FACULTY OF ENGINEERING

DEPARTMENT OF CHEMICAL AND ENVIRONMENTAL

ENGINEERING
UNIVERSITI PUTRA MALAYSIA

PRODUCTION OF METHANOL
(WEEK 1 PROPOSAL)

LECTURER: DR. HAMDAN B. MOHAMED YUSOFF

PREPARED BY:
IFFAH AMIRAH BT HUSSIN ALI

172719

MOHD AZMAN BIN SUWANDI

174824

NIK NOOR ASHIKIN BINTI NIK ZAMRI

173396

THAMIL CHELVI S RAJENDRAN

173600

ADHRAA ADBULRAHMAN ALBALUSHI

171676

TABLE OF CONTENTS
INTRODUCTION..................................................................................2
FIRST PATHWAY: PRODUCTION OF METHANOL FROM COAL THROUGH
GASIFICATION PROCESS....................................................................3
SECOND PATHWAY : PRODUCTION OF METHANOL FROM NATURAL
GAS....................................................................................................6
THIRD PATHWAY: PRODUCTION OF METHANOL FROM SYNGAS...........7
Synthesis of syngas to produce methanol..............................................7
Steam reforming..........................................................................8
Autothermal reforming................................................................9
Carbon dioxide reforming............................................................9
Methanol Synthesis.......................................................................10
SUSTAINABLE DEVELOPMENT IN DESIGNING A REACTOR.................11
LIST OF PATENT................................................................................13
Production of Methanol from coal and natural gas................................13
Production of methanol.....................................................................14
REFERENCES...................................................................................14

INTRODUCTION
Methanol which is also known as methyl alcohol is a chemical with the
formula CH3OH (MeOH). It is produced in a catalytic process directly from
2

carbon monoxide, carbon dioxide and hydrogen. Methanol is also the simplest
alcohol, being only a methyl group which is linked to a hydroxyl group. It is a
light, volatile, colourless, flammable liquid with a distinctive odour that is
similar to ethanol. Unlike ethanol, methanol is highly toxic and unfit for
consumption. At room temperature, it is a polar liquid and is used as an
antifreeze, solvent and fuel. Production of methanol is natural in the anaerobic
metabolism. Methanol burns oxygen including open air which forms carbon
dioxide and water.
2 CH3OH + 3 O2 2 CO2 + 4 H2O
Properties of Methanol:
Molar mass: 32.04 g/mol
Formula: CH3OH
Boiling point: 148.5F (64.7C)
Density: 792 kg/m
Melting point: -143.7F (-97.6C)
Vapour pressure: 13.02 kPa
Classification: Alcohol
Methanol is primarily used in industrial solvents for inks, resins, adhesives
and dyes. It also acts as a solvent in manufacturing cholesterols, vitamins,
hormones and other pharmaceuticals. Antifreeze in pipelines and windshield
washer fluid uses methanol as solvent.
Production of Methanol
Process Selection:
i.
ii.
iii.

Methanol from Coal

Methanol from Natural gas
Methanol from Syngas

FIRST PATHWAY: PRODUCTION OF METHANOL FROM COAL

THROUGH GASIFICATION PROCESS
As the prices of crude oil increases, methanol has been sought as an
alternative source of energy. It has been suggested that methanol may be
used as a foundation for meeting future energy needs and requirements. The
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coal-to-methanol process used for this project typically incorporates the

following process operations, as shown in Figure 1.

Feedstock:
Feedstock:
Coal
Coal

Methanol
Methanol
Refining
Refining

Coal
PreCoal Preprocessing
processing

Methanol
Methanol
Synthesis
Synthesis

Coal
Coal
Gasification
Gasification

Water-Gas
Water-Gas
Removal
Removal

Acid
Gas
Acid Gas
Removal
Removal

Figure 1: Process flow diagram of coal-to-methanol.

First, coal is pre-processed by methods such as crushing, sizing and
drying to prepare it for the coal gasification process. During the coal
conversion process, the coal is decomposed in a high pressure and
temperature using steam and oxygen supply which gives a stoichiometry
equation as below:

Cx H y

x
O
y 2

xCO +

y
H
2 2

where the reaction is depended on coal decomposition. The result is

synthesis gas which then proceeds through an acid gas removal step.
In this acid gas removal process, the hydrogen sulphide and carbon
dioxide are recovered in a solvent absorption process. Then the H 2S enters a

Claus unit where it is converted into elemental sulphur according to the

following equation:
3
3
3 H 2 S+ O2 S2 +3 H 2 O
2
8

This elemental sulphur may be further used in other chemical applications.

Some of the CO2 is removed in this process an it helps to prepare the syngas
for the water-gas shift reaction.
Next, the synthesis gas must be prepared by going through a watergas shift reactor to achieve the desired syngas ratio (H 2:CO) of 2:1. The
water-gas shift reaction is a commonly used method for further enhancing the
yield of hydrogen. The governing equation for the water-gas shift reactor is as
below:
CO+ H 2 O CO 2+ H 2

A methanol reactor is used to convert the synthesis gas coming out of

water-gas shift reactors into the desired methanol product. The amount of
water produced in methanol synthesis shows that the amount formed is more
than what it has been calculated thermodynamically bases on water-gas shift
reactor. As a result, the surplus of water must result from the direct synthesis
of methanol from CO2 which produced water. In addition, water-gas shift
reaction is a slow reaction compared to methanol formation reaction. As a
result, the contribution of water-gas shift reactor to the amount of water
formed is negligible. Since hydrogenation of CO only results in methanol
formation, it can be concluded that the water formed will be the result of the
methanol formation from CO2. Thus, the stoichiometry for methanol synthesis
is given as in (eq. 4):
C O+2 H 2 C H 3 OH

However, ethanol may also be produced as a side reaction shown as below:

2CO +4 H 2 C H 3

Finally, the equilibrium constant for the methanol synthesis reaction is

shown in the following equation:

ln K p

PCH 3 OH
1
=ln
2
2
psia
P CO PH 2

( )

=ln

y CH 3 OH 1
11284
=32.918+
2
2
T (K )
y CO y H 2 P

(eq. 6)

It is necessary to refine the raw methanol to meet the AA methanol grade purity
standards. Thus, refining is used to achieve methanol which has less than 0.1% by weight
of water and less than 50 ppmw of ethanol.

SECOND PATHWAY : PRODUCTION OF METHANOL FROM

NATURAL GAS.
The methanol synthesis conversion of synthesis gas into raw methanol
takes place. Raw methanol is a mixture of methanol, a small amount of water,
dissolved gases, and traces of by-products. The methanol synthesis catalyst
and process are highly selective. A selectivity of 99.9% is common. This is
remarkable when it is considered that the by-products are thermodynamically
more favoured than methanol. Typical byproducts include DME, higher
alcohols, other oxygenates and minor amounts of acids and aldehydes.
The conversion of hydrogen and carbon oxides to methanol is described by
the following reactions:
CO2 + 3 H2 CH3OH + H2O (-H298K, 50Bar = 40.9 kJ/mol)
CO + 2 H2 CH3OH (-H298K, 50Bar = 90.7 kJ/mol)
CO2 + H2 CO + H2O (-H298K, 50Bar = 49.8 kJ/mol)

The methanol synthesis is exothermic and the maximum conversion is

obtained at low temperature and high pressure. A challenge in the design of a
methanol synthesis is to remove the heat of reaction efficiently and
economically like at high temperature and at the same time to equilibrate the
synthesis reaction at low temperature, ensuring high conversion per pass.
Different designs of methanol synthesis reactors can be used. For example
quench reactor, adiabatic reactors in series and boiling water reactors (BWR).
A quench reactor consists of a number of adiabatic catalyst beds installed in
series in one pressure shell. Next, A synthesis loop with adiabatic reactors
normally comprises a number (2-4) of fixed bed reactors placed in series with
cooling between the reactors. The cooling may be by preheat of high pressure
boiler feed water, generation of medium pressure steam, and/or by preheat of
feed to the first reactor. Besides that, the BWR is in principle a shell and tube
heat exchanger with catalyst on the tube side. Cooling of the reactor is
provided by circulating boiling water on the shell side. By controlling the
pressure of the circulating boiling water the reaction temperature is controlled
and optimised. The steam produced may be used as process steam, either
direct or via a falling film saturator. The isothermal nature of the BWR gives a
high conversion compared to the amount of catalyst installed.

THIRD PATHWAY: PRODUCTION OF METHANOL FROM

SYNGAS

The main steps in producing methanol are the following:

Production of synthesis gas

Synthesis gas compression
Conversion of the synthesis gas into methanol
Distillation

Synthesis of syngas to produce methanol

Synthesis gas, or syngas, denotes mainly CO/H 2 mixtures in different

proportions. Raw materials for synthesis gas generation can be coal, natural gas or
mineral oil fractions. Due to the high H2 content, natural gas and light oil fractions are
best suited for synthesis gas. Since the methanol production in this study is based on
natural gas as raw material, production methods of synthesis gas from natural gas will
be explored. These methods are usually divided into three types (C.-J. Lee, 2009);

Steam reforming

Oxyreforming

CO2 reforming

The selection of the production method for syngas generation depends on the
price and composition of the natural gas, acceptance of energy export and the plant
capacity.
Steam reforming
A majority of the methanol plants operating today are based on steam
reforming of natural gas (I1). The reaction is described as follows:
CH 4 H 2 CO 3H 2

H(298K) = 247kJ/mol
The equation shows that there is an excess of hydrogen. This means that there
are more hydrogen obtained than is required to convert the carbon oxides to methanol.
The reaction in the steam reformer is endothermic, which means that it prefers high
temperatures. Nevertheless, a limitation for the reformer temperature is to make the
material of the reformer withstand the high temperatures. Today new tube materials
make it possible to design tubular reformers for tube wall temperatures up to 1050C.
Reactor simulations and experiments have shown that the reformer exit temperature
can indeed be reduced to below 700C while maintaining the same conversion
(Aasberg-Petersen, 2001). Process data for the steam reforming section are as follows:

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
This can be achieved by addition of carbon dioxide. CO 2 is added to match the
excess hydrogen, thereby producing a syngas containing carbon oxides and hydrogen
in stoichiometric proportions. This would reduce the feed and fuel requirement per
ton methanol (I1). Taking into account the CO2 politics of today one would actually
be paid for using CO2, so adding CO2 could be an economical gain. The hydrogencarbon ratio in the syngas can also be adjusted by a secondary reforming reaction,
such as oxyreforming or autothermal reforming (C.-J. Lee, 2009).

Autothermal reforming
Autothermal reforming (ATR) is the combination of steam reforming and
oxyreforming. Oxyreforming uses oxygen as a reactant to produce syngas and is
generally used to adjust the synthetic ratio. Oxygen, or air with high concentration of
oxygen, is fed into the reformer where it reacts with methane from the natural gas
through the following reaction:
2CH 4 O2 2CO 4 H 2

H(298K) = -36kJ/mol
This reaction is exoterm which makes it thermodynamically preferable
compared to the steam reforming process. Oxyreforming also gives syngas with the
synthetic ratio 2, which is the stoichiometric ratio for methanol production from
carbonmonoxide (C.-J. Lee, 2009). A drawback with this method is that one has to
separate oxygen from the air to avoid large amounts of nitrogen as an inert in the
system. The air separation can be a cost intensive operation.

Carbon dioxide reforming

This process uses CO2 as a reactant to produce syngas through the following reaction
CH 4 CO2 2CO 2 H 2

H(298K) = 206kJ/mol
As can be seen from the equation that the synthetic ratio for carbondioxide
reforming is 1, and the maximum yield for syngas can be obtained when the feed gas
is supplied with a CO2/CH4 ration of 1. The reaction is endothermic which means that
the conversion increases as the reaction temperature rises (S. Lee, 2009). It may be
argued that CO2 reforming would be better than steam reforming to meet the required
gas compositions, but CO2 reforming is rarely feasible. At the economic pressure of
the synthesis gas plant, stoichiometric reforming will result in incomplete conversion
of CH4 due to thermodynamics, and further the process economy depends strongly on
the pressure and the cost of the CO 2 available. An option can be combined steam and
CO2 reforming. This may be feasible with natural gas containing CO 2 and with cheap
CO2 available (Aasberg-Petersen, 2001). The production economics of CO 2 reforming
is known to be similar to the steam reforming process (C.-J. Lee, 2009).

Methanol Synthesis
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

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There are three common processes for methanol production existing today.
These are the BASF high pressure process, the UK-Wessling high pressure process
and the ICI low pressure process. Their characterizations are given below.
BASF is a German chemical company, founded in 1865. The BASF process,
also known as the high pressure process, for production of methanol is conducted at
320-380C and approximately 340 bar (Olah, 2006). The process uses the ZnO-Cr 2O3
catalyst. To avoid high temperatures (exothermic reaction) cold gas is injected in the
catalyst bed. Short residence time (1 to 2 seconds) is used to prevent equilibrium from
taking place. Conversions of 12-15% for a single pass through the reactor are typical
for this process. Another similar process was developed by UK Wesseling. This
process operates at low CO partial pressure (13 bar in gas recycle) and reaction
conditions at 300 bar and 350C (Olah, 2006).
To be able to operate at lower pressures, more active Cu-based catalysts were
introduced. In 2003 about 65% of the methanol production in the world was based on
the 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 240-260C. The ICI process uses a CuO-ZnO/Al2O3 catalyst.
An elegant method for methanol production is partial oxidation of methane,
known as the direct route. The reaction mechanism is
CH 4 0,5O2

k1

k2
CH
3 OH

CO 2 H 2

The problem with this method is that k 2 is much larger than k1 and thus methanol
production is not profitable with todays technology. However, there is currently being
put a lot of research on this field (Ldeng, 1991)

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SUSTAINABLE DEVELOPMENT IN DESIGNING A REACTOR

Sustainable development refers to economic development that is conducted
without depletion of natural resource. The development and integration of
carbon consuming processes in chemical industry and new energy production
is becoming a serious choice to stop the accumulation of carbon dioxide and
other greenhouse gases in the atmosphere. A new process for the
transportation of non-fossil energy combined with methanol synthesis from
CO2 hydrogenation developed.
The advances of renewable energy as well as greater utilization of existing
energy sources such as the sun and the geothermal, heat methanol evolves
not as an energy source but as an energy carrier with great potential. While
biomass and other waste materials is a possible and likely route to gradually
decrease our dependence on fossil energy sources there are technologies
available that allow us to produce methanol and at the same time reduce the
carbon dioxide emissions in our atmosphere.
The idea is to produce methanol from the carbon that are grab from the
atmosphere. Mainly it is from local emitters such as power plants and
industrial facilities but with improving technologies also from the atmosphere
itself.
Besides that, in sustainable development, the Polygeneration technology is
the co-production from syngas (short for synthesis gas) in a single facility of
several types of chemicals, clean fuels, hydrogen, heat for process
applications, and electricity. The separate coal gasification technologies, such
as IGCC and coal chemicals, are not competitive because of the high cost of
the fixed capital. However, by combining two or more systems, such as the
production

of

electric

power, clean

fuels,

chemicals,

or

hydrogen,

polygeneration systems will be easily commercialized. Ni et al. presented a

preliminary economic analysis of polygeneration systems and Jin et al.
presented an energy analysis of a polygeneration system. An exergy analysis
of

specific

methanol-IGCC

polygeneration
12

system,

including

coal

gasification, desulfurization, methanol synthesis, and combined cycle

electricity generation. Methanol, as a major clean fuel, is a typical product
from the synthesis of syngas. Energy analysis clearly shows the energy
efficiency of each part. Energy analysis also provides new insight into how
gasifiers can use cheaper low quality fuels, simplify systems, reduce
production costs, and reduce environmental pollution. Comparison of the
polygeneration system with separate IGCC and chemical systems shows that
the polygeneration system is an efficient and competitive clean coal system.
The clean coal technology based on gasification has been developed for
many years for use in IGCC systems and coal chemical production, but the
cost of the coal gasification section greatly influences the overall cost. The
high efficiency polygeneration system lowers the high cost of gasification.
Thermodynamic analysis of the polygeneration system shows that:
(1) The energy cost in the gasification and clean up sections which change
the dirty coal fuel to clean syngas is unavoidable;
(2) All the syngas can be used in a once-through process to synthesize
methanol after high-efficiency cleaning of the gas to produce a highly
integrated system;
(3) Changing the H2/C0 ratio using the water gas shift reaction will change the
methanol output and the electrical output in the combined cycle, which varies
with fuel gas composition;
(4) Optimization of the heat utilization can improve system energy efficiency
because the temperatures in the polygeneration system range from 100 to
1800K.

13

LIST OF PATENT
Production of Methanol from coal and natural gas

Production of methanol

14

REFERENCES
Mara, R. D., Daz, I., Rodrguez, M., & Siz, A. (2013). Industrial Methanol
from Syngas: Kinetic Study and Process Simulation. International Journal of
Chemical Reactor Engineering, 11(1).
Pisarenko, E. V., & Pisarenko, V. N. (2011). Power- and resource-saving
process for producing syngas from natural gas in methanol production.
Theoretical Foundations of Chemical Engineering Theor Found Chem Eng,
45(4), 349-354.
Skrzypek, J., Lachowska, M., Grzesik, M., Soczyski, J., & Nowak, P. (1995).
Thermodynamics and kinetics of low pressure methanol synthesis. The
Chemical Engineering Journal and the Biochemical Engineering Journal,
58(2), 101-108.
Supp, E. (1990). How to Produce Methanol from Coal. Retrieved May 25,
2016.

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