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Abstract

Global methanol production in 2016 was around 85 million metric ton. Methanol
undergoes at least one further chemical transformation, more likely two or three before
being turned into a final product. Methanol is one of the first building blocks in a wide
variety of synthetic materials that make up many modern products and is also used as a
fuel and a fuel additive.

Methanol is the simplest alcohol, appearing as a colorless liquid and with a distinctive
smell, and can be produced by converting CO 2 and H2, with the further benefit of
significantly reducing CO2 emissions in the atmosphere. Indeed, methanol synthesis
currently represents the second largest source of hydrogen consumption after ammonia
production. Furthermore, a wide range of literature is focused on methanol utilization as
a convenient energy carrier for hydrogen production via steam and autothermal
reforming, partial oxidation, methanol decomposition, or methanol–water electrolysis
reactions.

The aim of this work is to propose an overview on the commonly used feedstocks
(natural gas, CO2) and methanol production processes. Yet, for this report we only
focused on the production syngas. We managed to produce methanol of purity 99%
comparable with others in literature, also met the required production rate of 10 000
tonnes per annum.

TABLE OF CONTENTS

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Abstract........................................................................................................................................1
1. Introduction..........................................................................................................................3
a. Objectives.........................................................................................................................5
b. Limitations...........................................................................................................................6
2. Literature Review.................................................................................................................7
2.1 Production Process:............................................................................................................7
2.2 Early Catalysts background................................................................................................9
2.3 Early production processes...............................................................................................10
2.3.1 Adiabatic Reactors.....................................................................................................11
2.3.3 Catalysts....................................................................................................................12
2.4 Thermodynamic Model....................................................................................................13
3. Process Simulation.............................................................................................................15
3.1 Brief Process Description.................................................................................................15
4. Mass and Energy Balances.................................................................................................17
4.1 Plant Mass Balance..........................................................................................................17
4.2 Plant energy balance.........................................................................................................18
5. Discussion..........................................................................................................................19
6. Literature Cited..................................................................................................................20

1. Introduction

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Methanol production via CO2 hydrogenation is an important representative among the
chemical conversions of CO2 and offers challenging opportunities for sustainable
development. As a raw material, methanol constitutes the basis for the production of
hundreds of chemicals, such as formaldehyde, methyl tertbutyl ether (MTBE), acetic
acid, methyl methacrylate, dimethyl terephthalate, and olefins (ethylene and propylene),
all basic chemical building blocks for a number of common products [1]. Methanol can
also be used as transportation fuel, as a fuel cell hydrogen carrier, as well as in
wastewater treatment or in electricity production. It is then an excellent fuel and a key
starting material of important industrial reactions [2]. In the recent years, also, methanol
is suggested as alternative for chemical energy carrier [3, 4].

Generally, in industrial applications, methanol can be produced from syngas, a mixture

of CO, CO2 and H2 at 50–100 bar and 250–300 oC, using copper and zinc-based catalyst
[5, 6]. These catalysts are already active at 200 oC and selective towards the formation
of H2 and CO2. Alternative routes and its use as fuel and chemical are the core of
methanol economy [4, 7]. Pontzen et al. [8] experimentally show that methanol can be
produced from CO2 and H2 using conventional catalysts as CuO/Al 2O3/ZnO. However,
studies show that the equilibrium yield of methanol from CO2 at 200 oC and 50 bar is
slightly less than 40%, whereas the yield from a mixture of CO 2 and CO at the same
conditions is greater than 80% [9].

The production of methanol from pure CO2 and H2 has also some thermodynamic limits,
as shown by Zachopoulos and Heracleous [10], suggesting the removal of water through
sorbents. In fact, water inhibits the reaction rate of methanol formation via CO 2
hydrogenation [11]. In particular, water produced from reverse water gas shift greatly
reduces the methanol synthesis rate by suppressing the reaction of methanol production.

Works related to these considerations are few in literature. In fact, works about the
production of methanol by syngas are mainly present and different strategies are
proposed to improve the efficiency of the process. Mainly, studies involve the in situ
methanol removal. Examples are methanol adsorption on fine alumina powder or the
use of a solvent, such as tetraethylene glycol, n-butanol, or n-hexane [12]. Westerterp et
al. [13] suggest the selective adsorption of water and methanol on a solid, in a trickle
bed reactor. An alternative method is based on the in situ separation of reaction products

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by condensing them on the surface of a condenser inside the reactor, close to the
catalyst bed [14].

These solutions have some disadvantages due to the introduction of other chemicals,
complicated operations and low space time yields. An alternative to overcome chemical
equilibrium is the in-situ condensation of methanol without additional adsorbents or
coolers. Van Bennekom et al. [15] suggest the condensation of methanol in situ at high
pressure (200 bar) and low temperature (200 oC). It is evident that thermodynamic
barrier can be eliminated by removal of reaction products based on the principle of Le
Chatelier. Gallucci and Basile [16] suggest the recycle of unconverted synthesis gas
after product separation by condensation or the water removal using selective,
permeable membranes.

Many catalysts have been described for this reaction. One catalyst – Zinc based, also
used in this dominating the market for many years, and was the first to include
potassium as a promoter for the water-gas reaction. This catalyst is typically 84.3 % iron
as Fe2O3, 2.4 % chromium as Cr2O3, and 13.3 % as K2CO3. It has good physical
properties and good activity, and it gives fair yields.

In recent years, the situation has become more complex. The market has become more
competitive, causing manufacturers to seek new catalysts that produce higher yields
without compromising activity or physical properties, or catalysts that meet specific
requirements. A catalyst life of ca. two years is claimed.

It is of paramount importance to find optimum operating conditions for the above

reaction due to the fact that it is an exothermic reaction and operates at high pressures.
Furthermore, it is critical that all reactants are consumed due to high costs of separation
of reactants from products. The catalyst to be used is discussed in great detail in the
above.

Real process simulation packages are worldwide tools used for designing, testing,
controlling and optimization of chemical processes. Some simulation packages are
commercial (Hysis, Aspen, Chemcad, etc) while others like COCO, ChemSep, DWSIM
are open-source for the general public especially students. As such, this project has been
put forward to produce Styrene through DWSIM process simulation.

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 a. Objectives

The primary objective of this simulation is to design a plant that produces 10 000 tonnes
of methanol per year with purity ranging from 98 to 99 percent. In order to achieve the
above primary objective, we considered the following:

 The main type of reactor, separating unit(s)

 Operating conditions, mainly reactor volume, temperature and pressure
 Catalyst parameters (Loading, void, diameter and type)
 Correct equation of state (EOS)

The abovementioned considerations have to be optimized for high quality and purity
products.

b. Hypotheses

 The lower temperature of the reactor, the higher rate of CO2 carbon dioxide
 The higher the pressure the less the purer the methanol and production rate
 The NRTL will perform better that SRK thermodynamic model due to activity
models and temperature range

2. Literature Review

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In this chapter, we will look at the world demand for methanol, process selection,
background process, site selection. It is also of high importance to review equipment,
reactions and operating parameters including equations of state (thermodynamics
properties) that have been used previously in order to generate experimental data. This
section summarizes the theoretical background related to methanol production.

Methanol has been produced and used for millennia, with the ancient Egyptians using it
in the embalming process – it was part of the mixture of substances produced in the
destructive distillation (pyrolysis) of wood. However, it was not until 1661 that Robert
Boyle produced pure methanol through further distillation, and only in 1834 was the
elemental composition determined by Jean-Baptiste Dumas and Eugene Peligot. At a
similar time, commercial operations using destructive distillation were beginning to
operate [17].

There are many parallels between the industrial production of methanol and ammonia
and it was the early development of the high pressure catalytic process for the
production of ammonia that triggered investigations into organic compounds:
hydrocarbons, alcohols and so on. At high pressure and temperature, hydrogen and
nitrogen will only form ammonia, however the story is very different when combining
hydrogen and carbon oxides at high pressure and temperature, where the list of potential
products is lengthy and almost all processes result in a mixture of products. Through
variations in the process, the catalyst, the conditions, the equipment or the feedstock, a
massive slate of industrial ingredients suddenly became available and a race to develop
commercial processes ensued.

2.1 Production Process:

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 Early research into methanol production quickly focused on copper as a prime
contender for the basis of a catalytic process to methanol, with Paul Sabatier and Jean-
Baptiste Senderens [18] discovering in 1905 that copper effectively catalysed the
decomposition of methanol and to a lesser extent its formation. A lot of the early testing
looked at what catalysts could effectively destroy methanol, assuming they would be
equally as effective under alternative conditions at forming methanol. Following the
start of large scale ammonia production in Germany during 1913, the pace of research
picked up and in 1921 Georges Patart patented the basis of a high pressure catalytic
process that used a variety of materials including copper (along with nickel, silver or
iron) for methanol synthesis [19]. A small experimental plant was later built using this
process in Patart’s native France, near Asnières [20].

The wood-based processes were always very limited in scale and it was 1923 before
production could be considered ‘industrial’ with a catalytic process developed by
Mathias Pier at Badische Anilin- & Sodafabrik (BASF), Germany (Figure 1).

The BASF process produced methanol from synthesis gas (syngas), which at the time
was a mixture of hydrogen and carbon monoxide. The process works by the following
reactions:

CO + 2H2 → CH3OH ΔH = –90.6 kJ (i)

CO2 + 3H2 → CH3OH + H2O ΔH = –49.5 kJ (ii)
CO + H2O → CO2 + H2 ΔH = –41.2 kJ (iii)

Methanol formation (Equations (i) and (ii)) is favored by low temperatures and high
pressures. All three equilibrium reactions occur simultaneously, although it is common
to only consider two of the three to simplify any analysis, as it can be seen that
Equations (ii) and (iii) combined are the same as Equation (i).

The BASF process operated at above 300 atm and 300–400°C, using a zinc chromite
(Cr2O3-ZnO) catalyst developed by Alwin Mittasch [21], about a decade after his work
on the first industrial ammonia synthesis catalyst. The high pressures benefitted
conversion to methanol and to achieve sufficiently quick reaction rates, high
temperatures also had to be used. Further increases in temperature would have drastic
effects on the selectivity and equilibrium, so conditions were selected to be a
compromise. Methanol production began on 26th September 1923 at the Leuna site

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[22]. Method 2 is one of the commercialize process to produce styrene from propylene
oxide. In this process ethyl benzene is treated with oxygen to form ethyl benzene
hydroperoxide. Then, it is used to oxidize propylene to propylene oxide. The resulting
phenyl ethanol is dehydrated to give styrene.

Figure 1: First shipment of synthetic methanol from BASF Leuna, 1923 (Courtesy of
BASF Corporate Archives, Ludwigshafen/Rhine, Germany)

2.2 Early Catalysts background

The subsequent research into the catalyst was extensive, with the list of possible
candidates covering large swathes of the periodic table, from antimony to zirconium,
bismuth to uranium (itself a popular catalyst of the time) [15, 8]. Given the extensive
testing, it is perhaps unsurprising that in the list can be found many of the components
that make up the modern catalysts used in methanol plants in the 21st century.

Initially, iron was to be used for methanol production (as with ammonia production),
but this along with nickel was phased out in successive patent applications until the
requirement for the process to be ‘completely excluding iron from the reaction’ was

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included in the mid 1920s [23]. During the early years there was a lot of effort looking
at other combinations of carbon, hydrogen and oxygen. One major application was
Fischer-Tropsch reactions: the creation of straight chain saturated hydrocarbons, for
example for fuels. This is readily catalysed by iron at similar conditions to methanol
synthesis. With early iron-containing methanol synthesis catalysts, it was found that the
iron would react with the carbon monoxide to form iron carbonyl, which decomposes at
high temperatures to iron metal. It was therefore easy to transform the catalyst into one
much more efficient at making hydrocarbons than methanol; reactions that are even
more exothermic and not equilibrium limited, hence at risk of thermal runaway. The
catalyst is not the only source of iron in such processes, with the obvious choice for
construction of the early reactor vessels being steel, which itself contains iron. Many of
the early plants were therefore either lined or made of non-ferrous metals, such as
copper, silver or aluminium [24].

2.3 Early production processes

The equilibrium limitations of the methanol formation reactions (Equations (i)–(iii)),

especially under the early operating conditions, were such that conversion to methanol
in a single pass through a reactor was very low. To overcome this, the gas had to be
recycled over the catalyst a number of times. Each time, the gas is cooled to condense
any product methanol and the consumed reactants are replaced with fresh synthesis gas.
The gas is rarely pure hydrogen and carbon monoxide, and any non-reacting species,
such as methane or nitrogen, introduced through the fresh gas supply accumulate in
such a loop, so a small fraction of the gas must be purged, also losing some reactants.
Figure 2 shows the basic components of a methanol synthesis loop, which are still used
today.

The interchanger is a more modern concept, reducing energy consumption by using the
hot gas exiting the converter to heat the inlet gas. Early patents [24] show a lot of the
aspects of modern methanol production, including the recycle loop and the use of a
guard bed of additional catalyst or absorbent to remove “traces of substances deleterious
to the reaction”, early versions tending to be copper based. The loss of reactants through
the purge was also considered in early processes, with Forrest Reed filing a patent in

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1932 [25] for recycling the purged gas through an additional reactor in a loop with high
concentrations of non-reacting components, complete with condensation and separation.
This approach is now used to revamp and add capacity to modern methanol plants.

The general concept spread rapidly and plants could be found around the world by the
end of the 1920s producing a total of around 42,000 metric tonnes per year of methanol
in new, catalysed, high-pressure processes [26].

Fig. 2. Basic components of a pressurised methanol synthesis loop

2.3.1 Adiabatic Reactors

Adiabatic reactors are characterised by not having an external cooling system within
their reaction zone. There are different types of adiabatic reactors. Quench reactors cool
the reaction gas by adding cold reaction gas throughout the reactor. Other reactors are a
series of smaller catalyst beds with intermediate cooling. The general design of a
quench reactor is shown in figure 3. The conversion profile shows the injection points
of the quench gas at which the temperature of the gas decreases but also the methanol
fraction. In comparison, the reactor with intermediate cooling only reduces the
temperature while keeping the methanol fraction constant, figure 4.

The problem of adiabatic reactors is the temperature levels within the reactors. High
temperatures can develop, which leads to a reduction in production and shortening of

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the catalyst’s lifetime due to sintering. The traditional flow direction of these reactors is
axial, which leads to a very simple design but results in relatively large pressure drops
or large vessel diameters, as small diameters cause high gas velocities. Larger diameters
result in high material costs so different companies have developed radial flow reactors
which exhibit low pressure drops, can easily be scaled but require more complicated
designs and are thus more expensive.

This more complicated design stands in contrast to the advantages of adiabatic reactors
of having an easy design, easy operation and low cost. Adiabatic reactors are mostly
applied for smaller scales, e.g. the adiabatic reactor by Johnson Matthews produces up
to 3000 t/d [13, 14]. Table 1 gives an overview of the most commonly used methanol
reactors and their producers.

2.3.3 Catalysts

Through the development of a copper-zinc catalyst, that is made thermally stable due to
the support structure of alumina, ICI was able to produce methanol at pressures around
5MPa. This catalyst has now been adapted by a lot of companies with different atomic
ratios of the metal components (see table 1).

The catalysts have a strong vulnerability towards poisoning due to the susceptibility of
copper. They are especially susceptible to sulphur and chlorine compounds. While the
addition of ZnO reduces the sensitivity of the catalyst towards sulphur, the amount of
sulphur species in the gas is limited to 0.5 ppmv.

A concentration of above 0.8 wt% of sulphur on the catalyst deactivates it completely

[16, 37]. This limit excludes COS which does not poison the catalyst for concentration
of 0.6-9 ppm in its gas state. The catalysts show no COS adsorption or dissociation at
operation conditions for methanol formation [16].

The limit of chlorine species content, in any form, is of the order of magnitude of 1 ppb,
as it deactivates the catalyst by strongly reacting with copper and additionally increasing
the sulphur poisoning [21].

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Next to sulphur and chlorine compounds, liquid water can lead to premature
deactivation of the catalyst as it quickens the growth of copper crystals and destroys the
catalyst’s matrix. This water can come from high CO 2 content in the feed gas and the
resulting RWGS reaction [15].

Next to the poisoning of the catalyst, sintering of the copper, which leads to the
formation of copper crystals, can lead to deactivation. A maximum operating
temperature of 300 ∘C is considered to be acceptable [16].

All these factors together contribute to the catalysts’ average industrial lifetime of 2-5
years [17].

Table 1: Metal composition of catalysts provided by different manufacturers [16]

2.4 Thermodynamic Model

One of the most critical aspect of process simulation is selecting the correct
Thermodynamic Package for your process. Proper selection of thermodynamic models
during process simulation is absolutely necessary as a starting point for accurate process
simulation. A process that is otherwise fully optimized in terms of equipment selection,
configuration, and operation can be rendered essentially worthless if the process
simulation is based on inaccurate thermodynamic models. Because of this, good
heuristics and appropriate priority should be placed on both selecting thermodynamic
models and reporting the selections in process reports.

DWSIM has different thermodynamic models available such as Peng-Robinson (PR),

Universal Functional Activity Coefficient (UNIFAC), Universal Quasi Chemical
(UNIQUAC), Soave-Redlich-Kwong (SRK), Non-Random Two Liquid (NRTL) etc.
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The success of this project is dependent on the correct choice of model, taking the
wrong model can cause waste of time and will also give wrong results.

The choice of a thermodynamic model will have an impact on the following:

 Accuracy of Results

 Complexity of the calculations

 Convergence

Some of the most important Thermodynamic Models that will be considered for this
project are:

 NRTL for the distillation column.

 Soave-Redlich-Kwong – reasons for considering this model are similar to

the Modified Peng-Robinson although according to Ivan Lukec, the range of
application on this model is highly limited.

For this simulation SRK will be used because it is recommended for use with
hydrocarbons and non-condensables. It is also the recommended simulation
thermodynamic package.

3. Process Simulation

3.1 Brief Process Description

Figure 3 is process flow diagram (PFD) for methanol production process. The
production rate needs to be 35 000 tonnes per year and the raw material CO, CO 2, H2.
Copper based was the catalyst.

The EB is fed into a compressor-01 at 1 atm to 58 atm, and fed into another
compresssor-02 to rise the final pressure to 108.6 atm, and into a cooler for correct

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reaction Temperature. Then fed into a plug flow reactor operating at adiabatic and
temperature 200oC.

Table 2: Catalyst Properties

Parameters Values

Catalyst loading 1770 kg/m3

Catalyst diameter 5.47 mm
Catalyst void 0.03-0.05

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 Figure 2: Process Flow diagram for the Production of Methanol

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 4. Mass and Energy Balances

4.1 Plant Mass Balance

Table 2: Overall mass and component balance of the production plant

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 Material balance
Object Syngas Feed MSTR-002 MSTR-005 MSTR-009 MSTR-011 MSTR-013 MSTR-017 To the Vents MSTR-018 MSTR-026 Column Feed 99.3% Water 99 % MeOH Units
Temperature 25 836,223 1074,19 200 334,427 45 -120 5 -120 47,188 46,0016 100,695 -60,9196 C
Pressure 101,325 6586,13 12159 12159 12158,9 12158,9 12158,9 12158,9 12158,9 7852 302,325 101,325 101,325 kPa
Mass Flow 8640 8640 8640 8640 8640 8640 630,982 630,982 8009,02 8009,02 8009,02 925 7083,37 kg/d
Molar Flow 0,00971048 0,00971048 0,00971048 0,00971048 0,00461546 0,00461546 0,0014559 0,0014559 0,00315955 0,00315955 0,00315955 0,000591158 0,0025679 kmol/s
Molar Fraction (Mixture) / Carbon monoxide 0,21 0,21 0,21 0,21 0,00286733 0,00286733 0,00908786 0,00908786 9,50E-07 9,50E-07 9,50E-07 6,41E-23 4,01E-07
Mass Fraction (Mixture) / Carbon monoxide 0,571182 0,571182 0,571182 0,571182 0,00370687 0,00370687 0,0507464 0,0507464 9,07E-07 9,07E-07 9,07E-07 9,91E-23 3,51E-07
Mass Flow (Mixture) / Carbon monoxide 4935,02 4935,02 4935,02 4935,02 32,0273 32,0273 32,0201 32,0201 0,00726295 0,00726295 0,00726295 9,17E-20 0,002489 kg/d
Molar Fraction (Mixture) / Carbon dioxide 0,0539 0,0539 0,0539 0,0539 0,00040069 0,00040069 3,56E-05 3,56E-05 0,00056891 0,00056891 0,00056891 3,84E-20 0,000699406
Mass Fraction (Mixture) / Carbon dioxide 0,230344 0,230344 0,230344 0,230344 0,00081389 0,00081389 0,00031244 0,00031244 0,0008534 0,0008534 0,000853395 9,33E-20 0,000964111
Mass Flow (Mixture) / Carbon dioxide 1990,17 1990,17 1990,17 1990,17 7,032 7,032 0,197142 0,197142 6,83486 6,83486 6,83486 8,63E-17 6,82916 kg/d
Molar Fraction (Mixture) / Hydrogen 0,7 0,7 0,7 0,7 0,255829 0,255829 0,810999 0,810999 9,48E-06 9,48E-06 9,48E-06 8,06E-21 1,52E-06
Mass Fraction (Mixture) / Hydrogen 0,137026 0,137026 0,137026 0,137026 0,0238028 0,0238028 0,325922 0,325922 6,51E-07 6,51E-07 6,51E-07 8,97E-22 9,60E-08
Mass Flow (Mixture) / Hydrogen 1183,91 1183,91 1183,91 1183,91 205,656 205,656 205,651 205,651 0,00521547 0,00521547 0,00521547 8,30E-19 0,000680187 kg/d
Molar Fraction (Mixture) / Water 0,009 0,009 0,009 0,009 0,131935 0,131935 1,93E-11 1,93E-11 0,19273 0,19273 0,19273 0,993228 0,00847573
Mass Fraction (Mixture) / Water 0,0157443 0,0157443 0,0157443 0,0157443 0,109702 0,109702 6,92E-11 6,92E-11 0,118345 0,118345 0,118345 0,988019 0,00478266
Mass Flow (Mixture) / Water 136,031 136,031 136,031 136,031 947,827 947,827 4,37E-08 4,37E-08 947,827 947,827 947,827 913,918 33,8774 kg/d
Molar Fraction (Mixture) / Nitrogen 0,003 0,003 0,003 0,003 0,00631172 0,00631172 0,0200056 0,0200056 1,64E-06 1,64E-06 1,64E-06 1,11E-22 6,94E-07
Mass Fraction (Mixture) / Nitrogen 0,00816071 0,00816071 0,00816071 0,00816071 0,00816071 0,00816071 0,111724 0,111724 1,57E-06 1,57E-06 1,57E-06 1,72E-22 6,09E-07
Mass Flow (Mixture) / Nitrogen 70,5085 70,5085 70,5085 70,5085 70,5085 70,5085 70,4959 70,4959 0,012579 0,012579 0,012579 1,59E-19 0,0043108 kg/d
Molar Fraction (Mixture) / Methanol 0 0 0 0 0,551953 0,551953 4,21E-10 4,21E-10 0,806289 0,806289 0,806289 0,00677164 0,990511
Mass Fraction (Mixture) / Methanol 0 0 0 0 0,81627 0,81627 2,69E-09 2,69E-09 0,880579 0,880579 0,880579 0,0119808 0,994096
Mass Flow (Mixture) / Methanol 0 0 0 0 7052,58 7052,58 1,70E-06 1,70E-06 7052,58 7052,58 7052,58 11,0823 7041,55 kg/d
Molar Fraction (Mixture) / Methane 0,0241 0,0241 0,0241 0,0241 0,0507041 0,0507041 0,159872 0,159872 0,00040044 0,00040044 0,000400441 1,64E-19 0,00031087
Mass Fraction (Mixture) / Methane 0,037543 0,037543 0,037543 0,037543 0,037543 0,037543 0,511295 0,511295 0,00021896 0,00021896 0,000218962 1,45E-19 0,000156207
Mass Flow (Mixture) / Methane 324,371 324,371 324,371 324,371 324,371 324,371 322,618 322,618 1,75367 1,75367 1,75367 1,34E-16 1,10647 kg/d

4.2 Plant energy balance

Table 1: Overall energy balance of the production plant

Master Property
Table

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 Object ESTR- ESTR- ESTR- ESTR-
003 006 008 012
Energy Flow 2282.16 728.413 2539 0 kW

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 5. Discussion

The aim of this project is to simulate a design for a plant which produces 35,000 tonnes/year
methanol by using syngas to achieve 99.5% purity for the product over a catalytic reactor, used
as start point for material balance in the process, and with a stream time of 7041 kg/d,
respectively. In order to achieve this aim, one reactor (PFR), one distillation towers with
condensers and re-boilers, two compressors, were designed. While equipment necessary for the
process is designed, material and energy balance, design heuristics are used. The aim is defined
as methanol production with purity of 98-100 % wt and was met.

For this progress report I managed to produce methanol from main reaction and two side
reactions. For the final I will do economics to see the economic viability of the plant and plant
safety.

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 6. Literature Cited

1. Dalena, F.; Senatore, A.; Tursi, A.; Basile, A. Bioenergy production from second and third
generation feedstocks. In Bioenergy Systems for the Future; Dalena, F., Basile, A., Rossi, C.,
Eds.; Prospects for Biofuels and Biohydrogen; Elseiver Publishing: London, UK, 2017.

2. Dalena, F.; Senatore, A.; Marino, A.; Gordano, A.; Basile, M.; Basile, A. Methanol Production
and Application. An overview. In The Science and Engineering of Methanol; Basile, A., Dalena,
F., Eds.; Elsevier Publishing: London, UK, 2017; ISBN 978-0-444-63903-5.

3. The Methanol Industry. Available online: [Link]

(accessed on 17 October 2020).

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Convers. Manag.2007, 48, 519–527. [CrossRef]

5. Hughes, D.O. Methanol: The chemical of the future. Chemsa 1980, 6, 180–182.

6. Ali, K.A.; Abdullah, A.Z.; Mohamed, A.R. Recent development in catalytic technologies for
methanol synthesis from renewable sources: A critical review. Renew. Sustain. Energy Rev.
2015, 44, 508–518. [CrossRef]

7. Khadzhiev, S.N.; Kolesnichenko, N.V.; Ezhova, N.N. Slurry technology in methanol synthesis
(Review). Pet. Chem. 2016, 56, 77–95. [CrossRef]

8. Sabatier, P. How I have been led to the direct hydrogenation method by metallic catalysts. Ind.
Eng. Chem.1926, 18, 1005–1008. [CrossRef]

9. Tijm, P.J.A.; Waller, F.J.; Browna, D.M. Methanol technology developments for the new
[Link]. Catal. A 2001, 221, 275–282. [CrossRef]

10. Couper, J.R.; Beasley, T.; Penney,W.R. The Chemical Process Industries Infrastructure:
Function and Economics; CRC Press: Boca Raton, FL, USA, 2000; pp. 1–644, ISBN
9780824704353.

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11. Natta, G. Synthesis of Methanol, Ch. 8 of Catalysis; Emmett, P.H., Ed.; Reinhold Publishing
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