ACKNOWLEDGMENT

Firstly, we would like to pray gratitude to Allah SWT for giving us chance to finish
our integrated project and enabling us to complete this report. We would like to express our
deepest appreciation to those who provide us the possibility to complete this report. A special
appreciation goes to our team mates who helps each other and assemble the parts and also
gave the suggestions about the tasks.

Last but not least, many thanks goes to our lecturers, Dr. Istikamah Binti Subuki, Dr.
Norliza Binti Ibrahim, and Dr. Nurul Fadhillah Binti Kamalul Aripin who has invested their
full effort in guiding the team in achieving the goal. We also have to appreciate the guidance
given by our supervisor, Dr. Istikamah Binti Subuki as well as the panels especially in our
project presentation that has improved our presentation skills thanks for their comments and
advices.

1|Page
ABSTRACT

Methanol also known as methyl alcohol or wood alcohol is an odourless, colourless,

water-soluble liquid with mild alcoholic odour. It freezes at -97.6˚C and boils at 64.7˚C and
have a density of 791 kg/m3 at 20˚C. it is polar, acid-base neutral, and generally considered as
non-corrosive. It is miscible with most organic solvents and is capable of dissolving many
inorganic salts.

In this integrated project, the production of methanol is produced by a process called,

ICI low pressure process. Methanol also can be produced by variety of sources including
natural gas, coal, biomass, and petroleum.

Methanol also can be used as a fuel or fuel additive (eg. neat methanol fuel, methanol
blended with gasoline, MTBE, TAME, and methanol to gasoline). It can also be used for the
production of chemicals like formaldehyde, acetic acids, chloromethane, methyl methacrylate,
dimethyl terephthalate, methyl amines, and glycol methyl ethers. It is also used as a solvent
for windshield, antifreeze, inhibitor to gydrate formation in natural gas processing as a
substrate for crop growth.

Hydrocarbons Chemistry study is the simplest class of organic compounds, consisting

solely of hydrogen and carbon. The study of hydrocarbons is particularly important to the
fields of chemical engineering. Based on this study, field of hydrocarbon provide the
chemical reaction, chemical and physical properties of compound that involve in each
reaction.

Thermodynamics study is a branch of physics which relate to energy and work,

concerned with heat and temperature. In this methanol production, thermodynamics is
required to determine the boiling point, melting point, enthalpy, constant pressure and
constant volume of each compound involved. The melting point and boiling point of each
compound is necessary to relate and compare the pressure and temperature of unit in order to
determine their phases inlet and outlet.

Chemical Process Principle is the study of determination of flowrate, composition of a

compound, and production rate for each process unit that required to produce the desired
product.

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LIST OF TABLES

Table 1: Historical Development of Methanol

Table 2: The comparison between selected processes

Table 3: Description of Methanol Production Process

Table 4: Physical and Chemical Properties table of compound involve in Methanol synthesis

Table 5: Properties table of Process Unit

Table 6: Mass flowrate ouput (methanol)

Table 7: Synthesis Gas Composition

Table 8: Methanol Production Composition

Table 9: Fraction Conversion in Reactor

LISTS OF FIGURES

FIGURE 1: An overview of production of methanol from ICI Low Pressure

FIGURE 2: An overview of production of methanol from various carbon sources

FIGURE 3: An overview of production of methanol from Wood Waste

FIGURE 4: An overview of production of methanol from ICI Low Pressure

FIGURE 5: World Consumption of Methanol in 2013

FIGURE 6: Worlwide Methanol Applications

FIGURE 7: Site Location Map

FIGURE 8: Simplified Methanol Synthesis Process Flow Diagram

FIGURE 9: Methanol Synthesis Flow Diagram

FIGURE 10: Simplified Methanol Synthesis Flow Diagram

FIGURE 11: Process Flow Diagram of ICI Low Pressure

3|Page
TABLE OF CONTENTS

1.0 Process Selection

1.1 Process Background 7
1.1.1 Introduction 7
1.1.2 History of Methanol 8
1.2 Process Descriptions 9
1.2.1 ICI Low Pressure 9
1.2.2 Bio-Methanol 11
1.2.3 Production of methanol from Wood Waste 12
1.3 Screening Process for Process Selection 13
1.3.1 Reasons for selected process 15
1.4 Chemical Reaction Involve in Methanol Synthesis 16
1.4.1 Steam Reforming 16
1.4.2 Methanol Synthesis 17
1.4.3 Purification of methanol 19
1.5 Raw material 20
1.5.1 Raw materials involve 20
1.5.2 Description of raw material 20
2.0 Market analysis 24
2.1 Introduction 24
2.2 Methanol Demand by Major Region 25
2.2.1 World Wide Consumption 27
2.2.2 World Applications of methanol 28
2.3 Production rate 29
2.4 Raw material supplier 30
2.5 Site location 31
2.5.1 Introduction 31
2.5.2 Selected Plant Site 31
2.5.3 Reason details 32
2.5.4 Site location Map 32
2.6 References 33

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3.0 Hydrocarbon
3.1 Introduction 35

3.2 Stages involve in Methanol synthesis 36

3.2.1 Steam reforming 36
3.2.2 Methanol synthesis 36
3.2.3 Purification and distillation 37
3.3 Mechanism of methanol production 38
3.3.1 Steam Reforming 39
3.3.2 Methanol Synthesis (Compression) Stage 40
3.3.3 Purification and distillation 41

3.4 References 42

4.0 Thermodynamic
4.1 Introduction 44
4.2 Data Properties of Compound involve in Methanol synthesis 46
4.3 Data Properties of Process Unit 47
4.4 Data Performance of Chemical 48
4.4.1 Steam reformer 48
4.4.2 Compressor 48
4.4.3 Methanol Reactor 49
4.4.4 Distillation column 50

4.5 References 51

4.6 Appendix 52

5.0 Chemical Process Principle

5.1 Introduction 54
5.2 Reaction in production of methanol 56
5.2.1 Reactive system unit 56
5.2.2 Non-Reactive system unit 62
5.3 References 66

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1.0 PROCESS SELECTION

1.1 PROCESS BACKGROUND

1.1.1 INTRODUCTION

Methanol is a chemical formula with CH3OH. Methanol is the first

member of the homologous series of alcohols. This compound was
originally obtained by destructive distillation of wood as a by product in
the preparation of charcoal, hence the other name wood alcohol.
Methanol is a highly flammable liquid, with boiling point 64.7°C
(149°F) and is miscible with water and moist organic liquids. It is
highly poisonous substance, sublethanal amounts can cause permanent
blindness.

Methanol is one of the major industrial organic chemicals. It is

produced commercially from a mixture of carbon monoxide, CO and
hydrogen (H2) generally known as synthesis gas according to the
reaction, where the ∆H is the change in enthalpy.

CO + 2H2 → CH3OH ∆H = -90.8 kJ/mole

The synthesis gas used to produce methanol can be produced by coal,

natural gas, or petroleum fractions. The major source of synthesis gas is
by steam reforming of methane, CH4 or other hydrocarbons.

Methanol has the usual chemical properties of a primary alcohol

undergoing a traditional reaction to give methyl acetals, amines, ethers,
esters, and halides.

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 The potential of methanol as an alternative fuel has been widely used.
The volatility, ease the transport and distribution, and low combustion
emissions combine to make its used as an automotive fuel a realistic
possibility[ CITATION Par83 \l 1033 ]

1.1.2 HISTORY OF METHANOL

Table 1: Historical Development of Methanol

Year Events
1830 First commercial methanol process by destructive distillation of wood
1905 Synthetic methanol route suggested by French chemist Paul Sabatier
1923 First synthetic methanol plant commercialized by BASF
1927 Synthetic methanol processintroduced in United States
Late 1940s Conversion from water gas to natural gas as source of synthetic gas for feed to
methanol reactors
1966 Low pressure methanol process announced by ICI
1970 Acetic acids process by methanol carbonylation introduced by Monsanto
1973 Arab oil-embargo reassessment for alternative fuels
1970s Methanol to gasoline process introduced by Mobil
1989 Clean Air regulations proposed by Bush Administration
1990 Passage of the amended Clean Air Act in the United States
Early Discovery of enhanced crop yields with methanol treatment
1990s

Methanol was first produced by destructive distillation of wood in

1830. The process prevailed for about a century until the first synthetic
methanol plant was introduced by BadischeAnilin und Soda Fabrik
(BASF) in 1923. DuPont introduce the synthetic methanol plan in the
United States in 1927. In late 1940, natural gases replaced the water gas
as a source of syngas (i.e. CO and H2). Imperial Commercial Industry
(ICI) announced that a low pressure methanol process in 1966 using a
copper based catalyst. This operates at 5-10 Mpa (50-100 atm)
compared with 35 Mpa (35 atm) for the older high pressure process.
The Arab oil embargo in 1973 first generated much interest in methanol
as an alternative automobile fuel.

In 1989, the Bush administration proposed a clean air regulations that

would mandate the use of cleaner alternative automobile fuels. The

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 amended Clean Air Act, passed in 1990, requires a reduction in ozone
layer and carbon monoxide emissions, although it does not mandate
used of the alternative fuel. Currently, methyl-tert-butyl ether derived
from isobutene and methanol is the most widely used oxygenated in
reformulated gasoline, and automakers, and local government
authorities have announced plans to introduce methanol-fueled vehicles.
The interest in methanol fuel applications has shifted from the
economic considerations in the 1970’sto environmental considerations
in the 1990s. this environmental impact will continue into the next
century and could have a strong effect on demand for methanol.
Furthermore, it was recently discovered that some crops treated with
methanol or nutrient supplement methanolshowed significant increases
in crop yields. This has opened up another area of research and the
development for the methanol and provide another opportunity for
future methanol growth.

Source: Wu Hsun Cheng, Harold H. Kung (1994). Methanol

production and Use. New York, New York: Marcel Dekker.

1.2 PROCESS DESCRIPTION

Methanol is known as methyl alcohol and itself has the molecular

formula of  CH3OH. Methanol is a flammable liquid which miscible
with water in all proportions and has a distinctive odour but the odour is
slightly sweeter rather than ethanol. Methanol can be made from wide
array of feedstocks, that make methanol as the most flexible energy
sources that available today. From the wide types of production of
methanol, three have been choose in order to make the right selection of
process for this production of methanol. There are :

a) ICI Low Pressure

b) Bio-Methanol
c) Production of methanol from wood waste

1.2.1 ICI Low Pressure

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 These process consists of three stages, reforming, compression and
distillation which involve the use of Natural Gas.

Steam reforming CH4 + H2O = CO + 3H2

Shift reaction CO + H2O = CO2 + H2
Combustion 2H2 + O2 = 2H2O

The first stage of methanol manufacturing process is produced in the

reformer. Here, the natural gas is combined with steam under heat
pressure to produce synthesis gases, which are Hydrogen, H2, Carbon
Monoxide, CO and Carbon dioxide CO2. At the stage of reforming gas,
the synthesis gas and water will break down to their basic element.
Water will break down to hydrogen and oxygen, while natural gas
(methane) will break down to carbon and hydrogen gas [ CITATION
JJa06 \l 1033 ]. After the gases is break down to basic element , these
gases will reformed to a new gas.The process of breaking down a
bonding will need a much higher energy. Therefore this process in
under endothermic reaction. At the end of process reformer gas, the
reformed gas will produce which is consists of Hydrogen, Carbon
Dioxide and Carbon Monoxide.

Chemical equation in Reforming Gas:

CO + 2H2 = CH3OH

CO2 +3H2 = CH3OH + H2O

At the stage synthesis of methanol, the reformed gas will go through the
Methanol Converter. In this step, the reformed gas will react to each
other to form a Methanol. The process of making bond will produce
heat. Therefore in synthesis of methanol it categorized as a exothermic
reaction.

Chemical equation in Methanol synthesis:

2H2 + CO CH3OH

3H2 + CO2 CH3OH + H2O

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 Figure 1: An overview of production of methanol from ICI Low Pressure

Catalyst carried out the production of crude methanol stream at about

80% methanol and 20% water. . The methanol synthesis takes place in
the presence of copper-based catalysts at 250-260 oC.The crude
methanol is then separated from the uncondensed gases and those gases
are recirculated back again to the converter via the circulator.

1.2.2 Bio-Methanol

This process is the synthesis of methanol from biomass. Methanol is

crude glycerin. Glycerin is aa renewable byproduct of biodiesel
synthesis[ CITATION Bio11 \l 1033 ] . The compounds of biodiesel and
glycerin are produced from a mix of vegetable oils and fats and
methanol. Then the glycerin by-product is converted into methanol.
Recycling of glycerin closed the production cycle. This is because the
methanol that is produced from glycerin can again be used in the
biodiesel production.

Carbon Sources Air Separation

10 |CO2
Page Biogas;Nat,Gas Waste;Biomass;Coal
Oxygen

Gasification
 CO2 capture CH4 reforming Electrolysis

Hydrogen
Crude Syngas

Natural Gas
Reforming
Syngas conditioning
- Hydrocarbon reforming
- Water gas shift
- Hydrogen addition
- CO2 removal

Syngas

Bio methanol
synthesis

Figure 2: An overview of production of methanol from various carbon sources

1.2.3 Production of methanol from Wood Waste

Any carbonaceous material can be utilized for synthetic methanol. But

somehow it is really contrast to production from natural gas where these
kind of materials required additional processing steps in order to refine
the crude gas product into a final clean gas product which is syngas that
consisting two parts of H2 and CO[CITATION RMR77 \l 1033 ]. For the
first step, the wood waste is separately dried before they went through
the gasification, as most commercial gasifiers required and partially
burn or oxidise to produce crude gas consisting primarily of
hydroge,H2, Carbon dioxide, CO2 and carbon Gasifier is used to
convert the wood waste into a blonded gas. Several types of gasifieris
used. Then is passed through a gas (which is cleaned and compressed)
to a liquid fuel methanol.

11 | P a g e
 Figure 3: An overview of production of methanol from Wood Waste

1.3 SCREENING PROCESS FOR PROCESS SELECTION

Types of
process Raw Materials Advantages Disadvantages

ICI Low - Carbon monoxide a. Produce less exhaust
Pressure - Hydrogen emissions than burning the
- Carbon dioxide feedstock fuel.
- Water b. Since steam reforming stage is
endothermic process, this lead
to increase the burning value
of fuel resulting in a more
efficient fuel.
c. Low in cost since produced in
a. Soot is form at high
temperatures in the
reactor.
b. Water sequestration from
the exhaust is not easy to
handle.

12 | P a g e
 areas where a large supply of
Natural Gas available
(Kerteh,Terengganu) which at
an economical supply cost.
d. Low pressure operation means
lower methanol concentration
therefore higher recycle rates.

a. The cost of production is

Bio- -Feedstocks such as a. May reduce the use of fossil estimated much higher
Methanol waste biomass and fuels which can be used in than the cost of using
CO2 from flue automotive engines. natural gas. Since its
gases. b. Reduces greenhouse gas production is almost
- glycerin emissions since reusing the totally depends on prices
byproduct of biodiesel of feedstock, plant set up
production which is glycerin. and local conditions.
c. Helps limit the global Means, the production
warming since reducing the cost might be not stable,
emission of carbon dioxide. always change according
to the prices of
feedstocks.

b. It also may compete with

the use of biomass of
other products and
commodities such as
transportation of biofuels
and heat from biomass.

a. The methanol can be reformed a. It is not very clean and

Production - Wood waste into hydrogen to produce produces greenhouse gases.
from Wood electricity by power fuel cells. b. Combustion of biomass
Waste b. Not require any conditional or products require some land

13 | P a g e
 energy cost that make the east
of operation and maintenance.
c. Reuse the neglected biomass
residues to form and provide
renewable distribution power
generation.
to let them burn easily.
However the burning
produces gases likes
methane that harmful to
ozone layer of the Earth.
Thus, it must produced at
area quite far from
residential homes.

Table 2: The comparison between selected processes.

1.3.1 REASONS OF SELECTED PROCESS

First and foremost, from the short review about comparison between
three processes in production of methanol, we have selected ICI Low
Pressure process. This is because ofthis process applied low pressure
operation that means and produce methanol with lower cencentration in
the effluent stream and therefore higher recycle rates, thus high the rate
of production.However, a high pressure would involve bulkier
equipment and then energy costs and capital costs require to reach a
balance between them.

Although this ICI Low Pressure has its own disadvantages like those
two others, they can be overcome. The soot is formed in high
temperatures in the reactor, but it is can be prevented by using the right
catalyst such as copper. Besides the water sequestration from the
exhaust can be considered as exhaust gas reforming. This exhaust gas
can be brought in direct contact with the feed stock fuel from the
engine. The aforementioned reaction can take place with the water
present in the exhaust without storing a supply of water on-board or
having to separate the water from the exhaust.

14 | P a g e
 Besides, the production of methanol from Natural Gas does not lead to
greenhouse gases compared to the production of methanol from wood
waste. This is because, when the stock of wood waste is not enough to
produce the methanol, and when the demand is too high, tendency to
cut the trees and disturb the forests are high in order to fulfill the stock
of wood waste and the demand. Since the process from wood waste,
requires the burning half of the wood waste to produce crude gas, this
will really really bring to air pollution, increase the greenhouse gases
and many other harmful effects to the humans and environment. So this
is why this process of production of methanol from wood waste is not
the right choice to be choosen.

Moreover, the use of biomass to produce methanol required us to

compete with other products and commodities that used biomasssuch
as transportation of biofuels and heat from biomass. This will create
some difficulties in getting the source. So, that is why ICI Low Pressure
process is better than two others.

1.4 CHEMICAL REACTIONS INVOLVE IN METHANOL SYNTHESIS

Methanol is made from Methane, CH4 (natural gas) in a series of three reactions
:

1.4.1 Steam Reforming

This is the first major step in production of methanol. Steam reforming,

sometimes called Fossil fuel reforming is a method for producing
hydrogen or other useful products from hydrocarbon fuels such
as natural gas. This is achieved in a processing device called a reformer
which reacts steam at high temperature with the fossil fuel [ CITATION
Ste14 \l 1033 ]

The reaction is describe as follows:

CH4 + H2O  CO + 3H2 ∆H(298K) = 247kJ/mol

15 | P a g e
 The equation shows that some water, H 2O (as steam) was ‘cracks’ into
hydrogen, H2 molecules and the natural gas, Methane, CH 4 also was
‘cracks’ into carbon monoxide, CO.
The hydrogen gas are in excess means that there are more hydrogen
obtained than that is required to convert the carbon oxides into
methanol. The reaction in the steam reformer is an endothermic reaction
which means that it prefers high temperatures. Today, the new tube
materials like tubular reformer tube were designed to resist the
temperature of 1050˚C. The reactor simulations and experiments also
has shown that the reformer exit temperature can be reduced below
700˚C.

The synthetic ratio of the syngas from the steam reformer can be
adjusted by lowering the hydrogen concentration through the reverse
water-gas shift reaction shown below:

CO  H 2O  CO2  H 2 ∆H(298K) = -47kJ/mol

The equation is achieved by addition of carbon dioxide to match with

the excess hydrogen to produce a syngas containing the carbon dioxides
and hydrogen in stoichiometric proportions.

1.4.2 Methanol Synthesis

Methanol synthesis requires Copper based catalyst and the reaction

takes place at a feed temperature that allows the best conditions for
optimum production. Methanol synthesis by ICI low pressure process is
an adiabatic reactor with cold unreacted gas injected between the
catalyst beds.

16 | P a g e
 The conversion of methanol takes place at high temperature sensitivity
of catalyst. Temperature moderations is achieved by recycling large
amount of hydrogen gas, utilising the higher heat capacity of H 2 gas and
the higher gas velocity to enhance the heat transfer.

Methanol is produced from synthesis gas through the following

equations:

CO  2 H 2  CH 3OH ∆H(298K) = -91kJ/mol

CO2  3H 2  CH 3OH  H 2O ∆H(298K) = -50kJ/mol

In addition the water gas shift reaction occurs over the copper-catalyst:

CO  H 2O  CO2  H 2 ∆H(298K)= -47kJ/mol

At ICI low pressure process, the active Cu-based catalyst is used for it
is poisoned by both sulphur and chlorine but in the presence of zinc
oxides to help prevent poisoning. The methanol synthesis temperature is
typically between 230 - 300˚C, the reactor operates adiabatic. The
pressure is between 50 and 150 bar. Higher pressure will give the
economical benefit since the equilibrium than the favours methanol.
Only a portion of carbon monoxide, Co in the feed gas converted into
methanol in one pass through the reactor due to the low temperatures at
which the catalyst operates.

In the year of 2003, about 65% of methanol production in the world was
based on ICI low pressure process. (Olah, 2006). This process is
characterized by lower investment and process costs. The operating
conditions in the converter are 50-100 bar and 240-260C. The ICI
process uses a CuO-ZnO/Al2O3 catalyst. (Article of TheLurgi Process
on Methanol. 2009. Lurgi Mega Methanol, p. 3)

1.4.3 Purification of Methanol

Crude methanol contains approximately 18% of water, H2O at this stage

along with other impurities. Purification of methanol is achieved in two

17 | P a g e
 separate distillation columns. The first column is designed to remove all
the boiling impurities also called the ‘light ends’ and the next step is
that the liquid is again constantly boiled until the water, (which boils at
higher temperature) is separated from the product methanol (Production
of Methanol, 2nd April 2014. www.atlanticmethanol.com)

Good quality of methanol vapor separates on top of the column. From

here, it changed back to liquid (condensed). Part of this condensed
liquid, methanol (distillate) is taken to the product methanol storage
tanks. (Sungyu Lee, (1990). Book of Methanol Synthesis Technology.
p. 15)

ICI LOW-PRESSURE METHANOL SYNTHESIS PROCESS FLOW DIAGRAM

REFORMING STEP
SYNTHESIS

Methanol Reactor
Compressor 100 Bars &250 C
100 bars
P-20

Flash Drum
Centrifugal Heat Exchanger
40 C
Water pump
Heat
Heat
Exchanger
Natural Gas Exchanger
Steam Reformer
40 bars & 830 C

Heat Exchanger

Compressor
100 bars

Combustion Air

DISTILLATION &
Purge PURIFICATION
Refinary Methanol
Flash Drum
40 C
Steam Reformer Bunners
Heat Exchanger Topping Refining
column Column

Distillation column

Figure 4: An overview of production of methanol from ICI Low Pressure

1.5 RAW MATERIAL

1.5.1 RAW MATERIALS INVOLVE

Table 3: Description of Methanol Production Process

Feed stocks Process technology and main reactions Catalyst

18 | P a g e
Natural Gas Steam Reforming CuO/ZnO

Temperature : 830˚C
Pressure : 40 bars

CH4 + H2O  CO + 3H2

CO + H2O → CO2 + H2

Formation of Methanol
Syngas Methanol synthesis Cu/ZnO/Al2O3
Cu/ ZnO/Cr2O3
Temperature : 250 - 300 ˚C
Pressure : 100 bar

 CO+2H2  ↔ CH3OH
 CO + 3 H2     ↔    CH3OH + H2O

1.5.2 DESCRIPTION OF RAW MATERIALS

1. Synthesis gas

Syngas, or synthesis gas, is a fuel gas mixture consisting primarily

of hydrogen, carbon monoxide, and very often some carbon dioxide.
The name comes from its use as intermediates in creating synthetic
natural gas .Syngas is the direct end-product of the gasification process.
Though it can be used as a standalone fuel, the energy density of
Syngas is only about 50 percent that of natural gas and is therefore
mostly suited for use in producing transportation fuels and other
chemical products.

2. Carbon Dioxide

19 | P a g e
 Carbon dioxide gas is formed from the combination of two elements,
carbon and oxygen. It is produced from the combustion of coal or
hydrocarbons, the fermentation of liquids and the breathing of humans
and animals. Found in small proportions in the atmosphere, it is
assimilated by plants which in turn produce oxygen. CO 2 gas has a
slightly irritating odor, is colorless and heavier than air. It cannot
sustain life. It freezes at -78.5 °C to form carbon dioxide snow. In an
aqueous solution it forms carbonic acid, which is too unstable to be
easily isolated.(Linus Pauling, 1950. General Chemistry Book)

3. Hydrogen

Hydrogen is a chemical element with chemical symbol H and atomic

number 1. With an atomic weight of 1.00794 u, hydrogen is the lightest
element on the periodic table. Its monatomic form (H) is the most
abundant chemical substance in the universe, constituting roughly 75%
of allbaryonic mass. On Earth, hydrogen is found in the greatest
quantities in water, but is present in the atmosphere only in tiny
amounts less than 1 part per million by volume. Due to its low
molecular mass any hydrogen that does enter the atmosphere quickly
escapes the Earth’s gravity.

4. Carbon Monoxide

20 | P a g e
 Carbon monoxide (CO) is a colorless, odorless, and tasteless gas that is
slightly less dense than air. Carbon monoxide is produced from the
partial oxidation of carbon-containing compounds. It forms when there
is not enough oxygen to produce carbon dioxide (CO2). In the presence
of oxygen, including atmospheric concentrations, carbon monoxide
burns with a blue flame, producing carbon dioxide.

5. Methane

Methane is a chemical compound with the chemical formula CH4 (one

atom of carbon and four atoms of hydrogen). It is the
simplest alkane and the main component of natural gas. The relative
abundance of methane makes it an attractive fuel. However, because it
is a gas at normal conditions, it is difficult to store it. (Linus Pauling,
1950. General Chemistry Book)

6. Nitrogen

Nitrogen, symbol N, is the chemical element of atomic number seven.

At room temperature, it is a gas of diatomic molecules and is colorless

21 | P a g e
 and odorless. Nitrogen is a common element in the universe, estimated
at about seventh in total abundance in our galaxy and the Solar System.
On Earth, the element is primarily found as the gas molecule, it forms
about 80% of Earth's atmosphere. (Linus Pauling, 1950. General
Chemistry Book)

7. Catalyst

Modern methanol production has been made more efficient through the
use of catalysts (commonly copper based catalyst) that are capable in
operating at low pressures. Nowadays, the most widely used catalysts in
synthesis of methanol is a mixture of copper, zinc oxide, and alumina
oxide first used by Imperial Chemical Industries (ICI) in 1996. At 5-10
MPa and 250˚C, it can catalyze the production of methanol from carbon
monoxide and hydrogen with high selectivity. The reaction is carried
out in a gas phase in a fixed bed reactor.

Whereas formerly zinc oxide/chrome catalysts were in general in

applied in methanol synthesis under high pressures, about 300-400 bar,
which featured high temperature resistance and relative sensitivity to
catalysts. Today, the catalyst on a copper basis are used exclusively.
The copper based-catalyst permit methanol to be synthesized in an
economic manner at pressures between 50 and 100 bar temperatures
around 230˚C-270˚C. (Sybil P. Parker, 1983. McGraw Hill
Encyclopedia of Chemistry)

8. Water

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 Water is a chemical compound with the chemical formula H2O. A water
molecule contains one oxygen and two hydrogen atoms that are
connected by covalent bonds. Water is a liquid at standard ambient
temperature and pressure, but it often co-exists on Earth with
its solid state, ice, and gaseous state, steam (water vapor). Water covers
71% of the Earth's surface. (Bob Ishi. 1989. Chemical Structure and
Bonding)

2.0 MARKET AND ECONOMIC ANALYSIS

2.1 INTRODUCTION

In this chapter, we will discuss more detail about the methanol market and
economic analysis. This will include the methanol demand, raw materials cost
and raw materials supplier. Also, we will include the profit we will gain based
on the cost involve in production of methanol.

Worldwide, in 2010, over 45 million metric tons of methanol was consumed,

also can be roughly equivalent to global ethanol fuel demand. By 2012, the
methanol demands had reached over 50 million metric tons and there was an
increment in methanol demands around the globe from 2010 to 2012 which is
around 5 million metric tons. This steadily increasing in methanol demands
happened due to the expanded used of methanol in both a liquid fuel for
passenger’s cars and conversion to dimethyl ether which is a clean alternative
to diesel fuel for trucks and buses. Therefore, it indicates that there is a bright
opportunity to develop a methanol plant in this country based on the high
increment of methanol used in global market.

2.2 METHANOL DEMAND BY MAJOR REGION

1. North America

Methanolis a basic building block for many chemicals with formaldehyde

acetic acid and MTBE (for export) which are the three major application of
methanol in the US. This region accounted for about 10 percent of global

23 | P a g e
 methanol demand of 62 million metric tons in 2012.It is believed that by 2018,
the methanol capacity in the U.S. is set to increase by 12 times to a record 10.5
million tons per year[ CITATION GTL14 \l 1033 ]. The methanol production in
North America is also expected to increase around 26 percent by 2020, part of
a worldwide expansion that is expected to make it a meaningful market for
natural gas.

2. Western Europe

It is undeniable the largest manufacturer of methanol in Western Europe is

represented by Germany. The main consumer of methanol in Western Europe
is production of formaldehyde which is nearly 47%, 12% are used for methyl-
tert-butyl ether (MTBE) production and 7% for acetic acid production. Due to
the highly cost on the field of raw materials, have lead to the negative impacts
on methanol production in this region. High prices for natural gas make the
European methanol become noncompetitive.

3. South America

The big impact on methanol demand in South America has been the fairly new
requirement for blending into gasoline in Brazil. In late 1999, Brazil imported
large quantities of methanol as a replacement for fuel ethanol. However, in
2005, there is a net decrease in methanol demand in South America by about
6%. During this period, new methanol production is expected to come on-
stream in Trinidad and Venezuela, together with a debottleneck in Argentina,
which will more than double methanol production capability in South America.
At a production rate of 90% of nameplate, it reassures that South America will
have increasing quantities of methanol available for export during the study
period, which reaching almost 40 million ton in 2011.

4. Middle East

It is well known that this area of the world has large methanol feedstock in
form of natural, associated, and refinery gas. It is therefore not surprising that

24 | P a g e
 about 2 million ton new methanol production capacity came on-stream between
1983 and 1985 in the Persian Gulf. There is a very little current methanol
demand in this part of the world, and most of the production is exported. At the
present time, methanol production in the Middle East and Africa are dominated
by Saudi Arabia and Libya. International Octanes and Fluor Daniel Canada,
both Calgary, Alberta, have plans to build a joint methanol-MTBE facility in
Qatar. The methanol quantity would be 600,000 – 700,000 tonnes per year and
for MTBE is 500,000 tonnes per year. Currently, the analysts estimate the
global methanol demand is approximately 44.9 million tons per year, with
almost 25% of this demand stemming from applications in the energy sector.
For the near term, methanol demand in the Middle East is expected to increase
more than double during the 4 year study period within methanol export
availability is expected to continue at relatively high levels.

5. Asia

Over last five years, Asian methanol market is actively developed. According
to recent studies by GBI Research, the Asia–Pacific region accounted for 64%
of the global methanol demand already in 2010. Primarily this situation is due
to increased demand from China. China is experiencing a period of
unprecedented growth of demand for methanol and methanol production
capacity growth that changes the situation on the world market.Methanol has
also become a major feedstock for olefins production in China. More than 7
million metric tons per year of methanol is blended into gasoline each year in
China. Small volumes are used as high performance race car fuel.

According to a new IHS Chemical (NYSE: IHS) global market study, the
global methanol demand in Chinese increased by 23% during the two-year
period of 2010 to 2012, and it is expected that the annual demand for the
product will increase by more than 8%from 61 million metric tons in 2012, to
an unprecedented level of 137 million metric tons in 2022. The increased in
demand of methanol in this region indicate a good transformation of economic
growth when it compared to the economic downturn of 2008 to 2009 which

25 | P a g e
 showed the annual global methanol demand slowed to just 4% and 2%
respectively.

2.2.1 WORLDWIDE CONSUMPTION OF METHANOL

Figure 5: World Consumption of Methanol in 2013

Source: http://www.ihs.com/products/chemical/planning/ceh/methanol.aspx

Based on the IHS Chemical, China is the largest consumer in the world. It
indicated that about 50 % of methanol was consumed by China. In China, most
of the methanol is used in gasoline blending application to produce fuels. It is
expected that the average annual rate for fuels segment which developed in
China is increased about 12.5% in the next five years, growing from a market
share of 11% in 2013 to about 14% in 2018 [ CITATION Met14 \l 1033 ]. This
growth will be dependent largely upon the development of new applications as
well as general economic growth, since most of these applications (such as fuel
cells) go into durable goods uses (such as cars, which are directly linked to
general economic conditions. The second largest consumer is referred to
United States and followed by Western Europe which are 18% and 15 %
respectively[ CITATION Met14 \l 1033 ] . Another region that contributed in
consumption of methanol is Asia, Middle East, Southeast Asia, Japan, republic
of Korea, Taiwan and Eastern Europe.

26 | P a g e
 2.2.2 WORLD APPLICATIONS OF METHANOL

Worldwide, the largest consumer of methanol is the production of

formaldehyde. It is accounting that around 31% of world methanol demand in
2013[ CITATION Met14 \l 1033 ]. This demand is basically driven by the
construction of industry since the formaldehyde is used primarily to produce
adhesives for the manufacture of various construction board products. The
major end product has been plywood. Demand on formaldehyde is highly
dependent on general economic conditions, as an example, slowdown in
construction can reduce the formaldehyde demand. Overall, global methanol
demand for formaldehyde production will grow at an average rate of just over
5% per year from 2013 to 2018 and remain single-largest end use in
2018[ CITATION Met14 \l 1033 ] . There are many other applications of methanol
is to produce acetic acid, MMA, MTBE, dimethyl-ether (DME), gasoline,
MTO/MTP and biodiesel.

Worldwide Methanol Applications

22%
Formaldehyde
31%
Acetic Acid
Biodiesel
Fuel Blending
DME
11% MTBE
Other

7% 11%

13% 4%

Figure 6: Worlwide Methanol Applications

Source: http://www.methanex.com/investor/documents/Methanex

27 | P a g e
 2.3 PRODUCTION RATE

Based on the demand, it is estimated that the production rate should be around
127 000 metric tons/year. It is important to increase the economic growth in
Malaysia also in world global market.

Furthermore, it will be estimated that the supply region for methanol products
is in Asia since this area has the highest demands among the other region such
North America, Western Europe, South America and Middle East. It is
believed that, 50% from methanol production is being used in Asia.

2.4 RAW MATERIAL SUPPLIER

1. Methane

Methane is one of the main raw materials in production of methanol. This

element is available in Ecotech Pty Ltd, and Methanex Corporation which
located in the nation of Canada.

2. Carbon dioxide

In Malaysia, there are many suppliers of carbon dioxide gas such NIG Gases
Sdn. Bhd., Wipco Marketing Sdn. Bhd and XyracorpSdn. Bhd.

3. Hydrogen

28 | P a g e
 Air Products (NYSE: APD), the leading global hydrogen provider, is one of the
suppliers of this hydrogen gas in methanol formation. Also, it supplies the fast
growing merchant hydrogen market in central Malaysia.

4. Carbon Monoxide

Poly Gas SdnBhd is one of the most well-established producers and suppliers
of industrial gases in the Klang Valley. This company is one of the suppliers
for carbon monoxide gas in methanol production in Malaysia.
5. Nitrogen

Nitrogen gas suppliers such Poly Gas Sdn. Bhd., Airgaz Asia Sdn. Bhd., and
The Linde Group play important role in supplying this raw material for
production of methanol in Malaysia.

6. Catalyst

Topsoe is a leading catalyst supplier offering a diverse and full range of

catalysts to the methanol industry. With superior products combining features
such as activity, stability, selectivity and strength, Topsoe assists the methanol
industry with custom-made solutions which optimise production and match
other needs such as reduced energy consumption.

7. Water

This type of raw material is supplied by some company from few countries
such Malaysia, Singapore and Thailand for the use in methanol production.

2.5 SITE LOCATION

2.5.1 INTRODUCTION

It is important to choose a best location to build the methanol plant as it

has a major on the overall risk and profit of the company. The selection

29 | P a g e
 of a plant site is usually an exercise in economics. The main
considerations which determine the economics of any location are the
cost and availability of raw materials, labor and utilities; sales factors
such as markets and transportation considerations; government factors
such as local taxes, subsidies and regulations; and social factors like
living conditions and climate.

Based on these criteria, the location that has been chosen to build a
methanol plant is in Kerteh, Terengganu. The principal factors for this
site location are marketing area, raw material supply, transport
facilities, availability of labor, availability of land, effluent disposal
facilities, climate, strategic considerations, and availability of utilities.

2.5.2 SELECTED PLANT SITE

Kerteh, also known as one of the Malaysia Petrochemical Zones is

preferred as a location to build the methanol plant. This is because of it
have many specialities such as:

1) The strategic location which located near to the port and highway as
it able to get a good transportation network.
2) The raw material is available since its location is very close to the
gas processing plant.
3) The land price is quite cheaper.
4) Easily get some utilities and facilities from other sources.
5) Have stable climate

2.5.3 REASON DETAILS

1) Marketing area
 Located within the oil and gas industrial in Kerteh.
 Located near to the Arkema’s Industrial Chemicals who flown
in from France.

2) Price
 Land price is about RM 9/sqft.

30 | P a g e
 3) Raw material supply
 Near to the petrochemical plant.

4) Facilities
 There are two airports – Kuala Terengganu and Kerteh
 Kertih Port – as a shipping site of liquid petrochemical products.
 Dungun Water Supply – supply water which is used in
methanol production
 Kuantan Port
 Centralised tankage facilities, container and bulk liquid port.
 Centralised utility facilities.
5) Road facilities
 Two highways which will significantly enhance travel between
Peninsular Malaysia’s east and west coasts to Terengganu.
 Terengganu has almost 1,000 km of federal roads and almost
2,000 km of state roads.
 Railway linking Kerteh, Gebeng and Kuantan Port.

2.5.4 SITE LOCATION MAP

Figure 5: Kerteh Terengganu

31 | P a g e
 Figure 7: Site Location Map

2.6 REFERENCES

Cheng, W. H., & Kung, H. H. (Ed.).(1994). Methanol Production and Use. New York, United

State: Marcell Dekker, Inc.

How is Methanol Made? - Methanol Institute. (n.d.). Retrieved from

http://www.methanol.org/methanol-basics/overview/how-is-methanol-made-.aspx

Hui H. (2013, December 24). OUTLOOK â??14: Asia methanol demand to strengthen on

new uses. Retrieved March 28, 2014, from

http://www.icis.com/resources/news/2013/12/24/9738408/outlook-14-asia-methanol-

demand-to-strengthen-on-new-uses/

32 | P a g e
Jackson J. (2006). THE METHANOL PROCESS, A BASIC INTRODUCTION. Methanol

process basic description. Retrieved from

http://www.atlanticmethanol.com/cache/downloads/4tgucqxbgbcwsgwsk4cck08s4/a

mpcomethanolbasicprocess.pdf

Lee, S. G. (1990). Methanol Synthesis Technology. Florida, United State: CRC Press.

Parker, S. P. (1983).Encyclopedia of Chemistry. New York, United State: Mc- Graw Hill

Book Company.

33 | P a g e
 HYDROCARBON

3.0 HYDROCARBON

3.1 INTRODUCTION

Source: http://en.wikipedia.org/wiki/Methanol

Methanol is also known as methyl alcohol. Besides the other names of

methanol is wood alcohol, wood naphtha or wood spirits. The chemical
formula of methanol is CH3OH (often abbreviated MeOH). Modern methanol

34 | P a g e
 is produced in a catalytic industrial process directly from carbon
monoxide, carbon dioxide, and hydrogen.

Methanol is a highly flammable liquid, with boiling point 64.7°C (149°F) and
is miscible with water and moist organic liquids. It is highly poisonous
substance and sublethanal amounts can cause permanent blindness.

Methanol can be made from a wide array of feedstock, making it one of the
most flexible chemical commodities and energy sources available today. To
make methanol, first need to create synthesis gas, which have carbon monoxide
and hydrogen gas as its main component. The synthesis gas used to produce
methanol can be produced by coal, natural gas, or petroleum fractions. The
major source of synthesis gas is by steam reforming of methane, CH 4 or other
hydrocarbons. Methanol has the usual chemical properties of a primary alcohol
undergoing a traditional reaction to give methyl acetyls, amines, ethers, esters,
and halides.

The potential of methanol as an alternative fuel has been widely used. The
volatility, ease the transport and distribution, and low combustion emissions
combine to make its used as an automotive fuel a realistic possibility. [ CITATION
Par83 \l 1033 ]

3.2 STAGES INVOLVE IN METHANOL SYNTHESIS

Methanol is manufactured by ICI low pressure process. This ICI introduced the
low-pressure methanol process with a quench reactor system. It is widely used
as it applied low pressure operation that means and produce methanol with
lower concentration in the effluent stream and therefore higher recycle rates,
thus high the rate of production. This process consists of three stages,
reforming, compression and distillation which involve the use of Natural Gas.

3.2.1 Steam Reforming

The first stage of methanol manufacturing process is produced in the reformer.

Here, the natural gas is combined with steam under heat pressure to produce

35 | P a g e
 synthesis gases, reforming gas, the synthesis gas and water will break down to
their basic element. Water will break down to hydrogen and oxygen, while
natural gas (methane) will break down to carbon and hydrogen gas [ CITATION
JJa06 \l 1033 ]. After the gases are break down to basic element, these gases will
reform to a new gas. The process of breaking down a bonding will need a much
higher energy. At the end of process reformer gas, the reformed gas will
produce synthesis gases which are hydrogen, carbon dioxide and carbon
monoxide.

Chemical equation in reforming gas:

CH4 + H2O ❑
⇔ CO + 3H2

CO + H2O ❑
⇔ CO2 + H2

CH4 + 2H2O❑
⇔ CO2 + 4H2

3.2.2 Methanol Synthesis (Compression)

At the stage in synthesis of methanol, the reformed gas will go through the
Methanol Converter. In this stage, the reformed gas will react with each other
to form a methanol. The chemical equation in Methanol synthesis:

2H2 + CO CH3OH

3H2 + CO2 CH3OH + H2O

3.2.3 Purification and Distillation

Purification of methanol is achieved in two separate distillation

columns. The first column is designed to remove all the boiling
impurities also called the ‘light ends’ and the next step is that the liquid
is again constantly boiled until the water, (which boils at higher
temperature) is separated from the product methanol. Good quality of
methanol vapor separates on top of the column. From here, it changed
back to liquid (condensed). Part of this condensed liquid, methanol

36 | P a g e
 (distillate) is taken to the product methanol storage tanks. (Sungyu Lee,
(1990). Book of Methanol Synthesis Technology. p. 15)

Figure 8: Simplified methanol synthesis process flow diagram

Source: Website, Products from Syngas—Methanol (Catalyst)

http://bioweb.sungrant.org/Technical/Bioproducts/Bioproducts+from+Syngas/Methanol/Defa
ult.htm

3.3 MECHANISM OF METHANOL PRODUCTION

3.3.1 Steam Reforming Stage

Reaction: Cracking of Methane

The equation shows that some water, H 2O (as steam) was ‘cracks’ into
hydrogen, H2 molecules and the natural gas, Methane, CH 4 also was

37 | P a g e
 ‘cracks’ into carbon monoxide, CO over copper oxide, CuO catalyst.
The hydrogen gas is in excess means that there are more hydrogen
obtained than that is required to convert the carbon oxides into
methanol.
CH4 + H2O ❑
⇔ CO + 3H2

CO + H2O ❑
⇔ CO2 + H2

CH4 + 2H2O❑
⇔ CO2 + 4H2

Formation of carbon monoxide and hydrogen gas:

H
O +

+ H H
HC O + H H
H H
H

Methane Water Carbon monoxide

Hydrogen

Formation of carbon dioxide and hydrogen:

O
HC O
+
+ H H
O O + H H

Carbon monoxide Water Carbon dioxide Hydrogen

Adding a catalyst has exactly this effect on activation energy. A catalyst

provides an alternative route for the reaction. That alternative route has
a lower activation energy. The energy profile diagram is shown as
below:

Energy Activation energy without catalyst

38 | P a g e
 CH4 + H2O Activation energy with CuO catalyst

CO + H2

Progress of Reaction
Figure 8: Energy level diagram in Cracking of Methane (exothermic)

3.3.2 Methanol Synthesis (Compression) Stage

Reaction: Catalytic Carbon Dioxide Hydrogenation

The catalytic hydrogenation of CO2 to methanol produces water as a by-

product over a catalyst of copper, Cu. A third of the H 2 is thus
converted to water, which is much higher than that converted during the
commercial production of methanol via synthesis gas.

2H2 + CO CH3OH

3H2 + CO2 CH3OH + H2

Formation of methanol from carbon monoxide and hydrogen:

H
H
H
+ O
HC O + H H

39 | P a g e
 Carbon monoxide Hydrogen Methanol

Formation of methanol from carbon dioxide and hydrogen:

H
H
H O
O O + H H
O
+ H H

Carbon dioxide Hydrogen Methanol Water

Adding a catalyst has exactly this effect on activation energy. A catalyst

provides an alternative route for the reaction. That alternative route has
a lower activation energy. The energy profile diagram is shown as
below:

Energy Activation energy without catalyst

CH3OH Activation energy with Cu catalyst

2H2 + CO2

Progress of Reaction
3.3.3 Purification and Distillation

In this stage, there is no reaction occur since it only involves the

purification and distillation of methanol. The amount of distillation
required is dependent upon the by-product formation of the methanol
synthesis catalyst, which includes esters, ethers, ketones, aldehydes,
higher alcohols and paraffinic hydrocarbons. Good quality of methanol

40 | P a g e
 vapour separates on top of the column. From here, it changed back to
liquid (condensed). Part of this condensed liquid, methanol (distillate) is
taken to the product methanol storage tanks.

3.4 REFERENCES

Lee, S. G. (1990). Methanol Synthesis Technology. Florida, United State: CRC Press.

Parker, S. P. (1983).Encyclopedia of Chemistry. New York, United State: Mc- Graw Hill

Book Company.

41 | P a g e
Parker J. (n.d.). The Production of Methanol and Gasoline. VII-Energy-D-Methanol, 9-11.

Retrieved from http://nzic.org.nz/ChemProcesses/energy/7D.pdf

Petersan, K. A., & Nielsan, C. S. (n.d.). Large Scale Methanol Production from Natural Gas.

Haldor Topsoe. Retrieved from

http://www.topsoe.com/business_areas/methanol/~/media/PDF

%20files/Methanol/Topsoe_large_scale_methanol_prod_paper.ashx

Product from Syngas- Methanol. (n.d.). Retrieved June 4, 2014, from

http://bioweb.sungrant.org/Technical/Bioproducts/Bioproducts+from+Syngas/Methan

ol/Default.htm

42 | P a g e
THERMODYNAMIC

4.0 THERMODYNAMIC PROPERTIES

4.1 INTRODUCTION

43 | P a g e
 Source: http://en.wikipedia.org/wiki/Methanol

Methanol is also known as methyl alcohol. Besides the other names of

methanol is wood alcohol, wood naphtha or wood spirits. The chemical
formula of methanol is CH3OH (often abbreviated MeOH). Modern methanol
is produced in a catalytic industrial process directly from carbon
monoxide, carbon dioxide, and hydrogen.

Thermodynamics is a branch of physics which relate to energy and work,

concerned with heat and temperature. In this methanol production,
thermodynamics is required to determine the boiling point, melting point,
enthalpy, constant pressure and constant volume of each compound involved.
The melting point and boiling point of each compound is necessary to relate
and compare the pressure and temperature of unit in order to determine their
phases inlet and outlet. Here, we neglect the side products which are ether,
methyl formate, aldehydes, acetone and other ketones due to very small
amounts and we focused on the desired products.

Enthalpy is the sum of the internal energy of the system plus the product of the
pressure of the gas in the system and its volume while the enthalpy of reaction
is The difference between the sum of the enthalpies of the products and the
sum of the enthalpies of the reactants. Cp is the molar heat capacity at constant
pressure and Cv is the molar specific heat at the constant volume.

44 | P a g e
45 | P a g e
4.2 DATA PROPERTIES OF COMPOUND INVOLVE IN METHANOL SYNTHESIS

Table 4: Physical and Chemical Properties Table of compound involve in Methanol synthesis

Compound Formula Molecular Density Melting Boiling Enthalpy of Enthalpy Specific Specific
Weight (kg/m3) Point Point (℃ ¿ vapourisation ^ f°)h,j
(∆ H heat, Cp heat, Cv
(g/mol) (℃ )b d
(kJ/mol) (kJ/mol) (kJ/kg.K) (kJ/kg.K)

Methane CH4 16.04 -182.5 -161.5 8.179 -74.85 (g) 2.22 1.70

Carbon CO2 44.01 -56.6 -78 - -412.9 (l) 0.844 0.655

Reactants dioxide

Carbon CO 28.01 -205.1 -191.5 6.042 -110.52 1.02 0.72

monoxide (g)

Hydrogen H2 2.016 -259.2 -252.78 0.904 0 (g) 14.32 10.16

Nitrogen N2 28.02 -210.0 -195.8 5.577 0 (g) 1.04 0.743

Methanol CH3OH 32.04 -97.9 64.7 35.27 -238.6 (l) 79.5 75.4

Products Water H2O 18.016 0.00 100.00 40.656 -285.84 (l) 4.22 4.19
Catalysts Copper Cu 63.54 1083 2595 304.6 0 (c)

Source: Richard M. Felder and Ronald W. Rousseau, Elementary Principle of Chemical Processes, 3rd Edition,

46 | P a g e
4.3 DATA PROPERTIES OF PROCESS UNIT

Table 5: Properties table of Process Unit

Refining
Methanol Topping Column Column
Properties Compression Unit Synthesis Unit

Boiler Condenser Boiler Condenser

Temperature (℃ ¿ 130 250 60 50 120 60

Pressure (kPa) 2000 5000 700 500 700 500

Mole flow
(kmole/hr) 800 800 2528.22 312.54

Catalyst - Cu - - - -

Source: Chan Wei Nian and Fang You, Design of Methanol Plant, Department of Chemical & Biomolecular Engineering, National University
of Singapore, Engineering Drive 4, Singapore 117576, Republic of Singapore.

47 | P a g e
 4.4 DATA PERFORMANCE OF CHEMICAL

4.4.1 STEAM REFORMER (Steam Reforming)

This is an overall endothermic reaction involving catalytic cracking of

methane and steam into syngas at high temperature 80 ℃ and pressure
of 1200 kPa over CuO catalyst.

Steam Reforming : CH4 + H2O CO + 3H2 ∆H = 206 kJ/mol

Water Gas Shift : CO + H2O CO2 + H2 ∆H = - 41kJ/mol

P = 900 kPa T = 70℃ P = 1200 kPa T = 80 ℃

CH4 (g)∆ H f =−74.85 kJ/mol Steam Reformer

CO (g) ∆ H f =−110.52kJ/mol
H2O (l) ∆ H f =−285.84 kJ/mol H2 (g) ∆ H f =0
P = 1200kPa
T = 80 ◦C
CO2 (g) ∆ H f =−412.9kJ/mol
H2O (l) ∆ H f =¿ −285.84kJ/mol

4.4.2 COMPRESSOR

Compressor is used to increase the pressure from low to high of the

synthesis gas which is from 2000kPa to 4300kPa. The fresh gas
compressor and the recirculation compressor are driven by a common
electric motor. The fresh gas compressor has a suction throttle valve
feature that adjusts over a wide flow range with a constant outlet
pressure so that large pressure fluctuations are minimal.

P = 1200kPa T = 80 ℃ Compressor P = 2000kPa T = 130℃

CO (g) ∆ H f =−110.52kJ/mol P = 2000kPa CO (g) ∆ H f =−110.52kJ/mol

H2 (g) ∆ H f =0 = 130∆◦C
HT2 (g) H f =0
CO2 (g) ∆ H f =−412.9kJ/mol CO2 (g) ∆ H f =−412.9kJ/mol
CH4 (g) ∆ H f =−74.85 kJ/mol CH4 (g) ∆ H f =−74.85 kJ/mol
N2 (g) ∆ H f =0 N2 (g) ∆ H f =0

4.4.3 METHANOL REACTOR (Methanol synthesis)

48 | P a g e
 Syngas is catalytically converted to methanol via an overall exothermic
reaction at medium temperatures of 250˚C and high pressure of 5000
kPa, over copper catalyst. Methanol synthesis products containing
methanol and syngas are flashed to separate unconverted light ends and
crude methanol. N2 gas is functioned as internal standard and it does not
involve in the reaction. Possible side reactions result the formation of
dimethyl ethers, methyl formate, ethanol, and isobutanol [ CITATION
WuH94 \l 1033 ]

CO + 2H2 CH3OH ∆H = - 90.8 kJ/mol

CO2 + 3H2 CH3OH + H2O ∆H = - 49.2 kJ/mol

P = 2000kPa T = 130 ℃ P = 5000kPa T = 250 ℃

Methanol
CO (g) ∆ H f =−110.52kJ/mol CO (g) ∆ H f =−110.52kJ/mol
Reactor
CO2 (g) ∆ H f =−412.9kJ/mol CO2 (g) ∆ H f =−412.9kJ/mol
H2 (g) ∆ H f =0 H2 (g) ∆ H f =¿ 0
CH4 (g) ∆ H f =−74.85 kJ/mol P = 5000kPa CH4 (g) ∆ H f =−74.85 kJ/mol
N2 (g) ∆ H f =0 TCH
= 250 (g) ∆ H f =−238.6 kJ/mol
3OH◦C

N2 (g) ∆ H f =0
H2O( v) ∆ H f =40.66kJ/mol

Source : [ CITATION WuH94 \l 1033 ]

4.4.4 DISTILLATION COLUMN

49 | P a g e
 The conventional distillation unit consists of a topping and a refining
section. The function of Distillation column is to separate methanol
from water with purity of 99.6 %. The light compounds present in the
raw methanol are removed in the topping column. These would be
dissolved gases such as CO, CO2, H2, N2, and CH4 in addition to some

aldehydes, ketones, and dimethyl ether within temperature of 130 ℃

and pressure of 350 kPa. The raw methanol, which consists of
methanol, water, and minor amounts of higher alcohols, is then
fractionated in the refining section to produce grade AA methanol.

P = 500kPa T = 50℃ P = 700 kPa T = 60℃

CH3OH (l)∆ H f =−238.6 kJ/mol H2(g) ∆ H f =0

H2O (l) ∆ H f =−285.84 kJ/mol
CO (g) ∆ H f =−110.52kJ/mol
CO2 (g) ∆ H f =−412.9kJ/mol
CH4 (g) ∆ H f =−74.85 kJ/mol
N2 (g) ∆ H f =0
H2(g) ∆ H f =0
CO (g) ∆ H f =−110.5 2k J /mol
Topping Column CO2 (g) ∆ H f =−412.9kJ/mol
N2 (g) ∆ H f =0
CH4 (g) H2(g) ∆ H f =0

P = 500 kPa T = 50℃

CH3OH (l)∆ H f =−238.6 kJ/mol

H2O (l) ∆ H f =−285.84 kJ/mol

P = 500 kPa T = 50℃ P = 700 kPa T = 120 ℃

CH3OH (l)∆ H f =−238.6 kJ/mol H2O( v) ∆ H f =40.66kJ/mol

Refining Column
H2O (l) ∆ H f =−285.84 kJ/mol

P = 500 kPa T = 60 ℃

CH3OH (g) ∆ H f =35.27 kJ/mol

4.5 REFERENCES

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Lee, S. G. (1990). Methanol Synthesis Technology. Florida, United State: CRC Press.

Parker, S. P. (1983).Encyclopedia of Chemistry. New York, United State: Mc- Graw Hill

Book Company.

Parker J. (n.d.). The Production of Methanol and Gasoline. VII-Energy-D-Methanol, 9-11.

Retrieved from http://nzic.org.nz/ChemProcesses/energy/7D.pdf

Petersan, K. A., & Nielsan, C. S. (n.d.). Large Scale Methanol Production from Natural Gas.

Haldor Topsoe. Retrieved from

http://www.topsoe.com/business_areas/methanol/~/media/PDF

%20files/Methanol/Topsoe_large_scale_methanol_prod_paper.ashx

Graw Hill M. (n.d.). Property Tables and Charts Unit. Retrieved June 3, 2014, from

https://highered.mcgraw-hill.com/sites/dl/free/0073529214/395307/appdxs1_2.pdf

Product from Syngas- Methanol. (n.d.). Retrieved June 4, 2014, from

http://bioweb.sungrant.org/Technical/Bioproducts/Bioproducts+from+Syngas/Methan

ol/Default.htm

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4.6 APPENDICES

Figure 10: Methanol Synthesis Flow Diagram

Source: Website, Products from Syngas—Methanol (Catalyst)

http://bioweb.sungrant.org/Technical/Bioproducts/Bioproducts+from+Syngas/
Methanol/Default.htm

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 CHEMICAL
PROCESS
PRINCIPLE

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5.0 CHEMICAL PROCESS PRINCIPLE

5.1 INTRODUCTION

In this chapter, we will discuss about the production of methanol in term of

chemical process principle. In this chapter, it will be discuss and apply the
theory of non-reactive system, reactive system. With applied the theory, the
limiting reactant, excess reactant, yield and selectivity of the reaction can be
determine. The chemical reaction that involve in this reaction are this:

CO + 2H2 ---> CH3OH

CO2 + 3H2 ---> CH3OH + H2O

Figure 11: Process Flow Diagram of ICI Low Pressure

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 Mass flowrate Value

Mass flowrate , output 14500 kg/hr

Table 6: Mass flowrate ouput (methanol)

Source: Retrieved from http://www.ippe.com/plants/600304/process_description.pdf

Table 7: Synthesis Gas Composition

Component Mole %
CH 4 4.26
CO 14.75
CO 2 8.80
H2 72.10
N2 0.09

Source: Cheng, W. -H., & Kung, H. H. (1994). Production of methanol.In Methanol

production and use (p. 86). New York: M. Dekker.

Table 8: Methanol Production Composition

Component Mole fraction

CH 3 OH 0.9985

Source: Cheng, W. -H., & Kung, H. H. (1994). Production of methanol.In Methanol

production and use (p. 111). New York: M. Dekker.

Table 9: Fraction Conversion in Reactor

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 Component Fraction Conversion
CO2 25
CO 40.8

Source: Maréchal, F., HEYEN, G., & KALITVENTZEFF, B. (1997). Energy Savings

in Methanol Synthesis: Use of Heat Integration Techniques and Simulation
Tools. Computers & Chemical Engineering, 3.doi:10.1016/S0098-1354(97)00100-2

5.2 REACTION IN METHANOL

5.2.1 Reactive System Unit

This unit is a reactor, where reaction that produce methanol is occur . In

this reactor , there are two reactions occurs where carbonv monoxide is
react with hydrogen produce a methanol and carbon dioxide react with
hydrogen to produce methanol and water . In this reactor Methane and
Nitrogen not involve in any reaction. At the feed we assume that the
molar flowrate is 300 kmol/hr
Chemical equation :

CO + 2H2 ---> CH3OH ,

CO2 + 3H2 ---> CH3OH + H2O

Methanol

Reactor

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 Basis: 3000 kmol/hr

0.72 kmol Hydrogen / kmol n1kmol Methanol / kmol

0.009 kmol Nitrogen / kmol n2kmol Water / kmol
0.0426 kmol Methane / kmol n3kmol Hydrogen / kmol
0.1475 kmol Carbon Monoxide / kmol n4kmol Carbon Monoxide / kmol
0.088 kmol Carbon Dioxide / kmol n5kmol Carbon Dioxide / kmol
n6kmol Methane / kmol
Degree of freedom : Fractional Conversion
n7kmol Nitrogen / kmol
7 unknown (n1 n2 n3 n4 n5 n6 n7)
CO = 0.408
2
5 CO2 = 0.25
2
2

Extent of reaction
n1 = ξ1 + ξ2
n2 = ξ2
n3 = nH2 - 2ξ1 + 3ξ2
n4 = ninitialCO – nfinalCO = ξ1
n5 = ninitialCO2 – nfinalCO2 = ξ2

Calculation of composition at outlet of methanol reactor

n4 = mole in - (mole in)( fractional conversion)

n4 = 3000*0.1475 - 1000*0.1475*0.408
n4 = 261.96 kmol/hr

n5 = mole in - (mole in)( fractional conversion)

n5 = 3000*0.0880- 1000*0.0880*0.25
n5 = 198 kmol/hr
ξ2= ninitialCO2 – nfinalCO2
ξ2= 0.088*3000-66

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ξ2= 66 kmol/hr

ξ1 =ninitialCO – nfinalCO
ξ1 = 0.1475*3000-87.32
ξ1 = 180.54 kmol/hr

n1 = ξ1 + ξ 2
n1 = 147.5+88

n1 = 246.54kmol/hr

n2 = ξ2
n2 = 66kmol/hr

n3 = nH2 - 2ξ 1 + 3ξ 2
n3 = 3000*0.72 - 3*88.4 - 2*147.5

n3 = 1600.92 kmol/hr

Since methane and nitrogen not take place in the reaction. The molar flowrate for
methane and nitrogen at the output is same as the feed.

n6 = 3000*0.0426

n6 = 127.8 kmol/hr

n7 = 3000*0.009

n7 = 27 kmol/hr

Total molar flowrate for outlet :

Total molar flowrate outlet = n1+ n2 + n3+ n4 + n5+ n6 + n7

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Total molar flowrate outlet = 2528.22 kmol/hr

Change the output compositions in unit mol

n = molar flowrate / total molar flowrate

n1= 0.097515

n2 =0.026105

n3 = 0.63322

n4 = 0.103614

n5 = 0.078316

n6 = 0.050549

n7 = 0.010679

Reaction between carbon monoxide with hydrogen will give the highest production of
methanol. Therefore to the determine the limiting reactant in this reactor, we use a reaction
where the reaction produce a highest production of methanol.
Equation : CO + 2H2 ---> CH3OH

Calculation to determine the limiting reactant

nCO = 442.5 kmol/hr

nH2 = 2160 kmol/hr

(nCO/nH2)real = 442.5/2160
= 0.204861

(nCO/nH2)stoich = 1/2
= 0.5

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Since stoichiometry >real , CO is a limiting reactant and then H2 is an excess reactant.

Calculation to find H2 required(Stoich)

1 mol of CO = 2mol of H2
442.5 kmol of CO = 885kmol of H2

H2(stoich) = (442.5/1)(2)

nH2(stoich) = 885 kmol/hr

442.5 kmol/hr of carbon monoxide react with 885 kmol hydrogen nH2 (stoich)

Percentage yield , fractional excess and selectivity

Calculation to determine fractional excess of Hydrogen ;

fractional excess of H2 = (nH2 (feed) – nH2(stoich))/nH2(stoich) X 100%

fractional excess of H2 = (885-442.5) /442.5 X 100%
fractional excess of H2 = 144.0678 %

Calculation for fractional yield of Methanol ;

molarflowrate Methanol that formed at output = 246.54 kmol/hr

mole reacted with limiting reactant completely = 442.5 kmol/hr
moles of desired product formed
fractionalyield = moles that would have been formed if there were no side reaction
¿ limiting reactant had completely reacted
fractional yield = 246.54/442.5
fractional yield = 0.557

Calculation selectivity of Methanol over water ;

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 moles of desired product formed
Selectivity =
moles of undesired product formed
Selectivity = nCH3OH/nH2
Selectivity = 246.54/66
Selectivity= 3.735

Yield in chemical process plant refer to production of the desired product that obtained
from the process. From the calculation we find that the fractional yield is 0.557.Usually, the
value of the real yield is always less than the theoretical yield. The theoretical yield is the
amount of product that will be produce in an ideal and perfect condition. The theoretical yield
is obtained when the limiting reactant is reacted completely in the reaction. Usually in an
actual situation it is quite impossible to unsure the limiting is reacted completely.
The term selectivity can be described as mole product of methanol over the mole of
limiting reactant .The high value of selectivity shows that the desired product is successfully
formed more than the site product. The selectivity of this reactive system is 3.735. In
conclusion, the undesired side reactions not fully suppressed relative to the desired reaction.

5.2.2 Non-Reactive Unit

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 This unit is topping column. In this column there are no reaction involve. This column
is used to separate the unwanted product such as methane, hydrogen, nitrogen , carbon
monoxide and carbon dioxide. These five unwanted product will vaporized in the
upper stream, while water and methanol will go out to the downstream. Assume that
the outlet of the reactor is equal to the feed in topping column.

n1

A kmol Hydrogen / kmol

Topping B kmol Carbon Monoxide / kmol
2528.22kmol/hr column
C kmol Carbon Dioxide / kmol
D kmol Methane / kmol

0.097515 kmol Methanol / kmol E kmol Nitrogen / kmol

0.026105 kmol Water / kmol n2

0.63322 kmol Hydrogen / kmol
0.103614kmol Carbon Monoxide / kmol F kmol Methanol / kmol
0.078316kmol Carbon Dioxide / kmol G kmol Water / kmol

0.050549 kmol Methane / kmol

0.010679kmol Nitrogen / kmol

Assume : Hydrogen , Carbon Monoxide , Carbon dioxide , Methane , and Nitrogen

completely vaporized in upper stream
Assume : Methanol and water are completely go to the bottom stream

Composition in Upper Stream

Composition
Degree of freedom : outlet = composition inlet x flowrate inlet
9 unknown ( n1 , n2 , A,B,C,D,C,E,F,G)
A = 2528*0.6332
7 components (CH3OH, H2O, H2, CO, CO2, CH4, N2)
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total = 9-7-2 = 0
A = 1600.9 kmol/hr

B = 2528.2*0.1036

B = 261.96 kmol/hr

C = 2528.2*0.0783

C = 128.298 kmol/hr

D = 2528.2*0.0505

D = 127.8 kmol/hr

E = 2528.2*0.0107

E = 27 kmol/hr

Composition in down stream

Composition outlet = composition inlet x flowrate inlet

F = 2528.2*0.0975

F = 246.54 kmol/hr

G = 2528.2*0.0261

G = 66 kmol/hr

Calculation to determine flowrate n1

n1 = A+B+C+D+E

n1 = 1600.9+261.96+27+127.8+128.298

n1 = 2215.68 kmol/hr

Calculation to determine flowrate n2

n2 = F + G

n2 =66 + 246.54

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 n2 = 312.54 kmol/hr

Change molar flowrate F and G to mol fraction

n = molar flowrate / total molar flowrate

F = 0.78883 kmol Methanol / kmol

G = 0.21117 kmol Water / kmol

This unit is refining column. In this column there are no reaction involve. This
column is used to separate the water and methanol .At the end of the refining column . Water
will vaporized at the upper stream , while pure methanol will out at the downstream .

n1

Refining H kg Methanol / kg
312.54 kmol/hr I kg Water/ kg
Column

0.78883 kg Methanol / kg
0.21117 kg Water / kg
14500 kg/hr

0.9885 kg Methanol / kg
0.0015 kg Water / kg

Degree of freedom :
2 unknown ( n1,H )
2 components (CH3OH, H2O)2 assumptions
total = 2-2 = molar
Changing 0 flowrate, n1 of feed to massflowrate

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element mol molar mass mass mass fraction
21.117 380.449
H20 3 18.016 2 0.130835183
CH3O 78.882 2527.40
H 7 32.04 2 0.869164817
2907.85
Total 100 50.056 1 1

Mass flowrate at feed

= molar flowrate x
total molar mass

Mass flowrate at feed = 258.8*50

Mass flowrate at feed =15644.5 kg/hr

Calculation to determine the lower stream , n1

n1 = total mass flowrate – total mass flowrateupperstream

n1 = 15645 – 14500

n1 = 1144.5 kg/hr

Calculation to determine the mass fraction at the bottom stream

H = ((15645*0.869164817)-(14500*0.9985))/-1144.5
H = 0.76942
I = 1-0.76942
I = 0.23058

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5.3 REFERENCES

Cheng, W. H., & Kung, H. H. (Ed.).(1994). Methanol Production and Use. New York, United

State: Marcell Dekker, Inc.

How is Methanol Made? - Methanol Institute. (n.d.). Retrieved from

http://www.methanol.org/methanol-basics/overview/how-is-methanol-made-.aspx

Hui H. (2013, December 24). OUTLOOK â??14: Asia methanol demand to strengthen on

new uses. Retrieved March 28, 2014, from

http://www.icis.com/resources/news/2013/12/24/9738408/outlook-14-asia-methanol-

demand-to-strengthen-on-new-uses/

Jackson J. (2006). THE METHANOL PROCESS, A BASIC INTRODUCTION. Methanol

process basic description. Retrieved from

http://www.atlanticmethanol.com/cache/downloads/4tgucqxbgbcwsgwsk4cck08s4/a

mpcomethanolbasicprocess.pdf

Lee, S. G. (1990). Methanol Synthesis Technology. Florida, United State: CRC Press.

Parker, S. P. (1983).Encyclopedia of Chemistry. New York, United State: Mc- Graw Hill

Book Company.

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