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Table of Contents

Chapter # 1....................................................................................................................................6
INTRODUCTION...........................................................................................................................6
1.1 INTRODUCTION.................................................................................................................7
1.2 HISTORY.............................................................................................................................7
1.3 PROPERTIES OF AMMONIA..............................................................................................8
1.3.1 Physical properties........................................................................................................8
1.3.2 Chemical properties......................................................................................................9
1.3.3 Basicity..........................................................................................................................9
1.3.4 Acidity..........................................................................................................................10
1.3.5- Self-dissociation.........................................................................................................10
1.3.6 Combustion.................................................................................................................10
1.4 APPLICATION & USES.....................................................................................................10
1.4.1 As a direct fertilizer......................................................................................................10
1.4.2 As a raw material for other fertilizer............................................................................11
1.4.3 As a starting material for other industrial products.....................................................12
1.4.4 Uses............................................................................................................................13
1.5 DESCRIPTION OF STORAGE AND TRANSFER.............................................................13
EQUIPMENT........................................................................................................................13
1.5.1 Introduction..................................................................................................................13
1.5.3 Transfer equipment.....................................................................................................15
1.5.4 Rail road and rail loading............................................................................................15
1.5.5 Ships...........................................................................................................................16
Chapter # 2..................................................................................................................................17
LITERATURE REVIEW...............................................................................................................17
2.1 NITROGEN FERTILIZER COMPONENT..........................................................................18
2.2 PHOSPHOROUS FERTILIZER COMPONENT................................................................19
2.3 POTASSIUM FERTILIZER COMPONENT........................................................................19
2.4 SELECTION OF RAW MATERIALS..................................................................................19
2.4.1 L.P.G............................................................................................................................19
2.4.2 Naphtha.......................................................................................................................20
2.4.3 Natural Gas.................................................................................................................20
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2.4.4 Refinery gases .......................................................................................................... 22
2.4.5 Coke oven gas .......................................................................................................... 22
2.4.6 Heavy oil ................................................................................................................... 22
2.4.7 Hydrogen rich off gases ............................................................................................ 23
Chapter # 3 ................................................................................................................................ 24
FERTILIZER INDUSTRY IN ...................................................................................................... 24
PAKISTAN ................................................................................................................................. 24
FERTILIZER INDUSTRIES IN PAKISTAN ......................................................................... 25
3.1 PAK- AMERICAN FERTILIZERS LIMITED (NFC) Daudkhel ........................................... 25
3.2 PAK ARAB FERTILIZER LIMITED .................................................................................. 25
3.3 FAUJI FERTILIZER COMPANY LIMITED ....................................................................... 26
3.4 FAUJI FERTILIZER COMPANY LIMITED 3 .................................................................... 27
3.5 FFC – JORDAN FERTILIZER CO. LIMITED ................................................................... 28
3.6 ENGRO CHEMICAL PAKISTAN LIMITED ...................................................................... 28
3.7 DAWOOD HERCULES CHEMICAL LIMITED ................................................................. 29
3.8 HAZARA PHOSPHATE FERTILIZER LIMITED ............................................................... 29
3.9 CHEMICAL & FERTILIZER (NFC) Faisalabad and Jaranwala ........................................ 29
Chapter # 4 ................................................................................................................................ 31
PLANT LOCATION ................................................................................................................... 31
& ................................................................................................................................................ 31
PLANT LAYOUT ....................................................................................................................... 31
4.1 PLANT LOCATION AND LAYOUT .................................................................................. 32
4.1.1 RAW MATERIAL AVAILABILITY ............................................................................... 32
4.1.2 MARKETS ................................................................................................................. 33
4.1.3 ENERGY ................................................................................................................... 33
4.1.4 CLIMATE ................................................................................................................... 33
4.1.5 TRANSPORTATION ................................................................................................. 33
4.1.6 WATER SUPPLY ...................................................................................................... 34
4.1.7 WASTE DISPOSAL ................................................................................................... 34
4.1.8 LABOUR SUPPLY .................................................................................................... 34
4.1.9 SITE CHARACTERISTICS ....................................................................................... 35
4.1.10 FLOOD AND FIRE PROTECTION .......................................................................... 35
4.1.11 COMMUNITY FACTORS ........................................................................................ 35
4.2 PLANT LAYOUT .............................................................................................................. 35
4.3 PREPARATION OF THE LAYOUT .................................................................................. 36
4.3.1 PLANT OPERATION CONTROL .............................................................................. 37
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4.3.2 NOISE ....................................................................................................................... 37
4.3.3 NOISE CONTROL ..................................................................................................... 37
Chapter # 5 ................................................................................................................................ 39
MANUFACTURING ................................................................................................................... 39
PROCESS ................................................................................................................................. 39
Different processes for ammonia production ...................................................................... 40
5.1 OSAG Process ................................................................................................................ 40
5.2 Mont Cenis Process ......................................................................................................... 41
5.3 Claude and Casale System ............................................................................................. 41
5.4 Du-Pont system ............................................................................................................... 41
5.5 Chemico process ............................................................................................................. 41
5.6 Haber-Bosch process ...................................................................................................... 42
5.7 M.W.Kellogg’s Process .................................................................................................... 43
5.8 Kellogg Brown & Root Advanced Ammonia Process-Plus ............................................... 43
(KAAP) ................................................................................................................................... 43
5.9 Haldor Topsoe ................................................................................................................. 45
Chapter # 6 ................................................................................................................................ 46
Halder Topsoe process for ammonia production ....................................................................... 46
6.1 Why we selected Halder Topsoe ammonia technology? ................................................. 47
6.1-1 Integrated approach of research ............................................................................... 47
6.1-2 Optimum design approach ........................................................................................ 47
6.1-3 Alternative feedstock and plant integration ............................................................... 47
6.1-4 Revamp option .......................................................................................................... 47
6.1-5 The topsoe approach ................................................................................................ 48
6.2 Topsoe ammonia process ................................................................................................ 48
6.3 Process description [ref: 17] ............................................................................................ 48
6.3-1 Raw materials ........................................................................................................... 48
6.3-2 Natural gas from battery limits................................................................................... 48
6.3-3 knock out drum .......................................................................................................... 48
6.3-4 Natural gas pre heater .............................................................................................. 48
6.3-6 Primary reformer ....................................................................................................... 50
6.3-7 Secondary reformer .................................................................................................. 51
6.3-8 Shift Converters ........................................................................................................ 53
6.3-9 CO2 Absorber ............................................................................................................ 55
6.3-10 CO2 stripper ........................................................................................................... 56
6.3-11 Methanator ............................................................................................................ 57
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6.3-12 Ammonia synthesis section ................................................................................... 58
6.4 Working of ammonia converter ........................................................................................ 61
6.5 Factors influencing the converter reaction ....................................................................... 62
6.6 Role of catalyst in ammonia convertor ............................................................................. 64
6.6-2 Catalyst poisons ........................................................................................................ 65
6.6-3 Catalyst mechanical strength .................................................................................... 66
Chapter # 7 ................................................................................................................................ 67
INSTRUMENTATION ................................................................................................................ 67
& ................................................................................................................................................ 67
PROCESS CONTROL .............................................................................................................. 67
7.1 OBJECTIVES OF INSTRUMENTATION ......................................................................... 68
7.2 MAIN PROCESS VARIABLES ........................................................................................ 69
7.3 LOCATION OF MEASUREMENT DISPLAYS ................................................................. 69
7.3.1 Local display.............................................................................................................. 69
7.3.2 Local panel display .................................................................................................... 69
7.3.3 Centralized control room ........................................................................................... 70
7.3.4 Remote monitoring .................................................................................................... 70
7.4 CONTROL SYSTEM ........................................................................................................ 70
7.5 CONTROL LOOP ............................................................................................................ 71
7.5.1 Control loop on high temperature shift converter:...................................................... 71
7.5.2 Control loop on heat exchanger: ............................................................................... 71
7.5.3 Control loop on ammonia converter: ......................................................................... 72
Chapter # 8 ................................................................................................................................ 73
MATERIAL BALANCE ............................................................................................................... 73
Material Balance for Ammonia Plant .................................................................................. 74
8.1 PRIMARY REFORMER ........................................................................................... 76
8.2 SECONDARY REFORMER ..................................................................................... 77
8.3 MEDIUM TEMPERATURE SHIFT CONVERTER ........................................................ 79
8.4 LOW TEMPERATURE SHIFT CONVERTER ................................................................ 80
8.5 ABSORBER ................................................................................... 81
8.6 METHANATOR .............................................................................. 82
8.7 AMMONIA SYNTHESIS LOOP ........................................................................ 84
Chapter # 9 ................................................................................................................................ 85
ENERGY BALANCE ................................................................................................................. 85
9.1 PRIMARY REFORMER ........................................................................................... 86
9.2 SECONDARY REFORMER ..................................................................................... 93
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9.3 MEDIUM TEMPERATURE SHIFT CONVERTOR...........................................................101
9.4 LOW TEMPERATURE SHIFT CONVERTOR................................................................. 106
9.5 METHANATOR.......................................................................................................111
9.6 AMMONIA REACTOR..............................................................................................117
Chapter # 10.............................................................................................................................. 123
EQUIPMENT DESIGN...............................................................................................................123
10.1 DESIGN OF PRIMARY REFORMER.......................................................................124
10.2 ABSORPTION COLUMN DESIGN................................................................................129
10.3 MEDIUM TEMPERATURE SHIFT CONVERTOR.........................................................132
10.4 LOW TEMPERATURE SHIFT CONVERTOR............................................................... 134
Chapter # 11.............................................................................................................................. 137
COST ESTIMATION.................................................................................................................. 137
COST ESTIMATION...........................................................................................................138
11.1 PRIMARY REFORMER:................................................................................................ 138
11.2 MEDIUM TEMPERATURE SHIFT CONVERTOR......................................................... 139
11.3 LOW TEMPERATURE SHIFT CONVERTOR................................................................140
11.4 ABSORBER....................................................................................................................140
Chapter # 12.............................................................................................................................. 143
HAZOP STUDY......................................................................................................................... 143
12.1 INTRODUCTION........................................................................................................... 144
12.1.1 Industries in which the technique is applied............................................................144
12.2 BASIC CONCEPT..........................................................................................................144
12.2.1 Objective..................................................................................................................145
12.3 KEY WORDS................................................................................................................. 145
12.3.1 Primary key words:..................................................................................................145
12.3.2 Secondary key words:.............................................................................................146
12.4 HAZOP STUDY METHODOLOGY:...............................................................................147
12.4.1 Deviation..................................................................................................................147
12.4.2 Cause...................................................................................................................... 147
12.4.3 Consequences........................................................................................................ 148
12.4.4 Safeguards.............................................................................................................. 148
12.4.5 Action.......................................................................................................................148
12.5 HAZOP STUDY STEPS.................................................................................................149
REFRENCES.............................................................................................................................153

5
Chapter # 1

INTRODUCTION

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1.1 INTRODUCTION
Ammonia is a compound of nitrogen and hydrogen. It is normally encountered as a gas with
a characteristic pungent odor. Ammonia contributes significantly to the nutritional needs of
terrestrial organisms by serving as a precursor to foodstuffs and fertilizers. Ammonia, either
directly or indirectly, is also a building block for the synthesis of many pharmaceuticals. In
spite of having various uses, ammonia is both caustic and hazardous. It is used in
commercial cleaning products.

Ammonia as used commercially is often called anhydrous ammonia. This term emphasizes
0
on the absence of water in material. It boils at -33.34 C and must be stored under high
pressure or at low temperature. Its heat of vaporization is, however sufficiently high so
ammonia can be readily handled in ordinary beakers, in a fume hood (i.e. if it is already a
liquid it will not boil readily). “Household ammonia” or “Ammonium hydroxide” is a solution
of ammonia in water. The strength of such solution is measured in units of Baume (density),
0
with 26 degrees Baume (about 30 weight percent ammonia at 15.5 C) being the typical
high concentration commercial product. Household ammonia ranges in concentration from
5 to 10 weight percent ammonia.

1.2 HISTORY
Salts of ammonia have been known from very early times; thus the term Hammoniacus sal
appears in the writing of Pliny, although it is not known whether the term is identical with the
modern sal-ammoniac.

In the form of sal-ammoniac (nushadir), ammonia was known to Muslim alchemist as early
th
as the 8 century, first mentioned by Geber (Jabir bin Hayan), and to European alchemists
th
since the 13 century, being mentioned by Albertus Magnus. It was also used by dyers in
th
middle ages in the form of fermented urine to alter the color of vegetable dyes. In the 15
century, Basilius Valentinus showed that ammonia could be obtained by the action of alkalis
on salammoniac. At a later period, when sal-ammoniac 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. Gaseous ammonia was first isolated
by Joseph Priestley in 1774 and was termed by him alkaline air, however it was acquired by
alchemist Basil valentine.

Eleven years later in 1785, Claude Louis Berthollet ascertained its composition.

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The Haber process to produce ammonia from nitrogen in the air was developed by Fritz
Haber and Carl Bosch in 1909 and patented in 1910. It was first used on industrial scale by
Germans during World War one, following the allied blockade that cut off the supply of
nitrates from Chile.
The ammonia was used to produce explosives to sustain their war efforts. Prior to the
advent of cheap natural gas, hydrogen as a precursor to ammonia production was
produced via the electrolysis of water or using the chloralkali process.

Worldwide ammonia production in 2004 was 109 million metric tons. The China produced
28.4% of worldwide production (increasingly from coal as part of urea synthesis) followed
by India with 8.6%, Russia with 8.4% and United states with 8.2%. About 80% or more
ammonia produced is used for fertilizing agricultural crops.

Before the start of World War 1, most ammonia was obtained by dry distillation nitrogenous
vegetable and animal waste products, including camel dung, where it was distilled by the
reduction of nitrous acid and nitrites with hydrogen; in addition, it was produced by
distillation of coal, and also by the decomposition of ammonium salts by alkaline hydroxides
such as quick lime, the salt most generally used being the chloride thus:

2NH4Cl + 2CaO → CaCl2 + Ca (OH)2 + 2NH3

Today, the typical modern ammonia – producing plant first converts natural gas (i.e.
methane) or liquefied petroleum gas (such gases are propane and butane) or petroleum
naphtha into gaseous hydrogen.

1.3 PROPERTIES OF AMMONIA


1.3.1 Physical properties
Ammonia is a colorless gas with a characteristic pungent smell. It is lighter than air, its density
being 0.589 times than that of air. It is easily liquefied due to strong hydrogen bonding between
0 0
molecules; the liquid boils at -33.3 C and solidifies at -77.7 C to white crystals.

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Liquid ammonia has a very high standard enthalpy change of vaporization and can
therefore be used i9n laboratories in non-insulated vessels without additional refrigeration.

It is miscible with water. Ammonia in an aqueous solution can be expelled by boiling. The
aqueous ammonia solution is basic. The maximum concentration of ammonia in water has
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a density of 0.880 g/cm and is often known as “880 Ammonia”. Ammonia does not burn
readily or sustain combustion, except under narrow fuel to air mixtures. When mixed with
oxygen, it burns with a pale yellowish green flame. At high temperature and in the presence
of suitable catalyst, ammonia is decomposed into its constituent elements. Ignition occurs
when chlorine is passed through ammonia, forming nitrogen and hydrogen chloride; if
ammonia is present in excess, then highly explosive nitrogen tri-chloride is also formed.

Ammonia may be conveniently deodorized by reacting it with either sodium bicarbonate or


acetic acid. With both of these an odorless ammonium salt is formed.

1.3.2 Chemical properties


The nitrogen atom in the molecule has a lone pair, which makes ammonia a base, a proton
acceptor. This shape gives the molecule a dipole moment and makes it polar. The
molecule’s polarity and especially its ability to form hydrogen bonds, makes ammonia highly
miscible with water. Ammonia is moderately basic; a 1.0 M aqueous solution has a ph of
11.6 and is a strong acid is added to such a solution until the solution is neutral 99.4% of
ammonia molecules are propagated. Temperature and salinity also effect the proportion of
+
NH4 . It has the shape of regular tetrahedron and is isoelectronic with methane.

1.3.3 Basicity
One of the most characteristic properties of ammonia is its basicity. It combines with acids
to form salts: thus with hydrochloric acid it forms ammonium chloride; with nitric acid,
ammonium nitrate, etc. however, perfectly dry ammonia will not combine with perfectly dry
hydrogen chloride: moisture is necessary to bring about the reaction.

NH3 + HCl → NH4Cl

The salts produced by the action of ammonia on acids are known as the ammonium salts
and all contain the ammonium ion. Anhydrous ammonia is often used for the production of
methamphetamine. Dilute aqueous ammonia can be applied on the skin to lessen the
effects of acidic animal poisons, such as from insects and jellyfish.

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1.3.4 Acidity
Although ammonia is well known as a base, it can also act as an extremely weak acid. It is
a protic substance and is capable of formation of amides for example lithium and ammonia
reacts to give a solution of lithium amide:
2Li + 2NH3 → 2LiNH2 + H2

1.3.5- Self-dissociation
Like water ammonia is amphoteric as it reacts with itself to form its acid and base
conjugates giving ammonium ion and amide ion.

1.3.6 Combustion
The combustion of ammonia gives nitrogen and water. The reaction is exothermic and is as
follows:

4NH3 + 3O2 → 2N2 + 6H2O

The standard enthalpy change of combustion, expressed per mole of ammonia and with the
condensation of water formed is -382.81 Kj/mol. Di-Nitrogen is the thermodynamic product
of combustion: all nitrogen oxides are unstable with respect to nitrogen and oxygen, which
is the principle behind the catalytic converter. However, nitrogen oxides can be formed as
kinetic products in the presence of appropriate catalysts, a reaction of great industrial
importance in the production of nitric acid.

The combustion of ammonia in air is very difficult in the absence of a catalyst (such as platinum
gauze), as the temperature of the flame is usually lower than the ignition temperature of the
ammonia-air mixture. The flammable range of ammonia in air is 16-25%.

1.4 APPLICATION & USES


1.4.1 As a direct fertilizer
The fertilizer industry constitutes the largest market for ammonia. Some of the advantages
of anhydrous ammonia as direct fertilizer are:

• Having 32% nitrogen, it is the most concentrated nitrogen fertilizer available.


• It improves soil tilth, increasing the water holding capacity and decomposes crop
residue and organic matter.

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• It increases the number, size and strength of crop roots resulting in deeper
penetration, creative plant development and ability to withstand period of droughts.

• It is easy to apply; it flows under its own pressure from the applicator tank to the soil.
• It can be applied at various times, for winter or spring as a preplan or in the summer
as a side dress application.

• It releases other food elements that are present in the soil such as potassium,
phosphorous, calcium and magnesium.

1.4.2 As a raw material for other fertilizer


Ammonia is also the primary building block for downstream manufacturing of a wide range
of fertilizer products.

Following table gives the relative amounts of ammonia used for the manufacturing of these
nitrogen products.

Table 1.1

PRODUCT RAW MATERIAL RAW MATERIAL


USED
(ton per ton of
product)
Urea Ammonia 0.58
Nitric acid Ammonia 0.29
Ammonium nitrate Ammonia 0.21
Nitric acid 0.77

Nitrogen solution Urea 0.33


Ammonium nitrate 0.41

Ammonium sulfate Ammonia 0.27

Ammonia and nitric acid are two basic ingredients in the manufacture of ammonium nitrate
which is also used in the production of nitric acid. Urea is manufactured by reacting ammonia
and carbon dioxide. Urea manufacturing facilities are often located close to ammonia plants.

Nitrogen solution consist of fertilizer products combination e.g. ammonium nitrate –


ammonia, urea ammonium nitrate.

11
1.4.3 As a starting material for other industrial products
Nitric acid is made by the oxidation of ammonia to nitrogen dioxide which is subsequently
absorbed by water. Nitric is itself a starting material for ammonium nitrate, nitroglycerine,
trinitrotoluene, nitro cellulose and other nitrogen compounds used in the manufacture of
explosives.

Fibers, resins and plastics

• Ammonia is used in the fiber and plastics industry as a source of nitrogen for the
production of caprolactum, the monomer for nylon-6, 6.

• Oxidation of propylene with ammonia gives acrylonitrile, used for the manufacture of
acrylic fibers, resins and elastomers.

• Hexa-methylene tetra mine produced from ammonia and formaldehyde is used in


the manufacture of phenolic thermosetting resins.

• Urea which is produced from ammonia is used in the manufacture of urea-


formaldehyde synthetic resins.

Pharmaceutical

Ammonia is also used in large amounts in the manufacture of pharmaceuticals, i.e.


sulfanilamide, sulfathiazole, sulfa pyridine and other sulfur drugs, vitamins and other amino
acids.

Food and beverages

Ammonia is used as a source of nitrogen required for the growth of yeast and micro-
organisms.
It is also used for controlling ph in yeast production.

Refineries

Ammonia is used as a corrosion inhibitor at petroleum refineries and natural gas plants. It is
used to neutralize acid constituents of oil, thereby protecting refinery equipment.

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1.4.4 Uses
Most known uses of ammonia are:

• Ammonia is the single most widely used compound in the fertilizer industry. It is the
starting material for the production of various number of nitrogenous fertilizers like
ammonium phosphates, ammonium sulfate, ammonium nitrate etc.
• It is used directly or in directly as the source for the production of
hexamethylenediamine for the manufacture of nylon-6, 6. In the manufacture of
rayon, ammonia is used in the preparation of ammoiacal copper hydroxide solution
for dissolving copper linters. Oxidation of propylene with ammonia gives acrylonitrile,
used for the manufacture of acrylic fibers, resins and elastomers.

• Hexamethylenetetramine produced from ammonia and formaldehyde is used in the


manufacture of phenolic thermosetting resins. Toluene 2, 4 isocyanate employed in
the production of polyurethane foam, indirectly consumes ammonia because nitric
acid is a raw material in the TDI manufacturing process.

• Urea produced from ammonia is used in the manufacture of urea formaldehyde


synthetic resins.

Among other uses are:

• As a refrigerant in both compression and absorption systems.


• In the pulp and paper industry for the pulping of wood.
• In rubber production for the stabilization of natural and synthetic latex to prevent
coagulation.

• As a curing agent in tanning industries.

1.5 DESCRIPTION OF STORAGE AND TRANSFER


EQUIPMENT
1.5.1 Introduction
Liquefied ammonia from production plant is either used directly in downstream plants or
transferred to storage tanks. From these the ammonia be transferred to road tankers, rail
tank Ears or ships.

Ammonia is usually stored by using one or other three methods


13
• Fully refrigerated storage in large tanks with a typical capacity of 10,000 to 30,000
tons (up to 50,000)

• Pressurized storage spheres or cylinders up to about 1,7000 tons tanks


• Semi refrigerated tanks
It is therefore good practice to build ammonia storage and handling installations at a sufficient
distance from domestic housing schools, hospitals or any areas where substantial numbers of
people may assemble. In some countries there are planning procedures or regulations which
control the sitting of ammonia storage installations and similar establishments.

Where there are no formal controls, the sitting of ammonia storage facilities should be given
serious consideration at the design stage.

It is undesirable for ammonia storage tanks to be sited close to installations where there is a

risk of fine or explosion, since these could increase the possibility of a release of ammonia.

1.5.2 Storage tanks

Anhydrous ammonia is stored in three types of tank as outlined above:

• Fully refrigerated at a temperature of about -33 °C, these tanks are provided with
refrigeration equipment

• Non-refrigerated tanks in which the ammonia is stored at ambient temperature


Semi-refrigerated spheres

Refrigerated storage is preferred for storage of large quantities of liquid ammonia. The
initial release of ammonia in the case of a line or tank failure is much slower than the
pressurized ammonia.

There are several construction types for the storage of refrigerated liquid products. The
most important types are:-

SINGLE CONTAINMENT

a single-wall insulated tank, normally with a containment bund around it.

14
DOUBLE CONTAINMENT

This type of storage tank has two vertical walls, both of which are designed to contain the
stored amount of liquid and withstand the hydrostatic pressure of the liquid, but in this case
the roof rests on the outer wall.

FULL CONTAINMENT
the two walls of this closed storage tank are also designed to contain the stored amount of
liquid, but in this case the roof rests on the outer wall.

1.5.3 Transfer equipment


Liquid or gas pipelines should be fitted with isolation valves. The main isolation valves
should be backed up by remotely operated valves. The remote system should b of such a
type that closure is automatic in case of a power failure.

Liquid ammonia has a high thermal coefficient of expansion and, therefore, some means of
safe venting should be provided on pipelines in which any significant can be trapped
between valves, etc.

Liquid ammonia pipelines should be fitted with remotely operated valves at suitable
intervals to minimize the loss in the event of a line failure.

Ammonia is transported in road tankers, rail tanks cars (both pressurized) and ships
(pressurized or refrigerated)

1.5.4 Rail road and rail loading


Loading and unloading of rail tank cars and road tankers is usually done by loading arms.
During (un) loading both the liquid supply and vapor return lines must be connected to the
transport medium.

The ammonia vapors can be transferred during (un) loading ta a storage tank, an ammonia
vapor network of the site or to a scrubber/absorber, to prevent emissions to the atmosphere.

Before disconnection of equipment after (un) loading the liquid ammonia in these parts
must be removed to one of the reservoirs. Preferably, this should be done by using a
pressurized inert gas such as nitrogen or ammonia vapor.

15
If inert gas is used, attention should be paid to avoid getting inert gas into tankers and storage
tanks. There should be a scrubbing system or a flare in the event of venting inert gas.

A weigh check must be carried out after the loading, to ensure that the maximum allowable
content has not been exceeded. Modern road and rail car loading stations are equipped
with a safeguard against overfilling.
1.5.5 Ships
Both liquid and vapor connections must be equipped with isolation valves as near to the
ships as possible. It must be possible to close these valves quickly under all conditions and
the connections between tank and liquid line must be equipped with an isolation valve. The
ends of loading and unloading arms should be equipped with dry break couplings. The
isolation valves must be closed automatically, when these couplings are disconnected or
when the (un) loading are too far out of position.

After each loading operation, liquid ammonia contain within loading arms must be collected
in a suitable evaporation tank connected to the storage tank through the vapor line.

Loading arms are then purged by inert gas or ammonia vapor. If inert gas is used, attention
should be paid to avoid getting the inert gas into tankers and storage tanks. There should
be a scrubbing system or flare in case the inert gas has to be vented.

16
Chapter # 2

LITERATURE REVIEW

17
2.1 NITROGEN FERTILIZER COMPONENT
Ammonia is one nitrogen fertilizer component that can be synthesized from inexpensive raw
materials. Since nitrogen makes up a significant portion of Earth’s atmosphere, a process
was developed to produce ammonia from air. In this process, natural gas and steam are
pumped into a large vessel. Next, air is pumped into the system, and oxygen is removed by
the burning of natural gas and steam. This leaves primarily nitrogen, hydrogen and carbon
dioxide. The carbon dioxide is removed and ammonia is produced by introducing an electric
current into the system. Catalyst such as magnetite has been used to improve the speed
and efficiency of ammonia synthesis. Any impurities are removed from the ammonia, and it
is stored in tanks until it is further processed.

While ammonia itself is sometime used as a fertilizer, it is often converted to other


substances for ease of handling. Nitric acid is produced by first mixing ammonia and air in
a tank. In the presence of a catalyst, a reaction occurs which converts ammonia to nitric
oxide. The nitric oxide is further reacted in the presence of water to produce nitric acid.

Nitric acid and ammonia are used to produce ammonium nitrate. This material is a good
fertilizer component because it has a high concentration of nitrogen. The two materials are

18
mixed together in a tank and a neutralization reaction occurs, producing ammonium nitrate.
This material can then be stored until it is ready to be granulated and blended with other
fertilizer components.

2.2 PHOSPHOROUS FERTILIZER COMPONENT


To isolate phosphorous from phosphate rock, it is treated with sulphuric acid, producing
phosphoric acid. Some of this material is reacted further with sulphuric acid and nitric acid
to produce a triple super phosphate, an excellent source of phosphorous in solid form.

Some of the phosphoric acid is also reacted with ammonia in a separate tank. This reaction
results in ammonium phosphate, another good primary fertilizer.

2.3 POTASSIUM FERTILIZER COMPONENT


Potassium chloride is typically supplied to fertilizer manufacturers in bulk. The manufacturer
converts it into a more useable form by granulating it. This makes it easier to mix with other
fertilizer components in next step.
2.4 SELECTION OF RAW MATERIALS
Before world war two, 3 million tons per day of nitrogen were produced as ammonia, 90%
was derived from coke and coal. By 1960, about 16 million tons per day of ammonia was
produces using cheaply available natural gas in U.S.A. Naphtha became the most common
feed stock in other developed countries because of its low price and some fuel oil is also
used. Naphtha became more popular with the development of Imperial Chemical Industries
(ICI) steam reforming process for naphtha and led to many plants around the world. Soon
many of these plants closed as a result of the increase in the price of naphtha because of
its increased demand and the 1973 crisis. Since 1975, the primary feed stock of most new
plants is natural gas with about 78% of the world’s ammonia capacity. The percentage is so
large because of the low energy needs and investment costs of natural gas. Future
predictions had shown that natural gas as the main feedstock for ammonia especially in
developing countries, except China where primary feed stock is still Coal.

2.4.1 L.P.G
LPG, which primarily contains butane and propane, has been used as ammonia’s feed stock in
Japan. These materials are relatively expensive but are often less expensive than naphtha.

19
2.4.2 Naphtha
In those areas of the world where natural gas is unavailable, naphtha became the favored
feedstock for ammonia production by steam reforming, particularly in the period of 1952-
1974 when naphtha was relatively cheap. In many countries the amount of naphtha
produced in oil refining exceeded the demand. Naphtha is the lighter fraction of the
0 0
hydrocarbon; it boils from about 40 C – 130 C with an average molecular weight of about
88 and an H : C atomic ration of about 2 : 23. Straight-run naphtha is preferred to naphtha
produced from higher hydrocarbons by cracking or hydro-cracking because the latter
usually contains sulfur compounds that is difficult to remove.

Since 1974 the price of naphtha in the world market has risen more rapidly than that of
other feed stocks because of the demand of naphtha in the manufacturing of motor fuel and
petrochemicals.

Therefore, several plants originally designed to use naphtha have switched to other feed
stocks such as natural gas. As a result, few new plants are being built to use this feedstock.
The process for steam reforming of naphtha was developed mainly by ICI in England and
has been widely used in Europe, Japan and many developing countries. The main technical
problem was to avoid carbon for on the reforming catalyst without excessive steam
consumption. This problem was solved by modification of catalyst composition.

2.4.3 Natural Gas


Natural gas is classified as associated or non-associated. Associated gas occurs with crude
oil; it is liberated from the oil when the pressure is released in the oil-gas separator plant. Its
composition varies with the pressure at which the separator is operated, since methane is
the most volatile component, it can be released at relatively high pressure. By releasing gas
at successively lower pressure, a separator can be made in which methane is released first,
and the less volatile gases, ethane, butane and propane are collected separately.

The higher hydrocarbons usually have a higher value for petro-chemical production or for
sale as LPG than methane. Therefore, in most cases, these products are sold separately,
and the term natural gas usually refers to the fraction that contains mostly methane with
only small percentage of ethane and higher hydrocarbons, For use as ammonia feed stock,
methane is preferable to the higher hydrocarbons because all carbons in the feed stock is

20
converted to carbon dioxide or monoxide, which must be removed from the ammonia
synthesis gas. Therefore, the lower the carbon: hydrogen ratio the feed stock, the smaller
and the less expensive the purification units in the synthesis gas preparation section will be.

In ammonia urea complexes where all of the ammonia is used to make urea, the amount of
carbon dioxide derived from methane feed stock may not be sufficient for the urea plant
needs. Urea requires a CO2 : NH3 ratio of 1 : 2, whereas the production of ammonia by
reforming pure methane results in a CO 2 : NH3 of 7 : 16. In this case it would be
advantageous if the natural gas contains enough higher hydrocarbons to supply enough
carbon dioxide for urea production. This is often the case as shown by the example of
natural gas, composition given in table.

Associated and non- associated natural gases vary widely in composition; the example in
table 2 is only illustration. Gas from non –associated deposits may be nearly pure methane.
In order deposit gas may contain higher percentage of hydrogen di sulphide, carbon dioxide
or both. Other, usually minor constituents are nitrogen and sometimes helium. The carbon
dioxide and hydrogen di sulphide are usually removed by scrubbing before delivery by
pipeline to avoid corrosion of the pipeline; the hydrogen di sulphide may be converted to
elemental sulphur, which may be a profitable by product in so many cases.

Table 2: Sample composition of natural gas

Constituents %age by volume %age by volume


At well head As delivered by
pipeline
Methane 75.9 93.3
Nitrogen 2.0
Argon 0.4
Carbon dioxide 7.3 0.01
Hydrogen disulphide 8.9 <5ppm
Hydrocarbon
C2H6 3.3 3.3
C3H8 1.2 0.9
C4H10 0.8 0.2
C5H12 0.5 0.01

21
2.4.4 Refinery gases
Petroleum refineries and petro chemical operations produce a variety of gases as the
byproduct that can be used as fuel or feed stock or both. The composition of refinery tail
gas varies widely; it usually contains hydrogen, methane and higher hydrocarbon and can
be used as ammonia feed stock by steam reforming. The amount of available tail gas is
likely to be insufficient for an economical scale of ammonia production unless the refinery is
a very large one. Another drawback is that the volume and composition of the tail gas may
vary according to the demand for the various refinery products, and these variations can
cause difficulties in the ammonia plant operation. Also, refineries often have a use for the
components of the tail gas.

For instance, the hydrogen can be separated and used in “hydro cracking”. Only a few
ammonia plants in Europe and Japan use the refinery tail gas.

2.4.5 Coke oven gas


Before 1940’s, coke oven gas was used for a large portion of ammonia production. Coke oven
gas contains about 50% hydrogen, 25% methane, 8%CO, 6% nitrogen, minor amounts of
higher hydrocarbons, carbon dioxide and various impurities. Presumably it could be used for
ammonia production by steam reforming after purification, but the usual practice is to separate
the hydrogen by a cryogenic procedure involving a liquid nitrogen wash. Many steel producing
plants have an air separation unit to supply oxygen for use in steel production; thus, liquid
nitrogen is available from this source. The cryogenic process produces nitrogen-hydrogen gas
mixture suitable for ammonia synthesis, and the remaining gas mixture of CO, methane and
heavier hydrocarbons is used as a fuel. The main drawback is similar to the refinery tail gas; the
amount of coke oven gas depends upon coke production, which in turn depends on steel
production. Only few plants use coke oven gas for feed stock.

2.4.6 Heavy oil


Liquid hydrocarbons heavier than naphtha are used for ammonia feed stocks by partial
oxidation processes.

22
2.4.7 Hydrogen rich off gases
By product hydrogen sources have been used for ammonia production in the past. In the
1970’s, the price of light hydrocarbons began to rise, which led to other feed stocks such as
hydrogen rich off gases being reconsidered. Some large plant using methanol or other plant
purge gases were built.

23
Chapter # 3

FERTILIZER INDUSTRY
IN

PAKISTAN

24
FERTILIZER INDUSTRIES IN PAKISTAN

There are at present seven Nitrogenous fertilizer plants and three phosphatic fertilizer
plants operating in Pakistan.

The location and capacity of the plants in Pakistan is discussed in detail in the following
section.

3.1 PAK- AMERICAN FERTILIZERS LIMITED (NFC) Daudkhel


 Location
The plant is located in village Daudkhel, District Mianwali and was built by an
American Loan given in 1953.
 Plant Capacity
The plant is initial designed for a nominal capacity of 40 metric tons per day of
Ammonia, converted into 150 metric tons per day of Ammonium sulphate by gypsum
suiphitation. The plant started production in 1957-1958. The present capacity of the
plant is 74.5 metric tons per day of Ammonia and 273 metric tons of Ammonium
Sulphate.
 Raw Materials
The raw materials used initially in this plant were coal, gypsum. But now the plant
has been converted to use Natural Gas.

3.2 PAK ARAB FERTILIZER LIMITED


 Location
The plant is located in the out skirts of Multan city along the main Lahore - Multan
Highway. It is connected by 1.5 miles of railway line to Piran Ghaib railway station on
the Khanewal – Multan Sector of Pakistan Railway.
 Plant Capacity

25
The initial designed capacity of the main plant was 204 metric tons per day of
Ammonia which was increased to 180 metric tons per day of Urea (40% nitrogen)
and 300 tons per day of Ammonium Nitrate with 26.5 % Nitrogen. In order to meet
the requirements of

NH3 . Ammonia plant with a daily capacity of 80 tons ammonia was put into
production in 1967-1968. Now the capacity of the plant has been raised to 910
metric tons per day of ammonia and 1500 metric tons per day of Ammonium Nitrate,
and 1015 metric tons of Nitro-Phosphate and 280 metric tons per day of Urea.
 Raw Materials
Natural gas (Sui Gas) is the main raw material used for the production of Ammonia.
The other raw material used is lime stone, which in fact act as a filler of Calcium
Ammonium Nitrate manufacture, and the product manufactured contain 26.5%
Nitrogen.

The lime stone is obtained from Punjab Industries and Mineral Development
Corporation Lime Stone Quarries at Daudkhel.

The plant use the steam reforming process for cracking of N.G.

3.3 FAUJI FERTILIZER COMPANY LIMITED


 Location
The largest urea manufacturing facility of Pakistan consisting of two ammonia/urea
owned by FFC is built at Goth Machhi is situated at a distance of 2 Km from the
main Lahore – Karachi highway adjusted to the main railway line.
 Plant Capacity
The two plants are based on natural gas and gave an annual design production
capacity of 1.3 million tons of Urea. PROJECT 1(Base Unit)

26
Table 3.1

Commencement of Commercial June 14, 1882


Prod
Project Cost Rs 3,300 Million
Production Capacity
Ammonia-I 1220 Metric Tons per Day
Urea-I 2105 Metric Tons per Day

PROJECT- 2 (EXPANSION UNIT)


Commencement of Commercial cMarch 21, 1993
Produ
Production Cost Rs 7,215 Million
Ammonia-II 1100 Metric Tons per Day
Urea-II 1925 Metric Tons per Day

Current Production
Urea-I 2271 Metric Tons per Day
Urea-II 2271 Metric Tons per Day

Capacity Factor
Urea-I 107.90%
Urea-II 115.4%

 Raw Materials
The main raw material is natural gas which is coming from Mari Gas field situated at
52 km from plant side.

3.4 FAUJI FERTILIZER COMPANY LIMITED 3


 Location
The plant is located at Mirpur Mathelo District Ghothki and it is also located on the
main railway line of Lahore – Karachi. When the plant was built it was under
Government control and its name was Pak – Saudi Fertilizer Limited. But recently
FFC has purchased this plant and its new name is FFC 3.
27
 Raw Materials
The main raw material is natural gas is coming from Mari Gas field.

3.5 FFC – JORDAN FERTILIZER CO. LIMITED


 Location
The plant is located at Port Qasim Karachi. The plant is the joint venture of Pakistan
and Jordan.
 Plant Capacity
The major production of the plant is Di – ammonium Phosphate commonly known as
DAP. The plant also produces Urea but in small amount as compared to other Urea
plants.

 Raw Materials
The major raw material is Phosphate rock. When the plant was built, the phosphate
rock is imported from Jordan but now it is imported from Morocco.

3.6 ENGRO CHEMICAL PAKISTAN LIMITED


 Location
The plant is located in village Dharki District Sukkur. It is connected to the Lahore –
Karachi main railway line.

 Plant Capacity
The plant is designed for 300 metric tons per day of Ammonia and 750 metric tons
per day of Urea. Currently the production of Ammonia and Urea is increased from
designed capacity.
 Raw Materials
Natural Gas is used as raw material. The gas was discovered in village Mari which is
located at a distance of 7 miles from the plant started production in 1968 and has
been running smoothly.

28
3.7 DAWOOD HERCULES CHEMICAL LIMITED
 Location
The plant is located in the district Sheikupura at Chichoki Mallian. The plant is located in
between the grand trunk road (G.T. Road) and the Lahore – Faisalabad railway line. It is
a joint venture of Hercules Limited of U.S.A and Dawood Corporation of Pakistan.
 Plant Capacity
The plant is designed to produce 815 metric tons of Ammonia per day, which is all
converted to 1350 tons per day urea.

The plant uses the standard M.W. Kellogg process for ammonia and Mitsui Toatsu
Total Recycle for urea plant.
 Raw Material
The plant uses Natural Gas (Sui Gas) which is being supplied by the Sui Northern
Gas Pipeline Limited.

3.8 HAZARA PHOSPHATE FERTILIZER LIMITED


 Location
The plant is located at Hatter Road, Haripur, Pakistan
 Plant Capacity
The plant is designed to produce 300 metric tons per day of Sodium Super Phosphate.
 Raw Materials
Raw material used is Rock of Jordan (triple super phosphate)

3.9 CHEMICAL & FERTILIZER (NFC) Faisalabad and


Jaranwala
Chemical and Fertilizer Limited own two plants, one at Faisalabad and other at Jaranwala.
The Management and Financial Control is however, exercised from Faisalabad.

 Location
The Faisalabad plant is located on the main Lahore – Jaranwala Faisalabad
Highway, about 1 mile from Faisalabad railway station. The factory at Jaranwala is
located on the main Lahore – Jaranwala – Faisalabad at 66 mile from Lahore and
about ¼ mile from the road/railway crossing.

29
 Plant Capacity
Faisalabad
This plant produces Single Super Phosphate at rate of 60 metric tons per day.
Jaranwala
It produces Single Super Phosphate at rate of 240 metric tons per day.
 Raw Materials
Rock phosphate and sulphur are the main raw materials. Sulphur is imported by
Trading Corporation of Pakistan. Rock Phosphate is imported from Jordan.

30
Chapter # 4

PLANT LOCATION

&

PLANT LAYOUT

31
4.1 PLANT LOCATION AND LAYOUT
The geographic location of a final plant can have a strong influence on the success of an
industrial venture. Considerable care must be exercised in selecting the plant site, and
many different factors must be considered. Primarily, the plant should be located where the
minimum cost of production and distribution can be obtained; but other factors, such as
room for expansion and safe living conditions for plant operation as well as the surrounding
community, are also important.

The following factors should be considered in selecting a plant site:


 Raw material availability
 Markets
 Energy availability
 Climate
 Transportation facilities
 Water supply
 Waste disposal
 Labor supply
 Taxation and legal restriction
 Site characteristics
 Flood and fire protection
 Community factors

The factors must be evaluated in plant location study indicate the need for a vast amount of
information, both quantitative (statistical) and qualitative. Fortunately, a large number of
agencies, public and private, publish useful information of this type, greatly reducing the
actual gathering of the data.

4.1.1 RAW MATERIAL AVAILABILITY


The source of raw material is one of the most important factors influent the section of a
plant site. This is particularly true if large volumes of raw material are consumed, because
location near the source of raw material permits considerable reduction in transportation
and storage charges.

32
Attention should be given to the purchased price of the raw materials, distance from the
source of supply, freight or transportation expenses, availability and reliability of supply ,
purity of the raw materials, and storage requirement.

4.1.2 MARKETS
The location of markets or intermediate distribution centers affects the cost of product
distribution and the time required for shipping. Proximity to the major markets is an
important consideration in the selection of a plant site, because the buyer usually finds it
advantageous to purchase from nearby sources. Note that markets are needed for by
product as well as for major final product.

4.1.3 ENERGY
Availability power and steam requirements are high in most industrial plants, and fuel is
ordinarily required to supply these utilities. Consequently, power and fuel can be combined
as one major factor in the choice of a plant site.

Electrolytic processes require a cheap source of electricity, and plants using electrolytic
processes are often located near large hydro installations. If the plant requires large
quantities of coal or oil, location near a source of fuel supply may be essential for economic
operation. The local cost of power can help to determine whether power should be
purchased or self- generated.

4.1.4 CLIMATE
If the plant is located in a cold climate, cost may be increased by the necessity for construction
of protection shelters around the process equipment, and special cooling towers or air
conditioning equipment may be required if the prevailing temperatures are high. Excessive
humidity and extremes of hot or cold weather can have a serious effect on the economic
operation of a plant, and these factors should be examined when a plant site is selected.

4.1.5 TRANSPORTATION
Facilities water, railroads, and highways are the common means of transportation used by
major industrial concerns. The kind and amount of products and raw materials determine
the most suitable type of transportation facilities. In any case, careful attention should be
given to local freight rates and existing railroad lines. The proximity to railroad centers and
the possibility of canal, river, lake, or ocean transport must be considered.

33
Motor trucking facilities are widely used and can serve as a useful supplement to rail and
water facilities. If possible, the plants sites should have access to all three types of
transportation; certainly, at least two types should be available. There is usually need for
convenient air and rail transportation facilities between the plant and the main company
headquarters, and effective transportation facilities for the plant personnel are necessary.

4.1.6 WATER SUPPLY


The process industries use large quantities of water for cooling, washing, steam generation,
and as a raw material. Plant, therefore, must be located where a dependable supply of
water is available. A large river or lake is preferable, although deep wells or artesian wells
may be satisfactory if the amount of water required is not too great.

The level of the existing water table can be checked by consulting the state geological
survey, and information on the constancy of the water table and the year round capacity of
local rivers or lakes should be obtained.

If the water supply shows seasonal fluctuations, it may be desirable to construct a reservoir
or to drill several standby wells. The temperature, mineral content, bacteriological content,
and cost for supply and purification treatment must also be considered when choosing a
water supply.

4.1.7 WASTE DISPOSAL


In recent years, many legal restrictions have been placed on the methods for disposing of
waste materials from the process industries. The site selected for a plant should have
adequate capacity and facilities for correct waste disposal. Even through a given area have
minimal restrictions on pollution, it should not be assumed that this condition will continue
to exist. In choosing a plant site, the permissible tolerance levels for various methods of
waste disposal should be considered carefully, and attention should be given to potential
requirements for additional waste treatment facilities.

4.1.8 LABOUR SUPPLY


The type and supply of labor available in the vicinity of the proposed plant site must be
examined. Consideration should be given to prevailing pay scales, restrictions on number of

34
hours worked per week, competing industries that can cause dissatisfaction or high turnover
rates among the workers, and variations in the skill and productivity of the workers.

4.1.9 SITE CHARACTERISTICS


The characteristics of the land at a proposed plant site should be examined carefully. The
topography of the tract of land and the soil structure must be considered, since either or
both may have a pronounced effect on construction cost.

The cost of the land is important as well as local building costs and living conditions. Future
changes may make it desirable or necessary to expand the plant facilities. Therefore, even
though no immediate expansion is planned, a new plant should be constructed at a location
where additional space is available.

4.1.10 FLOOD AND FIRE PROTECTION


Many industrial plants are located along rivers or near large bodies of water, and there are
risks of flood or hurricane damage. Before a plant site is chosen, the regional history of
natural events of this type should be examined and the consequences of such occurrences
considered.

Protection from losses by fire is another important factor in selecting a plant location.

In case of a major fire, assistance, from outside fire departments should be available. Fire
hazards in the immediate area surrounding the plant site must not be overlooked.

4.1.11 COMMUNITY FACTORS


The character and facilities of a community can have quite an effect on the location of the
plant. If a certain minimum number of facilities for satisfactory living of plant personnel do
not exist, it often becomes a burden for the plant to subsidize such facilities. Cultural
facilities of the community are important to sound growth. Churches, libraries, schools, civic
theaters, concert associations, and other similar groups, if active and dynamic, do much to
make a community progressive.

4.2 PLANT LAYOUT


Alter the process flow diagrams are completed and before detailed piping, structural, and
electrical design can begin, the layout of process units in a plant and the equipment within
these process units must be planned.

35
This layout can play an important part in determining construction and manufacturing costs
and thus must be planned carefully, with attention being given to future problems that may
arise. Since each plant differs in many ways and no two plant sites are exactly alike, there
is no one ideal plant layout.

However, proper layout in each case will include arrangement of processing areas, storage
areas, and handling areas in efficient coordination and with regard to such factors as

 New site development or addition to previously developed site


 Type and quantity of products to be produced
 Type of process and product control
 Operational convenience and accessibility
 Economic distribution of utilities and services
 Type of buildings required and building code requirements
 Health and safety considerations
 Waste disposal requirements
 Auxiliary equipment
 Space available and space required
 Roads and rail roads
 Possible future expansion

4.3 PREPARATION OF THE LAYOUT


Scale drawing complete with elevation indications can be used for determining the best
location for equipment and facilities.

Elementary layouts are developed first. These show the fundamental relationships between
storage space and operating equipment; the next step requires considerations of the safe
operational sequence and gives a primary layout based on the flow of materials, unit
operations, storage, and future expansion.
By analyzing all the factors that are involved in plant layout, a detailed recommendation can
be presented, and drawings and elevations, including isometric drawings of the piping
system, can be prepared with appropriate software.

36
Errors in plant layout are easily located when three-dimensional models prepared with today’s
software are used, since the operations and construction engineers can immediately see errors
which might have escaped notice on two-dimensional templates or blueprints.

In addition to increasing the efficiency of a plant layout, these three-dimensional models are
very useful during plant construction and for instruction and orientation purposes after the
plant is completed.

4.3.1 PLANT OPERATION CONTROL


In the design of an industrial plant, methods which will be used for plant operation and control
help determine many of the design variables. For example, the extent of instrumentation can be
a factor in choosing the type of process and setting the labor requirements.

Remember the maintenance work will be necessary to keep the installed equipment and
facilities in good operation condition.

The engineer must recognize the importance of such factors which are directly related to
plant operation and control and must take them into proper account during the development
of a design project.

4.3.2 NOISE
Noise can cause a serious nuisance in the neighborhood of a process plant. Care needs to
be taken when selecting and specifying equipment such as compressors, air-cooler fans,
induced and forced draught fans for furnaces, and other noisy plant. Excessive noise can
also be generated when venting through steam and other relief valve, and from flare stacks.

4.3.3 NOISE CONTROL


The design engineer should include noise studies in the design stage of any commercial
facility. Generally, acoustical problems left for field resolution cost roughly twice as much.

37
Unnecessary cost incurred in post construction noise work may include the replacement of
insulation, redesign of piping configuration to accommodate silencer, modification of
equipment, additional labor costs, and possible downtime to make necessary changes.

Considerable judgment, therefore, must be exercised by the designer to establish final design
stage noise recommendation. These not only should consider the results of the equipment data
analysis procedure, but also should recognize additional factors such as administrative controls,
feasibility of redesign, economic alternatives, intrusion of noise into the community, and the
basic limitations of the equations employed in the applicable computer programs.

4.3.3.1 EQUIPMENT NOISE SOURCES, LEVELS, AND POTENTIAL CONTROL SOLUTIONS

Table 4.1

EQUIPMENT SOUND LEVEL, OBA


Air cooler 87-94
Compressor 90-120
Electric motors 90-110
Furnaces 95-110
Valves < 80-180
Piping 90-105

38
Chapter # 5

MANUFACTURING

PROCESS

39
Different processes for ammonia production

Ammonia production involves chemical reactions, sometimes at high temperature and/or


pressure, using natural raw materials. The transformation of these raw materials inevitably
leads to the process by-products, emissions and wastes which can be solid, liquid or
gaseous. The uncontrolled release of some of these substances could harm the
environment. To avoid this and also to maximize the process efficiency, a wide range of
processes and waste recovery and abatement technique is available. This chapter provides
a general description of the main fertilizer production processes, together with the best
available technique (BAT) for achieving emission limits and/or minimizing emissions to the
environment. Typical plant inputs, outputs and achievable emission levels are given for the
most types of emissions, and for both new and existing plants.

The products dealt with in this chapter are ammonia, urea, urea ammonium nitrate,
ammonium nitrate and calcium ammonium nitrate, sulphuric acid, phosphoric acid; single
and triple super phosphate and multi-nutrient fertilizers.

There are many processes for the manufacturing of ammonia. Some of the major
processes are listed below:

1. OSAG process
2. Mont Cenis process
3. Claude and Casale System
4. Du-pont process
5. Haber Bosch process
6. Chemico process
7. M.W Kellogg process
8. Kellogg Brown & Root Advanced Ammonia Process (KAAP)
9. Halder Topsoe

5.1 OSAG Process


In 1962, a company with manufacturing experience of ammonia at LINZ factory in Austria
published details of converter design developed in collaboration with Halder Topsoe of

40
Denmark. The operating pressure is 315 atm and maximum catalyst temperature is 525 C.
The feed gases are passed through the interchangers between the beds of catalysts, thus
removing the heat from the reactor and heating the gases entering the reactor.

5.2 Mont Cenis Process


This process is obsolete but it has some historical value. It requires a pressure between
120100 atm with iron cyanide catalyst which during the course of reaction reduces to alpha
iron, as in case of promoted iron oxide catalyst. The process was actually developed for the
use of low pressure feed stocks such as coke oven gas.

5.3 Claude and Casale System


In 1927, the first Claude unit, with modification from Casale process was installed in U.S.
The reaction which takes place in two converters in series gas stream recirculation where
the temperature in the first converter will vary from 482 C - 620 C. Depending upon catalyst
activity the conversion is about 80% per mass. Other advantages are that only one seventh
as much catalyst is needed to produce the same amount of ammonia and only one fifth as
much gas must be handled on the basis of actual volume at synthesis conditions. The
catalyst is purified magnetic iron oxide, doubly promoted with small percentages of
aluminum and potassium oxide. The Casale system is characterized by the design of
converter and condenser, also on the entering is passed on in contact with the outside wall
of the convertor in order to keep its temperature below 400 C.

5.4 Du-Pont system


In this system coal was first used. Hydrogen was produced by the reaction of water gas on
coke, expansion marked the advent of natural gas.

5.5 Chemico process


It is modified, improved Haber Bosch system. This process takes its basis from Nitrogen
Engineering Corporation and in early 1960s was used in about 25% of the installed
ammonia capacity in the U.S.A. and other plants around the world. Like all other processes
this one is based on the following reactions;

41
N2 + 3H2O ↔ NH3

This reaction is highly exothermic and design of the converter should be such as to control
the temperature at the point desired for the conversion deemed economical for particular
conditions. This synthesis is at 350 atm in a tube and can be accompanied by a steam
generator. The process includes an ammonia refrigeration cooler/ condenser, which is
claiming to prolong the catalyst life. This probable because low ammonia concentration will
exist in the converter permitting catalyst tube permitting catalyst tube operating at about
500 C compared with some other processes which operate at catalyst temperature of 530-
550 C.

5.6 Haber-Bosch process


This ammonia synthesis process was developed mainly by Fritz Haber starting in 1904, and
by 1909 he demonstrated the process on a laboratory scale of 80g of ammonia per hour.
Carrying out the high temperature, high pressure process on commercial scale presented
problem with the technology and material of construction available.

Carl Bosch, working with Haber, is generally credited with developing the process, first in
pilot plant then on commercial scale. Production started in 1913 at Oppau, Germany.

The chemistry of process is simple; the reaction is given in the following;

N2 + 3H2O ↔ NH3

The reaction is exothermic; the heat of reaction is about 11cals per gmol at 18 C assuming
ammonia in gaseous state. The net heat released by the reaction increase with increasing
temperature and may be 15-20% higher at usual operating conditions of 400 C-500 C.

The reaction does not go to completion, equilibrium conditions are such that increase in
pressure favors higher conversion to ammonia while increase in temperature decreases
conversion. Since the overall volume of system decreases as reaction proceeds, so
according to Le-Chartlier’s principle the increase in pressure will favor the increase in the
yield of the system. Since we know that the reaction is also exothermic in nature, so
decrease in temperature will increase the yield of the system with accordance to the Le-
chartlier’s principle.

42
However the rate of reaction is very slow at low temperature and increase with
temperature, thus a compromise must be maintained between reaction rate and yield
value. In order to bring about the reaction at reasonable, acceptable and economical rate,
he introduced a catalyst. Haber first study was made with an iron catalyst which was not
very active. Later he found that osmium and uranium was much more effective, but these
elements were rare and expensive.

After several experiments, it was found that certain impurities increase the activity of iron
catalyst and on the basis of these studies; he introduced a doubly promoted iron catalyst
that produced from magnetite with addition of potassium, alumina and calcium.

In order to improve conversion, Haber also originated the concept of ammonia synthesis
loop, in which the gas leaving the converter is cooled to condense most of ammonia as
liquid which is removed from the gas and the remaining unreacted hydrogen is reheated
and returned to the synthesis converter with fresh synthesis gas.

5.7 M.W.Kellogg’s Process


Most of the plants working at this time for the production of ammonia are modified form of M.W
Kellogg process. In this process, catalyst is in the form of cartridge consisting of four or five,
some of the gas is introduced between the cartridge and pressure shell act as coolant.

The gas is passed through the first and subsequent beds of catalyst. Inter bed temperature
control is carried out by the injection of remainder of the cold feed gas through suitable gas
mixing devices between catalyst beds decreasing the ammonia concentration across each
inter bed space. The convertor is optimized at to give minimum catalyst volume consistent
with suitable catalyst temperature and long catalyst life.

5.8 Kellogg Brown & Root Advanced Ammonia Process-Plus


(KAAP)
The KAAP plus (Kellogg Brown & Root Advanced Ammonia Process-plus) is an ammonia
process design made up of commercially proven technologies KBR Reforming Exchanger
System (KRES), KBR Purifier, and KBR Advanced Ammonia Process KAAP) for synthesis.
43
KAAP plus uses KRES with excess process air feed to the auto thermal reformer. Excess
nitrogen, along with the methane, most of the argon, and other impurities are removed in
KBR purifier. The resulting high purity makeup synthesis gas is compressed to the KAAP
synthesis loop pressure of about 90bar to 81bar. This process uses a ruthenium based, co-
promoted catalyst on a graphite support. It is much as twenty times more active as the iron
based catalysts. The new catalyst results in improved synthesis efficiency because the
synthesis pressure is lowered from a typical pressure of 150 bar (2175 psig) to 90 bar
(1305 psig). Typical conversion with the ruthenium catalyst is 20% compared to 5% to 16%
with conventional, iron based catalysts. His first application in 1992 used a two bed, hot wall
KAAP reactor that featured a low pressure drop and radial flow. Because of the KAAP
catalyst’s high activity, thin beds are necessary to keep operating temperatures within the
desired range 203. In 2002 the KAAP reactor had evolved to a four bed design.

A magnetite catalyst is used in the first bed of synthesis loop when the ammonia concentration
is below 2% of the feed. Then the ruthenium catalyst is used in the next three beds to bring the
ammonia level up to 18% or more. In most radial flow converters, the upper portion of the bed is
sealed with excess, unused catalyst settles. The KAAP reactor uses a proprietary sealing
system to overcome this problem. This sealing system avoids the catalyst maldistribution that
can lead to formation of hot spot in the catalyst bed. The system allows 100% of loaded catalyst
volume to be utilized for the ammonia conversion reaction. For startup the KAAP catalyst is
loaded in the oxidized state. It is reduced by passing fresh synthesis gas over the catalyst beds
and heating them to 300 C the KAAP catalyst generates a smaller amount of water during
reduction about because it contains much less metals than conventional iron catalysts. For this
reason, the catalyst reduction proceeds swiftly and required 19 hours in one installation. (Iron
catalyst reduction usually requires 36 to 48 hours.) Another item that can improve operation is
mass spectrometer that analyzes the KAAP streams for hydrogen and nitrogen. The mass spec
enables closer control of H/N ratio that enters the loop and as a result provides a more
consistent ammonia conversion.

Capital cost savings of 3% to 8% may be achieved with KAAP when compared with other
designs. These savings are the result of following features:
1. No air separation plant
2. No primary reformer
3. Single case synthesis gas compressor
4. Synthesis at 90 bar
44
5. No purge gas recovery unit and
6. Reduced plot space

The maintenance costs are lower because, KAAP plus eliminates the primary reformer and
greatly simplifies the syn-gas compressor- the two the highest maintenance items in a
conventional ammonia plant. KAAP plus also reduces the severity of the operating
conditions. Reforming exchanger and auto thermal reformer exit temperature are about 100
C lower than in conventional plants. Synthesis pressure at 90 bars is substantially lower
than other processes.

5.9 Haldor Topsoe


Haldor Topsoe’s ammonia synthesis technology is based on the S-200 convertor. This is
two bed radial flow convertor with indirect cooling between the beds. Features of the S-200
includes efficient use of convertor volume and low pressure drop (factors related to small
catalyst particles: 1.5 to 3.0mm) in modification projects to achieve higher capacity and/or
better energy efficiency. Modification may involve installation of a new S-200 basket in an
existing pressure cell with full opening closure or an in situ modification of the existing
internals of bottle-shaped convertors. Modification of this type will typically result in a
reduction in specific energy consumption of about 0.3 Gcal/tonne of ammonia and/or a
capacity increase of up to 20%.

Haldor Topsoe also offers the S-250 concept and the three bed S-300 converter. The S-250
uses the S-200 converter followed by a one bed S-50 converter with a steam boiler or
steam super heater between the two converters. The S-50 catalyst bed inlet temperature
(which is equal to the converter inlet temperature) is controlled by the amount of steam
superheating that occurs in the upstream of S-50. The S-300 has an internal heat
exchanger installed between the second and third catalyst beds. In 2001 a total of thirteen
S-300 converters were in operation or under construction.

45
Chapter # 6

Halder Topsoe process for


ammonia production

46
[19]
Process Selection
6.1 Why we selected Halder Topsoe ammonia technology?
For more than 60 years, topsoe has been one of the main suppliers of catalyst and
technology for ammonia industry. By introduction of new catalysts, new equipment design
and extensive process optimization studies, topsoe has contributed significantly to the
development of efficient ammonia production technology. Today approximately 50% of new
plants use topsoe technology.

6.1-1 Integrated approach of research


Our integrated approach of research-based catalysts and technologies ensures a
fundamental understanding of the ammonia process, reinforced by decades of industrial
experience as well as a full range of catalysts and technologies for ammonia production.

Topsoe ammonia experience is unmatched as a result of more than 60 years of industrial


experience with plant operation throughout the world. Topsoe can offer our clients a reliable
and optimized catalyst and technology solution.

6.1-2 Optimum design approach


Topsoe low energy ammonia process is adjusted according to the specific project
requirements. In the design of new plants, investment cost is often the deciding factor,
however in some parts of the world feedstock prices are very high, which means that
optimum design may change from client to client. Topsoe’s approach assures that an
optimum design is achieved for each individual project in term of minimizing investment
cost and operating cost. Furthermore, topsoe has led the trend toward plant economy of
scale, resulting in lower investment per ton of ammonia, and we have developed designs
for plants with capacity up to 5000 MTPD.

6.1-3 Alternative feedstock and plant integration


In addition to the design of ammonia plants, based on natural gas feedstock such as
synthesis gas from gasification of coal, residual refinery products and hydrogen containing
waste streams from other petrochemical plants.

Topsoe ammonia plant can be integrated with production of petrochemical such as methanol or
DME, thus achieving of a lower relative investment cost. Poly-production capabilities ensure
lower sensitivity to market prices and enable the clients to switch to producing a more valuable
product. Methanol and DME synthesis are both in-house technologies of topsoe.

6.1-4 Revamp option


Topsoe has always emphasized of the importance of continuous optimization of operating
plants. In many cases this has led to revamp projects based on detailed optimization
studies. Their flexible and project specific approach ensures that the revamp project is
performed efficiently based on the client requirements, depending upon the type and size of
the revamp project, topsoe provides a scope of supply ranging from basic process design
to complete equipment supply.

47
Topsoe has extensive experience with revamp of proprietary as well as out of house plant
designs with regard to lowering energy consumption, increasing capacity and flexibility of
feedstock.

6.1-5 The topsoe approach


The topsoe approach to revamp project is to divide the project into a study phase followed by
engineering and implementation phase. Based on the objective of revamp, which is defined in close
collaboration with the client, the study will establish with reasonable accuracy the possible capacity
increase and/or energy savings obtainable, and the capital expenditure required for materializing
these benefits, thus creating a sound basis for the client’s decision. Topsoe’s involvement in the
implementation of revamp scheme can be tailored to the needs of client.

6.2 Topsoe ammonia process


Topsoe ammonia process will typically consist up of the following main steps:

1. Feed purification
2. Reforming
3. CO conversion
4. CO2 removal
5. Methanation
6. Ammonia synthesis

6.3 Process description [ref: 17]

6.3-1 Raw materials


1. Natural gas
2. Steam
3. Air
6.3-2 Natural gas from battery limits
Process feed gas and fuel gas (natural gas) arises at plant site through pipe lines from Mari
2
gas field. At battery limits gas is present at a pressure of 49kg/cm . It contains moisture
which is separated in KNOCKOUT drum.

6.3-3 knock out drum


In knock out drum gas strikes the walls of the knock out drum and then passed through
demister pad where point velocity of moisture becomes zero and it falls down while the gas
at high velocity passes out and then sent to natural gas preheater.

6.3-4 Natural gas pre heater


In preheater temperature of gas is increased from 31-245 C it is then mixed with recycle
gas coming from compressor in order to convert organic sulfur to inorganic sulfur then it is
sent to steam super heater where its temperature is further increased to 410 C.

48
Air

Natural gas NH3

Ammonia synthesis

Water

6.3-5 Desulfurizer
Reaction:

ZnO + H2S ↔ ZnS + H2O Type: Exothermic Catalyst:

ZnO (HTZ-3)
2
Stream inlet temperature & pressure: 400 C, 40kg/cm
2
Stream out let temperature & pressure: 390 C, 40kg/cm
The natural gas feed stock contains up to 5ppm of sulfur compound which have to be
removed in order not to poison the reforming catalyst in the primary reformer and in the
st nd
shift catalyst in the 1 converter and in the 2 converter. Natural gas is heated into two
preheated coils up to 400 C which are installed in flue gas section of primary reformer.
Then the gas is passed through the sulfur absorber. The absorber contains two beds of
ZnO catalyst, type HTZ-3 second bed acting as safeguard. Downstream of second catalyst
bed the sulfur content should be less than 0.005ppm on dry volume basis on all time.
Organic sulfur is first converted into inorganic sulfur and then removed because for
removing organic sulfur we should require another catalyst which is costly process.

Sulfur Absorption Catalyst


HTZ-3

ZnO is standard sulfur absorption catalyst used for removal of H 2S, COS, mercaptans
(RSH) and to some extent other organic sulfur compounds.
Operating temperature: 350-400 C
2
Operating pressure: 50 kg/cm
HTZ-3 can be operated at ambient temperature although sulfur absorption capacity is
reduced at low temperature.
49
HTZ-4

Its absorption properties are similar to HTZ-3 but in addition it is capable of absorbing COS
even at ambient temperature.

HTZ-5

It is special version of HTZ-3 having a larger porosity and a larger internal surface and is
especially suited for cleaning up feedstock with low sulphur content (5ppm or less). It is
most efficient at low temperature.

Although three type of catalyst (HTZ-3, HTZ-4, HTZ-5) are in form of cylindrical extrudates.

6.3-6 Primary reformer


Reaction

CH4 + 2H2O ↔ CO2 + 4H2

Type: endothermic

Catalyst: nickel oxide.


Inlet temperature: 600 C
Outlet temperature: 808 C

The reforming unit comprise of:

1. Tubular catalytic primary reformer known as furnace


2. Auto thermal catalytic secondary reformer
3. Waste heat boiler
4. Convection section

The burner is self-aspirating radial wall black flame burner. Two types of air are introduced.

1. Primary air
2. Secondary air
2
Fuel is introduced at a pressure of 2kg/cm due to pressure difference air is sucked inside
automatically without any external source and is mixed with fuel and ignites. If we want to
increase the flame or temperature; we increase the amount of limiting reactant that is air
and this air is known as secondary air and it is introduced via negative pressure created
with the help of induced draft fan which is used to suck flue gases. The heat is transferred
to refractory bricks by radiation and then to catalyst tubes where first conduction takes
place and then convection.

50
Radiation

The flame of the burner is towards the refractory bricks due to which they are heated. The
burner transfer heat of reaction by means of radiation to a number of tubes.

Conduction

Heat is transferred through the solid tube walls to the inside fluid by conduction through the
tubes.

Convection

The flue gases produced due to combustion reaction transfer heat to the coils in the
convection sections which are used for preheating purpose by convection. The refractory
bricks are lined so as to prevent heat loss and protecting the furnace wall from being
damage by the heat. There are 384 burners which are supplied with excess air for
complete combustion 60% reforming is taking place in primary reforming.

The gas leaving primary reformer consist up of

Table 6.1

Components Composition (mole %)


H2 60
N2 7
CO 10.5
CO2 9.9
CH4 12.5
Ar 1.7

6.3-7 Secondary reformer


Reaction:

CH4 + O2 ↔ CO2 + 2H2

2H2 + O2 ↔ 2H2O

CH4 + H2O ↔ CO + 3H2

Type: Endothermic

Catalyst: Nickel oxide.

2
Inlet temperature & pressure: 808 C, 32kg/cm
51
2
Outlet temperature & pressure: 940 C, 30.9kg/cm

The process gas from the primary reformer at about 808°C is sent to the secondary
reformer which has dome (mixing chamber) where it is mixed with atmospheric air
compressed by the process air compressor and pre-heated to 600°C in the flue gas heat
recovery section. Auto-thermal burner is used here. The auto ignition temperature of
methane and hydrogen is 538°C and 578°C respectively.

Table 6.2

Components Composition (mole %)

CH4 1.26
H2 53.76
CO 13.8
CO2 7.34
N2 24.11
Ar 0.73

Waste heat recovery


Process gas leaving the reforming section flows through the combined waste heat boiler
and steam super heater to the waste heat boiler. In the boiler saturated steam of 115
2
kg/cm is produced. In the super heater the saturated steam from steam drum is
superheated before further superheating take place in the reformer flue gas section.

The HP steam drum is common to the waste heat boiler in the front end of the ammonia
plant; the process gas is cooled to 220 C in the BFW preheated before being introduced
into the first CO converter.

Process gas is cooled to the approximately 600 C in the WHB, subsequently to the
approximate 456 C in the KS super heater and finally to approximate 350 C in the WHB.

52
6.3-8 Shift Converters
The CO conversion is performed in two steps. Copper based catalysts are used in both
reactors. The major charges of the catalysts consist is based on oxides of copper, zinc and
chromium.

1. Medium Temperature Shift Converter (MTSC)/1st Shift Converter

Catalyst composition

Table 6.3(a)

ZnO (25-35%)
CuO (15-20%)
Cr2O3 (35-50%)
ZnCrO4 (5-10%)
2. Low Temperature Shift Converter (LTSC)/2nd Shift Converter

Catalyst composition

Table 6.3(b)

ZnO (25-35%)
CuO (15-20%)
Cr2O3 (40-50%)

6.3-8.1 Moderate temperature shift converter


2
Inlet temperature and pressure: 220 C, 29.7kg/cm
Outlet temperature: 316 C Reaction:

CO + H2O ↔ CO2 + H2 (Exothermic)

The conversion of CO into CO2 takes place in the MTS converter. The process of CO to
CO2 conversion is an exothermic reaction. The catalyst in the used is CuO. The CO
entering the 1st shift converter is about 13.9% while the process gas leaving the 1st shift
converter includes
1.58% of CO.

As the process gas entering 1st shift converter includes significant amount of water so its
dew point is kept under consideration. If the water reaches its dew point it will accumulate
inside the pores of the catalyst. This water when given sufficient temperature is converted
to vapors by expanding 1600 times thus damaging the catalyst.

53
Compositions at the outlet of MTSC

Table 6.4

Components Composition (mole %)


CH4 0.89
H2 58.46
CO 1.58
CO2 17.35
N2 21.51

6.3-8.2 Low temperature shift Converter:


2
Inlet temperature and pressure: 210 C, 29kg/cm Outlet temperature and pressure:
2
219 C, 27.7kg/cm Reaction:
CO + H2O ↔ CO2 + H2
Type: Exothermic

There was a need for 2nd shift converter because equilibrium is achieved in MTSC. The
process gas coming from the MTSC is first cooled before entering LTSC which shifts the
reaction backward and helps in further conversion.

The process gas approaching LTSC restrains 1.58% of CO which is then reduced here to
about 0.35%. Same reaction takes place in LTSC as in MTSC. Outlet composition of LTS is
following:

Table 6.5

Components Composition (mole %)


CH4 0.88
H2 58.97
CO 0.35
CO2 18.36
N2 21.24

54
6.3-9 CO2 Absorber
2
Inlet temperature and pressure of process stream: 75 C, 26.9kg/cm
Inlet temperature of lean MDEA: 50 C
2
Outlet temperature and pressure of process stream: 50 C, 26.6kg/cm
The process gas from LTSC contains about 18% of CO 2 and considerable amount of
recoverable heat due to content of steam in form of latent heat of condensation which is
recovered in LP steam boiler, the MDEA re-boiler and in the Dem. Water Pre-heater.
After separation of condensate in a separator vessel the gas enters the CO 2 Absorber at about
0
75 C. The CO2 is removed from the gas through MDEA solution. Methyl-Di-Ethanol-
Amine solution composition…
1. MDEA = 45%
2. Piperazine = 5%
3. Water = 50%
MDEA sol. includes H2O because MDEA has high viscosity and boiling point. H 2O helps in
its flow and reduces its boiling point.
Piperazine acts here as an activator and increases the mass transfer rate of CO 2 from gas
phase to the liquid MDEA. Due to the use of this solution the height of stripper is reduced
and also reduces CO, CO2 in the synthesis gas.
The overall reactions taking place in the CO2 Absorber are:

+ -
R3N + H2O + CO2 ↔ R3NH + HCO3
+ - -
2R2NH + CO2 ↔ R2NH2 + R2N COO In the absorber there are two beds of large size
and large surface area provided by 2″CS rings. The lower part of the absorber is provided

with semi-lean solution containing 5.6% coming from the LP Flash Drum for CO 2

absorption. Semi-lean sol. is used because absorption is abrupt in the lower part.

The lean sol. could have been used at the lower part also for more efficient CO 2 absorption
but processing of lean sol. is difficult as compared to Semi-Lean sol.
80% of CO2 is absorbed in the lower part which reduces CO 2 volume and causes difficulty
in further absorption. That’s why top of the absorber has shorter diameter and three small
pack beds with 1″Cs as packing material. The smaller diameter at top makes the gases to
move through a reduced diameter thus increasing amount of CO 2 per unit area. This
method is known as “scrubbing”. Top section is also provided with Lean sol. (0.3% CO 2)
from the stripper having higher absorption capacity than Semi-Lean sol.
There are 3 bubble cap trays in the top which are fed with approximately 650 kg/hr. of boiler
feed water to prevent losses of scrubbing sol. by entrainment in the purified gas.
The Rich solution (7.1% CO2) is then to be moved to flash drum. On the way to flash drum
the pressure of the sol. is to be reduced so a turbine is installed in the way which reduced
its pressure and also generates power and serves as a driver for main pump. This pump
shares 40% of its load with the turbine.

55
Flash Drums:
There are two Flash Drums used here…

1. HP Flash Drum
2. LP Flash Drum

1. HP Flash Drum
Flash drums carry out the flashing phenomenon.
The phenomenon of evaporation of a liquid due to significant pressure drop is known a
“Flashing”.
2
The sudden decrease in pressure to 5.6kg/cm causes flashing of the rich sol.
The HP Flash Drum includes 2″SS and 2″CS rings as packing material and two bubble cap
trays for efficient CO2 separation.
Most of the inert is removed from the sol. and is sent to LP Flash Drum. The flashed gases
containing CO2 to about 71% is sent to the recycle gas separator after passing through
recycle gas cooler. The condensate from the separator is sent to the LP Flash drum while
the gas is compressed and is reintroduced in the CO 2 absorber.

2. LP Flash Drum
2
LP Flash Drum further reduces the pressure to about 0.3kg/cm . This high pressure drop
facilitates the evaporation of CO2. Most of the CO2 is recovered in the LP Flash Drum. The sol.
from HP Flash Drum it introduced tangentially at the top of LP Flash Drum. This produces
cyclone and helps in increase in CO2 evaporation. The LP Flash Drum also includes 2″SS and
2″CS rings as packing material and two bubble cap trays for efficient CO 2 separation.
While the CO2 obtained in LP Flash Drum is 99.8% pure and is sent to CO 2 Separator. The
condensate in the vessel is sent back to LP Flash Drum while pure CO 2 is sent to Urea
plant. The sol. obtained at the bottom of LP Flash Drum is Semi-Lean sol. Major part of this
solution is sent to the CO2 Absorber while some of it is sent to the CO2 stripper through.

6.3-10 CO2 stripper

2
Inlet temperature and pressure of solution: 102 C, 0.39kg/cm
The Semi-lean solution from the LP Flash drum is first heated in a solution heat exchanger
by means of lean sol. coming from the bottom of the stripper. CO 2 is stripped off in the
stripper through steam with temperature 97 C-113 C coming from the MDEA re-boiler by
cooling process gas. A low residual CO2 loading is achieved by using 2″SS Pall rings as
packing material. The CO2 circulation rate must be controlled otherwise it can cause
foaming or flooding.

Foaming:
Due to high circulation rate bubbles are formed which restrict stripping of CO 2. Foaming can
also deceive the level transmitters as they show higher level due to bubbles whereas liquid
level is low in reality.

56
0
The CO2 leaving the top of the stripper is saturated with water at 97 C and is sent to LP
Flash Drum. By condensation of water the temperature of the LP flash Drum is increased
which facilitates better performance.
The lean solution from the bottom of the stripper is cooled in sol. heat exchanger, in DMW
preheater, and in lean sol. cooler before it is pumped to the top of the Lean sol. pump.

6.3-11 Methanator

2
Inlet temperature and pressure: 320 C, 26.6kg/cm
Reactions: (exothermic)

CO + 3H2 ↔ CH4 + H2O

CO2 + 4H2 ↔ CH4 +2H2O

Catalyst: Nickel Based Catalyst

Shape: rings

Ni content in reduced catalyst wt% =27%

Surface area =250

Size outside diameter (mm) =5-6


0
The reduction of Pk-5 catalyst starts at 250 C ensuring a fast activation. Exceptional
0
thermo resistance (exposure up to 700 C).
Deactivation of methanator catalyst occurs due to:

1. Malfunctioning of CO2 removal system-resulting in an abnormally high CO 2


concentration or causing carryover of absorption liquid.
2. Thermal ageing.
3. Gradual poisoning by impurities in the feed gas.

Methanation is the reverse of reforming process. CO and CO 2 are converted to methane as


the oxygen in CO and CO2 is poison for Fe based catalyst used later on for NH3 synthesis.
0
For Methanation process Ni based catalyst is used. The reaction starts at about 240 C but
0
for maximum conversion reaction is taken out at 320 C. The process gas from CO2 removal
section is first heated by Gas/Gas Exchanger through process gas from the outlet of the
methanator. The process of Methanation is exothermic.
The outlet stream of methanator has CO, CO2< 10ppm.The process gas is then sent to final
gas separator after being cooled by final gas cooler.

57
6.3-12 Ammonia synthesis section
a) Ammonia Synthesis Gas Compression

The synthesis gas produced is compressed by the synthesis gas compressor. The make-up
2
gas at 135 kg/cm pressure is introduced into the synthesis loop between second cold
exchanger and second chiller where it is mixed with synthesis gas and condensed
ammonia. In second chiller final condensation of ammonia takes place, and any carbon
dioxide contained in the make-up gas are dissolved in the liquid.

The liquid ammonia is separated in a vessel which is equipped with two inter-changeable
level control valves. The uncondensed gases at -5 degree are recycled from a vessel to the
second and first cold exchanger. The gases are finally led to the recycle stage of synthesis
gas compressor.

Now Liquid ammonia contains some dissolved gases with the following composition
analysis Table 6.6

Components Composition (mole %)


CH4 0.20%
NH3 99.28%
H2 0.34%
N2 0.16%
Ar 0.02%

These gases are subsequently separated from product ammonia.


b) Catalytic Conversion of Synthesis Gas to Ammonia in S-200 Radial Flow
Converter
2
Inlet temperature and pressure: 254 C, 144kg/cm
2
Outlet temperature and pressure: 443 C, 141kg/cm
Reaction: (exothermic)

3H2 + N2 ↔ 2NH3 + Heat

The ammonia converter is a radial flow series 200 converter. For startup of the converter a
start-up heater has been installed.

The composition of the inlet stream and outlet streams in ammonia converter is as follows:

58
Table 6.7

Components Inlet composition Outlet composition


(mole % (mole %
CH4 6.69% 7.54%
NH3 4.07% 17.30%
H2 65.95% 55.26%
N2 21.98% 18.42%
Ar 1.31% 1.48%

Ammonia refrigeration

The effluent from the synthesis converter passes through the waste heat boiler where its
0
temperature is reduced to 340 C. Saturated K.S steam is produced in the heat exchanger
0
which is super-heated to 510 C. Further cooling of the converter effluent takes place in the
0
BFW pre-heater where its temperature is reduced to 290 C. After recovery of heat for steam
0
generation, the converted gas is cooled to 67 C in hot heat exchanger. Further cooling takes
st
place in the water cooler than in the first cold exchanger, from where it enters in the 1
ammonia chiller and then in the second cold exchanger. After second cold exchanger the make-
0
up gas is added and the loop is closed. Gases are cooled down to -5 C in second ammonia
chiller where most of ammonia is condensed and separated in separator.

In order not to accumulate the inert gases in the synthesis loop, a small part of the gas
stream is purged at the outlet of the second cold exchanger. The purge gas is first sent to
ammonia recovery unit and then to purge gas recovery unit for further treatment.

The liquid ammonia is de-pressurized flowing through the level control valves. The gases
released by the pressure reduction are separated in let-down vessel. The letdown gas from
this vessel is sent to the ammonia recovery unit and the purge gas recovery unit for further
treatment. The product ammonia is sent to urea plant through heater where its temperature
is raised.

c) Refrigeration cycle

The ammonia produced in ammonia synthesis converter is condensed in the water cooler,
the two cold exchangers and the two ammonia chillers. The chillers are the part of the
refrigeration cycle. The refrigeration cycle has the following main parts:

1. Evaporation
2. Compression
3. Condensation
4. Accumulation

59
The pressure in the ammonia chiller is kept constant by a pressure control valve which
regulates the speed of the refrigeration compressor. Most of the dissolved gases in the
liquid ammonia from the ammonia separator are flashed off in the letdown vessel and led to
the ammonia recovery unit. Most of the ammonia product from vessel is sent to urea unit
through heater where its temperature is raised. Part of the ammonia sent to storage enters
the refrigeration circuit where it is depressurized to nearly atmospheric pressure in the flash
vessel. The vapors of ammonia are then compressed in the compressor together with the
evaporated ammonia from the other chillers. Ammonia vapors after compressing are
condensed in the condenser and collected in the ammonia accumulator.

The dissolved gases entering the refrigeration circuit accumulate in this part of the cycle.
Then they are directed back to the chillers where they are again evaporated, compressed,
condensed and accumulated thus the cycle continues. In this way an energy saving for
refrigeration circuit is obtained.

Hydrogen recovery unit

The feed gas enters the water cooler where it is cooled. The condensed water is separated
in the vessel. The gas passes the adsorber where ammonia and water are removed down
to traces. The purified gases enter the cold box.

The adsorbers are regenerated with a part of the hydrogen product out of the cold box. It is
either warmed up in the steam heater to deactivate the adsorber bed to be regenerated or it
bypasses it to cool down the bed.

After passing the adsorber bed, the regeneration gas is cooled down in the water cooler
before it is mixed with the main hydrogen stream and leaves the plant as hydrogen product.

In the cold box, the feed gas is cooled down in exchanger against cold separation products.
Argon and methane are part of nitrogen condenses and are separated in the vessel.

The gas phase, hydrogen with product purity, is expanded to product pressure, is warmed
up in exchanger and leaves the cold box.
The liquid which is a mixture of hydrogen, nitrogen, argon and methane is expanded to fuel
gas pressure then it is vaporized and warmed up in the exchanger and leaves the plant as
fuel gas.

NH3Recovery Unit

The purge stream from the NH 3 Synthesis loop is introduced in the NH 3 Recovery Unit.
Purge stream includes about 7% of NH3 which is to be recovered.
This Unit comprises of:
1. Two absorbers
2. One Stripper

60
Absorbers

2
1st Absorber includes absorption at higher pressure i.e. 90kg/cm than the 2nd Absorber.
Valve and orifice are used for pressure drop before the 1st Absorber. The Absorber has two
packed beds with pall rings are present for maximum absorption.
Demineralized water is introduced in the absorber to absorb NH 3 while washed gases with
NH3 as low as 0.08% leaves the absorber.
2nd Absorber absorbs NH3 present in the off-gases coming from the synthesis loop. Again
two packing beds with pall rings are used for efficient absorption.
After 2nd Absorber only 0.04% NH 3 remains. If more concentrated NH 3 is being produced
here than H2 Recovery section can handle then this NH3 is sent to burners in E-4601.

Stripper

Both the solutions from 1st and 2nd Absorbers are mixed together before they are sent to
the stripper.
Level Control Valve is also used here for pressure drop of sol. from the 1st absorber for
mixing with sol. from 2nd absorber.
2 2
The pressure is reduced from 90kg/cm to 22kg/cm . The sol. from the 2nd absorber is
pumped and is sent to level control valve where mixing of the two sol. takes place.
Then the sol. is introduced in the stripper with 20 valve trays. Rich sol. is introduced at 10,
13 number trays.
Water is sent to re-boiler from the stripper bottom and again showered to the bottom.
The NH3 from the top is sent to the condenser while vapors from exchanger are sent to the
2nd absorber.

NH3 obtained is used as reflux in the stripper. Excess ammonia is sent to store section.

6.4 Working of ammonia converter


The converter consists of high pressure shell containing a catalyst section, a heat exchanger.
The catalyst section is cylindrical shell which inside the pressure vessel leaving annular space
between them the catalyst section contains several beds of catalyst supported on screen grid.
The catalyst is employed in the form of pellets, which is graded from top to bottom of catalyst
bed. The top bed contains pellets of smaller in size, while the bottom bed is packed with the
catalyst beds of larger size. In order to prevent any blocking of catalyst to gases, we place
bigger pallets of catalyst at bottom and smaller at the top in the converter.

To maintain the catalyst, at optimum temperature for maximum yield of ammonia cold feed gas
quench is injected before each catalyst bed, since formation of NH 3 is an exothermic reaction
and if N2 and H2 stream is not cooled down, then material of construction of converter will
decompose ammonia back to nitrogen and hydrogen and we will not achieve maximum yield of
NH3, therefor we cooled down catalyst bed by cold feed gas by quench. In the catalyst bed the
temperature gradient is flattered in succeeding bed it means that temperature difference
between the incoming gas and the outgoing unconverted from the catalyst bed decreased from
top to bottom of the catalyst bed. The bed sizes are also therefor graduated and the largest
beds of catalyst are made at the bottom while the maximum reaction between the N 2 and H2
takes place it would yield maximum conversion of N 2 and H2 into NH3, so we
61
use minimum quantity of catalyst at the top. Beneath the catalyst section there is heat
exchanger. The quench point permits the introduction of feed gas without preheating and
provides temperature control to the catalyst bed the feed gas enters between the pressure
shell and walls of catalyst section. It cools the shell in other words gas gets heat and its
temperature will increase.it enters the exchanger at the bottom of the converter and is
further heated up against effluent hot gas by circulating around the tubes of heat
exchanger. Some feed gas is introduced directly to the top of first bed where it heats the
preheated gas rising through the annular space of catalyst chamber at a temperature of
370 C to 425 C. N2 and H2 are converted into NH3 as the gaseous mixture continues its
journey downward to catalyst bed.

Since the catalyst used being doubly promoted the conversion of N 2 and H2 ranges
between 1314%. The mixture of unreacted N 2 and H2 and the NH3 formed leaves at the
bottom of the converter, it is then sent to heat exchanger so as to heat the incoming N 2 and
H2 from the ammonia refrigeration section. From the heat exchanger the mixture is led to
nd
2 stage compression and then to a series of coolers to cool down the gaseous mixture to
about -24 C. The gaseous mixture at -24 C passes on to NH3 refrigeration separator, so as
to remove NH3 formed. The boiling point of NH 3 is -33.4 C, which differs from H2 and N2,
thus ammonia would be liquefied and gaseous mixture leaving the ammonia refrigeration
separation would comprises of N2 and H2.

6.5 Factors influencing the converter reaction


The synthesis reaction which is promoted by the catalyst may be illustrated by the following
reaction

N2 + 3H2 ↔ NH3

The equilibrium point for this reaction is such that, at the proposed operating conditions, the
ammonia content of the reactor effluent will be about 12 mole percent. The unconverted
gases are recycled back through the reactor to get the ultimate production. The factors that
affect the converter reactions are:

1. Temperature
2. Pressure
3. Space velocity
4. Nitrogen/hydrogen ratio
5. Inert gases
6. Synthesis gas rate

1) Temperature

The effect of change in temperature on the ammonia synthesis reaction is double one, as it
affects both equilibrium percentages and reaction rate. As the synthesis reaction is exothermic,
a rise in temperature lowers the equilibrium percentage of ammonia and at the same time
accelerates the reaction. This means that under conditions far from equilibrium, temperature
rise will lead to higher conversion, while on the other hand for a synthesis system

62
giving a conversion near the equilibrium percentage a rise in temperature will lead to a
lower conversion.

Table 6.8

Equilibrium in percentage of ammonia

Pressure, KPa
Temperature
i 10,133 20,265 30,398 40,350
Using 0% ine rt

633 35.10 49.62 58.91 65.72

713 17.92 29.46 38.18 45.26

793 8.32 16.13 22.48 28.14

Using 10% in ert

633 28.63 40.53 48.14 53.70

713 14.60 24.06 31.21 37.02

793 7.18 13.16 18.38 23.04

Efficiency always varies directly with temperature when catalyst deterioration is not taken
into account. Conversion efficiency is defined as the ratio of the actual percent ammonia in
the converted gas to that theoretically possible under the conditions in question.
2) Pressure
As the synthesis of ammonia involve a decrease in volume (decrease in the number of the
molecules), the equilibrium percentage of the ammonia will increase with pressure. At the
same time the reaction rate is accelerated by increasing the pressure; hence the
conversion will improve with higher pressure.

3) Space velocity
At higher process gas rate the synthesis reaction has less time to operate and does not
produce as high a concentration of ammonia in the converter effluent as is produced when the
gas is moving through more slowly. However in the reduction in the yield is for less than
proportional to the percent increase in space velocity. The increased production of ammonia

63
due to greater amount of gas put through the reaction zone, more than offsets the tendency
toward decreased production due to less complete reaction (less residence time).
Therefore, at normal or less normal throughputs, and increase in the gas through the
converter will give increased production. The usual method of changing the space velocity
is by altering the recycle rate. With more circulation the temperature will tend to decrease in
the converter belt due to less conversion per pass pressure will tend to drop because of
more total production of ammonia.

4) Nitrogen/hydrogen ratio
The fresh synthesis gas feed (excluding recycle) to the synthesis section should usually
have hydrogen to nitrogen ratio about 3 to 1. This is the case because of combining of
hydrogen with nitrogen for ammonia is in the ratio of 3 to 1. However, it should be
recognized that the hydrogen to nitrogen ratio within the ammonia converter can be other
than 3 to 1. It has been found maximum conversion percentage obtain below 3 to 1 ratio in
the converter. The ratio in the fresh feed gas may be altered slightly from 3 to 1 to obtain
the optimum ratio in the combine gas feed to converters. 5) Inert gases

A continuous bleed of gas will be maintained from the recycle compressor section header to the
purge gas system. This purge stream is required to control the concentration of methane and
other inert gases which would otherwise built up in the synthesis circuit, resulting in the lower
conversion and reduce production capacity. 6) Synthesis gas rate

Increase in the synthesis gas rate alone producing more ammonia and has these effect
upon the con dictions discussed above.

1. The system pressure will increase


2. The catalyst bed temperature will increase
3. The inert gas content will rise
4. The H2:N2 ratio may change.

Conversely, decreasing the synthesis gas rate will have the reverse effects.

6.6 Role of catalyst in ammonia convertor


The catalyst role is important in the reaction because reaction to form ammonia is very
slow. To avoid problem we add two type of promoters, one is amphoteric oxide (Al, Zr and
Si oxide) and second type is alkaline oxide (Ca, K, Na oxide).

Using doubly promoted catalyst the reaction between N 2 and H2 leading to formation of NH 3 is
very slow so to make the system economical use of suitable catalyst is made to speed up the
reaction. Fe is found to offer a fair solution to this problem. Iron can be promoted by the addition
of 3% aluminum and 1% K2O. These promoters prevent the catalyst from getting centered.
Many reactions are known which occur on reacting constituents combining with the catalyst to
form an intermediate compound capable of reacting of second reactant and finally from the
product and regenerate the catalyst. Iron seems to be most suitable catalyst for the synthesis of
ammonia from hydrogen and nitrogen. However it loses its activity at 500 C, so to maintain the
activity of catalyst it is promoted by the amphoteric oxides of Al, Zr, Si and

64
alkaline oxides such as K2O. The percentage conversion of N2 and H2 using doubly
promoted catalyst i.e. amphoteric and alkaline oxide at 100 atm with a space velocity of
2
5000 ft /hr. and 450 C is 13% to 14%. If the singly promoted catalyst is employed under the
same condition, the percentage conversion is decreased to 8-9%. If the unprompted iron is
employed under the same condition of temperature and pressure and space velocity the
percentage conversion ranges from 3-4%.

The catalyst is made by melting iron oxide with the promoted and deposited over the
surface of supporting material. The catalyst losses its efficiency if the promoter contains the
impurity of copper, phosphorus, asphalt and sulfur. Carbon monoxide reduces the efficiency
of iron carbonyl which poisons the catalyst. The mechanism of formation of ammonia from
nitrogen and hydrogen using iron as catalyst is as follow:

N2 + 2Fe ↔ 2Fe-N adsorbed

H2 + 2Fe ↔ 2Fe-H adsorbed

N adsorbed + H adsorbed ↔ NH adsorbed

NH adsorbed + H adsorbed ↔ NH2 adsorbed

NH2 adsorbed + H adsorbed ↔ NH3 adsorbed

NH3 adsorbed ↔ NH3 + Catalyst

The catalyst activity will decrease slowly during normal operation of the catalyst life time,
which will normally in the range of 5 to 10 years is influenced by the actual process
conditions notably the temperature in the catalyst bed and the concentration of the catalyst
poisons in the synthesis at the converter inlet.
Although the catalyst can be used at temperature up to 540 C to 550 C, it should be noted
that the lowest the catalyst are in operation, the slower will be the decrease in the catalyst
activity and accordingly the catalyst life time will be prolonged.

6.6-2 Catalyst poisons


Compound which are capable of catalyst activity and / or life, all called poisons, such
substances normally form more or less stable compound with the active material the
catalyst. These are permanent poisons lasting irreversible lowering of catalyst activity. They
form stable surface compound with the active part of catalyst. Other poisons may cause
only temporary decrease in catalyst activity; the initial effectiveness is restored in relatively
short time after removal of poison compound of the gas.

The most important group of poison of ammonia catalyst is oxygen compounds. These
cannot be classified as temporary poisons neither are they permanent poison. When an
oxygen compound such as carbon monoxide is present in the small quantities in the
synthesis gas, some active areas of catalyst combined with oxygen thus reducing catalyst
activity. When the oxygen compound is removed from the synthesis gas, the catalyst again
is fully reduced, but all the regenerated centers do not revert to initial state or regain the
initial activity, so the oxygen compound cause a strong temporary and a small permanent in
65
catalyst activity. The usual oxygen compounds which poison the catalyst are water vapor,
carbon monoxide, carbon dioxide, and molecular oxygen. Other significant poisons are
hydrogen sulfide (permanent) and oil spray deposit which is not real poison as this term is
used here, but which are capable of lowering the activity of catalyst by clogging the surface.

6.6-3 Catalyst mechanical strength


The synthesis mechanically strong; however it should not expose to excessive abuse. Mal
operation may cause very rapid temperature fluctuation, resulting catalyst breakage. During
the reduction period any fast temperature changes should be carefully avoided during this
interval catalyst thought to be particularly sensitive to mechanical crushing and quick
temperature variation.

66
Chapter # 7

INSTRUMENTATION

&

PROCESS CONTROL

67
INTRODUCTION
An instrument is a device that measures and/or regulates process variables such as flow,
temperature, level, or pressure. Instruments include many varied contrivances which can be
as simple as valves and transmitters, and as complex as analyzers. Instruments often
comprise control systems of varied processes such as refineries, factories, and vehicles.
The control of processes is one of the main branches of applied instrumentation.
Instrumentation can also refer to handheld devices that measure some desired variable and
with the help of control loop we able to control the desired variable value into acceptable
limits. Basically process control has three main incentives.

1. Suppressing the influence of external disturbances.


2. Ensuring the stability of a chemical process.
3. Optimizing the performance of a chemical process.

These are the main incentives of process control. Process control is the main thing any
process plant because without control, once disturbance comes into the system. The whole
plant will be shut down and production will be stop.

7.1 OBJECTIVES OF INSTRUMENTATION


There are few objectives which are given below:

1. Safe plant operation


2. Production rate.
3. Product quality.
4. Cost.

68
7.2 MAIN PROCESS VARIABLES
The main process variables are as follows:

1. Pressure
2. Temperature
3. Level
4. Flow
5. Concentration

7.3 LOCATION OF MEASUREMENT DISPLAYS


The measurement is displayed for observation by plant personnel. Typically, the display
uses analog principles, which means that the display presents the measurement as a
position in a graphical format, which could, for example, be the height of a slide bar or the
position of a pointer. Often, the value is displayed as a line on a trend plot that provides the
values for some time in the past. In addition, the measurement can be displayed as a digital
number to provide more accuracy for calibration. Finally, measurements that are
transmitted to a digital control system can be stored in a historical database for later recall
and for use in calculating important parameters useful in monitoring process behavior, for
example, reactor yields or heat transfer coefficients.

The engineer must ensure that the measurements are displayed where needed by personnel.
Several common approaches are briefly summarized in the following.

7.3.1 Local display


A sensor can display the measurement at the point where the sensor is located. This
information can be used by the people when monitoring or working on the equipment. A
measurement that has only local display involves the lowest cost, because the cost of
transmission and interfacing to a digital system are not required. Note that no history of
these measurements is available unless people record the values periodically.

7.3.2 Local panel display


Some equipment is operated from a local panel, where sensors associated with a unit are
collected. This enables a person to startup, shutdown and maintain the unit locally. This must
be provided for units that require manual actions at the process during normal operation
(loading feed materials, cleaning filters, etc.) or during startup and shutdown. Usually, the
values displayed at a local panel are also displayed at a centralized control room.

69
7.3.3 Centralized control room
Many processes are operated from a centralized control room that can be located a
significant distance (e.g., hundreds of meters) from the process. The measurement must be
converted to a signal (usually electronic) for transmission and be converted to a digital
number when interfaced with the control system. A centralized control system facilitates the
analysis and control of the integrated plant.

7.3.4 Remote monitoring


In a few cases, processes can be operated without a human operator at the location. In these
situations, the measurements are transmitted by radio frequency signals to a centralized
location where a person can monitor the behavior of many plants. Typical examples are remote
oil production sites and small, safe chemical plants, such as air separation units.

7.4 CONTROL SYSTEM


A control system is a device, or set of devices to manage, command, direct or regulate the
behavior of other devices or system.

There are common classes of control systems:


 Logical control system

 Linear control system On–off control:
 Feed forward control system
 Feedback control system
 Ratio control system
 Auctioneering control system.
 Split range control system
 Cascade control system

70
7.5 CONTROL LOOP
7.5.1 Control loop on high temperature shift converter:

TC TT
S e t p o in t

FC FT

S tr e a m 1

S tr e a m 2

7.5.2 Control loop on heat exchanger:

SP HTS
Feed+

P-8

Gass Steam

Steam

71
7.5.3 Control loop on ammonia converter:

H2

FT

I/P FC

Ammonia reactor
RS
RATIO (NH3)
STATION
I/P FC

FT

N2

AMMONIA REACTOR

72
Chapter # 8

MATERIAL BALANCE

73
Material Balance for Ammonia Plant

We have taken F.F.C plant-2 as a standard.

1100 MTPD ammonia requires= 41724Nmc/hr N.G.


1 MTPD ammonia requires = 41724/1100

1150 MTPD ammonia required = (41724/1100)*1150 = 43620 Nmc/hr.

43620 Nmc kgmol

hr 22.414 Nmc

= 1946.129 kgmol/hr = 46707 kgmol/day.

Steam Required

Steam: Carbon = 3.0


S/C = 3.0

Molecular weight of Natural Gas:

Component Mol % Mol.wt Wt

Methane 69.48 16 11.11

Hydrogen 4.3 2 0.086

Carbon dioxide 8 44 3.52

Nitrogen 18.50 28 5.18

Molecular weight of natural gas coming from Marri Gas Field = 19.896 kg N.G

1 kgmol N.G 12 kg C

19.896 kg N.G 1 kgmol N.G


=0.71 kg C/kg N.G

74
2.12 kg S 1 kgmol S 46707kgmol N.G 19.896 kg N.G

1 kg N.G 18 kg S Day 1 kgmol N.G


S= 3.0*0.71

S= 2.12 kg of steam/kg of N.G

= 109448.8 kgmol steam/day

= 4560 kgmol/hr.

Air required in secondary reformer

For the capacity of 1100 MTPD air required = 35204 Nmc/hr

Thus,

For the capacity of 1150 MTPD ammonia air required will be = (35204/1100)*1150

= 36804.18 Nmc/hr

= (36804.18/22.414)

= 1642.017 kgmol/hr.

75
8.1 PRIMARY REFORMER

Basis : 1 hr operation W = 3414.654 kgmol/hr

F = 1946.129 kgmol/hr PRIMARY P = 4801.473 kgmol/hr


REFORMER
CH4 = 69.48% CH 4 = 12.5%

H2 = 4.3% H2 = 60 %

CO2 = 8% Steam =4560kgmol/hr CO = 10.5


%
N2 = 18.8 % CO2=
9.93 %
N2 = 7.62
%
Applying elemental balance on nitrogen:

0.188*1946.129 = (0.0762) P

P = 365.87/0.0762 P = 4801.473 kgmol/hr.

Reactions:

CH4 + H2O ↔ CO + 3H2

CH4 + 2H2O ↔ CO + 4H2

CO + H2O ↔ CO 2 + H2

CO at outlet = 4801.473*0.105 = 504.154 kgmol/hr

CO2 at outlet = 4801.473*0.0993 = 476.786 kgmol/hr.

CO2 at inlet = 1946.129*0.08 = 155.69 kgmol/hr

76
CO2 produced in reaction = outlet – inlet

CO2 produced in reaction = 321.096 kgmol/hr

1 mole of steam produces 1 mole of CO

Steam consumed by CO = 504.154 kgmol/hr

2 moles of steam produces 1 mole of CO2

Steam consumed by CO2 = 642.192 kgmol/hr

Steam consumed in reformer = 1146.346 kgmol/hr

Steam out = steam in – steam consumed


Steam out = 3413.654 kgmol/hr.

8.2 SECONDARY REFORMER

Basis: 1 hr operation

Water = 3615 -929 kgmol/hr

F = 4801.473 kgmol/hr SECONDARY P = 6829.72 kgmol/hr

REFORMER

CH4 = 11.44% CH4 = 1.26%

H2 = 60% H2 = 53.76 %

CO2 = 9.93% Air = 1642.017 kgmol/hr CO = 13.8 %

N2 = 7.62% CO2 = 7.34 %

CO = 10.5% N2 = 24.11 %

Applying elemental balance on N2 :

77
0.0762*4801.473 = 0.2411 * P

P = 6829.72 kgmol/hr

For calculation of Water :

CH4 + 2O2 ↔ CO 2 + 2H2O

CH4 + 2H2O ↔ CO + 4H 2

CO + H2O ↔ CO2 + H2
CO at inlet = 4801.473*0.105 = 504.15 kgmol/hr

CO at outlet = 6829.72*0.138 = 942.50 kgmol/hr

CO produced = outlet – inlet = 942.50 – 504.15 = 438.35 kgmol/hr

CO2 at inlet = 4801.473*0.0993 = 476.79 kgmol/hr

CO2 at outlet = 6829.72*0.0734 = 501.301 kgmol/hr

CO2 produced = outlet – inlet = 24.511 kgmol/hr

From reaction, 1 mole of steam produces 1 mole of CO

Steam consumed in production of CO = 438.35 kgmol/hr

From reaction, 2 moles of steam produces 1 mole of CO 2

Steam consumed in production of CO2 = 49.022 kgmol/hr

Steam consumed in reaction = 438.35 + 49.022 = 487.372 kgmol/hr Combustion reaction at

the top is as follows

2H2 + O2 ↔ 2H O
2

O2 required for complete combustion = 1642.017*0.12 = 344.82 kgmol/hr

78
1 mole of O2 gives 2 moles of steam = 344.82*2 = 689.65 kgmol/hr

Steam from primary reformer + Steam produced in sec. reformer = 3413.654 + 689.65

= 4103.30 kgmol/hr

Steam leaving secondary reformer = 4103.30 – 487.372 = 3615.929 kgmol/hr

8.3 MEDIUM TEMPERATURE SHIFT CONVERTER

Basis : 1 hr operation

Water = 2787.526 kgmol/hr

F = 6829.72 kgmol/hr P = 7664 kgmol/hr Medium


Temperature
Shift Converter

CH4 = 1.26% CH4 =


0.89%
H2 = 58.46
H2 = 53.76%
%
CO =
CO2 = 7.34%
1.58%
CO2 =
N2 = 24.11%
17.35%
N2 =
CO = 13.8%
21.51%
Ar = 0.21
Ar = 0.23% %

Applying elemental balance on N2:

0.2414*6829.72 = 0.2151*P

P = 1648.69/0.2151

79
P = 7664 kgmol/hr

Steam calculation at inlet:

CO + H2O ↔ CO 2 + H2

CO2 at inlet = 0.0734*6829.72 = 501.301kgmol/hr

CO2 at outlet = 0.1735*7664 = 1329.704 kgmol/hr

CO2 produced = outlet – inlet

CO2 produced = 1329.704 – 501.301 = 828.403 kgmol/hr

From reaction, 1 mole of steam produces 1 mole of CO 2

Steam consumed in reactor = 828.403 kgmol/hr


Steam at outlet = 3615.929 – 828.403 = 2787.526 kgmol/hr.

8.4 LOW TEMPERATURE SHIFT CONVERTER

Basis : 1 hr operation

Water = 2692.236 kgmol/hr

F = 7664 kgmol/hr Low Temperature P = 7761.423 kgmol/hr


Shift Converter

CH4 = 0.89% CH4 = 0.88%

H2 = 58.46% H2 = 58.97
%
CO =
CO2 = 17.35%
0.35%
CO2 =
N2 = 21.51%
18.36%
80
N2 =
CO = 1.58%
21.24%
Ar = 0.21% Ar = %

Applying elemental balance on Nitrogen:

0.2151*7664 = 0.2124*P

P = 1648.5264/0.2124

P= 7761.423 kgmol/hr Shift reaction:

CO + H2O ↔ CO 2 + H2

CO2 at inlet = 0.1735*7664 = 1329.704 kgmol/hr


CO2 at outlet = 0.1836*7761.423 = 1429.99 kgmol/hr.

CO2 produced = outlet – inlet

CO2 produced = 1429.99 – 1329.704 = 95.29 kgmol/hr

From reaction, 1 mole of steam produces 1 mole of CO 2

Steam consumed = 95.29 kgmol/hr

Steam at outlet = 2787.526 – 95.29 = 2692.236 kgmol/hr.

8.5 ABSORBER

Basis : 1 hr operation

F = 7761.423 kgmol/hr P = 6335.61 kgmol/hr


ABSORBER
CH4 = 0.88% CH4=

1.08%
Applying elemental balance on N2:
81
H2 = 58.97% H2 =
72.16 %
CO2 = 18.36% CO =
0.42%
N2 = 21.24% CO2 =
0.05%
CO = 0.35% N2 =
26.02%
Ar = % Ar = %
0.2124*7761.423 = 0.2602*P
1648.53 = 0.2602*P

P = 1648.53/0.2602
P = 6335.61kgmol/hr

CO2 at inlet = 7761.423*0.1836 = 1424.997kgmol/hr

CO2 at outlet = 0.0005*6335.61 = 3.168 kgmol/hr

Amount of CO2 absorbed = outlet – inlet

Amount of CO2 absorbed = 1424.997 – 3.168 = 1421.83 kgmol/hr

8.6 METHANATOR

Basis : 1 hr operation

W = 32.95 kgmol/hr

F = 6335.61 kgmol/hr P = 6244.41 kgmol/hr


METHANATOR
CH4 = 1.08% CH 4 = 1.58 %

H2 = 72.16% H 2=

71.77 %

82
N2 =
CO2 = 0.05%
26.4%
N2 = 26.02% Ar = %

CO = 0.42%

Ar = %

Applying elemental balance on N2:

0.2602*6335.61 = 0.2641*P

P = 1648.525/0.2641
P = 6244.41 kgmol/hr.

For steam calculation:

CO + 3H2 ↔ CH 4 + H2O

CO2 + 4H2 ↔ CH 4 + 2H2O

CO at inlet = 0.0042*6335.61 = 26.61 kgmol/hr

CO2 at inlet = 0.0005*6335.61 = 3.168 kgmol/hr

From reaction, 1 mole of CO produces 1 mole of H2O

H2O produced from CO = 26.61kgmol/hr

From reaction, 1 mole of CO2 produces 2 moles of H2O

H2O produced from CO2 = 6.336 kgmol/hr

Total water produced = 6.336 + 26.61 = 32.95 kgmol/hr

83
8.7 AMMONIA SYNTHESIS LOOP
Applying overall material balance on the compressor:

A1 + A 3 A2 + A 4

6244.41 + 24956.11 = 6665.18 + A4

Thus,

A4 = 24535.34 kgmol/hr
Ammonia Converter

Applying Elemental Balance on Argon:

0.0131* 24535.34 = 0.0148* A5

A5 = 321.4129/0.0148

A5 = 21717.09 kmol/hr

Amount of ammonia at outlet = 21717.09*0.1730 = 3757.05 kgmol/hr

Ammonia at inlet = 0.0405*24535.3 = 993.67 kgmol/hr

Ammonia produced = outlet – inlet

Ammonia produced = 3757.05 – 993.67 = 2763.37 kgmol/hr

2763.37 kgmol 1 MT NH 3 17 kg NH3 24 hr

Hr 1000 kg NH3 1 kgmol 1 day

= 1127.455 MTPD

84
Chapter # 9

ENERGY BALANCE

85
ENERGY BALANCE
9.1 PRIMARY REFORMER

Amount of reactant = 1946.129 Kg


mol/hr
Amount of product = 4801.73 Kg
mol/hr
Amount of steam entering = 4560 Kg mol/hr
Temperature of entering stream = 600 °C = 873 K

Temperature of leaving stream = 808 °C =


1081.15 K
Datum temperature = 25 °C = 298 K

HEAT IN BY REACTANT

(H1) HEAT IN BY H2

Now,

4 5 2 10 3
Cp for H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Now mean temperature = (873 + 289)/2 = 585 K


86
2 5 2
Cp for H2 at mean temperature = 27.143 + 92.738x10ˉ (585) – 1.381x10ˉ (585) +
10 3
76.451x10ˉ (585)

Cp for H2 at mean temperature = 29.73 KJ/kmol K m = 0.043x1946.129 = 83.68 Kmol/hr

H1 = m.Cp.∆T

H1 = (83.68) x (29.37) x (873 – 298)

H1 = 1413166.92 KJ/hr = 1413.166 MJ/hr

(H2) HEAT IN BY N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2 9
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (585) – 0.073x10ˉ (585) – 0.313x10ˉ
3 11 4
(585) + 0.188x10ˉ (585)
Cp for N2 at mean temperature = 1.89 KJ/hr m = 0.185x1946.129 = 360.03 Kmol/hr

H2 = m.Cp.∆T

H2 = 360.03 x 1.89 x (873 – 298)

H2 = 391263.60 KJ/hr

H2 = 391.26 MJ/hr

(H3) HEAT IN BY CO2

5 2
Cp for CO2 = 0.244 + 0.000064 T + 0.46x10ˉ T

5 2
Cp for CO2 at mean temperature = 0.244 + 0.000064(585) + 0.46x10ˉ (585) Cp for CO2 at

mean temperature = 1.86 KJ/kmol K m = 0.08x1946.129 = 155.69 Kmol/hr

Now

H3 = 155.69 x 1.86 x (873 – 298)

H3 = 166510.45 KJ/hr = 166.510 MJ/hr

87
(H4) HEAT IN BY Ar

Cp for Ar = 0.062358 KJ/kmol K m = 0.0002 x 1946.129 = 0.3892 Kmol/hr

Now

H4 = m.Cp.∆T

H4 = 0.3892 x 0.062358 x (873 – 298)

H4 = 13.9809 KJ/hr = 0.01398 MJ/hr

(H5) HEAT IN BY CH4

2 4 2 7 3 11 4
Cp for CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T Cp for CH4
2 4 2 7 3
at mean temperature = 31.137 – 3.56x10ˉ (585) +1.71x10ˉ (585) – 1.36x10ˉ (585) +
11 4
3.50x10ˉ (585) Cp for CH4 at mean temperature = 45.63 KJ/kmol K m = 0.0648 x
1946.129 m = 1352.170 Kmol/hr

Now

H5 = m.Cp.∆T

H5 = 1335.170 x 45.63 x (873 – 298)

H5 = 34987398.75 KJ/hr = 34987.398 MJ/hr

(H6) HEAT IN BY C2H6

2 5 2 10 3
Cp for C2H6 = 5.408 + 17.811x10ˉ T – 6.938x10ˉ T + 87.127x10ˉ T

2 5 2
Cp for C2H6 at mean temperature = 5.408 + 17.811x10ˉ (585) – 6.938x10ˉ (585) +
10 3
87.127x10ˉ (585)

Cp for C2H6 at mean temperature = 87.68 KJ/kmol K m = 0.0019 x 1946.129 m = 3.6976 Now

H6 = m.Cp.∆T

H6 = 3.6976 x 87.68 x (873 – 298)

H6 = 186418.20 KJ/hr = 186.418 MJ/hr

88
HEAT IN BY STEAM

Latent heat of steam at 3.6 MPa = 1741.82 KJ/Kg


4560 Kg mol 18 Kg

Steam flow rate = hr 1 Kg mol

m = 82080 Kmol/hr

Specific enthalpy at 873K and 3.6 MPa = h 2 = 4319.2 KJ/Kg

Specific enthalpy at 519K and 3.6 MPa = h 1 = 2802.4 KJ/Kg

4 6 2 9 3
Cp of water = 32.243 + 19.23x10ˉ T + 10.555x10ˉ T – 3.59x10ˉ T
4 6 2
Cp of water at mean temperature = 32.243 + 19.23x10ˉ (585) + 10.555x10ˉ (585) –
9
3.59x10ˉ
3
(585)

Cp of water at mean temperature = 36.26 KJ/Kg K

Now

H7 = m.(ƛ + h2 – h1) + Cp.∆T

H7 = 82080(1741.82 + (4319.2 – 2802.4) + 36.26 (519 – 298)

H7 = 925211505.6 KJ/hr = 925211.505 MJ/hr

HEAT OUT BY PRODUCT

(H8) HEAT OUT BY H2

Now,

4 5 2 10 3
Cp for H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Mean temperature = (1081.15+298)/2 = 689.5K

89
² 5 2
Cp of H2 at mean temperature = 27.143 + 92.738x10ˉ (689.5) – 1.381x10ˉ (689.5) +
10 3
76.451x10ˉ (689.5)

Cp of H2 at mean temperature = 29.56 KJ/kmol K m = 0.6 x 4801.473

m = 2880.88 kmol/hr

H8 = m.Cp.∆T

H8 = 2880.88 x 29.56 x (1081 – 295)

H8 = 66679350.43 KJ/hr = 66679.350 MJ/hr

(H9) HEAT OUT BY N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (689.5) – 0.073x10ˉ (689.5) –
9 3 11 4
0.313x10ˉ (689.5) + 0.188x10ˉ (689.5)

Cp for N2 at mean temperature = 37.09 KJ/kmol K m = 0.0762 x 4801.473 m = 365.87 kmol/hr

Now,

H9 = m.Cp.∆T

H9 = 365.87 x 37.09 x (1801 – 298)

H9 = 10625402.63 KJ/hr

H9 = 10625.402 MJ/hr

(H10) HEAT OUT BY CO2

5 2
Cp of CO2 = = 0.244 + 0.000064 T + 0.46x10ˉ T

5 2
Cp for CO2 at mean temperature = 0.244 + 0.000064(689.5) + 0.46x10ˉ (689.5) Cp for CO2

at mean temperature = 2.475 KJ/kmol K m = 0.0993 x 4801.473 m = 476.48 kmol/hr H 10 =

m.Cp.∆T

H10 = 476.48 x 2.475 x (1081 – 298)


90
H10 = 923976.03 KJ/hr

H10 = 923.976 MJ/hr

(H11) HEAT OUT BY CH4

2 4 2 7 3 11 4
Cp of CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (689.5) +1.71x10ˉ (689.5) –
7 3 11 4
1.36x10ˉ (689.5) + 3.50x10ˉ (689.5) Cp for CH4 at mean temperature = 51.22 KJ/kmol
K m = 0.1144 x 4801.473 m = 549.28 kmol/hr

H11 = m.Cp.∆T

H11 = 549.28 x 51.22 x (1081 – 298)

H11 = 22029017.21 KJ/hr

H11 = 22029.01 MJ/hr

(H12) HEAT OUT BY CO

2 6 2 8 3
Cp of CO = 36.869 – 1.285x10ˉ T + 27.892x10ˉ T – 1.272x10ˉ T

2 6 2
Cp of CO at mean temperature = 36.869 – 1.285x10ˉ (698.5) + 27.892x10ˉ (689.5) –
8 3
1.272x10ˉ (689.5)

Cp of CO at mean temperature = 37.09 KJ/kmol K m = 0.105 x 4801.473 m = 504.145 kmol/hr

H12 = m.Cp.∆T

H12 = 504.145 x 37.09 x (1081 – 298)


H12 = 14641373.27 KJ/hr

H12 = 14641.373 MJ/hr

So

Total heat in by reactants = Ha = H1+H2+H3+H4+H5+H6+H7

Ha = 1413.166 + 391.26 + 166.510 + 0.013982 + 34987.398 + 186.418 + 925211.505


91
Ha = 962356.26 MJ/hr

Total heat out by products = Hb = H8+H9+H10+H11+H12

Hb = 66679.35 + 10625.402 + 923.97 + 22029.01 + 14641.37

Hb = 114899.102 MJ/hr

REACTIONS IN PRIMARY REFORMER

CH4 + H2O ↔ CO +3H2 (rxn:1)

CH4 +H2O ↔ CO2 +4H2 (rxn:2)

For Reaction 1:

Heat of formation of CH4 =∆Hf = -74.84 KJ/gmol = -74840 KJ/Kgmol

Heat of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol

Heat of formation of CO = ∆Hf = -110.52 KJ/gmol = -110520KJ/Kgmol

Heat of formation of H2 = 0

Heat of reaction of reaction 1 = (heat of formation of products – heat of formation of reactants)

∆Ĥrxn1 = (-110.52) – {(-74.84) + (-241.862)}

∆Ĥrxn1 = 206.24 KJ/gmol

For Reaction 2:

Heat of formation of CH4 = ∆Hf = -74.84 KJ/gmol = -74840 KJ/Kgmol

Heat of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol


Heat of formation of CO2 = ∆Hf = -393.519 KJ/gmol = -393510 KJ/Kgmol

Heat of formation of H2 = 0

∆Ĥrxn2 = [(-393510) – {(-74840) + 2(-241826)}]

∆Ĥrxn2 = 165.09 KJ/gmol

So

92
∆Ĥrxn = ∆Ĥrxn1 +∆Ĥrxn²

∆Ĥrxn = 371.33 KJ/gmol = 37133 KJ/Kgmol

Now

Qs = 4801.473 x 371330

Qs = 1782930.9 KJ/hr

Qs = 1728.9309 MJ/hr

Qp = H2 – H1 – Qs

Qp = 114899.102 – 962356.26 + 1728.9309

Qp = -846328.2 MJ/hr

9.2 SECONDARY REFORMER

Amount of reactants = 4801.473 kmol/hr

Amount of products = 6829.72 kmol/hr

Amount of air entering = 1642.017 kmol/hr

Temperature of entering stream = 808 °C = 1081 K

Temperature of leaving stream = 945 °C = 1218 K

Temperature of air = 600 °C = 873 K

Datum temperature = 25 °C = 298 K


HEAT IN BY REACTANTS

(H1) HEAT IN BY H2:

Now

4 5 2 10 3
Cp of H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Mean temperature = (1081.15 + 298)/2 = 689.5K

93
2 5 2
Cp of H2 at mean temperature = 27.143 + 92.738x10ˉ (689.5) – 1.381x10ˉ (689.5) +
10 3
76.451x10ˉ (689.5)

Cp of H2 at mean temperature = 29.56 KJ/kmol K m = 0.6 x 4801.473 m = 2880.88 kmol/hr

H1 = m.Cp.∆T

H1 = 2880.88 x 29.56 x (1081 – 295) H1 = 66679350.43 KJ/hr = 66679.350 MJ/hr

(H2) HEAT IN BY N2:

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (689.5) – 0.073x10ˉ (689.5) –
9 3 11 4
0.313x10ˉ (689.5) + 0.188x10ˉ (689.5)

Cp for N2 at mean temperature = 37.09 KJ/kmol K m = 0.0762 x 4801.473 m = 365.87 kmol/hr

Now,

H2 = m.Cp.∆T

H2 = 365.87 x 37.09 x (1801 – 298)


H2 = 10625402.63 KJ/hr

H2 = 10625.402 MJ/hr

(H3) HEAT OUT BY CO2

5 2
Cp of CO2 = = 0.244 + 0.000064 T + 0.46x10ˉ T

5 2
Cp for CO2 at mean temperature = 0.244 + 0.000064(689.5) + 0.46x10ˉ (689.5) Cp for CO2

at mean temperature = 2.475 KJ/kmol K m = 0.0993 x 4801.473 m = 476.48 kmol/hr

H3 = m.Cp.∆T

H3 = 476.48 x 2.475 x (1081 – 298)


94
H3 = 923976.03 KJ/hr

H3 = 923.976 MJ/hr

(H4) HEAT OUT BY CH4

2 4 2 7 3 11 4
Cp of CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (689.5) +1.71x10ˉ (689.5) –
7 3 11 4
1.36x10ˉ (689.5) + 3.50x10ˉ (689.5) Cp for CH4 at mean temperature = 51.22 KJ/kmol
K m = 0.1144 x 4801.473 m = 549.28 kmol/hr

H4 = m.Cp.∆T

H4 = 549.28 x 51.22 x (1081 – 298)

H4 = 22029017.21 KJ/hr
H4 = 22029.01 MJ/hr

(H5) HEAT OUT BY CO

2 6 2 8 3
Cp of CO = 36.869 – 1.285x10ˉ T + 27.892x10ˉ T – 1.272x10ˉ T

2 6 2
Cp of CO at mean temperature = 36.869 – 1.285x10ˉ (698.5) + 27.892x10ˉ (689.5) –
8 3
1.272x10ˉ (689.5)

Cp of CO at mean temperature = 37.09 KJ/kmol K m = 0.105 x 4801.473 m = 504.145 kmol/hr

H5 = m.Cp.∆T

H5 = 504.145 x 37.09 x (1081 – 298)

H5 = 14641373.27 KJ/hr

H5 = 14641.373 MJ/hr

(H6) HEAT IN BY AIR

(HN2 ) Heat In By N2

3 5 2 9 3 11 ²
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T
95
3 5 2
Cp of N2 at mean temperature = 2.13 – 0.257x10ˉ (589.5) – 0.073x10ˉ (589.5) –
9 3 11 ²
0.313x10ˉ (589.5) + 0.188x10ˉ (589.5)

Cp of N2 at mean temperature = 1.9 KJ/kmol K m = 0.79 x 1642.017 m = 1297.19 K mol/hr

(HN2 ) = m.Cp.∆T

(HN2 ) = 1297.19 x 1.9 x (873 – 298)

(HN2 ) = 1417189.075 KJ/Kmol k


(HN2 ) = 1417.18 MJ/hr

(Ho2) Heat In By O2

6 6 2 3 3
Cp of O2 = 28.106 – 3.68x10ˉ T + 17.495x10ˉ T – 1.065x10ˉ T

6 6 2
Cp of O2 at mean temperature = 28.106 – 3.68x10ˉ (589.5) + 17.495x10ˉ (589.5) –
3 3
1.065x10ˉ (589.5)

Cp of O2 at mean temperature = 31.95 KJ/Kmol k m = 0.21 x 1642.017 m = 344.823 Kmol/hr

(Ho2) = m.Cp.∆T

(Ho2) = 344.823 x 31.95 x (873 – 298)

(Ho2) = 6400932.108 KJ/hr

(Ho2) = 6400.93 MJ/hr

So,

H6 = (HN2 ) + (Ho2)

H6 = 1417.18 + 6400.93

H6 = 7818.11 MJ/hr

96
HEAT OUT BY PRODUCTS
(H7) Heat out by H2:

ˉ4 5 2 10 3
Cp for H2 = 27.143 – 92.738 x 10 T + 1.381 x 10ˉ T – 76.451 x 10ˉ T

ˉ4 5 2
Cp for O2 at mean temperature= 27.143 – 92.738 x 10 (758) + 1.381 x 10ˉ (758) – 76.451
3 3
x 10ˉ (758)

Cp for H2 at mean temperature = 29.6 KJ/Kmol K m = 0.5376 x 6829.72 m = 3671.65 Kmol/hr

H7 = m.Cp.∆T

H7 = 3671.65 x 29.6 x (1218 – 298)

H7 = 99986372 KJ/hr

H7 = 99986.372 MJ/hr

(H8) Heat out by N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2 9
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (758) – 0.073x10ˉ (758) – 0.313x10ˉ
3 11 4
(758) + 0.188x10ˉ (758)

Cp for N2 at mean temperature = 2 KJ/Kmol K m = 0.2411 x 6829.72 m = 1646.64 Kmol/hr

H8 = m.Cp.∆T

H8 = 1646.64 x 2 x (1218 – 298)

H8 = 3029817.6 KJ/hr

H8 = 3019.817 MJ/hr

97
(H9) Heat out by CO
2 6 2 8 3
Cp of CO = 36.869 – 1.285x10ˉ T + 27.892x10ˉ T – 1.272x10ˉ T

2 6 2
Cp of CO at mean temperature = 36.869 – 1.285x10ˉ (758) + 27.892x10ˉ (758) –
8 3
1.272x10ˉ (758)

Cp of CO at mean temperature = 37.62 KJ/Kmol K m = 0.138 x 6829.73 m = 942.50 Kmol/hr

H9 = m.Cp.∆T

H9 = 942.5 x 37.62 x (1218 – 298)

H9 = 32620302 KJ/hr

H9 = 32620.302 MJ/hr

(H10) Heat out by CO2

5 2
Cp of CO2 = = 0.244 + 0.000064 T + 0.46x10ˉ T

5 2
Cp for CO2 at mean temperature = 0.244 + 0.000064(758) + 0.46x10ˉ (758) Cp for CO2 at

mean temperature = 2.94 KJ/kmol K m = 0.0734 x 6829.72 m = 501.30 Kmol/hr

H10 = m.Cp.∆T

H10 = 501.30 x 2.94 x (1218 – 298)

H10 = 1278976.04 KJ/hr

H10 = 1278.976 MJ/hr

(H11) Heat out by Ar

Cp for Ar = 0.062358 KJ/kmol K m = 0.0023 x 6839.72 = 15.708 kmol/hr Now

H11 = m.Cp.∆T

H11 = 15.708 x 0.062358 x (1218 – 298)

H11 = 901.157 KJ/hr


98
H11 = 0.9011 MJ/hr

(H12) Heat out by CH4

2 4 2 7 3 11 4
Cp of CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2 7
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (758) +1.71x10ˉ (758) – 1.36x10ˉ
3 11 4
(758) + 3.50x10ˉ (758) Cp for CH4 at mean temperature = 54.73 KJ/kmol K m = 0.0126
x 6829.72 m = 86.0544 kmol/hr

H12 = m.Cp.∆T

H12 = 86.0544 x 54.73 x (1218 – 298)

H12 = 4332980.35 KJ/hr

H12 = 4332.9803 MJ/hr

(Ha) Total Heat In By Reactants

Total heat in by reactants (Ha) = H1 + H2 +H3 + H4 + H5 + H6

Ha = 66478.57 + 552.902 + 14641.257 + 906.522 + 23966.987 + 7818.11

Ha = 114364.34 MJ/hr

(Hb) Total Heat Out By Products

Total heat out by products (Hb) = H7 + H8 + H9 + H10 + H11 + H12

Hb = 99986.372 + 3029.817 + 32620.30 + 1378.976 + 0.9011 +4332.98


Hb = 141349.34 MJ/hr

REACTIONS IN SECONDARY REFORMER

CH4 +2O2 ↔ CO2 +2H2O

CO + H2O ↔ CO2 + H2 CH4 +2H2O ↔CO2 +4H2

For Reaction 1:

99
Heat of formation of CH4 =∆Hf = -74.84 KJ/gmol = -74840 KJ/Kgmol

Heat of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol

Heat of formation of CO2 = ∆Hf = -393.51 KJ/gmol = -393510 KJ/Kgmol

Heat of formation of O2 = 0

Heat of reaction of reaction 1 = (heat of formation of products – heat of formation of

reactants) ∆Ĥrxn1 = [{2(-241826) + ( - 393510)} – (- 74840)] ∆Ĥ rxn1 = - 802322 KJ/gmol

For Reaction 2

Heat of formation of CO = ∆Hf = -110.52 KJ/gmol = -110520 KJ/Kgmol

Heat of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol

Heat of formation of CO2 = ∆Hf = -393.519 KJ/gmol = -393510 KJ/Kgmol

Heat of formation of H2 = 0

∆Ĥrxn2 = [(-393510) – {(-110520) + (-241826)}]

∆Ĥrxn2 = -41164 KJ/gmol

For Reaction 3

Heat of formation of CH4 = ∆Hf = -78.840 KJ/gmol = -78840 KJ/Kgmol Heat


of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol

Heat of formation of CO2 = ∆Hf = -393.519 KJ/gmol = -393510 KJ/Kgmol

Heat of formation of H2 = 0

∆Ĥrxn2 = [(-393510) – {(-74840) + 2(-241826)}]

∆Ĥrxn2 = -678504 KJ/gmol

So

100
∆Ĥrxn = ∆Ĥrxn1 + ∆Ĥrxn2 + ∆Ĥrxn3

∆Ĥrxn = -678.504 KJ/gmol = 678504 KJ/Kgmol

Now

Qs = no of moles of product x ∆Ĥrxn

Qs = 786.868 x (-678504)

Qs = -5339736917 KJ/hr

6
Qs = -5.339 x 10 MJ/hr

Qp = H2 – H1 – Qs

6
Qp = 141349.34 – 114364.34 – 5.339x10

Qp = -5312015 MJ/hr

9.3 MEDIUM TEMPERATURE SHIFT CONVERTOR

Amount of reactant = 6829.72 kgmol/hr

Amount of product = 7664 kgmol/hr

Inlet temperature = 220 C = 493 K

Outlet temperature = 316 C = 589 K

Datum temperature = 25 C = 298 K


HEAT IN BY REACTANT

(H1) Heat in by H2

-4 -5 2 -10 3
Cp for H2 = 27.143 + 92.738×10 T - 1.381×10 T + 76.451×10 T

Mean temperature=395.5 K

Cp for H2 at mean temperature= 28.2 KJ/kmol K m = 0.5376×6829.72 m = 3671.65 Kgmol/hr

101
H1 = m.Cp.∆T

H1 = 3671.65 x 28.2 x 195

H1 = 20190403.35 KJ/hr

H1 = 20190.40 MJ/hr

(H2) Heat in by N2

-3 -5 2 -9 3 -11 4
Cp for N2 = 2.13 - 0.275×10 T - 0.073×10 T - 0.313×10 T + 0.188×10 T Cp for N2 at

mean temperature = 1.94 KJ/Kmol K m = 0.2411×6829.72 m = 1646.64 kgmol/hr

H2 = m.Cp.∆T

H2 = 1646.64 x 1.94 x 195

H2 = 622925.98 KJ/hr

H2 = 622.925 MJ/hr

(H3) Heat in by CO

-2 -6 2 -8 3
Cp for CO = 36.869-1.285×10 T+27.892×10 T -1.272×10 T
Cp for CO at mean temperature = 35.4 KJ/Kmol K m = 0.138 x 6829.72 m = 942.501 kgmol/hr

H3 = m.Cp.∆T

H3 = 942.501 x 35.4 x 195

H3 = 6506086.8 KJ/hr

H3 = 6506.0868 MJ/hr

(H4) Heat in by CO2

-5 2
Cp for CO2 = 0.244+0.000064T+0.46×10 T Cp for CO2 at mean temperature = 0.99 kj/kmol

k m = 0.2411 x 6829.72 m = 501.301 kgmol/hr

H4 = m.Cp.∆T
102
H4 = 501.301 × 0.99 × 195

H4 = 96776.15 KJ/hr

H4 = 96.776 MJ/hr

(H5) Heat in by CH4

-2 -4 2 -7 3 -11 4
Cp for CH4 = 31.37-3.56×10 T+1.71×10 T -1.36×10 T +3.50×10 T Cp for CH4 at mean

temperature = 36.23 KJ/Kmol K m = 0.0126 × 6828.72 m = 86.05 Kmol/hr

H5 = m.Cp.∆T

H5 = 86.05 x 36.23 x 195


H5 = 607961.9 KJ/hr

H5 = 607.961 MJ/hr

(H6) Heat in by Ar

Cp for Ar = 0.062358 kj/kmol k m = 0.0023×6828.72 = 15.7 kgmol/hr

H6 = m.Cp.∆T

ΔT = 195K

H6 = 15.7×0.06235×195 = 191.01 KJ/hr = 0.191 MJ/hr

Heat out by products

(H7) Heat out by H2

-4 -5 2 -10 3
Cp for H2 = 27.143+92.738×10 T-1.381×10 T +76.451×10 T Cp at mean temperature=

443.5 k = 29.21 kj/kmol k m = 0.5846×7664 = 4480.37 kgmol/hr

H7 = m.Cp.∆T

ΔT = 291K

H7 = 4480.37×29.21×291 = 38083675.24 KJ/hr


103
H7 = 38083.675 MJ/hr

(H8) Heat out by N2

-3 -5 2 -9 3 -11 4
Cp for N2 = 2.13-0.275×10 T-0.073×10 T -0.313×10 T +0.188×10 T Cp at mean

temperature = 443.5 k = 1.92 kj/kmol k m = 0.2151×7664 = 1648.52 kgmol/hr

H8 = m.Cp.∆T

ΔT = 291K
H8 = 1648.52×1.92×291 = 921061.09KJ/hr

H8 = 921.061 MJ/hr

(H9) Heat out by CO

-2 -6 2 -8 3
Cp for CO = 36.869-1.285×10 T+27.892×10 T -1.272×10 T Cp at mean temperature=

443.5 K = 35.54 kj/kmol k m = 0.0158×7664 = 121.0912 kgmol/hr

H9 = m.Cp.∆T

∆T = 291K

H9 = 121.0912×35.54×291 = 1252342.143 KJ/hr

H9=1252.342 MJ/hr

(H10) Heat out by CO2

-5 2
Cp for CO2 = 0.244+0.000064T+0.46×10 T Cp at mean temperature = 443.5 k = 1.177

kj/kmol k m = 0.1735×7664 = 1329.704 kgmol/hr

H10 = m.Cp.∆T

ΔT = 291K

H10 = 1329.704×1.177×291 = 455432.9279 KJ/hr

H10 = 455.432 MJ/hr


104
(H11) Heat out by CH4

-2 -4 2 -7 3 -11 4
Cp for CH4 = 31.37-3.56×10 T+1.71×10 T -1.36×10 T +3.50×10 T Cp at mean

temperature= 443.5 k = 38.276 kj/kmol k m = 0.0089×7664 = 68.2096 kgmol/hr

H11 = m.Cp.∆T
ΔT = 291K

H11 = 68.2096×38.276×291 = 759740.079 KJ/hr

H11 = 759.74 MJ/hr

(H12) Heat out by Ar

Cp for Ar = 0.062358 kj/kmol k m = 0.0021×7664 = 16.0944 kgmol/hr

H12 = m.Cp.∆T

ΔT = 291K

H12 = 16.0944×0.06235×291 = 292.051 KJ/hr

H12 = 0.292 MJ/hr

(Ha) Total heat in

Heat in = H1+H2+H3+H4+H5+H6

Ha =20190.40+622.925+6506.0868+96.776+607.961+0.191

Heat in (Ha) = 28024.33 MJ/hr

(Hb) Total heat out

Heat out (Hb) = H7+H8+H9+H10+H11+H12

(Hb) = 38083.675+921.061+1252.342+455.432+759.74+0.292

Heat out (Hb) = 41472.54 MJ/hr

Reactions in MTS

105
CO + H2O → CO2 + H2

Heat of formation of CO = ΔĤf = -110520 KJ/Kmol

Heat of formation of H2O = ΔĤf = -241826 KJ/Kmol

Heat of formation of CO² = ΔĤf = -393510


KJ/Kmol Heat of formation of H² = ΔĤf= 0 KJ/Kmol

Heat of reaction = ΔĤrxn= -41164 KJ/Kmol

Ha = 28024.33 MJ/hr

Hb = 41472.54 MJ/hr

QS = No of moles of product × ΔĤrxn

QS = 7664 × (-41164)

QS = -315480.896 MJ/hr

QP = H2 +H1+QS

QP = 41472.54-28024.33+315480.898

5
QP = 328929 MJ/hr =3.289×10 MJ/hr

9.4 LOW TEMPERATURE SHIFT CONVERTOR

Heat in by reactant

Amount of reactants = 7664 kgmol/hr

Amount of products =7761.423 kgmol/hr

Inlet temperature = 210 C = 483 K

Outlet temperature = 219 C = 492 K

Datum temperature = 25 C = 298 K

(H1) Heat in by H2

Mean temperature = 390.5 K


106
-4 -5 2 -10 3
Cp for H2 = 27.143+92.738×10 T-1.381×10 T +76.451×10 T Cp at mean temperature =

29.1 kj/kmol k m = 0.5846×7664 = 4480.37 kgmol/hr

H1 = m.Cp.∆T

∆T = 185K

H1 = 4480.37×29.1×185 = 24120095.58 KJ/hr

H1 = 24120.09558 MJ/hr

(H2) Heat in by N2

-3 -5 2 -9 3 -11 4
Cp for N2 = 2.13-0.275×10 T-0.073×10 T -0.313×10 T +0.188×10 T Cp at mean

temperature = 1.94 kj/kmol k m = 0.2151×7664 = 1648.53 kgmol/hr

H2 = m.Cp.∆T

∆T = 185K

H2 = 1648.53×1.94×185 = 591656.125 KJ/hr

H2 = 591.656 MJ/hr

(H3) Heat in by CO

-2 -6 2 -8 3
Cp for CO = 36.869-1.285×10 T+27.892×10 T -1.272×10 T Cp at mean temperature =

35.4 kj/kmol k m = 0.0158×7664 =121.0912 kgmol/hr

H3 = m.Cp.∆T

ΔT = 185K

H3 = 121.0912×35.4×185 = 793026.27 KJ/hr

H3 = 793.02627 MJ/hr

(H4) Heat in by CO2

-5 2
Cp for CO2 = 0.244+0.000064T+0.46×10 T
107
Cp at mean temperature = 0.971 kj/kmol k
m = 0.1735×7664 = 1329.704 kgmol/hr

H4 = m.Cp.∆T

ΔT = 185K

H4 = 1329.704×0.971×185 = 238861.378 KJ/hr

H4 = 238.861 MJ/hr

(H5) Heat in by CH4

-2 -4 2 -7 3 -11 4
Cp for CH4 = 31.37-3.56×10 T+1.71×10 T -1.36×10 T +3.50×10 T Cp at mean

temperature= 36.03 kj/kmol k m = 0.0089×7664 = 68.2096 kgmol/hr

H5 = m.Cp.∆T

ΔT = 185K

H5 = 68.2096×36.03×185 = 454654.4993 KJ/hr

H5 = 454.6545 MJ/hr

(H6) Heat in by Ar

Cp for Ar = 0.062358 kj/kmol k m = 0.0021×7664 = 16.0944 kgmol/hr

H6 = m.Cp.∆T

ΔT = 185K

H6 = 16.0944×0.06235×185 = 185.6687 KJ/hr

Heat out by products

(H7) Heat out by H2

Mean temperature = 395 K

-4 -5 2 -10 3
Cp for H2 = 27.143+92.738×10 T-1.381×10 T +76.451×10 T
Cp at mean temperature = 395 k = 28.2 kj/kmol k m = 0.5897×7761.423 = 4576.91 kgmol/hr
108
H7 = m.Cp.∆T

∆T = 194K

H7 = 4576.91×28.2×194 = 25039359.23 KJ/hr

H7 = 25039.359 MJ/hr

(H8) Heat out by N2

-3 -5 2 -9 3 -11 4
Cp for N2 = 2.13-0.275×10 T-0.073×10 T -0.313×10 T +0.188×10 T Cp at mean

temperature = 1.94 kj/kmol k m = 0.2124×7761.423 = 1648.53 kgmol/hr

H8 = m.Cp.∆T

∆T = 194K

H8 = 1648.53×1.94×194 = 620440.751KJ/hr

H8 = 620.440 MJ/hr

(H9) Heat out by CO

-2 -6 2 -8 3
Cp for CO = 36.869-1.285×10 T+27.892×10 T -1.272×10 T Cp at mean temperature =

35.4 kj/kmol k m = 0.0035×7761.423 = 27.16 kgmol/hr

H9 = m.Cp.∆T

ΔT = 194K

H9 = 27.16×35.4×194 = 186558.22 KJ/hr

H9 = 186.55822 MJ/hr

(H10) Heat out by CO2


-5 2
Cp for CO2 = 0.244+0.000064T+0.46×10 T Cp at mean temperature = 0.99 kj/kmol k m =

0.1836×7761.423 = 1424.997 kgmol/hr

H10 = m.Cp.∆T
109
∆T = 194K

H10 = 1424.997×0.99×194 = 273684.9742 KJ/hr

H10 = 273.68497 MJ/hr

(H11) Heat out by CH4

-2 -4 2 -7 3 -11 4
Cp for CH4 = 31.37-3.56×10 T+1.71×10 T -1.36×10 T +3.50×10 T Cp at mean

temperature = 36.23 kj/kmol k m = 0.0088×7761.423 = 68.30 kgmol/hr

H11 = m.Cp.∆T

∆T = 194K

H11 = 68.30×36.23×194 = 480058.42 KJ/hr

H11 = 480.05842 MJ/hr

(H12) Heat out by Ar Cp for Ar = 0.062358 kj/kmol k m = 0.0020×7761.423 = 15.52 kgmol/hr

H12 = m.Cp.∆T

∆T = 194K

H12 = 15.52×0.06235×194 = 187.79 KJ/hr

H12 = 0.18779 MJ/hr

(Ha) Total heat in


(Ha) Heat in = H1 + H2 + H3 + H4 + H5 + H6

(Ha) = 24120.0956+591.656+793.026+238.861+454.65+0.1857

Heat in (Ha) = 26198.4797 MJ/hr

(Hb) Total heat out

Heat out (Hb) = H7+H8+H9+H10+H11+H12

(Hb) = 25039.359+620.441+186.558+273.685+480.058+0.1878

110
Heat out (Hb) = 26600.288 MJ/hr

ΔH = HEAT IN – HEAT OUT

ΔH= - 401.81 MJ/hr

Reactions in LTS

CO + H2O → CO2 + H2

Heat of formation of CO = ΔĤf= -110520 KJ/Kmol

Heat of formation of H2O = ΔĤf= -241826 KJ/Kmol

Heat of formation of CO2 = ΔĤf= -393510 KJ/Kmol

Heat of formation of H2 = ΔĤf= 0 KJ/Kmol

ΔĤrxn = -41164 KJ/Kmol

Ha = 26198.48 MJ/hr

Hb = 26600.288 MJ/hr

QS = No of moles of product × ΔĤrxn

QS = 7761.423 × (-41164)

QS = -319491216.4 MJ/hr

QP = H2-H1-QS

QP = 26600.288-26198.48+319491.216
5
QP = 319893.02 MJ/hr =3.19893×10 MJ/hr

9.5 METHANATOR

Amount of reactant = 6723.56 Kg mol/hr

Amount of product = 6626.781 Kg mol/hr

111
Temperature of entering stream = 320 °C = 593 K

Temperature of leaving stream = 349 °C = 622 K

Datum temperature = 25 °C = 298 K

HEAT IN BY REACTANT

(H1) HEAT IN BY H2

Now,

4 5 2 10 3
Cp for H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Now mean temperature = (593+289)/2 = 445 K

2 5 2
Cp for H2 at mean temperature = 27.143 + 92.738x10ˉ (445) – 1.381x10ˉ (445) +
10 3
76.451x10ˉ (445)

Cp for H2 at mean temperature = 29.40 KJ/kmol K m = 0.7218 x 6723.56 = 4853.06 kmol/hr

H1 = m.Cp.∆T

H1 = (483.06) x (29.40) x (593 – 298)

H1 = 42090589.38 KJ/hr = 42090.589 MJ/hr

(H2) HEAT IN BY N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T
3 5 2 9
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (445) – 0.073x10ˉ (445) – 0.313x10ˉ
3 11 4
(445) + 0.188x10ˉ (445)

Cp for N2 at mean temperature = 1.91 KJ/hr m = 0.2601 x 6723.56 = 1748.79 kmol/hr

H2 = m.Cp.∆T

H2 = 1748.79 x 1.91 x (593 – 298)

112
H2 = 985355.72 KJ/hr

H2 = 985.355 MJ/hr

(H3) HEAT IN BY CO2

5 2
Cp for CO2 = 0.244 + 0.000064 T + 0.46x10ˉ T

5 2
Cp for CO2 at mean temperature = 0.244 + 0.000064(445) + 0.46x10ˉ (445) Cp for CO2 at

mean temperature = 1.183 KJ/kmol K m = 0.0005 x 6723.56 = 336178 kmol/hr

Now

H3 = 336178 x 1.183 x (593 – 298)

H3 = 1172.93 KJ/hr = 1.1729 MJ/hr

(H4) HEAT IN BY Ar

Cp for Ar = 0.062358 KJ/kmol K m = 0.0025 x 6723.56 = 16.808 kmol/hr

Now

H4 = m.Cp.∆T

H4 = 16.808 x 0.062358 x (593-298)

H4 = 309.193 KJ/hr = 0.309 MJ/hr


(H5) HEAT IN BY CH4

2 4 2 7 3 11 4
Cp for CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2 7
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (445) +1.71x10ˉ (445) – 1.36x10ˉ
3 11 4
(445) + 3.50x10ˉ (445) Cp for CH4 at mean temperature = 38.545 KJ/kmol K m =
0.0108 x 6723.56 m = 72.614 Kmol/hr

Now

113
H5 = m.Cp.∆T

H5 = 72.614 x 38.545 x (593 – 298)

H5 = 825677.45 KJ/hr = 825.677 MJ/hr

(H6) HEAT IN BY CO

2 6 2 8 3
Cp of CO = 36.869 – 1.285x10ˉ T + 27.892x10ˉ T – 1.272x10ˉ T

2 6 2
Cp of CO at mean temperature = 36.869 – 1.285x10ˉ (445) + 27.892x10ˉ (445) –
8 3
1.272x10ˉ (445)

Cp of CO at mean temperature = 35.55 KJ/kmol K m = 0.0042 x 6723.56 m = 28.23 kmol/hr

H6 = m.Cp.∆T

H6 = 28.23 x 35.55 x (593 – 298)

H6 = 296055.067 KJ/hr = 296.055 MJ/hr

HEAT OUT BY PRODUCT

(H7) HEAT OUT BY H2


Now,

4 5 2 10 3
Cp for H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Mean temperature = (622+298)/2 = 460K

² 5 2
Cp of H2 at mean temperature = 27.143 + 92.738x10ˉ (460) – 1.381x10ˉ (460) +
10 3
76.451x10ˉ (460)

Cp of H2 at mean temperature = 29.23 KJ/kmol K m = 0.7177 x 6626.781 m = 4756.04 kmol/hr

H7 = m.Cp.∆T

H7 = 4756.04 x 29.23 x (622 – 298)

H7 = 45042171.94 KJ/hr = 45042.17 MJ/hr

114
(H8) HEAT OUT BY N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2 9
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (460) – 0.073x10ˉ (460) – 0.313x10ˉ
3 11 4
(460) + 0.188x10ˉ (460)

Cp for N2 at mean temperature = 1.911 KJ/kmol K m = 0.264 x 6626.781 m = 1749.47 kmol/hr

Now,

H8 = m.Cp.∆T

H8 = 1749.47 x 1.911 x (622 – 298)

H8 = 1083208.84 KJ/hr = 1083.208 MJ/hr

(H9) HEAT OUT BY Ar


Cp for Ar = 0.062358 KJ/kmol K m = 0.0025 x 6627.781 = 16.569 kmol/hr

Now

H9 = m.Cp.∆T

H9 = 16.569 x 0.062358 x (622 – 298)

H9 = 334.759 KJ/hr = 0.334 MJ/hr

(H10) HEAT OUT BY CH4

2 4 2 7 3 11 4
Cp of CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2 7
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (460) +1.71x10ˉ (460) – 1.36x10ˉ
3 11 4
(460) + 3.50x10ˉ (460) Cp for CH4 at mean temperature = 39.27

KJ/kmol K m = 0.0156 x 6626.781 m = 104.703 kmol/hr

H10 = m.Cp.∆T

H10 = 104.703 x 39.27 x (622 – 298)

115
H10 = 1332186.52 KJ/hr = 1332.186 MJ/hr

Total heat in by reactants = Ha = H1 + H2 + H3 + H4 + H5 + H6

Ha = 42090.589 + 985.355 + 296.055 + 1.1729 + 0.3091+ 825.677

Ha = 44199.158 MJ/hr

Total heat out by products = Hb = H7 + H8 + H9 + H10

Hb = 45042.17 + 1083.208 + 0.3347 + 1332.186

Hb = 47457.89 MJ/hr

REACTIONS IN METHANATOR
CO +3H2 ↔CH4 +H2O (rxn:1)

CO2 +4H2 ↔CH4 +2H2O (rxn:2)

For Reaction 1:

Heat of formation of CO =∆Hf = -110.520 KJ/gmol = -110520 KJ/Kgmol

Heat of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol

Heat of formation of CH4 = ∆Hf = -74.84 KJ/gmol = -74840 KJ/Kgmol

Heat of formation of H2 = 0

Heat of reaction of reaction 1 = (heat of formation of products – heat of formation of reactants)

∆Ĥrxn1 = [{(-74840) + (-241826)} – (-110520)]

∆Ĥrxn1 = -305614 KJ/Kgmol

For Reaction 2:

Heat of formation of CH4 = ∆Hf = -74.84 KJ/gmol = -74840 KJ/Kgmol

Heat of formation of H2O = ∆Hf = -241.826 KJ/gmol = -241826 KJ/Kgmol

Heat of formation of CO2 = ∆Hf = -393.519 KJ/gmol = -393510 KJ/Kgmol

116
Heat of formation of H2 = 0

∆Ĥrxn2 = [{(-74840) + 2(-241826)} – (-393510)]

∆Ĥrxn2 = -164982 KJ/Kgmol

So

∆Ĥrxn = ∆Ĥrxn1 +∆Ĥrxn2

∆Ĥrxn = -470.596 KJ/gmol = -470596 KJ/Kgmol

Now

Qs = 6244.41 x (-470596)
Qs = -2938594368 KJ/hr

Qs = -2938594.368 MJ/hr

Qp = H2 – H1 – Qs

Qp = 47457.89 – 44199.15 + 2938594.368

6
Qp = -2941853 MJ/hr = -2.941x10 MJ/hr

9.6 AMMONIA REACTOR

Amount of reactant = 24535.34 Kg mol/hr

Amount of product = 21717 Kg mol/hr

Temperature of entering stream = 254 °C = 527 K

Temperature of leaving stream = 443 °C = 716 K

Datum temperature = 25 °C = 298 K

HEAT IN BY REACTANT

(H1) HEAT IN BY H2

117
4 5 2 10 3
Cp for H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Now mean temperature = 412 K

2 5 2
Cp for H2 at mean temperature = 27.143 + 92.738x10ˉ (412) – 1.381x10ˉ (412) +
10 3
76.451x10ˉ (412)

Cp for H2 at mean temperature = 29.15 KJ/kmol K m = 0.6595 x 23535 = 15521.33 kmol/hr

H1 = m.Cp.∆T

H1 = (15521.33) x (29.15) x (527 – 298)


H1 = 103610310.2 KJ/hr = 103610.310 MJ/hr

(H2) HEAT IN BY N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2 9
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (412) – 0.073x10ˉ (412) – 0.313x10ˉ
3 11 4
(412) + 0.188x10ˉ (412)

Cp for N2 at mean temperature = 1.932 KJ/hr m = 0.2198 x 24535 = 5392.79 kmol/hr

H2 = m.Cp.∆T

H2 = 5392.79 x 1.932 x (527 – 298)

H2 = 4589.58 KJ/hr

H2 = 4.589 MJ/hr

(H3) HEAT IN BY Ar

Cp for Ar = 0.062358 KJ/kmol K m = 0.0131 x 24535 = 321.40 kmol/hr

Now

H3 = m.Cp.∆T

H3 = 321.40 x 0.062358 x (527 – 298)

118
H3 = 5489.58 KJ/hr = 5.489 MJ/hr

(H4) HEAT IN BY CH4

2 4 2 7 3 11 4
Cp for CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (412) +1.71x10ˉ (412) –
7 3 11 2
1.36x10ˉ (412) + 3.50x10ˉ (412)

Cp for CH4 at mean temperature = 36.99 KJ/kmol


K m = 0.0669 x 24535 m = 1641.39 km/hr

Now

H4 = m.Cp.∆T

H4 = 1641.39 x 36.99 x (527 – 298)

H4 = 13903738.69 KJ/hr = 13903.738 MJ/hr

(H5) HEAT IN BY NH3

2 5 2 10 3
Cp for NH3 = 35.15 + 2.954x10ˉ T – 0.4421x10ˉ T + 6.686x10ˉ T
2 5 2
Cp for NH3 at mean temperature = 35.15 + 2.954x10ˉ (412) – 0.4421x10ˉ (412) +
10
6.686x10ˉ
3
(412)

Cp for NH3 at mean temperature = 47.603 KJ/kmol K m = 0.0407 x 24535 m = 998.57 Now

H5 = m.Cp.∆T

H5 = 998.57 x 47.603 x (527 – 298)

H5 = 10885498.45 KJ/hr = 10885.49 MJ/hr

HEAT OUT BY PRODUCT

(H6) HEAT OUT BY H2

Now,

119
4 5 2 10 3
Cp for H2 = 27.143 + 92.738x10ˉ T – 1.381x10ˉ T + 76.451x10ˉ T

Mean temperature = (716 + 298)/2 = 507K


2 5 2
Cp of H2 at mean temperature = 27.143 + 92.738x10ˉ (507) – 1.381x10ˉ (507) +
10 3
76.451x10ˉ (507)

Cp of H2 at mean temperature = 29.29 KJ/kmol K m = 0.5526 x 21717 m = 12000 kmol/hr

H6 = m.Cp.∆T

H6 = 12000 x 29.29 x (716 – 298)

H6 = 146918640 KJ/hr = 146918.640 MJ/hr

(H7) HEAT OUT BY N2

3 5 2 9 3 11 4
Cp for N2 = 2.13 – 0.257x10ˉ T – 0.073x10ˉ T – 0.313x10ˉ T + 0.188x10ˉ T

3 5 2 9
Cp for N2 at mean temperature = 2.13 – 0.257x10ˉ (507) – 0.073x10ˉ (507) – 0.313x10ˉ
3 11 4
(507) + 0.188x10ˉ (507)

Cp for N2 at mean temperature = 1.89 KJ/kmol K m = 0.1842 x 21717 m = 4000 kmol/hr Now,

H7 = m.Cp.∆T

H7 = 4000 x 1.89 x (716 – 298)

H7 = 3160080 KJ/hr = 31600.80 MJ/hr

(H8) HEAT OUT BY Ar

Cp for Ar = 0.062358 KJ/kmol K m = 0.0148 x 21717 = 321.4166 kmol/hr

Now
H8 = m.Cp.∆T

H8 = 321.4166 x 0.062358 x (716 – 298)

H8 = 8377.93 KJ/hr = 8.377 MJ/hr

(H9) HEAT OUT BY CH4


120
2 4 2 7 3 11 4
Cp of CH4 = 31.137 – 3.56x10ˉ T+1.71x10ˉ T – 1.36x10ˉ T + 3.50x10ˉ T

2 4 2 7
Cp for CH4 at mean temperature = 31.137 – 3.56x10ˉ (507) +1.71x10ˉ (507) – 1.36x10ˉ
3 11 4
(507) + 3.50x10ˉ (507) Cp for CH4 at mean temperature = 41.63

KJ/kmol K m = 0.0754 x 21717 m = 1637.46 kmol/hr

H9 = m.Cp.∆T

H9 = 1637.46 x 41.63 x (716 – 298)

H9 = 28493998.2 KJ/hr = 28493.998 MJ/hr

(H10) HEAT IN BY NH3

2 5 2 10 3
Cp for NH3 = 35.15 + 2.954x10ˉ T – 0.4421x10ˉ T + 6.686x10ˉ T
2 5 2
Cp for NH3 at mean temperature = 35.15 + 2.954x10ˉ (507) – 0.4421x10ˉ (507) +
10
6.686x10ˉ
3
(507)

Cp for NH3 at mean temperature = 50.37 KJ/kmol K m = 0.173 x 21717 m = 3757.041 Now

H10 = m.Cp.∆T

H10 = 3757.041 x 6.686 x (716 – 298)


H10 = 10499982.82 KJ/hr = 10499.98 MJ/hr

Total heat in by reactants = Ha = H1 + H2 + H3 + H4 + H5

Ha = 103610.310 + 4.589 + 5.489 + 13903.738 + 10885.49

Ha = 130790.04 MJ/hr

Total heat out by products = Hb = H6 + H7 + H8 + H9 + H10

Hb = 146918.640 + 31600.80 + 8.377 + 28493.998 + 10499.98

Hb = 189081.075 MJ/hr

REACTIONS IN AMMONIA REACTOR

121
N2 +3H2 ↔ 2NH3

For Reaction above

Heat of formation of NH3 =∆Hf = -46.191 KJ/gmol = -46191 KJ/Kgmol

Heat of formation of H2 = 0 Heat of formation of N2 = 0

So

∆Ĥrxn = -2x(46191)

∆Ĥrxn = -92382 KJ/Kgmol

Now

Qs = 21717 x (-92382)

Qs = -2006259894 KJ/hr

Qs = -2006259.894 MJ/hr

Qp = H2 – H1 – Qs

Qp = 1890981.075 – 130790.04 + 2006259.894

5
Qp = 264550 MJ/hr = 2.64550x10 MJ/hr

122
Chapter # 10

EQUIPMENT DESIGN

123
10.1 DESIGN OF PRIMARY REFORMER

Natural gas flow rate = 1946.12 kgmol/hr

Steam flow rate = 4560 kgmol/hr

Inlet temperature = 600 C

Outlet temperature = 808 C

Table 10.1

Components Inlet (%) Outlet (%)


CH2 69.48 12.5
H2 4.3 60
CO2 8 9.93
N2 18.8 7.62
CO -- 10.5

in
At inlet= (S/D) = 4560/1946.12 = 2.34

From material balance we can calculate steam to dry gas ratio at outlet

Steam flow rate = 3413.654 kgmol/hr

Dry gas flow at outlet = 4801.473 kgmol/hr

At outlet (S/D)Outlet = 3413.654/4801.473 = 0.71

Calculation of outlet flows


124
in in in
Ftotal = Fsteam + Fgas

in in
Ftotal = 4560 + 1946.129 Ftotal = 6506.129 kgmol/hr

Ftotalout = Fsteamout + Fgasout

out
Ftotal = 4801.473 + 3413.6

out
Ftotal = 8215.127 kgmol/hr

Enthalpy of formation at 600 C [ref 17]


Table 10.2

Components (%) Enthalpy


CH4 69.48 -11845
H2 4.3 3572
N2 8.8 3656
CO2 8 -88498

in in
Havg = XCH4HCH4 + XH2HH2 + XN2HN2 + XCO2HCO2 + (S/D) × H2O

in
1+(S/D)
in
Havg = -40090 kcal/kgmol

Enthalpy of formation at 808 C

Table 10.3

Components (%) Enthalpy


CH4 12.5 -7595
H2 60 5417
CO 10.5 -20717
CO2 9.93 -85210
N2 7.62 5638
H2O ----- 50942

125
[ref 17]

out out
Havg = XCH4HCH4 + XH2HH2 + XN2HN2 + XCO2HCO2 + XCO2HCO2 + (S/D) × H2O

out
1+(S/D)

out
Havg = -24486.120 kcal/kgmol

Average heat duty = Ftotalout × Havgout - Ftotalin × Havgin

= 59674126.07 kcal/hr

Average heat duty = 75189398.85 W

Average heat flux

Referring to plant 3 (FFC)

Average heat flux for 1250 MTPD = kcal/h-m2 [ref 17]

So,
2
Average heat flux for 1150 MTPD= (1150 × 55852)/1250 = 51383.84 kcal/h-m

2 -6
(51383.84 kcal/h-m )(1.162×10 KWh)(1000cal)(1000 W)/(1cal×1kcal×1Kw)

2
Average heat flux = 59708.022 W/m

Heated length = 11m

Di = 0.124 m

2
P = design pressure= 38kg/cm

2
F = yield strength of (25% Ch- 20% Ni) alloy = 310 Mpa = 3160 kg/cm Thickness of tube t
-4
= PDi/(2F-P) t = 7.5×10 m

126
OD = ID+2t

-
= 0.124+2(7.5×10
4
) OD = 0.1255 m

Number of tubes:

No of tubes = heat duty / (heat flux)(π×heated length × outer dia of tube)

No of tubes = (75189398.85)/(59708.022)(3.14×11×0.1255) = 290

Suppose that tubes are arranged in such a way that there are 25 tubes along length 12
tubes along width

Assumption,

Tubes are 0.102m apart from each side and 0.7m space from reformer walls to tube

Length of reformer = 25×0.102+ 25×(0.1255)+1.5 = 7.18m

Width of reformer = 12×0.102+12×(0.1255)+1.5 = 8.84m

2
Area of rectangular reactor= 8.84×7.18 = 63.52 m
(6506.12 kgmol/hr ×37.89 kg/kgmol) = 246516/290 = 850 kg/hr

Suppose NiO catalyst is used in the form of pallets of 177mm

3
dia Bulk density = 1105 kg/m

2 2 3
Volume of one tube = πr × total length = (3.14×0.06 ×12) = 0.141m

Volume of reactor = (0.141)(290) = 41.140 m3

2 2
Area of reactor = (3.14)(0.06) (290) = 3.27 m

Height of reactor = volume/area = 41.240/3.27

Height of reactor = 12.58m

Assumption,

127
Height of catalytic bed = 3.5m

Inner diameter of tube= 0.124 m

2
Volume of catalyst of one tube = πr ×height

2
= (3.14)(0.124) (3.5)

3
Volume of catalyst of one tube = 0.168 m

Volume of catalyst = 0.168×290

3
= 49 m

Weight of catalyst = bulk density × volume of catalyst = (1105)(49)

Weight of catalyst = 54145 kg

3
Volumetric flow rate of gas = 36804.18 Nm /hr

Molar flow rate of steam = 4560 kgmol/hr

Total molar flow rate = 1946.12+4560 = 6506.12 kgmol/hr

PV = nRT
V = nRT/P

38 kg 2 98066.5 Pa 1KPa
cm
cm
2 1kg 1000 Pa

= (6506.12)(8.314)(879k)/(3726.527)

3
V = 12759.00m

3
For one tube = 12759/290 = 43.99 m /hr

VS = VV/AB

2
(Area of bed) AB = 49/(3.5×290) = 0.048 m = 43.99/(0.048)(3600)

VS = 0.253 m/s

2 2 3 2 3
(ΔP)t = 150 [VSμ/DP ] [( (1-E) / E ) + 1.75 [ΡVS /DP] (1-E/E )
128
DP = 15.8mm = 0.0158m

-3
Μ = 0.0341 mPas = 0.0341×10 Pa-

s E= 0.42

3
Ρ = 9.18 Kg/m

Vs = 0.253 m/s

(ΔP)t = 150(0.035)(4.54)+1.75(37.19)(7.83) = 23.835+509.5

-4 2
(ΔP)t = 533.335/290 = 1.839 Pa/m = 0.02313 Kpa = 2.3586×10 kg/cm

²
Total pressure drop = 0.068 kg/cm

10.2 ABSORPTION COLUMN DESIGN


0
Inlet temperature of absorption column = 50 C = 323 K

0
Outlet temperature of absorption column = 102 C = 375 K
2
Inlet pressure of absorption column = 26.7 kg/cm = 19600 mmHg = 2620
2
kpa. Outlet pressure of absorption column = 0.39 kg/cm

Partial pressure of CO2 = (18.36/100)*19600 = 3598.56 mmHg.

Partial pressure of CO2 in exit stream at 97 % recovery = 3598.56*0.03 = 107.95 mmHg

From Equilibrium data:

0.09% w/w CO2 = 3600pa = 27mmHg.

Mole fraction in vapour = 27/19600 = 0.001.

Mole fraction in liquid = (0.02)/(0.02+1.480) = 0.013. Slope = 0.001/0.013 = 0.076 y 1/y2 =

P1/P2 = (3598.56/107.95) = 33.33 ref

m(Gm/Lm) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
NOG 3.9 4.1 4.5 5.0 5.5 6.0 8.0 10.2 14

129
Material balance :

Lm*x1 = Gm(y1 – y2) x1 = (m/0.076)(Gm/Lm)(0.1836 * 0.97) x1 = (m(Gm/Lm)) (2.343) m(Gm/Lm)

= 0.3 ; x1 = 0.702 m(Gm/Lm) = 0.6 ; x1 = 1.4058

NOG = 6.

Column Diameter:

Gas flow rate = (7761.423/3600) = 2.15 kgmol/s = 31.54 kg/s


Liquid flow rate = (m/0.1836) = (0.076/0.1836) * 2.15 = 0.8899 kgmol/s = 59.48 kg/s.

Gas density & viscosity at inlet temperature and pressure:

Component %age Density Viscosity


Methane 0.88 14.5206 -6
12.06 * 10

Hydrogen 58.97 1.8247 -6


9.95 * 10

Nitrogen 21.24 25.3557 -6


19.54 * 10

Carbon monoxide 0.35 25.351 -6


19.95 * 10

Carbon dioxide 18.36 39.83 17.608 *

10-6

3
Density of gaseous mixture = 13.99 kg/m

-6 2
Viscosity of gaseous mixture = 1.342 * 10 Ns/m

-7
Diffusivity = DG = 0.7 *10

130
Liquid used for absorption is MDEA:

3
Density of liquid = 1000 kg/m

-3 2
Viscosity of liquid = 1.371 * 10 Ns/m

-5
Diffusivity = DL = 1.5815 * 10

* * 0.5
(L w / V w) * (ρG / ρL) = 0.223

Design for pressure drop of 20 mmHg / m packing

K4 = 0.6

At flooding Ku = 2.0 = 54.7 %

(V*w)2 = K4 * ρG ( ρL - ρG)

0.1
13.1 * Fp (µL /ρL)

* 2 2
(V w) = 4.329 kg/m s.

2
Column area required = 31.54/4.329 = 7.28 m .

2
Diameter = (4*3.04 / 3.14) = 3.04 m

Column area =7.28 m

Packing size to column dia ratio = 78.9.

(Sc)v = ((µv / ρv *) Dv) = 1.37.

(Sc)L = ((µL / ρL *) DL) = 0.086.

*
L w = liquid flow rate/ column area = 0.122.

At 55% flooding; [ ref 1 : pg 778, fig 11.51]

K3 = 0.94

Ψh = 80 [ ref 1 : pg 778, fig 11.52]


131
*
L w = 0.122

Φh = 0.03 [ ref 1 : pg 779, fig 11.53]

Assume:

HOG = 1

Z = HOG * NOG

Z = 6.

0.5 0.15
HL = 0.305 * Φh (Sc)L * k3 (Z/3.05) = 0.0027 m

0.5 1.11 0.33 * 0.5


HG = (0.011 * Φh * (Sc)v * (Dc/0.305) *(Z/3.05) ) / (L W)

HG = 8.48 m

HOG = HG + (mGm/Lm)*HL = 8.48 + (0.6 * 0.0027)


HOG = 8.48162

Column height:

Z = HOG * NOG

Z = 8.48162 * 6

Z = 50.88 m

10.3 MEDIUM TEMPERATURE SHIFT CONVERTOR

Catalyst = Cu – Zn based.

Temperature = 493 k

2
Pressure = 29.7 kg/cm

Total feed rate = 6829.72 kgmol/hr.

Initial molar flow rate of carbon monoxide = 942.5 kgmol/hr

132
Initial molar flow rate of carbon dioxide = 501.30 kgmol/hr

Initial molar flow rate of water = 3615.929 kgmol/hr

Initial molar flow rate of hydrogen = 3667.5 kgmol/hr

Ratio of initial moles of water to carbon monoxide = 3.8 Ratio of initial moles of carbon

dioxide to carbon monoxide = 0.531

Ratio of initial moles of hydrogen to carbon monoxide = 3.89.

Equilibrium constant K at 493 K = 183

Rate constant = k =8441.535

Ψ = 4.33

3
Bulk density = 1442 kg/m Using rate expression : dX/dW = Ψ*k( (yco*ywater - yco2 *
yhydrogen)/K)(Fcoo * ρb) [ ref 16 ] using polymath to solve differential equation. For

X = 0.60

W = 4492.4263 kg

W/ρ = (4492.4263/1442)

3
Volume of catalyst = 3.11 m

3
Vessel volume = 3.73 m Diameter of column :

2
(π/4) * D * H = volume

2
(π/4) * D * 2D = volume

3
D = (volume * 2 /3.14)

D = 1.334 m = 4.27 ft H = 2*D = 2.668m = 8.55 ft.

Thickness:

133
t = (P*R/(S.E – 0.6 P))

P = design pressure (psig)

R = radius of column (inch)

Material of construction stainless steel.

S = design stress = 14503.8 psi E = efficiency t = 2.62 inch = 0.066 m Allowing 3 mm for
correction t = 0.066 + 0.003

t = 0.069 m outer diameter = inner diameter + wall thickness = 1.34 + 0.069 = 1.409 m

Bed height :

Dc =1.334m

2 2
Area occupied by catalyst = (π /4) * Dc = 1.396 m

3
Volume of bed = 3.11 m

Height =(3.11/1.396) = 2.22m = 7.139 ft.

10.4 LOW TEMPERATURE SHIFT CONVERTOR

Catalyst = Cu – Zn based.

Temperature = 483 k

2
Pressure = 29 kg/cm

Total feed rate = 7664 kgmol/hr.

Initial molar flow rate of carbon monoxide = 121.09 kgmol/hr

Initial molar flow rate of carbon dioxide = 1329.704 kgmol/hr

Initial molar flow rate of water = 2692 kgmol/hr

134
Initial molar flow rate of hydrogen = 4475.776 kgmol/hr

Ratio of initial moles of water to carbon monoxide = 22.23

Ratio of initial moles of carbon dioxide to carbon monoxide = 10.98

Ratio of initial moles of hydrogen to carbon monoxide = 36.96

Equilibrium constant K at 493 K = 183

Rate constant = k =8441.535


Ψ = 4.33

3
Bulk density = 1442 kg/m Using rate expression : dX/dW = Ψ*k( (yco*ywater - yco2 *

yhydrogen)/K)(Fcoo * ρb) [ref :16] using polymath to solve differential equation.

For X = 0.92

W = 1808.4746 kg

W/ρ = (1808.4746/1442)

3
Volume of catalyst = 1.254 m

3
Vessel volume = 1.504 m Diameter of column :

2
(π/4) * D * H = volume

2
(π/4) * D * 2D = volume

3
D = (volume* 2 /3.14)

D = 0.98 m = 3.15 ft H = 2*D = 1.96m = 6.281 ft.

Thickness:

t = (P*R/(S.E – 0.6 P))

P = design pressure (psi) = 420 psi

R = radius of column (inch)


135
Material of construction stainless steel.

S = design stress = 166793 psi

E = efficiency
t = 0.0811 inch = 0.0020 m Allowing 3 mm for correction t = 0.0020 + 0.003 t = 0.0831 m

outer diameter = inner diameter + wall thickness = 0.98 + 0.0831 = 1.0631 m

Bed height:

Dc = 0.98m

2 2
Area occupied by catalyst = (π /4) * Dc = 0.753 m

3
Volume of bed = 1.254 m

Height =(1.254/0.753) = 1.66m = 5.33 ft.

136
Chapter # 11

COST ESTIMATION

137
COST ESTIMATION

Fixed capital investment for the production of ammonia by Haldor Topsoe process for the
capacity of 1150 MTPD is US 241 million $ in year 2010. Now we want to find the value of
FCI for the capacity of 1150 MTPD in the year 2013 by Chemical Engineering Cost Index
(CECI).
Index value at 2010 = 1493

Index value at 2013 = 1582.9

Original fixed capital investment = 241 million $

Present fixed capital investment = PCI =?

PCI= original capital investment × (I.V. in 2013 / I.V. in 2013)

PCI= 241 × (1582.9 / 1493)

PCI = Present Capital Investment = 255.511 million $

11.1 PRIMARY REFORMER:

3
Volume of one tube = 0.141 m

3
Density = 7.89 g/cm

7.89 g (100) 3 1 kg
= 3 3
Cm (1m ) 1000g

138
3
= 7890 Kg/m

m = 1112.49

Kg = 2447.478

lb

3
= 2.4 x 10 lb
Cost of one 4 [Pg 708
= 3 x 10 dollar
tube peter 4]

Present cost = O.C x (1582.9/924)


= 51392.86 dollar of one
tube
=14903928.57 dollars of 290 tubes
11.2 MEDIUM TEMPERATURE SHIFT CONVERTOR

Stainless steel [Peter 4 Pg 166]


3
Density = 7.99 g/cm

7.99 g (100)3 1kg


=

Cm3 (1m)3 1000g

3
Density = 7990 Kg/m

3
Volume = 3.73 m

Density = mass/volume

Mass = density x volume

Mass = 29802.7 Kg 2.2

W = 65565.94 lb 1.4 Kg

5
Cost of MTS = 2.6 x 10 dollars

Present cost by using marshal and swift index

139
Present cost = original cost x ( index value at present cost / index value)

= 44540.7619 dollars

11.3 LOW TEMPERATURE SHIFT CONVERTOR

3
Density = 7.99 g/cm
7.99 g (100)3 1 kg
=
Cm 3 (1 m)3 1000 g

3
Density = 7990 Kg/m

3
Volume = 1.504 m

Density = mass/volume

Mass = density x volume

Mass = 12016.96 Kg
= 26437.312 lb

5
Cost of LTS in 1990 = 1.3 x 10 dollars

Present cost by using marshall and swift index.

5
Present cost = (1.3 x 10 ) x (1582.9/924)

= 222702.381 dollars

11.4 ABSORBER

Volume = area x height

= 7.28 x 50.88 Volume

3
= 370.406 m

140
Mass = volume x density

3
Density = 7990 Kg/m

Mass = 2956300 Kg

Mass = 6503860 lb

Diameter = 3 m

100 cm 3m 2 59 inch 1 inch


.
=
1 cm 2.54 cm 1m

Diameter = 118.11 inch

Cost of one distribution plate = 1000 £ [pg 224 vol 6 ]

= 6 x 1000 = 6000 £

Cost of vessel = 50.88 m (height) and 3m dia


= 200 x 1000 £ [pg 223 vol 6]

= 200,000 £

= 9 x (6000) x (1582.9 / 950)

= 9997.26 £

= 333242.105 £

Cost Of Packing:

141
3
Volume of packing = 296 m [pg 225 vol 6]

Cost of 38mm Pall rings(plastic packing) = 340

3
£/m = 340 x 296

Original cost = 100640 £

Present cost = 100640 x (1582.9 / 950)

= 167687.927 £

Total cost = for distributor + for column + for packing

Total cost = 510926.79 £

142
Chapter # 12

HAZOP STUDY

143
12.1 INTRODUCTION
The technique of hazard operability studies or in more common terms HAZOP, has been
used and develop approximately decades for identifying potential hazard and operability
problems caused by deviation from the design intent of both and new and existing process
plants. Before processing further, it might be as well to clarify some aspects of these
statements. HAZOP can be defined as:

“In it we look at the hazard associated with the process when the process departs from
normal Operation”

12.1.1 Industries in which the technique is applied


HAZOP were initially invented by ICI in the United Kingdom but the technique only started
to be more widely used within the chemical industries after the Fix borough disaster in
which a chemical plant explosion kill 28 people, many if were ordinary house holders living
nearby. Through the general exchange of ideas and personnel, the system was adopted by
the petroleum industries, which has a similar potential of major disasters. This was then
followed by the food and water industry, where the hazard potential is as great, but of a
different nature, the concern being more to do with contamination rather than explosions or
chemical release.

12.2 BASIC CONCEPT


Essentially the HAZOP procedure involves taking a full description of process and
systematically questioning every part of it establishes how deviation from the design intent
and their consequences can have a negative effect upon the safe end and efficient
operation of plant. If consider necessary action is then taken to remedy the situation. The
critical analysis is applied in a structured way by a HAZOP team and it relies upon them
releasing their imagination in an effort to discover credible causes of deviations. In practice,
many causes will be fairly, obvious such as pump failure causing of circulation loss in a
cooling water facility mentioned above. However, than a mechanistic checklist type of
review. The result is that there good chance that potential failures and problems will be
identified, which had not previously been experienced in the type of plant being studied.

144
12.2.1 Objective
The objectives of a HAZOP study can be summarized as follows:

1) To identify (areas of the design that may possess a significant hazard potential.
2) To identify and study features of the design that influence the probability of a
hazardous incident occurring.

3) To familiarize the study team with the design information available.

4) To ensure that a systematic study is made of the areas of significant hazard

potential. 5) To identify pertinent design information not currently available to the

team.

6) To provide a mechanism for feedback to the client of the study teams detailed
comments.

12.3 KEY WORDS


As essential feature in this questioning and systematic analysis in the use of Key words to focus
the attention of the team upon deviations and their possible causes. The key words are divided
into two subsets. Primary key words: which focus upon a particular aspect of the design intent
or an n associated process condition or parameter. Secondary key words: which when
combined with a primary key word, suggest possible deviations. The entire technique of
HAZOP revolves around the effective use of key words, so their meaning and use must be
clearly understood by the team. Example often used key words are listed below.

12.3.1 Primary key words:


These reflect both the process design intent and operational aspects of the plant being
studied. Typical process oriented words might be as follows. The list below is purely
illustrative, as the words employed in a review will depend upon the plant being studied.

145
Table 12.1

Flow Pressure

Temperature Level

Separate (settle, filter, Composition


centrifuge)
React Corrode

Remembering that the technique is called Hazard and Operability studies, added to the
above might be relevant operational words such as:
Table 12.2

Isolate Drain

Vent Purge

Inspect Maintain

Start up Shut down

12.3.2 Secondary key words:


As mentioned above, when applied in a conjunction with a primary key word, these suggest
the potential deviations or problems. They tend to be a standard set as listed below:

Table 12.3

Word Meaning

No The design intent does not occur (e.g. flow), or the


optional not achieved (Isolate/No)

Less A quantitative decrease in the design intent occur (e.g.


Pressu

146
More A quantitative increase in the design
intent occ
Temperature/More)

Reverse The opposite of the design intent occurs (e.g.


Flow/Reverse)
Other The activity occurs, but not in the way intended (e.g.
Flow/Oth indicate a leak or product flowing where it
should composition/other might suggest unexpected
proportions in a f

As well as A quantitative increase

Part of A quantitative decrease

12.4 HAZOP STUDY METHODOLOGY:


In simple terms the HAZOP study process involves applying in a systematic way all
relevant keywords combining to the plant in question in an effort to uncover potential
problems. The results are recorded in a columnar format under the headings,

Table 12.4

Deviation Cause Consequences Safeguard Action

In considering the information to be recorded in each of these columns is given below.

12.4.1 Deviation
The key words combination being applied (e.g. Flow/No)

12.4.2 Cause
Potential cause which would result in the deviation occurring (e.g. “strainer blockage due to
impurities in Dosing tank” might be a cause of Flow/No).

147
12.4.3 Consequences
The consequences which would arise, both from the effect of the deviation (e.g. “Loss of
dosing results in complete separation”) and, if appropriate from the cause itself (e.g.
“cavitation in pumps, with possible damage if prolonged”).

12.4.4 Safeguards
Any existing protective devices, which either prevent the cause or safeguards against the
adverse consequences, would be recorded in this column. For example you may consider
recording “Local pressure gauge in discharge from pump might indicate problem was
arising”. Note that safeguard need not to be restricted hardware where appropriate credit
can be taken for procedural aspects such as regular plants inspections (if you sure that they
will actually be carried out).

12.4.5 Action
Where a credible cause results in a negative consequence, it must be decided whether some
action should be taken. It is at this stage that consequences and associated safeguards are
considered. If it is deemed that the protective measures are adequate, then no action need to
take, and words to that effects are recorded in the action column. Action falls in two groups:

1. Action that remove the cause

2. Action that mitigate or eliminate the consequences

Whereas former is to be preferred, it is not always possible especially when dealing with
equipment’s malfunction. However, always investigate removing the cause first and only
where necessary mitigate the consequences. Finally always take into account the label of
training experience especially of personnel who will operate the plant. Actions, which call for
elaborate and sophisticated protective systems, are wasted, as well as being inherently
dangerous, if operators do not and never will, understand how they function. It is not
unknown for devices to be disabled, either deliberately or in error, because no one knows
how to maintain and calibrate them. Having gone through the operations involve in
recording a single deviation, these can now be put into the context of the actual study
meeting procedure. From the flow diagram below it can be seen that it is very much an
iterative process, applying in a structured and systematic way the relevant keyword
combinations in order to identify potential problems.

148
12.5 HAZOP STUDY STEPS
A HAZOP study is conducted in the following steps:

1) Specify the purpose, objective, and scope of the study. The purpose may he the
analysis of a yet to be built plant or a review of the risk of un existing unit. Given
the purpose and the circumstances of the study, the objectives listed above can
he made more specific. The scope of the study is the boundaries of the physical
unit, and also the range of events and variables considered. For example, at one
time HAZOP's were mainly focused on fire and explosion endpoints, while now
the scope usually includes toxic release, offensive odor, and environmental end-
points. The initial establishment of purpose, objectives, and scope is very
important and should be precisely set down so that it will be clear, now and in the
future, what was and was not included in the study. These decisions need to be
made by an appropriate level of responsible management.
2) Select the HAZOP study team. The team leader should be skilled in HAZOP and in
interpersonal techniques to facilitate successful group interaction. As many other
experts should be included in the team to cover all aspects of design, operation,
process chemistry, and safety. The team leader should instruct the team in the
HAZOP procedure and should emphasize that the end objective of a HAZOP survey
is hazard identification; solutions to problems are a separate effort.

3) Collect data. Theodore16 has listed the following materials that are usually
needed:

• Process description.
• Process flow sheets.
• Data on the chemical, physical and toxicological properties of all raw materials,,
intermediates, and products.

• Piping and instrument diagrams (P&IDs).


• Equipment, piping, and instrument specifications.
• Process control logic diagrams.
• Layout drawings.
• Operating procedures.
• Maintenance procedures.
• Emergency response procedures.
149
• Safety and training manuals.

HAZOP Method Flow Diagram

150
Table 12.4

Guide Words Meaning

No Negation of design intent


Less Quantitative decrease

More Quantitative increase

Part of Qualitative decrease

As well as Qualitative Increase

Reverse Logical opposite of the intent

Other than Complete substitution

4) Conduct the study. Using the information collected, the unit is divided into study
"nodes" and the sequence diagrammed in Figure , is followed for each node.
Nodes are points in the process where process parameters (pressure,
temperature, composition, etc.) have known and intended values. These values
change between nodes as a result of the operation of various pieces of
equipment' such as distillation columns, heat exchanges, or pumps. Various
forms and work sheets have been developed to help organize the node process
parameters and control logic information.

When the nodes are identified and the parameters are identified, each node is studied by
applying the specialized guide words to each parameter. These guide words and their
meanings are key elements of the HAZOP procedure.

Repeated cycling through this process, which considers how and why each parameter
might vary from the intended and the consequence, is the substance of the HAZOP study.

5) Write the report. As much detail about events and their consequence as is
uncovered by the study should be recorded. Obviously, if the HAZOP identifies a
not improbable sequence of events that would result in a disaster, appropriate
follow-up action is needed. Thus, although risk reduction action is not a part of
the HAZOP, the HAZOP may trigger the need for such action.
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The HAZOP studies are time consuming and expensive. Just getting the P & ID's up to date
on an older plant may be a major engineering effort. Still, for processes with significant risk,
they are cost effective when balanced against the potential loss of life, property, business,
and even the future of the enterprise that may result from a major release.

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REFRENCES
1) R.K. Sinnott “Coulson & Richardson Chemical Engineering Design” Volume 6, 4TH
edition, Butterworth Heinemann,
2) J.M. Smith, H.C. Van Ness, M.M. Abbot, “Introduction to Chemical Engineering
Thermodynamics” 6TH edition, McGraw-Hill,2001

3) David M. Himmelblau “Basic Principles and Calculations in Chemical Engineering”


6TH edition, Prentic Hall, 1996

4) Max S. Peter, Klaus D. Timmerhaus, Ronald E. West, “Plant Design and Economics
for
Chemical Engineers” 4TH edition, McGraw Hill Book Companies Inc, 2003
5) Max S. Peter, Klaus D. Timmerhaus, Ronald E. West, “Plant Design and Economics
for
Chemical Engineers” 5TH edition, McGraw Hill Book Companies
6) George T. Austin “ Shreve’s Chemical Process Industries” 5TH edition, McGraw Hill
Book Company, 1994

7) Krik-Othmer “Encyclopedia of Chemical Technology” Volume2, 4TH edition, John


Weily & Sons, 1998

8) Walas S. M. “Chemical Process Equipment Selection and Design” 2ND edition,


Butterworth- Heinemann, 1990

9) Perry R. H, Green D.W. ”Perry’s Chemical Engineer’s Handbook”, 7TH edition,


McGraw Hill Book Company, 1997

10) Yaws C.L. “ Physical Properties, a Guide to the Physical, Thermodynamics and
Transport Property Data of Industrially important Chemical Compounds’, New York,
McGraw Hill, 1987

11) Harry Silla, “ Chemical Process Engineering Design and Economics”, Marcel Dekker
Inc , 2003

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12) Nicholas P. Chopey, “Handbook of Chemical Engineering Calculation, 3RD edition,
13)International Fertilizer Industry Association , United Nations Environment program,
2002
14) Department of Statistical Data, Pakistan
15) International Fertilizer Development Department, United Nations
16) Research paper by Prof. Yogesh .J.Morabiya & Prof. Jalpa.A.Shah Title: Modeling &
Simulation of Water Gas Shift Reaction.

17) Operating manual of Fauji Fertilizer Limited, Sadiqabad & Mirpur Mathello plant. 18)
Multiple internet sources

19)
http://www.topsoe.com/business_areas/ammonia/~/media/PDF%20files/Ammonia/to
pso e_ammonia_technology.ashx

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