DESIGN OF A 40 MTPD METHANOL PLANT

Submitted by

Mohammad Nahidul Islam (1929005)

Abrar Hamim (1929011)

Md. Sohag Torofder (1929013)

Farabi Nusrat (1929015)

Ahmad Tawhid - Ur Rahman Dihan (1929024)

Supervised by

Faisal Ferdous

Lecturer

Department of Chemical Engineering

Khulna University of Engineering & Technology

Department of Chemical Engineering

Khulna University of Engineering & Technology
Khulna 9203, Bangladesh
 Declaration

This is to certify that design work entitled “Design of A 40 MTPD Methanol plant” has been
carried out by Mohammad Nahidul Islam (1929005), Abrar Hamim (1929011), Md. Sohag
Torofder (1929013), Farabi Nusrat (1929015) & Ahmad Tawhid - Ur Rahman Dihan
(1929024) under the guidance of our respected supervisor Faisal Ferdous, Lecturer,
Department of Chemical Engineering, Khulna University of Engineering & Technology,
Khulna, Bangladesh. The above work or any part of this work has not been submitted
anywhere for the award of any degree or diploma.

____________________

Signature of Supervisor

Faisal Ferdous

Lecturer,

Department of Chemical Engineering

Khulna University of Engineering & Technology, Khulna-9203

ii
 Acknowledgement

We Would like to express our sincerest gratitude to our supervisor Faisal Ferdous, Lecturer,
Department of Chemical Engineering, KUET, for his constant guidance and supervision of
our works throughout the course. His inception, skill, patience and care helped us to finish
this work. We would also like to thank our teachers for their valuable insights regarding
process design.

iii
 Abstract

In terms of various applications in the modern world, methanol holds significant importance
as a chemical. It is widely used across the world, including Bangladesh, where its usage is
experiencing a growth parallel with industrial development. A 40 MTPD methanol plant is
to be built in Anwara, Chittagong, Bangladesh, with a working day of 330 days. With all the
utilities, offices, and other facilities included, the factory will have a land area of around 35
acres. The primary raw materials for this plant will be liquefied natural gas (LNG) imported
from Qatar. A comprehensive project description was provided, establishing the design basis
to be aligned with climatic conditions, soil characteristics, socio-economic factors, and
existing environmental regulations. The material and energy balance were conducted for
the entire process.

Keywords: Methanol Plant, Natural Gas, Primary & Secondary Reformer

iv
 Work Load Distribution

Name Student ID Contribution Remarks Marks

Mohammad 1929005 Introduction, Project

Nahidul Islam Definition, Process
Description &
Selection, PBD, PFD,
Material & Energy
Balance
Abrar Hamim 1929011 Environmental
Nuren Assessment, Material
Balance
Md. Sohag 1929013 Material & Energy
Torofder Balance
Farabi Nusrat 1929015 Process Description,
Design Basis, Energy
Balance
Ahmad Tawhid - 1929024 Introduction, Material
Ur Rahman Dihan Balance

v
 Table of Contents

DESIGN OF A 40 MTPD METHANOL PLANT .................................................................. i

Acknowledgement ................................................................................................................ iii

Abstract ................................................................................................................................. iv

List of Tables ........................................................................................................................ ix

List of Figures........................................................................................................................ x

Chapter 01: Introduction ...................................................................................................... 11

Chapter 02 – Project Definition ........................................................................................... 20

2.1 Definition of the Project ............................................................................................ 20

2.2 Raw Material Specifications and Source ................................................................... 20

2.3 Product Specification ................................................................................................. 20

2.4 Plant Location and Area ............................................................................................. 22

Chapter 03- Design Basis .................................................................................................... 24

3.1 Geological Data ......................................................................................................... 24

3.2 Meteorological Data .................................................................................................. 25

3.2.1 Temperature and rainfall ..................................................................................... 25

3.2.2 Atmospheric Pressure .......................................................................................... 26

3.2.5 Wind .................................................................................................................... 28

3.3 Utility Condition ........................................................................................................ 28

3.3.1 Water Quality ...................................................................................................... 28

3.3.2 Air Quality ........................................................................................................... 29

3.4 Climate Conditions .................................................................................................... 29

3.4.1 Ambient conditions in summer: .......................................................................... 29

3.5 Developing Constrains ............................................................................................... 29

Chapter 04 - Selection of Process ........................................................................................ 30

vi
 4.1 Available process ....................................................................................................... 30

4.1.1 Methanol from natural ......................................................................................... 30

4.1.2 Methanol from Coal Gasification ........................................................................ 33

4.1.3 Methanol from Biomass ...................................................................................... 34

4.2 Process Selection ....................................................................................................... 35

4.3 Process Description.................................................................................................... 36

4.3.1 Regasification and Compression of LNG ........................................................... 36

4.3.3 Methanol Synthesis ............................................................................................. 37

4.3.4 Methanol Purification - Low-End and High-End Distillation Column ............... 38

Chapter 05: Environmental Assessment .............................................................................. 39

5.1 Hazard Analysis ......................................................................................................... 39

5.2 Environmental Effect ................................................................................................. 40

Chapter 06: Process Block Diagram .................................................................................... 42

Chapter 07: Process Flow Diagram ..................................................................................... 44

Chapter 08: Material Balance .............................................................................................. 46

8.1 Re-gasifier (E-101) .................................................................................................... 47

8.2 Split into Feed and Fuel ............................................................................................. 48

8.3 Mixer (Feed NG and stream) ..................................................................................... 50

8.4 Compressor (C-101) .................................................................................................. 52

8.5 Heat Exchanger (E-102) ............................................................................................ 53

8.6 Primary Reformer (R-101)......................................................................................... 55

8.7 Secondary Reformer (R-102):.................................................................................... 58

8.8 Heat Exchanger (E-103) ................................................................................................

......................................................................................................................................... 62

8.9 Waste heat boiler: ....................................................................................................... 63

8.10 Compressor (C-102) ................................................................................................ 65

8.11 Cooler (E-104) ......................................................................................................... 66

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 8.12 Flash Separator (V-101) ........................................................................................... 67

8.13 Compressor (C-103) ................................................................................................ 69

8.14 Mixing of Recycle with Reactor Feed ..................................................................... 70

8.15 Methanol Synthesis Reactor (R-103) ....................................................................... 72

8.16 Heat Exchanger (E-105) .......................................................................................... 75

8.17 Cooler (E-106) ......................................................................................................... 76

8.18 Flash separator (V-102)............................................................................................ 77

8.19 Purge splitter ............................................................................................................ 79

8.20 Light End Distillation Column (T-101) ................................................................... 80

8.21 Cooler (E-107) ......................................................................................................... 82

8.22 Heavy end distillation column (T-102) .................................................................... 83

Chapter 09: Energy Balance ................................................................................................ 85

9.1 Re-gasifier (E-101) .................................................................................................... 86

9. 2 Mixing (Feed NG and stream) .................................................................................. 89

9.3 Compressor (C-101) .................................................................................................. 92

9.4 Heat Exchanger (E-102) ............................................................................................ 94

9.8 Waste heat boiler ...................................................................................................... 106

9.9 Cooler (E-104) ......................................................................................................... 109

9.10 Compressor (C-103) .............................................................................................. 112

9.12 Heat Exchanger (E-105) ........................................................................................ 118

9.13 Cooler (E-106) ....................................................................................................... 123

9.14 Light End Distillation Column(T-101) .................................................................. 125

9.15 Heavy End Distillation Column ............................................................................. 128

Reference ........................................................................................................................... 130

viii
 List of Tables

Table 1: Raw material composition ..................................................................................... 20

Table 2: IMPCA reference specification ............................................................................. 21
Table 3: Monthly weather condition in Anwara, Chittagong ............................................. 25
Table 4: Major water properties of Karnaphuli river water ................................................ 28
Table 5: Hazard analysis of chemicals in methanol plant ................................................... 39
Table 6: Inlet and Outlet Conditions for Re-gasifier (E-101) .............................................. 47
Table 7: Inlet and Outlet Conditions for Splitter ................................................................. 49
Table 8: Inlet and Outlet Conditions for Mixer ................................................................... 51
Table 9: Inlet and outlet Conditions for Compressor (C-101) ............................................. 52
Table 10: Inlet and Outlet Conditions for Heat Exchanger (E-102) .................................... 54
Table 11: Inlet and Outlet Conditions for Primary Reformer (R-101) ................................ 57
Table 12: Inlet and Outlet Conditions for Secondary Reformer (R-102) ............................ 61
Table 13: Inlet and Outlet Conditions for Heat Exchanger (E-103) .................................... 62
Table 14: Inlet and outlet Conditions for Waste Heat Boiler ............................................... 64
Table 15: Inlet and Outlet Conditions for Compressor (C-102) .......................................... 65
Table 16: Inlet and Outlet Conditions for Cooler (E-104)................................................... 66
Table 17: Inlet and outlet Conditions for Flash Separator (V-101) ..................................... 68
Table 18: Inlet and Outlet Conditions for Compressor (C-103) .......................................... 69
Table 19: Inlet and Outlet Conditions for Mixing of Recycle with Reactor Feed ............... 71
Table 20: Inlet and Outlet Conditions for Methanol Synthesis Reactor (R-103) ................ 74
Table 21: Inlet and Outlet Conditions for Heat Exchanger (E-105) .................................... 75
Table 22: Inlet and Outlet Conditions for Cooler (E-106)................................................... 76
Table 23: Inlet and Outlet Conditions for Flash Separator (V-102) .................................... 78
Table 24: Inlet and Outlet Conditions for Purge Splitter ..................................................... 80
Table 25: Inlet and Outlet Conditions for Low End Distillation Column (T-101) .............. 81
Table 26: Inlet and Outlet Conditions for Cooler (E-107)................................................... 82
Table 27: Inlet and Outlet Conditions for Heavy End Distillation Column T-102) ............ 84

ix
 List of Figures

Figure 1-1: Market size of methanol in 2021, with a forecast until 2030…………………...15
Figure 1-2: Production of methanol worldwide from 2010-2022…………....…………….16
Figure 2-1: Location and Routes of Anwara Upazila……………………………………...22
Figure 2-2: Plant distance from LNG terminal using Google map left-by land, right-by
water…………………………………………………………………………………….....23
Figure 3-1: Tempreature Data in Chittagong Anwara……………………………………..26
Figure 3-2: Rainfall Data in Chittagong, Anwara Up to 2020……………………………...27
Figure 3-3: Humidity Data in Chittagong, Anwara Up to 2020………...…………………..27
Figure 3-4: Wind speed and direction in Chittagong, Anwara ............................................ 28
Figure 6-1: Process block diagram for the methanol plant………………..….……………..43
Figure 7-1: Process flow diagram for the methanol plant……...………………..…………..45

x
 Chapter 01: Introduction

1.1 Introduction

At present, methanol appears to be one of the very few alternatives to the typical non-renewable
energy sources, namely natural gases and fossil fuels. Methanol was first invented by the
ancient Egyptians; who obtained it by the pyrolysis of wood; and used it in their embalming
process. Later, in 1661, Robert Boyle first extracted pure methanol via boxwood distillation
[1]. It was thereafter referred to as "pyroxylic spirit". The elemental composition was
established in 1834 by French scientists Jean-Baptiste Dumas and Eugene Peligot [2]. In recent
times, hydrogen and carbon monoxide gas are directly combined while a catalyst is present to
create methanol. Methanol, CH3OH, also termed as methyl alcohol or carbinol, is an organic
compound with a molecular weight of 32.042 g/mole. It reaches a boiling point of 64.96 °C
(148.93 °F) and solidifies at -93.9 °C (-137 °F). Methanol has grown to become the 21st largest
commodity chemical with worldwide requirement of over 110 MMT annually, the cost of
which is estimated to be $55 billion per year.
Methanol is the most basic type of alcohol, a clear, colourless, flammable liquid with a peculiar
smell that is somewhat sweeter than ethanol (drinking alcohol) but still light and volatile. It
is toxic in nature and completely mixes with water. Due to its low weight, the vapors can travel
a considerable distance to an ignition source before flashing back. Contact can cause extreme
irritation to the eyes, mucous membranes, and skin [3]. Methanol has been produced and
utilised by mankind since prehistoric times. It served as a crucial component in the embalming
solution employed during the process of mummification in ancient Egypt. Prior to
technological progress, methanol was generated as a secondary outcome of the destructive
distillation of wood.
Most of the produced methanol is used to generate acetic acid, methyl and vinyl acetates,
methyl methacrylate, methylamines, methyl-tert butyl ether (MTBE), formaldehyde and its
derivatives. Methanol is used as a fuel in fuel cells because it can store a lot of energy while
taking up very little space. It produces the strongest, most heat-resistant, most durable
thermoplastic which is easy to color, has little friction, and is resistant to wear and tear. It is
also utilised in wastewater denitrification and is perfect for de-icing windows [4]. Pure
methanol was first synthesized by Robert Boyle in 1661 through extensive distillation.
However, this process was complex and could not be replicated in mass production scenario

11
with economic viability [5]. The interest in industrialising the synthesis of methanol arose soon
following the development of the industrial ammonia manufacturing technique by Haber and
Bosch in 1910. Haber and Bosch demonstrated the feasibility of using catalytic processes in an
industrial environment. As a result, there has been an increase in research efforts to incorporate
catalytic converters into methanol production [6]. During the early 19th century, scientists
started uncovering the catalytic capabilities of several metals. Later, two French chemists, Paul
Sabatier and Senderens, discovered that copper facilitated the transformation of methanol
under specific conditions. They hypothesised that copper, when conditions are reversed, can
serve as a catalyst for the production of methanol. This belief became a reality with the
development of a high-pressure catalytic process for producing methanol, which utilised
copper as one of the catalysts. The second industrial revolution ushered in an era of
economically viable and highly productive mass production. The wood-based techniques were
unable to meet the growing demand and were subsequently superseded by the Badische Anilin
and Sodafabrik (BASF) methods, which utilised synthesis gas (a combination of hydrogen and
carbon monoxide) as the primary material for producing methanol. The process involved the
following reactions:
CO + 2H2 ⇌ CH3 OH ΔH = −90.6 KJ
CO2 + 3H2 ⇌ CH3 OH + H2 O ΔH = −49.5 KJ
CO + H2 O ⇌ CO2 + H2 ΔH = −41.2 KJ

The BASF process first functioned at a temperature of approximately 300°C and a pressure of
300 atm. The initial operating conditions were inefficient as a result of a significantly low single
pass conversion rate in the reactor. In order to address this issue, a loop was established to
facilitate the repeated passage of the raw material gas over the reactor bed, hence enhancing
the total conversion rate. Makeup gas is supplied during each cycle to replenish the reactant
that has been used. This straightforward step completely transformed the entire synthesis
process, and as evidence of its effectiveness, the modified iterations of this fundamental
synthesis loop continue to be employed in industries worldwide to this day. In the early 20th
century, syngas was generated from coal and cokes. Nevertheless, due to the escalating risk of
environmental collapse and, more significantly, the motivation to optimise efficiency, the use
of natural gas has been adopted over coal for the generation of syngas. The syngas was
produced in reformers operating at low pressure. In the 1950s, the majority of coal-based
factories were substituted with facilities that had the capacity to utilise natural gas.
Nevertheless, the introduction of new technology brought forth their own distinct challenges.

12
The natural gas contains sulphur as a contaminant. Sulphur acts as a catalyst inhibitor, greatly
diminishing the catalytic activity of copper. As a result of this understanding, alkalized
reforming catalysts and hydrodesulfurization catalysts were subsequently developed [7]. In the
1960s, there was a significant increase in methanol production led by the British multinational,
Imperial Chemical Industries (ICI). They successfully created a high-pressure steam reformer
and a low-pressure reactor. The decreased pressure in the reactor facilitated rapid reaction rates
at a temperature of 200°C, leading to a decrease in the production of unwanted byproducts. In
addition, they developed a catalyst composed of copper, zinc, and aluminium oxides that
demonstrated exceptional efficiency and durability. The catalyst has the potential to attain
selectivity levels above 99% under ideal operating conditions. ICI integrated these technologies
with the traditional formation process to create the Low-Pressure Methanol Process (LPM).
The initial LPM facility regularly achieved the target of producing 300 metric tonnes per day
(MTPD). The LPM plants served as the foundation for contemporary plants [8]. Currently there
is no methanol plant situated in Bangladesh. As a result, the country has to import methanol
from other neighbouring countries like China, India, Singapore etc. Nonetheless, Bangladesh
can create enormous amounts of methanol annually due to its high natural gas reserves, thereby
meeting her demand for methanol and exporting it later.

1.2 Market analysis-world view

The worldwide methanol market has grown significantly in recent years because of its many
uses in sectors such as chemical, energy, and others. It should be noted that raw material
availability, technical improvements, government restrictions, and environmental concerns all
have an impact on the worldwide methanol market. Price changes in natural gas, coal, and
biomass (the most frequent feedstock for methanol synthesis) can all have an influence on
market dynamics. According to Statista Research, the methanol industry is expected to grow
from USD 37.04 billion in 2022 to USD 61.7 billion by 2030 [9]. Figure-1 shows global
methanol market size with a forecast until 2030.
In 2022, presumptively 27% of the global methanol was used by Formaldehyde industry.
Besides the market is expected to expand because of the need for adhesives from the consumer
stuffs and furniture industries. Methanol can be added with gasoline as a replacement of octane
enhancers in order to improve the fuel quality which can accelerate the expansion of the global
methanol demand. The Asia Pacific dominated the methanol market followed by North
America and Europe in 2022, consuming 65% of the net methanol. At present, Saudi Arabia

13
tops the list of leading methanol exporters; with an annual sale of 1594.22 million U.S. dollars;
followed by USA, with 903.29 million U.S. dollars. The worldwide production of methanol
experienced a significant increase, rising from 88.43 million metric tons (MMT) in 2017 to
111.02 MMT in 2022, depicting substantial growth within the span of five years.Figure-2
shows production of methanol worldwide from 2017 to 2022 [10].
Key global producers of methanol in 2023 were Methanex Corporation, Saudi Arabia Basic
Industries Corporation (SABIC) and Mitsubishi Gas Chemical.

Figure
Figure 0-2: 1-1: Market
Market size
size of of methanol
methanol in 2021,
worldwide in with
2021,a with
forecast until 2030
a forecast until 2030

The methanol sector has significantly influenced the world economy in terms of production,
demand, supply, and import-export activities. With a global yearly production of 98 million
tonnes, this chemical is extensively utilised. The methanol industry is responsible for 10% of
the world's total chemical production, and it is credited with the development of the Low-
Pressure Methanol Process (LPM). The initial LPM facility regularly achieved the target of
producing 300 metric tonnes per day (MTPD). The LPM plants served as the foundation for
contemporary plants [11].

14
Globally, economic activities totalling 55 billion dollars can be attributed to this industry. It
has been estimated that it employs over 90 individuals [12]. Saudi Arabia and the USA are the
primary manufacturers of methanol, which makes a substantial contribution to their Gross
Domestic Product (GDP). Exports and imports have a key role in the vast methanol economy.
In 2022, the total value of methanol exports reached $7.02 billion, with 80 countries
participating. This is a decrease compared to 2021, when the value was $8.82 billion, with 79
nations involved. However, in contrast to 2021 when 129 nations spent $13.2 billion on

Figure
Figure:1-2: Production
Production of methanol
of methanol worldwide
worldwide from
from 2017-2022
2010-2022
2017-2022
methanol imports, a total of 130 countries exceeded the $13.9 billion threshold for methanol
imports [13]. The data indicates a gradual global expansion of the methanol sector.

Saudi Arabia possesses abundant reserves of petroleum and hydrocarbon, enabling the
Kingdom to prioritise the manufacture and export of methanol. Their yearly export of 4.5
million tonnes of methanol in 2022 demonstrates their level of reflection. In addition to Saudi
Arabia, the United States and the Netherlands are prominent nations in terms of exporting
methanol, whereas China and India are significant importers of this chemical compound [14].
Due to the advent of the 4th industrial revolution, sustainability and renewable energy have
emerged as crucial factors in the global economy. Thus, methanol assumes a significant role.

15
The methanol business has the potential to minimise air pollution caused by the energy sector
by producing methanol from biomass, which is a more environmentally friendly way. Methanol
also indirectly enhances the world economy through its downstream derivative chemicals. In
2019, the global chemical industries were valued at over $4.7 trillion [15]. So, methanol
demand is expected to increase throughout the world in the coming days.

1.3 Demand and supply in Bangladesh:

According to the market analysis, there is a growing demand for methanol in Bangladesh,
which has been consistently expanding over time and in accordance with GDP. The tendency
is expected to continue. In addition, new applications for methanol present prospects for
increased demand. For example, methanol has good fuel characteristics; though it is not used
as such in the country. The main three uses of methanol in Bangladesh are as a solvent for
materials such as paint and dyestuff, as a part of adhesive in the wood industry and blending
of methanol with low octane fuel to produce higher octane fuels. Unfortunately, Bangladesh is
import-dependent in the case of methanol; though lying in the region of high level of production
of methanol. The average methanol import price was $575 in 2022, reducing by -7.3% against
the previous year [16].
Singapore is the largest supplier of methanol in Bangladesh, comprising 52% of the total
imports. In 2016, Bangladesh imported 250 metric tons of methanol from India through
Chittagong port. BEXIMCO had previously performed a market analysis on methanol and
obtained a permit for the establishment for a 1250 metric ton per day methanol production plant
in 2003, but that has yet to come into fruition. Bangladesh has a vast stockpile of natural gas,
so it can create a considerable amount of methanol each year and earn plenty of foreign
currency by exporting methanol abroad and fully meeting local demand.
The primary export sectors of Bangladesh in Fiscal Year 2021-2022 were as follows: The
industries in focus are Ready-Made Garments (RMG), Jute and Jute Products, Fish, Shrimps
and Prawns, Leather and Leather Products, Agricultural Products, and Pharmaceutical Products
[17]. All of the major foreign currency-earning sectors in Bangladesh rely on methanol either
as a raw ingredient or as a treatment agent during manufacturing. The RMG sector necessitates
the use of fibre as its primary raw material. Synthetic fibres account for approximately 50% of
the total fibres utilised in the RMG industry. Methanol serves as a primary ingredient in the
manufacturing process of cellulose acetate and triacetate fibres. Methanol is employed as a

16
treatment agent for the cellulose pulp in the manufacturing of Rayon [18]. Methanol is utilised
by the jute industry at different phases of manufacturing. The monomer, initiator, and catalyst
necessary for the grafting process of the fibre are dissolved in methanol. Methanol and water
are employed as washing solvents following the grafting reaction [19]. Methanol solution
containing dissolved lac is employed as a coupling agent to enhance the shear and flexural
strength of jute fibres when reinforcing them [20]. Methanol solution containing dissolved lac
is employed as a coupling agent to enhance the shear and flexural strength of jute fibres [21].
Acetic acid is employed by the fish business to extend the longevity of fish when stored at low
temperatures. A byproduct of this reaction, formic acid is widely used in leather tanning.
Formic acid removes undesired materials from raw animal hide during pickling process of
leather [22,23]. Tea and its processed derivatives are significant agricultural commodities in
Bangladesh. Methanol and its derivatives serve as solvents for the preparation of tea leaf
extracts [24]. Bangladesh is the leading manufacturer of pharmaceuticals among poor
countries. Bangladesh exports its products to approximately 127 countries globally, meeting
98% of the local requests. Methanol is utilised in the manufacturing of several vital
pharmaceuticals, including Aspirin, Fluoxetine, Streptomycin, and Vitamins. The therapeutic
properties of herbs are investigated by studying plant extracts in methanol [25]. Therefore,
methanol plays a crucial role not only in the manufacturing of medicine, but also in the process
of uncovering new medicinal compounds. The plastic industry is also a potential business in
Bangladesh. The company currently has a workforce of over 1.2 million individuals and
achieved $1.2 billion in exports during the fiscal year 2021-22. Methanol serves as a crucial
precursor in the manufacturing of plastics [26].
Nevertheless, as there is no methanol factory in Bangladesh, these companies depend on
imported methanol to maintain their operations. Due to their entire reliance on imports, the
industries are compelled to purchase methanol from overseas sellers at a higher price. This
negatively impacts the long-term viability of industries, as importers, suppliers, and foreign
methanol manufacturers have a significant influence on the availability of raw materials in the
market. Additionally, the industries are required to remit a substantial amount of import duty
to the government. These factors impede the development of new industries and hinder the
expansion of existing ones. This has the potential to pose a significant danger to the survival
of local companies in the future, since there may come a time when it becomes more cost-
effective to import the finished product rather than maintaining local production using imported
methanol.

17
1.4 Employment Creation:

The global methanol industry currently employs about 90,000 individuals in various roles such
as technicians, engineers, managers, transport workers, and safety officers. According to
estimates, U.S. methanol plants are expected to have generated approximately 2,700 direct
jobs, 2,800 indirect jobs, and 19,000 temporary construction jobs by the year 2020 [27].
Bangladesh has an enormous active labour force of 70.47 million individuals, with 2.58 million
(3.53%) of them being unemployed. Out of the total number of unemployed individuals who
are actively seeking employment, 800,000 individuals have successfully finished university
education [28]. Hence, the challenge of generating employment opportunities for this
substantial pool of educated workers poses a hindrance to the socio-economic development of
Bangladesh. The establishment of a methanol manufacturing facility at the local level has the
potential to significantly contribute to the generation of employment possibilities for
unemployed young individuals. The daily methanol demand in Bangladesh is approximately
80 tonnes. The anticipated employment of the methanol factory, which has a daily production
capacity of 100 tonnes, is 50 individuals. Approximately 200-300 individuals are need
throughout the construction phase [29]. Nevertheless, the potential for methanol to indirectly
create jobs is significant.
The methanol industry's emergence has spurred efforts to establish plants for derivative
chemicals including formic acid, acetic acid, and formaldehyde. This is primarily driven by the
abundance of precursor chemicals and the strong market demand. These secondary sectors
would generate job possibilities for a large number of individuals. One drawback of the
methanol business is its reliance on highly competent specialists for production, with a minimal
need for uneducated and inexperienced individuals. Nevertheless, the sectors would require an
extensive distribution network comprising of multiple transport vehicles, sales and distribution
centres, hence generating a plethora of job prospects for both seasoned and novice workers.
The creation of even a modest-sized facility can entail a substantial construction endeavour. In
Bangladesh, construction businesses can take advantage of the abundance of inexpensive
labour to hire a larger workforce. Therefore, the building of the facility would immediately
contribute to the creation of numerous temporary employment opportunities for individuals
from lower socio-economic backgrounds. A factory with a daily production capacity of 100
metric tonnes will not only satisfy the local need but also open up opportunities for exporting
to nearby countries. The surplus methanol can be utilised as an additive to conventional fossil
fuels, so helping to reduce fuel costs nationwide. Reduced fuel costs would stimulate economic

18
growth and facilitate the development of large-scale companies, resulting in increased job
opportunities and a positive impact on the economy.

19
 Chapter 02 – Project Definition

2.1 Definition of the Project

A methanol plant with a daily production capacity of 40 metric tons of methanol and an annual
capacity of 12,000 metric tons of methanol with 300 working days is planned to be set up at
Anwara, Chittagong. LNG imported from Qatar will be used as the raw material. With all the
utilities, offices, and other facilities included, the factory will have a land area of around 35
acres.

2.2 Raw Material Specifications and Source

Methane as raw material is availed from imported LNG (liquefied natural gas). The government
is negotiating with Qatar seeking long-term contracts for the import of liquefied natural gas
(LNG) as prices have abnormally climbed in international spot markets. Recently, the LNG
prices in the spot markets have gone up so high that the government finds it too much of an
expense to accommodate, for which it was seeking long-term contracts.

Table 1: Raw material composition [30]

Source Composition (%)

CH4 C2 H6 C3 H8 C4 + N2 CO2
Qatar (LNG 96.91 2.37 0.44 0.15 0.13 0.00
Imported)

2.3 Product Specification

Methanol product composition: 99.85 wt% or 99.73 mole%

Our product specification meets IMPCA (International Methanol Producers and Consumers
Association) defined specification. Most of the worldwide methanol sold is also IMPCA
specified product. The reference product specifications are given below-

20
Table 2: IMPCA reference specification

Test Unit Method Limits

Appearance IMPCA 003-98 Clear and free of

suspended matter
Purity on dry basis % W/W IMPCA 001-14 Min 99.85

Acetone mg/kg IMPCA 001-14 Max 30

Ethanol mg/kg IMPCA 001-14 Max 50

Water % W/W ASTM E1064-12 Max 0.100

Distillation Range at ℃ ASTM D1078-11 Max 1.0 to include

760 mm Hg 64.6° +/- 0.1°
Specific Gravity ASTM D4052-11 0.7910-0.7930
20°/20°
Potassium minutes ASTM D1363-11 Min 60
Permanganate Time
test at 15 ℃
Chloride as Cl mg/kg IMPCA 002-98 Max 0.5

Sulphur mg/kg ASTM D 3961-98 Max 0.5

ASTM D 5453-12
Hydrocarbons ASTM D 1722-09 Pass test

Carbonisable Pt-Co ASTM E 346-08 Max 30

Substances (Sulfuric
Acid Wash Test)
Acidity as Acetic acid mg/kg ASTM D 1613-12 Max 30

Iron in solution mg/kg ASTM E 394-09 Max 0.10

Non-Volatile Matter mg/1000ml ASTM D 1353-13 Max 8

21
2.4 Plant Location and Area

Proposed industry is located at Anwara, an upazila of Chittagong district in the Division of

Chittagong, Bangladesh. It comprises the Korean Export Processing Zone (Korean EPZ) and
Chinese Economic and Industrial Zone (CEIZ). It is located at 22.2167°N 91.9111°E. It has
38,008 households and a total area of 164.13 km2 .

Figure 2-1: Location and Routes of Anwara Upazila

[Map Courtesy: Ministry of Land-Bangladesh]

22
 ANWARA

ANWARA

Figure 2-2: Plant distance from LNG terminal using Google map left-by land, right-by water

23
 Chapter 03- Design Basis

3.1 Geological Data

River

• Nearest river – Karnaphuli river

• Minimum water level – 2.3 meters
• Maximum water level – 5.72 meters [31]
• Average depth of wells – 4.91 meters [32]
• Water level record during flood – 15-20 ft. (above ground) [33]
• Salinity: 4.8 mg/L with a range from 0.4 to 9.2 mg/L [34]

Soil Characteristics

• The soil types in urban areas of Chittagong city are sandy loam and silt loam with 53%-
83% sand.
• Surface clays – 10-12 meters thick underlain by slits and fine sands.
• Arsenic content was found in variation from 0.01 - 0.05 mg/L.
• The average of maximum heavy metals concentrations studied was found higher than
those of the World Health Organization (WHO). The water quality of Karnafuli River
is highly polluted which are continuously polluting the coastal zone, sea and the Halda
river of Chittagong. [33]
• Load bearing capacity: The soil has a bearing capacity of 0.47 ton/ft² required piling is
used.
• Corrosive tendency: Corrosive [35]

Cyclone history
Anwara, Chittagong has been repeatedly struck by cyclones in 1960, 1963, 1966, 1970, 1971,
1983, 1985, 1991, 1997, 1998, 2007, and 2017, causing a wide range of damages to human
lives and properties. [36]

24
Seismic Condition

Maximum earth quake – 6.2 in Richter scale

Seismic Zone – Anwara lies in Zone-2 which shows intermediate level of seismic activity
Seismic Coefficient – .15 g [35]

3.2 Meteorological Data

3.2.1 Temperature and rainfall
Chittagong, or Chattogram, has a tropical climate that is greatly impacted by the monsoon. It
goes through a dry period from November to March, while from May to October, it encounters
a wet season. The yearly average temperature in Anwara, Chittagong, stands at 25.99°C, with
an annual precipitation of 3194 mm.

Ambient temperature: Maximum 34ºC, Minimum 9ºC, Average 25.99ºC

Table 3: Monthly weather condition in Anwara, Chittagong [36]

Month Average maximum Average minimum Rainfall(mm)

temperature(ºC) temperature(ºC)
Jan 26.02 16.01 1

Feb 27.93 15.69 11

Mar 32.44 21.84 0

Apr 33.12 26.03 44

May 33.15 25.18 345

Jun 32.14 25.66 582

Jul 33.25 26.42 271

Aug 33.27 26.34 116

Sep 32.55 25.78 386

Oct 32.82 25 154

Nov 28.23 23.95 35.95

25
 Dec 25.39 21.04 13.68

Figure 3-1: Temperature Data in Chittagong Anwara

3.2.2 Atmospheric Pressure

Annual average atmospheric pressure: 1010 mbar
Maximum average atmospheric pressure: 1014.7 mbar
Minimum average atmospheric pressure: 1002.8 mbar [37]

3.2.3 Rainfall
Maximum: Usually 500 mm (but can be as high as 1000 mm)
Minimum: 20 mm

26
 Figure 3-2:6:Rainfall
Figure RainfallData
DataininChittagong,
Chittagong,Anwara
AnwaraupUp
to 2020
to 2020

3.2.4 Humidity
Annual average relative humidity: 76% [38,39]
Maximum monthly average relative humidity: 86.67%
Minimum monthly average relative humidity: 63.38%

Figure 3-3: Humidity Data in Chittagong, Anwara up to 2020

27
3.2.5 Wind
Wind direction: Generally, wind flows from north-east to south-east during winter and from
south to north during summer.
Wind velocity: 2.38 m/s. During cyclones, there is a notable increase in wind velocity. [40]

FigureFigure
3-4: Wind
1-1 1:Wind
speed and
speed
direction
and direction
in Chittagong,
in Chittagong,
AnwaraAnwara

3.3 Utility Condition

3.3.1 Water Quality

Table 4: Major water properties of Karnaphuli river water [38,41,42]

Temperature pH Chloride TDS COD Salinity Oil and

grease
(ºC) (ppm) (ppm) (ppm) (%)
(ppm)

28-30 8.2 3 57 6 2.25 3.5

28
3.3.2 Air Quality
The concentration of PM2.5 in industrial area is 32.1µg/m³ which was which is presently 6.4
times the WHO annual air quality guideline value [34].
In Chittagong city, major contributors to air pollution include road transportation,
manufacturing sectors, and ongoing construction projects. [40]

3.4 Climate Conditions

3.4.1 Ambient conditions in summer:
Maximum dry bulb temperature: 39ºC
Maximum wet bulb temperature: 34ºC
Minimum dry bulb temperature: 25ºC
Minimum wet bulb temperature: 22ºC
3.4.2 Ambient condition in winter
Maximum dry bulb temperature: 21ºC
Maximum wet bulb temperature: 16ºC
Minimum dry bulb temperature: 10ºC
Minimum wet bulb temperature: 7ºC
Maximum relative humidity: 70%
Minimum relative humidity: 50% [43, 44]

3.5 Developing Constrains

• Challenging communication exists across many regions due to extensive linear hill
ranges characterized by steep slopes, making road construction and upkeep costly.
• Soil fertility is generally poor, particularly in regions where jhum cultivation is
practiced.
• Heavy monsoon rainfall

29
 Chapter 04 - Selection of Process

4.1 Available process

Bangladesh possesses abundant natural gas resources. Despite a high demand for methanol, the
country lacks a methanol production facility. Methanol is synthesized from hydrocarbons,
necessitating the design of a reactor to transform these hydrocarbons into syngas. This syngas
can then be converted into methanol using established methods. There are mainly three
processes available for the production of methanol and the final process is determined by the
availability of the raw material. The three available processes are

• Methanol from natural gas

• Methanol from coal gasification
• Methanol from biomass

4.1.1 Methanol from natural gas

Throughout the world, one of the most used raw materials for methanol production is natural
gas. Natural gas can be obtained from oil and gas reservoirs and contains mostly methane.

1. Development of methanol production process from natural gas: BASF Company first
started the commercial synthesis of methanol in 1923. This high-pressure methanol synthesis
process was based on a zinc/chromium catalyst which converted syngas into methanol at 300
bar pressure and temperature exceeding 300°C. The maximum size of equipment was limited
due to high pressure and the energy consumption was also high. Then the low-pressure process
was developed by Imperial Chemical Industries in 1966 and then the medium pressure process.
A low-pressure process suitable for natural gas residue as raw material was developed by Lurgi
Company of Germany in 1971. The low-pressure method is based on the copper-based catalyst
with higher activity compared to that of the zinc chromium catalyst, and the reaction
temperature is low (240-270°C). Under low- pressure, higher methanol yield can be obtained,
and power consumption is reduced, the selectivity is good, the side reaction is reduced, the
methanol quality is improved, and the raw material consumption is reduced [10].

At present methanol production from natural gas accounts for about 90% of the total production
and the cost of methanol production from natural gas is about 50% lower compared to
production from other raw materials [10]. The fuel cost has a contribution of 50-60% in the

30
specific product cost. The payback period is usually 2 to 10 years, depending on the process.
[45]

2. Methanol production process from natural gas: A methanol plant with natural gas as raw
material generally consists of the following units: [46]

• Pretreatment unit for the removal of sulfur impurities

• Reforming unit for syngas generation
• Conditioning section for adjusting the syngas composition
• Synthesis unit for the conversion of syngas to methanol Purification section for refining
the crude product
• Steam-cycle for balancing the overall heat supply and demand of the process units

Pre-treatment section or desulphurization section is used to remove Sulphur from natural gas
by using absorption. In the reforming unit, syngas is generated from the clean natural gas.
Syngas production section accounts for about 60-70% of the total investment cost of the plant.
Syngas can either be prepared by partial oxidation or by steam reforming of the natural gas
feedstock. Partial oxidation-based units are more suited for heavy-hydrocarbons whereas steam
reforming is more suited for light-hydrocarbons like natural gas. Synthesis gas can be prepared
by following several schemes: [47]

I. One-step reforming with fired tubular reforming

II. Two-step reforming
III. Autothermal reforming (ATR)

The overall steam reforming and autothermal reforming reactions are given below: [46]

CH4 + H2 O → CO + 3H2

CH4 + 2O2 → CO2 + 2H2 O

CO2 + H2 → CO + H2 O (water gas shift reaction)

moles H −moles CO
2 2
The stoichiometric number, S= moles CO+moles should be 2 or higher in the synthesis moles
CO 2

gas. If the ratio is below 2, it should be adjusted to a value of about 2 before the syngas enters
the methanol synthesis section. The adjustment can be done in two ways, either by removing
carbon dioxide from the syngas or by recovering hydrogen from the synthesis loop purge gas
and recycling the recovered hydrogen to the synthesis gas. The adjustment done by CO2

31
removal results in a syngas resembling one used in coal-based methanol production. On the
other hand, adjustment done by H2 recovery using a membrane or a PSA unit is preferred for
producing high purity methanol. Oxygen blown reforming in combination with tubular steam
reforming or as pure autothermal reforming can be used. Autothermal reforming is a
combination of partial oxidation (in the combustion zone) and steam reforming (in the thermal
and catalytic zone).

Combustion zone reaction:

CH4 +1.5O2 → CO + 2H2 O

Thermal and catalytic zone reaction:

CH4 + H2 O → CO + 3H2

CO + H2 O → CO2 + H2

Stand-alone autothermal reforming for low steam to carbon ratio is the preferred technology
used for large scale plants due to high single line capacity and low investment. The prepared
synthesis gas is pressurized to 50-100bar and heated to 200-300°C before it enters the reactor.
The reaction is carried out in the presence of a copper-based catalyst consisting of
CuO/ZnO/Al2 O3 having one-way conversion rate of 7% ~ 8% and good selectivity, with trace
number of impurities like methane, CH3 O CH3), methyl formate and it is easy to get high-purity
methanol from the crude methanol afterwards [10]. To minimize reactor size and maximize
recovery of waste heat, quench type, multi-bed intercooled, or isothermal reactors are used.
The synthesis unit is operated with a loop for recycling the unconverted syngas back to the
inlet of the reactor due to low per pass conversion. Studies have shown that higher yields can
be achieved with an isothermal shell and tube reactor technology than with an adiabatic reactor
technology [46]. It is a shell and tube heat exchanger with catalyst on the tube side and boiling
water is circulated on the shell side and the reaction heat is transferred to the boiling water
through the tube walls to generate steam. The produced steam maybe used as process steam.
The main reactions involved in methanol synthesis are given below: Hydrogenation of carbon
monoxide:

CO + 2H2 → CH3 OH

This can be divided into two consecutive steps:

CO + H2 → CH2 O

32
Hydrogenation of carbon dioxide:

CH2 O + H2 → CH3 OH

CO2 + 3H2 → CH3 OH + H2 O

The above reactions are highly exothermic. The crude product containing different amounts of
impurities enter the purification section which is the three-tower distillation process designed
to remove the dissolved gas and low boiling point impurities in the crude methanol in a topping
column and to remove the water and heavy components in the pressurized tower and
atmospheric tower, therefore, as to prepare the refined methanol product meeting the quality
assessment standards. To sum up, using natural gas is more efficient than biomass or coal in
the production of methane. It also has less pollution impact and is cheaper compared to the
alternative raw materials. But natural gas requires removal of Sulphur before the syngas
production section and can be very flammable. Regardless of the drawbacks, natural gas is the
best available raw material for the production of methanol.

4.1.2 Methanol from Coal Gasification

Another process of methanol synthesis can be from coal. Coal is a brownish-black sedimentary
rock which mainly consists of carbon including variable amounts of other elements like
hydrogen, sulfur, oxygen, nitrogen.

Methanol can be produced from coal in 4 stages. The first step is coal preparation and
gasification. The solid coal chunk cannot be directly used for methanol synthesis, so coal is
first grinded to prepare coal slurry with water. The coal slurry is pumped to an elevated pressure
before feeding to the gasifier. Coal gasification is the most critical core technology here. Pure
oxygen if fed in a certain amount to the high temperature entrained flow gasifier. Raw syngas
is then produced with ash, slag, and other particulates as byproduct. Most of the slag is removed
from the bottom of the gasifier and ash and other particulates are removed using a cyclone
separator. A heat exchanger is used to recover the heat from the hot syngas and produce steam
which is further used in WGS reaction. If the syngas contains any sulfur compound like H2 S,
COS, SOx , or any CO2 , then they are removed otherwise they poison the catalyst bed of water
gas shift reactor and methanol synthesis reactor. For maximum efficiency, stoichiometric ratio
should be 2 in methanol reactor. To increase the H2 content, cleaned syngas is passed through
a two stage WGS where CO and steam reacts to form CO2 and H2 .

CO + H2 O ↔ CO2 + H2

33
Being an exothermic reaction, it increases the temperature of the product gas. So, the product
gas is then cooled and fed to the second reactor. Finally, the clean and shifted syngas is fed to
the catalytic packed bed reactor to produce the crude methanol.

CO2 + 3H2 → CH3 OH + H2 O

The methanol, which is in its raw and unrefined form, is isolated from the gas stream that has
not undergone a chemical reaction by decreasing the temperature and pressure of the waste
material. Following a minor purification and recycling process, distillation yields methanol
with a purity of 99.4 mol% [48]. Coal based methanol production is still popular to some extent
due to its vast reserves and popular pricing and its impact on national energy security. But it is
not so feasible yet. It is much more complicated than NG based process. Also, it includes heavy
emission of air pollutant (mercury, NOx , SOx ) and greenhouse gas happens here. If the CO2
could be converted to a more valuable product and the efficiency of power production could
be improved, it could be a more popular methanol synthesis process. Solid waste emerges from
this process too which undoubtedly affect the environment. Removal of the impurities and
pollutants need further processes which increase the cost. The investment and production cost
from coal to methanol is the highest. Thus, profit to cost ratio becomes lesser. Due to these
things, coal is used as raw material for only 2% methanol production of the world [10].

4.1.3 Methanol from Biomass

Syngas, which is composed of carbon monoxide (CO) and hydrogen (H2 ), serves as the primary
substance for the production of methanol. When biomass is used to make syngas, it becomes a
renewable supply of feedstock for methanol synthesis. Biomass encompasses agricultural
byproducts, such as crop residues and pasture crops, as well as forest residues, constituting
over 50% of the total biomass.

The municipal solid garbage and industrial waste. One ton of biomass can yield 721 litres of
methanol [48]. The biomass feedstock incurs significant costs, making this method more
expensive compared to the other two processes. Consequently, this procedure is not widely
employed for the industrial manufacture of methanol.

34
4.2 Process Selection
Synthesis of methanol from LNG was selected for this design according to the present scenario
of Bangladesh and based on the preceding discussion. Synthesis of methanol can be achieved
by mainly two approaches.

From synthesis gas (CO + 𝐇𝟐 ): Production of methanol from the synthesis gas is the most
common and conventional way in the present world. Syn gas is produced by reforming natural
gas, coal or biomass with steam. This is the most profitable process and most of the methanol
industries in the world follow this process.
From the hydrogenation of 𝐂𝐎𝟐 : In this process CO2 is captured from different sources and
reacted with H2 . H2 is produced from the electrolysis of water. The energy required for
hydrolysis is supplied by using any renewable source of power. This is the latest technology
for the production of methanol and can be considered as a renewable process [49].

In our problem, we followed the synthesis gas procedure to produce methanol. Synthesis gas
can be produced in various methods. By using catalytic methods such as partial oxidation,
steam reforming, and dry reforming of methane, synthesis gas is produced from natural gas. In
our case, we are using methane and steam to produce steam gas. This method is also known as
“Wet Reforming”.
According to the current scenario of our country, it is not feasible to production methanol from
the hydrogeneration of CO2 . For this process, CO2 is to be extracted from different source and
H2 is to be produced from the hydrolysis reaction. Both of these initial processes are very
expensive and needs strict supervision. This process might be a cleaner one, but for a
developing country like Bangladesh it is not efficient [50].

The steam reforming process is efficient enough in many aspects. It has a hydrogen yield of
more than 50%. This ensures a high ratio of syngas production (H2 /CO = 3) [51]. The process
is endothermic, and the heat must be supplied to the reformer to continue the reaction. The heat
that is generated from the combustion of natural gas. The exhaust gas from the combustion is
used to preheat different process materials. Hence, this process is energy efficient. Moreover,
the process can go on smoothly although it might be in a transient phase.

In case of dry reforming, methane reacts with CO2 to produce methanol. CO2 is captured from
different sources. This process yields a very low syngas ratio (H2 /CO = 1) [52]. Besides, during
the reforming process due to highly endothermic nature of the reaction, coke is formed and
deposited on the bed of catalyst. This decreases the activity of the catalyst. Moreover, there is

35
a significant rate of byproduct formation in this process. By taking all these things into
consideration, steam reforming (wet reforming) is used because these results in huge profits,
lesser emission and greater efficiency.

4.3 Process Description

4.3.1 Regasification and Compression of LNG
The process of using and transporting liquefied natural gas (LNG) requires the step of
regasification. LNG stands for liquefied natural gas, which is natural gas that has been cooled
to a temperature of -162°C, at which point it turns into a liquid and can be transported and
stored more effectively. The LNG must be transformed back into a gaseous state to be used for
power production, industrial activities, or as a fuel for automobiles, though, once it has arrived
at its destination. This process is known as regasification.
Regasification typically involves heating the LNG using seawater or other types of heat
exchangers. This process raises the temperature of the LNG, causing it to return to its gaseous
state. The gas is then sent through a series of compressors to increase its pressure, making it
suitable for storage or transport through pipelines.
4.3.2 Syngas Production (Primary and Secondary Reformer)
Syngas, or synthesis gas, is a mixture of carbon monoxide (CO) and hydrogen (H2 ) that can be
produced through a variety of methods, including the use of primary and secondary reformers.
The primary reformer is responsible for converting natural gas, or other hydrocarbon
feedstocks, into syngas by breaking down the hydrocarbons through a process called steam
methane reforming (SMR). The secondary reformer, on the other hand, is used to further purify
and increase the concentration of hydrogen in the syngas.

The primary reformer, also known as the steam methane reformer (SMR), is the key unit in the
production of syngas. It is a large, high-temperature reactor that uses steam and a catalyst to
convert natural gas or other hydrocarbon feedstocks into a mixture of CO and H2 . The process
takes place at high temperatures, typically between 800 and 1400 °C, and high pressures,
typically between 30 and 60 bar. In the primary reformer, natural gas is mixed with steam and
passed over a catalyst, usually nickel, which catalyzes the reaction between the methane and
the steam to produce CO and H2 . This reaction is exothermic and produces a large amount of
heat, which is used to generate steam for the process. The syngas produced by the primary
reformer contains CO, H2 , and various impurities such as CO2 , N2 , and CH4 .
The Secondary reformer, also known as the shift converter, is used to purify and increase the
concentration of hydrogen in the syngas. It is a large, high-temperature reactor that uses a

36
catalyst to convert CO into CO2 and H2 . The process takes place at high temperatures, typically
between 400°C and 600°C, and high pressures, typically between 1 and 5 bar. In the secondary
reformer, the syngas produced by the primary reformer is passed over a catalyst, usually iron
or cobalt, which catalyzes the reaction between the CO and the steam to produce CO2 and H2 .
This reaction is also exothermic and produces a large amount of heat, which is used to generate
steam for the process. The syngas produced by the secondary reformer contains CO, H2 , and
very low impurities such as CO2 , N2 , and CH4 .

4.3.3 Methanol Synthesis

Methanol synthesis is the process of converting syngas (a mixture of carbon monoxide and
hydrogen) into methanol. This process typically takes place in a methanol synthesis reactor,
which is a high-pressure and high-temperature reactor that uses a catalyst to convert syngas
into methanol. The process is typically carried out at a pressure of around 30-60 bar and a
temperature of around 180-220°C.
The primary reactant in the methanol synthesis process is syngas, which is typically produced
by steam methane reforming (SMR) or coal gasification. The syngas contains a mixture of CO
and H2 , which are then converted into methanol in the methanol synthesis reactor. The
methanol synthesis reactor is typically a fixed-bed reactor, which is filled with a catalyst,
usually copper-chromium-zinc (Cu-Cr-Zn) or copper-zinc (Cu-Zn) based. The syngas is then
passed through the reactor, where it comes into contact with the catalyst, which catalyzes the
reaction between the CO and H2 to produce methanol. The overall reaction can be represented
by the following equation:

CO + 2H2 → CH3 OH + Heat

The methanol synthesis reaction is exothermic, which means it produces heat, which can be
recovered and used to generate steam for the process. The methanol produced by the methanol
synthesis process is typically around 99% pure, and it is then cooled, distilled, and further
purified to remove any remaining impurities. The methanol produced through the synthesis
process can be used as a feedstock to produce various chemicals, such as formaldehyde, acetic
acid, and dimethyl ether. It can also be used as a fuel for power generation, and as a feedstock
to produce liquid fuels such as gasoline and diesel.

37
4.3.4 Methanol Purification - Low-End and High-End Distillation Column
Methanol separation in a low-end distillation column involves the use of a distillation process
to separate methanol from a mixture of other compounds. The process begins with the feed
mixture being heated and vaporized, and then the resulting vapor is fed into the distillation
column. The column is designed with a series of trays or plates that facilitate the separation of
the components in the mixture based on their differences in boiling points. As the vapor moves
up the column, it meets the trays or plates, which act as condensation and re-vaporization
points. The more volatile components, such as methanol, will condense and re-vaporize at the
lower trays or plates, while the less volatile components will condense and re-vaporize at the
higher trays or plates.

The condensed liquid, or distillate, from the lower trays or plates will contain a high
concentration of methanol and is collected as the desired product. The liquid that does not
vaporize and remains on the trays or plates is known as the residue and typically contains the
less volatile components. In a low-end distillation column, the goal is to separate methanol
from other components with similar boiling points. This can be achieved by carefully selecting
the operating conditions, such as the temperature and pressure, to ensure that the methanol is
efficiently separated from the other components. Additionally, the use of a high-performance
distillation column, such as a packed
column or a plate column, can also improve the efficiency of the separation process. Light
components will be present in the distillation column's top product. Methanol and other heavy
substances will be present in the distillation column's bottom product. The bottom product is
fed to another distillation column to obtain the necessary composition of methanol. Most of the
methanol will be found in the top product of the second distillation column.

38
 Chapter 05: Environmental Assessment

5.1 Hazard Analysis

Chemicals involved in methanol production plant –
• Raw Materials- CH4 , C2 H6 (in Natural Gas), Air, Steam
• Intermediate Products- CO, CO2 , H2
• Product- CH3 OH
• Catalysts- Ni
• Catalyst Promoter- Al2 O3

Table 5: Hazard analysis of chemicals in methanol plant

Components PEL/TLV LD50/LC50 Potential of fire

explosion
CH3 OH 200 PPM LD 50-Rat Fire and explosion
5600 mg/Kg
CH4 1000 PPM Not classified Fire and explosion

C2 H6 1000 ppm LC50 Inhalation – Fire and explosion

Rat 658 mg/l/4h
CO 25 ppm LC50 Inhalation – Fire and explosion
Rat 1880 ppm/4h
CO2 5000 ppm LC50 Human Explosion
Inhalation
49500 ppm/.5h
Steam Not Applicable LC50 Inhalation – Explosion
Rat ppm/4h 820000
H2 Asphyxiant Not Classified Fire and explosion

Ni 1.5mg/m3 LC50 – Fish Not Flammable

>100mg/L
Al2 O3 15 mg/m3 LC50 – Fish >5 Not Flammable
mg/l/4h

39
Control Measures to be taken:
• Ventilate area or move container to a well-ventilated area. Flammable vapors may spread
from the leak and could explode if reignited by sparks or flames. Explosive atmospheres may
linger. Before entering the area, especially confined areas.
• Check the atmosphere with an appropriate device. Prevent it from entering sewers, basements,
and work pits, or any place where its accumulation can be dangerous.
• Use self-contained breathing apparatus where needed.
• Remove all sources of ignition if safe to do so.
• Reduce vapors with fog or fine water spray, taking care not to spread liquid with water. Shut
off flow if safe to do so.

5.2 Environmental Effect

Methanol does not pose a significant hazard for aquatic or terrestrial life, except in the case of
spillage. Contamination of soil, water, and the atmosphere can be avoided by proper methods
of storage, handling, transport, and waste disposal.
Human Hazard: Air emissions from diverse industrial and residential solvent use, methanol
production, end-product manufacturing, and bulk storage and handling losses are the main
sources of methanol exposure for the general public. Air pollution levels in the general
population are currently 10,000 times lower than occupational norms. Methanol inhalation
exposure at work is normally modest, although it can be higher in less controlled environments.
Ingestion of methanol-containing products, whether by accident or on purpose, is associated
with a high rate of illness and fatality.
Methanol irritates the eyes, skin, and lungs. Longer-term occupational exposure to lower
quantities of methanol has been linked to a variety of eye problems. Acute oral and inhalation
exposures to large quantities of methanol, as well as percutaneous absorption to a lesser extent,
have resulted in central nervous system depression, blindness, coma, and death. Methanol
contact with the skin on a regular or extended basis can cause dermatitis. Methanol in liquid
form defats the skin. It's a good extracting solvent, but it can harm the skin's permeability
barrier.

Fire Hazard: Methanol burns with an undetectable or mild blue flame and is highly
flammable. Heat, sparks, or flames can ignite methanol, and the vapor can travel to the source
of ignition and flash back.

40
There should be no ignition sources near methanol storage or consumption, such as open fires,
sparks, or smoking. Methanol should not come into contact with oxidants. Methanol must be
used and stored in cold, enclosed spaces with enough ventilation and explosion-proof electrical
and lighting equipment. Small fires can be fought with dry chemicals, carbon dioxide, water
spray, alcohol-resistant foam or, if these are not available, by dilution with plenty of water.
Large fires can be attacked with water spray, fog, or alcohol-resistant foam. Water spray should
be used to cool down containers in the fire area.

Spillage and Disposal: Evacuate the hazardous area, collect the leaking liquid in sealable
containers, or construct a dike well ahead of the liquid spill to allow for later disposal. Spilled
liquids should be flushed with sufficient volumes of water, and run off should not be allowed
to enter waterways directly. The liquid can be absorbed into sand or vermiculite and transported
into suitable containers for relatively small spills (approximately 25 liters). The spillage place
should be carefully cleaned with water. Personnel should only visit the hazard area when
absolutely necessary, wearing protective clothing appropriate for the degree of spillage.
Complete protective equipment, including self-contained breathing apparatus, can provide
further personal protection.

41
Chapter 06: Process Block Diagram

42
 Fuel NG Air, 5% Excess
Air
30 C, 1 atm
LNG 450 C, 1 atm
Re-
gasifier
30 C, 1 bar
Feed NG
Synthesis Gas Wet Synthesis Gas
Preheated (10% CH 4 ) (0.5% CH ) Waste
Primary Secondary
Heat
Steam at 450 C, Reformer Reformer
600 C, 15.5 bar 900 C, 15 bar Recovery
16 bar
150 C, 1 bar

Exhaust Gas, 420 C

Purge Recycle
Dry Synthesis Wet Synthesis Gas
Methanol synthesis (0.5% CH )
Flash Gas Flash
Reactor
Seperator Seperator
220 C ,52.6 bar 60 C, 26 bar

Liquid to Waste
Methanol Methanol Condensate
Recovery Light Ends

Light End Heavy End

Distillation Distillation
Column Column
25 C , 12 bar

Heavy Ends

Figure 6-1: Process block diagram for the methanol plant

43
Chapter 07: Process Flow Diagram

44
 17 Stream Number
Steam 7 12
8
River 5
Water 3

C-101
C-101
P-101

LNG 1 2
E-101 9 E-103
WHB-101
4 11 13 15 18
E-102
R-102 16
14 R-101 19
10 Air
Air
6 C-102

20
31 32 22
C-103 E-104
29
R-103 24 21
V-101
23
V-102 28 27 26 25
E-105
E-106
R-103

33 39

T-102
35
34 T-101
VLV-101 38
40 TK-101
VLV-102 E-107

Figure 7-1: Process flow diagram for the methanol plant

45
Chapter 08: Material Balance

46
 8.1 Re-gasifier (E-101)

33°C, 1 atm
1750 Kmol/hr H2O

-161°C, 1 atm 30°C, 1 atm

161.709 Kmol/hr 161.709 Kmol/hr

1 E-101 2
0.9691 mol CH4 /mol Composition remains same as 1
0.0237 mol C2 H6 /mol
0.0044 mol C3 H8 /mol
15°C, 1 atm
4
0.0015 mol C4 H10 /mol 1750 Kmol/hr
HO
0.0013 mol N2 /mol

Since there is no mass balance, this portion is excluded from further calculations. An energy
balance has been conducted, and the detailed calculations are provided in Chapter 9.

Table 6: Inlet and Outlet Conditions for Re-gasifier (E-101)

Stream No. Inlet (mole%) Outlet (mole%)

01 03 02 04
Temperature (℃) -161 33 30 15
Pressure (atm) 1 1 1 1
Molar Flow (Kmol/hr) 161.709 1750 161.09 1750
CH4 0.9691 - 0.9691 -
C2 H6 0.0237 - 0.0237 -
C3 H8 0.0044 - 0.0044 -
C4 H10 0.0015 - 0.0015 -
N2 0.0013 - 0.0013 -
H2O - 1 - 1

47
8.2 Split into Feed and Fuel

30°C, 1 atm
5 126 kmol/hr
Composition same as stream 2

30°C, 1 atm
161.709 kmol/hr

2 Splitter 6
0.9691 mol CH4/mol
30°C, 1 atm
0.0237 mol C2H6/mol
35.709 kmol/hr
0.0044 mol C3H8/mol
Composition same as
0.0015 mol C4H10/mol stream 2

0.0013 mol N2/mol

78% splitting of stream 2 into stream 5

78
⸫ 161.709 × 100 = 126 kmol/hr stream 5

⸫ Stream 6 will be 35.709 kmol/hr

48
Table 7: Inlet and Outlet Conditions for Splitter

Stream No. Inlet (mole%) Outlet (mole%)

02 05 06
Temperature (℃) 30 30 30
Pressure (atm) 1 1 1
Molar Flow (Kmol/hr) 161.709 126 35.709
CH4 0.9691 0.9691 0.9691
C2 H6 0.0237 0.0237 0.0237
C3 H8 0.0044 0.0044 0.0044
C4 H10 0.0015 0.0015 0.0015
N2 0.0013 0.0013 0.0013
Total Flow (Kg/h) 1502.36 1502.36

49
8.3 Mixer (Feed NG and stream)

150°C, 1 atm
7 375 kmol/hr, H2O
30°C, 1 atm
126 kmol/hr
501 kmol/hr
5 Mixer 8
0.9691 mol CH4/mol
X1 mol CH4/mol
0.0237 mol C2H6/mol
X2 mol C2H6/mol
0.0044 mol C3H8/mol
X3 mol C3H8/mol
0.0015 mol C4H10/mol
X4 mol C4H10/mol
0.0013 mol N2/mol
X5 mol N2/mol
X6 mol H2O/mol
CH4 -balance:
126×0.9691 = 501× X1
∴ X1 = 0.2437 mol CH4/mol
C2H6 – balance:
126×0.0237 = 501× X2
∴ X2 = 0.00596 mol C2H6
C3H8 -balance:
126×0.0044 = 501× X3
∴ X3 = 0.00111 mol C3H8/mol
C4H10 -balance:
126×0.0015 = 501× X4
∴ X4 = 0.000377 mol C4H10/mol
N2 -balance:
126×0.0013 = 501× X5
∴ X5 = 0.000326 mol N2/mol
H2O -balance:
375 = 501× X6
∴ X6 =0.75 mol H2O/mol

50
Table 8: Inlet and Outlet Conditions for Mixer

Stream No. Inlet (mole%) Outlet (mole%)

05 07 08

Temperature (℃) 30 150 117

Pressure (atm) 1 1 1

Molar Flow 126 375 501

(Kmol/hr)
CH4 0.9691 - 0.2437

C2 H6 0.0237 - 0.00596

C3 H8 0.0044 - 0.00111

C4 H10 0.0015 - 0.000377

N2 0.0013 - 0.000326

H2O - 1 0.75

51
8.4 Compressor (C-101)

117°C, 1 atm 221.5°C, 16 bar

501 kmol/hr 501 kmol/hr
Compressor
8 9
0.2437 mol CH4/mol
Composition same as
0.0059 mol C2H6/mol stream 8

0.00111 mol C3H8/mol

0.000377 mol C4H10/mol
0.000326 mol N2/mol
0.75 mol H2O/mol

N.B: Since there is no mass balance, this portion is excluded from further calculations. An
energy balance has been conducted, and the detailed calculations are provided in Chapter 9.

Table 9: Inlet and outlet Conditions for Compressor (C-101)

Stream No. Inlet (mole%) Outlet (mole%)

08 09

Temperature (℃) 117 221.5

Pressure (bar) 1 16

Molar Flow (Kmol/hr) 501 501

CH4 0.2437 0.2437

C2 H6 0.00596 0.00596

C3 H8 0.00111 0.00111

C4 H10 0.000377 0.000377

N2 0.000326 0.000326

H2O 0.75 0.75

Total Flow (kg/hr) 8816.7 8816.7

52
8.5 Heat Exchanger (E-102)

414.03 kmol/hr
0.7187 mol N2/mol

0.1804 mol H2O/mol

12
0.0091 mol O2/mol

501 kmol/hr
501 kmol/hr
9 Heat Exchanger 11

0.2437 mol CH4/mol Composition same as

stream 9
0.0059 mol C2H6/mol
14 414.03 kmol/hr
0.00111 mol C3H8/mol
Composition same as
0.000377 mol C4H10/mol stream 12

N.B: Since there is no mass balance, this portion is excluded from further calculations. An
energy balance has been conducted, and the detailed calculations are provided in Chapter 9.

53
Table 10: Inlet and Outlet Conditions for Heat Exchanger (E-102)

Stream No. Inlet (mole%) Outlet (mole%)

09 12 11 14
Temperature (℃) 221 750 420 450
Pressure (atm) 16 1 1 16
Molar Flow (Kmol/hr) 501 414.03 501 414.03
CH4 0.2437 - 0.2437 -
C2 H6 0.00596 - 0.00596 -
C3 H8 0.00111 - 0.00111 -
C4 H10 0.000377 - 0.000377 -
N2 0.000326 0.7187 0.000326 0.7187
H2O 0.75 0.1804 0.75 0.1804

O2 - 0.0091 - 0.0091

C O2 - 0.0918 - 0.0918

54
8.6 Primary Reformer (R-101)
nCO2 kmol/hr

nN2 kmol/hr

nH2O kmol/hr

nO2 kmol/hr
12
nCO2 kmol/hr

501 kmol/hr

11 Primary Reformer 13

0.2437 mol CH4/mol nCH4 kmol/hr

0.0059 mol C2H6/mol nN2 kmol/hr
0.00111 mol C3H8/mol 6 10 nH2O kmol/hr
0.000377 mol C4H10/mol nCO kmol/hr
0.000326 mol N2/mol nCO2 kmol/hr
35.709 kmol/hr 376.64 kmol/hr
0.75 mol H2O/mol Composition 0.79 mol N2/mol nH2 kmol/hr
same as stream
5 0.21 mol O2/mol

Reaction Considered in Primary Reformer:

1. CH4 + H2O ⇌ CO + 3H2 60% Conversion

2. CO + H2O ⇌ CO2 + H2 30% Conversion

3. C2H6 + 2H2O⇌2CO + 5H2 100% Conversion

4. C3H8 + 3H2O ⇌ 3CO + 7H2 100% Conversion

5. C4H10 + 4H2O ⇌ 4CO + 9H2 100% Conversion

Here, Conversion of CH4 is 60%

40
∴ nCH4 = (501×0.2437) ×100 =48.84 kmol

Here, there is no reaction of N2.

55
∴nN2 = 501×0.000326 = 0.1633 kmol

Now, from the equations,

60
Total produced CO = {(501×0.2437) ×100}+{(501×0.0059) ×2} +(501×0.00111)

×3+(501×0.000377) ×4

=81.5918 kmol

From the equation 2, conversion of CO is 30%

30
∴ nCO2 = 81.5918× = 24.48 kmol/h
100

∴ nCO = (81.5918-24.48) = 57.1118 kmol/h

Atomic oxygen balance:

501×0.75 = nH2 O +nCO +nCO2

501×0.75 = nH2 O +57.1118+24.48

nH2O = 294.1582 kmol/h

Atomic H balance:

= 501× (0.2437×4+0.0059×6+0.001111×8+0.000377×10+0.75×2)

= 48.84×4+294.1582×2+nH2 ×2

nH2 = 240.135 kmol/h

For maintaining temperature for endothermic reaction, heat input is needed. That's why
combustion of fuel NG is occurred with excess air.

Here, CH4, C2H6, C3H8, C4H10 will be reacted completely that means complete combustion.

CH4 + 2O2 → CO2 + 2H2O ------(i)

C2H6 + 3.5O2 → 2CO2 + 3H2O ------(ii)

C3H8 + 5O2 → 3CO2 + 4H2O

C4H10 + 6.5O2 → 4CO2 + 5H2O

N2 -balance:

56
35.709×0.0013+376.64×0.79 = nN2

nN2 = 297.64 kmol/h

C-balance:

35.709(0.9691×1+0.0237×2+0.0044×3+0.0015×4) = nCO2

nCO2 = 36.98 kmol/h

H-balance:

35.709(0.9691×4+0.0237×6+0.0044×8+0.0015×10) = nH2O ×2

nH2O = 72.65 kmol/h

O2-balance:

376.64×0.21×2 = nCO2 ×2+nH2 O ×1+nO2 × 2

nO2 = 5.79 kmol/h

Table 11: Inlet and Outlet Conditions for Primary Reformer (R-101)

Stream No. Inlet (mole%) Outlet (mole%)

11 06 10 13 12

Temperature (℃) 450 30 30 600 750

Pressure (Bar) 16 16 1 15.5 1

Molar Flow 501 35.709 376.64 664.83 413.06

(Kmol/hr)
CH4 0.2437 0.9691 - 0.0732 -

C2 H6 0.00596 0.0237 - - -

C3 H8 0.00111 0.0044 - - -

C4 H10 0.000377 0.0015 - - -

N2 0.000326 0.0013 0.79 0.0002 0.7187

H2O 0.75 - - 0.4074 0.1804

57
 O2 - - 0.21 - 0.0091

CO - - - 0.0857 -

CO2 - - - 0.0367 0.0918

H2 - - - - -

8.7 Secondary Reformer (R-102):

380.97 kmol/air
17 0.79 mol N2/mol
0.21 mol O2/mol

13 15
Secondary Reformer
48.84 kmol CH4/hr
nCH4
0.1633 kmol N2/hr
nN2
24.48 kmol CO2/hr
nH2O
57.1118 kmol CO/hr
nCO
294.1582 kmol/hr
nCO2
240.135 kmol H2/h
nH2

Reaction considered in secondary reformer:

1
1. H2 + O2 ⇌ H2O conversion 10%
2

2. CH4 + 1.5 O2 ⇌ CO + 2H2O conversion 60%

3. CH4 + 2O2 ⇌ CO2 + 2H2O conversion 60%

4. CH4 + H2O ⇌ CO + 3O2 conversion 80%

5. CO + H2O ⇌ CO2 + H2 conversion 50%

All conversion percentage were assumed

58
nCH4 calculation:

nCH4 after 60% conversion of reaction 2

nCH4 = (48.84×0.4) = 19.536 kmol/h

nCH4 after 60% conversion of reaction 3

nCH4 = (19.536×0.4) = 7.8144 kmol/h

nCH4 after 80% conversion of reaction 4

final nCH4 = 1.56 kmol/h

nCO calculation:

From reaction 2, 60% CH4 converted into CO

∴nCO = 48.84×0.6 = 29.304 kmol/h

From reaction 4, 80% CH4 converted into CO

∴nCO = 7.8144×0.8 = 6.25 kmol/h

Again, from reaction 5, 505 CO converted.

∴final nCO = 35.554×0.5 = 17.777 kmol/h

CO2 calculation:

From reaction 3, 60% CH4 converted into CO

∴nCO = 19.536×0.6 = 29.304 kmol/hr

CO2 produced from reaction 4

∴nCO2 = 17.777 kmol/hr

∴final nCO2 = 11.7216 + 17.777 kmol/hr

N2 balance: Unreacted

nN2 = 301.1296 kmol/hr

O2 balance:

24.48×2+57.1118×1+294.1582×1+380.97×0.21×2

59
= nH2 O +nCO +nCO2 ×2

24.48×2+57.1118×1+294.1582×1+380.97×0.21×2

= nH2 O +17.7777×1+29.4986×2

nH2O = 503.46 kmol/hr

H-balance:

48.84×4+294.1582×2+240.135×2

= nH2 O × 2+nCH4 × 4+nCO2 ×2

48.84×4+294.1582×2+240.135×2

= nH2 O +17.7777×1+29.4986×2

nH2O = 503.46 kmol/hr

60
Table 12: Inlet and Outlet Conditions for Secondary Reformer (R-102)

Stream No. Inlet (mole %) Outlet (mole%)

13 17 15

Temperature (℃) 600 450 900

Pressure (Bar) 15.5 1 15

Molar Flow (Kmol/hr) 664.83 380.97 1045.8

CH4 0.0732 - 0.0015

N2 0.0002 0.79 0.2813

H2O 0.4074 - 0.3345

O2 - 0.21 -

CO 0.0857 - 0.0703

CO2 0.0367 - 0.0507

H2 0.3968 - 0.258

61
 8.8 Heat Exchanger (E-103)

Composition same
17 as stream 9

15 E-103
18 Composition same
nCH4=1.56 kmol/hr as stream 9

nCO= 0.7187 Kmol N2/mol

380.97 kmol/hr
nCO2 = 0.1804 Kmol H2O/mol 16 0.79 mol N2/mol
nN2 =301.1296 Kmol O2/mol
0.21 mol O2/mol
nH2O = 0.0918 Kmol CO2/mol
nH2= 125.3932 Kmol/hr

N.B: Since there is no mass balance, this portion is excluded from further calculations. An
energy balance has been conducted, and the detailed calculations are provided in Chapter 9

Table 13: Inlet and Outlet Conditions for Heat Exchanger (E-103)

Stream No. Inlet (mole%) Outlet (mole%)

15 16 18 17
Temperature (℃) 900 30 775 450
Pressure (atm) 15 1 15 1
Molar Flow (Kmol/hr) 1045.8 380.97 1045.8 380.97
CH4 0.0015 - 0.0015 -
C2 H6 - - - -
C3 H8 - - - -
C4 H10 - - - -
N2 0.2813 0.79 0.2813 0.79
H2O 0.3345 - 0.3345 -

O2 - 0.21 - 0.21
C O2 0.0507 - 0.0507 -
CO 0.0703 - 0.0703 -
H2 0.258 - 0.258 -

62
8.9 Waste heat boiler:

1692 kmol/h H2O

B2

30°C, 1 atm
161.709 kmol/hr

18 E-101 19

1.56 kmol CH4/hr Composition same as

stream 18
17.7 kmol CO/hr
29.4986 kmol CO2/hr B1
301.1296 kmol N2/hr
1692 kmol/h H2O
503.46 kmol/hr
125.3932 kmol/hr

N.B: Since there is no mass balance, this portion is excluded from further calculations. An
energy balance has been conducted, and the detailed calculations are provided in Chapter 9.

63
Table 14: Inlet and outlet Conditions for Waste Heat Boiler

Stream No. Inlet (mole%) Outlet (mole%)

18 B1 19 B2
Temperature (℃) 775 30 170 400
Pressure (atm) 15 15 15 15
Molar Flow (Kmol/hr) 677.75 1692 677.75 1692
CH4 0.0015 - 0.0015 -
C2 H6 - - - -
C3 H8 - - - -
C4 H10 - - - -
N2 0.2813 - 0.2813 -
H2O 0.3345 1 0.3345 1

O2 - - - -

C O2 0.0507 - 0.0507 -

CO 0.0703 - 0.0703 -
H2 0.258 - 0.258 -

64
8.10 Compressor (C-102)

19 Compressor 20

N.B: Since there is no mass balance, Stream 19 & 20 is same. This portion is excluded from
further calculations. An energy balance has been conducted, and the detailed calculations are
provided in Chapter 9.

Table 15: Inlet and Outlet Conditions for Compressor (C-102)

Stream No. Inlet (mole%) Outlet (mole%)

19 20

Temperature (℃) 170 250

Pressure (bar) 15 26

Molar Flow (Kmol/hr) 677.75 677.75

CH4 0.0015 0.0015

H2 0.258 0.258

CO2 0.0507 0.0507

CO 0.0703 0.0703

N2 0.2813 0.2813

H2O 0.3345 0.3345

65
8.11 Cooler (E-104)

20 Cooler 21

N.B: Since there is no mass balance, Stream 20 & 21 is same. This portion is excluded from
further calculations. An energy balance has been conducted, and the detailed calculations are
provided in Chapter 9.

Table 16: Inlet and Outlet Conditions for Cooler (E-104)

Stream No. Inlet (mole%) Outlet (mole%)

20 21

Temperature (℃) 250 60

Pressure (bar) 26 26

Molar Flow (Kmol/hr) 677.75 677.75

CH4 0.0015 0.0015

H2 0.258 0.258

CO2 0.0507 0.0507

CO 0.0703 0.0703

N2 0.2813 0.2813

H2O 0.3345 0.3345

66
8.12 Flash Separator (V-101)

21 22
Flash separator

1.56 kmol CH4/hr nCH4

17.7 kmol N2/hr nN2
29.4986 kmol CO2/hr 23 (nH2O)L nH2O
0.1633 kmol CO/hr liquid water
nCO
503.46 kmol/hr
nCO2
125.3932 kmol H2/h
nH2

(nH2O)V

Assuming that after flash separator, 98.59% feed water will be liquid at bottom.

98.5
⸫ (nH2O)L = 503.46× 100 = 495.9081 kmol H2O/hr

(nH2O)V = 7.5519 kmol H2O/hr

nCH4 = 1.56 kmol CH4/hr

nN2 =0.1633 kmol/hr

nCO2 =29.4986 kmol/hr

nCO =17.7 kmol/hr

nH2 = 125.3239 kmol/hr

67
Table 17: Inlet and outlet Conditions for Flash Separator (V-101)

Stream No. Inlet (mole%) Outlet (mole%)

21 22 23
Temperature (℃) 60 60 60
Pressure (atm) 26 26 26
Molar Flow (Kmol/hr) 677.75 181.87 495.90
CH4 0.0015 0.0022 -
H2 0.258 0.3839 -

CO2 0.0507 0.0754 -

CO 0.0703 0.1047 -
N2 0.2813 0.4186 -
H2O 0.3345 0.0100 1

68
8.13 Compressor (C-103)

22 Compressor 24

N.B: Since there is no mass balance, Stream 22 & 24 is same. This portion is excluded from
further calculations. An energy balance has been conducted, and the detailed calculations are
provided in Chapter 9.

Table 18: Inlet and Outlet Conditions for Compressor (C-103)

Stream No. Inlet (mole%) Outlet (mole%)

22 24

Temperature (℃) 60 176

Pressure (bar) 26 60

Molar Flow (Kmol/hr) 181.87 181.87

CH4 0.0022 0.0022

H2 0.3839 0.3839

CO2 0.0754 0.0754

CO 0.1047 0.1047

N2 0.4186 0.4186

H2O 0.0100 0.0100

69
8.14 Mixing of Recycle with Reactor Feed

33 8.18 kmol CH3 OH/h

7.27 kmol CH4 /h
18.2926 kmol CO/h
3 kmol CO2 /h
0.77 kmol N2 /h
8.07 kmol H2 O/h
24 25
1.56 kmol CH4 /h nCH4

17.7 kmol CO/h nCO

29.4986 kmol CO2 /h nCO2

0.1633 kmol N2 /h nN 2

125.3932 kmol H2 /h n H2

7.5519 kmol H2 O/h n H2 O

nCH3OH

nCH4 =1.56+7.27 =8.83 kmol/h

nCO = 17.7+18.2926 = 35.9926 kmol/h

nCO2 = 29.4986 + 3= 32.4986 kmol/h

nN2 = 0.1633 + 0.77= 0.9333 kmol/h

nH2 = 125.3932 kmol/h

nH2O = 7.5519 + 8.07 =15.6219 kmol/h

nCH3OH = 8.18 kmol/h

70
Table 19: Inlet and Outlet Conditions for Mixing of Recycle with Reactor Feed

Stream No. Inlet (mole%) Outlet (mole%)

24 33 25

Temperature (℃) 176 170 172.1

Pressure (atm) 60 52.6 54

Molar Flow 181.87 74.5826 256.45

(Kmol/hr)
CH4 0.0022 0.0048 0.0038

H2 0.3839 - 0.1370

CO2 0.0754 0.0036 0.0291

CO 0.1047 0.0506 0.0699

CH3 OH - 0.0054 0.0035

N2 0.4186 0.9233 0.7435

H2O 0.0100 0.0005 0.0036

71
8.15 Methanol Synthesis Reactor (R-103)

25 26
8.83 kmol CH4 /h nCH4

35.9926 kmol CO/h nCO

32.4986 kmol CO2 /h nCO2

0.9388 kmol N2 /h nN 2

125.3932 kmol H2 /h n H2

15.6219 kmol H2 O/h n H2 O

8.18 kmol CH3 OH/h nCH3OH

Reactions:

1. CO2 + 3H2 CH3 OH + H2 O ; 90% conversion

2. CO + H2 O CO2 + H2 ; 20% conversion

3. CO + 2H2 CH3 OH ; 80% conversion

There is no reaction for methanol. Hence, nCH4 = 8.83 kmol/h

There is no reaction for Nitrogen. Hence, nN2 = 0.9333 kmol/h

nCO calculation:

from reaction 2, unreacted CO = 35.9926 × 0.8

= 28.79 kmol/h

From reaction 3, nCO = 28.79 × 0.20

= 5.758 kmol/h

nCO2 calculation:

72
from reaction 1, nCO2 = 32.4986 × 0.10

=3.2498 kmol/h

From reaction 2, nCO2 =35.9926 × 0.20

= 7.19 kmol/h

Final nCO2 = 3.2498 + 7.19

= 10.45 kmol/h

Atomic carbon balance:

8.83 × 1 + 35.9926 × 1 + 32.4986 × 1 + 8.18 = 8.83 + 5.758 + nCH3OH + 10.45

nCH3OH = 60.46 kmol/h

Atomic oxygen balance:

35.9926 + 32.4986 × 2 + 15.6219 + 8.18 = 5.758 + 10.45 × 2 + 60.46 + nH2O

nH2O = 37.67 kmol/h

Atomic hydrogen balance:

8.83 × 4 + 125.3932 × 2 + 15.6219 × 2 + 8.18 × 4 = 8.83 × 4 + 60.46 × 4 + 37.67 × 2 + nH2

×2

nH2 = 0 kmol/h

There is no hydrogen in the methanol reactor outlet.

73
Table 20: Inlet and Outlet Conditions for Methanol Synthesis Reactor (R-103)

Stream No. Inlet (mole%) Outlet (mole%)

25 26

Temperature (℃) 172.1 220

Pressure (bar) 54 52.6

Molar Flow (Kmol/hr) 256.45 124.10

CH4 0.0038 0.0043

H2 0.1370 0.0000

CO2 0.0291 0.0033

CO 0.0699 0.0458

CH3 OH 0.0035 0.0662

N2 0.7435 0.8361

H2O 0.0036 0.0336

74
8.16 Heat Exchanger (E-105)

33

26 E-105
27

32

N.B: Since there is no mass balance. This portion is excluded from further calculations. An
energy balance has been conducted, and the detailed calculations are provided in Chapter 9.

Table 21: Inlet and Outlet Conditions for Heat Exchanger (E-105)

Stream No. Inlet (mole%) Outlet (mole%)

26 32 27 33
Temperature (℃) 220 35 130 170
Pressure (bar) 52.6 52.6 52.6 52.6
Molar Flow (Kmol/hr) 124.10 25.3 124.10 25.3
CH4 0.0043 0.0048 0.0043 0.0048
H2 0.0000 0.0005 0.0000 0.0005

CO2 0.0033 0.01 0.0033 0.01

CO 0.0458 0.00018 0.0458 0.00018

CH3 OH 0.0662 0.0054 0.0662 0.0054
N2 0.8361 0.9233 0.8361 0.9233

H2O 0.0336 0.0005 0.0336 0.0005

75
8.17 Cooler (E-106)

27 Cooler 28

N.B: Since there is no mass balance. This portion is excluded from further calculations. An
energy balance has been conducted, and the detailed calculations are provided in Chapter 9.

Table 22: Inlet and Outlet Conditions for Cooler (E-106)

Stream No. Inlet (mole%) Outlet (mole%)

27 28

Temperature (℃) 130 35

Pressure (bar) 52.6 52.6

Molar Flow (Kmol/hr) 124.10 124.10

CH4 0.0043 0.0043

H2 0.0000 0.0000

CO2 0.0033 0.0033

CO 0.0458 0.0458

CH3 OH 0.0662 0.0662

N2 0.8361 0.8361

H2O 0.0336 0.0336

76
8.18 Flash separator (V-102)

28 29
8.83 kmol CH4 /h nCH4

0.933 kmol N2 /h nN 2

5.758 kmol CO/h nCO [Gas stream]

10.45 kmol CO2 /h nCO2

60.46 kmol CH3 OH/h 30 nCH3OH

37.67 kmol H2 O/h n H2 O

nN 2

nCO

nCO2 [Liquid stream]

nCH3OH

n H2 O

Assuming 99.9% N2 , 99.9% CO, 99.5% CO2 , 100% CH4 are recovered to the gas stream and
95% CH3 OH, 75% H2 O recovered to the liquid stream.

(nN2 )L =0.000933 kmol/h

(nH2O ) =28.25 kmol/h

L

(nCO )L=0.005758 kmol/h

(nCO2 )L =0.02087 kmol/h

(nCH3OH ) =57.437 kmol/h

L

(nCH4 )v =8.83 kmol/h

77
(nN2 )v =0.9326 kmol/h

(nH2O )v =9.41 kmol/h

(nCO )v =5.7644 kmol/h

(nCO2 )v =10.40 kmol/h

(nCH3OH ) =3.023 kmol/h

v

Table 23: Inlet and Outlet Conditions for Flash Separator (V-102)

Stream No. Inlet (mole%) Outlet (mole%)

28 29 30
Temperature (℃) 35 35 35
Pressure (atm) 52.6 52.6 52.6
Molar Flow (Kmol/hr) 124.10 38.3269 85.7731
CH4 0.0043 0.0048 -
H2 - - -

CO2 0.0033 0.0036 0.0006

CO 0.0458 0.0506 0.0002

CH3 OH 0.0662 0.0054 0.6426
N2 0.8361 0.9233 0.0095
H2O 0.0336 0.0005 0.3470

78
8.19 Purge splitter

31
1.11 kmol CH4 /h
3 kmol CO/h
7.4 kmol CO2 /h
0.16 kmol N2 /h
29 1.35 kmol H2 O/h
0.002 kmol CH3 OH/h
8.83 kmol CH4 /h
5.74 kmol CO/h
10.40 kmol CO2 /h
3.023 kmol CH3 OH/h 32
9.412 kmol H2 O/h
0.9329 kmol N2 /h 7.72 kmol CH4 /h
2.74 kmol CO/h
3 kmol CO2 /h
0.77 kmol N2 /h
8.07 kmol H2 O/h
3.001 kmol CH3 OH/h

79
Table 24: Inlet and Outlet Conditions for Purge Splitter

Stream No. Inlet (mole%) Outlet (mole%)

29 31 32
Temperature (℃) 35 35 35
Pressure (atm) 52.6 52.6 52.6
Molar Flow (Kmol/hr) 38.3269 13.622 24.7049
CH4 0.0048 0.0048 0.0048
H2 - - -

CO2 0.0036 0.0036 0.0036

CO 0.0506 0.0506 0.0506

CH3 OH 0.0054 0.0054 0.0054
N2 0.9233 0.9233 0.9233
H2O 0.0005 0.0005 0.0005

8.20 Light End Distillation Column (T-101)

35

(nH2O )v

(nCH3OH )
v

(nCO2 )v

(nCO )v

34 (nN2 )v

57.437 kmol CH3 OH/h

28.25 kmol H2 O/h
0.02087 kmol CO2 /h
0.005758 kmol CO/h 36

0.000933 kmol N2 /h (nCH3OH )

L

(nH2O )L

80
Assuming 95% of CH3 OH and 90% of H2 O will be the bottom product. That means liquid.

(nH2O )L = 28.25 × 0.90 = 25.425 kmol/h

(nCH3OH ) = 57.437 × 0.95 = 54.5767 kmol/h

L

(nCH3OH ) =2.877 kmol/h

v

(nCO2 )v =0.02087 kmol/h

(nCO )v = 0.00578 kmol/h

(nN2 )v = 0.000933 kmol/h

Table 25: Inlet and Outlet Conditions for Low End Distillation Column (T-101)

Stream No. Inlet (mole %) Outlet (mole%)

34 35 36
Temperature (℃) 25 50 150

Pressure (atm) 12 12 12

Molar Flow (Kmol/hr) 85.714 2.9045 80

CH4 - - -

CO2 0.0006 0.0142 -

CO 0.0002 0.0048 -

CH3 OH 0.6426 0.0820 0.6659

N2 0.0095 0.2364 -

H2O 0.3470 0.6612 0.3341

81
8.21 Cooler (E-107)

37 Cooler 38

N.B: Since there is no mass balance, Stream 37 & 38 is same. This portion is excluded from
further calculations. An energy balance has been conducted, and the detailed calculations are
provided in Chapter 9.

Table 26: Inlet and Outlet Conditions for Cooler (E-107)

Stream No. Inlet (mole%) Outlet (mole%)

37 38

Temperature (℃) 110 50

Pressure (bar) 3 3

Molar Flow (Kmol/hr) 80 80

CH3 OH 0.6659 0.6659

H2O 0.3341 0.3341

82
8.22 Heavy end distillation column (T-102)
39

(nCH3OH )
T

(nH2O )T

38

54.567 kmol CH3 OH/h (nCH3OH )

B

25.425 kmol H2 O/h (nH2O )B

40
Assume 95% methanol recovery of the top and 95% H2 O recovery at the bottom.

So, (nCH3OH ) = 54.577 × 0.90 = 51.85 kmol/h ~ 52 kmol/h

T

(nCH3OH ) is our main product.

T

Now, 52kmol/h CH3 OH= 52 × 32 × 24 kg/h

= 40,000 kg/h
= 40 MTPD

(nH2O )T = 1.275 kmol/h

(nH2O )B = 24.15 kmol/h

(nCH3OH ) = 2.65 kmol/h

B

Now, top composition is-

(nCH3OH ) = 52 kmol/h
T

(nH2O )T = 1.275 kmol/h

52
So, (xCH3OH ) = 52+1.275 = 98.99%
T

∴ (xH2 O )T = 1%

83
Table 27: Inlet and Outlet Conditions for Heavy End Distillation Column T-102)

Stream No. Inlet (mole %) Outlet (mole%)

38 39 40
Temperature (℃) 50 64.5 91.5

Pressure (atm) 3 1 1

Molar Flow (Kmol/hr) 80 53.275 3.925

CH4 - - -

CO2 - - -

CO - - -

CH3 OH 0.6659 0.0027 0.9973

N2 - - -

H2O 0.3341 0.9973 0.0627

84
Chapter 09: Energy Balance

85
 9.1 Re-gasifier (E-101)

33°C, 1 atm
1750 Kmol/hr H2O

-161°C, 1 atm 30°C, 1 atm

161.709 Kmol/hr 161.709 Kmol/hr

1 E-101 2
0.9691 mol CH4 /mol Composition remains same as 1
0.0237 mol C2 H6 /mol
0.0044 mol C3 H8 /mol
15°C, 1 atm
4
0.0015 mol C4 H10 /mol 1750 Kmol/hr
HO
0.0013 mol N2 /mol

Reference: C(s), H2(g), N2 (g) O2(g) at 25°C and 1atm

Substance Input Output

Nin (Kmol) Hin (KJ/mol) Nout (Kmol) Hout (KJ/mol)
CH4 156.7 H1 156.7 H7
C2H6 3.83 H2 3.83 H8
C3H8 0.712 H3 0.712 H9
C4H10 0.2425 H4 0.2425 H10
N2 0.21 H5 0.21 H11
H20 1750 H6 1750 H12

H1= Hf (CH4) + CP∆T

−161
= ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3) dT -74.85

= (-74.85 -5.6968)

=-80.54 KJ/mol

86
H2= Hf(C2H6) + CP∆T

−161
=-84.676 +∫25 (49.37×10-3 + 13.92 ×10-5 T-5.816×10-8 T2 + 7.280×10-12 T3 ) dT

= (-84.676-7.3397)

=-92.016 KJ/mol

H3= Hf(C3H8) + CP∆T

−161
=-119.8 +∫25 ( 68.032×10-3 + 22.59 ×10-5 T- 13.11×10-8 T2 + 31.71×10-12 T3) dT

= (-119.8-9.61)

=-129.40 KJ/mol

H4= Hf (C4H10) + CP∆T

−161
=-147 +∫25 ( 92.30×10-3 + 27.88 ×10-5 T- 15.27 ×10-8 T2 + 34.967×10-12 T3) dT

= (-147-13.42)

=-160.42 KJ/mol

H5= Hf(N2) + CP∆T

−161
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3 ) dT

= (0-5.37)

=-5.37 KJ/mol

H6= Hf (H2O) + CP∆T

33
=-285.84 +∫25 (75.4×10-3) dT

= (-285.84+0.6)

=-285.24 KJ/mol

H7= Hf (CH4) + CP∆T

−30
=∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3) dT -74.85

= (-74.85+0.179) =-74.67 KJ/mol

87
H8= Hf(C2H6) + CP∆T

30
=-84.676 +∫25 (49.37×10-3 + 13.92 ×10-5 T-5.816×10-8 T2 + 7.280×10-12 T3) dT

= (-84.67+0.266)

=-84.40 KJ/mol

H9= Hf(C3H8) + CP∆T

30
=-103.8 +∫25 ( 68.032×10-3 + 22.59 ×10-5 T- 13.11×10-8 T2 + 31.71×10-12 T3 ) dT

= (-103.8+0.37)

=-103.43 KJ/mol

H10= Hf(C4H10) + CP∆T

30
=-124.7 +∫25 ( 92.30×10-3 + 27.88 ×10-5 T- 15.27 ×10-8 T2 + 34.967×10-12 T3) dT

= (-124.7+0.5)

=-124.2 KJ/mol

H11=Hf (N2) + CP∆T

30
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3 ) dT

=0.1453 KJ/mol

H12= Hf (H2O) + CP∆T

15
=-285.84 +∫25 (75.4×10-3) dT

=-286.594 KJ/mol

Over all enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

∆Q= (-513668168+512276342.1)

= -1391825.867 KJ/h = -386.61 kw

88
9. 2 Mixing (Feed NG and stream)

150°C, 1 atm
7 375 kmol/hr, H2O
30°C, 1 atm
126 kmol/hr
501 kmol/hr
5 Mixer 8
122.111 Kmol CH4/h
122.111 Kmol CH4/h
2.9862 Kmol C2H6/h
2.9862 Kmol C2H6/h
0.5544 Kmol C3H8/h
0.5544 Kmol C3H8/h
0.189 Kmol C3H8/h
0.189 Kmol C3H8/h
0.189 Kmol C4H10/h
0.189 Kmol C4H10/h
0.1638 Kmol N2/h
0.1638 Kmol N2/h
375 kmol/h H20

Reference: C(s), H2(g), N2 (g) O2(g) at 25°C and 1atm

Substance Input Output

Nin (Kmol) Hin (KJ/mol) Nout (Kmol) Hout (KJ/mol)
CH4 112.11 H1 112.11 H7
C2H6 2.9862 H2 2.9862 H8
C3H8 0.5544 H3 0.5544 H9
C4H10 0.189 H4 0.189 H10
N2 0.1638 H5 0.1638 H11
H20 375 H6 375 H12

H1= Hf (CH4) + CP∆T

−30
= ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3) dT -74.85

= (-74.85 +0.18) KJ/mol

=-74.67 KJ/mol

89
H2= Hf (C2H6) + CP∆T

30
=-84.67 +∫25 (49.37×10-3 + 13.92 ×10-5 T-5.816×10-8 T2 + 7.280×10-12 T3) dT

= (-84.67 + 0.266) KJ/mol

= -84.404 KJ/mol

H3= Hf(C3H8) + CP∆T

30
=-103.8 +∫25 ( 68.032×10-3 + 22.59 ×10-5 T- 13.11×10-8 T2 + 31.71×10-12 T3) dT

= (-103.8 + 0.37) KJ/mol

= -103.43 KJ/mol

H4= Hf(C4H10) + CP∆T

30
= -124.7 +∫25 ( 92.30×10-3 + 27.88 ×10-5 T- 15.27 ×10-8 T2 + 34.967×10-12 T3) dT

= (-124.7 + 0.5) KJ/mol

= -124.2 KJ/mol

H5= Hf(N2) + CP∆T

30
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3) dT

=0.1453 KJ/mol

H6= Hf (H2O) + CP∆T

150
=-241.83+∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

=-(241.83 + 4.27) KJ/mol

=-237.56 KJ/mol

H7= Hf (CH4) + CP∆T

117
= ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3) dT -74.85

= (-74.85 + 3.52) KJ/mol

=-71.33 KJ/mol

90
H8= Hf(C2H6) + CP∆T

117
=-84.67 +∫25 (49.37×10-3 + 13.92 ×10-5 T-5.816×10-8 T2 + 7.280×10-12 T3) dT

= (-84.67 + 5.42) KJ/mol

= -79.24 KJ/mol

H9= Hf(C3H8) + CP∆T

117
= -103.8 +∫25 ( 68.032×10-3 + 22.59 ×10-5 T- 13.11×10-8 T2 + 31.71×10-12 T3) dT

= (-103.8 + 7.67) KJ/mol

= -96.13 KJ/mol

H10= Hf(C4H10) + CP∆T

117
= -124.7 +∫25 ( 92.30×10-3 + 27.88 ×10-5 T- 15.27 ×10-8 T2 + 34.967×10-12 T3 ) dT

= (-124.7 + 10.23) KJ/mol

=-114.46 KJ/mol

H11= Hf(N2) + CP∆T

117
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3) dT

=2.68 KJ/mol

H12= Hf (H2O) + CP∆T

117
= -241.83+∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= (-241.83 + 3.13) KJ/mol

=-238.70 KJ/mol

Overall enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

∆Q= (-98533721.22 + 98449489.2) KJ/h

= -84232.02 KJ/h = -23.3977 kw

91
9.3 Compressor (C-101)

117°C, 1 atm 221.5°C, 16 bar

501 kmol/hr 501 kmol/hr

8 Compressor 9

0.2437 mol CH4/mol

Composition same as
0.0059 mol C2H6/mol stream 8

0.00111 mol C3H8/mol

0.000377 mol C4H10/mol
0.000326 mol N2/mol
0.75 mol H2O/mol

Reference: C(s), H2(g), N2 (g) O2(g) at 25°C and 1atm

Substance Input Output

Nin (Kmol) Hin (KJ/mol) Nout (Kmol) Hout (KJ/mol)
CH4 112.11 -71.33 112.11 H1
C2H6 2.9862 -79.24 2.9862 H2
C3H8 0.5544 -96.13 0.5544 H3
C4H10 0.189 -114.46 0.189 H4
N2 0.1638 2.68 0.1638 H5
H20 375 -238.70 375 H6

H1= Hf (CH4) + CP∆T

221.5
= ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3) dT -74.85

= (-74.85 + 8.07) KJ/mol

=-66.78 KJ/mol

H2= Hf(C2H6) + CP∆T

221.5
=-84.67 +∫25 (49.37×10-3 + 13.92 ×10-5 T-5.816×10-8 T2 + 7.280×10-12 T3) dT

= (-84.67 +9.89) KJ/mol

92
=-74.78 KJ/mol

H3= Hf (C3H8) + CP∆T

221.5
= -103.8 +∫25 ( 68.032×10-3 + 22.59 ×10-5 T- 13.11×10-8 T2 + 31.71×10-12 T3) dT

= (-103.8 +18.38) KJ/mol

=-85.42 KJ/mol

H4= Hf (C4H10) + CP∆T

221.5
= -124.7 +∫25 ( 92.30×10-3 + 27.88 ×10-5 T- 15.27 ×10-8 T2 + 34.967×10-12 T3 ) dT

= (-124.7 + 24.35) KJ/mol

=-100.34 KJ/mol

H5= Hf (N2) + CP∆T

221.5
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3) dT

=5.77 KJ/mol

H6= Hf (H2O) + CP∆T

221.5
= -241.83+∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= (-241.83 + 6.77) KJ/mol

=-235. 06 KJ/mol

Over all enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

∆Q=-96590689.82 + 98533721.22

=-1943031.4 KJ/h = -539 kw

93
9.4 Heat Exchanger (E-102)
750 o C, 16bar
297.56 Kmol N2/h
74.69 Kmol H2O/h
3.76 Kmol O2/h
38 Kmol CO2/h

221.5 o C, 16bar

450 o C, 16bar
122.111 Kmol CH4/h
2.9862 Kmol C2H6/h 122.111 Kmol CH4/h

0.5544 Kmol C3H8/h 2.9862 Kmol C2H6/h

0.189 Kmol C3H8/h 0.5544 Kmol C3H8/h

0.189 Kmol C4H10/h 420 o C, 1bar 0.189 Kmol C3H8/h

0.1638 Kmol N2/h 297.56 Kmol N2/h 0.189 Kmol C4H10/h

375 Kmol H2O /h 74.69 Kmol H2O/h 0.1638 Kmol N2/h

3.76 Kmol O2/h 375 Kmol H2O /h

38 Kmol CO2/h

94
 Reference: C(s), H2(g), N2 (g) O2(g) at 25°C and 1atm

Substance Input Output

N9 H9(KJ/mol) N12 H12(KJ/mol) N11 H11(KJ/mol) N14 H14(KJ/mol)

CH4 122.11 -66.78 - - 122.11 H5 - -

C2H6 2.9862 -74.74 - - 2.9862 H6 - -

C3H8 0.5544 -85.42 - - 0.5544 H7 - -

C4H10 0.189 -100.34 - - 0.189 H8 - -

N2 0.1638 5.77 297.56 H3 0.1638 H9 297.56 H13

H20 375 -235.06 74.69 H4 375 H10 74.69 H14

O2 - - 3.76 H1 - - 3.76 H11
CO2 - - 38 H2 - - 38 H12

H1=Hf(O2) + CP∆T

750
=0+∫25 (29.10×10 -3+ 1.158 ×10 - 5T -0.6076 ×10 -8T2 +1.311 ×10 -12T 3) dT

=23.605 KJ/mol

H2= Hf (CO2) + CP∆T

750
= -393.5 +∫25 (36.11×10 -3+ 4.233×10 - 5T -2.887×10 -8T2 +7.464×10 -12T 3) dT

=(-393.5+34.62)KJ/mol
= -358.88 KJ/mol

H3= Hf(N2) + CP∆T

750
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3) dT

=22.225 KJ/mol

95
H4= Hf (H2O) + CP∆T

750
= -241.83+∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= (-241.83 + 26.985) KJ/mol

=-214.845 KJ/mol

H5= Hf (CH4) + CP∆T

450
= ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3) dT -74.85

= -54.74 KJ/mol

H6= Hf (C2H6) + CP∆T

450
=-84.67 +∫25 (49.37×10-3 + 13.92 ×10-5 T-5.816×10-8 T2 + 7.280×10-12 T3) dT

=-51.327 KJ/mol

H7= Hf (C3H8) + CP∆T

450
= -103.8 +∫25 ( 68.032×10-3 + 22.59 ×10-5 T- 13.11×10-8 T2 + 31.71×10-12 T3) dT

= -55.74 KJ/mol

H8= Hf (C4H10) + CP∆T

450
= -124.7 +∫25 ( 92.30×10-3 + 27.88 ×10-5 T- 15.27 ×10-8 T2 + 34.967×10-12 T3 ) dT

= -61.67 KJ/mol

H9= Hf (N2) + CP∆T

450
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3) dT

=12.695 KJ/mol

H10= Hf (H2O) + CP∆T

450
= -241.83+∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= -2226.71 KJ/mol

H11= Hf (O2) + CP∆T

96
 420
=0+∫25 (29.10×10 -3+ 1.158 ×10 - 5T -0.6076 ×10 -8T2 +1.311 ×10 -12T 3) dT

=13.375 KJ/mol

H12= Hf (CO2) + CP∆T

420
= -393.5 +∫25 (36.11×10 -3+ 4.233×10 - 5T -2.887×10 -8T2 +7.464×10 -12T 3) dT

=-374.655 KJ/mol

H13= Hf(N2) + CP∆T

420
=0+∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3) dT

=12.5 KJ/mol

H14= Hf (H2O) + CP∆T

420
= -241.83+∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

=-226.82 KJ/mol

Overall enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

∆Q= -119271717 + 119572413.4

=300696.432 KJ/h =83.526 kw

97
9.5 Primary reformer(R-101):

297.56 kmol N2/hr

750°C, 1 bar 72.69 kmol H2O/hr

12 5.76 kmol O2/hr

36.98 kmol CO2/hr

450°C, 16 bar 600°C, 15.5 bar

11 13
122.11 kmol CH4/hr
48.84 kmol CH4/hr
2.9862 kmol C2H6/hr
0.1633 kmol N2/hr
0.5544 kmol C3H8/hr 34.61 kmol CH4/hr 24.48 kmol CO2/hr
0.189 kmol C4H10/hr 0.8463 kmol C2H6/hr 10
6 57.1118 kmol CO/hr
0.1638 kmol N2/hr 0.157 kmol C3H8/hr 294.1582 kmol H2O/hr
375 kmol H2O/hr 0.0535 kmol C4H10/hr 240.135 kmol H2/hr
0.046 kmol N2/hr 297.54 kmol N2
30°C, 1 atm
30°C, 1 atm 79.09 kmol O2

98
Substance Input Output
n11 Ĥ11(KJ/ n6(k Ĥ6(KJ/ n10(k Ĥ10( n12(km Ĥ12(K n13( Ĥ13(K
(kmol) mol) mol) mol) mol) KJ/m ol) J/mol) km J/mol)
ol) ol)

CH4 122.11 -54.74 34.6 -74.67 - - - - 48. Ĥ13.1

1 84
C2H6 2.9862 -51.327 0.84 -84.40 - - - - - -
6
C3H8 0.5544 -55.74 0.15 -103.43 - - - - - -
7
C4H10 0.189 -61.67 0.05 -124.2 - - - - - -
35
CO2 - - - - - - 36.98 - 24. Ĥ13.4
48
CO - - - - - - - - 57. Ĥ13.5
111
18
H2O 375 226.71 - - - - 72.69 - 294 Ĥ13.3
.15
82

N2 0.1638 12.695 0.04 0.1453 297.5 0.657 297.56 - 0.1 Ĥ13.2

6 4 633

H2 - - - - - - - - 240 Ĥ13.6
.13
5
O2 - - - - 79.09 0.67 5.76 - - -

99
Ĥ 13.1 = Hf (CH4) + CP∆T
600
=- 74.85 + ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3 ) dT

= -74.85 + 29.46 kJ/mol

= -45.38 kJ/mol

Ĥ 13.2 = Hf(N2) + CP∆T

600
=0 + ∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3 ) dT

= 17.39 kJ/mol

Ĥ 13.3 = Hf (H2O) + CP∆T

600
= -241.83 + ∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= -241.83+20.91 kJ/mol

= -220.92 kJ/mol

Ĥ 13.4 = Hf (CO2) + CP∆T

600
= -393.5 +∫25 (36.11×10 -3+ 4.233×10 - 5T -2.887×10 -8T2 +7.464×10 -12T 3) dT

= -393.5 + 26.53 kJ/mol

= -366.97 kJ/mol

Ĥ 13.5 = Hf (CO) + CP∆T

600
=∫25 (28.95×10-3+ 0.4110×10 -5T + 0.3548×10-8T2 – 2.220×10 -12T 3) dT

= -110.52 + 17.57 kJ/mol

= -92.95 kJ/mol

Ĥ 13.6 = Hf(H2) + CP∆T

600
=∫25 (28.84×10 -3+ 0.00765×10 - 5T -0.3288×10 -8T2 – 0.8698×10 -12T 3) dT

= 16.81 kJ/mol

100
Overall enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

ΔQ = { -77452268.16- 22139593.1} – { -71101971.97 – 2678607.626 + 248474.08}

=-26059755.74 kJ/hr = -7239 kw

9.6 Secondary Reformer(R-102):

450°C, 1 bar 300.966 kmol N2/hr

80.0037 kmol O2/hr

17

600°C, 15.5 bar

13
1.56 kmol CH4/hr

0.1633 kmol N2/hr

29.4906 kmol
15 CO2/hr

900°C, 17.77 kmol CO/hr

15 bar
503.46 kmol H2O/hr

125.39 kmol H2/hr

101
 Substance Input Output Input
n13(Kmol) Ĥ13(KJ/mol) n15(Kmol) Ĥ 15(KJ/mol) n17(Kmol) Ĥ17(KJ/mol)
CH4 48.84 -45.38 1.56 Ĥ 15.1 - -
CO2 24.48 -366.97 29.5 Ĥ 15.2 - -
CO 57.118 -92.95 17.77 Ĥ 15.3 - -
H2O 294.158 -220.92 503.46 Ĥ 15.4 - -
N2 .1633 17.39 .1633 Ĥ 15.5 300.966 Ĥ 17.1
H2 240.135 16.81 125.39 Ĥ 15.6 - -
O2 - - - - 80.08 Ĥ 17.2

Ĥ 15.1 = Hf(CH4) + CP∆T

900
=- 74.85 + ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3 ) dT

= -74.85 + 51.24 kJ/mol

= -23.611 kJ/mol
Ĥ 15.2 = Hf (CO2) + CP∆T

900
= -393.5 +∫25 (36.11×10 -3+ 4.233×10 - 5T -2.887×10 -8T2 +7.464×10 -12T 3) dT

= -393.5 + 42.94 kJ/mol

= -350.56 kJ/mol
Ĥ 15.3 = Hf (CO) + CP∆T
900
=∫25 (28.95×10-3+ 0.4110×10 -5T + 0.3548×10-8T2 – 2.220×10 -12T 3) dT

= -110.52 + 27.49 kJ/mol

= -83.03 kJ/mol
Ĥ 15.4 = Hf (H2O) + CP∆T
900
= -241.83 + ∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= -241.83 + 33.32 kJ/mol

= -208.51 kJ/mol

102
Ĥ 15.5 =Hf(N2) + CP∆T

900
=0 + ∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3 ) dT

= 27.19 kJ/mol, Ĥ 15.6 = 25.93 kJ/mol, Ĥ 17.1 = 12.695 kJ/mol, Ĥ 17.2 = 13.375 kJ/mol
Ĥ 15.6 = Hf(H2) + CP∆T

900
=∫25 (28.84×10 -3+ 0.00765×10 - 5T -0.3288×10 -8T2 – 0.8698×10 -12T 3) dT

=25.93 kJ/mol
Ĥ 17.1 = Hf(N2) + CP∆T

450
=0 + ∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3 ) dT

= 12.695 kJ/mol
Ĥ 17.2 = Hf(O2) + CP∆T
450
=0 + ∫25 (29.10×10 -3+ 1.158 ×10 - 5T -0.6076 ×10 -8T2 +1.311 ×10 -12T 3) dT

= 13.375 kJ/mol

Overall enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

ΔQ = -113574.438×103 – { 4892.74×103 – 71571619.12 }

= -46895558.88 kJ/hr = 13026.54 kw

103
9.7 Heat Exchanger (E-103):

450°C, 1 bar 300.966 kmol N2/hr

80.0037 kmol O2/hr

17

775°C, 15 bar
900°C, 15 bar
15
18
1.56 kmol CH4/hr 1.56 kmol CH4/hr

0.1633 kmol N2/hr 0.1633 kmol N2/hr

29.4906 kmol CO2/hr 30°C, 1 bar 29.4906 kmol CO2/hr

16
17.77 kmol CO/hr 300.966 kmol N2/hr 17.77 kmol CO/hr

503.46 kmol H2O/hr 80.0037 kmol O2/hr 503.46 kmol H2O/hr

125.39 kmol H2/hr 125.39 kmol H2/hr

Substance Input Output

n15 Ĥ15 n16 Ĥ16 n17 Ĥ17 n18 Ĥ18
CH4 1.56 -23.611 - - - - 1.56 Ĥ18.1
CO2 29.49 350.56 - - - - 29.49 Ĥ18.4
CO 17.77 -83.03 - - - - 17.77 Ĥ18.5
H2O 503.46 -208.51 - - - - 503.46 Ĥ18.3
N2 0.1633 27.19 300.96 0.657 300.96 12.695 0.1633 Ĥ18.2
H2 125.39 25.93 - - - - 125.39 Ĥ18.6
O2 - - 80.0037 0.67 80.0037 13.375 - -

104
Ĥ 18.1 = Hf (CH4) + CP∆T
775
=- 74.85 + ∫25 (34.31×10-3 + 5.469 ×10-5 T+0.3661×10-8 T2 -11×10-12 T3 ) dT

= -74.85 + 41.72 kJ/mol

= -33.134 kJ/mol
Ĥ 18.2 =Hf (N2) + CP∆T

775
=0 + ∫25 (29×10-3 + 0.2199 ×10-5 T+0.5723×10-8 T2 -2.871×10-12 T3 ) dT

= 23.04 kJ/mol
Ĥ 18.3= Hf (H2O) + CP∆T
775
= -241.83 + ∫25 (3.46×10-3+ 0.6880×10 - 5T + 0.7604×10 -8T2 – 3.593×10 -12T 3) dT

= -241.83 + 28.0175 kJ/mol

= -213.8125 kJ/mol
Ĥ 18.4 = Hf (CO2) + CP∆T

775
= -393.5 +∫25 (36.11×10 -3+ 4.233×10 - 5T -2.887×10 -8T2 +7.464×10 -12T 3) dT

= -393.5 + 35.99 kJ/mol

= -357.51 kJ/mol
Ĥ 18.5 = Hf (CO) + CP∆T
775
=∫25 (28.95×10-3+ 0.4110×10 -5T + 0.3548×10-8T2 – 2.220×10 -12T 3) dT – 110.52

= -110.52 + 23.30 kJ/mol

= -87.21 kJ/mol
Ĥ 18.6= Hf(H2) + CP∆T

900
=0 + ∫25 (28.84×10 -3+ 0.00765×10 - 5T -0.3288×10 -8T2 – 0.8698×10 -12T 3) dT

= 22.09 kJ/mol

Overall enthalpy balance = ∑𝑂𝑈𝑇( Nout × Ĥout) - ∑𝐼𝑁(Nin × Ĥin)

ΔQ = {4878549.488 – 117015535.7} – {251333.199 – 113702083.3}

= 1013763.88 kJ/hr

105
9.8 Waste heat boiler
𝐵1 =1692 kmol/h H2O
30ºC

30°C, 1 atm
Waste
161.709 kmol/hr
18 Heat 19
Boiler Composition same as
1560 mol CH4/hr
stream 18
17700 mol CO/hr
29498.6 mol CO2/hr
163.3 mol N2/hr
503460 mol/hr
𝐵2 =1692 kmol/h H2O
125393.2 mol/hr
775°C
400ºC

Reference: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm

Substance 18 B1 B2 19
nin ̂ in
H nin ̂ in
H nout ̂ out
H nout ̂ out
H
CH4 1560 ̂1
H 1560 ̂9
H
CO 17700 ̂2
H 17700 ̂ 10
H
CO2 29498.6 ̂3
H 29498.6 ̂ 11
H
N2 163.3 ̂4
H 163.3 ̂ 12
H
H2 O 503460 ̂5
H 1692000 ̂7
H 169200 ̂8
H 503460 ̂ 13
H
H2 125393.2 ̂6
H 125393.2 ̂ 14
H

̂ 1 = −74.85 + ∫775( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= 198.4579 mole

106
̂ 2 = −110.52 + ∫775( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −
H 25

−2.22 × 10−12 T 3 )dT

kJ
= −87.21897 mole

̂ 3 = −393.5 + ∫775( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −353.377 mole

̂ 4 = 0 + ∫775( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −23.297
mole

̂ 5 = −241.83 + ∫775( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3.593 × 10−12 T 3 )dT

kJ
= −213.908 mole

̂ 6 = 0 + ∫775( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

−0.8698 × 10−12 T 3 )dT

kJ
= −22.08466 mole

̂ 7 = −241.83 + ∫30( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −241.63 mole

̂ 8 = −241.83 + ∫400 ( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −228.607 mole

107
̂ 9 = −74.85 + ∫170( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −
H 25

11 × 10−12 T 3 )dT

kJ
= 69.0998 mole

̂ 10 = −110.52 + ∫170( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −106.257 mole

̂ 11 = −393.5 + ∫170( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −387.66 mole

̂ 12 = 0 + ∫170( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −4.24483 mole

̂ 13 = −241.83 + ∫170( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −236.739 mole

̂ 14 = 0 + ∫170( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

−0.8698 × 10−12 T 3 )dT

kJ
= 4.3167 mole

̂ in = −530963460.4 KJ/h
Total heat input= Σnin H

̂ out =−184130130.2 KJ/h

Total heat output= Σnout H

̂ out − Σnin H
ΔQ = Σnout H ̂ in

= 3460833330.2 KJ/h = 961342 kW

108
9.9 Cooler (E-104)

20 Cooler 21

1560 mol 𝐶𝐻4 /ℎ

1560 mol 𝐶𝐻4 /ℎ
17700 mol CO/h
17700 mol CO/h
29498.6 mol 𝐶𝑂2 /ℎ
29498.6 mol 𝐶𝑂2 /ℎ
163.3 mol 𝑁2 /h
163.3 mol 𝑁2 /h
503460 mol 𝐻2 𝑂/ℎ
503460 mol 𝐻2 𝑂/ℎ
125393.2 mol 𝐻2 /ℎ
125393.2 mol 𝐻2 /ℎ
Temperature - 250℃
Temperature - 60℃

Reference: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm

Substance nin ̂ in
H nout ̂ out
H

CH4 1560 ̂1
H 1560 ̂7
H

CO 17700 ̂2
H 17700 ̂8
H

CO2 29498.6 ̂3
H 29498.6 ̂9
H

N2 163.3 ̂4
H 163.3 ̂ 10
H

H2 O 503460 ̂5
H 503460 ̂ 11
H

H2 125393.2 ̂6
H 125393.2 ̂ 12
H

̂ 1 = −74.85 + ∫250( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −65.4299 mole

̂ 2 = −110.52 + ∫250( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −103.86127 mole

109
̂ 3 = −393.5 + ∫250( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −
H 25

−2.22 × 10−12 T 3 )dT

kJ
= −384.04932727 mole

̂ 4 = 0 + ∫250( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −6.620005616 mole

̂ 5 = −241.83 + ∫250( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −234.0522
mole

̂ 6 = 0 + ∫250( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

−0.8698 × 10−12 T 3 )dT

kJ
= −6.505 mole

̂ 7 = −74.85 + ∫60( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −73.56 mole

̂ 8 = −110.52 + ∫60( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −109.5001 mole

̂ 9 = −393.5 + ∫60( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −392.1729 mole

110
̂ 10 = 0 + ∫60( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×
H 25

10−12 T 3 )dT

kJ
= −1.0186 mole

̂ 11 = −241.83 + ∫60( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −240.648 mole

̂ 12 = 0 + ∫60( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

−0.8698 × 10−12 T 3 )dT

kJ
= −1.0096 mole

̂ in
Total heat input= Σnin H

=−131922017 KJ/h

̂ out
Total heat output= Σnout H

=−134904862.3 KJ/h

̂ out − Σnin H
ΔQ = Σnout H ̂ in

=−2982845.27 KJ/h = 828.56 kW

111
9.10 Compressor (C-103)

26
Compressor
176°C
1560 mol CH4 /h
17700 mol CO/h
29498.6 mol CO2 /h
163.3 mol N2 /h
7551.9 mol H2 O/h
125393.2 mol H2 /h
60°C

References: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm

Substance nin ̂ in
H nout ̂ out
H
H2 O 7551.9 ̂1
H 7551.9 ̂7
H
CH4 1560 ̂2
H 1560 ̂8
H
CO 17700 ̂3
H 17700 ̂9
H
CO2 29498.6 ̂4
H 29498.6 ̂ 10
H
N2 163.3 ̂5
H 163.3 ̂ 11
H
H2 125393.2 ̂6
H 125393.2 ̂ 12
H

̂ 1 = −241.83 + ∫60( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

3.593 × 10−12 T 3 )dT

kJ
= −240.648
mole

̂ 2 = −74.85 + ∫60( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −73.56 mole

112
̂ 3 = −110.52 + ∫60( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −
H 25

2.22 × 10−12 T 3 )dT

kJ
= −109.5001 mole

̂ 4 = −393.5 + ∫60( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

2.22 × 10−12 T 3 )dT

kJ
= −392.1729 mole

̂ 5 = 0 + ∫60( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −1.0186 mole

̂ 6 = 0 + ∫60( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 − 0.8698 ×

H 25

10−12 T 3 )dT

kJ
= 1.0096 mole

̂ 7 = −241.83 + ∫176( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25
3.593 × 10−12 T 3 )dT
kJ
= −236.661 mole

̂ 8 = −74.85 + ∫176( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25
−12 3
11 × 10 T )dT
kJ
= −68.8352 mole

̂ 9 = −110.52 + ∫176( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25
2.22 × 10−12 T 3 )dT
kJ
= −106.07923 mole

̂ 10 = −393.5 + ∫176( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25
−12 3
2.22 × 10 T )dT
kJ
= −387.3991142 mole

113
̂ 11 = 0 + ∫176( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×
H 25
−12 3
10 T )dT
kJ
= 4.422052 mole

̂ 12 = 0 + ∫176( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

0.8698 × 10−12 T 3 )dT

kJ
= 4.36175 mole

̂ in
Total heat input= Σnin H
= −15312375.87 kJ/h
̂ out
Total heat output= Σnout H
= −14652301.09 kJ/h
̂ out − Σnin H
ΔQ = Σnout H ̂ in

= 660074.78 kJ/h = 183.35410556 kW

9.11 Methanol synthesis reactor

25
25 2626
Reactor

8830 mol CH4 /h 8830 mol CH4 /h

35992.6 mol CO/h 28790 mol CO/h
32498.6 mol CO2 /h 10450 mol CO2 /h
933.3 mol N2 /h 933.3 mol N2 /h
125393.2 mol H2 /h 37670 mol H2 O/h
1562.19 mol H2 O/h 60460 mol CH3 OH/h
8180 mol CH3 OH/h 220°C
172.1°C

114
References: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm
Substance nin ̂ in
H nout ̂ out
H
CH4 8830 ̂1
H 8830 ̂8
H
CO 35992.6 ̂2
H 28790 ̂9
H
CO2 32498.6 ̂3
H 10450 ̂ 10
H
N2 933.3 ̂4
H 933.3 ̂ 11
H
H2 125393.2 ̂5
H 0 ̂ 12
H
H2 O 1562.19 ̂6
H 37670 ̂ 13
H
CH3 OH 8180 ̂7
H 60460 ̂ 14
H

̂ 1 = −74.85 + ∫172.1( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −69.0063842 mole

̂ 2 = −110.52 + ∫172.1( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

2.22 × 10−12 T 3 )dT

kJ
= −106.19635 mole

̂ 3 = −393.5 + ∫172.1( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −387.56 mole

̂ 4 = 0 + ∫172.1( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= 4.30684 mole

̂ 5 = 0 + ∫172.1( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

0.8698 × 10−12 T 3 )dT

kJ
= 4.24595 mole

115
̂ 6 = −241.83 + ∫172.1( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −
H 25

−3.593 × 10−12 T 3 )dT

kJ
= −236.7962039 mole

̂ 7 = −201.2 + ∫172.1( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

kJ
= −193.71506 mole

̂ 8 = −74.85 + ∫220( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −66.846 mole

̂ 9 = −110.52 + ∫220( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

2.22 × 10−12 T 3 )dT

kJ
= −104.7652977 mole

̂ 10 = −393.5 + ∫220( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −385.436 mole

̂ 11 = 0 + ∫220( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= 5.7261 mole

̂ 12 = 0 + ∫220( 28.84 × 10−3 + 0.00765 × 10−5 T + 0.3288 × 10−8 T 2 −

H 25

0.8698 × 10−12 T 3 )dT

kJ
= 5.63677 mole

̂ 13 = −241.83 + ∫220( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3.593 × 10−12 T 3 )dT

116
 kJ
= 5.6367 mole

̂ 14 = −201.2 + ∫220( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

kJ
= −190.9167 mole

̂ in
Total heat input= Σnin H

=−18444774.58 kJ/h

̂ out
Total heat output= Σnout H

=−18959385.75 kJ/h

̂ out − Σnin H
ΔQ = Σnout H ̂ in

=−514611.1739 kJ/h = 142.9475 kW

117
9.12 Heat Exchanger (E-105)
7720 mol 𝐶𝐻4 /ℎ
2740 mol CO/h
3000 mol 𝐶𝑂2 /ℎ

32 770 mol 𝑁2 /h
8070 mol 𝐻2 𝑂/ℎ
3001 mol 𝐶𝐻3 𝑂𝐻/ℎ
35°C

26 27

52.6°C
8830 mol 𝐶𝐻4 /ℎ

28790 mol CO/h

10450 mol 𝐶𝑂2 /ℎ

933.3 mol 𝑁2 /h 33

37670 mol 𝐻2 𝑂/ℎ 52.6°C

60460 mol 𝐶𝐻3 𝑂𝐻/ℎ

220°C

118
References: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm

Stream 26 32 27 33
no nin ̂ in
H nin ̂ in
H nout ̂ out
H nout ̂ out
H
CH4 8830 ̂1
H 7720 ̂7
H 8830 ̂ 13
H 7720 ̂ 19
H
CO 28790 ̂2
H 3000 ̂8
H 28790 ̂ 14
H 3000 ̂ 20
H
CO2 10450 ̂3
H 2740 ̂9
H 10450 ̂ 15
H 2740 ̂ 21
H
CH3 OH 60460 ̂4
H 3001 ̂ 10
H 60460 ̂ 16
H 3001 ̂ 22
H
N2 933 ̂5
H 770 ̂ 11
H 933 ̂ 17
H 770 ̂ 23
H

H2 O 37670 ̂6
H 8070 ̂ 12
H 37670 ̂ 18
H 8070 ̂ 24
H

̂ 1 = −74.85 + ∫220( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25
11 × 10−12 T 3 )dT
kJ
= −66.846 mole

̂ 2 = −110.52 + ∫220( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25
2.22 × 10−12 T 3 )dT
kJ
= −104.76529 mole

̂ 3 = −393.5 + ∫220( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25
2.22 × 10−12 T 3 )dT
kJ
= −385.436 mole

̂ 4 = −201.2 + ∫220( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25
8.03 × 10−12 T 3 )dT
kJ
= −190.9167 mole

̂ 5 = 0 + ∫220( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25
10−12 T 3 )dT
kJ
= −5.7261 mole

̂ 6 = −241.83 + ∫220( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25
3593 × 10−12 T 3 )dT
kJ
= −237.2178 mole

119
̂ 7 = −74.85 + ∫35( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −
H 25

11 × 10−12 T 3 )dT

kJ
= −74.49 mole

̂ 8 = −110.52 + ∫35( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −110.22 mole

̂ 9 = −393.5 + ∫35( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −393.126
mole

̂ 10 = −201.2 + ∫35( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

kJ
= −200.7459 mole

̂ 11 = 0 + ∫35( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= − 0.2907 mole

̂ 12 = −241.83 + ∫35( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −241.49 mole

̂ 13 = −74.85 + ∫52.6( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −66.846 mole

120
̂ 14 = −110.52 + ∫52.6( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −
H 25

−2.22 × 10−12 T 3 )dT

kJ
= −104.76529 mole

̂ 15 = −393.5 + ∫52.6( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −385.436 mole

̂ 16 = −201.2 + ∫52.6( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

kJ
= −5.7261
mole

̂ 17 = 0 + ∫52.6( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −0.80299 mole

̂ 18 = −241.83 + ∫52.6( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −240.90533 mole

̂ 19 = −74.85 + ∫52.6( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −66.846 mole

̂ 20 = −110.52 + ∫52.6( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −104.76529 mole

121
̂ 21 = −393.5 + ∫52.6( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −
H 25

−2.22 × 10−12 T 3 )dT

kJ
= −385.436 mole

̂ 22 = −201.2 + ∫52.6( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

kJ
= −5.7261 mole

̂ 23 = 0 + ∫52.6( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −0.80299
mole

̂ 24 = −241.83 + ∫52.6( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −240.90533 mole

̂ in
Total heat input= Σnin H

= −32652784.36 kJ/h

̂ out
Total heat output= Σnout H

= −20904452 kJ/h

̂ out − Σnin H
ΔQ = Σnout H ̂ in

= 11748332.33 kJ/h = 3263.4256472 kW

122
9.13 Cooler (E-106)

27 28

8830 mol CH4 /h 8830 mol CH4 /h

933 mol N2 /h 933 mol N2 /h
5758 mol CO/h 5758 mol CO/h
10450 mol CO2 /h 10450 mol CO2 /h
60460 mol CH3 OH/h 60460 mol CH3 OH/h
37670 mol H2 O/h 37670 mol H2 O/h

Reference: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 bar

Substance nin ̂ in
H nout ̂ out
H
CH4 8830 ̂1
H 8830 ̂7
H
N2 933 ̂2
H 933 ̂8
H
CO 5758 ̂3
H 5758 ̂9
H
CO2 10450 ̂4
H 10450 ̂ 10
H
CH3 OH 60460 ̂5
H 60460 ̂ 11
H
H2 O 37670 ̂6
H 37670 ̂ 12
H

̂ 1 = −74.85 + ∫130( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −70.801 mole

̂ 2 = 0 + ∫130( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −3.06685 mole

̂ 3 = −110.52 + ∫130( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −107.4438 mole

123
̂ 4 = −393.5 + ∫130( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −
H 25

−2.22 × 10−12 T 3 )dT

kJ
= −389.3615681 mole

̂ 5 = −201.2 + ∫130( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

kJ
= −196.031 mole

̂ 6 = −241.83 + ∫130( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3.593 × 10−12 T 3 )dT

kJ
= −238.255 mole

̂ 7 = −74.85 + ∫35( 34.31 × 10−3 + 5.469 × 10−5 T + 0.3661 × 10−8 T 2 −

H 25

11 × 10−12 T 3 )dT

kJ
= −74.49 mole

̂ 8 = 0 + ∫35( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −0.2907 mole

̂ 9 = −110.52 + ∫35( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −110.22 mole

̂ 10 = −393.5 + ∫35( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −393.126 mole

̂ 11 = −201.2 + ∫35( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

−8.03 × 10−12 T 3 )dT

124
 kJ
= −200.7459 mole

̂ 12 = −241.83 + ∫35( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −241.49 mole

̂ in
Total heat input= Σnin H

kj
= 26136873.54 h

̂ out
Total heat output= Σnout H

kj
= −26634314.35 h

̂ out − Σnin H
ΔQ = Σnout H ̂ in

= −26634314.35 − 26136873.54

kj
= −497440.81 h

9.14 Light End Distillation Column(T-101)

35
2877 mol (CH3 OH)v /h
20.87 mol(CO2 )v /h

Light End 5.78 mol(CO)v /h

34 Distillation Column 0.933 mol (N2 )v /h
2805 mol(H2 O)v /h
57437 mol CH3 OH/h
50ºC and 12 bar
28250 mol H2 O/h
36
20.87 mol CO2 /h
25425 mol(H2 O)L/h
5.758 mol CO/h
54576.7 mol(CH3 OH)L/h
0.933 mol N2 /h
150ºC and 12 bar
25ºC and 12 bar

125
Reference: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm

Substance nin ̂ in
H nout ̂ out
H

CH3 OH 57437 ̂1
H 2877 ̂6
H

(H2 O)v 28250 ̂2

H 2805 ̂7
H

CO2 20.87 ̂3
H 20.87 ̂8
H

CO 5.758 ̂4
H 5.78 ̂9
H

N2 .933 ̂5
H .933 ̂ 10
H

(CH3 OH)L - - 54576.7 ̂ 11

H

(H2 O)L - - 25425 ̂ 12

H

kJ
̂ 1 = −201.2
H
mole

̂ 2 = −241.83 kJ
H mole

̂ 3 = −393.5 kJ
H mole

̂ 4 = −110.52 kJ
H mole

̂ 5 = 0 kJ
H mole

̂ 6 = −201.2 + ∫50( 42.93 × 10−3 + 8.301 × 10−5 T − 1.87 × 10−8 T 2 −

H 25

8.03 × 10−12 T 3 )dT

kJ
= −200.049 mole

̂ 7 = −241.83 + ∫50( 33.46 × 10−3 + 0.688 × 10−5 T + 0.7604 × 10−8 T 2 −

H 25

−3593 × 10−12 T 3 )dT

kJ
= −240.986778 mole

̂ 8 = −393.5 + ∫50( 36.11 × 10−3 + 4.233 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

126
 kJ
= −392.5586 mole

̂ 9 = −110.52 + ∫50( 28.95 × 10−3 + 0.4110 × 10−5 T + 0.3548 × 10−8 T 2 −

H 25

−2.22 × 10−12 T 3 )dT

kJ
= −109.7922 mole

̂ 10 = 0 + ∫50( 29 × 10−3 + 0.2199 × 10−5 T + 0.5723 × 10−8 T 2 − 2.871 ×

H 25

10−12 T 3 )dT

kJ
= −0.72726 mole

̂ 11 = −238.6 + ∫150( 75.86 × 10−3 + 16.83 × 10−5 T)dT

H 25

kJ
= −227.2764 mole

̂ 12 = −285.84 + ∫150 75.4 × 10−3 dT

H 25

kJ
= −276.415 mole

̂ in
Total heat input= Σnin H

kj
= −19719332.24 h

̂ out
Total heat output= Σnout H

kj
= −20127145.09 h

̂ out − Σnin H
ΔQ = Σnout H ̂ in

= −20127145.09 + 19719332.24

kj
= −407812.8469 = 113.28134636 kW
h

127
9.15 Heavy End Distillation Column

52000 mol 𝐶𝐻3 𝑂𝐻/ℎ

1275 mol 𝐻2 𝑂/ℎ
38 64.5ºC and 1 bar

54567 mol 𝐶𝐻3 𝑂𝐻/ℎ

25425 mol 𝐻2 𝑂/ℎ

50ºC and 3 bar 40

2567 mol 𝐶𝐻3 𝑂𝐻/ℎ

24150 mol 𝐻2 𝑂/ℎ
91.5ºC and 1 bar
Reference: C(s), H2 (g) , N2 (g), O2 (g) at 25ºC and 1 atm
Substance nin ̂ in
H nout ̂ out
H

CH3 OH 54567 ̂1
H - -

H2 O 25425 ̂2
H - -

(CH3 OH)T - - 5200 ̂3

H

(H2 O)T - - 1275 ̂4

H

(CH3 OH)B - - 2567 ̂5

H

(H2 O)B - - 24150 ̂6

H

̂ 1 = −238.6 + ∫50(75.86 × 10−3 + 16.83 × 10−5 T)dT

H 25

kJ
= −236.5457 mole

̂ 2 = −285.84 + ∫50 75.4 × 10−3 dT

H 25
kJ
= −283.955 mole

̂ 3 = −238.6 + ∫64.5(75.86 × 10−3 + 16.83 × 10−5 T)dT

H 25

kJ
= −235.306 mole

128
̂ 4 = −285.84 + ∫64.5 75.4 × 10−3 dT
H 25
kJ
= −282.8617 mole

̂ 5 = −238.6 + ∫91.5(75.86 × 10−3 + 16.83 × 10−5 T)dT

H 25
kJ
= −232.9033789 mole

̂ 6 = −285.84 + ∫91.5 75.4 × 10−3 dT

H 25
kJ
= −280.8259 mole

̂ in
Total heat input= Σnin H
kj
= −201268 h

̂ out
Total heat output= Σnout H
kj
= −19976368.15
h

̂ out − Σnin H
ΔQ = Σnout H ̂ in

= −20127145.09 + 19719332.24
kj
= −19775100
h
= 5493 kW
= 5.493 MW

129
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