Project

Production of Methanol from Coal
Session: 2009-2013
Project Advisor
Engr.Usman Farooq
Group Members
Bilal Shafiq
09033123-058
Noman Arshad
09033123-056
Ahmad Zeeshan
09033123-005
Ch. Naveed Anwar
09033123-019
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF GUJRAT GUJRAT-PAKISTAN
Page 1
This report is submitted to department of Chemical Engineering,

University of Gujrat
Gujrat- Pakistan for the partial fulfillment of the requirements for the Degree
Of Bachelor of Science
In
CHEMICAL ENGINEERING
Internal Examiner
Signature:
(Supervisor)
Name
External Examiner
Signature:
(Supervisor)
Name
DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF GUJRAT GUJRAT-PAKISTAN
Page 2
Page 3
DEDICATED TO
Our
beloved
parents
teachers
and
sincere
friends
whose
love
affection and continuous

prayers for our success
is
the
most
precious
asset of our lives.
Page 4
Contents
Acknowledgement ......................................................................................................................... 11
Chapter 1 ........................................................................................................................................ 12
Introduction .................................................................................................................................... 12
1.1
Historical Development of Methanol ................................................................................. 14
1.2
Physical Properties ............................................................................................................. 14
1.3
Physical properties ............................................................................................................. 15
1.4
Reaction of methanol ......................................................................................................... 17
1.5
Chemical Properties of Methanol ...................................................................................... 17
1.5.1
Combustion of Methanol: .......................................................................................... 17
1.5.2
Oxidation of Methanol: .............................................................................................. 17
1.5.3
Catalytic Oxidation of Methanol: .............................................................................. 18
1.5.5
Dehydration of Methanol: .......................................................................................... 18
1.5.6
Esterification of Methanol: ........................................................................................ 18
1.5.7
Substitution of Methanol with Sodium: ..................................................................... 19
1.5.8
Substitution of Methanol with Phosphorus Pent chloride: ......................................... 19
1.5.9
Substitution of Methanol with Hydrogen Chloride:................................................... 19
1.6
Applications of Methanol .................................................................................................. 20
1.6.1
Transportation Fuel: ................................................................................................... 20
1.6.2
Wastewater Denitrification: ....................................................................................... 20
1.6.3
Fuel Cell Hydrogen Carrier: ...................................................................................... 21
1.6.4
Methanol as a cleansing agent: .................................................................................. 21
1.6.5
Biodiesel Transesterification: .................................................................................... 21
1.6.6
Electricity Generation: ............................................................................................... 21
1.6.7
Methanol as a solvent:................................................................................................ 22
1.6.8 Chemical Feed Stock ........................................................................................................ 22

Chapter 2 ........................................................................................................................................ 23
Process Selection ........................................................................................................................... 23
2.1
Choice of Feedstock:...................................................................................................... 24
2.1.1
Biomass: ................................................................................................................. 24
2.2.3
Natural Gas: ........................................................................................................... 25
2.2.4
Natural Gas Reserves in Pakistan: ......................................................................... 25
2.2.5
Coal: A Fossil Fuel: ............................................................................................... 25
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2.2
Choice of Syngas Technology: ...................................................................................... 26
2.2.1
Steam Methane Reforming: ................................................................................... 26
2.2.2
Partial Oxidation Reforming: ................................................................................. 27
2.2.3
Auto thermal Reforming: ....................................................................................... 28
2.2.4
Gas Heated Reforming: .......................................................................................... 30
Chapter 3 ........................................................................................................................................ 31
Process Description........................................................................................................................ 31
3.1 Process Flow Sheet .............................................................................................................. 32
3.2
Feed Preparations ........................................................................................................... 33
3.3
Production of Syn Gas ................................................................................................... 33
3.4
Cooling of Syn Gas ........................................................................................................ 33
3.5
Purification of Syn Gas .................................................................................................. 33
3.6
Rearrangement of H2 and CO ........................................................................................ 33
3.7
Production of Methanol ................................................................................................. 33
3.8
Refining of Methanol. .................................................................................................... 33
Chapter 4 ........................................................................................................................................ 38
Capacity Selection ......................................................................................................................... 38
4.1
Global Demand of Methanol: ........................................................................................ 39
4.2
South Asia Methanol Demand ....................................................................................... 40
4.3
China Methanol Industry ............................................................................................... 41
Chapter # 5 ..................................................................................................................................... 43
Material and Energy Balance ......................................................................................................... 43
5.1
Material Balance on Distillation Column: ..................................................................... 44
5.2
Material Balance on Flash Drum: .................................................................................. 45
5.3
Material Balance on Reactor:......................................................................................... 48
5.4
Material Balance on Water Gas Shift Reactor: .............................................................. 49
5.5
Material Balance on Acid Gas Absorber: ...................................................................... 51
5.6
Material Balance on Gasifier: ........................................................................................ 53
Energy Balance: ............................................................................................................................. 55

5.7
Energy Balance on Gasifier .......................................................................................... 55
5.8
Energy Balance on Heat Exchanger: ............................................................................. 57
5.9
Energy Balance on Water Gas Shift Reactor: ................................................................ 59
5.10
Energy Balance on Distillation Column: ....................................................................... 61
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5.11
Energy Balance on Gasifier: .......................................................................................... 62
Chapter 6 ........................................................................................................................................ 64
Designing of Gasifier ..................................................................................................................... 64
6.1
Types of Gasifier: ......................................................................................................... 65
6.1.1
Entrainment bed Gasifier ....................................................................................... 65
6.1.2
Fluidized Bed Gasifier: .......................................................................................... 66
6.1.3
Moving Bed Gasifier: ............................................................................................ 66
6.2
Design : .......................................................................... Error! Bookmark not defined.
6.3
Specification Sheet......................................................................................................... 75
Chapter 7 ........................................................................................................................................ 76
Designing of Methanol Reactor ..................................................................................................... 76
7.1
Purpose: ......................................................................................................................... 77
7.2
Reactor selection criteria: .............................................................................................. 77
7.3
Reactor types:................................................................................................................. 77
7.4
Designing ....................................................................................................................... 78
7.5
Specification Sheet......................................................................................................... 84
Chapter # 08 ................................................................................................................................... 85
Designing of Heat Exchanger ........................................................................................................ 85
Purpose........................................................................................................................................... 86
8.1
Types of Heat Exchanger ................................................................................................... 86
8.2
Selection Criteria ............................................................................................................... 86
8.4
Types of Shell and Tube Heat Exchangers: ....................................................................... 87
8.5
Designing ........................................................................................................................... 87
8.6
Specification Sheet............................................................................................................. 94
Chapter # 09 ................................................................................................................................... 95
Designing of Distillation Column .................................................................................................. 95
9.1
Purpose: ......................................................................................................................... 96
9.2
Choice between Plate and Packed Column .................................................................... 96
9.3
Plate Type Choice .......................................................................................................... 97
9.4
Construction ................................................................................................................... 97
9.4.1
Effect of temperature on the mechanical properties .............................................. 97
9.4.2
Pitting ..................................................................................................................... 98
9.4.3
Effect of stress........................................................................................................ 98
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9.4.4
High-temperature oxidation ................................................................................... 98
9.5
Designing ..................................................................................................................... 100
9.6
Specification Sheet....................................................................................................... 109
Chapter 10 .................................................................................................................................... 110

Coast Estimation .......................................................................................................................... 110
10.1
Introduction of Cost Estimation ................................................................................... 111
10.2
Accuracy and Purpose of Capital Cost Estimates ........................................................ 111
10.3
Preliminary Estimates .................................................................................................. 111
10.4
Authorization Estimates ............................................................................................... 111
10.5
Detailed Estimates ....................................................................................................... 112
10.6
Fixed Capital ................................................................................................................ 112
10.6.1
Direct Cost ........................................................................................................... 113
10.6.2
Indirect Cost ......................................................................................................... 113
Start-up expenses ......................................................................................................................... 113

10.7
Working Capital ........................................................................................................... 113
10.8
Operating Costs............................................................................................................ 114
10.8.1
Fixed Cost ............................................................................................................ 114
10.8.2
Variable Costs ...................................................................................................... 114
10.9
Cost Indices.................................................................................................................. 114
10.9.1
Types of Cost Indices........................................................................................... 115
Chapter 11 .................................................................................................................................... 116

Instrumentation and Process Control ........................................................................................... 116
11.1
Objective ...................................................................................................................... 116
11.1.1
Safe plant operation: ............................................................................................ 116
11.1.2
Production rate: .................................................................................................... 116
11.1.3
Product quality: .................................................................................................... 116
11.1.4
Cost: ..................................................................................................................... 116
11.2
Temperature Measurement and Control: ..................................................................... 117
11.3
Pressure measurement and control:.............................................................................. 118
11.4
Flow measurement and control: ................................................................................... 118
11.5
Control loops:............................................................................................................... 118
11.5.1
Feedback control loop: ......................................................................................... 118
11.5.2
Feed Forward Control Loop:................................................................................ 119
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11.5.3
Ratio control: ....................................................................................................... 119
11.5.4
Auctioneering control loop: ................................................................................. 119
11.5.5
Split range loop: ................................................................................................... 119
11.5.6
Cascade control loop: ........................................................................................... 120
11.6
Control loop around Gasifier ......................................... Error! Bookmark not defined.
11.7
Control loop around Absorber ..................................................................................... 120
11.8
Control loop around Waste Heat boiler ......................... Error! Bookmark not defined.
11.9
Control loop around Distillation Column .................................................................... 121
11.9.1
Objectives ............................................................................................................ 121
11.9.2
Manipulated Variables ......................................................................................... 121
11.9.3
Loads or Disturbances.......................................................................................... 121
11.9.4
Control Scheme .................................................................................................... 122
11.9.5
Advantage ............................................................................................................ 122
11.9.6
Disadvantage ........................................................................................................ 122
11.10
Control Loop around Flash Drum .............................. Error! Bookmark not defined.
Chapter 12 .................................................................................................................................... 123

HAZOP Study .............................................................................................................................. 123
12.1
Introduction .................................................................................................................. 124
12.2
Hazard and Operability Study Methodology ............................................................... 124
12.3
Sequence of Examination: ........................................................................................... 125
12.4
Details of Study Procedure: ......................................................................................... 126
12.5
HAZOP Effectiveness:................................................................................................. 127
12.6
The HAZOP Team ....................................................................................................... 128
12.7
HAZOP Study on a Distillation Column ..................................................................... 129
Chapter # 13 ................................................................................................................................. 131

Environmental Impact Assessment .............................................................................................. 131
13.1
HAZOP Effectiveness:................................................................................................. 132
An environmental impact assessment (EIA) is an assessment of the possible positive or

negative impacts that a proposed project may have on the environment, consisting of
the environmental, social and economic aspects. .................................................................... 132
13.2
Step-Wise Structure of EIA ......................................................................................... 132
13.2.1
Preliminary Activities & TOR ............................................................................. 133
13.2.2
Scoping ................................................................................................................ 133
13.2.3
Baseline Study ..................................................................................................... 134
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13.2.4
Environment Impact Evaluation .......................................................................... 134
13.2.5
Mitigation Measures ............................................................................................ 135
13.2.6
Assessment of Alternative Measures ................................................................... 135
13.2.7
Preparation of the final document ........................................................................ 136
13.2.8
Decision-making .................................................................................................. 136
13.2.9
Monitoring of project implementation & its environmental impacts ................... 137
13.3
Environment Impact Assessment of a Proposed Methanol Plant: ............................... 137
13.3.1
Air Emissions ....................................................................................................... 137
13.3.2
Noise .................................................................................................................... 139
13.3.3
Water ........................................................................................................................ 139
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Acknowledgement
All praises be to the "Allah Almighty "the most merciful, the most beneficent who guides
us in the darkness and helps us when despair surrounds us. Without His help one can't
reach ones destination. Undoubtedly these are His unlimited blessings that made us
complete this work. All respects and love for Prophet" Muhammad (PBUH) "who
enlightened our minds to recognize our creator.
We thank our dear parents, who brought us up, fed us and above all; made us educated.
Then we thank all our teachers who taught and guided us; and our dear friends who
encouraged us and moved us for the last four years. To our brothers and sisters who
stood by us and continue to stand by us because of their staunch belief in what we are
capable of.
We feel pleasure and deep sense of indebtedness for our teachers who have enriched the
text by their generous contribution. We express profound and cordial gratitude to our
learned, kind and experienced advisors Engr. Usman Farooq for his kind behavior,
constructive suggestions and all the way helpful supervision.
In the end, we thank all those who by any means helped us completing this project.
Page 11
Chapter 1
Introduction
Page 12
Methanol is a chemical building block used in making hundreds of products that touch
our daily lives. Methanol is also an emerging energy fuel for running our cars, trucks,
buses, and even electric power turbines. Methanol, also known as methyl alcohol or wood
alcohol is the simplest of all alcohols with the chemical formula CH3OH1.
Methanol is a light, colorless, flammable liquid at room temperature, and contains less
carbon and more hydrogen than any other liquid fuel. It is a stable biodegradable
chemical that is produced and shipped around the globe every day for a number of
industrial and commercial applications. Methanol occurs naturally in the environment,
and quickly breaks down in both aerobic and anaerobic conditions2.
The methanol industry spans the entire globe, with production in Asia, North and South
America, Europe, Africa and the Middle East. Worldwide, over 90 methanol plants have
a combined production capacity of about 75 million metric tons (almost 24 billion gallons
or 90 billion liters), and each day more than 100,000 tons of methanol is used as a
chemical feedstock or as a transportation fuel (33 million gallons or 125 million liters).
The global methanol industry generates $36 billion in economic activity each year, while
creating over 100,000 jobs around the globe.
This simple alcohol can be made from virtually anything that is, or ever was, a plant. This
includes common fossil fuels like natural gas and coal and renewable resources like
biomass, landfill gas, and even power plant emissions and CO2 from the
atmosphere.
With its diversity of production feedstocks and array of applications, its
no wonder that methanol has been one of the worlds most widely used industrial
chemicals since the 1800s.
1
2
www.methanol.org
See Appendix A for properties of methanol
Page 13
1.1 Historical Development of Methanol3

Year
Events
1830
1905
1923
1927
Late 1940s
First commercial methanol process by destructive distillation of wood

Synthetic methanol route suggested by French chemist Paul Sabatier
First synthetic methanol plant commercialized by BASF
Synthetic methanol process introduced in United States
Conversion from water gas to natural gas as source of synthetic gas for
feed to methanol reactors
Low-pressure methanol process announced by ICI
Acetic acid process by methanol carboxylation introduced by Monsanto
Arab oil embargo reassessment of alternative fuels
Methanol-to-gasoline process introduced by Mobil
Clan air regulations proposed by Bush administration
Passage of the amended Clean Air Act in United States
Discovery of enhanced crop yields with methanol treatment
1966
1970
1973
1970s
1989
1990
Early 1990s
1.2 Physical Properties

It is also called METHYL ALCOHOL, it is the simplest of a long series of organic
compounds called alcohols; its molecular formula is CH3OH. The modern method of
preparing methanol is based on the direct combination of carbon monoxide gas and
hydrogen in the presence of a catalyst at elevated temperatures and pressures. Methanol is
produced from the methane component of natural gas.
Pure methanol is an important material in chemical synthesis. Its derivatives are used in
great quantities for building up a vast number of compounds, among them many
important synthetic dyestuffs, resins, drugs, and perfumes. Large quantities are converted
to dimethyl aniline for dyestuffs and to formaldehyde for synthetic resins. It is also used
in automotive antifreezes, in rocket fuels, and as a general solvent.
Author: Kung, Harold H. Methanol Production And Use Chemical Industries
Page 14
Methanol is a colorless liquid, completely miscible with water and organic solvents and is
very hygroscopic. It forms explosive mixtures with air and burns with a nonluminous
flame. It is a violent poison; drinking mixtures containing methanol has caused many
cases of blindness or death. Methanol has a settled odor.
1.3 Physical properties

Molecular Weight
32.04
Vapour Pressure
97 Torr at 20 0C
Refractive index
1.3284 at 20 0C
Density
0.7913g/ml (6.602 lb./gal) at 20 0C

0.7866 g.ml (6.564 lb./gal) at 25 0C
Dielectric Constant
32.70 at 25 0C
Dipole moment
2.87 D at 20 0C
Solvent Group
Polarity Index (P)
5.1
Viscosity
0.59 cp at 20 0C
Surface Tension
22.55 dyne/cm at 200C
Solubility in water
Miscible in all properties
Flash point
11 0C
Auto ignition temperature
455 0C
Explosive limit
7-36%
Heat of formation
-210.3 MJ/kmol
Page 15
Critical pressure
81 bar
Critical volume
0.811 m3/kmol
Heat of Vaporization
35278 kJ/kmol
Melting Point
-97.7 0C
Boiling Point
65 0C
Relative Density
0.79
Formula
CH3OH
Molecular weight
32.042 kg/kmol
Heat of Formation
-201.3 MJ/kmol
Gibbs Free Energy
-162.62 MJ/kmol
Freezing point
-97.7 C
Boiling point
64.6 C (at atm pressure)
Critical temperature
512.6 K
Regulatory and Safety Data

Acute Data
Poisonous by ingestion or inhalation, may cause

respiratory failure, kidney failure, blindness
Chronic Effect
As Acute, skin contact can cause dermatitis.
Page 16
1.4 Reaction of methanol

Methanol is the 1st in a series of aliphatic, monohydric alcohol and it give many reaction
of this class. Methanol is a typical member of this class which has 1 carbon atom.
Methanol cannot give elimination of hydroxyl group as higher alcohol.
The reaction of methanol is generally breaking of C-0 or O-H bond and substitution of
the displacement of the H or Oh group. The O-H and C-O bond in alcohol are relatively
strong . Because of this bonding strength in alcohol is necessary to achieve acceptable
reaction rate.
1.5 Chemical Properties of Methanol

1.5.1 Combustion of Methanol:
Methanol burns with a pale-blue flame to form carbon dioxide and steam.
2CH3OH +
302 ===> 2CO2 +
4H2O
1.5.2 Oxidation of Methanol:

Methanol is oxidized with acidified Potassium Dichromate, K2Cr2O7, or with acidified
Sodium Dichromate, Na2Cr2O7, or with acidified Potassium Permanganate, KMnO4, to
form formaldehyde.
[O]
CH3OH
===>
Methanol
HCHO
H2
Formaldehyde
2H2 + O2 ===>
2H2O
If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid
and then to carbon dioxide and water.
[O]
HCHO
Formaldehyde
[O]
===> HCOOH ===> CO2 + H2O

Formic Acid
Page 17
1.5.3 Catalytic Oxidation of Methanol:

The catalytic oxidation of methanol using platinum wire is of interest as it is used in
model aircraft engines to replace the sparking plug arrangement of the conventional
petrol engine. The heat of reaction is sufficient to spark the engine.
1.5.4 Dehydrogenation of Methanol:

Methanol can also be oxidized to formaldehyde by passing its vapor over copper heated
to 300 C. Two atoms of hydrogen are eliminated from each molecule to form hydrogen
gas and hence this process is termed dehydrogenation.
Cu, 300C
CH3OH
===>
Methanol
HCHO
H2
Formaldehyde
1.5.5 Dehydration of Methanol:

Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid
the ester, dimethyl sulphate is formed.
Conc. H2SO4
2 CH3OH
===>
Methanol
(CH3)2SO4
Dimethyl
H2O
Water
Sulphate
1.5.6 Esterification of Methanol:

Methanol reacts with organic acids to form esters.
H(+)
CH3OH
Methanol
HCOOH ===>
Formic
Acid
HCOOCH3
Methyl
+ H2O
Water
Formate
Page 18
1.5.7 Substitution of Methanol with Sodium:

Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is
similar to the reaction of sodium with ethanol.
2 CH3OH +
2 Na ===>
Methanol
2CH3ONa
Sodium
+ H2
Sodium
Hydrogen
Meth oxide
1.5.8 Substitution of Methanol with Phosphorus Pent chloride:

Methanol reacts with phosphorus pent chloride at room temperature to form hydrogen
chloride, methyl chloride, (i.e. chloromethane) and phosphoryl chloride.
CH3OH
Methanol
PCl5 ===> HCl
+ CH3Cl
Phosphorus
Methyl
Phosphoryl
Pent chloride
Chloride
Chloride
POCl3
1.5.9 Substitution of Methanol with Hydrogen Chloride:

Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane) and
water. A dehydrating agent (e.g. zinc chloride) is used.
ZnCl2
CH3OH
Methanol
HCl
===>
CH3Cl
H2O
Methyl
Chloride
Page 19
1.6 Applications of Methanol

Methanol is one of the most versatile compounds developed and is the basis for hundreds
of chemicals, thousands of products that touch our daily lives, and is second in the world
in amount shipped and transported around the globe every year. A truly global
commodity, methanol is a key component of modern life and new applications are paving
the way forward to innovation. While numerous applications transform methanol into
vital products and commodities that drive modern life, methanol is also used on its own
in a number of applications.
1.6.1 Transportation Fuel:

Methanol is the most basic alcohol. It is easy to transport, readily available, and has a
high octane rating that allows for superior vehicle performance compared to
gasoline. Many countries have adopted or are seeking to expand methanol fueling
programs, and it is the fastest growing segment of the methanol marketplace today. This
is driven in large part by methanol's low price compared to gasoline or ethanol, and the
very small incremental cost to modify current vehicles to run on blends of methanol
fuel. Methanol also produces much less toxic emissions than reformulated gasoline, with
less particulate matter and smog forming emissions.
1.6.2 Wastewater Denitrification:

Methanol is also used by municipal and private wastewater treatment facilities to aid in
the removal of nitrogen from effluent streams. As wastewater is collected in a treatment
facility, it contains high levels of ammonia. Through a bacterial degradation process this
ammonia is converted into nitrate. If discharged into the environment, the nutrient rich
nitrate in sewage effluent can have a devastating effect on water ecosystems - creating
miles long algae blooms that sap oxygen and sunlight from aquatic life. Methanol, which
is quickly biodegrades, is a cost-effective way to help revitalize waterways tainted by the
effects of nitrates.
Page 20
1.6.3 Fuel Cell Hydrogen Carrier:

Methanol is used as a key component in the development of different types of fuel cells which are quickly expanding to play a larger role in our energy economy. From largescale fuel cells to power vehicles or provide back-up power to remote equipment, to
portable fuel cells for electronics and personal use, methanol is an ideal hydrogen
carrier. With a chemical formula of CH3OH, have more hydrogen atoms in each gallon
than any other liquid that is stable in normal conditions.
1.6.4 Methanol as a cleansing agent:

Methanol is used in many cleansing operation such as in washing steel surface before
coating are applied rinsing the interiors of electronic tubes before they are evacuated
cleaning resign sheets before further processing. It is employed as a reducing agent in the
vapor phase cleaning of copper. It is also used in special preparation for dry cleaning
leather goods, in glass and in flushing fluids for hydraulic brake system.
1.6.5 Biodiesel Transesterification:

In the process of making biodiesel fuel, methanol is used as a key component in a
process called transesterification - to put it simply, methanol is used to convert the
triglycerides in different types of oils into usable biodiesel fuel. The transesterification
process reacts methanol with the triglyceride oils contained in vegetable oils, animal fats,
or recycled greases, forming fatty acid alkyl esters (biodiesel) and the byproduct glycerin.
Biodiesel production continues to grow around the globe, with everything from large
commercial scale operations to smaller, backyard blenders mixing this environmentallyfriendly fuel for everyday use in diesel engines.
1.6.6 Electricity Generation:

Different companies are also exploring the use of methanol to drive turbines to create
electricity. There are a number of projects currently underway that are using methanol as
the fuel source to create steam to drive turbines - which is an excellent option for areas
rich in resources other than traditional electricity sources.
Page 21
1.6.7 Methanol as a solvent:

Methanol is miscible with most organic liquids and it is a solvent of substance like dyes,
nitrocellulose, polyvinyl and modified resin.it is use in the manufacturing of wood and
metal polishes. Water proofing formulation is coated fabrics and other inks. Its solution
has lower velocities than similar solution made from other alcohols. Methanol is use with
5 to 10 % combination of poly hydroxyl alcohol as a solvent for water aniline dyes in
manufacturing of none grain raising wood stain. Methanol does not dissolve cellulose
acetate and acetate butyrate, polyethene, polyvinyl chloride and co-polymers.
1.6.8 Chemical Feed Stock

Methanol is a key component of hundreds of chemicals that are integral parts of our daily
lives. Methanol is most often converted into formaldehyde, acetic acid and olefins - all
basic chemical building blocks for a number of common products. There are a number of
products that are developed from these materials, too many to list all on this page, but
needless to say methanol is all around us and is a critical component of modern life.
Here are just some types of materials that are made from methanol:
i.
Plastics
ii.
Synthetic fibers
iii.
Paints
iv.
Magnetic film
v.
Safety glass laminate
vi.
Adhesives
vii.
Solvents
viii.
Carpeting
ix.
Insulation
x.
Refrigerants
xi.
Windshield washer fluid
xii.
Particle
There are thousands more products that also touch our daily lives in which methanol
is a key component.
Page 22
Chapter 2
Process Selection
Page 23
Methanol is often called wood alcohol because it was once produced chiefly as a
byproduct of the destructive distillation of wood. Most methanols today is produced
from the methane found in natural gas, but methanol is also produced from all types of
biomass, coal, waste, and even CO2 pollution from power plants.
Methanol, unlike oil or gas, does not occur naturally, but, like hydrogen, it is an energy
vector. There are a very large number of routes to make methanol. These range from very
large scale processes based on gas, coal or other fossil resources, to a range of processes
based on renewable biomass feedstocks.
Methanol is manufactured in two major steps; the first step converts the feedstock into
syngas and the next step converts the syngas into methanol. The widest choices in the
route to methanol come in the choice of feedstock and the choice of syngas technology.
2.1 Choice of Feedstock4:

2.1.1 Biomass:
Using biomass as a feedstock for making methanol has the overarching benefit of being a
sustainable source. Its main raw material is woody biomass which is short in Pakistan.
This has led to an extensive research into technologies of making methanol from
biomass. The bottleneck arrives at the fact that yields from all biomass to methanol plants
are substantially low; lesser than about 32%. For this reason, biomass was overlooked as
a potential source for making methanol. The feedstock costs is much higher due to its
uneasy availability.5
Kirk Othmer Encyclopedia of Chemical Technology, Volume 10

http://www.nrel.gov/docs/legosti/old/17098.pdf
Page 24
2.2.3 Natural Gas:

The majority of worldwide methanol plants use natural gas as their feedstock. Natural gas
is preferred firstly, because of its wide availability and secondly, because the syngas it
generates has a favorable composition for methanol formation.
2.2.4 Natural Gas Reserves in Pakistan6:

Exploration of natural gas reservoirs in the recent past has shown that Pakistan can be
self-sufficient in its natural gas demand. The fields of natural gas that exist in the country
are7:
i.
Zarghun Gas Field
ii.
Mari Gas Field
iii.
Zindan Gas Field
iv.
Hanna
2.2.5 Coal: A Fossil Fuel:

Fossil fuels are derived from plant and animal matter. They formed naturally over
millions of years. These energy-producing fuels are the remains of ancient life that have
undergone changes due to heat and pressure. The primary fossil fuels are coal, petroleum
and natural gas. Together they account for 85% of the world's energy consumption.
Coal is a dark, combustible material formed, through a process known as coalification,

from plants growing primarily in swamp regions. Layers of fallen plant material
accumulated and partially decayed in these wet environments to form a spongy, coarse
substance called peat. Over time, this material was compressed under sand and mud, and
heated by the earth to be transformed into coal. Some scientists refer to coal as
sedimentary rock. Coal is primarily composed of carbon, hydrogen, oxygen and nitrogen
along with variable quantities of other elements, chiefly sulfur, hydrogen, oxygen and
nitrogen. It is easily combustible, and burns at low temperatures; it is also making coalfired boilers cheaper. It is use widely and easily distributed all over the world; it is
comparatively inexpensive to buy on the open market due to large reserves and easy
6
7
www.indexmundi.com
See Appendix B, Figure 1.1
Page 25
accessibility. The five largest coal users - China, USA, India, Japan and South Africa account for 82% of total global coal use.
2.2 Choice of Syngas Technology8:

A number of technologies are available for syngas formation9:
2.2.1 Steam Methane Reforming10:

The predominant commercial technology for syngas generation has been, and continues
to be, steam methane reforming SMR, in which methane and steam are catalytically and
endothermic ally converted to hydrogen and carbon monoxide. In this kind of reactors a
pre-heated mixture of natural gas and steam is passed through catalyst-filled tubes,
allocated inside a direct heated furnace. A part of the fuel is combusted inside the furnace
to generate the heat necessary for the endothermic reforming reactions inside the tubes.
Depending on the position of the burners these reformers are categorized within top-fired,
bottom-fired, side-fired, etc. In natural gas steam reforming, 35-50% of total energy input
is absorbed by the reforming process, of which half is required for temperature rise and
the other half for the reaction itself. The produced syngas leaves the reformer at a
temperature of 800900C. The heat of the flue gases is usually utilized in the convective
part of the reformer by generating steam and preheating the feedstock, thus bringing the
overall thermal efficiency to over 85%. In the SMR configuration the needed energy for
the endothermic reforming reaction must pass throughout to different barriers e.g. from
the combusted fuel to the tube walls and from the tube walls to the catalyst inside the
tubes. Typical operating parameters of the SMR process are: pressure 20-26 bar,
temperature 850950C H2/CO ratio 2,96,5. Complete conversion cannot be obtained in
the SMR process: typically 65% of methane is converted, at best it is about 98%, and so
secondary reforming must be used if a higher conversion rate is desired. The SMR
process is the most proven technology with a great deal of industrial experience; it
requires no oxygen and produces syngas with a high H2/CO ratio. It also has relatively
low operating temperatures and pressures in comparison to other technologies.
8
CHRISGAS October 2005_WP11_D89 Literature and State-of-the-Art review (Re: Methane Steam
Reforming
9
See Appendix B, Table 1.2
10
Page 26
Nevertheless, expensive catalyst tubing and a large heat recovery section make an SMR
plant a costly investment that can only be justified for very large-scale production.
2.2.1.1
Advantages:
i.
Most extensive industrial experience
ii.
Oxygen not required
iii.
Lowest process temperature requirement
2.2.1.2
Disadvantages:
i.
H2/CO ratio is often higher than required (3-6)
ii.
Highest air emissions
2.2.2 Partial Oxidation Reforming11:

An alternative approach is partial oxidation, the exothermic, non-catalytic reaction of
methane and oxygen to produce a syngas mixture. SMR and partial oxidation inherently
produce syngas mixtures having appreciably different compositions.
In partial oxidation reformers, a part of the fuel is combusted inside the reformer to
supply the heat necessary for the endothermic reforming reactions. A refractory-lined
pressure vessel is fed with natural gas and oxygen at a typical pressure of 40 bars. Both
natural gas and oxygen are preheated before entering the vessel and mixed in a burner.
Partial oxidation reaction occurs immediately in a combustion zone below the burner.
To avoid carbon deposition the reactants should be thoroughly mixed and the reaction
temperature should not be lower than 1200C. Sometimes steam is added to the mixture
to suppress carbon formation. In the case of catalytic partial oxidation steam is not
required and the temperature can be below 1000C. The syngas produced leaves the
reactor at temperatures of 13001500C. The syngas from the POX process has a H2/CO
ratio between 1.6 and 1.8, so a shift converter or steam injection is necessary to increase
this ratio for methanol synthesis.
11
Page 27
The non-catalytic process allows the use of a broad range of hydrocarbon fuels from
natural gas to coal and oil residue and remains the only viable technology for heavy
hydrocarbons. The catalytic process has a reduced size and consumes less oxygen, but
runs the risk of catalyst destruction by local thermal stress.
2.2.2.1
Advantages:
i.
Feedstock desulfurization is not required
ii.
Absence of catalyst permits carbon formation and therefore, operation

without steam, significantly lowering syngas CO2 content.
iii.
Low methane slip
iv.
Low natural H2/CO ratio is an advantage for applications requiring ratio

less than 2
2.2.2.2
i.
Disadvantages:
Low natural H2/CO ratio is an advantage for applications requiring ratio

greater than 2
ii.
Very high process operating temperatures
iii.
Usually requires Oxygen
iv.
High temperature heat recovery and soot formation/ handling adds process
complexity
v.
Syngas Methane content is inherently low and not easily low and not
easily modified to meet downstream processing requirements.
2.2.3 Auto thermal Reforming12:

This process combines partial oxidation and steam reforming in one vessel, where the
hydrocarbon conversion is driven by heat released in the POX reaction. Both light and
heavy hydrocarbon feed stocks can be converted. In the latter case, an adiabatic prereformer is required. In this process a preheated mixture of natural gas, steam and oxygen
is fed through the top of the reactor. In the upper zone, partial oxidation proceeds at a
temperature of around 1200C. After that, the mixture is passed through a catalyst bed,
where final reforming reaction takes place. The catalyst destroys any carbon formed at
12
See Appendix, Figure 1.4
Page 28
the top of the reactor. The outlet temperature of the catalyst bed is between 850 and
1050C.
The main advantages of ATR are a favorable H2/CO ratio (1.6 to 2.6), reduction of
emissions due to internal heat supply, a high methane conversion, and the possibility to
adjust the syngas composition by changing the temperature of the reaction. However, it
requires an oxygen source. The capital costs for auto thermal reforming are lower than
those of the SMR plant by 25%. Operational costs, however, are the same or even higher
due to the need to produce oxygen. The heat transfer to the catalyst bed is more favorable
in an auto thermal reformer than in the externally heated tubular reformers, since in the
former case the heat in the gas is supplied directly to the catalyst bed. This means that a
high temperature in the catalyst bed can be achieved by burning only a small portion of
the product gas. The quantity of the gas to be burned will be dependent to the inlet
concentration of the methane and other reform able compounds (such as tars) in the
gas. It is more likely that the initial temperature increase in the combustion zone will
reduce the concentration of the tars and other hydrocarbons sharply. However it must be
taken to account that the combustion reaction will consume a part of the hydrogen that is
present in product gas.
2.2.3.1
Advantages:
i.
Natural H2/CO ratio is often favorable
ii.
Lower process temperature requirement than partial oxidation
iii.
Low methane slip
iv.
Syngas Methane content can be tailored by adjusting reformer outlet

temperature
2.2.3.2
Disadvantages:
i.
Limited commercial experience
ii.
Usually requires Oxygen
Page 29
2.2.4 Gas Heated Reforming13:

In the gas heated reformer (GHR) concept the heat for the endothermic reaction is
supplied by cooling down the reformed gas from the secondary reformer. The feed in the
gas-heated reformer is passed first to the primary reformer where about 25% of reforming
takes place. The partially reformed gas is then passed to a secondary oxygen-fired
reformer. The effluent of the latter is used to heat up the feed in the primary reformer. For
start-up, an auxiliary burner is employed. The volume of a GHR is typically 15 times
smaller than the volume of a fired reformer (SMR or CO2) for the same output.
Overheating of hot metal parts and a poor temperature control can lead to problems
concerning the reliable operation of heat exchange reformers. To overcome these
problems, reformers usually use counter-current flows in the low-temperature part with
effective heat transfer and co-current flows in the hot section for a better temperature control.
2.2.4.1
Advantages:
i.
Compact overall size
ii.
Application flexibility offers additional options for providing incremental

capacity
2.2.4.2
Disadvantages:
i.
Limited commercial experience
ii.
In some configurations, must be used in tandem with another syngas

generation technology.
iii.
Increased compression costs in methanol plant
The choice of technology for manufacturing of synthesis gas depends on the scale of
operation. For capacities below 1000-1500 tons/day steam reforming would be cheapest,
whereas auto thermal reforming (ATR) would be cheapest at capacities around
5000 tons/day. For the intermediate range, a combination would be the optimal
solution14.
13
14

TKP 4170 Process Design Project, Norwegian University of Science and Technology
Page 30
Chapter 3
Process Description
Page 31
3.1 Process Flow Sheet
Page 32
Production of methanol from coal by gasification process is consisting of following steps.

3.2
Feed Preparations
3.3
Production of Syn Gas
3.4
Cooling of Syn Gas
3.5
Purification of Syn Gas
3.6
Rearrangement of H2 and CO
3.7
Production of Methanol
3.8
Refining of Methanol.
3.2 Feed Preparation

Coal is the main feedstock that should be prepared before
entering the Syn gas production area. Firstly coal is crushed in a crusher and eventually it
is made fine powder by using ball mill. The coal particle size should be less than 0.1 mm.
Although we can use coal slurry but our feed site contains only solid coal. The coal we
extract from THAR Coal is sub-bituminous Coal. This coal enters at room temperature
into the gasifier where it is reacted. The oxygen stream from Air separator system is
compressed to the desired temperature of 3200 kPa so that it may react with coal. The
steam used should be super saturated at a temperature of 230C.
3.3 Production of Syn Gas

SYN gas (synthetic gas) is the mixture of varying ratios of CO, CO2, and H2 mainly and
small quantities of CH4, NH3, and sulfur contents. Syn gas is produced from coal by
gasification process using Entrained flow gasifier.
We select Entrained flow gasifier because of following reasons.
i.
The fine coal particles react with flowing steam and oxygen.
ii.
Since the gasifier operates at a high temperature.
iii.
A good conversion of about 99% is obtained
iv.
The destruction of tar and oil yields a very pure syngas.
v.
It has a high oxygen demand.
vi.
The high ash content in the sub-bituminous would drive the oxygen consumption
to higher levels.
Page 33
Gasification is a process for converting carbonaceous materials to a combustible or

synthetic gas (e.g., H2, CO, CO2, CH4).In general, gasification involves the reaction of
carbon with air, oxygen, steam, carbon dioxide, or a mixture of these gases at 1,500C
and under pressure of 3200 KPa.
The Syn gas product ratio of H2: CO has a target of 2:1 for direct synthesis to methanol.
However, there are several different gasification operators that produce a variety of
products from Syn gas. The aim for methanol synthesis is to use the operation that will
minimize an extra processing step, namely the downstream water gas shift reactor to
adjust the levels of CO to meet the 2:1 ratio with methanol.
Reaction heat
Reaction
kj/kg.mol
Process
Solid Gas Reaction

C+O2
CO2
+393770
Combustion
C+ 2H2
CH4
+74900
Hydrogasification
C+ H2O
CO+H2
-175440
Steam-carbon
C+ Co2
2CO
-172580
Boudouard
Gas-Phase Reaction
H2o + CO
Co + 3H2
H2+ C02
+2853
Water gas shift
+250340
Methanation
CH4+ H2
A great deal depends on the gasifier system, coal reactivity and particle size, and method
of contacting coal with gaseous reactants (steam and air or oxygen). It is generally
believed that oxygen reacts completely in a very short distance from the point at which it
is mixed or comes in contact with coal or char. The heat evolved acts to pyrolysis the
coal, and the char formed then reacts with carbon dioxide, steam, or other gases formed
by combustion and pyrolysis.
Page 34
3.4 Cooling of Syn Gas

The hot Syn gas mixture from the gasifier outlet is at the temperature of about 1500C.
This is very much high temperature as for as Syn gas is concerned for further processing.
So it is cooled in multistage heat exchanger decreasing its temperature up to 300C.
3.5 Purification of Syn Gas

The Syn gas produced contains various types of impurity gasses the most prominent of
them are CO2 and sulfur containing gasses. They should be removed otherwise they can
damage the catalyst in methanol reactor.
A non-reactive absorption unit is installed for this purpose. The solvent employed here
may be
i.
MEA (mono ethanol amine)
ii.
DEA (di ethanol amine)
The solvent rich in sulfur gasses is then further processed by Clause Process to
produce elemental sulfur.
3.6 Rearrangement of H2 and CO

As we can see from the kinetics and equilibrium data that at this stage the exact ratio of
CO and H2 is not 1:2.It is very much important to achieve that ratio or their approximate
value. So in either adiabatic or isothermal reactor this ratio is achieved. Adiabatic
reactors have no heat transfer, but the temperature within the reactor increases due to the
reaction being exothermic.
Another consideration is the catalyst. According to the literature, the catalysts are
manufactured by iron oxide with 5-15% Cr2O3. The particle size, time in contact with the
stream and the pressure - all affect the reaction rate. The operating temperature of the
reactor is 400C.
Page 35
The reaction involved is

CO
HO
2
CO
+ H
As the reaction is exothermic so a cold water jacket is supplied around the

reactor to keep the temperature constant at 400C.
3.7 Production of Methanol

The next step is the reaction of CO and H2 to produce methanol. This may accompanied
by another reaction that also produce one mole of methanol and water. The reactor used
for this is plug flow reactor because as the feed moves forward it is converted into
methanol product.
CO +
CO
2H
+ 3H
CH OH
3
CH OH + H O
3
The first reaction is the primary methanol synthesis reaction, a small amount of CO2 from
the water gas shift reaction in the feed (210%) acts as a promoter of this primary
reaction and helps maintain catalyst activity. The stoichiometry of both reactions is
satisfied when the ratio is
2. Hydrogen builds up in the recycle loop; this leads to an actual R value of the Combined
synthesis feed (make up plus recycle feed) of 3 to 4. The reactions are exothermic and
give a net decrease in molar volume. Therefore, the equilibrium is favored by high
pressure and low temperature.
During production, heat is released and has to be removed to keep optimum catalyst life
and reaction rate. The produced methanol reacts further to form side products such as
dimethyl ether, formaldehyde, or higher alcohols (van Dijk et al. 1995) these by products
will be negligible in the preliminary design reported, but noted for awareness.
Conventionally, methanol is produced in two phase systems, the reactants and products
forming the gas phase and the catalyst forming the solid phase. Before refining of this
methanol solution, it is passed through a flash drum where pressure is reduced up to 500
KPa. Due to this pressure reduction, the syn gasses are separated from methanol-water
solution. These gasses are vented or recycled while methanol solution is sent for refining.
Page 36
3.8 Refining of Methanol

The stream entering the distillation column had a weight composition of 56.78%water,
42.225% methanol, 1.40% ethanol. The distillate from the distillation column had a
weight composition of 0.005% water, 99.95% methanol, 0.56% ethanol.
The AA methanol grade purity specifications require that the weight composition of the
methanol be greater than 99.85% methanol on a dry basis, less than 0.1% water, and less
than 50 ppmw ethanol will .be greater than 99.85% methanol on a dry basis, less than
0.1% water, and less than 50 ppmw ethanol. The distillate does not match these
specifications.
Page 37
Chapter 4
Capacity Selection
Page 38
The methanol industry is one of the worlds most dynamic and vibrant producing a
basic chemical molecule that touches our daily lives in a myriad of ways. From the basic
chemical building block of paints, solvents and plastics, to innovative applications in
energy, transportation fuel and fuel cells, methanol is a key commodity and an integral
part of our global economy.
4.1
Global Demand of Methanol:
The methanol industry spans the entire globe, with production in Asia, North and South
America, Europe, Africa and the Middle East. Worldwide, over 90 methanol plants have
a combined production capacity of about 75 million metric tons (almost 24 billion gallons
or 90 billion liters), and each day more than 100,000 tons of methanol is used as a
chemical feedstock or as a transportation fuel (33 million gallons or 125 million liters).
Methanol is also a truly global commodity, and each day there is more than 80,000 metric
tons of methanol shipped from one continent to another
.
In 2010, global methanol demand totaled about 45.6 million metric tons and is expected
to exceed 50 million metric tons in 2011, driven in large part by the resurgence of the
global housing market and increased demnd for cleaner energy.
Page 39
But the methanol industry is not just those companies large and small throughout the
globe that produce methanol every day from a wide array of feedstocks including
natural gas, coal, biomass, waste and even CO2 pollution the industry is also made up
of thousands of distributors, technology innovators, downstream manufacturers and
service providers.
4.2
South Asia Methanol Demand
Domestic Production
The production of Methanol totaled at 29291 tons in the June 2012, declined 14% y-o-y
but improved robustly261% sequentially. Indian companies have produced 23191 tonne
of Methanol in May and 27594 tons in April.
i.
Deepak Fertilizers & Petrochemicals Corporation is the second largest methanol

producer with installed capacity of 1, 00,000 TPA.
ii.
Rashtriya Chemicals & Fertilizers (RCF) is the third largest methanol producer
with installed capacity of 72,600 TPA.
iii.
Assam Petrochemicals has an installed capacity of 33,000 TPA of methanol.
iv.
Total domestic production of methanol in India is 4743000 TPA.
v.
More than 60% of Methanol domestic demand is being meeting by imports and
the international market has a direct bearing on domestic prices.
Page 40
vi.
If we add this methanol import in total methanol domestic production then we can
say from calculations that total methanol demand of India in last year is 1182500
TPA.
4.3
China Methanol Industry
China has been the largest methanol consuming country, and will increase its share of
world consumption from almost 41% in 2010 to about 54% in 2015. With total installed
methanol capacity in China does around 38 million tons comprise 60% of the global
capacity with a production of 15.88 million tons indicating capacity utilization of 65%. In
spite of such a low capacity China is further adding around 15 million capacity of
methanol in the coming years on prospect of less reliable on crude oil. Increased demand
in the Chinese market has been fueled by methanol gasoline blending and dimethyl ether
(DME), which combined account for 33% of the Chinese methanol demand and are
expected to grow by 30% this year alone.
Page 41
Total Demand of methanol in China is around 21 million tons comprising 5 million tonne
of imports mainly from import from Middle East Countries. Middle East countries
produces methanol at a much cheaper cost due to lower natural gas prices while in China,
methanol is mainly produced from coal, which accounts for about 60% to 70% of the
total production cost of methanol.
Coal is the major raw material for the production of methanol in China constituting
around 57% followed by natural gas of around 28% and coke oven gas of around 15%.
Middle East Countries too are adding around 11 million tons of methanol capacity.
China to overcome excess methanol capacity is developing and exploiting new
application potentials for methanol. Millions of metric tons of methanol will be mainly
used for direct blending into gasoline and for conversion into DME - again for use as a
fuel. China is promoting methanol to olefin technology.
Methanol is used to produce acetic acid, formaldehyde, and a number of other chemical
intermediaries that are utilized to make countless products throughout the global
economy and by volume, methanol is one of the top 5 chemical commodities shipped
around the world each year. The global methanol industry generates $36 billion in
economic activity each year, while creating over 100,000 jobs around the globe.
Keeping in view the trends of the methanol industry and the global demand, the capacity
selected for our process is 250 Metric tons per day (MTPD).
Page 42
Chapter # 5
Material and Energy

Balance
For the material and energy balance of the entire plant, the following conditions used:
Page 43
Basis=1 hour
Reference Temperature= 25 oC
Reference Pressure= 1 bar
Methanol grade AA=99.95 wt %

m1
m2
m3
m4
m5
m6
m7
m8
m9
m10
m11
m12
m13
m14
5.1
279.05
48.71
580.08
872.94
818.34
818.34
872.94
28.28
846.62
846.62
578.08
268.54
328.08
250
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Mt/day
Material Balance on Distillation Column:

m 14
m 11
m 13
In Stream
m 11= 578.08 MT/Day
No
Component
% Age
Flow rate
CH3OH
43.225
249.87508
H2O
56.78
328.23382
Out Stream
Page 44
m14 = 250 MT/Day
No
Component
% Age
Flow Rate
CH3OH
99.95
249.875
H2O
0.05
0.125
m13=328.08 MT/Day
No
Component
% Age
Flow Rate
H2O
100
328.28
Capacity = m14 = 250 Metric Ton /Day
(1)
Overall Balance
m11
m13 + m14
(2)
m11 (0.43225) = m14 (0.995) + m13 (0)

From (1)
m11 =
578.08 MT/Day
Similarly from Eq. (2)

m13 =
5.2
328.08 MT/Day
Material Balance on Flash Drum:
m 12
m 10
Page 45
m 11
In Stream
m10 = 846.62 MT/Day
No
Component
% Age
Flow Rate
CH3OH
29.5
249.7529
H2O
38.77
328.2345
CO
1.86
15.7471
CH4
0.59
4.995
N2
0.54
4.5717
H2
1.7
14.392
CO2
27.03
228.841
Ethanol
0.00573
0.04851
Solvent
0.0047
0.03979
No
Component
% Age
Flow Rate
CO
5.86
15.7364
H2
5.36
14.39
CH4
1.86
4.99
N2
1.7
4.565
CO2
85.19
228.76
Solvent
0.0148
0.03974
Ethanol
0.018
0.04833
Out Stream
m12=268.54 MT/Day
m11=578.08 MT/Day
Page 46
No
Component
% Age
Flow Rate
CH3OH
43.225
249.875
H2O
56.78
328.233
m11 =
578.08 MT/Day
(3)
Overall Balance
m10 = m11 + m12
(4)
m10 (0.3877) = m11 (0.5678) + m12 (0)

From Eq (3)
m10 =
846.62 MT/Day
m12 =
268.54 MT/Day
Put this in Eq (4)
Page 47
5.3
Material Balance on Reactor:
m9
m 10
CO +
CO2
2H2
+ 3H2
CH3OH
CH3OH + H2O
In Stream
m9= 846.62 MT/Day
No
Component
% Age
Flow Rate
CO
24.54
207.760
H2
49.07
415.436
CH4
0.47
3.979
N2
0.43
3.640
CO2
22.15
187.526
H2O
3.34
28.277
Solvent
0.0037
0.03132
m10 =
846.62 MT/Day
Overall Balance
m9 =
m10
m9 =
846.62 MT/Day
(5)
From Eq. (5), we get
Page 48
5.4
Material Balance on Water Gas Shift Reactor:

m8
m9
m6
CO
H2O
CO2 + H2
In Stream
m8=28.28 MT/Day
No
Component
% Age
Flow Rate
Stream
100
28.28
No
Component
% Age
Flow Rate
CO
55.82
456.797
H2
38.83
317.761
CH4
0.61
4.991
N2
0.54
4.419
CO2
4.2
34.370
Absorber
0.3928
0.3928
m6= 843.28MT/Day
Page 49
Out Stream
m9=846..62MT/day
No
Component
% Age
Flow Rate
CO
24.54
207.760
H2O
3.34
28.277
N2
0.43
3.640
H2
49.07
415.436
CO2
22.15
187.526
CH4
0.47
3.979
Solvent
0.0037
0.0313
m9 =
846.62 MT/Day
(6)
m9 =
m6 + m8
(7)
Overall Balance
Water Balance
m9 (0.0334) = m6 (0) + m8 (1.0)
From Eq (6)
m8 =
28.28 MT/Day
m6 =
818.34 MT/Day
Put this in Eq (7)
Page 50
5.5
Material Balance on Acid Gas Absorber:
m5
m7
m4
m6
In Stream
m5= 818.34MT/day
no
Component
% age
Flow rate
Absorber Solvent
100
818.34
No
Component
% Age
Flow Rate
CO
52.17
455.412
H2O
5.58
48.710
N2
0.54
4.713
H2
36.27
316.615
CO2
3.92
34.21
CH4
1.12
9.776
NH3
0.049
0.4277
m4=872.94 MT/day
Page 51
Out Stream
m7=872.94 MT/day
No
Component
% Age
Flow Rate
N2
0.027
0.235
H2O
5.36
46.789
CH4
0.53
4.626
H2 S
0.39
3.40
Solvent
93.7
817.944
No
Component
% Age
Flow Rate
CO
55.82
456.797
H2
38.83
317.76
CH4
0.61
4.99
N2
0.54
4.419
CO2
4.2
34.37
Absorber
0.048
0.392
m6= 818.73MT/day
m6 =
818..28 MT/day
(8)
Overall Balance
m4 + m5 = m6 + m7
(9)
Solvent Balance
m4 (0) + m5 (1.0) = m6 (0) + m7 (1.0)
m4 =
817.947 + m7 (0.063)
(10)
H S Balance
2
m4 (0.0039) + m5 (0) = m6 (0) + m7 (0.0039)

m4
= m7
Put in (10), we get

m4 = 872.94 MT/Day
From Eq. (9)
m5 = 818.34 MT/Day
Page 52
5.6
Material Balance on Gasifier:
m1
m4
m2
m3
In Stream
m1=279.05MT/day
No
Component
% Age
Flow Rate
66.84
186.517
4.89
13.645
1.49
4.15
1.22
3.40
13.04
36.38
Ash
12.51
34.90
No
Component
% Age
Flow Rate
Steam
48.71
48.71
No
Component
% Age
Flow Rate
O2
100
580.08
m2=48.71MT/Day
m3= 580.08 MT/day
Page 53
Out Stream
m4=872.94 MT/Day
No
Component
% Age
Flow Rate
CO
52.17
455.412
H2
36.27
316.615
CO2
3.92
34.219
H2O
5.58
48.71
N2
0.54
4.713
H2S
0.39
3.404
CH4
1.12
9.776
NH3
0.049
0.427
m4 = 872.94 MT/Day
(11)
Overall Balance
m1 + m2 + m3 =
m4 + A
(12)
Steam Balance
m1 (0) + m2 (1) + m3 (0) = m4 (0.0558) + A (0)
From (11)
m2 = 48.71 MT/Day
Ash Balance
m1 (0.1251) + m2 (0) + m3 (0) = m4 (0) + A (1)
A
= (0.1251) m1
(13)
Atomic Sulfur Balance

m1 (0.0122) + m2 (0) + m3 (0) = m4 (0.0039
m1 = 279.05 MT/Day
From (13)
A
= (0.1251)(279.05)
= 34.9 MT/Day
put in (12)
279.05 + 48.71 + m3 = 872.94 + 34.9

m3 = 580.08 MT/day
Page 54
Energy Balance:
5.7
Energy Balance on Gasifier

Coal 25 C
3200KPa
Syn Gas 1500 C

3200KPa
Steam 230 C
3200KPa
O2 25 C
3200KPa
Overall Energy Balance

QW
K.E + P.E + H
W, K.E and P.E is neglect

So it becomes,
Q
H
= H(product) - H(reactant) + H(formation)
Component
hf
hf
Flow
KJ/Mol
KJ/Mol
Rate
O2
36.38
H2
13.64
H2O
-241.8
48.71
N2
4.15
186.517
H2S
-20.7
3.40
CO2
-293.59
34.21
CH4
-74.6
9.77
CO
-110.25
455.412
Flow Rate Components
Page 55
Enthalpy of Formation:
H = ( Hf) (products) - ( Hf) (reactants)
Hf K J/mol
Reaction
C+O2
CO2
-393.59
C+0.5 O2
CO
-110.525
C+ H2O
CO+ H2
131.275
C+ Co2
2CO
283.065
H2o + CO
H2+ C02
-41.256
Co + 3H2
CH4+ H2 O
205.875
C+ 2H2
CH4
-74.6
H2 + S
H2 S
-20.6
N2 +3H2
2NH3
-45.90
Hf=Hf1 + Hf2 + Hf3+Hf4 + Hf5 + Hf6 + Hf7 + Hf8 + Hf9

Hf = -478.011
Hf = -0.022
KJ/mol of feed reacted

KJ/s
Heat Output
Hproduct
= mCp T
After putting values Cp, we get

Cp
= 26330* 1017 J/Kmol. C
Hproduct = 519.67 * 26330 * 1017 * (1500-25)

Hproduct = 5606192.27 * 1017 KJ/s
Heat Input
From Steam Table
Hin = 420.345 KJ/s
Heat Required = Hin - Hout + Hf
420.345 5.6.6 * 1023 + 227.84
Heat Required = -5.61E23
KJ/s
Page 56
5.8
Energy Balance on Heat Exchanger:

Water in 25 C
Water Out 616 C
Cooled Syn 300 C

Gas
3127 KPa
Hot Syn 1500 C

Gas
3200KPa

QW
K.E + P.E + H

So it becomes,
H
= H(product) -
H(reactant)
Q = H = m Cp T
Heat in by Syn Gas

As from previous
23
Heat in = 5.6.6 * 10
KJ/s
Heat in by Water
As water is in at reference temperature, so heat in by water is 0
Heat out by Cooled Syn Gas

Q=
m Cp T
Cp of Syn gas is = 2.633 * 1023 J/Kmol. C

Q = 520 * 2.633 * 1021 * (300 C - 25 C)
Q = 0.1045886 * 1 023
KJ/s
Page 57
Heat out by Water

From steam table
H = 67327.38
KJ/gmol
From ASPEN
Flow rate of outlet water n = 300.269 Kmol/hr
Q = H = 67327.38 * 300.269
Q
= 5615.64 KJ/s
So total
Qout
= 1.0458886 * 1022 + 5615.645
Qout
= 5.61669 * 1023 KJ/s
So proved,
Qin
= Qout
Page 58
5.9
Energy Balance on Water Gas Shift Reactor:
Steam 400 C
3100KPa
Syn Gas
400 C
2400 KPa
Hot purified Gas 400 C

3100KPa
Reaction:
CO + H2 O
CO2+ H2

QW
K.E + P.E + H

So it becomes,
Q
H
= H(product) - H(reactant) + H(formation)
Component
Hf KJ/mol.K
Flow Rate
H2 O
-241.8
28.27
CO
-110.525
207.76
H2
415.43
CO2
-393.509
187.52
Enthalpy of Formation
Hf = { (-393.509) + (0) }
Hf
- { (-110.525) + (-241.8) }
= - 41.184 KJ/mol
Page 59
Heat input
H reactant = m Cp T
There are two reactants
H steam = 3231 KJ/Kg
Mass flow rate = m = 2.28 MT/day
m
m H steam
= 0.3273
Kg/s
= 3231 * 0.327
m H steam = 1075.55 KJ/s

H Syn Gas = m Cp T
Cp of Syn Gas = -8.53992E16 J/gmol. C
Q = m Cp T
= 487.17 * (-8.53992E16)(400 25)(100
Q = -433.374E16 KJ/s
Heat Output
H out = m Cp T
Cp = 2.4737E16 J/kmol. C
m = 504.019 Kmol/hr.
Q = 504.019 * 2.4737E16 * (400 25) (1000)
Q = 129.87E16 KJ/s
Q = 129.87E16 KJ/s
Page 60
5.10 Energy Balance on Distillation Column:

110 C
400 KPa
10 C
500 KPa
130 C
450 KPa
QW
K.E + P.E + H

So it becomes,
Q
Input =
Put Out
H in = Q = mCp T
Cp = 7.2174E20 J/gmol. K
Q = 1084.96 * 1.5458E20 * (283 298)
Q = 416.185E20 KJ/s
H out of methanol =
mCp T
Cp = 7.8911E20 J/gmol. K
Q = 325.52 * 7.8911E20 * (383 273)
Q = 78.49E20
Page 61
5.11 Energy Balance on Gasifier:
Syn Gas 200 C

3200 KPa
Methanol mixture 200 C

3200 KPa
CO + H2
CH3 OH
CO2 + H2
CH3 OH + H2 O
QW
K.E + P.E + H

So it becomes,
H
= H(product) -
H(reactant) + H(formation)
Components
Hf KJ/mol.K
Flow Rate
CO2
-393.5
228.84
CO
-110.525
15.74
H2
14.39
CH3OH
-238.6
249.75
H2 O
-285.84
328.23
Page 62
Enthalpy of formation
Reaction: 1
CO + H2
CH3 OH
Hf = { (- 238.84) }
Hf
- { (-110.5) + (-393.5) }
- 265.16 KJ/mol
Reaction: 2
CO2 + H2
CH3 OH + H2 O
Hf = { (- 238.84) }
Hf
+ { (-258.84) - (-393.5) + ( 0 ) }
=
- 103.94 KJ/mol
Total Hf
= - 161.22 KJ/mol
Total Hf
= - 22571.65 KJ/s
Heat input
H in = m Cp T
Cp = 3.1829E20 J/gmol. C
Q = 504.019* 3.1829E20 * (400 25)
H in = 167.06E16 KJ/s
Heat Output
H out = m Cp T
Cp = 1.268E21 J/gmol. C
Q = 1588.97* 1.268E21 * (400 25)
H in = 209.88E21 K
Page 63
Chapter 6
Designing of
Gasifier
Page 64
Purpose
Gasification with a usable heating value of gaseous products is a process to convert
carbonaceous fuels. Carbonaceous fuel solids, liquids and such coals, biomass, residual
gases as oil and natural gas are included. Entrained flow, fluidized bed and moving bed
(sometimes, somewhat erroneously, called fixed bed) - similar to traditional solid fuel
boilers, gasifies can be divided into three basic categories. Fluidized bed gasifier
fluidized bed combustors are just as; entrained flow gasifier PF-firing is similar in
concept and moving bed gasifier fire to penetrate bear some similarities. Different types
of gasification processes are compared in the following sections. However, these
categories are different types of gasifier equipment that should be noted the air / oxygen
flow directions are based classification.
6.1
Types of Gasifier:
i.
Entrainment bed Gasifier
ii.
Fluidized Bed Gasifier
iii.
Moving Bed Gasifier
6.1.1 Entrainment bed Gasifier

This gasifier, the fuel and oxygen co-flow type. Be
gasified fuel gas flow and oxygen fuel mixture is introduced from the top inlet taken from
the gasifier sized fine particles (around 100 micron) to Earth. These gasifier is generally
high temperatures (10000C and above) and high temperature to prevent combustion due
to the short residence time.
Page 65
6.1.2 Fluidized Bed Gasifier:

Gasifier fuel in the air / oxygen flow and therefore is
fluidized by name. The gasifier to promote heat and mass transfer, coal and air / oxygen
and steam mixture provides good mixing. Usually the fluidized bed gasification in overall
carbon conversion is limited. Syn-gas is taken out of the top shops. "Gasification Process
type 'refer to the details of the process.
6.1.3 Moving Bed Gasifier:

Moving in bed coal gasifier, coal or other fuel line inlet
and air / oxygen / steam are introduced below comes from. Accident or gasified coal fuel
gas down by counter current is taken out of the bottom ash.
Page 66
Comparison of gasifier types
Entrained Flow
Fluidised Bed Moving Bed
Fuel Types
Solid Liquid
Solid
Solid
Fuel Size
<500m
0.5-5mm
5-50mm
Fuel Residence time
1-10s
5-50s
15-30min
Gas outlet
900-1400
700-900
400-500
temperature
Gasifier technical issues that affect the selection of material to be gasified and project
scale features are added.
Coal: Gasifier all three major categories (ie, entrained flow, fluidized bed and moving
bed) coal gasification can be used to do. Gasifier selection may affect the properties of
the coal and coal ash content and reactivity include melting point. Viscosity high ash coal
and limestone are reduced using. Fluidized bed gasifier ash melting does not depend on
the high ash content coal is used for fluidized bed gasifier and entrained bed gasifier for
such a low ash content coal is used.
Reactivity: fluidized bed gasifier lower the reaction temperature gasification of

lignites of makes them very attractive, but on the other hand, less reactive fluidized bed
coal gasifier conversion efficiency is very low.
Plant size: Entrained bed gasifier plant size can be up to 300 MW. Move the bed and
fluidized bed gasifier plants compared with multiple gasifiers require a higher capacity
for the plant is small and therefore. Some of scale economies we can afford to lose.
Oxidant: oxidant for the use of 'air' option and 'oxygen' is. Oxygen and entrained bed
gasifier operates mostly in the fluidized bed gasifier is used both oxidants can be used.
Page 67
The use of air in a plant that is a very expensive commodity ASU (Air Separation Unit)
helps to get rid of but is in a flipside, the nitrogen flow processing equipment as large.
Typical Raw Product Gas Composition Of Koppers Totzek Gasifier

(Oxygen Blown Type)15
Component
Percentage
CO
52.5
H2
36.0
CO2
10.0
H2S + COS
0.4
N2 + Ar
1.1
Note: Average heating value = 286 Btu/scf: All percentage are in volume percent
We select entrained flow gasifier Koppers-Totzek Gasifier.
15
From Lloyd,W.G, The Emerging Synthetic Fuel Industry, Thumann, A,, Ed, Atlanta, GA: Fairmont
Press,1981.pp. 19-58
Page 68
6.2
Design:
Reactions:
C+O2
CO2
C+0.5 O2
CO
C+ H2O
CO+ H2
C+ Co2
2CO
H2o + CO
H2+ C02
Co + 3H2
CH4+ H2 O
C+ 2H2
CH4
H2 + S
H2 S
N2 +3H2
T = temperature of gasifier
2NH3
= 1500 C
= 1500 + 273
= 1773 K
P = pressure of gasifier
3200 KPa
= 31.58atm
= 464.12 Psi
Page 69
Main Reaction:
There are three main reactions
C+O2
CO2
C+0.5 O2
CO
C+ H2O
CO+ H2
Among this reaction (3) is slowest step according to thermodynamic study of these
reactions
i.
Order of Reaction:
According to thermodynamic and kinetic studies of gasification process its order
is 2nd.
Considering plug flow reactor behavior of gasification.
We get,
Performance eq. of PFR:
-rA
= k CA2
CA0
= Initial Concentration
CA
= Final Concentration
-rA
= Fractional Conversion Of A
= Rate of Reaction
As carbon is almost all converted (99.9 % conversion)

Fractional conversion of carbon = Xc= 0.99
To find the concentration of any component the formula is
Page 70
Concentration = molar flow rate/volumetric flow rate
ii.
Moles of carbon:
279.05 ton/day * 1000kg/1 ton * 1Kmol/12kg * 1day/24hr * 66.84%
= 647.628
Kmol/hr
To convert it into VFR, we divided it with density of carbon (graphite)
= 2000
Kg/m3
So,
Volumetric flow of carbon = 3.886 m3/hr.
Initial concentration of C = Cc0 = 647.628 / 3.886
= 166.666 Kmol/m3
Now final concentration
= ??
Final concentration
= Cc = Cc0 (1-XA) / (1+EcXA)
Where
Ec = fractional change in volume
Ec = (Vf - V 0)/ V 0) = 2-2/2 = 0
As there is no change in volume
So,
Cc = Cc0 (1-XA)
Put values
Cc = (166.66 Kmol/m3) (1-0.99)
Cc = 1.667 Kmol/m3
Now rate eq. for reaction
C+H2O
-rc
=
=
CO+ H2
k Cc2
kc [Cc ] [CH2O ]
Where
[Cc]
= final concentration of carbon
[CH2O] = concentration of H2O

Kc
= rate constant
so,
Page 71
-rA
kc [C] [H2O]
We know the value of [C]

But we do not know [H2O]
As we know
Pv = nRT
n/v = P/RT
Concentration= P/RT
So concentration of H2O
[H2O] = P/RT
As steam is entering at
P = 3200 KPa
T = 230 C
= 230 + 272 = 502 K
so put
[H2O] = 3200/8.314*502
= 0.7667 Kmol/m3
K = 1.392
K = kf/kr = [CO][H2]/[C][H2O]
-rA
iii.
1.78Kmol/m3.s
Residence time
Now residence time = t

t
= [Co
= 166.67 (0.99/1.78)
= 92.7 sec
Residence Time = 93 Sec
iv.
Volume of solid
Now we find the volume of solid we know,

For plug flow reactor
t = [Co] * V/ Fc
Fc = flow rate of carbon in feed
Page 72
V = volume of gasifier
t = residence time
[Co] = initial concentration of Carbon
[Co]
= 166.67 K mol/m3
Fc
= 647.628 Kmol/hr
= 0.18 Kmol/s
So,
V = t* Fc / [Co]
V = 93 * 0.18/166.67
V = 0.1 m3
This is volume of solid
v.
Volume Of Product Gas:
Flow rate of product gas out

PV = nRT
Vg = nRT/P
n = flow rate of product gas out of gasifier
From Mass balance data
n = 4.693 Kmol/s
P = 3200 KPa
R = 8.314 KPa m3/Kmol.K
T = 1772.0 K
Put values,
Vg = nRT/P
= 4.693 * 8.314 *1772/3200
= 21.6 m3
Page 73
vi.
Volume of Gasifier
Total volume = volume occupied by solid +
volume occupied by product gas
= 0.1 + 21.6
Volume = V = 21.7 m3
vii.
Diameter of Gasifier:
Volume = 21.7 m3
Area * length = 21.7 m3
D2 /4 * L
= 21.7 m3
Normally L/D ratio lies b/w
(1)
36
Assume L/D = 5.0

L = 5D
put in (1)
D2 /4 * 5D
= 21.7
5 /4 * D3
= 21.7
3.925 D3
= 21.7
D = 1.77m
L = 1.77 * 5
L = 8.85m
viii.
Thickness Of Gasifier Wall
Thickness =
Where,
P = Pressure on which gasifier is operating = 464.12Psi
Inside radius =
= 0.0885m
= stainless steel pipe pressure allowance= 10500 Psi

= Joint Efficiency = 0.85
= Corrosion allowance = 0.125 for 10 years
By putting Values we get,
Thickness =
Thickness = 0.1725 m
Page 74
6.3
Specification Sheet
Type of gasifier
Entrained flow
Reactor behavior
Plug flow type
Residence time:
92 sec
Length:
8.85m
Thickness:
0.1725m
Volume of solid
o.1 m3
Volume of product gas
21.6 m3
Volume of gasifier
21.7 m3
Dia of gasifier
1.77 m
Thickness
0.175 m
Page 75
Chapter 7
Designing of
Methanol Reactor
Page 76
7.1
Purpose:
Methanol reactor is used in the process for the production of methanol from the inlet feed
CO2 ,H2 , CO from water gas shift reactor by hydrogenation of CO2 & Hydrogenation of
CO . Methanol is recovered.
7.2
Reactor selection criteria:
The type of reactor is selected based in the following characteristics:
7.3
i.
Conversion
ii.
Selectivity
iii.
Productivity
iv.
Safety
v.
Economics
vi.
Flexibility
vii.
Compatibility with processing
viii.
Energy utilization
ix.
Feasibility
x.
Investment operating cost
Reactor types:
Following are the three main types of the reactor

i.
Batch Type ( only for batch type process)
ii.
CSTR ( for liquid reactants)
iii.
PFR
(for the gases reactant )
Page 77
Selection between PFR & CSTR:

CSTR
PFR
Useful for liquid-liquid systems
Use for gases system
Useful for slow reactions requiring
High conversion per unit volume
Large hold up time.

Useful where high mixing is
Run for long periods of time without
Required
maintenance
High heat and mass transfer
High heat and mass transfer
Efficiencies
Efficiencies
7.4
Designing
Overview the following aspect & parameter we selected the PFR for the methanol
synthesis
Design Steps
Once the material balance is over the reactor is performed. The next step is to determine
the following parameter.
i.
Rate of reaction
ii.
Residence time
iii.
Volume of reactor
iv.
Space velocity
v.
Space time
vi.
Diameter
Page 78
Operating conditions
T = temperature of Methanol reactor = 200C
= 200 + 273.15
= 473.15 K
P = pressure of Methanol reactor
= 2328 KPa
Main Reaction:
Synthesis of methanol takes place via two main reactions.
Hydrogenation of CO
C0 + 2H 2
CH3OH
Hydrogenation of CO 2
C0 2 + 3H 2
CH3OH +H2O
Order of Reaction:According to thermodynamic and kinetic studies of methanol synthesis process its order
is 2nd considering plug flow reactor. We get
Calculations:-
i.
Step 1:
Performance equation of plug flow reactor: = CA0
CA0
= Initial Concentration
CA
= Final Concentration
XA
= Fractional Conversion Of A
-ra
= Rate of Reaction
As hydrogen is almost consumed (97% conversion)

Fractional conversion of hydrogen = XH = 0.97
Page 79
Concentration of hydrogen:= 415.43 ton/day * 1000kg/1 ton * 1Kmol/2.016kg * 1day/24hr
= 8586.10 Kmol/hr
To convert it into volumetric flow rate, we divided it with density of hydrogen at32 Bar,
473.15k
= 1.64 Kg/m3
= 10554.6 m3/hr.
Volumetric flow of hydrogen
Initial concentration of Hydrogen = 8586.10/10554.6

= 0.8134 Kmol/m3
Now final concentration
=??
Final concentration = CH = CHO(1-XA) / (1+EcXA )

Where
Ec= fractional change in volume. There is no change in volume
CH = CHO(1-XA)
Put values
CH = (0.8134 Kmol/m3) (1-0.97)
CH = 0.024 Kmol/m3
ii.
Step 2:-
Now we have to calculate rate equation. for reaction
C02+ 3H2O
CH3OH+ H2
Page 80
Where
[K1]
= Reaction Rate
[KEq ]
= Equilibrium Constant for methanol synthesis reaction
[KCO]
= Equilibrium Constant for hydrogenation of CO
[KCO2]
= Equilibrium Constant for hydrogenation of CO2
[K H2 ]
= Equilibrium constant for hydrogen
[K H2O ] = Equilibrium constant for Water

[C Co]
= Concentration of Coin inlet stream
[C Co2]
= Concentration of Co2in inlet stream
[C H2]
= Concentration of H2in inlet stream
[CCH3OH] = Concentration of CH3 OH in outlet stream

As we calculate these values the following
[Cco]
= 0.820 kmol /m3
[CCO2] = 0.813 kmol/m3

[CH2]
= 0.8134 kmol/m3
[CH2O] = 0.812 kmol/m3

[K1]
= 0.533 sec -1
[KH2]
= 0.0031 sec -1
[KH20] = 0.013 sec -1

[KEq]
= 1.011 sec -1
[K CO] = 0.0022 sec -1

[KCO2] = 0.0185 sec-1
Page 81
Now putting the values in equation

(0.0533)*(0.0022) [0.820 *(0.8134)3/2- 0.813 (0.8134)1/2 *(1.011)
[1+0.0022*(0.820) +(0.0185)*(0.813)][(0.813)1/2 (0.0013)/ (0.003) *0.813
- rCH3OH
iii.
= 0.02042 mol/m3.sec
Step 3:
Now calculate residence time = t for methanol reactor

= [Co]
= 0.8134(0.97/0.0204)
= 38.6 sec
Residence Time = 38.6 Sec
iv.
Step 4:
Now we find the volume of reactor we know,

For plug flow reactor
= [Co] * V/ Fc
Fc = flow rate of hydrogen in feed
V = volume
= residue time
[Co] = initial concentration
[Co]
= 0.8134 K mol/m3
Fh
= 8586.10 Kmol/hr.
= 2.38 Kmol/s
v = * Fh / [Co]
v = 38.6 * 2.38 /0.8134
v = 112 m3
Page 82
v.
Step 5:
Space Velocity:
Space Velocity =
vi.
= 0.0259 s -1
step 6:
Diameter of Methanol reactor:Then we calculate the reactor diameter by the following.

Volume = 112 m3
Area * length = 112 m3
D2 /4 * L = 112 m3
(1)
Normally L/D ratio lies b/w 2 5

Assume L/D = 4.0
Hence
L = 4D
put in (1)
D2 /4 * 4D
= 112m3
4 /4 * D3
= 112m3
3.14 D3
112m3
D = 3.292m
L = 3.292 * 4
L = 13.16m
vii.
Step 7:
Thickness Of methanol reactor:

Thickness =
Where,
P = Pressure on which methanol reactor is operating = 3200kpa
P = 32 bar=32 * 1.415 * 10-3 psi
P = 0.04528 psi = 0.3121 kPa
Page 83
Inside radius =
Inside radius = 1.646m

= stainless steel pipe = 10500 Psi
= Joint Efficiency
= 0.85
= Corrosion allowance = 0.125 inch for year
By putting Values we get,

Thickness =
Thickness = 0.1253 inch = 0.00318262 m
7.5
Specification Sheet
Reactor behavior
Plug flow type
Volume:
112m3
Length:
13.16 m
Thickness:
0.00318262 m
Residence time:
38.6 sec
Diameter:
3.292 m
Space velocity
0.0259 s-1
Pressure drop
.3121 kPa
Inside radius
1.646 m
Page 84
Chapter # 08
Designing of Heat
Exchanger
Page 85
Purpose
Heat exchanger is a device which is used to transfer heat between two streams, having
different temperatures, through a boundary wall. The plan of the heat exchanger reactor
outlet heat exchanger between process streams in the Utility is used for. Follow the river
methanol mixture and utility boiler feed water stream. Our goal reactor outlet temperature
of the process stream is to reduce the methanol mixture. Its purity can be increased so
that the temperature is lower for the separation of methanol from other components.
8.1
Types of Heat Exchanger
Following are the basic types of heat exchangers being used in chemical industry;
i.
Double pipe heat exchanger
ii.
Shell and tube heat exchanger
iii.
Air cooled heat exchanger
iv.
Plate and frame heat exchanger
v.
Gas to gas heat exchanger
vi.
Spiral heat exchanger
vii.
Plate Fin heat exchange
8.2
Selection Criteria
i.
Cost - least expensive
ii.
Efficiency is one that operates most efficiently, with the minimum loss of energy
in the transfer, and minimum drop in pressure of the fluids.
iii.
Space must be compact
iv.
Materials must be built from materials that are compatible with the process
streams and are not expensive
v.
Maintenance easy to clean
vi.
Ease of construction
Page 86
8.3
Selection Of Shell And Tube Heat Exchanger:
The shell and tube heat exchanger was selected due to following reasons:
In process industries , shell and tube exchangers are used in great numbers, for more than
any other type of exchanger
i.
It has well-established procedures for design
ii.
It can be manufactured from a wide variety of materials
iii.
It has provided many years of satisfactory service
iv.
Its codes and standards for design and fabrication are easily available
v.
Due to their design, shell and tube heat exchangers offer a large heat transfer area
and provide high heat transfer efficiency
vi.
It has good mechanical layout
vii.
It can be easily cleaned
8.4
Types of Shell and Tube Heat Exchangers:
There are three principal types of shell and tube heat exchangers, including;
i.
Fixed tube-sheet exchanger
ii.
U-tube exchangers
iii.
Floating head exchangers
8.5
Designing
Methanol = q = m Cp
Water
= q=m Cp
Q = UAT
Cp = 33.53
= 33.53 * 1000 * 18.5296/1000
= 612.30
C = 33.54
p
T = 400K
Page 87
Q = m Cp
= 519.9*33.53*400/3600
Q = 1936.9 KJ/s
That is heat load now to find the mass flow rate of water
Q = mwCp
1936. = mw 4.18* (887-297)
mw = 0.7854kg/s
So this is the rate flow of water.
LMTD =
=
LMTD
I.
976.86K
Selection of Ud(overall coeff.)

Hot fluid = gases
Cold fluid = water
Ud = 20 300 w/m2 * C
Coulson vol. # 06 page #819 table #12.1

We take
II.
Ud = 80 W/m C
Total Surface Area:

Q = UdTLMTD
A = Q/UdTLMTD
A = 19369/80*976.86
2
A = 24.78 m
Now from
Kern heat transfer table #10
Tube outside dia (do) = 1 in
Tube inside dia (di ) = o.870 in
Page 88
Standard lengths of tubes in shell &tube heat exchanger are

6,8,12,16,20,24 ft. We selected length of tube = 14 ft. =4.28 m
III.
No Of Tubes:
Area of one tube = d

= 3.14*0.0254*4.268
= 0.306 m
Nt =
= 3.655ft2
= 24.78/o.306
= 80.98 = 81 tubes
IV.
Tube pitch:
Pt. = 1.25d * square pitch
= 1.25* 0.0254
Pt. = 0.3175m
if we use two tubes passes them.

Tubes per pass = 40tubes Tube cross section area = At =
At
= 3.14 * 0.022/4
= 0.00380 m
= 40*0.0038=0.0152 m2
Area per pass
V.
Tube Bundle And Shell Dia:
For 2 tube passes &square pitch

k1 = 0.156
n1 =2.291
As we know for square pitch = Pt.
Foe bundle dia
= D
=
=
1.25 D
D (Nt/k1)1/n
= 0.0254(81/0.156)1/2.2
Page 89
= 0.389 m
Shell clearance = 65mm

Ds = Shell inside dia = 0.434 = 0.057 = 0.490 m
Re =
First we find
G=
Wc = Syn Gas inlet flow
At = tube cross section area
W = 872.94 * 1000 / 24 * 3600
= 10.1034 kg/s
2
At = 0.00380 m
G = 10.10134/0.00380
= 2658.8 kg/m2.C
Re =
As water is in tube side so we take viscosity of water at 320 Bar
=
0.000017kg/m.s
Re =
2658.8 * 0.002/0.000017
Re =
312800 turbulent flow
Prenatal Number:
Pr =
As steam produce is so for super-heated steam
C = 1.59 Btu/lb.F
K = 0.0282 Btu/hr.ft.F
K = 0.0145 KJ/Kg.K
Or
K = 0.000000388 KJ/s.m.K
By putting values,
Page 90
Pr = 0.0145 *
Pr = 0.6353
From fig # 25 of process heat transfer by Kern
As tube side velocity =
= 0.984 m/s
Heat transfer coefficient:
hi = JH RePr1/3 (k/d)
1/3
hi = 630 * 31200 * (0.6353)
* 0.000000368/0.0254
hi = 2615.727
VI.
Shall side heat transfer Coefficient:
Inside dia of shell = Ds = 0.490m

From Coulson volume 6
Assume
Baffle spacing is ranges from 0.2 to 1 times the shell dia
So
= Ds * 0.8
= 0.490 * 0.8
= 0.392 m
Number of baffles = length of tube/baffle spacing

= 4.268/0.392
= 10.88
Now we find the flow area of shell tube
Area =
inner dia*c*b/144pt
= 0.490(o.3175-0.0254) *10.88/144*0.3175
Area = 0.0341m2
Page 91
VII.
Shell Side Eq. Dia

De =1.27/do (pt2-0.785do2)
De = o.o246
Mass velocity = G =W/a
(Kern fig #28)
W =shell side =10.10kg/s

a = 0.0341m2
s
G = 10.10/0.0341 = 296kg/m2
Reynolds no:
Re = ds*G/u
u
= o.33cp
Re = o.490*296/0.033
= 4395.15
Pr
= C *u/K
= 0.033 cp *0.0064/o.ooooo156
Pr = 134.64
Jh = 170
From fig28 kern
1/3
Ho = Jh*Re*Pr
*k/de
= 170*4395.15*134.8651/3*(0.000001566/0.0246)
Ho =
VIII.
239.96 kj/s. m .k
Area Of Heat Exchanger:
Surface area per linear ft. = 0.2618ft

As = Nt *L*as
= 81 *14*0.2618
=296.88ft2
= 296 *1/(3.280)2
=27.53m2
Page 92
IX.
Tube Side Pressure Drop:

Re = 993*1.28*0.0184/0.6*103
Re = 38978.56
Re = 3.8*104
Now value of Jf according to R figure 12.24 page 668

e
Jf = 3.3*10
-3
Now putting all value in Eq

Pt= NP[8Jf(L/di)+2.5] ut2/2
=2[8*3.3*10-3(4.28/0.0022) +2.5] * 993(1.25)2/2 = 2 * 0.147 * 813.
= 2.4 KPa
X.
Shell Side Pressure Drop:

Ps = 8jf(Ds/de)(L/lB)uS2 / 2(/ )
w
Viscosity neglected so
Ps = 8jf(Ds/de)(L/lB)uS2
So shell dia is
Ds = 0.490m
L = 5m
De= 0.0242m
lb = 0.107m
= 947.48 kg/m3
u = 0.023
Re = 4395.15
Jf = 3.9*10-2
Now putting values in Eq
Ps= 8*3.9*102(0.490/0.0242)(5/0.107)947.48/2(0.023)2
= 0.312*23.189*46.72*0.37
= 125.54 kg*N*sec2/m.sec2*kg.m
N/m2 = Pa = Ps = 73 KPa
Page 93
8.6
Specification Sheet
No of tubes
81 tubes
Shall inside dia
0.490 m
Shall side heat transfer coefficient
0.0341m2
Tube Side Pressure Drop
2.4 KPa
Tube surface area
24.78 m2
Area per pass
0.0152 m2
Area
27.53m2
Shell Side Pressure Drop
73 KPa
LMTD
976.86 k
Tube pith
0.317 m
Bundle dia
0.389 m
Re
312800 turbulent flow
Pr
0.6353
Shall Side pressure drop
73 kPa
Page 94
Chapter # 09
Designing of
Distillation Column
Page 95
9.1 Purpose:
Ddistillation column is to produces grade AA at the top of the distillation column has a
purity of 99.95% by weight. The feed to the column is methanol has a fraction of
0.43225.
9.2
Choice between Plate and Packed Column
Vapour liquid mass transfer plate column or a packed column operation can be taken.
These are two very different types of operation. Selection depends on the following
factors column.
i.
Aspects of the system depends on the scaling, foaming, fouling factors, corrosive
systems, thermal evolution, pressure drop, liquid holdup.
ii.
Fluid flow is dependent on the element moment.
iii.
Maintenance, weight, the river, the physical column size and price Depends On
the properties of the element and its internals.
Pack Column Plate Relative Merits Are As Follows:

i.
Without flooding the plate columns wide range of liquid flow rates are designed
to handle. If a system is composed of solid material concrete voids, coating and
packaging materials shall be stored in non-efficient because will be handled in a
plate column
ii.
Packed columns, plate columns are greater than the weight.
iii.
Periodic cleaning is needed, the holes shall be provided for cleaning. Packed in
columns packing must be removed before cleaning.
iv.
System for non-foaming plate column is preferred plate for column
v.
Packed column design information is more readily available and more reliable
than this.
For this particular process, i have chosen the plate column:
Diameter> 0.67m Is
Average temperature (81o C) is higher.
Column height as it contains 25 steps is too large.
Page 96
9.3 Plate Type Choice

Three main types of trays,
i.
Bubble cap,
ii.
sieve trays,
iii.
Valve trays are.
In the sieve tray is selected:

i.
They are less expensive and lighter in weight. It's easy and cheap to install.
ii.
Than bubble cap trays is less pressure drop.
iii.
The wide variations in flow rate easily can handle.
iv.
Maintenance cost is low for ease of cleaning.
As well as the basic principles are established and entailing less risk.
9.4 Construction
Many factors have to be considered when selecting engineering materials, but for
chemical process plant the overriding consideration is usually the ability to resist
corrosion. The process designer will be responsible for recommending materials that will
be suitable for the process conditions. He must also consider the requirements of the
mechanical design engineer; the material selected must have sufficient strength and be
easily worked. The most economical material that satisfies both process and mechanical
requirements should be selected; this will be the material that gives the lowest cost over
the working life of the plant, allowing for maintenance and replacement. Other factors,
such as product contamination and process safety, must also be considered.
The unit handling water & methanol can face the following challenges due to the effect
of thermodynamic properties of the mixture;
9.4.1
Effect of temperature on the mechanical properties
The tensile strength and elastic modulus of metals decrease with increasing temperature.
For example, the tensile strength of mild steel (low carbon steel, C < 0.25 per cent) is 450
N/mm2 at 25C falling to 210 at 500C, and the value of Young's modulus 200,000
N/mm2 at 25C falling to 150,000 N/mm2 at 500C. If equipment is being designed to
Page 97
operate at high temperatures, materials that retain their strength must be selected. The
stainless steels are superior in this respect to plain carbon steels.
Creep resistance will be important if the material is subjected to high stresses at elevated
temperatures. Special alloys, such as Inconel (International Nickel Co.), are used for high
temperature equipment such as furnace tubes. At low temperatures, less than 10C,
metals that are normally ductile can fail in a brittle manner. Serious disasters have
occurred through the failure of welded carbon steel vessels at low temperatures. The
phenomenon of brittle failure is associated with the crystalline structure of metals. Metals
with a body-centered-cubic (bcc) lattice are more liable to brittle failure than those with a
face-centered-cubic (fee) or hexagonal lattice. The brittle fracture of welded structures is
a complex phenomenon and is dependent on plate thickness and the residual stresses
present after fabrication; as well as the operating temperature.
9.4.2
Pitting
Pitting is the term given too much localized corrosion that forms pits in the metal surface.
If a material is liable to pitting penetration can occur prematurely and corrosion rate data
are not a reliable guide to the equipment life.
9.4.3
Effect of stress
Corrosion rate and the form of attack can be changed if the material is under stress.
Generally, the rate of attack will not change significantly within normal design stress
values. However, for some combinations of metal, corrosive media and temperature, the
phenomenon called stress cracking can occur. This is the general name given to a form of
attack in which cracks are produced that grow rapidly, and can cause premature, brittle
failure, of the metal.
9.4.4
High-temperature oxidation
Corrosion is normally associated with aqueous solutions but oxidation can occur in dry
conditions. Carbon and low alloy steels will oxidize rapidly at high temperatures and
their use is limited to temperatures below 50QC, Chromium is the most effective
Page 98
alloying element to give resistance to oxidation, forming a tenacious oxide film.

Chromium alloys should be specified for equipment subject to temperatures above 500C
in oxidizing atmospheres.
Owing the above information the material of construction for the manufacture of
distillation column can be decided. The best material available with optimum
considerations should be selected.
A material chosen should possess the following properties;
i.
Should be capable of withstanding the temperature & pressure inside
ii.
Should have sufficient strength not to rupture with excessive pressure inside the
vessel
iii.
Should be resistant to the vital behavior of the mixture
iv.
Should not react or corrode for contact with the mixture
v.
Should withstand the harsh effects of weather
vi.
Should not be too expensive
vii.
Should be easily available
Since, this column can has a maximum pressure of 490 KPa & a temperature as high as
1380C. Moreover water vapors present inside can cause pitting or cavitations to the
plates.
Conventionally most of the distillation columns are made up of stainless steel. The reason
being its stability against the influence of vapors & the weather conditions which
consequently would cause rusting or corrosion if any weaker material has been used.
Keeping in view the properties of the material & the requirement, the following material
is selected16.
Stainless steel (18Cr, 8Ni)
Keeping in mind the above information, a plate column has been selected for the purpose.
16
From: Table 7.2. Mechanical properties of common metals and alloys of Chemical
Engineering by Coulson & Richardson Vol.6th Ed. 3rd
Page 99
9.5
Designing
From the material balance we get,

F =D+W
24088.5936 = 10412.29 + 13671.0936
24088.5936 kmol = 24088.5936 kmol
Moles In = Moles Out
Water
= Light key component
Methanol = high key component

Feed
Top Product
Bottom Product
(kg/hr)
(kg/hr)
(kmol/hr)
water
13677.50
5.21
12864.5
methanol
10411.0936
10412.29
806.6
Total
24088.5936
10417.5
13671.0936
Component
The fractions are as following

Feed
Top Product
Bottom Product
Mole Fractions
Mole Fractions
Mole Fractions
Methanol
0.43225
0.995
0.059
Water
0.5678
0.0005
0.941
Component
From the table the mole fraction of methanol as under:

Xf
= feed mole fraction
= 0.43225
Xd
= top mole fraction
= 0.995
Xw
= bottom mole fraction = 0.059

1. Nature of feed:
Feed is entering in column as a saturated liquid at T=100C & P=500 KPa

Component
Xf
Ki
Ki*Xf
Methanol
0.43225
2.01
0.8688
Water
0.56775
0.99
0.562
Ki*Xf =1.42
By Bubble point; it is verified that feed is at saturated liquid state.

Page 100
2. Estimation of Top Temperature

By Dew point calculation, yi/ ki= 1.0 ; T=110 and P=400 KPa
Component
yi
Ki
yi / ki
Methanol
0.995
1.09
1.084
Water
0.0005
0.4478
0.00028
yi/ki =1.08
3. Estimation of Bottom Temperature

By Bubble point calculations:Ki.Xw= 1.0 ;T=130& P=450 KPa
Component
Xw
Ki
Ki*Xw
Methanol
0.059
5.301
0.3127
Water
0.941
0.7737
0.728
Ki*Xw=1.040
Hence by bubble-point calculations; T=97.5& P=120 KPa
Standard Design Steps of Distillation Column:

1. Calculation of minimum reflux ratio rm
2. Calculation of actual reflux ratio
3. Calculation of theoretical number of stages
4. Calculation of actual number of stages
5. Calculation of diameter of the column
6. Calculation of flooding point
7. Calculation of entrainment
8. Calculation of pressure drop
9. Calculation of the height of the column
1. Calculation of minimum Reflux Ratio

Page 101
Where,
K1 for methanol = 2.01 & K2 for water = 0.99
= K1/K2
= 2.01/0.99
= 2.03
Rmin;by using Underwood method:
Using Underwood equation;
Rm =
=
=
[2.31231 -
[2.31231 -
= 0.9708 [2.31231 -
]
]
Rm = 2.2
Calculation Of Actual Reflux Ratio
For optimum Reflux Ratio; Using rule of thumb:

Ropt= (1.2 to1.35) Rm
Ropt = 1.2* 2.2
Ropt = 2.64
Calculation of Theoretical number of stages.
First calculating the minimum number of stages

Using Fenskes equation;
n
Page 102
=
=
=
= 6.4
n=7
So minimum number of plates is 7
Theoretical Number Of Plates
Gilliland related the number of equilibrium stages and the minimum reflux ratio and the
no. of equilibrium stages with a plot that was transformed by Eduljee into the relation;
]0.566 ]
= 0.75 [1 (R -
]0.566]
= 0.75 [ 1 ( 2.64 = 0.75 [ 1 0.3024]

= 0.5232
N-7 = 0.5232(N+1)
N-7 = 0.5232N + 0.6232
0.4768N = 7.5232
N = 15.77
N =16
Location of Feed:
The Kirk bride method is used to determine the ratio of trays above and below the feed
point.
= 0.206 log [( )(
)F {
= 0.206 log [(
}2]
)(
)F {
}2]
Page 103
= 0.206 log [(2.154)(0.7613) (13924)]

= 0.206 log (22833.13)
= 0.206 * 4.358
log[
] = 0.89786
Taking anti log we get,

=7.9
ND =7.9 NB
So feed will be entered at the plate number 8
Calculation Of Actual Number Of Stages :
Average column temperature =

=
= = 130
Feed viscosity at average column temperature = ave = 0.0251 cp

Relative volatility =
= 2.03
Putting values in following relation;

= 51-32.5[log (avgavg)]
= 51 32.5 [log (0.0251)(2.03)]
= 92 %
Number of actual stages =
= 17.3
Number of trays = 18
Calculation of the Column Diameter
Because liquid and vapor flow rates are greater at bottom so based upon bottom flow
rates. The following parameters are required to be calculated before getting the column
diameter;
Page 104
a) Vapour load at bottom
V
m
V 3600
V
Vm = maximum vapor flow rate in Stripping section
Q
v = Density
of vapor
QV =
= 1.768 m3/s
b) Liquid load at bottom
QL
Lm
L 3600
=
= 0.015 m3/s
c) Tray dynamics
Flow Parameter
L
FLV m v
Vm L
=(
0.5
0.5
= 0.2543
Assumed tray spacing = 18 = 0.457 m
From Fig 15-5 (b) of Plant Design & Economics for Chemical Engineers, sieve tray
Flooding capacity,
Csb = 0.08 m/s
Surface tension of system = =21.73 dynes/cm
Page 105
d) Net vapor velocity at flooding;
After putting values, we get

= 2.3865 m/s
e) Actual Vapor Velocity:
VN = 0.80 Vnf
= 0.80 * 2.3865
VN = 1.909 m/s
Volumetric flow rate of vapor= m/
= 36.11/11.21
= 3.221 m3/s
f) Net-Area:
An
= Volumetric flow rate of vapor

Actual vapor velocity
= 3.221/1.909
An
= 1.687 m2
Assume that down comer occupies 15% of Cross-sectional Area; then

g) Cross-Sectional Area:
AC = 1.687/0.85
Ac = 1.984m2
Diameter of Column
Since we have;
Ac =
D=
D2
4 Ac
Page 106
D=
D =1.589 m
D= 1.60 m
Calculation of flooding point

Vn =
QV
An
=
= 1.048 m/s
* 100
= 62.1%
This is safe enough.
10 Calculation of Entrainment
As FLV = 0.254 and F = 60.1%
From Figure 11.29 of Coulson 6, we calculate
= 0.045
= Fractional Entrainment factor
Since, < 0.1, so now the process is satisfactory
Net area= An = 1.687 m2
Active area = Aa = Ac - 2Ad = 1.389 m2
Down comer area = Ad = 0.15 Ac = 0.298 m2
Hole area = Ah = 0.1 Aa = 0.138 m2
Take weir height; hw= 25 mm = 0.025 m
Hole diameter; dh= 5 mm = 0.005 m
Plate thickness= xw= 5 mm = 0.005 m
Page 107
11 Pressure Drop Over The Entire Column:

PT = 0.64 * 18
PT = 11.52 KPa
12 Height of Distillation Column:

Height of column Hc= (Nact-1) Hs+ H+ plates thickness
No. of plates = 18
Tray spacing = 0.457 m
Distance between 25 plates = 0.457 * 18 = 8.1 m
Top clearance
= 1.0 m
Bottom clearance = 1.40 m

Tray thickness
0.005 m per plate
Total thickness of trays = 0.005 * 18 = 0.09 m

So
Total Height
= 8.1 + 1 + 1.40 + 0.09
= 10. 59 m
Length / Dia ratio (L/D) ratio:
L/D =
= 6.67
Page 108
9.6
Specification Sheet
Packing type
Tray Column
Reflux ratio
2.64
Number or trays
18
Tray spacing
0.457 m
Height of column
10.59m
Diameter of column
1.589m
Flooding
62.1 %
Tray type
Sieve tray
Hole area
0.1389 m2
Pressure drop
16.01 kPa
Hole size
0.005 m
Down comer area
0.298 m2
Hole area/Active area
0.138 m2
Page 109
Chapter 10
Coast Estimation
Page 110
Introduction of Cost Estimation

Cost estimation is a specialized subject and a profession in its own right. The design
engineer, however, needs to be able to make quick, rough, cost estimates to decide
between alternative design and for project evaluation. Chemical plants are built to make a
profit and an estimate of the investment required and the cost of production are needed
before the profitability of a project can be assessed.
10.1 Accuracy and Purpose of Capital Cost Estimates

The accuracy of an estimate on the amount of design detail available, the accuracy of the
cost data available and the time spent on preparing the estimate. In the early stages of a
project only an approximate estimate will be required and justified by the amount of
information by then developed. Capital cost estimated can be broadly classified into three
types according to their accuracy and purpose.
10.2 Preliminary Estimates

Preliminary (approximate) estimates, accuracy typically 30%, which are used in initial
feasibility studies and to make coarse choices between design alternatives. They are
based on limited cost data and design detail.
10.3 Authorization Estimates

Authorization (Budgeting) estimates, accuracy typically 10 to 15%.These are used for
the authorization of funds to proceed with the design to the point where an accurate and
more detailed estimate can be made. Authorization may also include funds to cover
cancellation charges on any long delivery equipment ordered at this stage of the design to
avoid delay in the project. In a contracting organization this type of estimate could be
used with a large contingency factor to obtain a price for tendering. Normally however an
accuracy of about +/-5% would be needed and a more detailed estimate would be made,
if time permitted. With experience, and where a company has cost data available from
similar projects, estimates of acceptable accuracy can be made at the flow sheet stage of
the project. A rough P & I diagram and the approximate sizes of the major items of
equipment would also be needed.
Page 111
10.4 Detailed Estimates

Detailed (quotation) estimated accuracy 5 to 10%, which are used for project cost
control and estimated for fixed price contracts. These are based on the completed (or near
to complete) process design, firm quotations for equipment and a detailed breakdown and
estimation of the construction cost. The cost of preparingan estimate increases from about
0.1 percent of the total project cost for 30 accuracy to about 2% for a detailed estimate
with an accuracy of 5%.
Before industrial plant can put into operation, a large sum of money must be supplied to
purchase and install the necessary machinery and equipment. Land and service facilities
must be obtained and the plant must be erected complete with all piping, controls and
service. In addition, it is necessary to have money available for the payment of expenses
involved in the plant operation. The total capital required for the installation and working
of a plant is called total capital investment.
Total Capital Investment = Fixed Capital +Working Capital
10.5 Fixed Capital

Fixed capital is the total cost of the plant ready for start-up. It is the cost paid to the
contractors. It includes the cost of:
i.
Design, and other engineering and construction supervision.
ii.
All items of equipment and their installation.
iii.
All piping, instrumentation and control systems.
iv.
Buildings and structures.
v.
Auxiliary facilities, such as utilities, land and civil engineering work.
It is a once-only cost that is not recovered at the end of the project life, other than the
scrap value.
The fixed capital investment classified in to two sub divisions:
i.
Direct Cost
ii.
Indirect Cost
Page 112
10.5.1 Direct Cost

The direct cost items are incurred in the construction of the plant in addition to the cost of
equipment.
i.
Purchased equipment cost
ii.
Purchased equipment installation
iii.
Insulation cost
iv.
Instrumentation and control
v.
Piping
vi.
Electrical installation
vii.
Building including services
viii.
Yard improvement
ix.
Service facilities
x.
Land
10.5.2 Indirect Cost

In Direct cost can be estimated by estimating following costs.
Engineering and supervision
i.
Construction expenses
ii.
Contractors fee
iii.
Contingencies
Start-up expenses
10.6 Working Capital

Working capital is the additional investment needed, over and above the fixed capital, to
start the plant up and operate it to the point when income is earned. It includes the cost
of:
i.
Start-up.
ii.
Initial catalyst charges.
iii.
Raw materials and intermediates in the process.
iv.
Finished product inventories.
v.
Funds to cover outstanding accounts from customers.
Page 113
Most of the working capital is recovered at the end of the project. The total investment
needed for a project is the sum of the fixed and working capital.
10.7 Operating Costs

An estimate of the operating cost, the cost of producing the product is needed to judge the
viability of the project and to make choices between possible alternative processing
schemes. These costs can be estimated from the flow sheet, which gives the raw material
and service requirements and the capital cost estimate. The costs of producing a chemical
product will include items listed below they are divided into two groups:
1. Fixed cost
2.
Variable cost
10.7.1
Fixed Cost
i.
Maintenance (labor and materials)
ii.
Operating labor
iii.
Laboratory costs
iv.
Supervision
v.
Plant overheads
vi.
Capital changes
vii.
Rates and other local taxes
viii.
Insurance
ix.
License fees and Royalty payments
10.7.2 Variable Costs

i.
Raw materials
ii.
Miscellaneous operating materials
iii.
Utilities
iv.
Shipping and packaging
10.8 Cost Indices

A cost is nearly an index value for a given point in time showing the cost at that time
relative to certain base time. So, present cost is estimate from cost index as follows:
Page 114
Present Cost /Index at Present Time=Original Cost /Index Value at Time of Original
Cost.
10.8.1 Types of Cost Indices

Many different types of cost indices are published regularly. Some of these can be used
for estimating equipment cost; others apply specifically to labor, construction, materials
or other specialized fields. The most common of these indices are:
i. Marshal-and-Swift all industry and process industry equipment index.
ii. Engineering news record contraction cost index (Coulson, J.M., and Richardson, J.F.
1991, vol 6).
Page 115
Chapter 11
Instrumentation and
Process Control
11.1 Objective
Primary objective of the designer when specifying instrumentation and control schemes
are:
i.
11.1.1 Safe plant operation:

To help the process variables within know safe operating limits.
ii.
To detect dangerous situations as they develop and to provide alarms and

automatic
iii.
Shutdown systems.
iv.
To provide inter locks and alarms to prevent dangerous operating procedures.
11.1.2 Production rate:

To achieve the design product output.
11.1.3 Product quality:
To maintain the product composition within specified quality standard.

11.1.4 Cost:
To operate at the lowest production cost, commensurate with the other objective. These
are not separate objectives and must be considered together. Measurement is a
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fundamental requisite of process control either the control will be affected automatically,
semi-automatically or manually.
The quality of the control obtainable is a function of the accuracy, repeatable and
reliability of the measuring devices employed. The objective of an automatic process
control is to use the manipulated variable to maintain the controlled variable at its set
point in spite of disturbances. Instruments are provided to monitor the key process
variables during plant operations. Instruments monitoring critical process variables will
be fitted with automatic alarms to alert, the operations to critical and hazardous
situations.
Pneumatic instruments are used in this plant. The main process parameters are all
indicated in the control room where automatic or remote control is carried out centrally.
The process parameters e.g. temperatures, pressure flow, liquid level etc. are converted to
signals with transducers and then indicated, recorded and controlled with secondary
instruments.
11.2 Temperature Measurement and Control:

This is used to control the temperature of outlet and inlet streams in heat exchanger,
condenser, heater and column, most temperature measurement in the industrial processes
is made by means of thermocouples to facilitate bringing measurements to a centralized
location. Usually where high measurement accuracy is required resistance thermometer
are used. For the control of temperature, pneumatic feedback control is used.
Outlet temperature of the system is measured, with the help of thermocouple. This
temperature is fed to a comparator. The difference between the set point and the input
signal is called error, is fed to the controller, which controls diaphragm valve to adjust the
flow of hot or cooling medium.
Page 117
11.3 Pressure measurement and control:

The temperature and pressure are valuable indications of material state and composition.
In fact, these two measurements considered together are the evaluating devices of
industrial materials. In compressed gas systems etc., pressure is of primary importance;
pumping equipments are furnished with pressure measuring devices. Pressure
measurement becomes an indication of the increase or decrease. Most pressure
measurement in the industry is made through elastic devices, either directly connected for
local use or transmission type to a centralized location.
11.4 Flow measurement and control:

Most flow measurements in the industry are done by variable head devices. To lesser
extent variable area and displacement types are used.
11.5 Control loops:

For instrumentation and control of different sections and equipment of plants, following
control loops are most often used.
1. Feedback control loop
2. Feed forward control loop
3. Ratio control loop
4. Auctioneering control loop
5. Split range control loop
6. Cascade control loop
Following is a short outline of these control schemes.
11.5.1 Feedback control loop:
A method of control in which a measured value of a process variable is compared with
the desired value of the process variable and any necessary action is taken. Feedback
control is considered as the basic control loops system. Its disadvantage lies in its
operational procedure.
Page 118
For example if a certain quantity is entering in a process, then a monitor will be there at
the process to note its value. Any changes from the set point will be sent to the final
control element through the controller so that to adjust the incoming quantity according
to desired value (set point). But in fact changes have already occurred and only corrective
action can be taken while using feedback control system.
11.5.2 Feed Forward Control Loop:
A method of control in which the value of disturbance is measured than action is taken to
prevent the disturbance by changing the value of a process variable. This is a control
method designed to prevent errors from occurring in a process variable. This control
system is better than feedback control because it anticipates the change in the process
variable before it enters the process and takes the preventive action. While in feedback
control system action is taken after the change has occurred.
11.5.3 Ratio control:
A control loop in which, the controlling element maintains a predetermined ratio of one
variable to another. Usually this control loop is attached to such as system where two
different systems enter a vessel for reaction that may be of any kind. To maintain the
stoichiometric quantities of different streams, this loop is used so that to ensure proper
process going on in the process vessel.
11.5.4 Auctioneering control loop:
This kind of control loop is normally used for a huge vessel where readings of a single
variable may be different at different locations. This type of control loop ensures safe
operation because it employs all the readings of different locations simultaneously, and
compares them with the set point, then the controller sends appropriate signal to final
control element.
11.5.5 Split range loop:
In this loop controller is preset with different values corresponding to different actions to
be taken at different conditions. The advantage of this loop is to maintain the proper
conditions and avoid abnormalities at very differential levels.
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11.5.6 Cascade control loop:
This is a control in which two or more control loops are arranged so that the output of one
controlling element adjusts the set point of another controlling element. This control loop
is used where proper and quick control is difficult by simple feed forward or feed
backward control. Normally first loop is a feedback control loop.
11.6 Control loop around Heat Exchanger

The control objective is to keep the exit temperature
at 300 oC for our shell and tube heat exchanger.
The possible disturbances are:
(1) Offset of temperature value from its desired value of 300 oC.
(2) Variation in temperature of down term used as a coolant media.
Nomenclature:
TC = Temperature Controller
TT = Temperature Transmitter
Primary Controller
Set Point
TC
TT
115 degree C
Secondary Controller
TC
TT
Dowtherm In
Dowtherm Out
Page 120
11.7 Control loop around Distillation Column

11.7.1 Objectives
In distillation column control any of following may be the goals to achieve
1. Overhead composition.
2. Bottom composition
3. Constant overhead product rate. .
4. Constant bottom product rate.
11.7.2 Manipulated Variables

Any one or any combination of following may be the manipulated variables
1. Steam flow rate to reboiler.
2. Reflux rate.
3. Overhead product withdrawn rate.
4. Bottom product withdrawn rate
5. Water flow rate to condenser.
11.7.3 Loads or Disturbances
Following are typical disturbances
1. Flow rate of feed
2. Composition of feed.
3. Temperature of feed.
4. Pressure drop of steam across reboiler
5. Inlet temperature of water for condenser.
Page 121
11.7.4 Control Scheme

Overhead product rate is fixed and any change in feed rate must be absorbed by changing
bottom product rate. The change in product rate is accomplished by direct level control of
the reboiler if the stream rate is fixed feed rate increases then vapor rate is approximately
constant & the internal reflux flows must increase.
11.7.5 Advantage
Since an increase in feed rate increases reflux rate with vapor rate being approximately
constant, purity of top product increases.
11.7.6 Disadvantage
The overhead reflux change depends on the dynamics of level control system that adjusts
it.
Page 122
Chapter 12
HAZOP Study
Page 123
Introduction
An important element of any system for the prevention of major accidents is conducting a
hazard and operability study (HAZOP) at the detail design stage, of the plant in general
and the operating and safety control systems in particular. HAZOPs seek to minimize the
effect of an atypical situation in the operation/process by ensuring that control and other
safety systems such as functional safety (e.g. emergency safe shutdown) are in place and
work with a high level of reliability to achieve a safe outcome from a situation that could
have resulted in a major accident.
The HAZOP process is used to identify potential hazards and operational problems in
terms of plant design and human error. The technique is applied during final design of the
process and plant items before commencement of construction.
HAZOPs have also proven to provide financial benefits to the plant owner/operator by
minimizing the time and money spent in installing add on control and safety systems, the
need for which may become evident at the time of plant commissioning in the absence of
a HAZOP. On the operability front benefits are gained by implementing at design stage,
the remedial recommendations to operability issues identified during the HAZOP.
12.1 Hazard and Operability Study Methodology

Essentially, the HAZOP examination procedure systematically questions every part of a
process Or operation to discover qualitatively how deviations from normal operation can
occur and whether further protective measures, altered operating procedures or design
changes are required. The examination procedure uses a full description of the process
which will, almost invariably, include a P&ID or equivalent, and systematically questions
every part of it todiscover how deviations from the intention of the design can occur and
determine whether these deviations can give rise to hazards.
The questioning is sequentially focused around a number of guide words17 which are
derived from method study techniques. The guide words ensure that the questions posed
17
See Appendix D, Figure 1.1
Page 124
to test the integrity of each part of the design will explore every conceivable way in
which operation could deviate from the design intention.
Some of the causes may be so unlikely that the derived consequences will be rejected as
not being meaningful. Some of the consequences may be trivial and need be considered
no further. However, there may be some deviations with causes that are conceivable and
consequences that arc potentially serious. The potential problems are then noted for
remedial action. The immediate solution to a problem may not be obvious and could need
further consideration either by a team member or perhaps a specialist. All decisions taken
must be recorded.
The main advantage of this technique is its systematic thoroughness in failure case
identification. The method may be used at the design stage, when plant alterations or
extensions are to be made, or applied to an existing facility
18
12.2 Sequence of Examination :

The main elements under consideration in a HAZOP study are as follows:
i.
Intention
ii.
Deviation
iii.
Causes
iv.
Consequences
Hazards
Operating Difficulties
v.
Safeguards
vi.
Corrective Action.
Typically, a member of the team would outline the purpose of a chosen line in the
process and how it is expected to operate. The various guide words such as MORE are
selected in turn. Consideration will then be given to what could cause the deviation.
Following this, the results of a deviation, such as the creation of a hazardous situation or
operational difficulty, are considered. When the considered events are credible and the
18
See Appendix D, Figure 1.2
Page 125
effects significant, existing safeguards should be evaluated and a decision then taken as to
what additional measures could be required to eliminate the identified cause. A more
detailed reliability analysis such as risk or consequence quantification may be required to
determine whether the frequency or outcome of an event is high enough to justify major
design changes.
12.3 Details of Study Procedure:

The study of each section of plant generally follows the following pattern:
i.
The process designer very briefly outlines the broad purpose of the section of
design under study and displays the P&ID (or equivalent) where it can be readily
seen by all team members.
ii.
Any general questions about the scope and intent of the design are discussed.
iii.
The first pipeline or relevant part for study is selected, usually one in which a
major material flow enters that section of the plant.
iv.
The process designer explains in detail its purpose, design features, operating
conditions, fittings, instrumentation and protective systems, etc., and details of
the vessels immediately upstream or downstream of it.
v.
Any general questions about the pipeline or relevant part are then discussed.
vi.
The detailed 'line by line' study commences at this point. The discussion leader
takes the group through the guide words chosen as relevant. Each guide word or
prompt, such as HIGH FLOW, identifies a deviation from normal operating
conditions. This is used to prompt discussion of the possible causes and effects of
flow at an undesirably high rate. If, in the opinion of the study team, the
combination of the consequences and the likelihood of occurrence are sufficient
to warrant action, then the combination is regarded as a 'problem' and minuted as
such. If the existing safeguards are deemed to be sufficient then no further action
is required. For major risk areas the need for action may be assessed
quantitatively using such techniques as Hazard Analysis (HAZAN) or Reliability
Analysis. For less critical risks the assessment is usually based on experience and
judgement. The person responsible for defining the corrective action is also
nominated.
Page 126
vii.
It should always be remembered that the main aim of the meeting is to find
problems needing solution, rather than the actual solution. The group should not
be tied down by trying to resolve a problem, It is better to proceed with the study,
deferring consideration of the unsolved problems to a later date.
viii.
When the guide word requires no more consideration, the chairperson refers the
team to the next guide word.
ix.
Discussion of each guide word is confined to the section or pipeline marked, the
vessels at each end and any equipment, such as pumps or heat exchangers, in
between.
x.
When all guide words have been covered, the line is fully highlighted to show
that it has been completed, and the next line is chosen.
xi.
When all the lines in a plant sub-section have been reviewed, additional guide
words are used for review (overview) of the P&ID as a whole.
12.4 HAZOP Effectiveness:

The effectiveness of a HAZOP will depend on:
i.
The accuracy of information (including P&IDs) available to the team

information should be complete and up-to-date
ii.
The skills and insights of the team members
iii.
How well the team is able to use the systematic method as an aid to identifying
deviations
iv.
The maintaining of a sense of proportion in assessing the seriousness of a hazard

and the expenditure of resources in reducing its likelihood
v.
The competence of the chairperson in ensuring the study team rigorously follows
sound procedures.
Key elements of a HAZOP are:

i.
HAZOP team
ii.
full description of process
iii.
relevant guide words
iv.
conditions conducive to brainstorming
v.
recording of meeting
Page 127
vi.
follow up plan
12.5 The HAZOP Team

The group carrying out the HAZOP will typically consist of a team of approximately five
to eight people. Team members should possess a range of relevant skills to ensure all
aspects of the plant and its operations are covered, Engineering disciplines, management,
and plant operating staff should be represented. This will help prevent possible events
from being overlooked through lack of expertise and awareness. It is essential that the
chairperson is experienced in HAZOP techniques. This will ensure that the team follows
the procedure without diverging or taking short-cuts. Apart from the chairperson, it is
important that the study team be highly familiar with the information contained in the
P&ID of the plant or alternative description of the process being considered. For existing
plant, the group should include experienced operational and maintenance staff.
Page 128
12.6 HAZOP Study on a Distillation Column
Page 129
GUIDE
CAUSE
CONSEQUENCE
RECOMMENDAT
WORD
High flow
ION
Flow
Level in column rises and
controller
hence, temperature falls.
fault
Product
re-boiler
attempt
to
Independent high flow

alarm on LO.
will
maintain
temperature in column until

re-boiler
capacity
is
reached.
The
column
stops
operating.
Low flow
1.
Product
feed
pump
Temperature
rise
in
column.
failed.
Drop in liquid level in
2.
column.
Isolating
Over-heating.
valve
jammed.
High level
Level
Flooding
controller
re0boiler operation stops.
of
L6
and
fault
High
level
alarm,
independent of level
controller LIC.
Alarm level below L6.
High pressure
Water failure
Condenser vent will act as
in condenser.
a relief device.
No adverse effect.
Pressure indicator on
column.
High pressure alarm,
plus trip on gas/air
control valve V1.
Reverse flow
Cooling
of
condenser
Suck back of air into H3
Consider N2 purge.
on cooling.
and H3 after
shut down.
Page 130
Chapter # 13
Environmental
Impact Assessment
Page 131
13.1 HAZOP Effectiveness:

An environmental impact assessment (EIA) is an assessment of the possible positive or
negative impacts that a proposed project may have on the environment, consisting of
the environmental, social and economic aspects.
The purpose of the assessment is to ensure that decision makers consider the ensuing
environmental impacts when deciding whether or not to proceed with a project. The
International Association for Impact Assessment (IAIA) defines an environmental impact
assessment as "the process of identifying, predicting, evaluating and mitigating
the biophysical, social, and other relevant effects of development proposals prior to major
decisions being taken and commitments made."
EIA as it is practiced today is being used as a decision aiding tool rather than decision
making tool. However, as well as direct effects, developments cause a multitude of
indirect effects through consumption of goods and services, production of building
materials and machinery, additional land use for activities of various manufacturing and
industrial services, mining of resources etc. The indirect effects of developments are
often an order of magnitude higher than the direct effects assessed by EIA. Large
proposals such as airports or ship yards cause wide ranging national as well as
international environmental effects, which should be taken into consideration during the
decision-making process.
13.2 Step-Wise Structure of EIA19

EIA Process can be itemized into the following 9 steps.
Public disclosure and participation are the key factors throughout the EIA system, and
should be implemented at the effective timing at every step. Practically, however, the
timing of implementation differs by systems applied by each country/organizations.
1) Preliminary Activities and Decision of Terms of Reference (TOR)
2) Scoping
19
Modified Ahmad, Y.J. and Sammy G.K.(1985) Guidelines to Environmental Impact Assessment, Hodder
and Stoughton, London
Page 132
3) Baseline Study
4) Environmental Impact Evaluation
5) Mitigation Measures
6) Assessment of Alternative Measures
7) Preparation of Final Document
8) Decision-making
9) Monitoring of Project Implementation and Its Environmental Impacts
13.2.1 Preliminary Activities & TOR
Preliminary activities include the defining of the Terms of Reference (TOR)for the
project and also the determining of the personnel required for the assessment. A brief
summary of the project is extremely helpful at this stage. The summary should be clear
and explicit and should list exactly what the development project entails.
13.2.2 Scoping
The existing laws and regulations that are applicable to the project should also be
reviewed along with the regulating authorities. The same procedure must be adopted for
technical, financial and managerial resources available for the project.
It is very important to identify the team that will carry out the EIA procedure along with a
coordinator and the decision-maker who will read the final report.
Members of the EIA team usually have the specialized professional expertise of different
areas related to the various aspects of the project. Thus, an EIA team might include an
engineer, an economist, a physical geographer and a sociologist, with a senior
government official to play the role of a coordinator.
All these need to be identified and declared before the actual EIA process may begin.
The composition of the EIA team varies from country to country. In the United States,
the developer carries out the functions of both the EIA preparation, and the decisionmaking with the Environmental Protection Agency (EPA), involved only in reviewing
and monitoring the project. In other countries, a government organization may actually
carry out the EIA process. Some countries may not have the appropriate means and
facilities for this purpose, and therefore, in such cases, a team of consultants may be
Page 133
employed to help with the assessment. This often turns out to be an expensive
proposition. A team partly of local governmental personnel and partly of consultants
might serve the purpose very well in such cases. Similarly, the decision-maker may be a
person, a committee, or a number of organizations, etc.
The following techniques are used for scoping:
i.
Checklist technique
ii.
Matrix technique
iii.
Networks technique
iv.
Overlay technique15
13.2.3 Baseline Study
A baseline study is the study of the original status of the environment in the area before
the development work of the project is started. This study serves the purpose of a base
reference against which the changes due to implementation of the project are measured.
Baseline studies are based on the experience with respect to environmental aspects and
cover everything important about the environmental impacts of the project. On the other
hand, a proper scoping highlights the significant environmental issues of the project with
respect to its locality and regional environment. Hence, scoping and baseline studies
often run into each other. Baseline studies are rather easily carried out in the countries
where the required technical expertise, long-term database for environmental measures
(for instance in the case of river flow)and relevant research papers and reports are
available for the area concerned.
Thus, the baseline studies are more easily prepared in developed countries. The local
expertise, such as consulting a forester or a soil scientist, could be utilized instead to
complete the baseline studies in the developing countries. In such cases, the team
responsible for the EIA must have the ability to find out the appropriate personnel for the
required information.
13.2.4 Environment Impact Evaluation

Environmental impact evaluation actually grows out of scoping and baseline study of the
project. In principle, EIA assigns various quantified values to different levels of all the
Page 134
impacts affecting the project. This step is generally considered as the most technical in
nature and therefore is the most difficult and controversial part of the EIA. It is difficult
because not every impact, especially natural and social impacts, can be quantified. For
example, it is very difficult to agree on a number that can sum up all the negative impacts
of deforestation. Occasionally, it is possible to use surrogate measures, such as the
amount of money required to mitigate the damage or the amount of money local
inhabitants are willing to pay to clean up the river. However, the accuracy and
appropriateness of such techniques can be questioned. Again, an existing data set can be
extremely useful for impact evaluation, but it is also costly.
Impact evaluation actually calls for very careful considerations of the most important
impacts and their accurate numerical representation. This has to be done not only for the
proposed project but also for all possible alternatives, so that a well-balanced final
decision can be reached regarding the fate of the project. Impact evaluation is therefore
dependent on the quality of the scoping that is done earlier on the project.
13.2.5 Mitigation Measures

Mitigation measures are taken after the impact evaluation. These measures are taken to
reduce the magnitude or intensity of the impacts affecting the environment. This of
course will incur some costs, but it is expected that such measures will, in the long run,
mitigate the impacts so as to make the project both economically and environmentally
viable. The EIA team has to decide between two alternatives, either having a high cost
and low pollution program or having a low cost but a high pollution situation.
13.2.6 Assessment of Alternative Measures

Assessment of alternative measures becomes possible at this stage. The proposed project
and all other relevant versions have been examined for environmental impacts by now.
They have also been corrected by applying the mitigation measures to minimize the
adverse effects on the environment. They have also been subjected to some kind of
standardization such as impact quantification so that all the relevant versions can be
easily compared. The next step is to assess the environmental degradation and
improvement in terms of economic losses and gains. In standard EIAs, a summary for
Page 135
each version of the project is given together with the comparative assessment using
benefit-cost analysis (BCA). Benefit-cost analysis has a long history of use as a method
for evaluating development projects and therefore is popular with a very wide range of
people, such as, engineers, economists, bureaucrats, etc. However, there is a difficulty in
the assessment as not everything is quantifiable. There is no exact numerical
representation for a beautiful view, for instance, although attempts have been made to
describe such situations numerically. Therefore, not all assessments use net benefit
criteria. The benefit-cost analysis, when used, is equally applied to all options to make
the comparative assessment easy. For instance, it is more desirable to put up with limited
pollution at a lower cost of mitigation than to remove the pollution completely at a much
higher cost.
13.2.7
Preparation of the final document
Preparation of the final document should meet the following two objectives.
First is to prepare a complete and detailed account of the EIA. The second is to prepare a
brief summarized account for a decision-maker, who may not be a technical person.
The detailed document is usually called as the reference document. This document is
used by the technical personnel that is associate with the project. It is also referred for
preparing future EIAs in the same geographical area, or for the same type of project in a
different area
The summarized non-technical account is usually called as the working document, which
is written clearly without using technical language to communicate to the decision-maker
the findings of the EIA team. Main objective of this document is that the non-technical
decision-makers must properly understand the findings and recommendations of the EIA
team so that they can take a well-informed and correct decision promptly.
13.2.8 Decision-making
Decision-making is the process which starts after the above-mentioned steps of EIA are
completed. Usually the decision is taken by a manager or committee, or personnel from
the concerned ministry who had not been associated with the EIA during its preparation.
Page 136
Technical and economic aspects of project alternatives are thoroughly considered but, at
times, political expediency and project feasibility control the final choice.
In general, a decision-maker has three choices:
accepting one of the project alternatives
returning the EIA with a request for further study in certain specific areas
totally rejecting the proposed project along with alternative versions

13.2.9
Monitoring of project implementation & its environmental impacts
Monitoring of project implementation and its environmental impacts is usually carried

out while the selected project is under actual implementation. The monitoring is basically
the process of inspection to make sure that the proper guidelines and recommendations
stated in the EIA are faithfully followed. Such inspections may also be carried out after
the completion of the project to determine as to what accuracy the environmental impacts
have been predicted by the EIA. This could be a very valuable exercise for the
environmental impact assessors.
20
13.3 Environment Impact Assessment of a Proposed Methanol Plant :

13.3.1 Air Emissions
i.
Dust emissions will be produced during construction activities related to

excavation works both on and offshore. Heavy equipment and vehicle movements
also give rise to dust emissions.
ii.
Other gaseous emissions will include exhaust from vehicles and generators.
The principles sources of potential air emissions to atmosphere during the operational
phase are:
i.
Reformer flue gas from the primary flue gas stack: The natural gas fuel to the
primary reformer is normally de sulphureted and therefore SO2 emissions will be
zero. The burner selected for the reformer will be low NOx, and hence NOx
content of the flue gases will be designed to be less than 300 mg/ Nm3.
Furthermore, the reformer flue gases will have a particulate level of less than 100
20
Environmental impact assessment (EIA) for a proposed methanol facility in Damietta Port,
WorleyParsons Komex (resources and energy)
Page 137
mg/ Nm3. The effluent will consist of water, carbon dioxide, oxygen, nitrogen,
and argon. Of less than 100 mg/Nm3. The disposal method will be via flue gas
stack to atmosphere at 18.5 meter height stack.
ii.
Cooling tower evaporation and drift loss in form of water vapour.
This loss is continuous during the operation phase.

i.
ATR jacket vent: This effluent is mainly steam vented to the atmosphere.
ii.
Package boiler intermittent blow down drum vent: Vent only occurs during
periods of intermittent blow down from the package boiler drum.
iii.
Diesel emergency generator exhaust: The composition of the exhaust is similar to

the combustion products. Generators only run during start-up weekly testing or on
power failure.
iv.
Fire water pumps diesel engine exhaust: These pumps are only run in case of fire
and weekly testing (i.e. intermittent flow rate). The composition of the exhaust is
similar to combustion products. The exhaust is vented to the atmosphere at 5.4
meter height.
v.
Crude/off-spec methanol tank vent: The main composition of this intermittent

flow which occurs only during periods of ship loading is nitrogen, methanol and
water. The effluent is vented to the atmosphere at 31oC temperature and 13 meter
height.
vi.
Ship loading vent gas scrubber from vapor recovery package: The main
composition of this intermittent flow which occurs only during periods of ship
loading is nitrogen or air, and methanol.
vii.
Truck loading vent: The composition of this intermittent flow which occurs only
during periods of truck loading is mainly oxygen, nitrogen, and methanol.
The principles sources of potential air emissions to flare are:

i.
Natural gas liquid drum vent: Typical composition of this effluent is natural gas
which will be vented to flare.
ii.
Compressor seal gas losses from compressor seal systems: The composition will
vary dependent on plant operation. Seal gas is typically the same composition as
the compressor discharge gases.
Page 138
Process condensate drum vent.

Flare for nitrogen purge.
13.3.2
Noise
Sources of construction noise include:

i.
Construction vehicles and plant;
ii.
Construction camp noise;
iii.
Pile driving; and,
iv.
Other special localized activities.
The methanol plant has a significant number of major noise sources during the
operational phase, including:
i.
Compressors
ii.
Turbines
iii.
Air Coolers;
iv.
Fans (Flue gas, and Combustion air);
v.
Primary reformer;
vi.
Pumps
vii.
Flares.
viii.
Refining column reflux drum vent.
13.3.3 Water
Pollution problems related to water, during normal operation, may occur due to process
condensates or due to the scrubbing of gases. Carbon dioxide & other toxic based
effluents discharged into the regions waterways, under some conditions, depending on
water pH and temperature can become highly toxic to fish and other animals living in the
water. These substances are not found to be bio -accumulative, or to transfer up the food
chain. Freshwater organisms are most at risk from releases of these gases in the aquatic
environment because they highly soluble in water. These gases considered to be entering
the aquatic environment in a quantity or concentration or under conditions that have or
may have an immediate or long-term harmful effect on the regions environment or its
biological diversity.
Page 139

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Production of Methanol from Coal

Ch. Naveed Anwar

DEPARTMENT OF CHEMICAL ENGINEERING

Production of Methanol from Coal

This report is submitted to department of Chemical Engineering,

DEPARTMENT OF CHEMICAL ENGINEERING

Production of Methanol from Coal

affection and continuous

asset of our lives.

Production of Methanol from Coal

Historical Development of Methanol ................................................................................. 14

Physical Properties ............................................................................................................. 14

Physical properties ............................................................................................................. 15

Reaction of methanol ......................................................................................................... 17

Chemical Properties of Methanol ...................................................................................... 17

Combustion of Methanol: .......................................................................................... 17

Oxidation of Methanol: .............................................................................................. 17

Catalytic Oxidation of Methanol: .............................................................................. 18

Dehydration of Methanol: .......................................................................................... 18

Esterification of Methanol: ........................................................................................ 18

Substitution of Methanol with Sodium: ..................................................................... 19

Substitution of Methanol with Phosphorus Pent chloride: ......................................... 19

Substitution of Methanol with Hydrogen Chloride:................................................... 19

Applications of Methanol .................................................................................................. 20

Transportation Fuel: ................................................................................................... 20

Wastewater Denitrification: ....................................................................................... 20

Fuel Cell Hydrogen Carrier: ...................................................................................... 21

Methanol as a cleansing agent: .................................................................................. 21

Biodiesel Transesterification: .................................................................................... 21

Electricity Generation: ............................................................................................... 21

1.6.8 Chemical Feed Stock ........................................................................................................ 22

Natural Gas: ........................................................................................................... 25

Natural Gas Reserves in Pakistan: ......................................................................... 25

Coal: A Fossil Fuel: ............................................................................................... 25

Production of Methanol from Coal

Choice of Syngas Technology: ...................................................................................... 26

Steam Methane Reforming: ................................................................................... 26

Partial Oxidation Reforming: ................................................................................. 27

Auto thermal Reforming: ....................................................................................... 28

Gas Heated Reforming: .......................................................................................... 30

Feed Preparations ........................................................................................................... 33

Production of Syn Gas ................................................................................................... 33

Cooling of Syn Gas ........................................................................................................ 33

Purification of Syn Gas .................................................................................................. 33

Rearrangement of H2 and CO ........................................................................................ 33

Production of Methanol ................................................................................................. 33

Refining of Methanol. .................................................................................................... 33

Global Demand of Methanol: ........................................................................................ 39

South Asia Methanol Demand ....................................................................................... 40

China Methanol Industry ............................................................................................... 41

Material Balance on Distillation Column: ..................................................................... 44

Material Balance on Flash Drum: .................................................................................. 45

Material Balance on Reactor:......................................................................................... 48

Material Balance on Water Gas Shift Reactor: .............................................................. 49

Material Balance on Acid Gas Absorber: ...................................................................... 51

Material Balance on Gasifier: ........................................................................................ 53

Energy Balance: ............................................................................................................................. 55

Energy Balance on Gasifier .......................................................................................... 55

Energy Balance on Heat Exchanger: ............................................................................. 57

Energy Balance on Water Gas Shift Reactor: ................................................................ 59

Energy Balance on Distillation Column: ....................................................................... 61

Production of Methanol from Coal

Energy Balance on Gasifier: .......................................................................................... 62

Types of Gasifier: ......................................................................................................... 65