Progress in Energy and Combustion Science 56 (2016) 71–105

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Progress in Energy and Combustion Science

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / p e c s

Efficient methanol synthesis: Perspectives, technologies and

optimization strategies
Giulia Bozzano *, Flavio Manenti
Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio Natta”,
Centre for Sustainable Process Engineering Research (SuPER), Piazza Leonardo da Vinci, 32, 20133 Milano, Italy

A R T I C L E I N F O A B S T R A C T

Article history: In economy nowadays, methanol is already a key compound widely employed as building block for pro-
Received 26 October 2015 ducing intermediates or synthetic hydrocarbons, solvent, energy storage medium, and fuel. This status
Accepted 5 June 2016 is expected to last in the near future or even improve to the point of making this compound a central
Available online 5 July 2016
participant in the worldwide economic landscape. For these reasons, every improvement to its produc-
tion process, in terms of energy savings, optimization, etc., has potential to promote relevant economic
Keywords:
benefits. Methanol production comprises three main steps: preparation of syngas, methanol synthesis
Modeling
and downstream separation. This paper aims at reviewing technologies and procedures for modeling and
Optimization
Kinetics optimizing the second aforementioned phase: the synthesis reactor. Specifically, we focus on packed-
Transport phenomena bed units, which represent the most widespread technology. In the manuscript, we are going to describe
Catalyst deactivation and compare both steady-state and dynamic reactor models as well as analyze typical assumptions and
implementation schemes. The kinetics of methanol synthesis is also reported in detail due to a long debate,
present in the literature, concerning the real carbon source for methanol, the nature of the active sites
and the effect of their morphology and oxidation state.
© 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................... 72
1.1. History ........................................................................................................................................................................................................................................................ 72
1.2. Impact of methanol on energy and environment ....................................................................................................................................................................... 73
1.3. Methanol production ............................................................................................................................................................................................................................ 73
1.3.1. Traditional chemistry ........................................................................................................................................................................................................... 73
1.3.2. Some alternatives to methanol production other than syngas ............................................................................................................................. 75
1.3.3. Green chemistry .................................................................................................................................................................................................................... 76
2. Existing technologies ......................................................................................................................................................................................................................................... 78
2.1. Gas phase technologies ........................................................................................................................................................................................................................ 78
2.1.1. Adiabatic reactors .................................................................................................................................................................................................................. 78
2.1.2. Isothermal reactors ............................................................................................................................................................................................................... 79
2.1.3. Gas phase fluidized bed converter .................................................................................................................................................................................. 82
2.2. Liquid phase technologies .................................................................................................................................................................................................................. 82
2.3. Membrane reactors ............................................................................................................................................................................................................................... 83
2.4. One-step technologies ......................................................................................................................................................................................................................... 84
3. The catalyst ............................................................................................................................................................................................................................................................ 84
4. Reactor modeling ................................................................................................................................................................................................................................................. 84
4.1. Kinetics ...................................................................................................................................................................................................................................................... 84
4.2. Transport phenomena around and inside the catalyst ............................................................................................................................................................. 88
4.3. Catalyst deactivation ............................................................................................................................................................................................................................ 88

* Corresponding author. Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “Giulio Natta”, Centre for Sustainable Process Engineering Research
(SuPER), Piazza Leonardo da Vinci, 32, 20133 Milano, Italy. Fax: +39 (0)2 2399 3280.
E-mail address: giulia.bozzano@polimi.it (G. Bozzano).

http://dx.doi.org/10.1016/j.pecs.2016.06.001
0360-1285/© 2016 Elsevier Ltd. All rights reserved.
72 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

4.4. Steady-state models .............................................................................................................................................................................................................................. 91

4.5. Dynamic models .................................................................................................................................................................................................................................... 95
5. Optimization ......................................................................................................................................................................................................................................................... 98
5.1. Optimal design and nominal conditions ........................................................................................................................................................................................ 98
5.2. Operations management ..................................................................................................................................................................................................................... 98
6. Conclusions ......................................................................................................................................................................................................................................................... 102
References ............................................................................................................................................................................................................................................................ 102

1. Introduction manufacturing. Initially, it was used for lighting, cooking and heating
purposes but it was quickly replaced by more economical fuels. On
Large amounts of energy must be consumed to preserve human- the other hand, methanol was increasingly required by the chem-
ity’s actual living standards. Oil, natural gas and coal, still constitute our ical industry. In 1905, Sabatier proposed the first synthetic pathway
principal energy sources and offer the raw materials for producing a for producing methanol, which implied reacting CO and H2. Based
large variety of derivatives. Unfortunately, these resources are limited on this earlier discovery, the Badische Anilin und Soda Fabrik (BASF)
and not renewable on the human time scale, thus we will probably run patented a syngas-based methanol production process, where syngas
out of coal, oil and natural gas within 3 centuries [1]. For this reason, was supplied via coal gasification. This process required a zinc/
all feasible alternatives must be investigated to seek feasible and long- chromium oxide catalyst as well as high temperature and pressure
term solutions. Besides the problem of power generation, an important (300–400 °C and 250–350 atm). It was first deployed in Leuna,
question is/will be how to store and efficiently use energy. The utili- Germany, in 1923. The following technology developments aimed
zation of hydrogen is an option that is being discussed worldwide. at reducing the pressure and temperature levels in order to improve
However, its storage and transportation raises serious (safety) prob- process economics. Thanks to the invention of the steam reform-
lems, and no infrastructures are available. A feasible alternative could ing of methane, which allowed producing a purer syngas, a more
be liquid methanol. Methanol can serve as convenient energy storage active Cu/ZnO catalyst could be employed, thus decreasing the
medium, easily transportable fuel, solvent and building block for pro- process temperature and pressure to about 300 °C and 100 atm. This
ducing intermediates and synthetic hydrocarbons, also including significant improvement was proposed by ICI (Imperial Chemical
polymers and single-cell proteins. Therefore, it might be a key com- Industries) in 1966. Few years later, Lurgi developed a process with
pound in the global economy of the future. even lower operating pressure and temperature (230–250 °C and
The methanol economy [2], based on green-methanol synthe- 40–50 atm). Subsequent developments further improved the process
sis pathways, has been proposed in contrast to the hydrogen such that, nowadays, the production of methanol from carbon dioxide
economy, which requires a deep change in energy storage and trans- can be considered a mature technology. In fact, the actual metha-
portation means. Methanol has an octane number of 113 and its nol selectivity is over 99.8% with an energy efficiency of around 75%.
energy density is about half of that of gasoline (by volume). The blend Most of the current research efforts are now targeted to finding new
of 10%/90% methanol/gasoline can lead to an octane up to 130. Pure ways to synthetize methanol using both diverse origin carbon
methanol engines can reach efficiency close to 43% and maintain dioxide/hydrogen feeds and different chemistries, e.g. the direct ox-
it above 40% in a wide speed and load range [1]. Methanol can favor idation of methane.
the transition from fossil fuels to renewable energies. Later on, we Nowadays, methanol is used as primary feedstock for a large
will briefly comment on green processes for methanol production. variety of chemicals. Among the most important, we can mention
Other than the traditional production pathway via synthesis gas, formaldehyde (it consumes about 70% of the methanol produced
methanol could be manufactured in different and new ways. The worldwide), methyl-tert-butyl ether (MTBE, 20%), acetic acid and
carbon source may be natural gas (in this case, methanol could be dimethyl ether. In addition, a variety of intermediates employed in
directly produced at the gas well by direct oxidative transforma- manufacturing many products of our daily life derive from meth-
tion) or CO2, which can be recovered from industrial sites and, anol: paints, resins, silicones, adhesives, antifreeze, plastics, and so
eventually, from the atmosphere. This second production pathway on. Methanol is also used as transportation fuel in addition to gas-
would allow mitigating global warming due to the increasing pres- oline, and in the future, it will certainly play an increasing role in
ence of greenhouse gases in the atmosphere. All energy sources can such field. In fact, the emissions (hydrocarbons, NOx, SOx and par-
be exploited for methanol production, thus the “Methanol Economy” ticulate) associated with it are reduced. However, before being able
offers a feasible means of using and storing all sources of energy to use pure methanol as fuel, we still need to solve issues like metal
(renewable, atomic, etc.). At this point, it is clear how important meth- corrosion (especially, aluminum, zinc and magnesium can be at-
anol may be for our future economy. Since improvements in methanol tacked) and/or cold engine start, which is related to the absence of
synthesis process are still feasible, there is great research interest highly volatile compounds. In any case, adding a certain percent-
in this field. New production technologies have been proposed after age of methanol to gasoline improves the performance of internal
the first process start-up [3], which are principally aimed at reduc- combustion engines (ICE), thus mixtures of methanol and gaso-
ing investment costs (relevant for methanol production). The line are already being marketed. In China, starting from 2009,
modeling of methanol manufacturing process, and particularly the national fuel blending standards of M85 (85% methanol, 15% gas-
reactor model, allows improving energy savings and optimizing oline) and M100 (100% methanol) went into effect, and M15 standard
the production itself. Therefore, this review focuses on modeling is in adoption. In Shanxi province alone, there are more than 1000
strategies and optimization techniques for the methanol synthesis petrol stations, which are equipped to sell M15, and other 40 M85-
reactor. M100 refueling points are present. The Shanxi government plans
to expand rapidly the number of vehicles using methanol and the
1.1. History number of petrol stations. Therefore, China appears to play a leading
role in the methanol market and, consequently, the global metha-
Methanol was first isolated by Robert Boyle in 1661 via wood nol demand is growing rapidly as shown in Fig. 1.
distillation while its chemical composition was first discovered by The development of fuel cell vehicles (FCV) will certainly involve
Dumas and Peligot in 1834. At that time, production volumes the use of methanol as hydrogen carrier. Direct methanol fuel cells
were still small, e.g. 10–20 L per ton of wood treated for charcoal (DMFCs) are under development for a number of possible
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
80
MILLIONS OF METRIC TONS
60
40
20
0 by reforming or partial oxidation of different carbon-based mate-
2000 2005
Fig. 1. Global methanol industry demand forecast [4].
applications including low power DMFCs for portable devices, such
as smartphones and laptops, DMFCs for automotive systems and high
power DMFCs for large-scale electricity production. However, con-
siderable technological improvements are still necessary in order
to achieve higher efficiency for large DMFCs.
1.2. Impact of methanol on energy and environment
In recent times, methanol has been employed in a number of
innovative applications. It is a clean and sustainable energy re-
source that can be produced starting from different sources,
traditional or renewable: natural gas, coal, biomass, landfill gas and
power plant/industrial emissions.
As already discussed, the fact that methanol is liquid at ambient
temperature makes it an attractive alternative fuel for automotive
applications. Methanol is also a reagent for some common
transesterification reactions, e.g. those for the production of bio-
diesel and MTBE, but is also suitable for replacing diesel fuel. In
addition, it can be exploited in on-grid and off-grid power turbines
for electric energy production and is very good hydrogen carrier for
fuel cell technology.
When burnt, methanol demonstrates to be cleaner than most
energy sources because of its molecular structure, which is packed
with hydrogen and presents no carbon-to-carbon bonds [5].
Methanol is spontaneously produced by a number of natural
sources like volcanoes, vegetation, microbes, insects, animals and
decomposing organic matter. Its accidental release in the environ-
ment, which may lead to contamination of ground and water, is
mainly related to its use as solvent but is not particularly hazard-
ous. In fact, methanol is rapidly degraded by photo-oxidation and
biodegradation processes, both in aerobic and anaerobic condi-
tions. No evidence of bioaccumulation in fresh water, soils, ground
waters and sediments has ever been observed. Many microorgan-
isms living in the ground consume methanol as nutrition substance
and convert it into CO2 and water. Methanol has low toxicity to ter-
restrial and aquatic organism. It is even used for the denitrification
of wastewaters in sewage treatment plants. An accidental release
of methanol into the environment would have lower impact than
a corresponding crude oil or gasoline spill. Methanol, in fact, is totally
miscible with water, thus a potential leak would be rapidly diluted
and dissipated to non-toxic levels by biodegradation. Finally, meth-
anol releases are less dangerous than gasoline leaks. Compared to
gasoline and other fuels, methanol is safer and less toxic [1].
1.3. Methanol production
This paragraph aims at describing possible methanol produc-
tion pathways.
73
1.3.1. Traditional chemistry
The industrial process for producing methanol is relatively simple.
Currently, it is comprised of three basic steps:
• production of synthesis gas (syngas)
• conversion of the synthesis gas into methanol
• distillation of the reactor effluent
Different technologies are under investigation but cannot be
implemented at the industrial scale yet due to unsatisfactory
efficiency.
Currently syngas (a mixture of H2, CO and CO2) is mainly produced
by reforming of natural gas. However, it can be potentially synthesized
rials, e.g. petroleum, coal, petroleum coke, heavy oil, asphalt or biogas
2010
[6,7]. Economic considerations typically suggest which raw mate-
rials are more suitable for use, even though long-term availability,
political considerations, energy consumption and environmental
aspects play an important role in the final decision as well.
The composition of syngas is usually characterized by the stoi-
chiometric number S given by the ratio of two quantities: the
difference between the moles of hydrogen and CO2 and the sum-
mation of the moles of CO2 and CO:
moles H 2 − moles CO2
S= (1)
moles CO2 + moles CO
For the production of methanol and under ideal conditions, S
should assume a value of 2. However, a value slightly larger than
2 appears to be optimal for most of the commercial catalysts. Notice
that a value larger than 2 indicates excess of hydrogen while a value
lower than 2 means hydrogen deficiency. The stoichiometric value
S takes into account the presence of CO2 that consumes hydrogen
via the reverse water–gas shift reaction. The value of S depends on
the adopted raw material, e.g. when syngas is produced by means
of natural gas reforming, an S value of 2.8 to 3 is usually achieved.
Excess hydrogen can be used in an adjacent plant for ammonia pro-
duction, if CO2 can be added. Methane is still the preferred feedstock
because the corresponding technology for syngas production is as-
sociated with lower energy consumption, capital investment and
operating costs. Moreover, the syngas synthesized from methane
shows lower concentration of impurities such as sulfur and halo-
genated compounds or metals. This eases all downstream purification
steps and mitigates catalyst-poisoning issues (all methanol syn-
thesis reactors use catalysts).
Currently, methanol is produced via synthesis processes oper-
ating at pressures of 50–100 atm and temperatures of 200–300 °C.
However, a very limited number of different process layouts is avail-
able. In particular, 60% of the methanol produced worldwide is
manufactured via the Johnson Matthey (ex Synetix, ICI company)
process and 27% of it is produced via Lurgi (nowadays, a company
of Air Liquide) process (see Fig. 2).
Most of the actual processes operate in gas phase and use copper-
based catalysts. The main differences among them are related to the
reactor design and catalyst arrangements, as discussed in Section
2.1. Crude methanol leaving the reactor has to be separated from
water and other impurities, which depend on the type of feed-
stock adopted. Different grades of methanol are commercialized:
fuel grade, “A” grade (used as solvent), and “AA” grade (associated
with purity exceeding 99.85% and suitable for chemical applica-
tions). Therefore, the features of the distillation train, located
downstream the reactor, depend on the desired purity/grade.
Syngas manufacturing and purification is a crucial part of the
overall process for methanol production. It usually represents more
than half of the total investment when the feedstock is natural gas
and up to 70–80% when the raw material is coal.
74 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Methanol producon by process
1%
3%
8%
27%
60%
Synex Lurgi MGC Kellog Others
Fig. 2. Worldwide methanol production processes (Source: ICI, now Johnson Matthey
[8]).
The most common technology used for producing syngas is a
highly endothermic process known as methane steam reforming,
whose operating temperatures and pressures are in the range of 800–
1000 °C and 20–30 atm [9], respectively. CO and H2 are produced
along with CO2, which originates from the water gas shift reaction
(WGS):
CH 4 + H 2O ↔ CO + 3H 2 ΔH 298 K = 49.1 kcal mol
CO + H 2O ↔ CO2 + H 2 ΔH 298 K = −9.8 kcal mol
High temperatures and low pressures favor the production of
syngas. In fact, increasing the process temperature reduces the im-
portance of the WGS reaction and promotes the generation of CO
and H2. Heat is supplied to the system by burning a part of the
natural gas fed to the reactor. Formation of coke and soot may occur
and represents a serious issue. In fact, this waste product can coke
the catalyst, thus reducing its activity, and can deposit on all of the
internals of the reformer and downstream equipment.
A different syngas production technology relies on the partial
oxidation of methane:
CH 4 + 1 2O2 ↔ CO + 2H 2 ΔH 298 K = −8.6 kcal mol
CO + 1 2O2 ↔ CO2 ΔH 298 K = −67.6 kcal mol
H 2 + 1 2O2 ↔ H 2O ΔH 298 K = −57.7 kcal mol
The reaction system is exothermic, operates at 1200–1500 °C [10]
and generally yields syngas that is ideal for methanol production
because its S factor is about 2. However, CO and H2 can be oxi-
dized to CO2 and H2O, thus leading to S values smaller than 2. In
addition, a large amount of heat is produced and wasted in absence
of proper heat integrations with other processes. An air separa-
tion plant is necessary in order to avoid the separation of large
amounts of nitrogen, which is the common drawback of using air.
The need for producing syngas without heat generation/
consumption has led to the modern production technology that
combines exothermic partial oxidation and endothermic steam re-
forming, thus achieving a thermodynamically neutral system and
synthesizing syngas, whose S is around 2. This is the so-called “auto-
thermal reforming”. It can be operated by simultaneously reacting
CH4 with H2O and O2 inside a single reactor. This takes to lower costs
and significant simplification of the process layout. However, because
the two aforementioned reaction sets should be optimally con-
ducted at different temperatures and pressures, sometimes the
effluent of the steam reforming is fed to a partial oxidation reactor,
which allows consuming most of the remaining methane [11].
As already mentioned, other alternatives for producing syngas
exists. In particular, once can think of starting from mixtures of
higher hydrocarbons, like liquefied petroleum gas, or petroleum re-
fining cuts (especially naphtha). The chemistry involved is the same
as that described for natural gas: steam reforming and partial ox-
idation, or a combination of the two. The problem with such
technologies is the higher concentration of impurities in the raw
materials (especially sulfur or chlorine) that can poison the cata-
lyst loaded into the methanol synthesis reactor. In addition, the
syngas produced may suffer from hydrogen deficiency.
Coal was originally the feedstock used in syngas production and
is still the raw material of choice in those countries, like South Africa
and China, where natural gas is not available. In this case, syngas
is synthesized via gasification, combining partial oxidation and steam
treatment.
C + 1 2O2 ↔ CO (7)
C + H 2O ↔ CO + H 2 (8)
CO + H 2O ↔ CO2 + H 2 (9)
CO2 + C ↔ 2 CO (10)
The design of the gasifier highly depends on the type of coal
(lignite, sub-bituminous, hard coal, graphite, etc.) and on its water,
ash and impurity content. The syngas produced is obviously defi-
(2) cient in hydrogen but the hydrogen content can be increased thanks
to the WGS reaction. Analogously, an innovative pathway is the gen-
(3)
eration of syngas from acid gases (or emissions) [12–14]. The overall
reaction is:
2H 2 S + CO2 ↔ H 2 + CO + S2 + H 2O (11)
This production technology is supposed to become a promis-
ing route for CO2 reuse in the near future.
After possible purification steps, the synthesis gas may be pres-
surized with a compressor, added to the unconverted recycled
synthesis gas and heated. Heating could also take place inside the
methanol converter. The mixed gases, having a H2/CO ratio from 3:1
to 5:1, are fed to the reactor.
Methanol production from synthesis gas involves the follow-
(4)
ing reactions:
(5) CO + 2H 2 ↔ CH 3OH (12)
(6) CO2 + 3H 2 ↔ CH 3OH + H 2O (13)
CO + H 2O ↔ CO2 + H 2 (14)
The first is a combination of the remaining two, thus the reac-
tion set comprises dependent chemical transformations. The first
two reactions are exothermic and result in a reduction of moles. There-
fore, low temperatures and high pressures favor the reagents
conversion. Today’s synthesis processes take place at lower pres-
sures (in the range of 50–100 bar), preferably close to the pressure
required for producing synthesis gas by steam reforming. This allows
reducing the costs of gas compression. However, lower pressure pro-
cesses result in lower conversion of synthesis gas per pass (typically
10%). Therefore, a recycle loop is necessary to reach sufficient yield.
Of course, a gas purge is necessary to avoid accumulation of impurities.
All the above-mentioned reactions are promoted by the use of
catalysts, e.g. Cu/Zn/Al2O3. In particular, the catalyst is essential for
the shift reaction, which allows coal-based synthesis gas (with a
lower S value) to be optimally exploited. Later on, we will provide
a detailed description of both the catalyst and the process kinet-
ics. Although thermodynamic considerations suggest operating at
temperatures as low as possible, the process of methanol synthesis
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
is carried out at about 200–300 °C because the catalyst is active only
inside this temperature range. Thermodynamic equilibrium limi-
tations and catalyst deactivation seriously affect methanol production.
In particular, the decay in the catalyst activity takes to unavoid-
able unsteady process operation.
A good catalyst should remain active for several years (up to 4).
The deactivation of Cu/Zn/Al2O3-based catalysts is usually due to
chemical poisoning and thermal sintering. In general, any of sulfur
compounds, chlorine and heavy metals represents a catalyst poison.
However, due to preemptive feed treatment and purification, sin-
tering is often the only source of loss of activity. Sintering is a solid-
state transformation, which takes place at high temperatures and
is promoted by water vapor. This said, methanol converters are de-
signed based on the estimated average catalyst activity and should
be able to operate at their maximum capacity even at the so-
called “end-of-run” condition.
Improvements to the process of methanol synthesis can derive
from the invention of new, more active and more resistant cata-
lysts as well as novel reactor designs.
1.3.2. Some alternatives to methanol production other than syngas
The first process we want to describe is that for producing meth-
anol via methyl formate. This route has been proposed a century
ago by Christiansen [15]:
CH 3OH + CO ↔ HCOOCH 3 (15)
HCOOCH 3 + 2H 2 ↔ 2CH 3OH (16)
CO + 2H 2 ↔ CH 3OH (17)
It consists of two reaction steps. The first is the methanol
carbonylation reaction, which occurs in liquid phase and requires
homogeneous catalysis that is usually provided by sodium or po-
tassium methoxide. The subsequent reaction, which involves
hydrogen, can occur in both liquid and gas phases and requires
copper-based catalysts. Patents (from Mitsui Petrochemicals,
Brookhaven National Laboratories and Shell) claim that their tech-
nology allows producing methanol from syngas at 80–120 °C and
10–50 atm instead of 200–300 °C and 50–100 atm. The main problem
with this pathway is the presence of water and CO2 in the syngas,
which react with sodium methoxide and produce undesired
byproducts. Therefore, further separation steps are necessary. Some
catalysts have been found, which are more resistant to these poisons
[16], but further improvements are still needed for the technolo-
gy to be mature for industrial application.
Extensive research is also being conducted in manufacturing
methanol directly from selective oxidation of methane without the
need for syngas. The reaction path is reported below:
CH 4 + 1 2O2 → CH 3OH (18)
CH 4 + O2 → CH 2O + H 2O (19)
CH 4 + 1.5O2 → CO + 2H 2O (20)
CH 4 + 2O2 → CO2 + 2H 2O (21)
The main drawback is that most of the side products are very
reactive, thus can be easily overoxidized. Notice that this is the same
problem experienced in the case of partial oxidation of methane.
Operating conditions, which allow mitigating the aforementioned
drawback, are being explored but high yield, high selectivity and
catalyst stability have not been obtained yet.
Methane selective oxidation can be carried out in homoge-
neous gas phase and in heterogeneous catalytic setups as well.
75
In the homogeneous gas-phase oxidation process, methane and
oxygen react at high pressure (30 to 200 atm) and temperature (200
to 500 °C). It has been shown that 70–80% selectivity can be achieved
with 8–10% conversion in optimized conditions and by using cold
flames at 450 °C, 65 atm and less that 5% O2 content. Other studies
suggest a selectivity to methanol of 30–40% at 450–500 °C and 30–
60 atm, with a conversion of 5–10%. At high pressures, radical
reactions are predominant, thus the effect of the catalyst is limited.
Most of the methanol produced is rapidly oxidized or decom-
posed to formaldehyde, carbon oxides and formic acid. If the resulting
mixture is post processed with proper technologies, the methanol
content can be increased [17]. This post-processing can be per-
formed in different ways. However, it is highly desirable to produce
methanol directly from methane, thus avoiding any additional steps.
In order to achieve higher selectivity, lower temperatures are pref-
erable (less than 250 °C). Current catalysts are not sufficiently active
at low temperatures and new types of catalysts are therefore nec-
essary. This problem has suggested investigating liquid phase reactions,
which can be conducted at milder temperature. Such reactions involve
the use of superacids, whose acidity is million times stronger than
concentrated sulfuric acid. At ambient temperature and in liquid phase,
methane can react with H2O2 in presence of superacids and produce
methanol with high selectivity. The reaction mechanism implies in-
serting a protonated hydrogen peroxide (H3O2+) molecule into the C—H
bond of methane. In such acidic environment, methanol is proto-
nated (CH3OH2+) and protected from further oxidation. However, H2O2
is not suitable for use in large-scale production facilities and superacids
are very expensive. Therefore, the search for cheaper peroxides and
superacids is still ongoing [1].
Methanol can be also synthesized in a two-step process involv-
ing methyl-halides as intermediates (the halogen behaves like a
catalyst and is not consumed in the reaction process). Methyl chlo-
ride or bromide (CH3Cl, CH3Br), catalytically produced from methane,
can be hydrolyzed to methanol and HCl or HBr, which can be
reoxidized [18]:
CH 4 ⎯X⎯
2
→ HX + CH 3 X ⎯H⎯⎯
2O
→ CH 3OH + HX (22)
2HX ⎯1⎯⎯
2O2
→ X 2 + H 2O (23)
X = Cl, Br (24)
Recycling the hydrogen halides generated in the first reaction
is essential for the economics of the process. The reoxidation of hy-
drogen chloride is possible but remains technologically difficult,
especially at industrial scale. On the contrary, air readily oxidizes
hydrogen bromide to bromine.
The chlorination of paraffins was discovered by Dumas in 1840
and is a very old and well-known substitution reaction that is widely
adopted in industry. It comprises several thermally or photochemi-
cally initiated free radical reactions. The main drawback of this route
is its low selectivity:
CH 4 ⎯X⎯
2
→ CH 3 X ⎯X⎯
2
→ CH 2 X 2 ⎯X⎯
2
→ CHX 3 ⎯X⎯
2
→ CX 4 (25)
X = Cl, Br (26)
As the halogenation of a hydrogen-halide including “n” halogen
atoms is more favorable than that of a hydrogen-halide including
“n - 1” halogen atoms, it is necessary to use high methane to halogen
ratios (at least 10:1) to produce mostly the desired mono-
halogenated compound. The catalytic mono-halogenation of methane
has been tested at temperatures of 180–250 °C and, at such con-
ditions, has proven to provide conversions from 10% to 60% and
selectivity over 90%. Only one side product has been observed:
methylene halide. The subsequent catalytic hydrolysis of mono-
halogenated compounds can produce methanol or dimethyl ether.
76 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Natural gas
Intermediates
other than
syngas
Petroleum
Syngas
Coal
Heavy oil
Tar sands Existing technologies
Shale oil Technologies to be developed
Fig. 3. Methanol from fossil fuel resources (re-arranged from Olah et al. [1]).
Finally, Periana investigated the use of Iodine in 2002 [19] and
this pathway appears to be of interest even though no apparent pro-
gress has been reported so far. Therefore, even if this route seems
to be promising, its yield and selectivity make it noncompetitive
with traditional syngas-based strategies for methanol production.
A summary of the current technologies for producing metha-
nol and those still under development is shown in Fig. 3:
1.3.3. Green chemistry
Green chemistry aims at synthesizing methanol entirely from
renewable resources. A possible pathway is provided below:
CO2 + 3H 2 ↔ CH 3OH + H 2O
Hydrogen may originate from water dissociation by electroly-
sis, where the source of electricity should be renewable as well (wind,
biomass, solar, tides, waves, etc.). Other H2 sources can be biomass
pyrolysis or steam/oxygen gasification processes and the reform-
ing of biomass-derived products (for instance ethanol, methane, etc.).
Other routes are still under investigation. One of them implies pro-
ducing biological H2 by means of microorganisms activated by
sunlight while another is a water splitting process assisted by photo-
semiconductor catalysts [20]. CO2 could be collected from industrial
waste or even from the atmosphere. In the long term, our depen-
dence on fossil fuels and on oil-producing countries would probably
cease to exist. However, for this to happen, methanol should be pro-
duced in large amount and this target is difficult to achieve only
by means of renewable resources.
Waste biomass can be a potential feedstock for producing meth-
anol. If unused, it accumulates and can lead to socio-economic
problems. However, we can exploit it as renewable resource for pro-
ducing energy and as raw material for synthesizing chemicals, e.g.
methanol. Biomass is every material produced by any kind of life
forms, vegetal or animal. Therefore, it includes wood, wood waste,
agricultural crops, municipal solid waste, animal waste, aquatic plants
and algae. To some extent, it is the same as going back to the origins
and producing methanol from wood, but more efficiently. Most of
the technologies for methanol production that use biomass as feed-
stock are similar to those adopted when fossil fuels are exploited
as raw materials. Biomass is usually dried and ground to yield par-
ticles of small and uniform size. Moisture should not overcome 15–
20%. The gasification of biomass generates a gas mixture containing
H2, CO, CO2 and H2O. During the gasification process, oxygen burns
a part of the biomass to generate heat [21]. The combustion gases
(CO2 and water) react with the remaining part of the biomass leading
to CO and H2. No external heating source is necessary. The “one step”
Increase atmospheric
CO2 concentration
contributing to global
Methane partial
climate change
oxidation
Methanol Fuel uses
Chemicals, synthetic
hydrocarbons and
their products
partial oxidation of biomass is attractive but presents technical prob-
lems, so generally two steps are necessary. In the first step, biomass
is heated up to 400–600 °C with low oxygen content in order to avoid
complete combustion. Pyrolysis mainly occurs and the gases pro-
duced in the process are essentially CO, H2, CH4, CO2, H2O and volatile
organics. A solid residue, called charcoal, is generated and ac-
counts for about 10–25% of the original fuel mass. In the second
step, charcoal and O2 react at 1300–1500 °C producing CO. The re-
sulting syngas still requires some purification steps before being used
in methanol production facilities but the concentration of sulfur and
heavy metals is lower than that usually observed in the syngas origi-
nating from coal. Methanol production plants are typically large-
(27) scale due to economic reasons, thus approximately 1.5 Mt/y of biomass
should be needed to produce methanol at a rate of 2500 t/d (most
of the existing plants insure such production capacity). Therefore,
biomass should be collected over vast areas of land and trans-
ported over long distances. Consequently, it has been proposed to
convert it into an easy-to-transport liquid by means of fast pyrol-
ysis. Fast pyrolysis takes place at 400–600 °C with very low residence
times, about 2 s, as to obtain maximum yield for liquid tar (70–
80%), called “biocrude”, and minimum amount of the other gaseous
and solid products, which can be partially used to drive the process.
In fact, the combination of temperature and residence time regu-
lates the distribution of the pyrolysis products among gaseous, liquid
and solid substances. Higher temperature and longer residence times
increase biomass conversion to gas while lower temperatures and
longer vapor residence times favor the production of charcoal. Fast
pyrolysis requires very high heating rates, such that the biomass
has to be ground down to particles smaller than 3 mm. Short vapor
residence times minimize secondary reactions and the rapid removal
of char minimizes the cracking of vapors. Vapors must then be cooled
down rapidly to recover the bio-oil. Part of the char could also be
ground and added to the biocrude, thus forming a slurry.
All biomass sources can be gasified toward methanol produc-
tion but low-moisture materials are the most suitable for such purpose
and provide efficiencies up to 55%. Several demonstration projects
are under investigation around the world [22]. In addition, black
liquor originating from paper manufacturing is an interesting feed
for gasification and methanol production. This holds true mainly in
small countries, like Finland and Sweden, where paper mills are wide-
spread. In fact, these countries could satisfy up to 50% of their motor
fuel demand this way. Fig. 4 shows how to use biomass for meth-
anol production while preventing the CO2 concentration in the
atmosphere from increasing, thus mitigating greenhouse effects.
In the future, the increase in biomethanol demand will require
larger and larger quantities of biomass, thus large-scale cultivation
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Fig. 4. The carbon cycle of biomethanol (rearranged from Olah et al. [1]).
of energy-devoted plants will be necessary. This is a feasible sce-
nario for all countries with low population density like United States,
Australia, or Brazil, where large part of the territory could be used
to grow energy-devoted plants. Unless surplus land is available,
energy-devoted crop cultivation would compete with food and
fiber production. For instance, limited to the European area, biomass
is expected to be able to cover only up to 10–15% of the energy
demand. Aspects like nutrients for plant growth and rotation of cul-
tivations must also be accounted for. Moreover, proper crops must
be identified, which require minimum amount of fertilizers to grow.
This is essential to avoid increasing N2O emissions significantly (N2O
is 296 times worse than CO2 as a greenhouse gas). Biotechnology
and genetic modifications will boost the yield in crop cultivation.
Another option is to produce methanol from biological pro-
cesses using CO2 waste as raw material. Certain bacteria, called
methanotrophs, survive by extracting carbon and energy from
methane. They selectively convert methane to methanol by using
oxygen and an enzyme, called methane monooxygenase (MMO),
which operates at ambient temperature and pressure in aqueous
solution. Two types of MMO have been identified: the first con-
tains copper and is difficult to isolate and characterize while the
second includes a pair of iron atoms and seems more appealing. Re-
search has been conducted to find a way of designing simple catalytic
systems that mime the MMO behavior. However, their practical ap-
plication to the production of methanol has proven to be difficult.
In fact, MMO requires oxygen as oxidant and the presence of a re-
ducing agent, known as NADH. In model experiments, H2O2 is used
while, in practical applications, hydrogen should be used as reduc-
ing agent, thus making the process less economically attractive.
Methanol can be also produced from biogas. Most mammals
produce a flammable gas termed “biogas” during food digestion.
Biogas originates from the anaerobic decomposition of organic ma-
terial performed by anaerobic bacteria. It is a waste product for those
microorganisms and is composed mainly of CH4 (55–75% depend-
ing on composition and efficiency) and CO2 but includes traces of
other elements, like H2S. The oil crisis in 1970s renewed the inter-
est in biogas production, where the feedstock is usually sewage
sludge, municipal organic wastewater and animal dung. The envi-
ronmental impact due to the disposal of such waste can be reduced
by adopting anaerobic digestion [23]. In large-scale operations, the
feedstock can be fed to the digester in continuous fashion: the gas
leaves the unit from a gas outlet on top and the sludge, which is
recovered, can be used as soil fertilizer or conditioner. At present,
biogas is mainly used for producing heat or electricity but could be
directly used for the manufacturing of methanol after proper
77
purification steps. The CO2 can partially react with the excess hy-
drogen coming from methane steam reforming in order to produce
methanol. Another source for biogas is landfill, which is widely
adopted by municipalities. However, the amount of methanol coming
from this source is limited. The third generation of biomass com-
prises algae and their derivatives and seems very appealing for a
variety of reasons: algae are not food-competing and can be pro-
duced much faster than other land-based cultures such as corn and
soy; finally, they can be harvested continuously upon production.
Aquatic plants and organisms show considerable potential because
water covers more than 70% of the Earth’s surface. Once collected,
they can be processed to form methane by anaerobic digestion and
then methanol. Algae consists both of macroalgae, up to 60 m length,
and of microscopic organisms named microalgae. Further re-
search is expected to provide additional knowledge about such
aquatic organisms and to find a way to optimize the conversion of
solar energy into biomass by means of algae. At present, the pro-
duction of energy from algae is too expensive and not competitive
with respect to fossil fuels or other type of biomass.
The most promising approach to converting CO2 to hydrocar-
bons is the catalytic or electrochemical hydrogenation to methanol.
Efficient catalysts are available and are very similar to those used
to produce methanol from syngas. Many methods for producing
methanol from CO2 are known [24,25]. The factor that limits the
large-scale application of such process is the availability of CO2 and
H2. While carbon dioxide is widely available in exhaust sources (flue
gases of power plants using fossil fuels, industrial plants, and so on)
and in the atmosphere, hydrogen is currently generated from fossil
sources, thus its availability is limited. A possible option is to de-
compose methane and produce hydrogen and carbon. Then, we could
synthesize methanol from recycled CO2. However, the potential
success of this route strongly depends on the availability of natural
gas. The solid carbon formed as byproduct could be used for dif-
ferent applications, e.g. as pigment for ink and paints, in tires, as
filler for road construction, and so on. Combustion is obviously
excluded in order to avoid further CO2 production. Thermal decom-
position occurs when methane is heated up to temperatures above
800 °C in absence of oxygen. This process is at its first stages and
significant research is still necessary to get to a mature and effi-
cient technology for commercial applications. It could be a promising
alternative to produce methanol at zero CO2 emissions. This tech-
nology would allow using natural gas resources, including
unconventional ones such as methane hydrates. Water electroly-
sis is also an alternative hydrogen source for methanol production.
The required electricity can originate from atomic, solar, hydro, wind,
78 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

geothermal or wave energy. Notice that the process for producing

methanol requires 3 molecules of hydrogen per molecule of CO2.
Therefore, water-electrolysis-based methanol synthesis is not at-
tractive because of the energy consumption needed for the hydrogen
manufacturing. However, electrochemical or photochemical reduc-
tion of CO2 produces by-products such as formaldehyde and formic
acid that, in turn, can be reduced to methanol.

2. Existing technologies

In every chemical process, the reactor is the most important piece

of equipment. The methanol synthesis comprises globally exother-
mic reactions, thus the reactor is designed to provide efficient
temperature control. Heat has to be removed efficiently and pos-
sibly recovered in order to optimize the economics of the process.
High conversion per pass is required in order to minimize the down-
stream separation costs [26]. This said, existing reactor technologies
fall into two main categories: gas and liquid phase technologies.

2.1. Gas phase technologies

Gas phase reactors can be either adiabatic or isothermal. As for

the adiabatic units, there exists the multi-bed quench configura-
tion with direct cooling (lozenge, ARC, collect-mix-distribute (CMD))
or the multi-bed configuration with interstage heat exchange (in-
direct cooling). Fig. 5 provides a visual insight of common layouts
for methanol reactors.
2.1.1. Adiabatic reactors
A quench converter comprises multiple adiabatic beds (up to five)
installed in series inside one single pressurized shell (Fig. 6). The
ICI (now Johnson Matthey) low pressure quench converter [27] is
the most common solution applied in industry. The operating con-
ditions are 50–100 bar and 270 °C. The supported catalyst, consisting
of Cu/ZnO/Al2O3, is loaded in a single bed. The cooling gas is in-
jected into the bed by means of distributors, called lozenges. The
addition of fresh and recycled syngas allows mitigating the reac-
tion temperature, thus optimizing the reactor design. The lozenges
run horizontally across the converter from side to side and a central
pipe is used to deliver the cold gas.
This configuration is simple and reliable and allows producing
up to 3000 t/d. Moreover, the heat of reaction is recovered and
reused. However, because of irregular flux distribution, due to vari-
able void fraction along the bed, no single catalyst pellet receives
the same gas flow. Therefore, cold (low reaction rate) and hot
Fig. 6. Quench reactor showing quench gas inlet.
(catalyst deactivation or byproducts formation) zones can be found
inside the bed.
The vessel construction as well as the loading and unloading of
the catalyst are simpler with respect to tubular reactors. On the other
hand, tuning the reactor performance is more complicated, the heat
recovery is less effective and the conversion is lower, thus requir-
ing a high recycle stream. In contrast, if adiabatic reactors are
separated in different shells in series, large capacities up to 10,000
t/d are potentially achievable.
Another example is the Kellogg, Brown and Root reactor, which
is comprised of a series of adiabatic, fixed bed reactors. The shape
of the reactors is spherical with the catalyst loaded between the
external wall and an inner spherical shell (Fig. 7). As the wall thick-
ness is approximately half of that of a conventional reactor, the cost
for manufacturing, transport and installation is lower [28]. These
reactors provide radial flow from the outer wall, through the cat-
alyst layer and eventually into the inner sphere, thus resulting in
smaller pressure drops and consequent reductions in investment

Fig. 5. (a) Adiabatic reactor with direct cooling; (b) adiabatic reactor with indirect heat exchange; (c) reactor with external cooling.
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Gas outlet
Gas inlet
Dome
Perforated spherical
segments
Compensator
Catalyst
Gas inlet
Gas inlet
Fig. 7. Spherical reactor.
and operating costs. During start-up operations, shrinkage of the
catalyst bed occurs. In order to avoid the presence of voids, which
may lead to irregular flow distribution, the catalyst dome is filled
up to approximately 10% of the total catalyst volume. This catalyst
slips down and fills the empty areas. The reaction heat is removed
by intercoolers. In such type of reactors, the fresh feed of syngas
enters directly the first reactor, thus increasing the overall reac-
tion rate and decreasing the necessary volume of catalyst with
respect to other quench-type units. The design of the gas distribu-
tors and the heat exchangers is simple. In addition, Haldor Topsoe
and Krupp Uhde propose multi-vessel adiabatic reactor systems for
methanol production. However, Kellogg, Brown and Root solu-
tions guarantee higher yields with respect to a quench reactor, thus
requiring a smaller recycle stream.
The solution from Casale comprises a quench-cooled converter
called ARC (Advanced Reactor Concept), whose design originated
from a collaboration with ICI. This type of design is reliable and ef-
ficient and has been adopted for revamping several plants that were
previously relying on the quench-lozenge technology (Fig. 8). Thanks
to the revamping, the methanol production capacity usually in-
creases by 20%. This technology has a very effective quench gas
redistribution. In contrast to adiabatic bed reactors, here the bed
is separated into different sections by means of distribution plates.
Fig. 8. ARC technology (courtesy of Casale SA).
79
Fig. 9. Toyo MRF-Z® reactor [29].
Haldor Topsoe proposes a Collect-Mix-Distribute reactor (CMD)
to revamp conventional quench converters. It includes several cat-
alyst beds separated by vertical support beams similarly to the
Halliburton reactors. The fresh syngas is fed at the bottom of the
reactor and flows radially through the first catalyst bed. The gas exits
at the top of the bed and is mixed with cold quench gas before being
redistributed and forced to flow radially down through a second cat-
alyst bed. This configuration allows to increase the reagents
conversion and control the temperature with beneficial effects on
the catalyst life as well.
The Toyo Engineering Corporation (TEC) reactor, called MRF-Z®
reactor, is a multi-stage radial flow reactor with intermediate cooling
(Fig. 9). Here heat is removed by means of blade boiler tubes and
the catalyst is loaded into concentric beds. The reaction tempera-
ture is kept close to its maximum allowable value, thus the
conversion per pass is optimal and the volume of the catalyst bed
is reduced of about 30% with respect to quench converters of same
production capacity. This solution also allows efficient heat recov-
ery by producing steam, which can be employed to synthesize the
syngas feedstock. Apparently, savings corresponding to about 50%
of the steam required for producing the syngas feedstock are pos-
sible. The production capacity of just one of these reactors can be
up to 5000–6000 t/d. The mild temperature conditions achieved with
this design allow to increase the catalyst life. Moreover, the cata-
lyst replacement is reasonably simple. The radial flow configuration
allows reducing pressure drops across the catalyst bed by about one-
tenth of those experienced with axial flow configurations, thus the
recompression of unreacted synthesis gas is more economical.
Moreover, the reactor can be easily scaled-up by preserving the
same diameter and simply increasing its height. In fact, the same
pressure drop across the bed is experienced independently of the
reactor height.
2.1.2. Isothermal reactors
The first example of this type of technology is the so-called Linde
isothermal reactor. It is equipped with helically tubes inserted in
the catalyst bed (Fig. 10). Therefore, the heat exchange is indirect.
This type of reactor configuration is suitable for both endothermic
and exothermic catalytic reactions and for gas/gas, gas/liquid or
80 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Fig. 10. Linde isothermal reactor [30].
liquid/liquid systems. The heating or cooling tubes allow insuring
the maximum possible reaction rate as well as an optimum tem-
perature profile. As a result, this solution guarantees higher
productivity, increased catalyst life, fewer by-products, efficient re-
action heat recovery and lower operating costs. The configuration
with helically tubes avoids the generation of stresses due to axial
temperature variations. The same problem usually arises in straight
fixed bed reactors. In addition, the required reaction volume is
reduced thanks to the fact that the heat transfer on the catalyst side
is significantly more efficient than that achievable when the cata-
lyst itself is loaded inside any sort of tubes. Consequently, the
required cooling area is reduced and material costs are lower as well.
Linde reactors can insure production capacities up to 4000 t/d.
Fig. 11. Lurgi combined methanol converters [34].
The Lurgi (now a company of Air Liquide) converter is one of the
most commonly adopted reactors for methanol production [31–33],
particularly in large-scale plants. It is a fixed bed reactor with a shell
and tube design similar to that used by the same company for the
Fischer Tropsch (FT) reaction. The catalyst is loaded inside the reactor
tubes whereas cooling water flows on the shell side. This layout
ensures tight control of the temperature profile and allows pro-
ducing high-pressure steam. The reaction temperature is controlled
via the steam pressure. Typical operating conditions are in the range
of 50–100 bar and 230–265 °C. Steam is produced at 40–50 bar and
can be reused in the compression section (note that a recycle is nec-
essary) or in the distillation process. The high yields and low recycle
ratios allow attaining a productivity of about 1200/1400 t/d.
Lurgi also proposes a two-stage converter system (Fig. 11) that
is able to guarantee high production capacities. This unit is simply
the combination of two Lurgi methanol converters. The first oper-
ates at higher space velocities and temperatures than a single-
stage converter, thus achieving only partial conversion of syngas to
methanol. Therefore, it is also smaller than a single converter and
allows producing high-pressure steam because of the higher tem-
peratures enforced. The gas coming out of the first converter is fed
to a second reactor. Here it flows in the shell side in countercurrent
with the cold fresh gas flowing inside the tubes. In this way, the
driving force for the reaction is preserved and the heat recovery allows
reducing production costs. For a capacity up to 3000 t/d, the two
stages can be also included in a single vessel while larger capaci-
ties are more efficiently achieved by using two separate converters.
Mitsubishi Gas Chemical (MGC) and Mitsubishi Heavy Industry
(MHI) developed an isothermal reactor named MGC/MHI
Superconverter [35]. It possesses double-walled tubes and the catalyst
is loaded in the space between the outer and inner tubes (Fig. 12).
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Fig. 12. Mitsubishi Superconverter [36].
The gas is fed at the bottom of the vessel through flexible tubes
and flows upward inside the inner shell of those tubes. Once the
end of such tubes is reached, it turns downward and flows into the
annular space where the catalyst is loaded. The cooling water flows
outside the tubes. The mixture of methanol and unreacted syngas
comes out of the bottom of the vessel.
The temperature profile in the catalyst bed decreases from the
inlet section to the outlet section because of the heat exchange with
the fresh gas. This solution insures high conversion per pass (about
14% methanol is produced) because it allows maximizing the reaction
rate. This reactor configuration also allows safe operation and pos-
sesses high mechanical stability [37].
Fig. 13. Isothermal methanol converter (courtesy of Casale SA).
81
The first commercial scale plant (520 t/d) using the Mitsubishi con-
verter is located in Niigata (Japan) and has demonstrated to be
successful. A new plant, associated with higher production capacity
(2500 t/d) is under construction in Saudi Arabia. Projects for facilities
with capacities of 5000–10,000 t/d are currently under investigation.
Casale SA developed an Isothermal Methanol Converter (IMC)
in which the heat exchange surface is made of plates surrounded
by the catalyst (Fig. 13). A cooling fluid, which can be fresh syngas,
water or some other liquid, flows inside the plates. The size of the
converter has potentially no limit and its construction is simple
because it implies manufacturing a conventional vessel including
the catalyst bed and the plates. A tight control of the temperature
profile inside the mass of catalyst is achieved. This allows the con-
verter to track the optimal reaction rate locus. The reactor can be
designed with a mixed axial–radial flow configuration. The size and
number of pieces of equipment and pipes are minimized and the
energy consumption and size of the front end are optimized as well.
Handling the loading/unloading of the catalyst is easy and thanks
to the good temperature control, the average life of the catalyst lasts
longer. The catalyst temperature is controlled by changing the satu-
rated steam pressure according to the process requirements. The
heat of reaction is entirely recovered to produce steam. In the axial–
radial configuration, the gas only crosses one catalyst bed and
experiences a pressure drop smaller than one bar. The recycle ratio
can be adjusted to minimize syngas consumption independently of
the level of activity of the catalyst.
Davy Process Technology is currently licensing different and pe-
culiar technologies for methanol synthesis (to some extent, the Casale
Group is following the same business strategy). An Axial Steam-
Raising Converter (A-SRC) employs a simple shell-and-tube design
with axial counter-current flow. Compressed syngas enters the A-SRC
and moves downward inside a number of catalyst-filled tubes. Water
from the steam drum enters the base of the vessel, vaporizes upon
absorbing the heat of reaction and keeps the temperature under control
(Fig. 14a). An alternative configuration is the radial steam-raising
82 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

Fig. 14. Davy Process Technology’s converters [38].

(R-SRC) converter (Fig. 14b), where syngas moves radially across a
fixed catalyst bed on the shell-side of a reactor. As the syngas exo-
thermically reacts to form methanol, tube-side water absorbs the heat
of reaction and generates to steam. JM Davy’s R-SRCs are particular-
ly useful for large-capacity methanol production processes. Finally,
the Tube-Cooled Converter (TCC) uses its feed stream to cool down
the catalyst bed in which the methanol synthesis reaction takes place
(Fig. 14c). The syngas moves down through the catalyst bed, thus trans-
ferring heat to the fresh feed flowing up inside the tubes.
by designing larger-scale facilities for methanol production thanks
to novel technologies. A fluidized bed converter was developed
where 50–60 μm catalyst particles are fluidized by the fresh gas fed
at the bottom. The temperature is controlled by using cooling pipes
that allow to recover the heat of reaction at high pressure. The pos-
sibility of easily replacing the catalyst in operation allows constant
and stable operating conditions.
2.2. Liquid phase technologies

2.1.3. Gas phase fluidized bed converter Liquid phase processes for producing methanol might repre-
In 1993 the New Energy and Industrial Technology Develop- sent the future of methanol industry because they allow efficiently
ment Organization (NEDO) and the Petroleum Endowment Center removing the heat of reaction and enforcing tight temperature
(PEC) in Japan started a project aimed at lowering production costs control. Methanol synthesis technologies using three phase
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
(gas–solid–liquid) systems have also been proposed. In particular,
notice that gas-phase fixed-bed reactors (GPFBR) cannot be the
system of choice when the feedstock is coal-derived synthesis gas
because its low H/C ratio promotes coking phenomena [39]. To over-
come the problem, trickle bed reactors (TBR) and slurry converters
have been proposed. In particular, TBRs combine the advantages of
both slurry and fixed bed reactors and appear to be more effi-
cient. In TBRs the catalyst is still laid out in a fixed bed fashion but
a co-current gas–liquid stream flows though the bed. This type of
reactor insures higher heat removal efficiency than fixed bed re-
actors and direct use of coal-derived synthesis gas is possible.
Moreover, high gas space velocity can be reached. In slurry and TBR
reactors, methanol is absorbed by the liquid phase and removed from
the reaction system, thus allowing higher conversions due to the
mass action law. Therefore, the entity of the recycle is reduced with
respect to conventional fixed bed reactors. In particular, a gas phase
process typically requires a recycle ratio of 5:1 while a liquid phase
process operates with recycle ratios of 1:1 to 2:1.
Unfortunately, trickle bed and slurry reactors have not been used
for methanol production so far because of both modeling and scale-
up issues. In fact, a priori scale-up of trickle bed and slurry reactors
from lab-scale units and data is not possible. Therefore, these tech-
nologies are still under investigation.
Just to provide a few examples, Air Products developed a slurry
liquid phase technology (LPMEOH™) [40]. The fine catalyst par-
ticles were suspended in inert mineral oil (Fig. 15). This technology
allows better temperature control and faster mass transfer as well
as lower operating and capital costs compared to traditional tubular
fixed-bed reactors. The heat and mass transfer is very efficient and
the catalyst can be easily replaced. In 1997 this technology was
adopted in a commercial methanol facility at the Eastman Chem-
ical’s coal gasification complex (Kingsport, Tennessee, USA) and
demonstrated to be able to produce methanol at a rate of 300,000
l/d. The process can operate in continuous fashion or discontinu-
ously. An internal heat exchanger allows heat transfer from the
mineral oil and enforces the temperature control. A higher conver-
sion rate is achieved and the recycle is significantly reduced.
Brookhaven National Laboratory (BNL) in NY (USA) developed a
methanol synthesis process (via the methyl formate reaction pathway)
operating at lower pressures (<5 MPa) and low temperatures. The
Fig. 15. LPMEOH slurry reactor (Air Products).
83
process, operated in liquid phase, claimed to be able to achieve con-
versions over 90%, thus avoiding to recycle the unreacted synthesis
gas. AMOCO [41], since 1995, tried to develop a process operating
at low pressure and temperature. In 1998, a mini-pilot unit (50 ml
pressured vessel) was built at AMOCO Naperville R&D Center but
problems were encountered. In particular, the system provided in-
sufficient recovery of low-quality heat but also required additional
capital costs for the catalyst containment and the size of the reactor,
which seemed to be larger compared to fixed bed units due to the
lower achievable reaction rate. Nowadays no industrial application
of this technology is known.
Catalytica Advanced Technologies, USA, declared to have found
a catalyst capable of converting methane directly into methanol [42].
They proposed a liquid phase oxidative process that uses mercury(II)
compounds and concentrated sulfuric acid. The letter acts as the
oxidant while mercury is the catalyst. Methane could be con-
verted to methanol with 50% yield and 85% selectivity. However,
mercury and sulfuric acid are not environmentally friendly and sub-
sequent efforts were devoted to investigating a stable, active and
selective platinum complex ((2,2,-bipyridimine)PtCl2) for the oxi-
dation of methane to methyl esters. The new process yielded
conversions to methyl bisulfate up to 72%. Methyl-bisulfate, must
be subsequently hydrolyzed to sulfuric acid and methanol.
A co-current slurry phase process, operating at lower tempera-
tures (100–200 °C), was finally proposed by Pittsburgh University.
In this process, two methanol molecules are synthesized via the
hydrogenolysis of methyl formate, which originates from the
carbonylation of one methanol molecule. The global process is equiv-
alent to the reaction of H2 and CO to give methanol. Conversions
up to 90% and selectivity up to 98% were achieved. However, methyl
formate was the limiting reactant at the adopted operating condi-
tions (170 °C – 50 bar) and this is the reason why the process was
never scale up.
As a final consideration, liquid phase technologies show higher
catalyst deactivation rates with respect to gas phase processes
[43,44]. Other than sintering of copper crystallites, further deacti-
vation phenomena may occur. For example, carbon formation and
subsequent coking of the catalyst might happen either by the
Boudouard reaction (Lee, p. 27 [44]) or via the decomposition of the
hydrocarbon oil used to suspend the catalyst. Alumina leaching may
be also important (Lee, p. 175 [44]). Finally, the catalyst deactiva-
tion can be triggered by carbonyl compounds (such as Fe(CO)5 and
Ni(CO)4), which attack and block active sites. COS was also found
to be a poisoning agent.
2.3. Membrane reactors
Membrane reactors have been proposed as valid alternative to
conventional technologies because they allow removing the prod-
ucts (methanol and water) from the reaction environment [45]. The
integration of reaction and separation allows to improve the process
yield and to reduce the capital investment. One method to in-
crease the process conversion is to remove water, which is a reaction
product, with a water-permselective membrane. This can take the
reaction to completion at lower temperature and pressure. Sea and
Lee produced methanol from CO2 and H2 using a membrane reactor
where the membrane was based on a silica/alumina composite and
was able to selectively remove water. They improved the metha-
nol yield up to 150% compared to conventional reactors [46]. Gallucci
et al. [47] demonstrated that the selectivity and yield to methanol
can be improved by adopting a membrane reactor. Iliuta et al. in-
vestigated how to use a composite membrane to remove water vapor
from a mixture of CH3OH, H2, CO, CO2 and DME during single step
DME synthesis [48]. Membrane reactors, other than increasing the
methanol production capacity, allow to decrease the catalyst de-
activation rate and to achieve better product quality with consequent
84 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

decrease in process costs. Currently, no industrial scale applica- CuO ranges between 20% and 80%, ZnO ranges between 15% and
tion of this type of technology is known. 50% and Al2O3 ranges from 4% to 30%. Additives, for instance MgO,
can also be present.
2.4. One-step technologies Magnesia (MgO) is a promoter and acts as catalyst stabilizer. It
was firstly adopted in the catalyst series Katalco (formerly ICI), par-
As discussed above, methanol can be produced with different tech- ticularly in Katalco 51-7. Later on, it has been incorporated in
nologies mainly based on two stage fixed-bed tubular reactors [49], subsequent variants named Katalco 51-8 and Katalco 51-9. It insures
even though other routes seem to be feasible [50]. According to the higher and more stable catalytic activity, thus allowing operation
final production target, methanol synthesis can be coupled with other at lower temperatures and favoring the reaction thermodynamics
syntheses such as the production of formaldehyde [51], dimethyl and the carbon efficiency of the process. It also helps to slow down
ether [52], acetic acid [53] or olefins [54]. These latter compounds thermal sintering and is beneficial to the catalyst selectivity. Now-
are usually manufactured by means of a series of processes [55] adays, catalyst selectivity is over 99% [60,61].
although more and more frequently the so-called “one-step” tech- Most authors believe that metallic copper is the main active com-
nologies are gaining importance. Such technologies rely on new ponent [62,63], while ZnO acts as a supporter and Al2O3 is a promoter.
catalysts as well as catalyst blends capable of favoring the simul- ZnO is also supposed to enhance the dispersion of copper par-
taneous (in a single reactor) synthesis of methanol and one or more ticles and stabilizes the copper crystals. However, it is disputed
of its derivatives. The main benefit is the possibility of shifting the whether the active site is Cu dissolved in ZnO [64] or metallic copper
equilibrium of the methanol synthesis reaction toward the prod- dispersed on the ZnO surface [65,66]. The catalyst activity has been
ucts due to the in situ consumption of methanol itself. The typical shown to correlate quasi-linearly with the exposed area of metal-
case is the co-production of methanol and dimethyl ether, which lic copper [65,66]. This statement is also supported by in situ X-ray
initially was considered only as a by-product of methanol synthe- photoelectron spectroscopy [67] and surface X-ray diffraction studies
sis. Nowadays, it is an interesting compound when the syngas [68]. However, Fujitani and Nakamura [69] showed conflicting results.
feedstock originates from renewable resources (e.g. biomass) [11]. By means of surface science techniques, they found that ZnO forms
Dimethyl ether (DME) is a good alternative to diesel fuel because it the active site other than dispersing Cu particles. Also, Ostrovskii
has a high cetane number, produces smoke-free combustion thanks [70] reported on ZnO being an active site for methanol synthesis.
to its high oxygen content and quickly vaporizes in the engine because The methanol synthesis reaction is an example of a structure in-
of its low boiling point. Traditionally it is produced starting from sensitive catalytic reaction, in which the activity is wholly dependent
methanol in a dehydration reactor [56]: on the total exposed copper area and not affected by the structure
of the crystallites. Variations in the CuO:Al2O3 ratio have a remark-
2CH 3OH ↔ CH 3OCH 3 + H 2O (28) able effect on the relative activity, as shown in accelerated life tests
[71].
Whenever a bifunctional catalyst is available that includes CuO/
ZnO/Al 2 O 3 for methanol synthesis and γ-Al 2 O 3 for methanol 4. Reactor modeling
dehydration, reaction (28) takes places together with the metha-
nol synthesis and water gas shift in the same reaction environment As mentioned in Section 2, the most common technology for pro-
(the same reactor). Reaction (28) is limited by the thermodynamic ducing methanol is the Packed-Bed Reactor (PBR) or, more
equilibrium, but this limitation is not a significant drawback as it specifically, the shell-and-tube boiler-reactor, which was separate-
was for the methanol synthesis reaction. Finally, this DME synthe- ly proposed by different industrial players. PBRs or fixed-bed reactors
sis reaction is exothermic, occurs without change in the number of are commonly used in the chemical industry [72,73]. In the case
moles and is not affected by pressure. It is favored at low temperatures. of methanol and of most processes based on strongly exothermic
reactions, reactors are designed for efficient cooling [3] and are often
3. The catalyst tubular and carry solid catalyst particles on a single side (usually
the tube side). The chemical reactions involved in the chemical
Since the CuO/ZnO/Al2O3 catalyst is the most commonly adopted process take place on the catalyst active surface. PBRs are usually
in industry [57], that is the only catalyst we are going to analyze. the equipment of choice for two principal reasons: they take to
Its composition can vary depending on the manufacturer as dis- higher conversions per weight of catalyst compared to other con-
played in Table 1. verters and they insure efficient heat removal. The observed
conversion depends on the amount of catalyst rather than on the
reactor volume. The reactor modeling requires the characteriza-
Table 1 tion of the process kinetics, of the transport phenomena occurring
Examples of compositions of the catalysts from different manufacturers. inside and around the catalyst, of the catalyst deactivation mecha-
Manufacturer Cu wt% Zn wt% Al wt% Other Ref. nisms and, eventually, the resolution of the mass and energy
IFP 45–70 15–35 4–20 Zr-2-18 [58] balances. Therefore, all of these aspects will be addressed in the next
Synetix (formerly ICI) 20–35 15–50 4–20 Mg [58] chapters. Then, steady state and dynamic models will be analyzed.
BASF 38.5 48.8 12.9 Rare Earth [58]
oxide -5 4.1. Kinetics
Shell 71 24 12 [58]
Süd Chemie 65 22 31 [58]
Dupont 50 19 17 [58] Kinetic modeling is fundamental for the design and optimiza-
United Catalysts 62 21 17 [58] tion of chemical reactors. A detailed knowledge of the reaction
Haldor Topsoe MK-121 >55 21–25 8–10 [58] mechanism leads to a better description of the process, thus al-
Mitsubishi Gas Chemical 63.6 33.4 3 [59]
lowing to optimize it and ensure larger profits. The reaction kinetics
Company
Ammonia Casale 30 50 3 Cr (16) [59]
and the mechanism involved in the production of methanol are still
Lonza 40 20 Zr (40) [59] open issues. Many kinetic studies have been published, but they differ
AIST, RITE 45.2 27.1 4.5 Zr (22.6) [59] in terms of feed gas composition and operating conditions, thus
Si (0.6) conclusions concerning the kinetics and the mechanisms cannot be
YYK Corporation 76.3 11 12.7 [59]
drawn yet. Later on, we will focus on the kinetics of the methanol
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105 85

Table 2 The kinetic modeling of methanol synthesis via CO/CO2/H2 mix-

Methanol carbon source. tures has been widely studied since the first works of Natta [99]
Authors Carbon source and Bakemeier et al. [100], which were related to the high pres-
Leonov et al., 1970-1973 [74] CO sure process (taking place in presence of ZnO/Cr2O3 catalysts). Natta’s
Rozovskii et al., 1975-1977 [75,76] CO2 expression did not account for the presence of CO2 in the feed, while
Schermuly and Luft, 1977 [77] CO Bakemaier et al. rate equation accounts for the presence of CO2, but
Denise and Sneeden, 1982 [78] CO+CO2 not as a reactant.
Klier et al., 1982 [57] CO+CO2
Monnier et al, 1984 [79] CO
Leonov et al. [74] were the first to face the challenging problem
Bardet et al., 1984 [80] CO+CO2 of modeling the low-pressure methanol synthesis on Cu/ZnO/
Chincen et al., 1984 [81] CO2 Al2O3 catalysts, which is that currently adopted in industry. In their
Villa et al., 1985 [82] CO work, CO is considered as the only source of carbon from which
Liu et al., 1985 [83] CO+CO2
methanol is generated. They did not take into account the pres-
Seyfert and Luft, 1985 [84] CO
Dybkjaer, 1985 [85] CO2 ence of CO2 in the feed. In a series of papers, Rozovskii and co-
Takagawa and Ohsugi, 1987 [86] CO workers [75,76] proposed the conversion of CO to CO2 via the WGS
Chincen et al., 1987 [65] CO+CO2 reaction and the production of methanol via the hydrogenation of
Graaf et al., 1988 [87] CO+CO2 CO2. In fact, CO2 hydrogenation is faster than CO hydrogenation at
Shack et al., 1989 [88] CO+CO2
McNeil et al., 1989 [89] CO+CO2
lower temperature and pressure. This might explain why Rozovskii
Skrzypek et al., 1991 [90] CO2 et al. [76] found a large production of methanol from CO2, when op-
Askgaard et al., 1995 [91] CO2 erating at 495 K, while other researchers observed that the
Vanden Bussche and Froment, 1996 [92] CO2 hydrogenation of CO is faster under typical lab synthesis condi-
Kubota et al., 2001 [93] CO2
tions, i.e. 5–10 MPa and 500–575 K. In 1980, Andrew proposed a
Setinc and Levec, 2001 [94] CO2
Rozovskii and Lin, 2003 [95] CO+CO2 power law that included a function of the CO2 concentration and
Lim et al., 2009 [96] CO+CO2 accounted for the observation of a maximum in the carbon con-
Grabow and Mavrikakis, 2011 [97] CO+CO2 version to methanol in presence of CO2. After the first correlative
Park et al., 2014 [98] CO+CO2 approaches, subsequent efforts were aimed at developing kinetic
models allowing extrapolation outside the operating conditions of
the experimental window. Gradually the importance of CO2 was rec-
ognized and experimental data was collected by varying the CO/
CO2 ratio confirmed the presence of a maximum in the conversion
production process for the only Cu/ZnO catalyst, which is the com- rate at fixed total pressure and hydrogen concentration [57]. Vedage
monest in industrial setups. It is generally accepted that methanol et al. [101] used D2O instead of H2O to demonstrate a similar effect
is predominantly produced via the hydrogenation of carbon dioxide, connected to the presence of H2O. Klier et al. [57] showed that meth-
at least at the typical operating conditions of industrial processes. anol was first produced by the interaction of CO and H2 adsorbed
However, the role of CO2 and H2O in the methanol synthesis as well on the catalyst. They postulated the presence of two states for the
as the nature and number of the active sites and the chemical state catalyst active sites: oxidized (Sox) and reduced (Sred). They sug-
of copper are still debated. Table 2 summarizes the hypotheses on gested that the oxidized state was the active one and existed thanks
the origin of methanol proposed by different authors over the course to the CO2: CO2+Sred = CO+ Sox. Therefore, CO2 was only a promoter
of almost forty-five years. in their model. A competitive adsorption of CO2 and CO or H2 on
Even after forty-five years, there is still disagreement in the lit- the catalyst active sites was also postulated. The main limitation
erature about the most reliable kinetic pathway. However, the of the model of Klier et al. is that their rate expressions equal zero
mechanism involving both CO and CO2 hydrogenations seems to be when no CO2 is present in the feed while experiments show that
the most likely. In addition, Graaf et al. [87] pointed out that not- methanol is still produced [102–104]. Herman et al. [105] and Liu
withstanding the doubt whether methanol derives from CO or CO2, et al. [83] observed that the presence of an oxidizing agent, such
it is useful to include both hydrogenation reactions inside any kinetic as CO2 or water, is necessary to avoid partial deactivation of the CuO/
scheme together with the WGS reaction. In fact, thanks to the WGS ZnO catalyst. Moreover, Herman postulated a dual site mechanism
reaction, CO and CO2 interconvert rapidly such that the three re- in which ZnO is a good hydrogenation catalyst activating H2 but CO
actions reported below are dependent on one another. is scarcely adsorbed on it while univalent Cu adsorbs CO but not
As already reported, the macro kinetics of the methanol syn- H2. Liu et al. [83] did not find a maximum in the reaction rate as a
thesis is described by the following reactions: function of the CO2 content but found that the reaction rate itself
decreased for increasing content of CO2. The increase in the CO2 con-
CO + 2H 2 ↔ CH 3OH (ΔH = −91 kJ mol ) (29)
centration was accompanied by an increase in water production.
In fact, CO2 prevents the reduction of some catalyst active sites, thus
CO2 + 3H 2 ↔ CH 3OH + H 2O (ΔH = −49.5 kJ mol ) (30)
increasing the catalytic activity. However, an excess of CO2 in-
creases the water content and water strongly adsorbs on the active
and the water gas shift reaction:
sites, thus too much CO2 takes to reducing methanol production rates.
CO + H 2O ↔ CO2 + H 2 (ΔH = −28.6 kJ mol ) (31) Herman et al. [105] also explained the observed deactivation claim-
ing that, in presence of a strongly reducing environment, Cu1+ sites
Microkinetic models including adsorbed intermediates and up dispersed in ZnO (where carbon monoxide hydrogenation occurs)
to about 50 reactions have also been proposed. Most authors assume underwent agglomeration and formed large crystallites that reduce
Langmuir–Hinshelwood or Eley–Rideal mechanisms and consider the active surface.
one or more of the steps to be rate determining steps (RDS). For the Mochalin et al. [106] and Malinovskaya et al. [107] investi-
first type of mechanism, the product derives from the interaction gated different models of some Russian research groups and finally
of two adsorbed atoms or species while, for the second, the product reported a kinetic model but they did not mention the numerical
is generated by interaction between one adsorbed atom or species values of the parameters. Bardet et al. [80] found that even small
and another atom/species (not adsorbed on the catalytic surface) quantities of water can accelerate methanol production when CO/
bumping into the first one. H2 feed mixtures are adopted while this effect is not present when
86 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
CO/CO2/H2 mixtures are used. Dybkjaer [85] suggested a rate ex-
pression based on a dual-site Langmuir–Hinshelwood mechanism:
H2 is adsorbed, dissociated and reacts with the adsorbed CO2. In this
model H2 and H2O compete for one specific active site, while CO
and CO2 adsorb on a second, different active site.
In 1985 and after a detailed study, Liu et al. [83] proposed that
the hydrogenation of CO2 is the main source of methanol in absence
of water, at low temperature and at low conversion. However, in
presence of water and at high temperature and conversion, meth-
anol is mainly produced from CO hydrogenation. Villa et al. [82]
considered CO as the only source of methanol and included the water
gas shift reaction in their kinetic scheme, thus recognizing its im-
portance in the overall reaction mechanism. In 1987, Kuczynski et al.
[104] used Villa’s expression for fitting experimental data related
to low pressure synthesis from CO and H2 (CO mole fraction from
0.1 to 0.54, 3–9 MPa, 483–545 K).
Takagawa and Ohsugi [86] performed experiments with CO/H2,
CO 2 /H 2 and CO/CO 2 /H 2 mixtures at 4–10 MPa and 483–573 K.
However, some carbon dioxide was present in the experiments with
CO/H2. In contrast to the results of Klier et al. [57], they did not find
any optimum CO2/CO ratio. They were not able to demonstrate the
promoting effect of CO2 in the lower CO2/CO range but affirmed that
all the three reactions are fundamental in methanol synthesis.
However, they declared their results to be in line with those of Klier
et al. [57] and Liu et al. [83].
Chincen et al. [65] demonstrated CO2 to be the main reactant in
methanol synthesis by using 14C-labeled reactants.
Shack et al. [88] showed that CO2 inhibits CO hydrogenation but
not its own hydrogenation to methanol. These results suggest that
CO and CO2 hydrogenation occur on separate sites. Starting from
this evidence, separate sites for adsorption of CO and CO2 were
assumed. The experiments of Liu et al. [83], carried out with 18O
labeled carbon dioxide, supported this hypothesis. The identifica-
tion of the active sites involved in the methanol synthesis generated
controversies too. McNeil et al. [89] reported on all the hypoth-
eses presented in the literature about the possible (different) active
sites on which the CO and CO2 hydrogenation could take place. They
proposed a phenomenological model for methanol production in-
volving both the hydrogenation of CO and CO2 and including also
an inhibition effect of CO2 on CO hydrogenation. They also justi-
fied the presence of a maximum in methanol production as a
function of the ratio between CO and CO2 in the feed. Two differ-
ent sites were assumed for the adsorption of CO and CO2: Cu1+ for
CO and Cu0 for CO2. Hydrogen was assumed to adsorb on ZnO. The
inhibition effect of CO2 was explained with the absorption of CO2
itself on Cu1+ sites, which are the only ones active for CO hydroge-
nation. They proposed a rate expression for methanol production
based on 6 parameters fitted based on their experimental data. The
main difference of the proposed expression with respect to that of
Klier et al. [57], from which they started their study, is that the hy-
drogenation of CO2 is included and its inhibition effect on CO
hydrogenation is accounted for. Moreover, their rate expression
covers also the case in which CO2 in not present in the feed, where
it has been showed that methanol is still produced. The microkinetics
of the process is also proposed in their paper. They identify the
methoxy hydrogenation as Rate Determining Step (RDS) for meth-
anol production from CO, under the assumption that the methoxy
species is the Most Abundant Reaction Intermediate (MARI). On the
other hand, formate was considered as the MARI for methanol pro-
duction from CO2 and its hydrogenation was assumed the RDS for
this process.
Graaf et al. [87,108] suggested that CO/CO2 and H2/water could
adsorb on two different active sites. They proposed that methanol
could be generated via successive hydrogenation of CO and CO2 and
the WGS reaction followed a formate-based path. However, their
kinetic expressions do not take into account that some intermediates
show up in two different overall reactions. Therefore, the model si-
multaneously provides two different concentrations for some
intermediates like formyl and methoxy species. Notwithstanding
these limitations, the rate expressions of Graaf et al. are the most
commonly used in reactor modeling and fit well the experimental
data they generated with a spinning basket reactor at 210–245 °C
and 1.5–5 MPa. They demonstrated that methanol originates si-
multaneously from CO and CO2. Moreover, they compared their model
with those proposed by Seyfert and Luft [84], Villa et al. [82], Klier
et al. [57], and Dybkiaer [85] by fitting the parameters of such models
with their experimental data. Based on this analysis, they showed
their model reproduces more accurately the experimental data.
In 1991, Skrzypek et al. [90] proposed a reaction mechanism
based only on the hydrogenation of CO2 and on the water gas shift
reaction. In fact, they performed experiments with a CO and hy-
drogen feed at different concentrations and they did not find any
production of methanol. The same results were previously achieved
by Kagan et al. [109]. On the contrary, they observed that metha-
nol was generated with high selectivity when feeds containing only
CO2 and H2 were employed. Therefore, they assumed that the role
of CO was restricted to participating in the WGS reaction and re-
moving water from the reaction environment. Thus, CO was
supposed to have a beneficial effect on the synthesis reaction. They
proposed their own rate expressions that captured the trend of the
reaction rate (observed experimentally and including a maximum)
as a function of CO2 and hydrogen concentrations in the feed. Finally,
they used a deactivated catalyst to produce the pool of measure-
ments on which the model parameters were fitted. However, because
the effect of deactivation was not taken into account, the model pre-
dicts reaction rates that are too small.
Similar results were achieved by Millar et al. [110] and by Ras-
mussen et al. [63]. Millar et al. demonstrate that Cu is the active
site where the hydrogenation to methanol takes place when CO2/H2
feeds are used.
Askgaard et al. [91] proposed a kinetic model based on param-
eters evaluated by means of gas phase thermodynamics for the
chemisorption process. This is an extension to a previous model pre-
sented in 1992 by Ovesen [62,111]. This approach was necessary
to overcome the large pressure and temperature difference between
the operating conditions of lab reactors and industrial converters.
They also performed experiments with Cu single crystal and surface
studies. A mechanism involving 16 elementary steps was pro-
posed. Askgaard et al. accounted for the only hydrogenation of CO2
and water gas shift reaction. The RDS of the methanol synthesis was
identified as the formate hydrogenation to methoxide and oxide.
Their calculated rates showed good fitting to the experimental data,
upon adaptation to the actual process operating conditions. They
also identified that the methanol synthesis reaction undergoes self-
inhibition at temperatures lower than 500 K because stable and
abundant formate species block most of the available active sites.
The model of Askgaard et al. shows a systematic deviation from ex-
perimental data at small or large pCO/pCO2 ratio. Complex calculations
are necessary to evaluate the model parameters.
In 1996,Vanden Bussche and Froment proposed a mechanistic
model for methanol production based on a detailed reaction scheme
that assumes CO2 as the main carbon source [92]. Temperature, pres-
sure and gas phase composition effects are adequately accounted
for in their model. All the parameters included in their rate equa-
tions were evaluated by solving a fitting problem. Based on their
model, both hydrogen and carbon dioxide undergo dissociative ad-
sorption on copper active sites. Carbonate species are produced,
suddenly hydrogenated to bicarbonates and subsequently reduced
to Cu formate, methoxy species, formaldehyde, and, eventually, to
methanol. The RDS is the hydrogenation of formate. The mecha-
nistic nature of the model allows careful extrapolation outside of
the experimental conditions with regard to which the model
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
parameters are computed. This model accurately predicts the
maximum conversion rate at 2% CO2.
Ovesen et al. proposed a dynamic microkinetic model for meth-
anol synthesis based on surface measurements [112]. They started
from the model of Askgaard et al. [91] (a steady state model) and
applied the so-called Wulff construction to evaluate the surface and
interface free energies in order to clarify the changes in particle mor-
phology. The change in the number of active sites as a function of
the operating conditions is included in their model. They sug-
gested that the observed modification in particle morphology is
related to a modification in the number of oxygen vacancies at the
Zn–O–Cu interface. For their model, the number of active sites
depends on the conditions of the gas phase mixture in contact with
the catalytic surface. When larger CO/CO2 ratios are employed, the
number of available active sites increases on the (110) surface plane,
where methanol synthesis is faster. This type of model allows better
reproduction of the experimental data (taken from Graaf et al. [87])
with respect to static microkinetic models. Moreover, it gives better
explanation of the behavior of the system in transient conditions.
The system dynamics seems to justify the apparently conflicting re-
action orders reported in the literature. In fact, under dynamic
conditions, different reaction orders are deduced depending on the
oxidizing or reducing environment. Once again, metallic Cu appears
to be the active phase in the methanol synthesis. However, the in-
teraction with ZnO is crucial in promoting the uniform dispersion
of the Cu particles on the support. Ovesen’s model is more consis-
tent with experimental data than Askgaard’s model is.
Kubota et al. [93] proposed another kinetic model where CO2 was
the principal responsible for methanol generation. They found their
equations to be reasonably in accordance with experimental data
coming from a test plant. Setinc and Levec [94] proposed a kinetic
scheme for the methanol synthesis in liquid phase where the meth-
anol yield is proportional to both CO2 and CO concentrations.
Rozovskii and Lin [95] tested their kinetic models on two dif-
ferent gas phase compositions, where one was rich in CO2 and the
other was rich in CO. They found their scheme to be accurate when
applied to a CO2 rich mixture but not in the other case.
Lim et al. [96] proposed a kinetic model based on the analysis
of 48 elementary reactions, which takes into account the most likely
rate determining steps (RDS). They found that the surface reac-
tion of methoxy species is the RDS for CO hydrogenation while the
hydrogenation of a formate intermediate is the RDS for the water
gas-shift reaction. They claimed to have explained the effect of CO2
on the process for methanol production for the first time and added
the reaction of synthesis of DME to their scheme. This was neces-
sary to justify the negative values of CO2 conversion that came up
in their experiments. Based on their analyses, the existence of CO2
in the reactor feed increases the methanol yield. In fact, a small
amount of CO2 reduces the average rate of the WGS reaction, thus
the increasing content of water inhibits the production of DME.
Therefore, as they proposed in a subsequent paper [113], the pro-
duction of methanol can be optimized by selecting the proper feed
composition. Because they used a Cu/ZnO/Al2O3/Zr2O3 catalyst, it
would be interesting to repeat the same studies with a Cu/ZnO/
Al2O3 catalyst.
Grabow and Mavrikakis [114] developed an extended
microkinetic model. They confirmed methanol to be produced by
both from CO and CO2 hydrogenation and argued that CO2 is the
source of 2/3 of the produced methanol at industrial operating con-
ditions. They derived model parameters by using Density Functional
Theory (DFT) calculations performed on the Cu(111) surface. Sub-
sequently, they fitted the same parameters to published experimental
data measured at industrial operating conditions [87]. They con-
cluded that a more exposed plain like Cu(100), Cu(110) or Cu (210)
can offer a better model surface for studying the active sites in-
volved in the methanol synthesis. Ovesen et al. [112] found a larger
87
fraction of Cu(110) facet under reducing environment, which is in
contradiction with what was suggested by Hansen et al. [115]. TEM
in combination with a MicroElectroMechanical System (MEMS) will
enable atomic resolution microscopy at ambient pressure and pos-
sibly clarify which type of surface is active at the usual synthesis
conditions employed in industry. Grabow and Mavrikakis mainly
addressed CO2 hydrogenation as a mean for CO2 fixation but they
also included several other CO and CO2 hydrogenation pathways,
the WGS reaction and the reactions of formation of some byproducts
and intermediates, such as formic acid (HCOOH) and formalde-
hyde (CH2O). No assumption on RDS was adopted to calculate the
model parameters, which came from DFT. The proposed model ac-
counts for 49 elementary steps is a mean-field microkinetic model.
This is justified because adsorbed spices are well-mixed and dis-
tributed on the catalyst surface and diffusion limitations are reduced
at those temperatures at which the methanol synthesis takes place.
In this paper, an accurate description of the elementary steps is given
and the model parameters are fitted to the experimental data of Graaf
et al. [87]. The sensitivity of the catalytic activity to the WGS rate
for CO/CO2/H2 mixtures is small but larger WGS rates consume CO
and reduce the adsorption of CO2. The beneficial effect of CO is found
to be related to the removal of OH*/H2O* (* indicates adsorbed
species) via the WGS reaction, thus shifting the CO2 hydrogena-
tion toward the production of methanol. Simulations with different
feed compositions show that the carbon source, from which meth-
anol originates, depends on the operating conditions and a general
rule does not exist. Finally, the model of Grabow et al. shows some
discrepancies with regard to the data of Graaf et al. for CO-rich feeds,
even though those data were extrapolated out of the experimen-
tal range. This can be related to the structural changes in the catalyst
under reducing environment.
Peter et al. [116] compared three different kinetic models: two
global kinetic models and a microkinetic model. The first two are
a power low kinetics and a semi-empirical Langmuir–Hinshelwood–
Hougen–Watson model taken from Vanden Bussche and Froment
[92]. The microkinetic model is that of Ovesen et al. [112]. All the
models have demonstrated to be accurate in fitting experimental
data. The global models describe more accurately the kinetics at the
adopted experimental conditions and are more useful for reactor
modeling. On the other hand, the microkinetic model takes into
account the changes in the catalyst morphology, which can be crucial
in methanol synthesis and are still under investigation. The model
requires further improvements, i.e. high pressure in situ studies to
enlighten the synergistic effects of ZnO and Cu, which at present
are not included in Ovesen’s model.
Park et al. [98,117] extended the work of Lim et al. [96,118] and
presented a kinetic model based on a three-site adsorption (Cu+1,
Cu0 and ZnO) where they also assumed the typical RDSs of com-
mercial catalysts. The kinetic parameters were computed by fitting
the rate equations to 188 experimental sets of data collected at dif-
ferent operating conditions. They argued that when both CO and
CO2 hydrogenation occurs, CO conversion is affected by tempera-
ture, pressure and space velocity changes while CO2 conversion in
only marginally influenced by these factors, thanks to the WSG re-
action. Moreover, conversion is deeply influenced by the CO–
hydrogen ratio. The contribution of each reaction shows to be related
to the content of CO as well as the maximum methanol concen-
tration. In particular, the maximum methanol production can be
attained by optimal selection of the temperature and the CO frac-
tion. Increases in space velocity have negative effects while an
increase in pressure, which is related to higher reactants concen-
tration, proves to be beneficial. Moreover, studies with different
particle sizes were performed in order to identify the importance
of internal diffusion limitations. The presented model shows a dual
contribution of CO and CO2 to the production of methanol. If coupled
with a model for evaluating the effectiveness factor, this set of rate
88 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
equations allows modeling and designing large-scale reactors quite
easily.
The rate equations of all of the presented kinetic models are sum-
marized in Table 3 along with the experimental conditions under
which such models were derived/validated.
Given the reported analysis, both CO and CO2 seem to be in-
volved in the synthesis of methanol. It could be interesting to
compare the behavior of the different proposed kinetic models when
applied to a real reactor model. In fact, the Graaf et al. and Vanden
Bussche and Froment rate equations are the only ones extensively
used in reactor modeling. The problem of the kinetic model of Graaf
et al. is that in their complex reaction mechanism, based on 48 re-
actions, different intermediate species are present in two different
reaction pathways. The result is that two different concentrations
of the same product are predicted. Thus, the mechanism pro-
posed by Vanden Bussche and Froment seems to be more convincing.
4.2. Transport phenomena around and inside the catalyst
The mass transport limitations inside the catalyst are signifi-
cant especially for the low-pressure methanol synthesis and when
the CuO/ZnO/Al2O3 catalyst is used. For 4.2 mm catalyst pellets, which
is the size usually adopted, Seyfert and Luft [84] reported an ef-
fectiveness factor of 75% at 538 K and 80 bar. Graaf et al. [108]
evaluated effectiveness factors ranging from 32% to 92% depend-
ing on the temperature and on the component and observed a
reduction in the effectiveness factor for increasing temperature.
The problem of intra-particle diffusion inside the catalyst used
in the production of methanol has been tackled in several contri-
butions [84,108,119–122]. The pellets are usually supposed to have
an isotropic pore size distribution as well as an isotropic distribu-
tion of tortuosity, porosity, and thus conductivity. Lommerts et al.
[119] investigated the different diffusion models proposed for the
evaluation of the catalyst efficiency. They analyzed five principal
approaches:
1. The dusty-gas model [123,124];
2. The modified or extended Stefan–Maxwell equations [125–127];
3. The classic multi-component pore diffusion (constant diffusion
coefficients) combined with convective mass transport;
4. The classic multi-component pore diffusion model (constant dif-
fusion coefficients);
5. A model based on Thiele modulus and “first-order” kinetics for
CH3OH and H2O production.
Models 1 and 2 implicitly account for convective mass trans-
port while the others take into account it explicitly. Models 1, 3, 4
and 5 allow for Knudsen diffusion. By analyzing the predictions of
these models via comparison to experimental data by Seyfert and
Luft [84], one can notice that convective mass transport, due to the
consumption of gas phase reactants during the methanol synthe-
sis, is negligible compared to mass diffusion. The same conclusions
apply to pressure and temperature gradients inside the particle. In
addition, Lommerts et al. [119] concluded that it is acceptable to
apply the simplest concept of Thiele modulus to account for intra-
phase diffusion and surface reaction phenomena. In fact, such simple
model is more easily incorporated into methanol reactor models and
less consuming in terms of computational time. Moreover, by com-
paring such simple model to more complex ones, such as the dusty
or the Stefan–Maxwell models, we find acceptable deviations in the
values of both methanol and water effectiveness factors.
Jacobsen’s group deeply analyzed the flux models from the point
of view of both pellets and reactor modeling [120–122]. They studied
the intra-particle multicomponent diffusion by comparing Maxwell–
Stefan, Dusty gas, Wilke [128] and Wilke–Bosanquet [129] models.
The dusty model is an extension of the Maxwell–Stefan model
including Knudsen diffusion. The Wilke model uses the binary Fick’s
law substituting the binary diffusivity with multicomponent
diffusivity. It is a simplification of the Maxwell–Stefan equation in
the Fickian form. The Dusty gas model can be simplified by using
the Wilke–Bosanquet model. This latter comprises the Wilke model
and the Bosanquet formula (1944), which evaluates the diffusivity
as the reciprocal of the summation of the reciprocal of bulk and
Knudsen diffusion coefficients. Dusty gas and Wilke–Bonsanquet
models include Knudsen diffusion while Maxwell–Stefan and Wilke
models neglect it by considering only bulk diffusion. Knudsen dif-
fusion coefficients are related to the mean pore diameter of the
pellets and independent of pressure, whereas bulk diffusion is in-
dependent of the mean pore diameter and inversely proportional
to pressure. Knudsen diffusion prevails for Knudsen numbers (ratio
of the molecular mean free path and the pore diameter) over 10.
Usually commercial methanol plants are operated in such a way that
Knudsen diffusion is negligible as Knudsen number is below 1. Thus
we can disregard this phenomenon at the pellet level. In practice,
if the catalyst mean pore diameter exceeds 10 nm, Knudsen diffu-
sion has minor influence on diffusive mass transport [121]. However,
if it is significant, then a combined bulk and Knudsen diffusion model
should be adopted because this affects significantly the predicted
reactor conversions. The same authors [120,122] compared the mass
and mole based models in order to test the equations consistency.
For methanol synthesis, the deviations of the two approaches were
less than 4% [120]. Rout et al. [122] found a discrepancy of 2%
between mass and mole based models. They suggested that this dis-
crepancy might depend on a contradiction between the species
boundary condition and total continuity equation in the case of
molar-based models. They also showed that the two so-called rig-
orous models, dusty gas and Maxwell–Stefan, insure slightly better
agreement between mass and molar based pellet equations. Exist-
ing simulations [120–122], in agreement with Lommerts et al. [119],
also pointed out that pressure [130], temperature variations and
viscous flow within the catalyst particles are irrelevant and have
no effect on the reactor performance.
The use of parallel or random pore models is discussed by Rout
et al. [122]. The parallel pore model assumes that the catalyst par-
ticle has cylindrical pores with plane surface [131]. In the random
pore model, the pellet is disassembled and reassembled, thus forming
macro and micro structures [132]. Mass transport is supposed to
originate from a combination of diffusion fluxes through the micro
and macro regions. Rout et al. could get good agreement with ex-
perimental data by using the parallel model, thus this is the model
recommended for reactor simulations. They also suggested using
the Maxwell–Stefan model to simulate intra-particle diffusion but
Solvik and Jacobsen [120] concluded that Wilke and Wilke–
Bosanquet models are a good enough approximation for the
simulation of methanol synthesis reactors. This has to do with re-
ducing model complexity and computational time. Based on this
review, it is evident that no conclusions can be drawn on which
model is more accurate and reliable. However, the simpler model
based on Thiele modulus is commonly adopted for online
optimization/control/simulation purposes.
4.3. Catalyst deactivation
The effective average life of the CuO/ZnO/Al2O3 catalyst depend
on its stability over time, thus the formulation has to be designed
to stabilize the copper agglomerates on the catalytic surface at the
usual operating conditions of the process. Thermal sintering and
poisoning are the principal phenomena responsible for catalyst de-
activation. Poisons such as sulfur, sometimes iron and nickel
carbonyls can be introduced into the reactor with fresh syngas. Sulfur
content has to be as low as 5 ppm or even 1 ppm, if possible. Chlo-
ride impurities can promote catalyst sintering as well. Because the
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105 89

Table 3
Equations rates.

Operating conditions Equation rates Author, year Ref.

4–5.5 MPa ⎛ p0.5 pH 0.34

pCH ⎞ Leonov et al., 1973 [74]
493–533 K rCO→CH3OH = k ⎜ CO0.66
2
− 3OH
⎟
⎝ pCH3OH pCO 0.5
pH2 K *2 ⎠

2–8 MPa k ( fCO f H22 − fCH3OH K eq ) Schermuly and Luft, 1977 [77]
rCO→CH3OH =
483–538 K (1 + AfCO + Bf H2 + CfCH3OH + DfCO2 )2
7.5 MPa ⎛ 1 pCO ⎞
rCO→CH3OH = krCO→CH3OH ⎜ 1 + eq
−3
(
K CO K H2 2 pCO pH2 2 − pCH3OH K reqCO→CH3OH ) Klier at al., 1982 [57]
498–523 K ⎝ kredox pCO2 ⎟⎠ (1 + K CO pCO + K CO2 pCO2 + K H2 pH2 )
⎛ 1 pCH3OH pH2O ⎞
rCO2 →CH3OH = krCO2 →CH3OH ⎜ pCO2 − eq ⎟
⎝ K rCO2 →CH3OH pH3 2 ⎠

8–14 MPa k ( fCO f H2 − fCH OH K eq ) Seyfert and Luft, 1984 [84]

rCO→CH3OH = 2 3

503–538 K (1 + AfCO + BfH + CfCH OH + DfCO fH2

2 3 2
+ EfCO2 )
2

3–9.5 MPa fCH3OH Villa et al., 1985 [82]

fCO f H 2 −
488–518 K 2
K *2
rCO→CH3OH =
( A + BfCO + Cf H2 + GfCO2 )
3

f f − fCO f H2O K *3
rRWGS = CO2 H2
M2

N/A A1 A2 A30.5 [ fCO2 f H2 − fCH3OH f H2O ( fH2 K eq,CO )] Dybkjaer, 1985 [85]
rCO2 →CH3OH = 1 2

(1 + A2 fCO2 ) ⎡⎣1 + A30.3 f H02.5 + A4 f H2O ( A3 f H2 )0.5 ⎤⎦

A5 A2 A31 2 ( fCO2 f H122 − fCO f H2O f H122K eq,WGS )

rRWGS =
(1 + A2 fCO2 ) ⎡⎣1 + A31 2 f H02.5 + A4 f H2O ( A3 f H2 )1 2 ⎤⎦

0.3–1.5 MPa ⎛ p ⎞ Agny and Takoudis, 1985 [102]

rCO→CH3OH = k ( pCO pH0.25 )
−1.3
pCO pH2 2 − CH3OH ⎟
523–563 K ⎝⎜ K eq ⎠

4–9.5 MPa ⎡ ⎛ fCH3OH ⎞ ⎤

0.8
Takagawa and Ohsugi, 1987 [86]
rCO→CH3OH = k1 ( fCO f H22.5 )
0.35
488–574 K ⎢1 − ⎜ fCO f H22 ⎟ ⎥
⎢⎣ ⎝ K eq ⎠ ⎥⎦

3–9 MPa k ( fCO f H22 − fCH3OH K eq ) Kuczynski et al.,1987

rCO→CH3OH =
483–563 K (1 + K CO fCO + K H2 f H2 )3
1.5–5 MPa
rCO→CH3OH =
k1K CO ⎡⎣ fCO f H322 − fCH3OH ( fH1 2K 1eq )⎤⎦
2
Graaf et al., 1988 [87]
483–518 K (1 + K CO fCO + K CO2 fCO2 ) ⎡⎣ f H122 + ( K H2O kH1 22 ) f H2O ⎤⎦
k2K CO2 ⎡⎣ fCO2 f H2 − f H2O fCO K 2eq ⎤⎦
rRWGS =
(1 + K CO fCO + K CO 2 fCO2 ) ⎡⎣ f H122 + ( K H2O kH1 22 ) f H2O ⎤⎦

rCO2 →CH3OH =
k3K CO2 ⎡⎣ fCO2 f H322 − fCH3OH f H2O ( fH3 2K 3eq )⎤⎦
2

(1 + K CO fCO + K CO2 fCO2 ) ⎡⎣ f H122 + ( K H2O k1H22 ) f H2O ⎤⎦

2.89 MPa
rCO CO2 →CH3OH =
( pCO pH2 2 − pCH3OH K eq ) + McNeil et al., 1989 [89]
4.38 MPa apCO p1H.25 + bpH2 + cpCO2
513 K
( pCO2 pH2 − pCH3OH pH2O /(K eq 2
″ pH2 ))
+
a ′pCO2 pH0.25 + b′pCO
2
2
+ c ′p 3
H2O

3–9 MPa ⎡ p
pH2 2 pCO2 − rCOCH2 →3OH
pH2O ⎤ Skrzypek et al., 1991 [90]
460–550 K ⎢ K eq CH3OH pH2 ⎥
rCO2 →CH3OH = k1K H2 2 K CO2 ⎢ ⎥
⎢ (1 + K H2 pH2 + K CO2 pCO2 + K CH3OH pCH3OH + K H2O pH2O + K CO pCO ) ⎥
3

⎢⎣ ⎦⎥
⎡ pCO pH2O
pH2 pCO2 − rRWGS ⎤
⎢ K eq ⎥
rRWGS = k2K H2 K CO2 ⎢ ⎥
⎢ (1 + K H2 pH2 + K CO2 pCO2 + K CH3OH pCH3OH + K H2O pH2O + K CO pCO ) ⎥
2

⎢⎣ ⎥⎦

32
0.1–0.4 MPa ⎛p ⎞ ⎛ pCO2 ⎞ 2 Askgaard et al., 1995 [91]
r+ = k−11K 5−3 2K 8−1K 9 K 10 K 11 ⎜ H2 ⎟ θ*
483–563 K ⎝ po ⎠ ⎝⎜ p ⎠⎟o

1 pCH3OH pH2O 2
r− = k−11K 5−3 2K 8−1K 9 K 10 K 11 θ*
K G pH3 22 po1 2
rCO2 →CH3OH = r+ − r−

po is the thermodynamic reference pressure

1.5–5.1 MPa
453–553 K
k5′ a K 2′ K 3K 4 K H2 pCO2 pH2 ⎡⎢1 − 1
⎣ K* ( ) ⎛⎜⎝ p H2O pCH3OH ⎞⎤
pCO2 pH3 2 ⎟⎠ ⎦⎥
Vanden Bussche and Froment, 1996 [92]
rCO2 →CH3OH =
( ( )( ) K p + K p )
3
K pH2O
1 + H2O + H2 H2 H2O H2O
K 8 K 9 K H2 pH2

k′ p ⎡1 − K * (
p p )⎥⎦
p p ⎤ H2O CO
⎢⎣ 1 CO2 3
= CO2 H2

(1+ ( K K K )( p ) + K p + K p )
rRWGGS
K H2O p H2O
H2 H2 H2O H2O
8 9 H2 H2
(continued on next page)
90 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

Table 3 (continued)

Operating conditions Equation rates Author, year Ref.

4.9 MPa
473–548 K rCO2 →CH3OH =
kM { pCO2 pH2 − pCH3OH pH2O
[ K M p2H ]2
} Kubota et al., 2001 [93]

[1 + K CO 2
pCO2 + K H2O pH2O ]
2

rRWGS =
kR { pCO2 − pCO pH2O
[ K R pH2 ] }
[1 + K CO 2
pCO2 + K H2O pH2O ]

3.4–4.1 MPa ⎛ ECH3OH ⎞

⎜ − RT ⎠⎟ cCO2 (c H2 − c H2,eq ) Setinc and Levec, 2001 [94]
rCO2 →CH3OH = ACH3OH e⎝
473–513 K ⎛ ⎛ Ew ⎞
⎞
2
⎝⎜ RT ⎠⎟
⎜⎝ 1 + AW e c H2O ⎟
⎠
⎛ EH2O ⎞
⎜− ⎟ cCO2 − cCO2,eq
rH2O = AH2Oe⎝ RT ⎠
⎛ ⎛ Ew ⎞
⎜⎝ ⎟
RT ⎠
⎞
⎜⎝ 1 + AW e c H2O ⎟
⎠

5.2 MPa ⎛ pCH3OH pH2O ⎞ Rozovskii and Lin, 2003 [95]

k3 pH2 ⎜ 1 −
513 K ⎝ K p(CH3OH ) pH3 2 pCO2 ⎠⎟
rCO2 →CH3OH =
1 + K −2 pH2O + K −2 pH2O (K 1pCO2 )
where
ki and Ki are the corresponding rate constant and equilibrium constant
of step i; Kp(CH3OH) is the methanol synthesis equilibrium constant.

5 MPa krCO→CH3OH K CO K H2 2 K CH ,CO ( pCO pH2 2 − pCH3OH K PrCO→CH3OH ) Lim et al., 2009 [96]
rCO→CH3OH =
523–553 K (1 + K CO pCO ) (1 + K H0.25 pH0.25 + K H2O pH2O )
krCO2 →CH3OH K CO2 K H2 K CH ,CO2 ( pCO2 pH3 2 − pCH3OH pH2O K PrCO2 →CH3OH )
rCO2 →CH3OH =
(1 + K CO2 pCO2 ) (1 + K H0.25 pH0.25 + K H2O pH2O ) pH2 2
k K K 0.5 ( p p − pCO pH2O K PrRWGS )
rRWGS = rRWGS 0.5CO20.5 H2 CO2 H2
(1 + K H2 pH2 + K H2O pH2O ) (1 + K CO2 pCO2 ) pH0.25
5–9 MPa
rCO→CH3OH =
kr′CO→CH3OH K CO ⎡⎣ fCO f H02.5 − fCH3OH ( fH0.5K Pr
2 CO →CH3OH )⎤⎦ Park et al., 2014 [98]
503–613 K (1 + K CO fCO ) (1 + K H0.25 f H02.5 + K H2O f H2O )

kr′RWGS K CO2 [ fCO2 f H2 − fCO f H2O K PrRWGS ]

rRWGS = −
(1 + K CO2 fCO2 ) (1 + K H0.25 f H02.5 + K H2O f H2O )

kr′CO2 →CH3OH K CO2 ⎡⎣ fCO2 f H12.5 − f H2O fCH3OH ( f H12.5K PrCO2 →CH3OH )⎤⎦
rCO2 →CH3OH =
(1 + K CO2 fCO2 ) (1 + K H0.25 f H02.5 + K H2O f H2O )

syngas used as feedstock is purified, usually the sintering of Cu par- life. Sintering rates increase for increasing temperature and in pres-
ticles is considered the only source of loss of catalytic activity. This ence of water. Due to the highlighted mechanism, sintering is related
is also suggested by Chincen et al. [133]. The fresh catalyst is black to the absolute Melting Point Temperature (MPT; copper = 1356 K).
because the Cu particles are small while the sintered catalyst is pink. However, two other temperatures have to be accounted for: the Huttig
Sintering results from crystallite growth and has two effects: it temperature (0.3*MPT [K]; copper = 407 K) and the Tamman tem-
reduces the surface area of the catalyst and causes loss of support perature (0.5*MPT [K]; copper = 678 K). At the Huttig temperature,
area. In the case of methanol synthesis, the main mechanisms of surface atoms located at any lattice imperfection start dissociating
crystallite growth are related to crystallite and atomic migrations. and diffusing on the surface. At the Tamman temperature, bulk atoms
The crystallite migration comprises entire crystallites moving on the become mobile. Therefore, sintering starts at the Huttig tempera-
support surface, colliding and coalescing. In the atomic migration, ture and becomes faster and faster up to the Tamman temperature.
metal atoms move on the support surface and join larger crystal- Traces of chlorine in the feed of the methanol reactor promote sin-
lites. Atomic migration is favored at lower temperatures than tering by reacting at about 230 °C with the active metal/metal oxide
crystallite migration. In any case, the global mechanism of sinter- and producing a highly mobile copper chloride phase having a Tamman
ing is rather complex and involves several elementary steps [134]: temperature of 79–174 °C. These temperatures can justify why Tohji
et al. [135] indicated that sintering starts over 227 °C, Supp [136] reports
– dissociation and emission of metal atoms from metal crystallites copper to recrystallize at temperatures over 270 °C and Roberts found
– adsorption and trapping of metal atoms on the surface that copper crystals begin growing at 250 °C. Therefore, we can con-
– diffusion of metal atoms across the surface clude that sintering starts at 190–227 °C and becomes faster and more
– metal or metal oxide particle dispersion severe at 270–300 °C.
– surface wetting by metal particles The sintering of copper crystallites takes to a reduction in the
– metal particle nucleation catalyst active surface area with a resulting decrease in activity. Sun
– coalescence of metal particles et al. [137] studied the effect of the feed composition on the cata-
– capture of atoms by metal particles lyst deactivation. They performed experiments both with differential
– liquid formation and finite conversion reactors and with different feeds: CO2/H2 and
– metal volatilization CO/H2. For differential conversion reactors, they found that CO/H2
– splitting of crystallites feeds cause rapid catalyst deactivation because of the reducing nature
– metal atom vaporization of CO while CO2/H2 feeds practically do not induce any deactiva-
tion. The previous conclusions are flipped at finite conversion
The type of chemical process and the corresponding operating con- conditions. In particular, CO/H2 feeds insure slower catalyst deac-
ditions influence which of the abovementioned steps happen in real tivation in virtue of the presence of reaction products (such as CO2
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105 91

produced by the WGS reaction) that slow down the over-reduction da1 kd1pCO2

of Cu and ZnO due to CO. Reversely, CO2/H2 feeds cause faster de- = −a1d1 2

dt 1 + K CO pCO + K CO K H3 2K CH pCO pH3 22

activation because of the generation of CO by the reverse WGS
reaction. Other authors [43,138] suggested that the optimal value 2
da2 kd 2 pCO
of CO2 concentration for reducing catalyst deactivation is in the range = −a2d 2 2

of 2–5%. This is because of the optimal oxidation state of copper
under such conditions. Higher CO2 concentrations lead to higher de-
activation rates. This seems to occur due to the production of H2O
that disaggregates the catalyst matrix and reduces the surface of
copper crystallites [43,139,140].
The catalyst deactivation due to sintering can be modeled with
a power law expression (PLE):
dt 1 + K CO2 pCO2 + K CO2 K 1H 2K HCO2 pCO2 p1H22
A pseudo-homogeneous reactor model including this hybrid
kinetic scheme was simulated for 3 months by Løvik [147]. At the
end of the run, a2 was small and a1 was nearly zero, thus this coupled
kinetic-deactivation model overestimates the rate of deactivation
(typically, a catalyst for methanol production lasts for 3–4 years).

da
= −kd (T ) a n (32)
dt 4.4. Steady-state models

where the deactivation order n varies from 1 to 16 and a is the ratio

of the reaction rate at time t and the initial rate (at t = 0).
The kinetic constant kd varies with temperature according to an
Arrhenius type of equation. It has also been proposed [141,142] to
model the sintering rate via the following expression, called gen-
eralized power law expression (GPLE):
da
= −kd (T ) (a − aeq )
n
(33)
dt
Eq. (33) is based on the idea that deactivation is faster at the be-
ginning and reaches a plateau after a proper time span. The term
–aeq accounts for this asymptotic behavior. The order n is general-
ly reduced to 1–2. The deactivation models reported in the literature
are summarized in Table 4 and are only PLE-type models.
Rahimpour et al. [146] proposed a mechanistic model for the cat-
alyst deactivation where CO and CO2 adsorb on different active sites.
Deactivation occurs when CO2 sticks to a CO-site and vice-versa. This
mechanism is in disagreement with other literature [43,139,140] that
indicates H2O (synthesized during CO2 hydrogenation) as the re-
sponsible for deactivation. These authors proposed a LHHW-type
model to describe both kinetics and deactivation:
k f 1K CO K H2 K CH pCO pH2 2
rCO = a1
1 + K CO pCO + K CO K H3 2K CH pCO pH3 22
12
k f 2K CO2 K H K HCO2 pCO2 p
rCO2 = a2 H2
1 + K CO2 pCO2 + K CO2 K 1H 2K HCO2 pCO2 p1H22
Several steady-state models of the PBR for methanol synthesis
have been proposed. Each of them introduces specific assump-
tions aimed at both simplifying the complex phenomena involved
and reduce the computational time without significantly affecting
the reliability of the model predictions.
PBRs are particularly difficult to model because they show axial
and radial gradients together with gradients along the radius of the
single catalytic pellets and temporal dynamics. Despite such com-
plexities, some authors consider a model satisfactory whether the
axial profiles are accurately predicted, especially for simulation prob-
lems (here the goal is modeling the operation of an existing unit).
Instead, modeling the gradients in the catalyst particles becomes
more and more important for design purposes [148].
Radial variations are often neglected due to the relatively small
tube diameter (e.g., 4 cm) and the turbulent flow regime inside the
tubes. Common assumptions for steady-state models include [149]:
(1) negligible axial diffusion; (2) negligible radial diffusion; (3) con-
stant radial velocity; (4) constant temperature/pressure in the catalyst
particle; (5) negligible catalyst deactivation; (6) no side reactions;
and (7) effectiveness of the single catalytic particle evaluated via
the modified Thiele modulus. Literature models for PBRs can be clas-
sified in 4 types (Table 5):
(1) The pseudo-homogeneous models based on molar bal-
ances. Two additional assumptions are usually introduced:
(8) negligible gradients between gas and solid phases; and
(9) no axial variations in the overall molar flow.

Table 4
Deactivation models.

Exp. conditions Reactor type Deactivation model Kinetic constant Author, year Ref.
[h−1]

250 °C Liquid phase bubble column da kd,1 = 2.1⋅ 10−4 Roberts et al., 1993 [143]
= −kd ,1a
5.27 MPa dt
240 °C Gas phase Berty Reactor da ⎛ f ⎞
m
kd,2 = 1.5 ⋅ 10−2 Kuechen and Hoffmann, 1993 [144]
5 MPa = −kd ⎜ CO ⎟ a 2 = −kd ,2a 2
dt ⎝ fCO2 ⎠
(m is not reported)
250 °C Liquid phase pilot plant da kd,3 = 2.1⋅ 10−4 Cybulski, 1994 [145]
= −kd ,3a
dt E = 91270 [ J mol]

240 °C Fixed bed da kd,4 = 8.78 ⋅ 10−3 Skrzypek et al., 1994 [132]
= −kd ,4a5
7 MPa dt (data from Bart and Sneeden, 1987)
250 °C Slurry auto clave reactor da kd,5 = 2.4 ⋅ 10−3 Skrzypek et al., 1994 [132]
= −kd ,5a5
5.27 MPa dt (data from Roberts et al., 1993)
250 °C Liquid phase bubble column da kd,6 = 2.7 ⋅ 10−4 Skrzypek et al., 1994 [132]
= −kd ,6a1.5
5.27 MPa dt (data from Roberts et al., 1993)
250 °C Gas phase Berty Reactor da kd,7 = 4 ⋅ 10−4 Sahibzada et al., 1997 [134]
= −kd ,7a n
5.27 MPa dt
(n equal to 10 at start and 1 after 10 h)
92 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

Table 5
Constitutive equations of the reactor model for methanol synthesis. Molar and mass quantities are in capital and lower case letters, respectively; ̃ and ̂ define quantities
referring to moles or mass, respectively.

Model no. Equation type Equation

1 Mole balance M dyi NR

= ρcat (1 − ε b ) ∑ υi, jη j R j
Aint dz j

1 Energy balance   p dT
Mc NR
mix

Aint dz
d
( )
= π int U (Tshell − Tbulk ) + ρcat (1 − ε b ) ∑ − ΔH rjeac η j R j
Aint j

1 − ε b ⎞ ⎞ u2ρ gas ⎛ 1 − ε b ⎞
= − ⎜ 1.75 + 150 ⎛⎜
1 Momentum balance dP ⎛
dz ⎝ ⎝ Re ⎟⎠ ⎟⎠ d p ⎜⎝ ε b3 ⎟⎠

2 Mass balance m dω i NR
= ρcat (1 − ε b ) ∑ MWiυi, jη j R j
Aint dz j

 ˆ pmix dTbulk NR
2 Energy balance mc
Aint dz
d
(
= π int U (Tshell − Tbulk ) + ρcat (1 − ε b ) ∑ − ΔĤˆ reac
Aint j
j )
η j rj

1 − ε b ⎞ ⎞ u2ρ gas ⎛ 1 − ε b ⎞
= − ⎜ 1.75 + 150 ⎛⎜
2 Momentum balance dP ⎛
dz ⎝ ⎝ Re ⎟⎠ ⎟⎠ d p ⎜⎝ ε b3 ⎟⎠

3 Mole balance, gas phase M dyi

= k gi avC gas ( yisup − yi )
Aint dz
NR
3 Mole balance, solid phase
ρcat (1− ε b ) ∑ υi, jη j R j = −k gi avC gas ( yisup − yi )
j

3 Energy balance, gas phase   p dT

Mc d
mix bulk
= π int U (Tshell − Tbulk ) + hint av (1 − ε b ) (Tsup − Tbulk )
Aint dz Aint
NR
3 Energy balance, solid phase
( )
hint av (Tbulk − Tsup ) = ρcat ∑ − ΔH j reac η j R j
j

1 − ε b ⎞ ⎞ u2ρ gas ⎛ 1 − ε b ⎞
= − ⎜ 1.75 + 150 ⎛⎜
3 Momentum balance dP ⎛
dz ⎝ ⎝ Re ⎠⎟ ⎠⎟ d p ⎝⎜ ε b3 ⎠⎟

4 Mass balance, gas phase m dω i

= k gi av ρ gas (ω isup − ω i )
Aint dz
NR
4 Mass balance, solid phase
ρcat (1− ε b ) ∑ υi MWiη j R j = −k gi av ρ gas (ω isup − ω i )
j

4 Energy balance, gas phase  ˆ pmix dTbulk

mc d
= π int U (Tshell − Tbulk ) + hint av (1 − ε b ) (Tsup − Tbulk )
Aint dz Aint
NR
4 Energy balance, solid phase
( )
hint av (Tbulk − Tsup ) = ρcat ∑ − ΔHˆ j reac η j rj
j

1 − ε b ⎞ ⎞ u2ρ gas ⎛ 1 − ε b ⎞
= − ⎜ 1.75 + 150 ⎛⎜
4 Momentum balance dP ⎛
dz ⎝ ⎝ Re ⎠⎟ ⎠⎟ d p ⎝⎜ ε b3 ⎠⎟

(2) The pseudo-homogeneous models based on mass balances. As-
sumption (9) is removed while assumption (8) is still enforced.
(3) The heterogeneous models based on molar balances. As-
sumption (8) is removed but assumption (9) is still in place.
(4) The heterogeneous models based on mass balances. Both as-
sumptions (8) and (9) are removed.
As already mentioned, intra-phase mass transport phenomena
are modeled by means of the catalyst effectiveness factor, which is
generally calculated from the modified Thiele modulus [150–152],
even though different options have been discussed in Section 4.2.
The pseudo-homogeneous formulation can be employed in order
to reduce the computational effort required by heterogeneous
models. Notice that by neglecting both concentration and temper-
ature gradients between the gas and the solid phase, solid and gas
phase mass and energy balances, which were previously derived
separately, can be combined.
In fact, pseudo-homogeneous formulations allow completely
changing the nature of the mathematical problem to address. Het-
erogeneous models lead to systems of differential-algebraic equations,
which are stiff by definition [153]. Instead, pseudo-homogeneous
models lead to ordinary differential equation systems, which are easier
to solve. Moreover, it is well-known that by employing mass balances
formulated in terms of mass fractions, once can get two additional
benefits: a conservative description of reactive systems with vari-
able number of moles (this is the case of methanol synthesis); and
the overall molar conservation equation is no longer necessary. The
recent literature presents a number of contributions aimed at pro-
posing models for the methanol synthesis reactor based on mole
balances [154–156]. These authors state that the assumptions in-
troduced in such models are reasonable because the methanol yield
per pass is smaller than 7%. However, those assumptions might be
risky when it comes to estimate the hydrogen fraction. Other re-
searchers propose to use mass balances [148,157] and compare the
predictions originated from the two different types of models. The
molar fraction of methanol calculated via molar balances are in-
evitably underestimated compared to those computed via mass
balances. In fact, there is no apparent reason for assuming that any
variation in molar flows due to chemical reactions is negligible. Very
likely, this erroneous belief derives from a misunderstanding dating
back to 1990s. Some well-established reaction engineering books
(i.e. [73,158]), which several authors referred to, proposed ex-
amples of models of heterogeneous reactors based on molar balances.
However, this was just because the trivial examples used as case
studies included only equimolar reactions. These models are no longer
valid for the methanol synthesis.
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
The difference between heterogeneous and pseudo-homogeneous
models is essentially the presence/absence of gradients between gas
and solid phases. The simplification introduced in pseudo-
homogeneous models can be justified every so often by the high
gas velocity adopted in industrial reactors. In fact, these operating
conditions take to very thin boundary layers around the catalyst
pellets. For the current industrial operating conditions, Manenti et al.
[148] demonstrated that the pseudo-homogeneous model pro-
vides predictions for temperature and composition profiles that
overlap those of the heterogeneous model. In addition, Rezaie and
co-workers [155] performed the same type of comparison and
achieved similar results showing that the pseudo-homogeneous
model slightly overestimates the temperature hot spot. This is not
due to neglecting the species diffusivity in the boundary layer. In
fact, the presence of transport limitations around the particle would
yield opposite effects. The explanation for that resides in thermal
exchange issues. The temperature profile of the synthesis reactor
is particularly sensitive to the inlet feed flowrate. In particular, the
position of the hot spot significantly shifts upon changes in the feed
flow. Analogously, a feed flow reduction leads the reacting system
toward the thermodynamic equilibrium, thus the molar fraction of
methanol increases and the throughput of the reactor drops. Studies
conducted by Rezaie and co-workers [155] highlighted that upon
reducing the inlet gas flowrate, the behavior of the two phases (solid
and gas) drastically changes. Consequently, the results coming from
pseudo-homogenous and heterogeneous models no longer overlap.
This is because when the inlet flowrate is larger, the gas flowing
through the reactor heats up slower and the methanol yield de-
creases. On the other hand, the feed temperature does not affect
significantly the reactor behavior, even though there is a connec-
tion between the operating temperature of the steam reformer and
the final methanol yield, at least from a process viewpoint [159].
Thus, the tube side is suitably designed to cope with even strong
oscillations in the inlet temperature. In industrial best practice, the
feed temperature is adjusted to control or partially compensate for
catalyst deactivation [155,160]. The rate of heat transfer toward the
boiling water flowing outside the tubes affects methanol conver-
sion in such a way that the optimal performance of the reactor is
a function of the shell side temperature: high temperatures reduce
the maximum achievable conversion due to the thermodynamic
equilibrium while low temperatures reduce the rate of reaction. Since
the shell side is practically a steam generator, its temperature can
be controlled by adjusting the steam pressure with a roof valve. From
former analyses, it derives that the reactor behavior can be accu-
rately described via heterogeneous models but can be also properly
predicted via pseudo-homogeneous models, when both feed flowrate
and shell temperature and are reasonably close to nominal condi-
tions. A qualitative validity range is also proposed [148].
Interesting research work was presented by Petera et al. [161],
which introduces a powerful method for solving multi-dimensional
differential systems thanks to a universal coupling of macro- and
micro-geometries represented by a two-mesh finite element frame-
work. The micro-mesh refers to the catalyst particle while the macro-
mesh is applied to the catalyst bed. They developed a numerical
algorithm for solving multidimensional heterogeneous reactor
models and applied it to a methanol reactor. Their model includes
all of the four dimensions previously mentioned: axial and radial
reactor coordinates, catalyst particle radius and time. In this way,
they could compute the concentration and temperature profiles in
the axial and radial directions as well as inside the catalyst parti-
cle. The effect of incidental crushing of the catalyst was simulated
and showed the birth of a hotter hot spot due to the reduction in
particle diameter. In addition, the buoyancy effect was accounted
for, which relates to the increase in temperature and consequent
decrease in density. This combination of these phenomena is ex-
pected to take to an irreversible dynamics generating a high
93
temperature zone inside the catalyst bed. The full computation re-
quired less than half an hour. Their simulations also show that the
reverse water gas shift reaction occurs mainly close to the reactor
inlet. The concentration of carbon dioxide decreases while it is con-
verted to methanol, carbon monoxide and water. At the same time,
the gas temperature increases, thus generating a slight increase in
gas velocity close to the reactor inlet. A difference between the tem-
perature of gas and catalyst is also observed. However, note that
the inlet gas velocity they used is about 0.3 m/s in while other
authors mention spatial velocities around 0.7 m/s [162] or even
higher [163] (related to industrial operating data). For such higher
gas velocities no temperature difference between the solid and the
gas phase is observed.
Another important aspect to consider is that the most common
configuration of the methanol synthesis reactor comprises two stages:
the water-cooled section, which is that previously described, and
the gas-cooled section, where the fresh syngas entering the reactor
is preheated thanks to the hot effluent of the water-cooled section.
All the aforementioned assumptions and considerations are still valid
for the gas-cooled section of the two-stage configuration and the
same applies to the reported models. There is only the need for
adding an additional conservation equation, i.e. the energy balance
for the cooling gas that flows though the shell side of the gas-
cooled section [164]:
  pg dT
Mc D
= −π i U shell (T − Tshell ) (34)
Ac dz Ac
Rahimpour and Lotfinejad assessed the effectiveness of the coun-
tercurrent configuration of the gas-cooled section of the two-
stage reactor [165]. They assumed that both the shell and the tube
side could be modeled as one-dimensional plug flow equipment,
neglected the intra-phase diffusion in the catalyst pellets, ne-
glected the axial heat dispersion, and assumed the gas mixture to
be ideal. As shown in their article (Fig. 16), the total production of
methanol is slightly larger for the countercurrent configuration. The
aforementioned considerations have general validity as they apply
to different syngas sources and different PBR types. Other reactor
configurations deserve special models. For instance, Arab et al. [166]
analyzed the impact of arranging the solid catalytic phase as either
a packed bed or monoliths. For this study, the reactor feed com-
prised only CO2 and H2. The production of methanol via PBRs and
reactors exploiting catalyst monoliths (monolithic reactors, Fig. 17)
was analyzed by modeling the heat and mass transfer phenomena
Fig. 16. Co-current/counter-current comparison for the two-stage synthesis reactor.
94 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

Fig. 17. Monolithic reactor.

occurring in each reactor. The analysis demonstrated that PBRs and

monolithic reactors perform similarly at low gas hourly space ve-
locity. On the other hand, at high gas velocities, the PBR technology
appears to be limited by considerable pressure drops that cause rel-
evant losses in productivity due to the thermodynamic equilibrium.
A much smaller number of studies focus on the three-phase reactor
for methanol production. One of those is that proposed by Air Prod-
ucts (Section 2.2). Gamwo et al. developed a detailed computational
fluid-dynamics simulation to optimize parameters related to the
optimal catalyst design and compared their solution to that pro-
posed by Air Products [167]. The mole fraction of methanol in the
reactor effluent is very close to 4% in both cases. Farsi and Jahanmiri
[168] proposed to carry out the synthesis of methanol in mem-
brane reactors. This idea is appealing because it allows overcoming
the thermodynamic issues of the methanol synthesis reaction via
elimination of one product (water) from the reaction environ-
ment. This solution is closer to the PBR from the modeling viewpoint.
In addition, this membrane-based technology allows coupling re-
action and downstream separation into a single piece of equipment
(Fig. 18). In this reactor, syngas is fed to the reaction zone that is
surrounded with a hydrogen-permselective membrane tube allow-
ing water to be removed from the reacting environment. A steady-
state heterogeneous one-dimensional model for such membrane
reactor was developed and validated on available experimental data.
Catalyst deactivation was also studied for fluidized membrane re-
actors [169]. For one-/two-stage reactors the separation of methanol
(and water) from the unreacted reactants, which are then re-
cycled back to the synthesis reactor, is usually performed via a pre-
flash or flash drum separator. Then, the liquid stream comprising
principally methanol and water is transferred to the downstream
purification process. The easiest model for the separation section
(in terms of both assumptions and implementation) was pro-
posed by Manenti et al. [170]. It consists of the overall mass balance
and the component balances of a flash drum separator:
F =V +L
Fzi = Vyi + Lxi
∑
N
i =1
yi = 1
∑
N
i =1 i
x =1
and the solution is computed by means of the Rachford and Rice
method [171]:
zi ( K i − 1) y φL
f (V F ) = ∑ i=1
N
= 0, K i = i = Vi
V xi φi
(K i − 1) + 1
F cesses is PRO/II (by SimSci, Schneider Electric) [175]. The usage of
Fig. 18. Two membrane layers reactor.
Different and more complex models, based on commercial
process simulators, have also been proposed. Different authors
[21,149,172,173] studied the problem in detail. In particular, Feng
et al. [173] analyzed a process comprising a biomass gasifier, a steam
reformer and the methanol synthesis reactor and proposed the in-
teresting logic diagram reported in Fig. 19. Such a schematic suggests
that it is possible to fix into methanol about one-third of the carbon
and seven-eighth of the hydrogen of syngas. In addition, starting
from the moles of carbon and hydrogen included in the biomass
and the moles of steam required in the gasification process, the same
number of moles of methanol are synthesized. Such a prediction
is subject to the type of biomass adopted in the production process.
They identified that the equivalence ratio in the biomass gasifica-
tion, the temperature in the steam reforming and the recycle of
hydrogen in the methanol synthesis are the key parameters affect-
ing the effectiveness of the methanol synthesis itself and especially
the possibility of using CO2 as feedstock in the process. Other papers
are also proposing different ambitious solutions, i.e. the sequestra-
tion of CO2 from flue gases and its conversion to methanol. Van-
Dal and Bouallou [174] proposed a power-plant-based methanol
(35)
production process (Fig. 20). CO2 is captured by chemical absorp-
tion from the flue gases of the thermal power plant and hydrogen
(36)
is produced by water electrolysis. Such process proves to be feasi-
ble, even though very energy intensive. Steady state simulations
(37) carried out in AspenOne (a commercial suite by Aspen Technolo-
gy) demonstrate it. The key point in converting CO2 to methanol is
(38) the absence of CO in the feedstock. Park et al. [98] also adopted a
commercial suite for steady-state simulation (AspenHysys by Aspen
Tech) to investigate which parameters are more influential on the
methanol yield within the overall production plant. Specifically, they
analyzed the effect of the reactor temperature, the amount of CO2
in the feed and the recycle of unreacted gas. The other platform
(39)
adopted for steady-state simulation of methanol synthesis pro-
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105 95

Fig. 19. Scheme of element fluxes from biomass to methanol production.

commercial tools forces to model the methanol synthesis reactor
by means of predefined models and the unit of choice is usually the
Gibbs reactor. Only few articles mention the possibility of integrat-
ing external, more detailed, models into such commercial suites (i.e.
using CAPE-OPEN directives) [176].
4.5. Dynamic models
Dynamic modeling is traditionally more complex to imple-
ment and more time consuming than steady-state modeling. This
is why it is less common to find detailed models for the dynamics

Fig. 20. Flue gas to methanol process.

96 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

Table 6
Dynamic models. Heterogeneous PBR by Rezaie et al. [155] (model 1); homogeneous PBR by Rezaie et al. [155] (model 2); homogeneous model by Manenti et al. [177]
(model 3)).

Model no. Equation type Equation

(1) Molar balance, solid phase dyiS

ε SCt = k giC t ( yi − yiS ) + ηri ρBa, i = 1, … , N − 1
dt
(1) Energy balance, solid phase ∂TS NR
*
ρBcˆ pS = ρBa ∑ ηri (− ΔHri ) + aV (1 − ε B ) h f (T − TS )
∂t i =1

* Corrected equation for consistency reasons.

(1) Molar balance, gas phase ∂y M ∂yi *
ε BC t i = − + aV (1 − ε B ) C t k gi ( yiS − yi ) i = 1, ….., N − 1
∂t Ac ∂z
* Corrected equation for consistency reasons.
(1) Energy balance, gas phase ∂T M ∂T π Di
ε BC t c pg = − c pg + aV h f (TS − T ) + U shell (Tshell − T )
∂t Ac ∂z AC

(1) Boundary conditions z = 0; yi = yi 0; T = T0

(1) Initial conditions t = 0; yi = yiss; yiS = yiSss; T = T ss; TS = TSss; a = 1

(ss stands for steady-state condition)
(2) Molar balance ∂yi M ∂yi
ε BC t =− + ηri ρBa i = 1, ….., N − 1
∂t Ac ∂z

(2) Energy balance ∂T M ∂T NR

π Di
ε BC t c pg = − c pg + ρBa ∑ ηri (− ΔHri ) + U shell (Tshell − T )
∂t Ac ∂z i =1 AC

(3) Mass balance, methanol ∂ω CH3OH m ∂ω CH3OH

ε B ρ gas =− + MWCH3OH rCH3OH
∂t Aint ∂z

(3) Mass balance, water ∂ω CO2 m ∂ω H2O

ε B ρ gas =− + MWH2OrH2O
∂t Aint ∂z

(3) Mass balance, carbon monoxide ∂ω CO m ∂ω CO

ε B ρ gas =− + MWCO (−rCH3OH + rH2O )
∂t Aint ∂z

(3) Mass balance, carbon dioxide ∂ω CO2 m ∂ω CO2

ε B ρ gas =− + MWCO2 (−rH2O )
∂t Aint ∂z

(3) Mass balance, hydrogen ∂ω H 2 m ∂ω H 2

ε B ρ gas =− + MWH2 (−2rCH3OH − rH2O )
∂t Aint ∂z

(3) Energy balance ∂T m ∂T 4

[ε B ρ g cˆ pmix + (1 − ε B ) ρscˆ ps ] ∂t =−
Aint
cˆ pg
∂z
+ U shell (Tshell − T ) +
Di
+ [rCH3OH (− ΔHr2 ) + rH2O (− ΔHr2 )]

(3) Rates rCH3OH = ρs (1 − ε B ) η1 (r1 + r3 ) , rH2O = ρs (1 − ε B ) η2 (r2 + r3 )

where εS void fraction of catalyst; Ct total concentration (mol/m3); a catalyst activity; yi molar fraction in the fluid phase; η catalyst effectiveness factor; yiS, mole fraction of
component i in the solid phase; ρB density of the catalytic bed (kg/m3); ri, reaction rate of component i (mol/kg/s); kgi, mass transfer coefficient for component i (m/s); ĉ pS
specific heat of the solid at constant pressure (J/g); TS temperature of the solid phase (K); T bulk gas phase temperature (K); ΔHrienthalpy variation of the reaction i; aVspecific
surface area of catalyst pellet (m2/m3); hf gas–solid heat transfer coefficient (W/m2/K); M  total molar gas flow rate (mol/s); Ac cross section area of each tube; c pg specific
heat of the gas at constant pressure (J/mol); Di tube inside diameter (m); Ushell overall heat transfer coefficient between coolant and process streams (W/m2/K); Tshell tem-
perature of coolant stream (K).

and control of methanol synthesis reactors in the literature. Sim-
ilarly to steady-state modeling, the majority of the contributions
address the dynamics modeling of PBRs while only very few authors
try to assess the dynamic performances of other reactor configu-
rations such as membrane or slurry reactors. Rezaie et al. [155]
proposed a first paper aimed at comparing different dynamic models
for the PBR and test their capability of fitting industrial data (col-
lected under decaying catalyst performance). Table 6 reports the
pseudo-homogeneous and heterogeneous models (model (1) and
model (2)) analyzed by Rezaie et al. and model (3), which is based
on mass balances and was proposed by Manenti et al. [177,178]. It
is important to note that the first two models, based on molar bal-
ances, should be implemented in terms of mass balances (see Section
4.4). The dusty gas model [124] and kinetic scheme by Graaf et al.
[87] were used. According to Jackson’s formulation [123] the im-
plementation of any model for the methanol synthesis could benefit
from using elemental balances rather than component balances. This
logic was applied by Manenti et al. and proved to be correct.
A common problem of dynamic models is their numerical so-
lution and the corresponding convergence issues. A finite-difference
approach is usually adopted to discretize the partial differential
equation system deriving from the dynamic modeling of the methanol
synthesis reactor. From a conceptual viewpoint, the easiest way to
proceed implies discretizing the axial profile and then solve a series
of ordinary differential equation or differential-algebraic equation
systems. Parvasi and co-workers [179,180] detailed the procedure
to initialize numerically the solution of such a system but anyway
very misleading results can be easily achieved due to numerical issues.
They used a first order upwind discretization scheme to approxi-
mate the convective terms and a centered difference scheme for the
diffusive terms. Manenti et al. [177] solved the system using the Back-
ward Euler method, which is typically implemented in commercial
suites, and the trend is reported in Fig. 21. It is worth noting that,
when the system is subject to a perturbation, the model is predict-
ing a discontinuity in the dynamic trends, which has no physical
meaning. In fact, we are assuming the gas flow inside each single
tube of the PBR to be experience turbulent motion. This infeasible
result originates from the stiffness of the system of equations that
easily leads to numerical divergence. Moreover, even though it is
neglected in steady-state models, it is apparently essential to account
for axial dispersion in dynamic models. In fact, by doing so, the orig-
inal hyperbolic partial differential equation system is transformed
into a parabolic partial differential equation system and the non-
physical fluctuations are somehow removed.
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105 97

Fig. 21. Effect of flux segregation assumption and Forward Euler integration method. The trends deal with three snapshots at 16 s, 20 s, and 80 s after the step-
perturbation has occurred [177]. The existence and validation of dynamic models led to studies of process control for the methanol synthesis reactor and process (see Section
5.2).

Other reactor configurations are being studied in the litera-
ture, even tough not systematically. For example, Rahimpour’ group
is investigating a membrane reactor. Parvasi et al. proposed a hy-
drogen perm-selective membrane reactor, whose model has to
account for the hydrogen permeation through the palladium mem-
brane (Table 7). The hydrogen permeation has to be also calculated
in the model. If the membrane is composed by pure palladium, the
model equations has been proposed by Itoh [181] while if the mem-
brane is palladium-silver, the model equations were proposed by
different authors [182,183]. Other authors [184] proposed similar
water-perm-selective membrane reactors and studied also differ-
ent membrane reactor configurations [185,186].
It is worth noting that the proposed model does not enforce total
mass conservation because the total mass flowrate in the retentate
and permeate sections are not constant with z. This is because there
exists mass transfer between the two phases. A continuity equa-
tion should be added to the system to make the model consistent.
However, since the molecular weight of hydrogen is small, the error
induced might be small as well.
Wu and Gidaspow proposed hydrodynamic models for slurry re-
actors [187]. In particular, they implemented a two-dimensional
hydrodynamic model of the Air Products slurry bubble column reactor
for producing methanol from syngas. Their model is the first to compute
the gas and the particle holdups as well as the particle rheology.

Table 7
Perm-selective membrane reactor model [179].

Model part Equation type Equation

Reaction side Mass balance, all components except hydrogen ∂yi M ∂yi N R
ε BC t =− + ∑ ηrj ρBa i = all except hydrogen
∂t Ac ∂z j =1

 ∂y H N R α
Reaction side Mass balance, hydrogen
ε BC t
∂y H
∂t
=−
M
Ac ∂z
+ ∑ ηrj ρBa + H
j =1 Ac
( pHt − pHr )
Reaction side Energy balance ∂T M ∂T 3
π Di
ε BC t c pg =− + ηρBa ∑ ri (− ΔHi ) + U shell (Tshell − T ) +
∂t Ac ∂z i =1 Ac
π Do
+ Utube (Ttube − T )
Ac

Reaction side Conditions z = 0; yi = yi 0; T = T0; t = 0; yi = yiss; T = T ss; a = 1

 ∂y H α H
Tube side Mass balance, hydrogen
Ct
∂y H
∂t
=−
M
Ac ∂z
+
Ac
( pHr − pHt )
Tube side Energy balance ∂T M ∂T π Do
C t c pg =− + Utube (Ttube − T )
∂t Ac ∂z Ac

Tube side Conditions z = 0; yH = yHR; T = T0; t = 0; yH = yHR

ss
; T = T ss

αH is the hydrogen permeation rate constant. It is not clear in the reference if the balances are referring to the atomic or molar hydrogen.
98 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
5. Optimization
Optimization can positively affect methanol synthesis at differ-
ent levels: the catalyst design, the chemical kinetics, the reactor
configuration and operating conditions and the entire process scale,
including energy requirements and pinch technology. Optimiza-
tion problems can be classified under many different categorizations
[188] but we prefer to divide them into two main classes: optimi-
zation for design purposes and optimization for operational purposes.
The former is mainly related to the definition of optimal geom-
etries and operating conditions of the reactor and the latter has to
do with control and (safe) management of existing reactors.
5.1. Optimal design and nominal conditions
Each chemical reactor aims at producing a commodity. Thus, the
principal aspect to optimize is its conversion and yield. For PBRs,
the conversion to methanol is strongly influenced by different pa-
rameters. According to the proposed sensitivity analyses [148] the
inlet flowrate and the shell-side temperature are the two most rel-
evant variables to consider. Since the PBR is a tubular reactor, the
optimal inlet flowrate has to do with the calculation of the number
of tubes during the design phase. On the other hand, the shell side
temperature can only be estimated via models, which allow relat-
ing the tube side yield to the shell-side temperature itself. Shahrokhi
and Baghmisheh [156] defined that the tube side temperature should
optimally range between 493K and 573K to favor the methanol syn-
thesis and prevent the catalyst from sintering. For safer operation
and methanation prevention, a more conservative upper limit on
the temperature is usually considered (543 K). The operating range
for the shell side temperature (cooling system) is about 20 K lower.
According to their suggestions, Manenti et al. [148] carried out a
sensitivity analysis (Fig. 22) using 3.8 cm (internal diameter) tubes
and a feed flowrate of 0.64 mol/s per tube. Larger diameters
Fig. 22. Optimal shell side temperature.
unavoidably lead to significant hot-spots and consequent viola-
tion of the safe operation ranges. The figure proves that the
conversion to methanol shows a maximum at a shell side temper-
ature of 526 K. It is possible to define a priori the optimal shell side
temperature because of external constraints on the properties of
the steam generated by the water-cooled reactor. In particular, what
usually counts is the steam pressure. A well-known approach for
reactor optimal design is the systematic staging proposed by Hillestad
[189,190]. Hillestad defined the basic operations to perform during
any reactor design based on their corresponding design function,
for instance: the mixing function for fluid mixing operations; cat-
alyst dilution and catalyst type for the chemical reaction; exchange
area distribution and coolant temperature for heat exchange; feed
distribution and feed temperature and composition for the extra
feeding; and pressure profile for pressure drops. Subsequently, he
applied the systematic staging to the PBR for methanol synthesis
[191] to demonstrate the effectiveness of his methodology. He com-
pared a base design case to the new reactor originated from the
systematic staging, which comprised three different sections. No eco-
nomic considerations were given on such a demonstrative paper.
Economic considerations about PBRs were provided later on by
Manenti et al. [164]. They analyzed the two-stage water-cooled and
gas-cooled PBR applying the systematic staging for several ex-
change area distributions, catalyst types and coolant temperatures.
This was done in order to assess the industrial best practice that
requires a ratio of 7:3 for the water-cooled to gas-cooled reactor stage
length. They showed that the optimal ratio should be 5.5:4.5, as re-
ported in Fig. 23. For the fourth case, the methanol yield increased
from 6.4% v/v to 6.8%v/v. The authors estimated an additional net
income of 1.75M€/y for a medium scale plant. In a subsequent work
based on the combined (one-step) production of methanol and
dimethylether [170], they showed that the optimal ratio for the same
stage lengths is 0.78:0.22, which is much closer to the industrial
best practice. Configurations different than PBR have been studied
in the literature as well. Montebelli et al. [192] optimized the per-
formance of a compact water-cooled tubular reactor loaded with
high-thermal-conductivity structured catalysts (washcoated copper
honeycomb monoliths and copper open-cell foams). The authors
simulated and optimized the reactor operation while considering
the recycle loop, including an ideal condenser (see also [170]) and
accounting from a purge system as well (see also [193]). Detailed
studies have also been proposed for membrane reactors for meth-
anol production coupled with other reactive systems [194]. The so-
called multi-objective/multi-criteria optimization has also been
adopted to optimize combined methanol/hydrogen production
systems [195]. Such an approach is particularly effective when the
overall process for methanol synthesis is taken into account. Espe-
cially in the case of combined heat and power production, it could
provide opportunities for additional savings as showed by Kralj and
Glavic [196]. They simultaneously considered chemical synthesis,
heat integration and electricity cogeneration and optimized the inlet
flowrates along with the separation and chemical reaction equip-
ment. The estimated additional profit due to the optimization was
2.51 M€/y. Other authors optimized the operating conditions of the
methanol reactor by simultaneously accounting for the entire plant.
Zhang et al. [197] included the tri-reforming process in the overall
optimization of methanol synthesis and applied a mixed-integer non-
linear programming approach to completely redefine the process
layout and promote heat integration. They achieved a novel tri-
reforming/methanol process with minimum capital investment and
operational costs.
5.2. Operations management
The concept of operational management includes different
actions because the reactor has to be monitored over time. Thus,
 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Fig. 23. Systematic staging optimal design applied to the two-stage water-cooled/gas-cooled PBR. The traditional case is the best industrial practice; the 3rd case is the
systematic staging applied to the methanol yield; the 4th case is the systematic staging accounting for the steam generation in the shell side of the water-cooled stage.
measurement of the most relevant information is performed and
measures are sent to a dedicated server located inside the distrib-
uted control system (DCS). Before using the measures for control
and optimization purposes, a crucial step is to purge them from pos-
sible stochastic errors and from possible outliers (or gross errors)
as well [198,199]. This step is essential to prevent any misleading
operation of the automatic control due to temporary or persisting
wrong measurement. Such a purification procedure goes under the
name of process data reconciliation [200,201]. Reconciled data can
be used for control purposes and, subsequently, for online optimi-
zation purposes like in a stiff pyramid of decisions where the
information flows upward and actions flow downward. Kordnejad
et al. [202] proposed a real-time optimization (RTO) based on simu-
lated plant data to optimize the operational performance of a PBR
reactor. They measured the temperature of the tube side outflow
and used the shell-side temperature as unique optimization vari-
able. In this way, they improved methanol yield by 15%. Such a
methodology originates from the best industrial practice, i.e. the use
of steady-state models. While in the past optimization was based
on steady models and was completely independent of control in the
operational management pyramid [203], nowadays control and op-
timization are completely integrated in the so-called integrated
optimal control or model predictive control (MPC) [204] and dynamic
real-time optimization (DRTO) [205], where one unique dynamic
model is used to handle all the operational targets. Unfortunately,
due to the complexity of the methanol reactor, there is lack of con-
tributions and advances in process control and optimization (based
on the new dynamic-simulation-based approach) concerning such
process unit. It is well-known that the typical PBR for methanol syn-
thesis could evolve dynamically along 4 different coordinates: axial
and radial directions, catalyst radius, and time [178]. Shahrokhi and
Baghmisheh [156] applied different control techniques to the Lurgi-
type one-stage water-cooled methanol synthesis reactor. They
modeled both the tube side storing the catalyst and the shell side
comprising the steam drum unit. Then, they applied the proportional–
integral (PI) and the proportional–integral–derivative (PID) techniques
to manage the system when feed flow perturbations and shell-side
pressure changes occurred. Their target was to assess the optimal
operating conditions of an industrial reactor subject to typical fluc-
tuations in the feedstock (tube-side) and in the pressure/temperature
of the boiling water (shell-side), which are more conservative than
those coming from the optimal design. During transient operation,
there could be any temperature hot-spot along the catalyst bed, which
is not identified via steady-state studies. This might accelerate the
catalyst sintering and deactivation as well as favor the so-called
methanation reaction (CO + 3 H2 → CH4 + H2O), which is extremely
99
exothermic. Shahrokhi and Baghmisheh confirmed that well-
tuned PID loops provide faster control actions and smaller overshoot
in terms of reactor temperature profile (the overshoot is the maximum
deviation from the original set point). Based on these results, they
redefined the optimal temperature profile deriving from the optimal
design and suggested a “constrained optimal temperature” for safer
operation as reported in Fig. 24. More recently, advances have been
proposed to insure improved operation of methanol synthesis
reactors/plants: the plantwide process control for the overall meth-
anol production plant (Luyben [193]) and the nonlinear model
predictive control (MPC) for the only PBR (Manenti et al. [206,207]).
Luyben proposed a plantwide control system based on PID loops
for the overall process including the synthesis section and the pu-
rification section (Fig. 25). The philosophy is not to have any
uncontrolled battery limit and to saturate all the degrees of freedom
of the plant with the minimum amount of control loops. The sim-
plest control scheme is the best control scheme [208].
Following the process flow, Luyben proposes a flow controller
on the inlet syngas stream. Then, the syngas is compressed in the
rotating units K1 and K2 in between of which the gas flow is cooled
down by a utility exchanger. The temperature controller regulates
the inlet temperature to K2 by manipulating the coolant flowrate.
A pressure controller is also applied to the rotating shaft of K2 to
ensure the pressure on the downstream line is in line with its
setpoint. The compressed syngas goes to the Feed Effluent Heat
Enchanger (FEHE), where it is preheated by the hot effluent of the
methanol synthesis reactor. The FEHE has no degrees of freedom
for control and its target is to recover as much energy as possible
(energy-saving process intensification). Since the inlet tempera-
ture of the reactor is a key parameter, it is controlled via a
temperature loop that manipulates the utility fluid of a heat ex-
changer. It is worth saying that, in contrast to what Fig. 25 shows,
the utility exchanger usually heats up the process stream (its cor-
responding arrow should point down, thus indicating that the utility
fluid is cooling down). The reactor effluent is pre-cooled in the FEHE
and its temperature is refined in a utility exchanger, where a tem-
perature controller is managing the corresponding coolant flow rate.
After the cooling step, a good portion of methanol condenses and
is recovered in a flash drum separator. The drum aims at separat-
ing the unreacted syngas from condensable compounds, thus
methanol and water. The syngas is recompressed and recycled back
the reactor. Since recycles introduce an additional degree of freedom
in the control paradigm [209], a control loop is also associated with
this process stream. Moreover, in order to prevent any accumula-
tion of by-products due to the gas recycle, a vent is always present.
Here, it is managed via a composition controller.
100 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105

Fig. 24. Constrained optimal temperature accounting for PID actions in smoothening perturbations.

On the other hand, the liquid accumulated in the drum is trans-
ferred to a second flash drum separator to refine the recover
additional syngas. The liquid level in the first and second drums is
managed by level controllers that manipulate the liquid outflows.
The second drum is also equipped with a gas recycle line that goes
back to the reactor and is managed via a pressure controller. Since
a gas purge is already performed on the recycle stream leaving the
first drum, it is unnecessary to insert another one and a potential
control loop is avoided. The liquid flow exiting the second drum is
transferred to the distillation column C1 for methanol/water sep-
aration. The minimum number of control loops for a distillation
column is usually six [210]. The conventional control scheme
comprises: (I) two loops controlling the liquid levels of reflux drum
and reboiler; (II) one loop taking care of the pressure on the last
tray; (III) another loop controlling the inlet flowrate (possibly jointly
to the reflux flowrate); (IV) and two loops managing the column
temperatures on the first and last tray (sometimes different trays
are selected). In this specific case, one single temperature control
loop is enough to manage the temperature profile along C1. In ad-
dition, it is important to say that the temperature of the inlet flow
is a key parameter and is usually refined with a utility exchanger.
In the Luyben scheme, the second flash drum separator is sup-
posed to already predispose the temperature for proper operation
of the distillation column. The liquid level controllers applied to the

Fig. 25. Plantwide control of methanol synthesis and purification plant.

 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
Fig. 26. Optimal tracking for handling catalyst bed deactivation.
reflux drum and the reboiler define the flowrates of methanol (the
final product) and water, respectively. The last outlet stream is the
gas effluent from the partial condenser, which is recycled back to
the reactor after recompression. This process line is managed by a
flowrate controller as well. Another advance to the control/
optimization of PBRs for producing methanol was recently proposed
by Manenti and Bozzano [207]. It does not relate to the whole plant
scale, but it has to do with the control of the methanol converter
and introduces a technique called optimal control or MPC. The MPC
has been invented at the end of 1970s in its linear formulation
[211–213] and counts many applications worldwide [214]. In the
last decades, nonlinear MPC [215,216] has proven to be more ef-
fective than its linear counterpart because model mismatch is
minimized (all chemical plants exhibit nonlinear dynamics). The
basic idea is to exploit the prediction potential of dynamic models
to foresee the future behavior of the plant and thus select and apply
the right/better control action in advance. In other words, the MPC
runs the dynamic process model several times to build different
control trajectories and the control actions associated with the best
trajectory are selected and implemented onto the system (servo-
mechanism, regulation and hybrid problems can be efficiently
handled). Since real plants are continuously subject to distur-
bances, the calculation procedure is iterated every sampling time
in a so-called receding horizon fashion [217,218]. The MPC is for-
mulated as a weighted multivariable constrained nonlinear
programming problem with a quadratic objective function subject
to the differential or differential-algebraic equations of the dynamic
model and to specific bounds on the states and the manipulated
variables as well:
⎧ k+hp k +hp −1
⎪ ∑ ω j ( x j − x j ) + ∑ ω1,l (ul − ul ) ⎪
set 2 tar 2
⎪ j =k+1 l =k
min
u(k )…. u(k +hc −1)
⎨ k +hp −1
⎪ ⎪
∑ ( (i ) (i −1)
)
2
⎪ + ω 2,l u l − ul
⎩ l =k
subjject to:
⎧ x min
j ≤ x j ≤ x max
j
⎪ min
⎪ul ≤ ul ≤ ul
max
⎨ (i),min
⎪Δul ≤ Δul(i) = ul(i) − ul(i−1) ≤ Δul(i),max
⎪Convolution Model
⎩
where u stands for the manipulated variables; x stands for con-
trolled variables, ω stands for the weight of each single term; hp
stands for prediction horizon; k stands for the number of sam-
pling times; set and tar stand for setpoint and target, respectively.
101
The first quadratic term ensures that the controlled variables stay
as close as possible to their respective setpoints. The second qua-
dratic term suggests desired values for the manipulated variables
(usually related to energy saving policies). Finally, the third qua-
dratic term is the so-called anti-ringing that aims at preventing
possible close-loop instabilities. In practice, it smoothens the optimal
trajectory of the manipulated variables, thus avoiding repeated fluc-
tuations over time. All the aforementioned terms are represented
as vectors of differences properly weighted (w). The weighting co-
efficients allow balancing the order of magnitude of each term and/
or hierarchically rank them. Despite its benefits, the application of
MPC to real life systems is still an open issue when the dynamic
system model has a distributed nature, as PBR does. Some authors
are working in this direction on other systems [219] but general
methodologies are still unavailable. The reason for this has to do
with the computational time required to solve optimization problem
and the issue of handling the solution of partial differential equa-
tions automatically. Both of these are still challenging problems.
Manenti and Bozzano [207] proposed an MPC framework applied
to the methanol synthesis reactor in order to simultaneously control
the dynamic temperature profile and the axial position of the hot-
spot. These goals were achieved by manipulating the shell-side
temperature and the recycle flowrate. Thanks to this control scheme,
two major benefits are ensured: the reactor is optimally con-
trolled and the position of the temperature hot-spot is managed to
prevent the catalyst from sintering. An approach similar to MPC is
called DRTO [220,221]. The difference is that MPC solves a control
problem via a quadratic objective function while DRTO refers to eco-
nomic aspects and relies on an economic objective function.
Moreover, the degrees of freedom of MPC are the manipulated vari-
⎫ ables whereas those of DRTO are the setpoints of the controlled
⎪ variables. It means that the DRTO is able to suggest operating con-
⎬ ditions that optimally track the market trends (e.g. the methanol
⎪ grade production) without modifying the conventional control loops
⎭ (instead MPC overwrites these conventional loops). Rahimpour and
co-workers [222,223] applied the DRTO to a membrane reactor and
a spherical-bed reactor for methanol synthesis proposing optimal
state/manipulate variable trajectories. Kordabadi and Jahanmiri [224]
(40) extended the concept of DRTO (usually adopted on the short-
term) to the identification of optimal trajectories related to the
catalyst bed deactivation. Fig. 26 reports the optimal trend they found
for the shell side temperature and the related profile of the tube
side temperature during 1400 days of operations. Clearly, as the cat-
alyst loses activity, the DRTO raises the shell temperature
progressively. Fuad et al. [225] have also implemented the newest
techniques for DRTO included in the Interior Point OPTimizer (IPOPT)
102 G. Bozzano, F. Manenti / Progress in Energy and Combustion Science 56 (2016) 71–105
[203] for the long-term optimization of methanol synthesis subject
to catalyst deactivation.
6. Conclusions
Methanol is a very important compound. The development of
processes capable of producing it from residues and waste is a hot
research topic worldwide. Methanol is also expected to be a po-
tential solution to the partial deployment of fossil source-based
economies. Moreover, it is a recognized energy carrier that is
better than other alternatives in terms of transportation, storage
and reuse.
Technologies to produce it are mature and of different nature.
Improvements are expected from new processes based on slurry
and membrane reactors. In addition, heat removal and recovery is
a potential field of innovation for single and multi fixed-bed reactor
configurations. In every case, new or improved catalysts for meth-
anol production are likely to be discovered in the near future. These
catalytic materials are expected to allow lowering the tempera-
ture and pressure required for the methanol synthesis reaction. While
pressure is still useful to favor the reaction that is limited by the
thermodynamic equilibrium, the current temperature of the meth-
anol synthesis process is over the Huttig temperature, thus promoting
the catalyst sintering.
Since the operating conditions of current industrial processes are
rather different from those of several decades ago, the scientific com-
munity should start expanding the validity range of the current
available kinetic models. In addition, new kinetic models will be nec-
essary, which account for morphological modifications in the catalyst
structure due to different operating conditions. These new models
will clarify the contribution of the single mechanisms through which
methanol is synthesized (CO and CO2 routes). This will be of inter-
est for the relevant problem of CO2 reuse. Kinetic models both for
methanol synthesis and for similar systems, which are able to
account for the dynamic modifications in the catalyst structure in
operation, are going to spread.
Transport phenomena have been studied in detail and under-
stood. Moreover, there seems to be a certain convergence in the
literature between the need of academia for complex models and
that of industry for simpler models. This is going to take to rea-
sonable compromises between accuracy of the model predictions
and computational efforts.
Steady-state models for fixed-bed reactors are very well con-
solidated, even though there is still the need for further refinements,
e.g. the conversion of molar balances to mass balances to improve
the prediction accuracy. Conversely, other reactor configurations have
not been exhaustively studied yet. This is the case of slurry and mem-
brane reactors. The scientific community is expected to explore all
main chemical and physical phenomena governing these very prom-
ising and emerging technologies.
A different picture emerges for dynamic models because the dis-
tributed nature of the fixed-bed methanol reactor makes their
development rather cumbersome. According to the future need for
producing methanol from biomass and biogas, significant variabil-
ity in the feedstock, in the syngas composition and in the operating
conditions will be experienced. This will soon demand detailed a
priori analyses unavoidably based on dynamic models. The main
problem is still the complex numerical solution of partial differ-
ential equations. Moreover, the assumptions required to model the
dynamics of the methanol synthesis reactor differ from those in-
troduced for steady-state modeling. The future development of
reliable and possibly low computational demanding dynamic models
as well as the improvements in computing infrastructures will allow
applying concepts like model predictive control and dynamic op-
timization, already successfully adopted elsewhere, to the complex
methanol reactor as well. The literature lacks of contributions
concerning operations management studies but the industrial ten-
dency to integrating different production processes to save energy
and capital cost (e.g. methanol synthesis and biomass gasifica-
tion) will stimulate research in such field.
Another expected development is related to the number of
process parameters to design/optimize in methanol plants. The lit-
erature is proposing self-consistent cases, which consider single units
or parts of the methanol synthesis process. Others are considering
simplified optimization procedures to improve the design of the
whole plant. The perspective is to move toward an overall plant op-
timization based on detailed models, which includes process yield,
CO2 conversion, steam co-generation, pre-heating/pre-cooling energy
intensification, and so on.
Beyond all the aforementioned concepts, there is still strong lack
of experimental and industrial data concerning methanol-related
production systems.
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