R.V.

College of Engineering, Bengaluru

(Autonomous Institution Affiliated to VTU, Belagavi)
Department of chemical engineering

5th Semester

Self-study Report

Reactor design for methanol synthesis

Submitted by-

Yashaswini (1RV18CH042)

Abstract

Methanol is an efficient fuel and has gained attention due to its excellent properties. Since
its discovery, different methods of production of methanol have been continuously
experimented but only a few methods have been successfully commercialized. Kinetics
and dynamics of the reactions involved and optimization of parameters of a reactor has
greater effect on cost and maintenance of production plant. Hence, there are different
reactors and methodology used for methanol synthesis. In this report, I have made
attempts to review the major types of reactors and methods of production of methanol. I
have also thrown light upon the different models of methanol synthesis that gives us the
information of kinetics and thermodynamics of process.
Introduction
Methanol also known as methyl alcohol or wood alcohol is a colourless, water-soluble
liquid with mild alcoholic odour. It is polar, acid-base neutral, and generally considered
non-corrosive. It is miscible with most organic solvents and is capable of dissolving many
inorganic salts.

Chemical formula CH3OH

Molecular weight 32.04
Chemical composition (%)
Carbon 37.5
Hydrogen 12.5
Melting point -97.6oC
Boiling point 64.6oC
Density at 20oC 791kg/m3
Energy content 173.2kcal/mol
Energy of vaporization 9.2kcal/mol
Flash point 11oC
Explosive limits in air 6-11%
Auto-ignition temperature 455oC
Table 1: properties of methanol

The total annual methanol demand is 70 000 kilo-tons, with an annual growth rate of 6–8
%. Nearly 50 % of the global methanol demand is for producing chemicals such as
propylene (C3H6) or polypropylene (C3H6) n, acrylic acid (C3H4O8) or acrylates
(CH2=CHCOO–), ethylene (C2H4), acetic acid (CH3COOH), formaldehyde (CH2O), etc.
The methanol demand for gasoline blending and the production of diesel, MTBE, biodiesel,
DME and other compounds is approximately 33% of total methanol produced across the
world. Other methanol applications are in fuel cells and for power production. In addition,
the fossil fuel dependence could be mitigated if oil and gas are substituted with methanol.
Methanol is a good energy storage option in order to store the intermittent power by
electrolyzing water to hydrogen and further reaction with CO2 to produce methanol. Pure
methanol is an important material in chemical synthesis. Its derivatives are used in great
quantities for building up a vast number of compounds, among them many important
synthetic dyestuffs, resins, pharmaceuticals, and perfumes.
Methanol synthesis

Methanol synthesis stands as one of the most prominent industries in the area of CO2
reutilization. The first experiment to synthesize methanol from CO and H2, using zinc
chromate as a catalyst was done by M. Pier in 1922 in Leuna, Germany and since then,
methanol had been produced in reactors operating under high pressure of 25-35MPa and
high temperature of 320-450oC. In 1966, Imperial Chemicals Industries introduced its low-
pressure methanol process in Billingham, England, using a more active (but less poison-
resistant) ZnO–CuO catalyst under 5–10 MPa and 220–300oC. Hence, generally, in
industries, methanol is produced from syngas (a mixture of CO, CO2 and H2) at 50-100 bar
and 250oC-300oC, using copper and zinc-based catalyst. These catalysts are usually used
because they are active at 200oC and selective towards the formation of H2 and CO2
formation. Other researchers have experimentally shown that methanol can be produced
from CO2 and H2 using conventional catalysts such as CuO/Al2O3/ZnO.

Feed Process and reactions Catalysts

Syngas Methanol synthesis
CO+2H2↔CH3OH Cu/ZnO/ Al2O3
CO2+3H2↔CH3OH+H2O Cu/ZnO/Cr2O3/ZnCr
Syngas Two-step methanol synthesis:
CH3OH+CO↔HCOOCH3, then K-methoxide
HCOOCH3+2H2↔2CH3OH Cu chromite

Methane Direct oxidation:

CH4 + (1/2) O2(N2O) ↔ CH3OH

Methane Bioprocessing Metal oxides,

Enzymes
Table 2: different processes of production of methanol.

One of the problems associated with methanol production is the difficulty of securing
sufficient temperature control across the catalytic bed. The conversion of syngas to
methanol is highly exothermic and causes a steep temperature rise in the catalytic bed
unless an appropriate means of heat removal is applied. If the reaction heat is not excreted
from the reactor, the temperature will rise to the maximum equilibrium temperature, which
is usually as high as 300°C in a typical methanol synthesis reactor. Such a high temperature
will not only generate a considerable number of various by-products, but also deactivate
the catalyst due to a sintering phenomenon.
Methods of production of methanol

1) Lurgi low‐pressure methanol synthesis process - The process developed by Lurgi

Corporation for the synthesis of methanol consists of a reactor operating at a
temperature of 250-260°C and a pressure of 50-60bar. The reactor is a shell and
tube type with the catalysts filled in the tubes. The heat of reaction is removed by
circulating cold water on the shell side and this generates high pressure steam for
other usage. Feedstock for the production of syngas includes gaseous hydrocarbons
such as methane as well as liquid hydrocarbons like naphtha. The syngas can be
produced via two routes namely steam reforming and partial oxidation. Steam
reforming is carried out at temperatures of 850 - 860°C. De-sulphurised naphtha is
contacted with steam at this temperature to produce hydrogen and carbon oxides.
The syngas produced is compressed to 50 – 80bar before it is fed into the methanol
reactor. For the second route, heavy residues are fed into a furnace along with
oxygen and steam at 1400 - 1450°C and the operating pressure is at 55 – 60bar and
this does not require any further compression.

Fig 1: Flow sheet of Lurgi low-pressure methanol process

2) ICI low‐pressure methanol process - This process utilizes the use of an adiabatic
reactor and a single catalyst bed. The heat of reaction is quenched by introducing
cold reactants at different heights of the catalyst bed. First, fresh synthesis gas is
compressed and mixed with recycled gas and heated by heat exchange with the
reactor effluent. Then about 40% of the stream is sent to the reactor after undergoing
supplementary preheating along with reactor effluent. Then the rest is used as a
quench gas for removing the heat of reaction. The products emanating from the
reactor is cooled by heat exchanged with the feed and water for the generation of
high-pressure steam. It was further cooled with an air-cool heat exchanger in which
 methanol and water are condensed. The separation of gas/liquid takes place in a
flash drum under pressure. The gas is recycled after purging small part to keep the
inert level in the loop within limits. Purification of the methanol is done in two
different columns. The first column removes gases and other light impurities whiles
the second separates methanol from other heavy alcohols.

Fig 2: Flow scheme of the low-pressure methanol process

3) Haldor Topsoe methanol process - This process uses several adiabatic reactors
arranged in series and the heat of reaction is removed by intermediate coolers. The
syn-gas flows radially through the catalyst bed and this reduces pressure drop as
compared to axial flow. The purification is the same as the other processes.

Fig 3: Flow scheme of the reaction section of the Haldor Topsoe methanol process
4) The MGC low‐pressure process - developed by Mitsubishi Gas Chemical
Company, process uses copper-based methanol synthesis catalyst. It operates at
temperatures ranging from 200 - 280ºC and a pressure range of 50 – 150 atm. The
temperature of the catalyst bed is kept under control by using quench type converter
design, and also some of the heat of reaction is recovered in an intermediate stage
boiler. This process utilizes hydrocarbon as feedstock. The raw material is de-
sulphurised and then fed into a steam reformer at 500ºC. The exit stream from the
 reformer contains hydrogen, carbon monoxide and carbon dioxide at 800 - 850ºC.
The gases are compressed in a centrifugal compressor and mixed with the recycle
stream before being fed into the converter.

Fig 4: Mitsubishi Gas Chemical low-pressure methanol synthesis process

Methanol reactor

As of 2017, there are 4 types of methanol synthesis reactor commercially in operation: -

1) Adiabatic quench cooling reactor – it is the most popular reactor designed in

operation. After quench fractions are separated, the main flow of the feed gas is fed
to the reactor inlet and each quench fraction is fed to each intermediate bed
respectively. The efficiency of quench distributors for mixing the hot and cold gases
is most important in this type of reactor. Poor distribution of the quench gases will
cause hot spots in the catalyst bed and shorten the catalyst life as well as increase
by-product formation. In comparison with other types of reactors, the adiabatic
quench cooling reactor does require a relatively large catalyst volume since the
reaction path is away from the maximum reaction rate curve. This reactor has
number of control variables and is complex to optimize. The largest possible
capacity for this type reactor is estimated as 3,000– 3,500 tons/day due to
manufacturing limitations in building a high-pressure vessel with the necessary
diameter and also due to the drawback of an increase in pressure drop through the
catalyst beds which causes an increase of re-circulator power resulting in penalty
for energy consumption.
2) Adiabatic external indirect cooling reactor – in this reactor, all the gas is passed to
the first adiabatic bed. The exit gas from the first bed enters the first heat exchanger
where steam is raised. The total catalyst volume is smaller than in the adiabatic
 quench cooling reactor since all the gas passes through all of the catalyst. However,
the reaction path is still away from the maximum reaction rate curve. The major
drawback of this system is the need to have much larger numbers of high-pressure
reactors, heat exchangers and interconnecting piping which inhibit cost savings.

Fig 5-6: process configuration of quench cooling reactor and adiabatic external
indirect cooling reactor.
3) Tube cooling reactor – it uses reaction heat directly to pre-heat the inlet gas of the
reactor. The main advantage of this reactor is the need of a relatively small catalyst
volume since the reaction curve closely follows the maximum reaction rate curve.
This type of reactor is easier to control because all the temperatures in the reactor
are set only by the inlet temperature. The limit of single train capacity is due to the
same reason as for the adiabatic quench cooling reactor, but the capacity could be
up to approximately 2,000–2,500 tons/day due to restricted usage of the reactor
internal space which is shared by the cooling tubes.
4) Steam rising isothermal tubular bed reactor – it has the most efficient way to recover
the reaction heat of methanol synthesis and uses the heat directly in generating
steam in the synthesis reactor. It has an advantage of considerably small catalyst
requirement due to good catalyst stability because of operation at low catalyst peak
temperature. The low peak temperature also ensures a lower level of by-products
formation. The recovered heat is used to generate qualitative steam to be applied
for steam reforming in the upstream unit of the methanol plant. A drawback with
having a catalyst in the tubular reactor is to require a large number of tubes in order
to accommodate the catalyst. This requirement is very expensive and the
 manufacturing restriction would limit a single train capacity of this type reactor up
to 1,200–1,500 tons/day.

Fig 7-8: process configuration of tubular cooling reactor and isothermal steam
rising tubular bed reactor.

Thermodynamics and kinetics of methanol synthesis

The three main reactions for the formation of methanol from synthesis gas is made up of
hydrogenation of CO, hydrogenation of CO2 and the reverse water-gas shift reaction.
Methanol is thermodynamically less stable and hence the catalyst used should be very
selective. The three reactions are as follow:

Table 3: thermodynamic data of all reactions

The rate of reaction constants combined with the equilibrium rate constants provides
enough information about kinetics of methanol synthesis. The reaction rate constants,
adsorption equilibrium constants and reaction equilibrium constants which appear in
kinetics expressions are given below
Table 4: kinetic and equilibrium data.

The studies made on the kinetics varies due to the reaction conditions (temperature and
pressure), feedstock and catalyst used. Some models derive the rate expressions from the
synthesis of CO and H2 while others take into consideration CO2 as a feed. The basic of
the rate expression also varies due to the different limiting conditions assumed. This gives
rise to the different variety of kinetic equations with different level of details.

Some of the major methods are: -

1) Vanden Bussche and Froment model – in 1996, Vanden Bussche and Froment based
their research on equation proposed by Natta. Natta only considered CO
hydrogenation and proposed the kinetic equation,

fi-denotes the fugacity of the

component i and A, B, C and D are estimated constants. They first assumed that
only CO hydrogenation occurred in the synthesis. It was later discovered that CO2
must be considered as a feed and that it also contributes to the reaction kinetics.
Bakemier et al. included the presence of CO2 in the kinetic equation with a
Langmuir-type isotherm and also studied the catalytic process with ZnO/Cr2O3
catalyst and ended up with the kinetic equation,

The first kinetic equation was published by Leonov et al assuming that methanol
was produced from CO and neglected CO2,
2) Klier model – in 1982, they considered methanol synthesis solely through CO
hydrogenation but also included CO2 in the kinetic equation. They found that the
reaction rate reaches a maximum with certain Pco / Pco2 ratio keeping the operating
conditions 498-523K temperature and 75bar pressure in a tubular integral fixed bed
reactor.

3) Graaf model – in 1990, Graaf and his team derived the kinetic model by looking at
both the hydrogenation of CO and CO2 as well as the water gas shift reaction under
the operating conditions 483-513K temperature and 15-20bar pressure in a gradient
less spinning basket. Their kinetic model equations are:

4) Ledakowicz model – another group of scientists studied synthesis of methanol in

stirred autoclave and bubble column slurry reactor at 490-533K temperature and 20-
60bar pressure. The two catalysts used in their experiments were suspended in two
different inert liquids; paraffin oil and molten wax. Hence, their kinetic model:
 5) Skrzpek model – in 1992, they presented Langmuir-Hinshelwood-type kinetic
equation for lower-pressure methanol synthesis. The commercial catalysts used were
polish CuO (60% wt)-ZnO (30%)-Al2O3 (7.5%) under 460-550K temperature and
30-90bar pressure in an integral fixed bed reactor. They discovered that the synthesis
reaction favours CO2 inspite of the fact that CO is considered as the carbon source.
They performed a couple of simple experiments by using a feed consisting of only
CO2 and H2 methanol formed with no difficulties. Another observation was made
by using feed flow made up of CO and H2 without CO2 and H2O (steam was
completely removed from the feed), methanol was not formed. Methanol was
formed as soon as water was introduced in the feed. This was due to the water gas
shift reaction, where CO and H2O produce CO2, which further reacts with H2 to form
methanol.

Conclusion

Methanol and its importance as a compound were studied as a part of introduction.

Synthesis of methanol from CO2 and CO was reviewed in detail considering the
thermodynamics and kinetics that occur in every step of the reactions involved. Different
types of methanol reactors and different methods of production of methanol was listed with
considerable explanation.
References

• Kunio Hirotani, Hitoshi Nakamura and Kazuo Shoji, Optimum catalytic reactor
design for methanol synthesis with TEC MRF-Zr reactor, Catalysis Surveys from
Japan 2 (1998) 99–106.
• Grazia Leonzio, Methanol Synthesis: Optimal Solution for a Better Efficiency of
the Process, Processes 2018, 6, 20.
• Theophilus Arthur, Control structure design for methanol process, Trondheim, June
2010.
• Md. Firoz Kalam, Methanol Synthesis Model and Reactor Design.
• Haldor topsoe, method and reactor design for the production of methanol, 2
December 2015, with international search report (Art. 21(3)).