included
• Limited ability to handle fines; and
• Special requirements for handling caking coal.

43
2. Fluidized bed:
It uses finely pulverized coal particles. The gas (or gasifying medium) flows upward through
the bed and fluidizes the coal particles. Owing to the ascent of particles and fluidizing gas,
larger coal surface area is made available, which positively promotes the gas-solid chemical
reaction, which in turn results in enhancement in carbon conversion. This type of reactor
allows intimate contact between gas and solid coal fines, at the same time providing
relatively longer residence times than entrained flow reactor. Dry ash is either removed
continuously from the bed, or the
gasifier is operated at such a high temperature that it can be removed as agglomerates. Such
beds, however, have limited ability to handle caking coals, owing to operational
complications in fluidization characteristics. Winkler and Synthane processes use this type of
reactor.
The best existing fluidized bed devices offer a carbon conversion of 97%. In comparison,
both moving-beds and entrained-flow processes offer carbon conversions of 99%. The use of
lignite is mainly focused on fluidized bed reactor. For coal gasification, the most common
technology is entrained flow gasification with oxygen and steam as a gasification agent.

Generic characteristics of fluidized bed gasifiers include: [36]

• Extensive solids recycling
• Uniform and moderate temperature
• Moderate oxygen and steam requirements.

3. Entrained bed:
This type of reactor is also referred to as entrained flow reactor, because there is no bed of
solids. This reactor system uses finely pulverized coal particles blown into the gas stream
before entry into the reactor, with combustion and gasification occurring inside the coal
particles suspended in the gas phase. Because of the entrainment requirement, high space
velocity of gas stream and fine powdery coal particles are very essential to the operation of
this type of process. Because of the very short residence time (i.e., high space velocity) in the
reactor, a very high temperature is required to achieve good conversion in such a short period
of reaction time.
This can also be assisted by using excess oxygen. This bed configuration is typically capable
of handling both caking and non-caking coals without much operational difficulty. Examples
of commercial gasifiers that use this type of reactor include the Koppers-Totzek gasifier and
Texaco gasifier.
Generic characteristics of entrained flow gasifiers include : [36]
• High-temperature slagging operation
• Entrainment of some molten slag in the raw syngas
• Relatively large oxidant requirements
• Large amount of sensible heat in the raw syngas
• Ability to gasify all coal regardless of rank, caking characteristics or amount
of fines.

4. Molten salt bath reactor:In this reactor, coal is fed along with steam or oxygen in the
molten bath of salt or metal operated at 1,000–1,400ºC. Ash and sulfur are removed as slag.
This type of reactor is used in Kellogg and at gas processes. [37]

44
2.8 Classification of Gasifiers
Gasifier equipment are generally classified as :
∑ Upward draft
∑ Downward draft and
∑ Cross draft gasifiers,
based on the direction of air/oxygen flow in the equipment.
2.8.1 Up Draft Gasifier
The air intake is at the bottom and the gas leaves at the top. Near the grate at the bottom the
combustion reactions occur, which are followed by reduction reactions somewhat higher up in the
gasifier. In the upper part of the gasifier, heating and pyrolysis of the feedstock occur as a result of
heat transfer by forced convection and radiation from the lower zones. The tars and volatiles produced
during this process will be carried in the gas stream. Ashes are removed from the bottom of the
gasifier[38].

The major advantages of this type of gasifier are its simplicity, high charcoal burn-out and internal
heat exchange leading to low gas exit temperatures and high equipment efficiency, as well as the
possibility of operation with many types of feedstock (sawdust, cereal hulls, etc.)[38] .

Major drawbacks result from the possibility of "channelling" in the equipment, which can lead to
oxygen break-through and dangerous, explosive situations and the necessity to install automatic
moving grates, as well as from the problems associated with disposal of the tar-containing
condensates that result from the gas cleaning operations. The latter is of minor importance if the gas is
used for direct heat applications, in which case the tars are simply burnt [38].

Fig 2.4 Updraft gasifier.

45
2.8.2 Down Draft Gasifier

A solution to the problem of tar entrainment in the gas stream has been found by designing
co-current or downdraught gasifiers, in which primary gasification air is introduced at or
above the oxidation zone in the gasifier. The producer gas is removed at the bottom of the
apparatus, so that fuel and gas move in the same direction. On their way down the acid and
tarry distillation products from the fuel must pass through a glowing bed of charcoal and
therefore are converted into permanent gases hydrogen, carbon dioxide, carbon monoxide
and methane. Depending on the temperature of the hot zone and the residence time of the
tarry vapours, a more or less complete breakdown of the tars is achieved [39].

A solution to the problem of tar entrainment in the gas stream has been found by designing
co-current or downdraught gasifiers, in which primary gasification air is introduced at or
above the oxidation zone in the gasifier [39]. The producer gas is removed at the bottom of
the apparatus, so that fuel and gas move in the same direction shown in figure below:

Fig 2.5 Downdraught or co-current gasifier

On their way down the acid and tarry distillation products from the fuel must pass through a
glowing bed of charcoal and therefore are converted into permanent gases hydrogen, carbon
dioxide, carbon monoxide and methane.

46
Depending on the temperature of the hot zone and the residence time of the tarry vapours, a
more or less complete breakdown of the tars is achieved.The main advantage of downdraught
gasifiers lies in the possibility of producing a tar-free gas suitable for engine applications.

In practice, however, a tar-free gas is seldom if ever achieved over the whole operating range
of the equipment: tar-free operating turn-down ratios of a factor 3 are considered standard; a
factor 5-6 is considered excellent.

Because of the lower level of organic components in the condensate, downdraught gasifiers
suffer less from environmental objections than updraught gasifiers.

A major drawback of downdraught equipment lies in its inability to operate on a number of

unprocessed fuels. In particular, fluffy, low density materials give rise to flow problems and
excessive pressure drop, and the solid fuel must be pelletized or briquetted before use.
Downdraught gasifiers also suffer from the problems associated with high ash content fuels
(slagging) to a larger extent than updraught gasifiers.

Minor drawbacks of the downdraught system, as compared to updraught, are somewhat lower
efficiency resulting from the lack of internal heat exchange as well as the lower heating value
of the gas [39]. Besides this, the necessity to maintain uniform high temperatures over a
given cross-sectional area makes impractical the use of downdraught gasifiers in a power
range above about 350 kW (shaft power).

2.8.3 Cross Draft Gasifier

Charcoal gasification results in very high temperatures (1500 °C and higher) in the oxidation
zone which can lead to material problems. In cross draught gasifiers insulation against these
high temperatures is provided by the fuel (charcoal) itself. Cross-draught gasifiers, are an
adaptation for the use of charcoal. Charcoal gasification results in very high temperatures
(1500 °C and higher) in the oxidation zone which can lead to material problems. In cross
draught gasifiers insulation against these high temperatures is provided by the fuel (charcoal)
itself [40].

Advantages of the system lie in the very small scale at which it can be operated. Installations
below 10 kW (shaft power) can under certain conditions be economically feasible. The
reason is the very simple gas-cleaning train (only a cyclone and a hot filter) which can be
employed when using this type of gasifier in conjunction with small engines.

A disadvantage of cross-draught gasifiers is their minimal tar-converting capabilities and the

consequent need for high quality (low volatile content) charcoal [41].It is because of the
uncertainty of charcoal quality that a number of charcoal gasifiers employ the downdraught
principle, in order to maintain at least a minimal tar-cracking capability.

47
2.8.4 Other types of gasifiers

A number of other biomass gasifier systems (double fired, entrained bed, molten bath), which
are partly spin-offs from coal gasification technology, are currently under development. In
some cases these systems incorporate unnecessary refinements and complications, in others
both the size and sophistication of the equipment make near term application in developing
countries unlikely [42]. For these reasons they are omitted from this account.

48
 CHAPTER: 3
MATERIAL BALANCE

49
 FLOW SHEET OF AMMONIA FORMATION

Raw coal

Crusher

Screen

980C 25C
370C 500C 150C 250C

35.2atm

Heat exchanger H.T.S.R Heat exchanger L.T.S.R Heat exchanger

(water cooler) 1 (water cooler)2 (water cooler) 3
Dryer
Gasifier Lean
Steam solution
water water
O2

500C CO2 TO
Air UREA
200atm
Air PLANT
separation Ammonia Reactor
unit

LIME
Rich
N2 Lean Solution
Solution
GYPSUM

200atm
500C

Heater

200atm
48⁰C

Recycle H2,N2

Purge stream
Pre-heater CH4,Argon,inerts
Waste Heat Boiler
Converter effluent exchanger

AMMONIA TO UREA PLANT

50
 MATERIAL BALANCE
3.1 DEFINITION:
Generally, a term used in comparisons of the inputs and outputs of processes
A mass balance, also called a material balance, is an application
of conservation of mass to the analysis of physical systems. By accounting for
material entering and leaving a system, mass flows can be identified which
might have been unknown, or difficult to measure without this technique. The
exact conservation law used in the analysis of the system depends on the
context of the problem, but all revolve around mass conservation, i.e.
that matter cannot disappear or be created spontaneously. [43]

3.2 MATHEMATICAL FORM:

Mathematically the mass balance for a system without a chemical reaction is as
follows:[43 ]
EQUATIONS:

51
3.3 MATERIAL BALANCE FOR
EQUIPMENTS

52
 SECTION 3.3.1
AMMONIA REACTOR

53
3.3.1 .AMMONIA REACTOR:
The mass balance for PFR is [44] :

Nitrogen
N2 temp= 25⁰C Ammonia Gas

NH3 temp= 500⁰C

Ammonia reactor
Temp= 500⁰C
Pressure = 200atm
Hydrogen

H2 temp = 500⁰C

Recycled
N2& H2
85%

Fig 3.1 mass balance across ammonia

Chemical Reaction
N2+3H2 ↔ 2NH3
Hydrogen Balance
10^6 kg/day NH3 → (6/34) kg of H2 * 10^6
176470.5882 kg H2/ day
No of moles of H2 = Given weight /M.Wt
= 176470.5882/2
= 88235.29412 kmol of H2/day
Nitrogen Balance
10^6 kg/day NH3 → (28/34) kg of N2 * 10^6
823529.4 kg N2/ day
No of moles of N2 = Given weight /M.Wt
= 823529.4/28
= 29411.765 kmol of N2/ day

54
 Ammonia Reactor
Yield= 0.15= Actual/Theoretical
Theoretical = Actual/ 0.15
= (58823.53Kmol/day)/0.15
= 392156.87 kmol NH3/day
H2 Converted = 3/2 *392156.87
= 588235.3 Kmol H2/day
N2 Converted = 0.5*392156.87
= 196078.43 Kmol N2 /day
H2 Recycled = 588235.3 – 88235.3
H2 Recycled = 500000 Kmol H2 / day
N2 Recycled = 196078.43-29411.76
N2 Recycled = 166666.67 Kmol N2 / Day
Table 3.1 mass balance across ammonia reactor
Components Reacted inlet Recycled Product
(kmol/day) (kmol/day) (kmol/day) (kmol/day)

N2 29411.76 196078.43 166666.7 -

H2 88235.3 588235.3 500000 -

NH3 - - - 58823.53

55
 SECTION 3.3.2
COAL COMPOSITION

56
3.3.2 COAL:
Thar coal :
Table 3.2 Thar coal data for coal [45]
Moisture Content 45.87%
Ash content 5.5%
Volatile Matters 28.1%
Fixed Carbon 20.53%

%C = 0.97(Fixed Carbon) +0.7 (Volatile matter – 0.1 Ash) - Moisture (0.6-

0.01M).
%C = 19.9141+19.285-6.481431
%C= 32.72
%H = 0.036(F.C) +0.086(VM-0.1A)-0.0035(M2) (1-0.02M)
%H = 0.73908+2.3693-0.6083
%H=2.50008
%N= 2.1-0.020(V.M)
%N= 1.538
%O =10.533531%
%Sulphur=1.4%
Heating Value (btu/lb) = 5780 btu/lbm

57
 SECTION 3.3.3
BALANCE ON HIGH TEMPERATURE AND LOW
TEMPERATURE SHIFT REACTOR

58
3.3.3. BALANCE ON HIGH TEMPERATURE AND LOW
TEMPERATURE SHIFT REACTOR:
The water-gas shift reaction (WGSR) describes the reaction of carbon monoxide and water
vapor to form carbon dioxide and hydrogen (the mixture of carbon monoxide and hydrogen is
known as water gas):

CO + H2O CO2 + H2

The water gas shift reaction was discovered by Italian physicist Felice Fontana in 1780. It
was not until much later that the industrial value of this reaction was realized. Before the
early 20th century, hydrogen was obtained by reacting steam under high pressure with iron to
produce iron, iron oxide and hydrogen. With the development of industrial processes that
required hydrogen, such as the Haber–Bosch ammonia synthesis, the demand for a less
expensive and more efficient method of hydrogen production was needed [46].

Syngas at 370⁰C will enter the reactor where it will be reacted with water to form hydrogen
and carbon dioxide as shown below in figure 3.2

n⁰Syn (370⁰C) n⁰ H2O

kmol/day
0.35 H2, X CH4
0.35CO, XH20
XCO2, n⁰H2S, n⁰ N2 H2O
Fig 3.2 mass balance across shift gas reactor

Chemical Reaction
CO+H2O↔CO2+H2
28 kg CO =2kg H2
1 mole of CO = 1mole of H2
For 99% conversion of CO:
n⁰ H2 = 0.99 * x CO (n⁰ Syn)
Balance on combined HTS and LTS for H2;
→ n⁰ H2 inlet + (0.99* x CO (n⁰ Syn)) = n⁰ H2
→ 0.35 (n⁰ Syn) + (0.99*0.35) (n⁰ Syn) = 88235.3 kmol/day
→ 0.6965 (n⁰ Syn) = 88235.3 kmol/day
→ n⁰ Syn = 126683.85 kmol/day

59
 Chemical Rxn
C+2H2↔CH4
2 2
K1= (XCH4* P)/ (XH2) * P ------------------------------------------------------------
→ Eq 1
Gasifier Temperature 980⁰C
Temperature =1253 K
lnk1 = 7082.848/T -6.567 ln T + 7.466*10-3*T/2 -2.164*10-6T2/6+0.701*10-
5
/2T2=32.541
lnk1 = -4.5388
k1 = 0.01068622
Equation 1 → XCH4=0.03405
→ 1-XCH4-XH2-XCO-XCO2-XH2O =0
→ 1-0.03405-0.35-0.35-XCO2 =XH20
→ XH20 = 0.26595-XCO2
CO+H2O↔CO2+H2
K2 = XCO2 *XH2/ XCO*XH20
→ Log 10 K2 = -2.4198 + 0.0003855 T+ 2180.6/T
→ K2 = 0.636114
→ 0.636114 = XCO2* 0.3/ 0.35* (0.26595-XCO2)
→ XCO2= 0.1133
→ XH20 = 0.26595-0.1133
= 0.15265

Table 3.3 mole balance across shift reactor.

Inlet Mole Fraction Amount (kmol/day)
n⁰Syn 1 126683.85
H2 0.35 n⁰Syn * 0.35 =44339.35
CO 0.35 n⁰Syn * 0.35 =44339.35
CO2 0.113 n⁰Syn * 0.113 =14353.3
CH4 0.03405 n⁰Syn * 0.03405= 4313.59
H2O 0.15265 n⁰Syn * 0.153= 19338.3

60
 SECTION 3.3.4
GASIFIER BALANCE

61
3.3.4. GASIFIER BALANCE:
Gasifier will convert coal into carbon monoxide, hydrogen and carbon dioxide (also known
as syngas) by reaction with steam and the temperature will be kept at 980 oC. Ash is produced
as a side product.

O2
Temp= 980⁰C
Syn gas
GASIFIER

Coal

Steam Ash

Fig 3.3 mass balance for gasifier

Carbon Balance
→ (0.35) (n⁰Syn) (12) + (0.1133) ( n⁰Syn) (12) + (0.03405 )( n⁰Syn) (12) = m⁰
coal (0.3)
→ m⁰coal = 2520248.512 kg/day
Gasifier Efficiency 97%
→ m⁰coal + (100-97) % m⁰coal = m⁰ total coal
→m⁰ total coal = 2595855.967 kg/day
Mass of moisture
= 0.4587 *2595855.967 kg/day
=1190719.132 kg/day
After 90% moisture removal we have,
→m⁰ total coal = 1524208.748 kg/day
Mass of ash
=0.055*1524208.748 kg/day
=83831.48114 kg/day
Mass of Hydrogen
=0.025*1524208.748 kg/day
=38105.2187 kg/day
Mass of Oxygen
=0.15033*1524208.748 kg/day
=229134.3011 kg/day
Mass of Nitrogen
=0.01538*1524208.748 kg/day

62
=23442.33054 kg/day
Mass of Sulphur
= 0.014*1524208.748 kg/day
=213389.2236 kg/day
Sulphur balance on gasifier
→21700.84 kg/day= n⁰H2S *34
→ n⁰H2S= 638.26 kmol/day
→Moles of sulphur = 638.3 kmol/day
Moles of Nitrogen
→ (23442.33054 kg/day)/28 = n⁰N2
→ n⁰N2 = 837.226 kmol/day
Hydrogen balance
→ m⁰steam (2/18) + 10% ( m⁰moisture (2/18)) + mass of H2 = m⁰H2 syn +m⁰ of
hydrogen in CH4 syn + m⁰ of hydrogen in H2O syn +m⁰ of hydrogen in H2S
→ m⁰steam (2/18)+ 10% (132302.1258) +( 38105.2187) = (0.35*126683.85 * 2)
+ (0.034405*126683.85*4) + (0.15265* 126683.85*2) + (638.26* 34* (2/34))
→ m⁰steam (2/18) + (13230.21) + (38105.2187) = 146065.96
→ m⁰steam= 852574.8 kg/day
→n⁰steam= 473865.3 kmol/day
Oxygen balance
→ (m⁰ of oxygen coal) + (m⁰ O2* 32) + (m⁰ of oxygen in m⁰steam) + (m⁰ oxygen
in moisture) = (m⁰ of oxygen in CO + m⁰ of oxygen in CO2 + m⁰ of oxygen in
H20)syn
→ (229134.3011 kg/day) + (m⁰ O2*32) + (852574.8 kg/day* 16/18) +
(119071.91* 16/18) = (0.35*126683.85 * 16) + (0.1133*126683.85 * 32) +
(0.15265* 126683.85*16)
→ m⁰ O2 = 385326.89kg/day
→ n⁰ O2 = 12041.46 kmol/day

Table 3.4 mass of reactant for gasifier

Reactants Amount (kg/day)

Coal 1524208.748 kg/day

Steam 852574.8 kg/day

Oxygen 385326.89kg/day

63
Table 3.5 mass of product for gasifier
Product Amount (kg/day)

(H2)
(CO)
(CO2)
Syn gas (CH4) 2366562.2kg/day
(H2O)
(H2S)
(N2)
Ash 83831.48114 kg/day

64
 SECTION 3.3.5
BALANCE ON HIGH TEMEPRATURE SHIFT
REACTOR

65
3.3.5. BALANCE ON HTSR (High temperature shift reactor):

370⁰C 500⁰C

Syn gas (n⁰ CO2)out

(n⁰ CO2)in (n⁰ CO)out
(n⁰ CO)in (n⁰ H2)out
(n⁰ H2)in (n⁰ N2)out
(n⁰ N2)in (n⁰ H2S)out
(n⁰ H2S)in (n⁰ H2O)out
(n⁰ H2O)in (n⁰ CH4)out
(n⁰ CH4)in HTSR

Water

Fig 3.4 Mass balance on HTSR.

Chemical Rxn
CO+H2O↔CO2+ H2
K2 = (n ⁰CO2) (n⁰H2)/ (n⁰CO) (n⁰ H2O) -------------------------------------- Eq 2
For 60% conversion of CO
→ n⁰CO out = 0.40 * (n⁰CO)in
= 0.40 * (0.35*126683.85)
=17735.74 kmol/ day
→ ɛ = (n⁰CO) in – (n⁰CO) out
ɛ = 0.60(n⁰CO) in
ɛ = 26603.6085 kmol/day
→ (n⁰CO2) out = (n⁰CO2) in + ɛ (n⁰CO2) out = 40956.88 kmol/day
→ (n⁰H2) out = (n⁰H2) in + ɛ
(n⁰H2) out = 44339.35 + 26603.61
(n⁰H2) out = 70942.96 kmol/day
→ (n⁰H2O) out = (n⁰H2O) in - ɛ + n⁰H2O syn
(n⁰H2O) out = (n⁰H2O) in – (7265.31 kmol/day) ----------------------------Eq3
As temperature = 500 ⁰C = 773 K for 99% equilibrium
→ log10 k2 = -2.4193+ 0.0003855 T + 2180/T
K2 = 5
Equation 2 becomes,
→K2 = (n ⁰CO2) (n⁰H2)/ (n⁰CO) (n⁰ H2O)
66
 0.99* 5= (40956.88 kmol/day) (70942.96 kmol/day)/ (17735.74 kmol/ day)
(n⁰H2O) out
→ (n⁰H2O) out= 33096.5 kmol/day
Equation 3 becomes,
→ (n⁰H2O) in= 40361.7 kmol/day
Table 3.6 Inlet and Outlet amount of high temperature shift reactor.
Inlet Amount( kmol/day) Outlet Amount(kmol/day)
(H2)in 44339.35 (H2)out 70942.96
(CO) in 44339.35 (CO) out 17735.74
(CO2)in 14353.3 (CO2)out 40956.88
(CH4)in 4313.59 (CH4)out 4313.59
(H2O)in 19338.3 (H2O)out 33096.5
(H2S)in 638.26 (H2S)out 638.26
(N2)in 837.226 (N2)out 837.226
n⁰H2O 40361.7 kmol/day
Total 168521 Total 168521

67
 SECTION 3.3.6
BALANCE ON LOW TEMPERATURE SHIFT
REACTOR

68
3.3.6. BALANCE ON LTSR (Low temperature shift reactor):

150⁰C 250⁰C

(n⁰ CO2)out
(n⁰ CO)out
(n⁰ CO2)out
(n⁰ H2)out
(n⁰ CO)out
(n⁰ N2)out
(n⁰ H2)out
(n⁰ H2S)out
(n⁰ N2)out
(n⁰ H2O)out
(n⁰ H2S)out
(n⁰ CH4)out
(n⁰ H2O)out
LTSR (n⁰ CH4)out

Water

Fig 3.5 mass balance on LTSR

Temperature = 250 ⁰ C = 523 K
K2 = 89 ( by using formula Log 10 K2 = -2.4198 + 0.0003855 T+ 2180.6/T)

K2 = (n ⁰CO2) (n⁰H2)/ (n⁰CO) (n⁰ H2O)

→ (n⁰ CO) out’ = 0.05 * n⁰ Syn * 0.35
(n⁰ CO) out’ = 2216.97 kmol/day
→ ɛ = [(n⁰ CO) out - (n⁰ CO) out’]/ 1
ɛ= 17735.74 – 2216.97
ɛ= 15518.8 kmol/day
→ n⁰ CO2 out’ = n⁰ CO2 out + ɛ
n⁰ CO2 out’ = 40956.88 +15518.8
n⁰ CO2 out’= 56475.65 kmol/day
→ n⁰ H2 out’ = n⁰ H2 out + ɛ
n⁰ H2 out’= 70942.96 + 15518.8
n⁰ H2 out’ = 86461.76 kmol/day
→ n⁰ H2O out’= n⁰ H2O out -ɛ + n⁰H2O
n⁰ H2O out’= 33096.5 – 15518.8 +n⁰H2O
n⁰ H2O out’= 17577.7 kmol/day + n⁰H2O
→ K2 = (n ⁰CO2) out’ (n⁰H2) out’/ (n⁰CO) out’ (n⁰ H2O) out’
n⁰ H2O out’= 24747.7 kmol/day
n⁰H2O = 7170.0 kmol/day

69
Table 3.7 Inlet and Outlet amount of low temperature shift reactor.
Inlet Amount( kmol/day) Outlet Amount(kmol/day)
(H2)out 70942.96 (H2)out’ 86461.76
(CO) out 17735.74 (CO) out’ 2216.97
(CO2)out 40956.88 (CO2)out’ 56475.65
(CH4)out 4313.59 (CH4)out’ 4313.59
(H2O)out 33096.5 (H2O)out’ 24747.7
(H2S)out 638.26 (H2S)out’ 638.26
(N2)out 837.226 (N2)out’ 837.226
n⁰H2O 7170.0
Total 175691 total 175691

70
 SECTION 3.3.7
BALANCE ON DESULPHURIZTION UNIT

71
3.3.7 BALANCE ON DESULPHURIZTION UNIT

PRODUCT GAS

DESULPHURIZATION
LIME

UNIT SULPUR
OXIDIZING
GAS

SYNGAS

Fig 3.6 Mass balance for desulphurization unit

Chemical Reaction
2H2S + O2 → 2H2O + 2S
The Claus process involves burning one-third of the H2S with air in a reactor
furnace to form sulfur dioxide (SO2) according to the following reaction:
2H2S + 3O2 → 2SO2 + 2H2O + heat
Total hydrogen sulphide= n⁰H2S= 638.26 kmol/day
As one third is used so moles become:
638.26 * (1/3) = 212.766 kmol.day
And mass become:
212.766 * 34 = 7243.044 Kg /day
∑ Amount of Oxygen:
7234.044 kg/day H2S → (3* 32/ 2*34) kg of O2 * 7234.044 kg/day
Mass of O2 = 10212.8 Kg/day
Moles of O2 = 319.15 Kmol/day
∑ Amount of Sulphur dioxide:
7234.044 kg/day H2S → (2* 64/ 2*34) kg of SO2 * 7234.044 kg/day
Mass of SO2 = 13617.024 kg/day
Moles of SO2 = 212.766 kmol/day
∑ Amount of Water:
7234.044 kg/day H2S → (2* 18/ 2*34) kg of H2O* 7234.044 kg/day
Mass of H2O =3829.8 kg/day
Moles of H2O =212.766 kmol/day

72
The remaining uncombusted two-thirds of the hydrogen sulfide undergoes
Claus reaction (reacts with SO2) to form elemental sulfur as follows:
2H2S + SO2 ←→3S + 2H2O + heat
As two third is used so moles become:
638.26 * (2/3) = 425.554 kmol.day
And mass become:
425.554 * 34 = 14468.84 Kg /day
∑ Amount of Sulphur dioxide:
14468.84 kg/day H2S → (64/ 2*34) kg of SO2 * 14468.84 kg/day
Mass of SO2 = 13617.73kg/day
Moles of SO2 = 212.7 Kmol/day
∑ Amount of Sulphur:
14468.84 kg/day H2S → (3*32/ 2*34) kg of S* 14468.84 kg/day
Mass of S= 20426.6 kg/day
Moles of S = 638.3 kmol/day
∑ Amount of Water:
14468.84 kg/day H2S → (2*18/ 2*34) kg of H20* 14468.84 kg/day
Mass of H2O =7659.97 kg/day
Moles of H2O =425.5 kmol/day
Table 3.8 amount for desulphurization unit at inlet
Inlet Amount (kmol/day)
Oxygen 319.15
Syn gas 175691

TABLE 3.9 amount for desulphurization unit at outlet

Out let Amount (kmol/day)
Sulphur 638.3
Syngas (no sulphur ) 175691
Water 638.3

73
Recovery of Hydrogen Sulphide:
Hydrogen sulphide is recovered and converted to elemental sulphur by the Claus process
recovery unit. The process consists of multistage catalytic oxidation of hydrogen sulphide
according to the following overall reaction:
2H (1) 2S O2 → 2S 2H2O
Each catalytic stage consists of a gas preheater, a catalyst chamber, and a condenser. The
Claus process involves burning one-third of the H2S with air in a reactor furnace to form
sulphur dioxide (SO2) according to the following reaction: [47]
2H (2) 2S 3O2 → 2SO2 2H2O heat
The furnace normally operates at combustion chamber temperatures ranging from 980 to
1540°C with pressures rarely higher than 70 kilopascals (kPa)
Before entering a sulphur condenser, hot gas from the combustion chamber is quenched in a
waste heat boiler that generates high to medium pressure steam. About 80 percent of the heat
released could be recovered as useful energy. Liquid sulphur from the condenser runs through
a seal leg into a covered pit from which it is pumped to trucks or railcars for shipment to end
users. Approximately 65 to 70% of the sulphur is recovered. The cooled gases exiting the
condenser are then sent to the catalyst beds.
The remaining uncombusted two-thirds of the hydrogen sulphide undergoes Claus reaction
(reacts with SO2) to form elemental sulphur as follows:[48]
2H (3) 2S SO2 ←→3S 2H2O heat

74
 CHAPTER: 4
ENERGY BALANCE

75
 ENERGY BALANCE
4.1. DEFINITION:
Energy Balance concerned with energy changes and energy flow in a
chemical process. [49]

System
Mass in, H in Mass out, H out
Q

Fig 4.1 Energy balance

∑ Heat transferred to a system is +ve and heat transferred from a system is
–ve
∑ Work done on a system is+ve and work done by a system is -ve

4.2. MATHEMATICAL FORM:

Conservation of energy – first law of thermodynamics. [49]

Accumulation of energy in a system = energy input – energy

output

76
 SECTION 4.3
ENERGY BALANCE FOR EQUIPMENTS

77
 SECTION 4.3.1
AMMONIA REACTOR

78
4.3.1. AMMONIA REACTOR:

Nitrogen
N2 temp= 25⁰C Ammonia Gas

NH3 temp= 500⁰C

Ammonia reactor
Temp= 500⁰C
Pressure = 200atm
Hydrogen Q net =?
H2 temp = 500⁰C

Recycled
N2& H2
85%

Fig 4.2 energy balance across ammonia reactor

Equations [50]
Q NET = Q OUT – Q IN
QIN = mΣ∆Hf Reactants+ (mCp∆T) R
QOUT= mΣ∆Hf Products+ (mCp∆T) P
Q NET = [mΣ∆Hf Products+ (mCp∆T) P] – [mΣ∆Hf Reactants+ (mCp∆T) R]
Q NET = [mΣ∆Hf Products - mΣ∆Hf Reactants] + [ (mCp∆T) P - (mCp∆T) R]
Q NET = Q RXN+ [ (mCp∆T) P - (mCp∆T) R]



∑ m ∫




For Products
Cp mean:
Cp/R= A + BT+ CT2+ DT-2 [51]
-3 +5 -2
CpNH3= R (3.578 + 3.020*10 T -0 .186*10 T )* 0.15
Cp N2= R (3.280 + 0.593*10-3 T + 0.040*10+5T -2)* 0.2125
CpH2= R (3.249+ 0.422*10-3 T + 0.083*10+5T -2)* 0.6375
Cp mean = R (3.305 + 0.84*10-3T +0.033*10+5T-2)
Cp mean = 27.47 + 6.98*10-3 T + 0.27*10+5 T-2
(mʃCp∆T) P = (392156.83) [27.47(773-298) + 6.98*10-3/2 (7732- 2982) +
0.27*10+5/ (-1) (773-1-298-1)
mCp ∆T = 5.8*109 KJ/Day
∑ Qrxn = m⁰∆Hf:
Qrxn = (392156.83)* (-46.1Kj/gmol)*(1000gmol/1kmol)
Qrxn = - 1.808*10 10 Kj/day
For Reactant:
Q N2= 0KJ/day

79
QH2 = mʃCp∆T
Table 4.1 Energy balance across ammonia reactor
Temp in 500⁰C= 773K
Temp ref 25⁰C=298K
Mass 588235.3Kmol/day
mʃCp∆T 588235.3* [28.51*(773- 298)+ 0.001755*(7732-2982)-69006.2
*(773-1-298-1)]
QH2 8.5* 10 9 KJ/day
∑ Q NET= Q RXN + [ (mCp∆T) P - (mCp∆T) R]
Qnet= -2.1*1010kj/day
Table 4.2 Reaction Temperature and Q.
Rxn temp 500⁰C
Qnet -2.1*1010kj/day

80
 SECTION 4.3.2
DESULPURIZATION UNIT

81
4.3.2. DESULPURIZATION UNIT:
PRODUCT GAS
980⁰C

DESULPHURIZATION
LIME

OXIDIZING UNIT SULPUR

GAS 980⁰C
T= 400⁰ C
SYNGAS
25⁰C
Q net=?
Fig 4.3 energy balance on desulphurization unit
For Reactants:
Syn gas:
QIN= mΣ∆Hf R + (mCp∆T) R
mΣ∆Hf R :
∑ Heat of formation (Hf):
Table 4.3 mole fraction of components of desulphurization unit
Components Hf Amount Mole fraction Mol frac* Hf
(kj/mol) Kmol/day
(H2) 0 86461.76 0.492 0
(CO) -110.5 2216.97 0.013 -1.4365
(CO2) -393.5 56475.65 0.3214 -126.5
(CH4) -74.87 4313.59 0.0245 -1.834
(H2O) -241.82 24747.7 0.141 -34.0966
(H2S) -20.63 638.26 0.0036 -0.0743
(N2) 0 837.226 0.0048 0
Total 175691 1.00 -163.94
m ∆Hf product = -2.8*1010 Kj/day
For Oxygen:
Table 4.4 Oxygen data
Temp In 450C= 723K
Temp Ref 25C=298 K
Mass 319.2 kmol/day
Cp 1.03 Kj/mol.k
Q 4.34112 * 10 9 kj/day
82
For Product:
Product gas:
Table 4.5 Data for product gas.
Components Hf Amount Mole Mol frac* Hf
(kj/mol) Kmol/day fraction
(H2) 0 86461.76 0.492 0
(CO) -110.5 2216.97 0.013 -1.4365
(CO2) -393.5 56475.65 0.3214 -126.5
(CH4) -74.87 4313.59 0.0245 -1.834
(H2O) -241.82 24747.7 0.141 -34.0966
(N2) 0 837.226 0.0048 0
H2O produce -241.82 638.26 0.0036 -0.87
during reaction
Total 175691 1.00 -164.8

m ∆Hf product = -3*1010 Kj/day

m ʃCp dt:
∑ (mCp∆T) p:
Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.3214
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.492
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.013
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.141
CpH2O= (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R * 0.0036
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.0048
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.0245
Cp mean= 32.9 + 8*10-3T -2.6*10+5 T-2- 0.44*10-6 T2
Table 4.6 Energy absorbed
Temperature 980⁰C= 1253K
out
Temperature 25⁰C=298K
Ref
Cp mean 32.9 + 8*10-3T -2.6*10+5 T-2- 0.44*10-6 T2 =36542.8
j/mol.k
Mass 175691 kmol/day
Mass*ʃCp dt 6.3*109 Kj/day

Sulphur:
Table 4.7 Data for Sulphur
Temp out 980C= 1253K
Temp Ref 25⁰C =298K

83
Mass 638.3 kmol/day
Cp 54 J/mol.K
Q =mCp dt 3* 10 7 kj/day

Total:
Qnet = Qproduct gas + Q sulphur – Q syn
Qnet = -9.1* 10 7KJ/mol

84
SECTION 4.3.3
COOLER 3

85
4.3.3. COOLER 3:

Water in
25⁰C

Syn gas Syn gas

Temp out = 25⁰C
Temp in = 250⁰C

Water out
Temp out =140⁰C
Mass of water =?
Fig 4.4 Energy balance on cooler



Q1= m ∫





Table 4.8 mole fraction of component for cooler 3
Components Amount kmol/day Mole fraction
(H2)out’ 86461.76 0.492
(CO) out’ 2216.97 0.013
(CO2)out’ 56475.65 0.3214
(CH4)out’ 4313.59 0.0245
(H2O)out’ 24747.7 0.141
(H2S)out’ 638.26 0.0036
(N2)out’ 837.226 0.0048
Total 175691 1.00

Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.321
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.492
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.13
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.141
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.0036
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.0048
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.0245
Cp mean= 36.2 + 8.735*10-3T -2.63*10+5 T-2- 0.441*10-6 T2


2 2 5 -1
∫





= 36.2 (298-523) + (0.008735/2) (298 -523 ) – (2.63*10 / -1) (298 -
523-1) – (0.441*10-6/3) (2983-5233)
= -8555 J/mol



Q1= m ∫





= - 1.5*109 KJ/day

86
Q1 = Q2



Q2= m ∫






=m kmol/day * 8.314J/mol.K*ʃ (3.470+ 1.450*10-3 T + 0.121*10+5T-2) dt
1.5*109 KJ/day = m * 8.314J/mol.K* [3.470 (413-288) + (1.450*10-3 /2) (4132-
2882 + (0.121*10+5) (413-1- 288-1)]
Mass of water= 1.6*106 kmol/day
Table 4.9 Energy balance for cooler.
T in 250⁰C
Tout 25⁰C
Twater 15⁰C
Tsteam 140⁰C
Q - 1.5*109 KJ/day
Mass of water 1.6*106 kmol/day

87
 SECTION 4.4.4
LOW TEMPERATURE SHIFT REACTOR

88
4.4.4. LOW TEMPERATURE SHIFT REACTOR:

150⁰C 250⁰C

(n⁰ CO2)out
(n⁰ CO)out
(n⁰ CO2)out
(n⁰ H2)out
(n⁰ CO)out
(n⁰ N2)out
(n⁰ H2)out
(n⁰ H2S)out
(n⁰ N2)out
(n⁰ H2O)out
(n⁰ H2S)out
(n⁰ CH4)out
(n⁰ H2O)out
LTSR (n⁰ CH4)out

Water
T=130⁰C

Qnet=?

Fig 4.5 balance across LTSR

Table 4.10 mole fraction at Inlet and Outlet of LTSR
Inlet Amount Mol Outlet Amount Mol
Fraction Fraction
(H2)out 70942.96 0.404 (H2)out’ 86461.76 0.492
(CO) out 17735.74 0.1 (CO) out’ 2216.97 0.013
(CO2)out 40956.88 0.233 (CO2)out’ 56475.65 0.3214
(CH4)out 4313.59 0.024 (CH4)out’ 4313.59 0.0245
(H2O)out 33096.5 0.19 (H2O)out’ 24747.7 0.141
(H2S)out 638.26 0.0036 (H2S)out’ 638.26 0.0036
(N2)out 837.226 0.0048 (N2)out’ 837.226 0.0048
n⁰H2O 7170.0 0.041
Total 175691 1.00 Total 175691 1.00

Formula [50]:
Q NET = Q OUT – Q IN
QIN = mΣ∆Hf Reactants+ (mCp∆T) R
QOUT= mΣ∆Hf Products+ (mCp∆T) P

89
 Q NET = [mΣ∆Hf Products+ (mCp∆T) P] – [mΣ∆Hf Reactants+ (mCp∆T) R]
Q NET = [mΣ∆Hf Products - mΣ∆Hf Reactants] + [ (mCp∆T) P - (mCp∆T) R]
Q NET = Q RXN + (mCp∆T) P
For Reactants:
∑ Heat of formation (Hf):
Table 4.11
Components Hf Amount Mole fraction Mol frac*
(kj/mol) Kmol/day Hf
(H2)out 0 70942.96 0.404 0
(CO) out -110.5 17735.74 0.1 -11.05
(CO2)out -393.5 40956.88 0.233 -91.6855
(CH4)out -74.87 4313.59 0.024 -1.79688
(H2O)out -241.82 33096.5 0.19 -45.946
(H2S)out -20.63 638.26 0.0036 -0.0743
(N2)out 0 837.226 0.0048 0
n⁰H2O -241.82 7170.0 0.041 -9.91462
Total 175691 1.00 -160.5

m ∆Hf reactant= 175691*(-160.5) Kj/day

m ∆Hf reactant= -2.82* 1010 Kj /day
∑ (mCp∆T) R:
Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.233
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.404
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.1
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.19
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.0036
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.0048
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.024
Cp mean= 30.35 + 8.0*10-3T -1.8*10+5 T-2- 0.432*10-6 T2
Table 4.12
Temperature In 150⁰C= 423K
Temperature Ref 25⁰C=298K
Cp mean 30.35 + 8.0*10-3T -1.8*10+5 T-2- 0.432*10-6 T2
Mass 175691 kmol/day
Mass*ʃCp dt 6.9*108 Kj/day

∑ For Water:
Table 4.13
Temperature In 130 ⁰C= 403 K
Temperature Ref 25⁰C =298 K
Cp H20 (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R = 3561.30

90
Mass 7170.0 Kmol/day
Mass*ʃCp dt 2.5* 10 7 kj/day
(mCp∆T) R = 6.9*108 Kj/day + 2.5* 10 7 kj/day = 7.22 *108 Kj/day
For Product:
∑ Heat of formation (Hf):
Table 4.14
Components Hf Amount Mole fraction Mol frac* Hf
(kj/mol) Kmol/day
(H2)out’ 0 86461.76 0.492 0
(CO) out’ -110.5 2216.97 0.013 -1.4365
(CO2)out’ -393.5 56475.65 0.3214 -126.5
(CH4)out’ -74.87 4313.59 0.0245 -1.834
(H2O)out’ -241.82 24747.7 0.141 -34.0966
(H2S)out’ -20.63 638.26 0.0036 -0.0743
(N2)out’ 0 837.226 0.0048 0
Total 175691 1.00 -163.94

m ∆Hf product = -2.9*1010 Kj/day

∑ (mCp∆T) p:
Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.3214
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.492
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.013
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.141
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.0036
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.0048
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.0245
Cp mean= 33 + 8.2*10-3T -2.6*10+5 T-2- 0.44*10-6 T2
Table 4.15
Temperature out 250⁰C= 523K
Temperature Ref 25⁰C=298K
Cp mean 33 + 8.2*10-3T -2.6*10+5 T-2- 0.44*10-6 T2 = 7790
j/mol.k
Mass 175691 kmol/day
Mass*ʃCp dt 1.4*109 Kj/day

Q NET = [mΣ∆Hf Products - mΣ∆Hf Reactants] + [ (mCp∆T) P - (mCp∆T) R]

Qnet = [-2.9*1010 – (-2.82* 1010)] + [1.4*109 -7.22*10 8 ]
Qnet = -1.2*108 kj/day

91
SECTION 4.4.5
COOLER 2

92
4.4.5. COOLER 2:

Water in
25⁰C

Syn gas Syn gas

Temp out = 150⁰C
Temp in = 500⁰C

Water out
Temp out =140⁰C
Mass of water =?
Fig 4.6 energy balance across cooler 2
Tin 500⁰C
Tout 150⁰C
Twater 25⁰C
Tsteam 140⁰C



Q1= m ∫





Mass=168521kmol/day
Table 4.16 Molr Fraction
Components Amount(kmol/day) Mole fraction
(H2)out 70942.96 0.42
(CO) out 17735.74 0.105
(CO2)out 40956.88 0.2431
(CH4)out 4313.59 0.026
(H2O)out 33096.5 0.12
(H2S)out 638.26 0.0038
(N2)out 837.226 0.005
Total 168521 1.00

Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.2431
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.42
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.105
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.12
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.0038
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.005
93
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.026
Cp mean= 29.4 + 7.55*10-3T -1.95*10+5 T-2- 0.46*10-6 T2


2 2 5 1
∫





= 29.4 (423-773) + (0.00755/2) (423 -773 ) – (1.95*10 / -1) (423 -
773-1) – (0.46*10-6/3) (4233-7733)
= -11602.3 J/mol



Q1= m ∫





= - 1.95*109 KJ/day
Q1 = Q2



Q2= m ∫






=m kmol/day * 8.314J/mol.K*ʃ (3.470+ 1.450*10-3 T + 0.121*10+5T-2) dt
1.95*109 KJ/day = m * 8.314J/mol.K* [3.470 (413-288) + (1.450*10-3 /2)
(4132- 2882 + (0.121*10+5) (413-1- 288-1)]
Mass of water= 2.0*106 kmol/day
Table 4.17 Stream Data
T in 500⁰C
Tout 150⁰C
Twater 15⁰C
Tsteam 140⁰C
Q -1.95*109 KJ/day
Mass of water 2.0*106 kmol/day

94
 SECTION 4.4.6
HIGH TEMPERATURE SHIFT REACTOR

95
4.4.6. HIGH TEMPERATURE SHIFT REACTOR:

370⁰C 500⁰C

(n⁰ CO2)in
(n⁰ CO)in
(n⁰ CO2)out
(n⁰ H2)in
(n⁰ CO)out
(n⁰ N2)in
(n⁰ H2)out
(n⁰ H2S)in
(n⁰ N2)out
(n⁰ H2O)in
(n⁰ H2S)out
(n⁰ CH4)in
(n⁰ H2O)out
LTSR (n⁰ CH4)out

Water
T=130⁰C

Qnet=?

Fig 4.7 balance across HTSR

Reactants:
Syn gas :
Table 4.18 Heat of formation
Inlet Amount Mole Hf Mol
(kmol/day) fraction Kj/mol frac*Hf
(H2)in 44339.35 0.263 0 0
(CO) in 44339.35 0.263 -110.5 -29.0615
(CO2)in 14353.3 0.085 -393.5 -33.45
(CH4)in 4313.59 0.0256 -74.87 -1.92
(H2O)in 19338.3 0.115 -241.82 -27.8
(H2S)in 638.26 0.0038 -20.63 -0.078
(N2)in 837.226 0.005 0 0
n⁰H2O 40361.7 0.24 -241.82 -58.04
Total 168521 1.0 -150.35

m∆Hf (reactant) = -2.5*1010 kj/day

96
 ∑ (mCp∆T) R:
Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.085
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.263
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.263
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.115
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.0036
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.005
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.026
Cp mean= 22.3 + 6.3*10-3T -1.04*10+5 T-2- 0.47*10-6 T2
Table4.19 Energy absorbed
Temperature In 370⁰C= 643K
Temperature Ref 25⁰C=298K
Cp mean 22.3 + 6.3*10-3T -1.04*10+5 T-2- 0.47*10-6 T2= 8761.4
Mass 168521
Mass*ʃCp dt 1.48*109 kj/day

∑ For Water:
Table 4.20
Temperature In 130 ⁰C= 403 K
Temperature Ref 25⁰C =298 K
Cp H20 (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R =3561.30
Mass 40361.7Kmol/day
Mass*ʃCp dt 1.44* 10 8 kj/day

For Product:
∑ Heat of formation (Hf):
Table 4.21 Heat of formation for product.
Outlet Amount Mole Hf Mol
(kmol/day) fraction fract* Hf
Kj/mol
(H2)out 70942.96 0.42 0 0
(CO) out 17735.74 0.105 -110.5 -11.6025
(CO2)out 40956.88 0.2431 -393.5 -95.7
(CH4)out 4313.59 0.026 -74.87 -1.95
(H2O)out 33096.5 0.12 -241.82 -29.02
(H2S)out 638.26 0.0038 -20.63 -0.08
(N2)out 837.226 0.005 0 0
Total 168521 1.00 -138.35

m∆Hf product = -2.33*1010 Kj/mol

∑ (mCp∆T) p:

97
 Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.2431
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.42
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.105
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.12
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.0038
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.005
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.026
Cp mean= 29.4 + 7.55*10-3T -2.4*10+5 T-2- 0.47*10-6 T2
TABLE 4.22 Energy absorbed by product
Temperature out 500⁰C= 773K
Temperature Ref 25⁰C=298K
Cp mean 29.4 + 7.55*10-3T -2.4*10+5 T-2- 0.47*10-6 T2= 15458.76
Mass 168521 kmol/day
Mass*ʃCp dt 2.6* 10 9Kj/day

Q NET = [mΣ∆Hf Products - mΣ∆Hf Reactants] + [ (mCp∆T) P - (mCp∆T) R]

Qnet = [-2.33*1010 – (-2.5* 1010)] + [2.6*109 -1.62 *10 9 ]
Qnet = 2.6 * 109 Kj/day

98
SECTION 4.4.7
COOLER 1

99
4.4.7. COOLER 1:

Water in
25⁰C

Syn gas Syn gas

Temp out = 370⁰C
Temp in = 980⁰C

Water out
Temp out =140⁰C
Mass of water =?
Fig 4.8 energy balance across cooler 1
Table 4.23 Streams data
Tin 980⁰C=1253K
Tout 370⁰C= 643K
Twater 25⁰C =298 K
Tsteam 140⁰C= 413 K

Q1= m ∫





Mass=168521kmol/day
Table 4.24 Mole Fraction
Inlet Amount Mole fraction
(kmol/day)
(H2)in 44339.35 0.346
(CO) in 44339.35 0.346
(CO2)in 14353.3 0.112
(CH4)in 4313.59 0.034
(H2O)in 19338.3 0.15
(H2S)in 638.26 0.005
(N2)in 837.226 0.0065
Total 128156 1.0

Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.112
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.346
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.346
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.15
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.005

100
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.0065
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.034
Cp mean= 29.3 + 8.25*10-3T -0.8*10+5 T-2- 0.61*10-6 T2


2 2 5 -1
∫





= 29.3 (643-1253) + (0.00825/2) (643 -1253 ) – (0.8*10 / -1) (643 -
1253-1) – (0.61*10-6/3) (6433-12533)
= -14830 J/mol



Q1= m ∫





= - 1.9*109 KJ/day
Q1 = Q2



Q2= m ∫






=m kmol/day * 8.314J/mol.K*ʃ (3.470+ 1.450*10-3 T + 0.121*10+5T-2) dt
1.9*109 KJ/day = m * 8.314J/mol.K* [3.470 (413-288) + (1.450*10-3 /2) (4132-
2882 + (0.121*10+5) (413-1- 288-1)]
Mass of water= 1.95*106 kmol/day
Table 4.25 Mass of water
T in 980⁰C
Tout 370⁰C
Twater 15⁰C
Tsteam 140⁰C
Q - 1.9*109 KJ/day
Mass of water 1.95*106 kmol/day

101
SECTION 4.4.8
GASIFIER

102
4.4.8. GASIFIER:

O2 Temp= 980⁰C Syn gas

T= 25⁰C GASIFIER T= 980⁰C

Coal
T=?

Steam
Ash
T= 138⁰C
fig 4.9 energy balance across gasifier
Table 4.26 Reactant
Inlet Amount (kg/day) Outlet Amount (kg/day)
Coal 1524208.748 Syn gas 2366562.2
Steam 852574.8 Ash 83831.48114
Oxygen 385326.89

Outlet:
∑ Syn gas:
Table 4.27 Product
Inlet Amount Mole Hf Mol*Hf
(kmol/day) fraction (kj/mol)
(H2) 44339.35 0.346 0 0
(CO) 44339.35 0.346 -110.5 -38.233
(CO2) 14353.3 0.112 -393.5 -44.072
(CH4) 4313.59 0.034 -74.87 -2.5456
(H2O) 19338.3 0.15 -241.82 -36.3
(H2S) 638.26 0.005 -20.63 -0.10315

103
 (N2) 837.226 0.0065 0 0
Total 128156 1.0 -121.254
m*∆Hf syn = -1.554*10 10 KJ/day



∑ m ∫




:
Table 4.28 Mole Fraction
Inlet Amount Mole fraction
(kmol/day)
(H2)in 44339.35 0.346
(CO) in 44339.35 0.346
(CO2)in 14353.3 0.112
(CH4)in 4313.59 0.034
(H2O)in 19338.3 0.15
(H2S)in 638.26 0.005
(N2)in 837.226 0.0065
Total 128156 1.0
Cp mean:
Cp CO2= (5.457 + 1.045*10-3T – 1.15*10+5T-2) R * 0.112
Cp H2= (3.249+ 0.422*10-3T+ 0.083*10+5T-2) R* 0.346
Cp CO = (3.376+ 0.557*10-3 T -0.031*10+5 T-2) R* 0.346
Cp H2O = (3.470+ 1.450*10-3 T + 0.121*10+5T-2) R *0.15
CpH2S= (3.431+ 1.49*10-3T- 0.232*10+5T-2) R* 0.005
Cp N2 = (3.28 + 0.593*10-3T + 0.040*10+5 T-2) R * 0.0065
Cp CH4 = (1.702+ 9.08 *10-3T – 2.164*10-6 T2) R* 0.034
Cp mean= 29.3 + 8.25*10-3T -0.8*10+5 T-2- 0.61*10-6 T2


2 2 5 -
∫





= 29.3 (1253-298) + (0.00825/2) (1253 - 298 ) – (0.8*10 / -1) (1253
1
- 298-1) – (0.61*10-6/3) (12533-2983)
= 29940.6



m ∫





= 3.84*109 KJ/day
Ash:
∆h ash = 1.32826 Kj/kg @ Temp = 1253K
m∆h ash = 83831.48114 kg/day* 1.32826 Kj/kg.
m∆h ash = 111350 KJ/day

Inlet:
Steam:
Table 4.29 Mass of steam
Temp water 138 ⁰C
Temp Ref 25⁰C
Cp 8.314J/mol.K*(3.470+ 1.450*10-3 T
+ 0.121*10+5T-2)

104
 Hf -241.82 KJ/mol
Mass 852574.8 kg/day

mCp ∆T = mCp( tin – tref)

= (852574.8/18)kmol/day *[28.85*(411-298) +6.03 *(4112-2982)-
100599*(411-1-298-1)] J/mol.K
= 2.3 *1010 KJ/day
m∆Hf = 852574.8 kg/day *(-241.82) KJ/mol *(1mol/18 gm)
= -8.2 *109 KJ/day
Oxygen:
Heat of formation = 0
mCp ∆T = 0 (no difference in temperature)
Table 4.30 Data to find T
Temp in Unknown
Temp ref 25⁰ C
Mass 1524208.748 kg/day
Cp 1.218 KJ/kg.k

m∆h coal :
m∆h coal= 1524208.75* 1.218 KJ/kg.k *( T- 298)
= 1.86* 10 6 (T -298) KJ/day
m∆ Hf coal :
Heat of combustion =m ∆ Hf product - m∆ Hf reactant --------------------------- Eq 1
Heat of combustion = Heating value * mass of coal
= 13425.4 KJ/kg * 1524208.75 kg/day
= 2.0 * 10 10 KJ /day
Equation 1 becomes;
Heat of combustion = m*∆Hf syn – (m*∆Hf steam + m*∆ Hf coal)
2.0 * 10 10 KJ /day = -1.554*10 10 KJ/day – (-8.2 *109 KJ/day + m*∆ Hf coal)
m*∆ Hf coal = -2.7 * 10 10 KJ/day
Qnet = Qin – Qout
0= Qin – Qout
Qin = Qout
Qcoal + Qsteam+ Qoxygen = Q Ash + Q Syn
→ (m*∆ Hf coal + m∆h coal ) + (m*∆ Hf steam + mCp∆T steam )+ (0) = (m*∆ Hf ash +
mCp∆T ash )+ (m*∆ Hf syn + mCp∆T syn)
→ (-2.7 * 10 10 KJ/day +1.86* 10 6 (T -298) KJ/day) + (-8.2*109 KJ/day + 2.3
*10 10 KJ/day) = (0 + 111350 KJ/day) + (-1.554*10 10 KJ/day + 3.84*109
KJ/day)
→ Temp coal= 294 ⁰C

105
 SECTION 4.4.9
WASTE HEAT BOILER

106
 4.4.9. WASTE HEAT BOILER:
In case of process boilers, waste heat in the exhaust gas is passed along a recuperator that
carries the inlet fluid for the boiler and thus decreases thermal energy intake of the inlet
fluid [52].
Water
Temp in= 25⁰C

Stream: NH3
Stream: NH3 Temp out = 250⁰C
Temp in = 500⁰C

Water
Temp out=140 ⁰C
Fig 4.10 Mass balance across waste heat boiler.
∑ For ammonia:
Q1= m ʃCp dt
Table 4.31 Ammonia Data
Tin 500⁰C= 773K
Tout 250⁰C= 523K
Cp R (3.578 + 3.020*10-3 T -0 .186*10+5 T -2)J/mol.K
Mass 58823.5305 kmol/day
m ʃCp dt 58823.5305* [29.75*(523-773)+ 0.012554*(5232-7732)+
154640.4 *(523-1-773-1)]
Q1 - 6.7 * 108 KJ/day

∑ For water:
Q2= m ʃCp dt
Table 4.32 Water Data
Tin 25⁰C= 298K
Tout 140⁰C= 413K
Mass Unknown
Cp 8.314J/mol.K*(3.470+ 1.450*10-3 T + 0.121*10+5T-2)
Q2= - Q1 6.7 * 108 KJ/day
m ʃCp dt m *[28.85*(413-298)+6.03 *(4132-2982)-100599*(413-1-298-1)]

Mass of water = Q2/ ʃCp dt

= (6.7* 108 KJ/day) / (496454.7J/mol)
= 1349.6 kmol/day

107
SECTION 4.4.10
PREHEATER

108
4.4.10. PREHEATER:
Device designed to heat gas before another process (for example, combustion in a boiler)
with the primary objective of increasing the thermal efficiency of the process

Hydrogen gas
Temp in=400⁰C

Stream: NH3
Stream: NH3
Temp out = ?
Temp in = 250⁰C

Hydrogen gas
Temp out =500⁰C
Fig 4.11 energy balance across preheater
∑ For Hydrogen:
Q1= m ʃCp dt
Table 4.33 Hydrogen data
Tin 400⁰C= 673K
Tout 500⁰C=773K
Cp R (3.249+ 0.422*10-3 T + 0.083*10+5T -2)J/mol.K
Mass 88235.3 kmol/day
m ʃCp dt 88235.3* [28.51*(773- 673)+ 0.001755*(7732-6732)-69006.2
*(773-1-673-1)]
Q1 2.75*108 KJ/day

∑ For ammonia:
Q2= m ʃCp dt
Table 4.34 Ammonia Data
Tin 250⁰C= 523K
Tout ?
Cp R (3.578 + 3.020*10-3 T -0 .186*10+5 T -2)J/mol.K
Mass 58823.5305 kmol/day
m ʃCp dt 58823.5305* [29.75*(Tout- 523)+ 0.012554*(Tout2-5232)+
154640.4 *(Tout-1-523-1)]
Q2 = -Q1 -2.75*108 KJ/day
Q2= m ʃCp dt
For temperature:
→-2.75*108 KJ/day =58823.5305* [29.75*(Tout- 523)+ 0.012554*(Tout2-
5232)+ 154640.4 *(Tout-1-523-1)]
→ Tout = 138⁰ C

109
 SECTION 4.4.11
CONVERTER EFFLUENT EXCHANGER

110
 4.4.11. CONVERTER EFFLUENT EXCHANGER:

Hydrogen gas
Temp out=?

Stream: NH3
Stream: NH3
Temp out = 60⁰C
Temp in = 138⁰C

Hydrogen gas
Temp in =48⁰C
Fig 4.12 energy balance across converter effluent exchanger
∑ For ammonia:
Q1= m ʃCp dt
Table 4.35 Ammonia data
Tin 138⁰C= 411K
Tout 60⁰C = 333K
Cp R (3.578 + 3.020*10-3 T -0 .186*10+5 T -2)J/mol.K
Mass 58823.5305 kmol/day
m ʃCp dt 58823.5305* [29.75*(33-411)+ 0.012554*(3332-4112)+
154640.4 *(333-1-411-1)]
Q1 -1.742*108 KJ/day

∑ For Hydrogen:
Q1= m ʃCp dt
Table 4.36 Hydrogen data
Tin 48⁰C= 321K
Tout ?
Cp R (3.249+ 0.422*10-3 T + 0.083*10+5T -2)J/mol.K
Mass 88235.3 kmol/day
m ʃCp dt 88235.3* [28.51*(Tout- 321)+ 0.001755*(Tout2-3212)-69006.2
*(Tout-1-321-1)]
Q1= - Q2 1.7*108 KJ/day
Q2= m ʃCp dt
For temperature:
→1.742*108 KJ/day =88235.3* [28.51*(Tout- 313) + 0.001755*(Tout2-3132)-
69006.2 *(Tout-1-313-1)]
→ Tout = 105⁰ C

111
SECTION 4.4.12
HEATER

112
4.4.12. HEATER:

Water in
140⁰C

Hydrogen
Hydrogen
Temp out = 400⁰C
Temp in = 105⁰C

Water out
Temp out =25⁰C
Fig 4.13 energy balance across heater

∑ For Hydrogen:
Q1= m ʃCp dt
Table 4.37 Hydrogen data
Tin 105⁰C= 378K
Tout 400⁰C=673K
Cp R (3.249+ 0.422*10-3 T + 0.083*10+5T -2)J/mol.K
Mass 88235.3 kmol/day
m ʃCp dt 88235.3* [28.51*(673- 378)+ 0.001755*(6732-3782)-69006.2
*(673-1-378-1)]
Q1 7.9*108 KJ/day

∑ For water:
Q2= m ʃCp dt
Table 4.38 Water data
Tin 140⁰C= 413K
Tout 25⁰C= 298K
Mass Unknown
Cp 8.314J/mol.K*(3.470+ 1.450*10-3 T + 0.121*10+5T-2)
Q2= - Q1 -7.9 * 108 KJ/day
m ʃCp dt m *[28.85*(298-413)+6.03 *(2982-4132)-100599*(298-1-413-1)]

Mass of water = Q2/ ʃCp dt

= (-7.9* 108 KJ/day) / (-496604.3J/mol)
= 1590.8 kmol/day

113
 CHAPTER: 5
PLANT DESIGN

114
PLANT DESIGN
5.1. PLUG FLOW REACTOR: [53]

Mole Balance:

Rate Law:
5.2. RETENTION TIME: [53]
t= V/VO = ʃd XA/ -rA
5.3. RATE OF REACTION: [53]
For ammonia formation:

Conversion= 15 % =0.15
ʃ
t = (2/ CA0 0.5 K1) dXA/{[( 1.3* (1-x)2.5/x2 (1-.15x)] – [(332.554x2/(1-x)1.5(1-
.15x)]}
t = 2.09 hrs
5.4 VOLUME OF REACTOR:
Volumetric flow rate = mass flow rate /density
Mass flow rate = 106 kg/day
Density Of ammonia = 0.73 kg/m3
Volume = (277.77 kg/sec) / (0.73 * 2.09)
Volume = 182 m3
Volume Allowance = V* (10 -15) %
Let Volume allowance is 10 %
Now Volume =200 m3
Volume =

L


= d2 (3d) let L= 3d


200m3= (3.14/4) * 3d3
Diameter = 4.4 m
Length = 13.2 m
5.5 SURFACE AREA:
Surface area =
DL +2

2

=212.8 m2
5.6. OUTER DIAMETER:
For Cylindrical Vessels: [54]
British Standards:
Minimum wall thickness =i = Pi Di /( 2f E-Pi )+C c

115
(any set of consistent units can be used).
Where Pi = Psig
S = f = (working stress factor) Psi
Ej = j = Joint Efficiency,
P=max.allowable internal pressure, psig
R i= inside radius of the shell,
t=e=min. wall thickness and Cc = corrosion allowance.
Material of construction = Medium carbon steel
0.4% C steel
F = 4.44
Stress=135 MPa
Temperature= 500⁰C
E=0.9
Pi= 1.1 * operating pressure
Pi= 1.1* 20.265
i = Pi Di /( 2f E-Pi )+C c
i=22.3 MPa *4.4 m /(2*135 MPa *0.9)-(22.3) +2mm
i = 0.45
i = (Dout –Din)/2
Outer Diameter = 5.3 m
5.7 VOLUME OF MATERIAL USED IN PLUG FLOW REACTOR:
Volume = 3.14/4 *(DO3-DI3)
Volume = 50 m3
5.8 MATERIAL OF CONSTRUCTION OF REACTOR:
Medium Carbon Steel – Composition of 0.29%-0.54% carbon, with 0.60%-1.65%
manganese. Medium carbon steel is ductile and strong, with long-wearing properties.
Mass of carbon steel:
Mass= density * Volume
Mass= 7.85g/cm3*50 m3
Mass = 392500 kg
5.9 ELLIPSODIAL HEAD: [54]
t= PiDi / (2Jf- 0.2Pi) + Cc
t= [22.3 * 4.4 /( 2* 0.9 *135 – 0.2*22.3)] + 2mm
t = 0.4133m
Mass of (head+bottom) = density*( /4 (OD +OD/24+ at )2 * t )
= 7.85 g/cm3 *( 3.14 /4 (5.3 +5.3/24+ 3*0.4133 )2 *
0.4133)
mass = 116410.55kg
2* wt of steel = 232821.1 kg
Total mass = Mass of body + Mass of (head+bottom)
= 392500 kg + 232821.1 kg
= 625321.1 kg

116
5.10 .PRESSURE DROP ACROSS THE BED [55]
Ergun equation:

Let Dp/Dt = 0.05

Dt = 4.4 m
Volume of cylindrical bed = 191.63 m3 (L=13m)
2
Area of Cylindrical bed = (2* 3.14 * r ) + (2* 3.14 r L)
= 210 m2
Volume of sphere= 4 /3 *3.14 * r 3
Volume of pallet = 4/3*3.14 * (0.11)3
= 5.5724 * 10 -3 m3
Area of pallet = 4 * 3.14 * r 2
= 0.152 m2
Volume of one row of bed = 3.14 * r2* length
= 0.49 m3
Mass of iron catalyst = volume * density
= 3877.3 kg
Area of one row of bed = (2* 3.14 * r2) + (2* 3.14 r L)
= (2 * 3.14 * 0.112) + (2 * 3.14 * 0.11* 13)
= 9.06m2

TABLE 5.1
Terms Values
Dt 4.4m

Dia. Of pallet 0.22 m

Dp.

Porosity ɛ 0.36
Viscosity µ of fluid 2.55 * 10-5 kg/ms
3
Density of fluid 0.69 kg/m
Velocity V0 0.1 m/s

Length L 13 m

∆P = [150 * 0.5 * 2.55* 10-5(1-0.36)2/ 0.22 2*.363] + [1.75 *0. 69 *(0.5)2* (1-
0.36)/ (0.22 *.363)]
∆P =2.46K Pa
117
5.11 COMPRESSSOR DESIGN

Fig 5.1 Three stage Adiabatic Compression with Intercooling.

Table 5.2 Compressor Design Calculations.
Compressor P1. Inlet P2. Outlet V. Volumetric Pressure Head. H Power
Stage Pressure
(atm)
Pressure
(atm)
flow rate at
inlet −










(hp)
H*V

−





conditions(m3)

1st stage 30 56.4 123.24 20.63 4

2nd stage 56 106 65.54 38.8 4
3rd stage 106 200 34.86 72.92 4
=12 hp















γ=

















CV = ∗ R


Cp=CV+R where R=8.314kJ/mole

For N2
CV=0.7423J/kg
Cp=1.212J/kg

118
For H2
CV=10.4J/kg
CP=14.55J/kg
CP of mixture (H2, N2) =15.762J/kg
CV of mixture (H2, N2) =11.1348J/kg















So γ= =1.41

119
 CHAPTER: 6
COST ESTIMATION

120
COST ANALYSIS
6.1. PROCESS ECONOMICS: [56]
Process economics has three basic roles in process design:
1. Evaluation of design options.
Costs are required to evaluate process design options; for example, should a
membrane or an adsorption process be used for purification?
2. Process optimization.
The settings of some process variables can have a major influence on the
decision-making in developing the flowsheet and on the overall profitability of
the process. Optimization of such variables
is usually required.
3. Overall project profitability.
The economics of the overall project should be evaluated at different stages
during the design to assess whether the project is economically viable.

6.2. AMMONIA REACTOR COST: [56]

6.2.1. COST EQUATIONS:
CE =fM fP fT * CB (Q/QB) ^M
Fixed cost:
CF =∑ [fMfP fT (1 + fPIP)] ∑ CE+ (fER + fINST + fELEC + fUTIL + fOS + fBUILD
+ fSP + fDEC + fCONT + fWS ) ∑ CE
Table 6.1 Constant Values from table.
CB $ 1.15*10^4
QB 5
M 0.53
Q (vol) 200 m3
Pressure 200atm
Temp 500⁰C
fM 1
fP 2.7
fT 2.1

The cost of a specific item of equipment will be a function of:

• Size
• Materials of construction
• Design pressure
• Design temperature.

121
 CE = CB (Q/QB)M fMfP fT

Where
CE = equipment cost for carbon steel at moderate pressure and temperature
with capacity Q
CB = known base cost for equipment with capacity QB
M = constant depending on equipment type
fM = correction factor for materials of construction
fP = correction factor for design pressure
fT = correction factor for design temperature
CE = $ 1.15 *10 4 (200/5).53 (1*2.7*2.1)
CE = C2= $ 460651.72
Presents data for a number of equipment items on the basis of January 2000
costs (CE Composite Index =391.1, CE Index of Equipment = 435.8). [57]
C1/C2 = INDEX 1/ INDEX 2
C1 = equipment cost in year 1
C2 = equipment cost in year 2
INDEX1 = cost index in year 1
INDEX2 = cost index in year 2
C 1 = $ 460651.72 * (541.2/ 435.8)
C1 = $ 572062.2
Table 6.2 Cost Estimation

Cost (CE) $6.9*10^5

Cost (CF) $ 2.1*10^6
With project costs of around $2.1 million, the plant achieved a simple payback of less than 10
months.

122
 CHAPTER: 7
INSTRUMENTATION AND
PROCESS CONTROL

123
7.0 INSTRUMENTATION & PROCESS CONTROL:
Instrumentation is the use of measuring instruments to monitor and control a process. During
operation a chemical plant must satisfy the requirement for safety, production specification,
environmental regulation, operational constraints and economics[58]. All these requirements
dictate the need for continues monitoring of operation of chemical plant and external control
to guarantee the satisfaction of operational objectives. This is accomplished through
measuring the value of plant parameter such as pressure, temperature, flow, level etc and
supplying the signal that is proportional to measured parameter. The output signals are
standard signal and can be processed by other equipment to provide indication, alarm or
automatic control[59]. Definition of few terms for process control[60]:
1. Controlled Variable output quantity of system (Level, Temperature, etc.).
2. Manipulated Variable – means of maintaining controlled variable at the setpoint.
3. Error signal – equals the difference between the setpoint and the measurement. (e =
SP – M).
4. Setpoint desired process level. (SP)
5. Measurement actual process level. (M)
6. Closed Loop automatic control.
7. Open Loop – manual control.
8. Feedback control is error correction following a disturbance.
9. Feedforward control is control of disturbances, which could cause a process error.
Ammonia synthesis reactions are usually conducted at relatively high temperatures and
pressures. In such processes, which are both temperature and pressure sensitive, a very stable
heat removal system is desired.
Parameters to be monitored continuously are:
∑ Pressure
∑ Temperature
∑ Flow
∑ pH

7.1 Pressure Measurement:

Most pressure sensor translates pressure into physical motion that is proportion to applied
pressure[60]. The pressure for reactor to occur between nitrogen and hydrogen is maintained
at 200atm. If it exceeds the threshold value the indicator will give signal to transmitter and it
will transmit signal to controller where the pressure will release with pressure relief valve in
order to regulate the pressure.

7.2 Temperature Measurement:

Temperature measurement for ammonia is done by thermocouple whose function is based on
is the difference in the conductivities of the two wire materials that the thermocouple is made
of, at a given temperature [60]. This conductivity difference increases at higher temperatures
and conversely, the conductivity difference decreases at lower temperatures. This disparity
results in the thermocouples being more efficient and useful at higher temperatures.
Temperature measurement is very necessary for ammonia production. Increase and decrease
in temperature can end up changing the composition for ammonia. Moreover it is exothermic
reaction so the temperature in reactor can reach very high and can cause damage to it, so two
thermocouple sensors are used. Temperature sensor 1 check the temperature of inlet
hydrogen in order for the completion of reaction and the increase in temperature to 500oC
whereas temperature sensor 2 is within the reactor in order to signal the significant change in
temperature and can be regulated by heat exchanger or recycling of heat so it doesn’t exceed
the threshold value.

124
7.3 Flow Controller:
A flow control system requires some form of restriction to provide a pressure differential
proportional to flow (e.g. orifice plate) plus a square root extractor to provide a linear signal.
The controller action depends upon the choice of control valve.[60].
The separated nitrogen will flow from air separator unit into reactor and is controlled by flow
control valve. A flow transmitter will give signal to controller to allow the specific amount of
flow required for the reaction to occur between nitrogen and hydrogen.

7.4 Control Element:

To keep in check different parameters of ammonia reactor, several types of control element
are present.

Table 7.1 Parameters and Control elements.

Parameter Control Element
Temperature Thermocouple
Pressure Pressure relief valve
pH pH meter
Flow Flow meter

7.5 Threshold value for Parameter of Ammonia Reactor:

Table 7.2 Parameters and Threshold Values.
Parameter Threshold value
Temperature Sensor 1 500oC
Pressure 200atm
Ph 13± 0.4

125
 Fig 7.1 Ammonia Process Instrumentation
∑ PI= Pressure Indicator,
∑ PC= Pressure Controller
∑ TI=Temperature Indicator,
∑ TT=Temperature Transmitter,
∑ TC=Temperature Controller,
∑ TE=Temperature Element
∑ FT=Flow Transmitter ,
∑ FC= Flow Controller.

126
 CHAPTER: 8
HAZOP STUDY AND
SAFETY

127
8.0 SAFETY
Safety means constant evaluation of things we do and how we go about doing them so that
we won’t get hurt, that equipment’s condition will not contribute to an accident, and that
workers won’t get hurt.
8.1 HAZOP study:
HAZOP means Hazards and Operability Study which was adopted by OSHA on May 26,
1992, [61]. This law established regulations for Process Safety Management which has now
been globally accepted adopted as law or as best industry practice.
The HAZOP study analyzes how a plant is operated, constructed and maintained. The main
objective is the protection of the employees and third parties by minimizing the consequences
of accidents involving hazardous chemicals. Scope of study does not include making detailed
design changes, although recommendations and follow-up questions should be produced[62].
The hazards associated with ammonia are a little more severe. It was determined that at levels
of 300 ppm, ammonia is considered immediately dangerous to life. Ammonia has guidelines
regarding threshold limit value. For an 8-hour work day, the total weighted average that is not
to be exceeded is 25 ppm.

Table 8.1 Results of HAZOP are presented in the table below.

Unit Parameter Guide word Possible Possible Required
Causes Consequences Action
Gasifier Temperature Low Steam not Less H2 Heat the
heated to formation steam to
required required
temperature temperature
by recycling
heat from heat
exchangers
High Steam exceed More formation
the final limit of carbon- High
of given monoxide. temperature
temperature alarm
Reactor Pressure Low control valve Low yield of Check valves
sticking open ammonia during normal
or leaking operation and
through fix the leak
valve.

High Ammonia is Explosion Control

not separated Pressure
at synthesis valve
Temperature loop
High Damage of
Due to catalyst High
exothermic temperature
reaction heat alarm
releases
Flow No Excess ammonia
Valve fails or in reactor and Automatic
closed release in work closure of

128
 area another valve
with reactor
on loss of
flow

Storage tank Level High Level Overflow of LI at storage

indicator fails ammonia tank to
± Low solution, monitor level
(Indication of potential release of ammonia
an incorrect of ammonia to solution
level of atmosphere/work
amount of area resulting in
solution in the 1) Economic
Ammonia loss.
storage tank) 2) Adverse
effects to human
health due to
personnel
exposure.

Carbon Temperature High Temperature Can end up in Intercooling

dioxide controller poor absorption
absorption fails of absorption
column column

High and Temperature High Exothermic Side reactions Temperature

Low reaction control
temperature
Shift
Converter

129
8.2 Fire Protection [63]:
Spontaneous combustion of flammable gases, fires and explosions are a major risk hazard in
plants. The scope of fire protection includes the design and installation of firefighting
facilities including a new fire station building, fire trucks, plant wide firefighting systems,
firewater storage and pumping, a ring main and firewater loop grid, sprinkler systems, dry
gas system, fire trucks and fireproofing of all relevant equipment. The firefighting station
is assigned to be independent and fully capable of putting out any major fires such as a fire
by the rupture of the ammonia tank. In particular the arrangement of fire protection will be;
1. Fire alarms will provided throughout the plant and in particular, in the fire station and
the operation control room
2. Point smoke detectors will be provided throughout the plant and in particular, at the
power distribution room and the transformer room
3. Cable‐type linear model heat detectors will be provided in the interlayer of the power
cable
4. Manual alarm buttons and voice and light alarms will be provided on each floor plane
in the production Plant building
5. The low‐pressure fire water pipes and industrial water pipes are integrated and they
installed in loop form in the unit area
6. Fire hydrants will be installed in all buildings conforming to the relevant national
building codes
7. The fire hydrants will be mounted on the fire water pipes with spacing of less than
120m
8. Steel pipes will be used as material selection for the loop fire water system
9. High‐pressure fire water system will be installed with water supply capacity of
10m3/h and water supply pressure of 1.0MPa

8.3 Emergency Procedures:

The emergency plan for the plant provides effective understanding of possible accident
scenario within the plant and necessary responses in terms of plants and personnel. For short
time available for response, planning and training for immediate recognition of emergencies
and evacuation to safe areas for toxic release is essential.
Apart from emergency procedures work out for specific operational requirements procedures
will also be developed to cover the requirement of site which includes;
∑ Definition of emergencies (e.g fire,gas leaks)
∑ Organization of emergency control teams
∑ Escape routes and assembly points for personnel

8.4 Personal Protective Equipment:

For protection of personnel the following equipment should be available:
1. Safety helmets and shoes which should be worn by the personnel when they
are in the plant.
2. Goggles for protection against liquids and gases.
3. Gloves for protection against acid and alkaline solutions (rubber) and heat
(asbestos).
4. Respiration masks with filters for dust and poisonous gases (H2S, NH3,
natural gas, etc.).
5. Compressed air masks for protection against CO.
6. Various clothing such as boots, hoods, aprons or complete suits for protection
against acid and alkaline solutions, catalyst dust, heat, etc.

130
 7. Ear mufflers or other devices for protection against noise.
8. Explosion meters.
9. Dragger equipment (tubes and “sniffer”) for measurements of poisonous gases
like CO, H2S, NH3, natural gas, etc.
8.5 Security:
Security is very necessary for the safety of plant. It is ensured by installation of chain-link
boundary fences with access to plant by single gate house and emergency exists. Regular
security patrol should also be carried out for more protection. The export pipeline should be
regularly inspected.

131
 CHAPTER: 9
CONCLUSION

132
9. CONCLUSION:
Coal gasification offers one of the most versatile and clean ways to convert coal into
electricity, hydrogen, and other valuable energy products.
Coal gasification technology for ammonia plants offers an economically attractive option for
manufacturing ammonia, especially in countries with large coal reserves and limited or high
cost natural gas deposits.
One main advantage of this process is usage of low rank coal as a raw material instead of
using natural gas which is expensive. From this process 1.85* 10 ^10 kj/mol energy is
produced which can be used to run turbine, for heating purpose and electricity production and
638 kmol/day Sulphur is produced which can be used for different industrial application.
With project costs of around $2.1 million, the plant achieved a simple payback of less than 10
months.
Total Ammonia Production 1000MTPD
Total cost $ 2.1*10^6
Total energy production -1.85 * 10 ^ 10 kj.mol
Sulphur Production 638 Kmol/day

133
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