1.

LITERATURE REVIEW

1.1 Properties
Methanol also known as methyl alcohol is a colourless, water soluble and flammable liquid
at room temperature. At atmospheric pressure, it has a boiling point of 64.6 C, a freezing
point of -97.6 C and a density of 791 kg/m3 at 20 C.

1.2 Applications
Methanol is considered as one of the most useful chemical compounds which is used in the
chemical industry and in the production of energy. The global methanol production capacity
has increased from 40 million tons per year in 2006 to about 85 million metric tonnes in
2016 (1).
Methanol is used largely in the production of formaldehyde with 27% of methanol produced
used in this process. In the production of Methyl Tert-Butyl Ether (MTBE) and Tert-Amy
Methyl Ether, methanol is used as raw material for both processes. It is raw material in the
production of other chemicals such as acetic, chloromethane and glycol methyl ethers. It is
also used as a solvent in antifreeze and as a substrate for crop growth.

1.3 Production of Methanol

There are three main steps which are involved in the production of methanol which are:

 Reforming (Synthesis Gas Production)

 Methanol production
 Purification (Distillation of Crude Methanol)

1.3.1 Synthesis Gas Production

Synthesis gas also referred to as syngas is a mixture of carbon dioxide, hydrogen and oxygen
in different proportions. Syngas can be produced from different raw materials which include
natural gas, biomass and coal. Natural gas is preferred over the other raw materials in the
production of syngas due its high H2 concentration.

The M module, which is the stoichiometric ratio (H2 – CO2)/ (CO + CO2) characterises the
formation of syngas for methanol production, with a module of 2 favoured for methanol
synthesis. There are various methods for the production of syngas and their use depends on
the raw material being used. Gasification is used when the raw material is either coal or
biomass but since our raw material is natural gas, the following methods will be explored:

 Steam reforming
 Partial oxidation
 Autothermal reforming
 Carbon Dioxide reforming
1.3.1.1 Steam Reforming
Steam reforming is governed by an endothermic reaction in which methane reacts with
steam in the presence of nickel catalyst.
CH4 + H2O ⇌ CO + 3H2 (∆H298K = 247 kJ/mol) (1.1)

The water gas shift reaction shown below occurs to a small extent in steam reforming and it
helps to adjust the value of the M module and be able to meet the requirements.
CO2 + H2 ⇌ CO + H2O (∆H298K = -47 kJ/mol) (1.2)

Steam reforming in moderate pressure conditions and temperatures around high

temperatures (around 850 °C). Even though this method requires high temperatures, it is
the most used method in methanol production plants due to the extensive industrial
experience it possesses and not having oxygen as reactant, which is used in other methods
and tend to be expensive (2).

1.3.1.2 Autothermal Reforming

This method is a combination of partial oxidation and steam reforming. Oxygen or air
preferably oxygen, reacts with methane in a reformer by the following reaction:
2CH4 + O2 ⇌ 2CO + 4H2 (∆H298K = -36 kJ/mol) (1.3)

The partial oxidation of methane reaction, (1.3), is exothermic hence providing heat for the
steam methane reaction, (1.1), to occur. The water gas shift reaction also occurs in
autothermal reforming also at a small extent.

This method is favoured for its natural M module ratio but it is not suitable for small plants,
with steam reforming being a better option for small plants. This method requires oxygen in
order to avoid impurities hence requiring an air separation unit (ASU) which is cost intensive
(3).
Autothermal reforming requires pre-reforming of natural gas in order to reduce energy
consumption lower investments. The aim of pre-reforming is to react the hydrocarbon feed
with steam to give a rich methane product stream suitable for autothermal reforming. Pre-
reforming works as an adiabatic steam reforming in the presence of a nickel based catalyst.

1.3.1.3 Carbon Dioxide Reforming

This method uses carbon dioxide as a reactant to produce syngas by the following
endothermic reaction:
CO2 + CH4 ⇌ 2CO + 2H2 (∆H298K = 206 kJ/mol) (1.4)

From equation (1.4), it is visible that the maximum yield of syngas can only be achieved
when they reactants are fed in equal amounts. However, carbon dioxide reforming in not
used for commercial plants due to that the stoichiometric conversion would result in
incomplete conversion of methane and method being strongly dependant on pressure (3).
1.3.2 Methanol Production
The production of methanol is through the catalytic conversion of syngas by the following
equilibrium reactions:
CO + 2H2 ⇌ CH3OH (∆H298K = -90.7 kJ/mol) (1.5)
CO2 + H2 ⇌ H2O + CO (∆H298K = 41.1 kJ/mol) (1.6)
CO+ H2O ⇌ CO2 + H2 (∆H298K = 206 kJ/mol) (1.7)
The synthesis of methanol is limited by chemical equilibrium and favours high pressures and
low temperatures. Increase in temperatures tend to deactivate the copper based catalysts
utilised in methanol production hence the control of equilibrium is essential in order to
obtain maximum since methanol synthesis is strongly exothermic (10). The conversion per
pass in methanol plants is usually low.

Adiabatic reactors and isothermal reactors are the commonly used reactors in the
production of methanol and their performance is assessed by conversion, selectivity and
reactor yield. The ICI process accounts to 60% and the Lurgi process accounts to 30% of the
worldwide methanol production.

1.3.2.1 Conversion
The methanol synthesis reactor temperature affects the conversion rate, recycle ratio and
the production of unwanted by-products during methanol production. The single per pass
conversion of commercial plants is limited to about 25% (7). Due to the use of low pressure
for methanol synthesis, the single per pass conversion can be as low as 10% in some plants
due to slow equilibrium conversion at low pressures. Recycling of unreacted gas
components and purging of impurities which can cause a build-up in the plant if not purged
is required in order to increase the conversion.

1.3.2.2 ICI Process

This process was a major advance in methanol production since it uses lower pressures than
the BASF process which was used prior to it. The process uses Cu based catalysts making
selectivity’s of about 99% possible and possibility of ignoring side reactions. The operating
conditions are temperatures above 210 °C and pressure between 40 and 110 bar for activity
of the CuO-ZnO-Al2O3 catalyst used (11).
Figure 1.1 – ICI Low Pressure Process Flow Scheme(11)

The ICI process uses an adiabatic reactor with a single bed of catalyst. The heat of reaction is
quenched by introducing cold reactant gas at different heights of the bed (12). Fresh syngas
is compressed and mixed with the recycle before being heated up by the effluent stream in
a heat exchanger. 60% of the stream is used as quench gas whilst the remainder is fed to the
reactor. The reactor product stream is cooled through a heat exchanger producing steam,
then by the reactor feed and lastly by an air cooled heat exchanger resulting in the
condensing of water and methanol. Gas/ liquid separation separates and recycles the gas
with some purged. The purification of crude methanol is occurs in two distillation columns
as shown in Figure 1.1.

1.3.2.3 The Lurgi Process

The ICI process and Lurgi process are similar with a major difference of the type of reactors
used. The Lurgi process uses a tubular cooled reactor attached to a boiler feed water (BFW)
as show in Figure 1.2.
Figure 1.2- Lurgi Reactor Schematic (11)
The Lurgi process reactor is an isothermal reactor. Isothermal reactors are better suited for
methanol production because of their longer catalyst lifetime, recovery of energy in the
coolant and high yield due to the methanol favouring equilibrium.

1.3.3 Purification
In order to meet the standards of grade AA methanol, which has a purity of 99.85 wt%
minimum methanol, the distillation unit of crude methanol requires two-three distillation
columns. This enables the separation of methanol from the light impurities and the heavy
alcohols which are present in crude methanol (9).

2. PROJECT BASIS

2.1 Production Capacity

Chemical plant design producing 5000 MTPD of methanol using natural gas is required.
Assuming the plant to be operational for 360 days/year results in a required production
capacity of 1800 000 metric tons per year.

2.2 Plant Location

Komatipoort is the selected location for the plant. Chemical plants require a lot of water for
cooling and the selected area has sufficient supply of water from both the Crocodile river
and Komati river. The location was also chosen because it would allow us to choose to
source the natural gas from the Sasol pipeline before or after the Komatipoort Compressor
Station depending on whether we use a low pressure or high pressure methanol synthesis
method.
 2.3 Selected Production Method
Selection of the technology to be used for methanol synthesis depends on the production
capacity required. Autothermal reforming is better suited for plant capacities above 5000
MTPD. Steam reforming is cheaper for plant capacities less than 1500 MTPD and for the
plants ranging between 1500 – 5000 MTPD, a combination of both methods is sufficient (7).
ATR reforming was chosen for our plant design in order to produce the 5000 MTPD
required. Even though this method is expensive due to the need for an Air Separation Unit
(ASU), the unit is a good investment for large capacity plants.

3. PROJECT DESCRIPTION

3.1 Block Flow Diagram

Water
Natural Gas

Reforming Separation Methanol

Syngas
Synthesis
Water
Crude
Oxygen Recycle
Methanol

Methanol Purification Separation

By-Products Purge
Figure 1.3- Block Diagram for Methanol Production using Autothermal Reforming.

3.1.1