processes

Article
A Detailed Process and Techno-Economic Analysis of Methanol
Synthesis from H2 and CO2 with Intermediate Condensation Steps
Bruno Lacerda de Oliveira Campos *, Kelechi John, Philipp Beeskow, Karla Herrera Delgado * , Stephan Pitter ,
Nicolaus Dahmen and Jörg Sauer

Institute of Catalysis Research and Technology (IKFT), Karlsruhe Institute of Technology (KIT),
Hermann-von Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany
* Correspondence: bruno.campos@kit.edu (B.L.d.O.C.); karla.herrera@kit.edu (K.H.D.)

Abstract: In order to increase the typically low equilibrium CO2 conversion to methanol using
commercially proven technology, the addition of two intermediate condensation units between
reaction steps is evaluated in this work. Detailed process simulations with heat integration and
techno-economic analyses of methanol synthesis from green H2 and captured CO2 are presented here,
comparing the proposed process with condensation steps with the conventional approach. In the new
process, a CO2 single-pass conversion of 53.9% was achieved, which is significantly higher than the
conversion of the conventional process (28.5%) and its equilibrium conversion (30.4%). Consequently,
the total recycle stream flow was halved, which reduced reactant losses in the purge stream and the
compression work of the recycle streams, lowering operating costs by 4.8% (61.2 M€·a−1 ). In spite of
the additional number of heat exchangers and flash drums related to the intermediate condensation
units, the fixed investment costs of the improved process decreased by 22.7% (94.5 M€). This was a
Citation: Lacerda de Oliveira
consequence of the increased reaction rates and lower recycle flows, reducing the required size of the
Campos, B.; John, K.; Beeskow, P.;
main equipment. Therefore, intermediate condensation steps are beneficial for methanol synthesis
Herrera Delgado, K.; Pitter, S.;
from H2 /CO2 , significantly boosting CO2 single-pass conversion, which consequently reduces both
Dahmen, N.; Sauer, J. A Detailed
Process and Techno-Economic
the investment and operating costs.
Analysis of Methanol Synthesis from
H2 and CO2 with Intermediate Keywords: methanol synthesis; CO2 utilization; power-to-X; intermediate condensation steps;
Condensation Steps. Processes 2022, product removal; techno-economic analysis; heat integration; plant simulation
10, 1535. https://doi.org/10.3390/
pr10081535

Academic Editors: Elio Santacesaria,

1. Introduction
Riccardo Tesser and Vincenzo Russo
Sustainable solutions are required to reduce the greenhouse gas emissions of the
Received: 13 July 2022 transportation and industrial sectors, shrinking the dependency on fossil fuels. With the
Accepted: 3 August 2022
continuously increasing installed capacity of wind and solar power plants [1], adequate
Published: 5 August 2022
energy storage solutions have to be implemented in order to deal with their fluctuating
Publisher’s Note: MDPI stays neutral nature. Therefore, the conversion of electricity into valuable chemicals and fuels, a concept
with regard to jurisdictional claims in often called power-to-fuels or power-to-X, can make an important contribution to the
published maps and institutional affil- future energy system [2]. In this context, key process steps are hydrogen generation via
iations. electrolysis (primary conversion) [3,4] and methanol synthesis (secondary conversion) [5].
Methanol can be used as a fuel substitute or additive, either in fuel cells or via
combustion [2], as a feedstock in the production of base chemicals (e.g., formaldehyde)
and liquid fuels (e.g., gasoline, oxymethylene ethers, jetfuel) [6–8], and also as a solvent.
Copyright: © 2022 by the authors.
Methanol fuel has recently attracted significant interest, especially in China, where the
Licensee MDPI, Basel, Switzerland.
consumption of methanol for thermal applications (e.g., boilers, kilns, cooking stoves) and
This article is an open access article
in the transportation section amounted to 5.7 Mton·a−1 (year 2019) [9].
distributed under the terms and
The current global capacity of methanol production is 164 Mton·a−1 (year 2021), with
conditions of the Creative Commons
Attribution (CC BY) license (https://
an annual increase of 10% projected for the next decade [10]. Traditionally, methanol
creativecommons.org/licenses/by/
synthesis is fed by fossil-based syngas, which comes either from steam reforming of natural
4.0/).
gas or from coal gasification [11]. However, sustainable syngas production is gaining

Processes 2022, 10, 1535. https://doi.org/10.3390/pr10081535 https://www.mdpi.com/journal/processes

 (e.g., boilers, kilns, cooking stoves) and in the transportation section amounted to
5.7 Mton·a−1 (year 2019) [9].
The current global capacity of methanol production is 164 Mton·a−1 (year 2021),
with an annual increase of 10% projected for the next decade [10]. Traditionally,
Processes 2022, 10, 1535 methanol synthesis is fed by fossil-based syngas, which comes either from steam 2 of 24
reforming of natural gas or from coal gasification [11]. However, sustainable syngas
production is gaining importance, such as from renewable electricity and captured
CO 2, and also
importance, suchfrom biomass.
as from In electricity
renewable Figure 1,anda scheme
capturedisCOpresented showing the
2 , and also from biomass.
intermediate
In Figure 1, a scheme is presented showing the intermediate position of methanol inand
position of methanol in the conversion of both fossil-based the
sustainable
conversion ofsyngas to added-value
both fossil-based chemicals
and sustainable and to
syngas fuels, as well as
added-value methanol
chemicals and end-
fuels,
use applications.
as well as methanol end-use applications.

Figure 1.
Figure The key
1. The key position
positionofofmethanol
methanoltotoconvert
convertsyngas
syngassources into
sources added-value
into chemicals
added-value and
chemicals
fuels. Icons from: Freepik, Flaticon [12].
and fuels. Icons from: Freepik, Flaticon [12].

The current world-scale technology for methanol synthesis is mostly based on the
The current world-scale technology for methanol synthesis is mostly based on
application of Cu/ZnO/Al2 O3 (CZA) catalysts in either multi-tube reactors with boiling
the application of Cu/ZnO/Al2O3 (CZA) catalysts in either multi-tube reactors with
water as the cooling fluid, normally called isothermal reactors (e.g., the Lurgi process, the
boiling water as the cooling fluid, normally called isothermal reactors (e.g., the
Linde process), or adiabatic reactors with intermediate cold syngas quenching, generally
Lurgi process, the Linde process), or adiabatic reactors with intermediate cold
named quench reactors (e.g., ICI and the Casale process, the Haldor Topsoe process) [11,13].
syngas quenching, generally named quench reactors (e.g., ICI and the Casale
Less common but also industrially applied are the adiabatic reactors with intermediate
process, the Haldor Topsoe process) [11,13]. Less common but also industrially
cooling (e.g., the Kellogg process, the Toyo process) [11,14]. Normally, temperatures
applied are the adiabatic reactors with intermediate cooling (e.g., the Kellogg
between 200 and 300 ◦ C and pressures between 50 and 100 bar are applied [13].
process, the Toyo process) [11,14]. Normally, temperatures between 200 and 300 °C
Methanol can be produced from either CO (Equation (1)) or CO2 (Equation (2)),
and pressures between 50 and 100 bar are applied [13].
with the reverse water–gas shift reaction (rWGSR, Equation (3)) also occurring. If the
feedMethanol canboth
gas contains be produced
CO and from
CO2 , either CO
there is (Equation (1))
a prevailing or CO
opinion 2 (Equation (2)),
that direct CO hy-
with the reverse water–gas shift reaction (rWGSR, Equation (3)) also
drogenation (Equation (1)) on Cu/Zn-based catalysts is significantly slower occurring.
than CO If
2
the feed gas contains both CO and CO 2, there is a prevailing opinion that direct CO
hydrogenation [15,16], and kinetic models not considering this reaction can adequately
hydrogenation (Equation
simulate experimental data(1)) on Cu/Zn-based catalysts is significantly slower than
[17–19].
CO2 hydrogenation [15,16], and kinetic models not considering this reaction can
0 −1
adequately CO (g) + 2·experimental
simulate H2(g)  CH3 OH (g) [17–19]. ∆H25 ◦ C = −90.6 kJ·mol
data (1)
CO( ) + 2 ∙ H ( ) ⇄ CH OH( ) ∆𝐻 ° =0 −90.6 kJ ∙ mol (1)
−1
CO2(g) + 3·H2(g)  CH3 OH(g) + H2 O(g) ∆H25 ◦ C = −49.4 kJ·mol (2)
0 −1
CO2(g) + H2(g)  CO(g) + H2 O(g) ∆H25 ◦ C = 41.2 kJ·mol (3)
With regard to the general use of CO2 as a carbon source, several process simulations
and techno-economic analyses of methanol synthesis from green hydrogen and captured
CO2 have been reported, with the CO2 source being either a cleaned industrial flue gas or
concentrated atmospheric CO2 (i.e., through carbon capture units, CCUs) [20–22]. Pérez-
Fortes et al. [20] and Szima et al. [21] simulated a methanol synthesis plant with CZA,
 With regard to the general use of CO2 as a carbon source, several process
simulations and techno-economic analyses of methanol synthesis from green
hydrogen and captured CO2 have been reported, with the CO2 source being either
a cleaned industrial flue gas or concentrated atmospheric CO2 (i.e., through carbon
Processes 2022, 10, 1535 capture units, CCUs) [20–22]. Pérez-Fortes et al. [20] and Szima et al. [21] simulated 3 of 24
a methanol synthesis plant with CZA, having a total production of 440 and 100 kton
MeOH·a−1, respectively. Heat integration was considered in both studies, with the
plant
havingbeing
a totalenergetically
production ofself-sufficient.
440 and 100 kton Cordero-Lanzac et al. [22]Heat
MeOH·a−1 , respectively. simulated the
integration
production of 275 kton MeOH·a −1 with an In2O3/Co catalyst. In all studies, it was
was considered in both studies, with the plant being energetically self-sufficient. Cordero-
concluded
Lanzac et al. that
[22]economic
simulatedviability can be achieved
the production of 275 kton if MeOH
reactant·a−prices
1 with significantly
an In2 O3 /Co
decrease or if CO taxation is enforced. Nonetheless, it is expected
catalyst. In all studies, it was concluded that economic viability can be achieved
2 that theifcosts of
reactant
electrolysis and CCUs
prices significantly mightor
decrease considerably
if CO2 taxation decrease in the foreseeable
is enforced. Nonetheless,future [23,24],
it is expected
and the costs
that the first of
industrial-scale
electrolysis andplants CCUs to produce
might e-methanol
considerably decreaseandine-gasoline
the foreseeable are
expected to start operating in 2024–2025 [25,26].
future [23,24], and the first industrial-scale plants to produce e-methanol and e-gasoline
A general
are expected argument
to start is the
operating thermodynamic
in 2024–2025 [25,26]. restrictions of CO2 conversion to
methanol compared to CO conversion
A general argument is the thermodynamic (see Figure of2),COwhereby
restrictions 2 conversion only limited
to methanol
methanol
comparedyields
to COare achievable
conversion (seeeven at elevated
Figure 2), wherebypressures and lower
only limited temperatures.
methanol yields are
Consequently,
achievable even at a elevated
low CO pressures
2 single-pass
and lowerconversion
temperatures. 𝑋 ,
( Consequently,
) is aobtained
low CO2
independently of the reactor
single-pass conversion (XCO2 ,SPsize, leadingindependently
) is obtained to large recycle streams,
of the reactorwhich increase
size, leading to
operating costs
large recycle and cause
streams, whichhigher
increase reactant losses
operating in and
costs purge streams.
cause higher reactant losses in
purge streams.

Figure 2.2.Methanol
Figure Methanol equilibrium
equilibriumyieldyield
as a function of temperature
as a function and pressure.
of temperature andData generatedData
pressure. with
generated
Aspen Plus.with Aspen
(a) H2 /CO Plus.
feed (a)
in a H
2:12/CO
ratio.feed
(b) in
H 2 a 2:1
/CO 2 ratio.
feed in(b)
a H
3:12/CO
ratio.
2 feed in a 3:1 ratio.

IfIf the
the products
products (i.e., methanol
(i.e., methanoland water) are removed
and water) from the from
are removed reactingthesystem, the
reacting
thermodynamic
system, equilibrium equilibrium
the thermodynamic is shifted towards a higher
is shifted towardsmethanol
a higheryield. This strategy
methanol yield.
has been
This studied
strategy hasusing
beenalternative
studied reactor designs withreactor
using alternative in situ condensation
designs with[27,28] or
in situ
membrane reactors [29], but these technologies are not yet ready for
condensation [27,28] or membrane reactors [29], but these technologies are not yet commercialization.
A feasible
ready for approach using commercially
commercialization. proven
A feasible technology
approach usingiscommercially
the implementationprovenof
intermediate condensation steps between reactor units displaced
technology is the implementation of intermediate condensation steps between in series. In the Davy
series loop
reactor methanol
units displaced process, two reactors
in series. with an
In the Davy intermediate
series condensation
loop methanol unittwo
process, are
proposed for large scale methanol production from CO-rich syngas
reactors with an intermediate condensation unit are proposed for large scale [13,30]. Although the
implementation
methanol of intermediate
production from CO-rich condensation steps is Although
syngas [13,30]. a promising thestrategy to increase
implementation
methanol yield from H2 /CO2 syngas, such an approach has still not received particular
attention, and plant simulations with heat integration and techno-economic analyses are
not available in the literature yet, to the best of our knowledge.
In this work, the conventional approach (named here the ‘one-step process’) is com-
pared with a new alternative approach including two condensation steps (named here the
‘three-step process’). Using our recently developed kinetic model for methanol synthesis [19],
both processes were implemented in Matlab in order to critically analyze and select key
process parameters (i.e., cooling fluid temperature, number of reactor modules, and purge
fraction). With the optimized parameters, detailed methanol synthesis plants with heat inte-
gration were implemented in Aspen Plus, and techno-economic analyses were performed.
Processes 2022, 10, 1535 4 of 24

2. Methodology
2.1. Process Overview
In the present work, a methanol synthesis plant from H2 /CO2 with a production of
145 ton·h−1 is considered. This value is based on an ongoing power-to-gasoline project
via H2 /CO2 conversion to methanol [26], whose final goal is a gasoline production of
5.5·108 L·a−1 , which corresponds to a methanol production of 1.16 Mton·a−1 or 145 ton·h−1
(assuming a yield of 80% in the methanol-to-gasoline process and plant operating hours
of 8000 h·a−1 ).
In our simulations, feed carbon dioxide comes from the cleaned flue gas of nearby
industries (e.g., a cement industry) at 25 ◦ C and 1 bar, with a purity of 99.5% mol/mol (the
rest was water). Feed hydrogen comes from water electrolysis at 25 ◦ C and 30 bar, with a
purity of 99.5% mol/mol (the rest was nitrogen). Although it is possible to obtain these
feedstocks in an extremely high purity (e.g., 99.99% mol/mol) [31,32], we chose a more
conservative scenario, which also allows a proper simulation of inert material accumulation
in the plant.
As pressure has a significant influence on the thermodynamic equilibrium of methanol
synthesis (see Figure 2), the reactor operating pressure was set to 70 bar. Although higher
pressures are reported to have potential in methanol synthesis [33,34], they were out
of the scope of this work, since considerable extrapolations in the kinetic model would
be necessary, and condensation inside the reactor might have to be taken into account.
Besides, higher pressures increase compression costs and might also require more expensive
materials to build the equipment.
The dimensions of the reactor modules were chosen to be close to the upper size
limits that are currently commercially available. That is, each reactor module consisted of
a shell containing 33,000 tubes with 12.5 m length and an inner diameter of 3.75 cm.
Since the heat generation in CO2 hydrogenation is lower than in CO hydrogenation
(Equations (1) and (2)), less heat transfer area is necessary. Because of that, the tube inner
diameter chosen in this work (3.75 cm) was larger than the size typically used for CO
conversion to methanol (2.5 cm). Considering 1050 kg·m−3 as the apparent catalyst bed
density [35], the total CZA catalyst loading of each reactor module was 478.13 ton. A total
pressure loss of 0.75 bar was considered for each reactor module [36].

2.1.1. One-Step Approach—Process Description

In Figure 3, a detailed flowsheet of the one-step process is presented. This is an
adapted version from a concept reported in the literature [37–39]. Feed CO2 is mixed
with a low-pressure recycle stream, and then compressed from 1 to 70 bar in a three-stage
process, including intermediate cooling (reducing compression work) and intermediate
phase separation (to remove condensed methanol and water from the recycle stream). The
resulting compressed stream is mixed with feed H2 (compressed from 30 to 70 bar in one
stage) and with a high pressure recycle stream. The mixed stream is preheated with the
product gas and enters the inner tubes of parallel reactor modules, with the temperature
being controlled by boiling water on the shell side.
The product stream is cooled down to 30 ◦ C in four heat exchangers, condensing
water, methanol, and some CO2 , which are separated from the light gases in a flash drum.
A fraction of the gas stream is purged, and the remaining stream is recompressed to 70 bar
and recycled. The liquid stream from the flash drum is depressurized to 1 bar and heated
to 30 ◦ C, vaporizing most remaining CO2 . A liquid–gas separation is performed in another
flash drum. A fraction of the gas stream from the low-pressure flash drum is purged, and
the rest is recycled by mixing with feed CO2 . The liquid stream from the low-pressure
flash drum is preheated and fed to a packed column, where methanol in high purity
(>99.5% m/m) is recovered in the liquid distillate, water is recovered in the bottom, and
most of the remaining CO2 is recovered in the gas distillate.
 Processes 2022, 10, x FOR PEER REVIEW 5 of 26

Processes 2022, 10, 1535 5 of 24

parallel reactor modules, with the temperature being controlled by boiling water
on the shell side.

Figure 3. One-step process—detailed flowsheet with a total of three reactor modules.

Figure 3. One-step process—detailed flowsheet with a total of three reactor modules. Cooling water
Cooling water streams are omitted.
streams are omitted.
The product stream is cooled down to 30 °C in four heat exchangers,
The purge streams are burned with 15% air excess in a fired heater [40]. The heat of
condensing water, methanol, and some CO2, which are separated from the light
reaction
gases inofabothflashthe purge
drum. A combustion
fraction of the andgas
thestream
methanol synthesis
is purged, arethe
and used in a water
remaining
Rankine ◦
stream is recompressed to 70 bar and recycled. The liquid stream from the 99.6
cycle to produce electricity. The cycle starts with liquid water at 1 bar and flash C
being
drum pumped to a certain to
is depressurized pressure,
1 bar andwhose boiling
heated to temperature corresponds
30 °C, vaporizing most to the desired
remaining
reactor
CO2. A temperature. Pressurizediswater
liquid–gas separation reaches
performed inits boilingflash
another temperature
drum. Ainfraction
two steps (heat
of the
exchanger
gas stream andfromfired
theheater) and vaporizes
low-pressure flash druminside the reactor
is purged, andmodules.
the rest is The produced
recycled by
mixing with
saturated steamfeed CO2. heated
is further The liquid
in thestream fromand
fired heater thethen
low-pressure
performs work flashindrum is
a turbine,
preheated
with a dischargeand pressure
fed to a of packed
1.43 barcolumn, = 110 ◦ C).
(Tboiling where methanol in high
The resulting purity (>99.5%
low-pressure steam
m/m) is recovered
condenses partially in in the
the column
liquid distillate,
reboiler, water is recovered
and total condensationin the is bottom,
completed andinmost
a heat
of the remaining CO 2 is recovered in the gas distillate.
exchanger, closing the water cycle.
The purge streams are burned with 15% air excess in a fired heater [40]. The
heat of reactionApproach—Process
2.1.2. Three-Step of both the purge combustion
Description and the methanol synthesis are used
in a water Rankine cycle to produce electricity. The cycle starts with liquid water at
1 barIn Figure
and 99.6 4, a°C
detailed
being flowsheet
pumped to of the three-step
a certain processwhose
pressure, is presented.
boilingIntemperature
this approach,
the feed compression and recycling of non-converted reactants
corresponds to the desired reactor temperature. Pressurized water reaches occurs similarly to theits
one-
step process.
boiling The mixedinfeed
temperature twostream is preheated
steps (heat exchangerand and
enters the heater)
fired first reactor
and module.
vaporizes The
product ◦ C in three steps, and the condensed stream (mostly water,
inside gas
the is cooledmodules.
reactor down to 45 The produced saturated steam is further heated in the
methanol, and some CO2 ) is separated from the light gases in a flash drum. The gas stream
is preheated and enters the second reactor module. The second product gas is cooled down
to 30 ◦ C in three steps, and the condensed stream (mostly water, methanol, and some CO2 )
is separated from the gas stream in another flash drum.
 approach, the feed compression and recycling of non-converted reactants occurs similarly
to the one-step process. The mixed feed stream is preheated and enters the first reactor
module. The product gas is cooled down to 45 °C in three steps, and the condensed stream
(mostly water, methanol, and some CO2) is separated from the light gases in a flash drum.
The gas stream is preheated and enters the second reactor module. The second product
Processes 2022, 10, 1535 6 of 24
gas is cooled down to 30 °C in three steps, and the condensed stream (mostly water,
methanol, and some CO2) is separated from the gas stream in another flash drum.

Figure 4. Three-step process—detailed flowsheet with a total of three reactor modules. Cooling
Figure 4. Three-step process—detailed flowsheet with a total of three reactor modules. Cooling water
water streams are omitted.
streams are omitted.

The gas phase is preheated and enters the third reactor module. The third product
gas is cooled down, mixed with the condensed streams from the first and second reaction
stages, and further cooled down to 30 ◦ C.
Similar to the one-step process, component separation of the product stream is per-
formed with one flash drum at high pressure, one flash drum at ambient pressure, and one
distillation column.
The purge stream is burned in a fired heater with preheated air. In the water cycle,
pressurized water is preheated and distributed to the reactor modules. A fraction of the
produced saturated steam is split and used to preheat the water while the remaining steam
is further heated in the fired heater. Supersaturated steam performs work in a turbine, with
a discharge pressure of 1.43 bar (Tboiling = 110 ◦ C). The resulting low-pressure steam is
partially condensed in the column reboiler, and total condensation is completed in a heat
exchanger, closing the water cycle.
Processes 2022, 10, 1535 7 of 24

2.2. Process Simulation in Matlab

Before implementing the final version of each plant in Aspen Plus, different scenarios
were investigated in Matlab. Therefore, optimal key parameters were selected, such as the
total number of reactor modules, the purge fraction, and the temperature of the cooling
fluid in the reactor.
In order to simulate the reactor, the following considerations were made: there are only
variations along the length of the reactor (1D assumption), the influence of back-mixing is
neglected (plug flow assumption), and the cooling fluid temperature (Tw , in K) is constant.
Starting from mass and energy balances, the differential equations of the total mole flow of
.
a single tube (n, in mol·s−1 ), the mole fraction of each component j (y j ), and the temperature
(T, in K) in the axial direction z are shown as follows:
. 6 2
dn m
= Cat · ∑ ∑ (νjk ·rk ) (4)
dz L j =1 k =1
( . )
dy j 1 mCat 2 dn
L k∑
= .· · (νjk ·rk ) − y j · (5)
dz n =1
dz
" . 6 
#
dy j

dT 1 dn .
= .  · − ·h f − n· ∑ h j · + U ·π · Di ·( Tw − T ) (6)
dz n·CP, f dz j =1
dz

where mCat is the catalyst mass (kg), L is the reactor length (m), y jk is the stoichiometric
coefficient of component j in reaction k, rk is the rate of reaction k (mol·kgcat ·s−1 ), CP, f is the
heat capacity of the fluid (J·mol·K−1 ), h f is the specific enthalpy of the fluid (J·mol−1 ), h j is
the specific enthalpy of component j, U is the global heat transfer coefficient (W·m−2 ·K−1 ),
and Di is the inner diameter of a single tube (m).
The temperature-dependent parameters (CP, f , h f , h j , U) were updated in each in-
tegration point in the axial direction. Heat capacity and enthalpy were calculated with
the thermodynamic functions provided by Goos et al. [41], which are detailed in the
Supplementary Material (Section A) along with the derivation of the differential equations.
The global heat transfer coefficient was estimated (U) by summing the heat transfer resis-
tances in the axial direction, according to the methodology described in the literature [42,43]
(see Section B of the Supplementary Material).
The methodology to calculate the reaction rates (rk ) is described in Section 2.3. The
system of differential equations was solved with the Matlab function ode45, with absolute
and relative tolerances set to 10−10 .
In order to simplify the simulation of the separation steps in Matlab, the following
procedure was applied. Both processes were implemented in Aspen Plus, considering a
total of six reactor modules, a purge fraction of 2%, and Tw = 235 ◦ C. The values of the split
ratio of each component in the liquid and gas phase of each flash drum and the distillation
column were extracted. For example, in the column of the one-step process, the methanol
distribution in the outlet streams was: 3.80% in the gas distillate, 96.13% in the liquid
distillate, and 0.06% in the bottom. The split ratio of all the components were taken from
Aspen Plus and were considered constant for the different scenarios investigated in Matlab
(i.e., variations in the number of reactor modules, purge fraction, and Tw ). These split ratios
are provided in the Supplementary Material (Section C).
Flowsheet convergence was achieved in Matlab by an iterative method, as there were
two cycles of streams due to recycling unconverted reactants. First, educated initial guesses
of the composition and total mole flow of each recycle stream were given. In each iteration,
the recycle stream mole flow and its composition were calculated and used in the next
iteration until the tolerance criterion was fulfilled:
Processes 2022, 10, 1535 8 of 24

. .
2
n Re f ,k+1 − n Re f ,k
. 2 ≤ Tolerance (7)
n Re f ,k+1
.
where n Re f ,k is the total mole flow of the recycle stream at iteration k. The tolerance of the
inner cycle and the outer cycle were set to 10−9 and 10−8 , respectively.

2.3. Kinetic Modeling of the Methanol Synthesis

The kinetic simulation of the methanol synthesis was performed with our previously
published six-parameter model (Model-6p) [19], whose considerations regarding the reac-
tion mechanism, the assumption of the rate determining steps, and the most abundant sur-
face species were based on our detailed microkinetic model [15]. This six-parameter model
was validated with 496 experimental points from different laboratory plants [15,18,44],
which contemplated temperatures between 210 and 260 ◦ C, pressures between 20 and 60 bar,
gas hourly space velocities (GHSV) between 1.8 and 40 LS ·h−1 ·gcat −1 , and a variety of
syngas (H2 /CO/CO2 /N2 ) feed compositions, including 126 points with only H2 /CO2 /N2
in feed.
In this model, two main reactions are considered: CO2 hydrogenation (Equation (2))
and the rWGSR (Equation (3)). The reaction rates (rCO2 hyd. , rrWGSR ) in mol·kgcat −1 ·s−1 are
described as follows:
!
f CH3 OH · f H2 O
 
E A,2 1.5
rCO2 hyd. = exp A2 − ·φZn ·θb ·θc · f H2 · f CO2 · 1 − 3 (8)
R· T f H2 · f CO2 ·K0P,CO hyd.
2

!
f CO · f H2 O
 
E A,3
rrWGSR = exp A3 − ·φZn ·θb ·θc · f CO2 · f H2 O · 1 − (9)
R· T f H2 · f CO2 ·K0P,rWGSR
Here, A2−3 and E A,2−3 are kinetic parameters, R is the universal gas constant, φZn is
the zinc coverage on the surface, θb and θc are the free active sites b and c, f j is the fugacity
of gas component j (bar), and K0P,k is the global equilibrium constant of reaction k.
The Peng–Robinson equation of state is used to calculate the fugacities [45], consider-
ing the binary interaction parameters reported by Meng et al. [46] and Meng and Duan [47],
and an effective hydrogen acentric factor of −0.05 proposed by Deiters et al. [48].
The zinc coverage is dependent on temperature and gas concentration [49], and its
exact quantification under reaction conditions is difficult to predict. The zinc coverage is
then considered to be constant and equal to φZn = 0.50 for a general case, while it is set to
φZn = 0.10 for CO2 -rich feed (CO2 /COx > 0.90). The free active sites are calculated with the
following equations:
  −1
0.5
θ b = K2 · f H 2
· f CO2
+ 1 (10)
  −1
−0.5
θ c = K3 · f H2
· f H2 O + 1 (11)

where K2−3 are adsorption parameters. In Table 1, the equilibrium constants as well as the
previously estimated kinetic and adsorption parameters are summarized [19].
The side products of methanol synthesis on Cu/Zn-based catalysts (e.g., hydrocarbons
or dimethyl ether) are typically at low concentrations [13,50]. Several studies reported that
syngas conversion to hydrocarbons or dimethyl ether on commercial CZA at moderate
temperatures (T ≤ 260 ◦ C) is significantly low or even below detection range [15,18,44],
while Condero-Lanzac et al. [22] reported low methane production from H2 /CO2 on CZA
at high temperatures (T ≥ 275 ◦ C). Saito et al. [51] observed that side product formation is
further reduced by increasing CO2 /COX feed concentration. Therefore, the generation of
side products is not considered in this work.
Processes 2022, 10, 1535 9 of 24

Table 1. Equilibrium constants, kinetic and adsorption parameters of Model-6p [19]. Reprinted with
permission from [19]. Copyright 2021 American Chemical Society.

Parameter Value | Equation Unit

A2 14.41 ± 0.99 –
A3 29.13 ± 1.74 –
E A,2 94.73 ± 4.18 kJ·mol−1
E A,3 132.79 ± 7.46 kJ·mol−1
K2 0.1441 ± 0.0289 bar−1.5
K3  ± 11.08
49.44  bar−0.5
K0P,CO2 − 4.481 4755.7 bar−2
hyd. T · exp + 8.369
 T
−5337.4

K0P,rWGSR T − 1.097
· exp + 12.569 –
T

2.4. Process Analysis and Optimization

Considering the fixed methanol production of 145 ton·h−1 or 1257.1 mol·s−1 and the
99.5% mol/mol purity of the reactants, the minimum required feed is 1263.4 mol·s−1 of
.
CO2 and 3790.3 mol·s−1 of H2 , totalizing n f eed,min = 5053.7 mol·s−1 . Since there are reactant
losses in the purge and product streams, an excess of feed is required. With a fix feed ratio
H2 :CO2 of 3:1, the excess of feed (Exc) is defined here as:
. .

n f eed − n f eed,min
Exc = . ·100% (12)
n f eed,min

It is, of course, of interest to minimize feed consumption, due to its high costs. Feed
consumption is affected by key variables, such as reactor temperature and pressure, the
number of reactor modules (which defines the total catalyst mass), and purge fraction.
Avoiding large recycle streams is also important, as compressor work is required to get
the pressure back to 70 bar, and larger equipment (i.e., heat exchangers, flash drums,
compressors) are required to process higher flows.
Simulations were performed for a different number of reactor modules (from 3 to 12)
and different purge fractions (from 0.5 to 5%). For each case, an initial guess for the feed
excess was given (Exc = 5%), and a fix feed ratio H2 :CO2 of 3:1 (a stoichiometric ratio) was
applied. Then, an optimization problem was solved in Matlab with the function fminsearch
(function tolerance = 0.1 mol·s−1 , step tolerance = 0.1 ◦ C), whose objective was to maximize
methanol production by varying the reactor coolant temperature (Tw ).
With the optimum Tw , the required excess of feed was calculated to meet the methanol
demand (1257.1 mol·s−1 ) with Newton’s method (function tolerance: 0.1 mol·s−1 ). The
steps of the temperature optimization and Exc calculations were repeated until the temper-
ature update was lower than 0.25 ◦ C.

2.5. Detailed Plant Simulation in Aspen Plus

After analyzing the results of the Matlab simulations, optimum parameters were
selected for each approach (i.e., the number of reactor modules, purge fraction, cooling fluid
temperature) and a detailed plant simulation including heat integration was implemented
in Aspen Plus V10.
The Peng–Robinson property method was selected for the reactor modules. All other
equipment were simulated with the Non-Random Two-Liquid Model with a second set of
binary parameters (NRTL2) as the property method.
The methanol synthesis reactor was simulated with the rigorous plug flow reactor
model (RPLUG unit) and the kinetics described in Section 2.3 were implemented as a
Langmuir–Hinshelwood–Hougen–Watson (LHHW) reaction model. The rearrangement
of the model parameters to follow the software’s specific input format is detailed in the
Supplementary Material (Section D). Since the reactor cooling fluid is at a constant tem-
perature due to water evaporation, both co-current and counter-current operations give
Processes 2022, 10, 1535 10 of 24

the same results. Therefore, the co-current operation was selected in order to simplify the
mathematical calculations.
The combustion of the purge streams in a fired heater was simulated with the RGIBBS
unit, which considers that chemical equilibrium is achieved when the free Gibbs energy of
the system is minimized.
The heat exchangers were simulated in counter-current flow with the HeatX unit, with
a minimum temperature approach of 25 ◦ C for the heat exchangers located inside the fired
heater and a minimum temperature approach of 10 ◦ C for all the other heat exchangers.
The compressors were modeled using the ASME method, assuming a mechanical
efficiency of 0.95 and an isentropic efficiency of 0.80 [22]. The pump was simulated assum-
ing an efficiency of 0.70. The turbine was simulated with the ASME method, assuming a
mechanical efficiency of 0.95 and an isentropic efficiency of 0.90 [52].
The distillation column was simulated with the rigorous RadFrac model, considering a
kettle reboiler and a partial condenser at 53 ◦ C with liquid and vapor distillate. A Murphree
efficiency of 0.75 was set to all intermediate stages [53,54]. In both processes, the column
had 30 stages and a reflux ratio of 2, with the feed entering above the 24th stage.
The relative tolerance of all equipment calculations was set to 10−5 . Flowsheet conver-
gence was achieved using the Broyden method, with a relative tolerance of 10−4 , which
corresponds to a mass balance closure of 99.99%.

2.6. Efficiency Evaluation

The chemical conversion efficiency (ηCCE ) accounts for how much fuel energy remains
in the final product in relation to the reactants. For methanol synthesis from H2 /CO2 , it is
calculated as follows: [55] .
m MeOH · LHVMeOH
ηCCE = . (13)
m H2 · LHVH2
. .
where m MeOH is the methanol mass production, m H2 is the hydrogen feed demand, and
LHV is the low heating value. The maximum possible efficiency (ηCCE,max ) occurs at 100%
overall H2 conversion to methanol (stoichiometric conversion):

M MeOH · LHVMeOH
ηCCE,max = = 0.876 (14)
3· M H2 · LHVH2

Here, M j is the molar mass of component j. In order to also account for heat and the
work input, the exergy efficiency (ηEx ) is calculated: [39]
.
m MeOH ·e MeOH
ηEx = . . (15)
m H2 ·e H2 + mCO2 ·eCO2 + Pel + EQ

where e j is the specific exergy of component j, Pel is the total required electric power, and
EQ is the total exergy input associated with heat demand.
The specific exergy of a component (e j ) is divided between thermal and chemical exergy: [39]
h i h i
e j ( T, p) = e j,therm + e j,chem = Hj − S j · T0 − Hj0 + S0j · T0 + HHVj (16)

Here, e j,therm and e j,chem are the thermal and chemical exergies, Hj is enthalpy, S j is
entropy, Hj0 and S0j are the enthalpy and entropy at reference conditions (298.15 K and 1 bar),
T0 is the reference temperature, and HHVj is the high heating value. In the exergy efficiency
calculation, the HHV is used instead of the LHV, as water is liquid at reference conditions.

2.7. Techno-Economic Evaluation

In order to calculate the production costs, the standardized methodology from
Albrecht et al. [56] was considered, which is a further development based on the work
of Peters et al. [57].
Processes 2022, 10, 1535 11 of 24

The main equipment costs (EC) were estimated based on reference equipment costs [57,58].
The scale up to the required capacity was performed with specific equipment scaling factors,
and price inflation was corrected to 2020 with the Chemical Engineering Plant Cost Indexes
(CEPCI). In Equation (23), the costs of equipment j (ECj ) is described:
!M !
Cj CEPCI2020
ECj = ECj,re f · · (17)
Cj,re f CEPCIre f

Here, the subscription ref relates to the reference equipment, C is the characteristic
capacity, and M is the equipment scaling factor. The equipment is constructed with carbon
steel. When the reference price is in US dollars (USD), a conversion to euros (EUR) of
1.13 USD·EUR−1 is applied (February 2022) [59].
The dimensions of the flash drums and the packed distillation column were calculated
with the methodology reported by Towler and Sinnott [60]. The required heat transfer area of
the heat exchangers, column condenser, and reboiler were estimated by assuming the typical
global heat transfer coefficients reported by the VDI Atlas [43], according to each specific
situation. Equipment dimensioning is detailed in the Supplementary Material (Section G).
The fixed capital investment (FCI) was estimated by multiplying the total EC with the
Lang Factor (LF), which accounts for all direct and indirect costs related to the plant
construction. In this work, LF was assumed to be 4.86 (details are provided in the
Supplementary Material, Section H) [56,57]. A working capital (WC) of 10% of the total
capital expenses (CAPEX) was considered [56]. Summarizing the equations:

FCI = LF · ∑ ECj (18)

CAPEX = FCI + WC (19)

WC = 0.10·CAPEX (20)
The equivalent annual capital costs (ACC) were estimated by applying the annuity
method on the FCI, assuming an annual interest rate (IR) of 10%, a plant operating life (t P )
of 20 years, and no salvage value [61]. The working capital does not depreciate in value,
and only its interest has to be taken into account [56].

FCI · IR·(1 + IR)tP

ACCFCI = (21)
[(1 + IR)tP − 1]

ACCWC = WC · IR (22)
tP
FCI · IR·(1 + IR)
ACC = ACCFCI + ACCWC = + WC · IR (23)
[(1 + IR)tP − 1]
The operating expenses (OPEX) were divided between direct and indirect costs. The
costs related to the direct OPEX (OPEXdir ) are presented in Table 2, which include raw
materials, catalysts, process water treating, and electricity. A catalyst lifetime of three years
was considered. In the Rankine water cycle, a clean water replacement of 1% of the total
flow was considered [62].
The indirect OPEX consisted of operating labor (OL), operating supervision, mainte-
nance, operating supplies, laboratory charges, taxes on property, insurance, plant overhead,
administration, distribution, marketing, research, and development. The estimation of each
of these items was based on typical values, which are dependent on OL, FCI, and the net
production costs (NPC) (see Section H of the Supplementary Material) [56,57]. The total
indirect OPEX (OPEXind ) is calculated as follows:

OPEXind = 2.2125·OL + 0.081· FCI + 0.10· NPC (24)

Processes 2022, 10, 1535 12 of 24

Table 2. Costs of feedstock, catalyst, water treating, and electricity.

Item Costs Ref.

Hydrogen 3097.4 €·ton−1 [22]
Carbon dioxide 44.3 €·ton−1 [22]
Cooling water 0.00125 €·ton−1 [56]
Clean water 2 €·ton−1 [56]
Total organic carbon (TOC) abatement of process water 1938 €·(ton C)−1 [63]
Electricity 90 €·MWh−1 [53]
Catalyst (Cu/ZnO/Al2 O3 ) 18,100 €·ton−1 [64]

The required number of operators in a shift (nOP ) was estimated with the following
equation: [65,66]
nOP = (6.29 + 0.23· Nnp )0.5 (25)
where Nnp is the number of non-particulate main processing units. Considering daily
working shifts, resting periods and vacations, the number of operators to fulfill each
position in a continuous operation is approximately FOP = 4.5. Therefore, the total number
of operators (NOP ) is: [65,66]
NOP = FOP ·nOP (26)
The total costs of operating labor (OL) is then calculated as follows:

OL = WOP · NOP (27)

where WOP is the wage rate of each operator (WOP = 72,000 €·a−1 ) [53].
The net production costs (NPC) are calculated in terms of average annual costs and in
terms of average costs per kg of methanol:

€
 
NPC = ACC + OPEXdir + OPEXind (28)
a

€
 
( ACC + OPEXdir + OPEXind )
NPC = . (29)
kg m MEOH

3. Results and Discussion

In this section, process simulation and analysis are presented separately for the one-
step and the three-step approaches. Finally, the techno-economic analysis of both ap-
proaches is presented and discussed jointly.

3.1. One-Step Process

3.1.1. One-Step Process—Selecting Key Parameters
The one-step process was successfully implemented in Matlab. Different scenarios
were simulated by varying the number of reactor modules and the purge fraction, with
the optimal temperature for a fixed methanol production (145 ton·h−1 ) being estimated
in each case. In Figure 5, several contour plots are shown, where CO2 single-pass conver-
sion (XCO2 ,SP ) (Figure 5a), the required feed excess (Figure 5b), the optimal temperature
(Figure 5c), and the total recycle stream (Figure 5d) are plotted against the number of reactor
modules and the purge fraction.
CO2 single-pass conversion (Figure 5a) was considerably enhanced by increasing
the number of reactor modules. This was not only because the gas hourly space velocity
(GHSV) decreased, but also because the optimal temperature had lower values (Figure 5c),
shifting the thermodynamic equilibrium towards higher methanol concentrations. In
contrast, reducing the purge fraction had little effect on XCO2 ,SP . This should be the result
of two competing effects: on one hand, a lower purge fraction means higher recycle
streams (Figure 5d), which increases the GHSV, reducing XCO2 ,SP . On the other hand, the
recycle stream has a H2 :CO2 ratio greater than three due to a limited rWGSR extension.
 Processes 2022, 10, 1535 13 of 24

Processes 2022, 10, x FOR PEER REVIEW 14 of 26

By increasing the recycle stream, the H2 :CO2 ratio of the reactor feed stream is enhanced,
positively contributing to XCO2 ,SP .

Figure 5.Figure
One-step process—CO
5. One-step 2 single-pass
process—CO conversion
2 single-pass (a), required
conversion feed excess
(a), required feed(b), optimal
excess (b), optimal
temperature (c), and total recycle stream (d) as a function of the number of reactor modules and
temperature (c), and total recycle stream (d) as a function of the number of reactor modules the and the
purge fraction.
purge fraction.

3.1.2. One-StepTheProcess—Detailed
required feed excess Plant wasSimulation and decreased
significantly Process Analysis
both by increasing the number
of reactor
A detailed modulesofand
flowsheet theby reducing
one-step the purge
process fraction.
presented This occurred
in Figure because the former
3 was implemented
in Aspen procedure increased2%
Plus, considering XCOpurge
2 ,SP and the
fraction,latter
six maintained
reactor modulesX CO working
2 ,SP roughly constant while
in parallel,
and the increasing
optimized the gas flow inside
temperature of thethe reactor
reactor modules.
cooling fluid (𝑇 = 247.5 °C). A picture of
the flowsheetSince the reactants
in Aspen Plus, the(H 2 , CO2 ) represent
properties the highest
of the streams, and acosts of the
detailed plant,
plant it is important to
description
minimize the required feed excess,
are provided in the Supplementary Material (Section E). which according to Figure 5b, occurred at 0.5% purge
In Figure 6, the concentration of the products along the reactor length is shown.considerably
fraction. However, with such a low purge fraction, the total recycle stream was The
methanol high,
anddemanding larger heat exchangers,
water feed concentrations were close flash drums,
to zero, andandtheircompressors, as well as higher
outlet concentrations
were 7.4power
and 7.2%consumption. Therefore, an
mol/mol, respectively. Theintermediate value of 2%remained
nitrogen concentration as the purge fraction was
relatively
selected
low (inlet: 4.95%for the detailed
mol/mol, outlet:simulation
5.65% mol/mol).in AspenDue Plus, agreeing
to the recyclewith otherCO
streams, studies
enteredand typical
industrial values [22,39,58].
the reactor modules at 1.50% mol/mol, although it was not a feedstock in the plant. CO
was produced With the purge
through fraction until
the rWGSR fixed the
at 2%, six reactor
length modules
of 1.5 m, wherewere used in the detailed
its concentration
study, because further increasing the number of reactor
reached 3.3% mol/mol. Then, due to the high water concentration (4.30% mol/mol), modules only slightly reduced
the the
required excess feed, not justifying further expenses in equipment and catalyst.
WGSR became faster than its reverse reaction and started to consume CO, which exited
The value of the global heat transfer coefficient was updated point by point within mathe-
the reactor at 1.76% mol/mol and a marginal selectivity (0.5%). This virtually stabilized −2 −1
matical integration along the reactor length. For the selected condition, Uz=0 = 160 W·m ·K
CO content in the plant led to a high methanol selectivity (99.5%).
 Processes 2022, 10, 1535 14 of 24

and Uz=12.5 = 150 W·m−2 ·K−1 . Since Aspen Plus requires a constant value, the average
value was used (Uavg = 155 W·m−2 ·K−1 ).

3.1.2. One-Step Process—Detailed Plant Simulation and Process Analysis

A detailed flowsheet of the one-step process presented in Figure 3 was implemented
in Aspen Plus, considering 2% purge fraction, six reactor modules working in parallel, and
the optimized temperature of the reactor cooling fluid (Tw = 247.5 ◦ C). A picture of the
flowsheet in Aspen Plus, the properties of the streams, and a detailed plant description are
provided in the Supplementary Material (Section E).
In Figure 6, the concentration of the products along the reactor length is shown. The
methanol and water feed concentrations were close to zero, and their outlet concentrations
were 7.4 and 7.2% mol/mol, respectively. The nitrogen concentration remained relatively
low (inlet: 4.95% mol/mol, outlet: 5.65% mol/mol). Due to the recycle streams, CO entered
the reactor modules at 1.50% mol/mol, although it was not a feedstock in the plant. CO was
produced through the rWGSR until the length of 1.5 m, where its concentration reached
3.3% mol/mol. Then, due to the high water concentration (4.30% mol/mol), the WGSR
Processes 2022, 10, x FOR PEER REVIEW became faster than its reverse reaction and started to consume CO, which exited15theof reactor
26
at 1.76% mol/mol and a marginal selectivity (0.5%). This virtually stabilized CO content in
the plant led to a high methanol selectivity (99.5%).

Figure 6. One-step
6. One-step
Figure process—productconcentration
process—product concentration along
along the
thereactor length.
reactor Reactor
length. feed concentra-
Reactor feed
concentration: H2/CO/CO
tion: H2 /CO/CO 2/CH
2 /CH 3OH/HO/N
3 OH/H 2 2O/N22 = 71.3/1.5/21.9/0.3/0.0/5.0%
71.3/1.5/21.9/0.3/0.0/5.0% mol/mol.
mol/mol.

The The
CO2 CO 2 single-pass
single-pass conversion
conversion was was 28.5%,
28.5%, closeclose
to thetoequilibrium
the equilibrium conversion
conversion
(30.4%), while the feed excess was 6.05%, which corresponded to an overall CO
(30.4%), while the feed excess was 6.05%, which corresponded to an overall CO22 con-
version to
conversion to methanol
methanolofof 94.3%.
94.3%.These
Thesevalues are in
values areagreement with the
in agreement Matlab
with simulations
the Matlab
(XCO2 ,SP (𝑋
simulations = 29.7%,
,
feed
= excess
29.7%, =
feed 5.75%,
excess overall
= CO
5.75%, conversion
overall
2 CO 2 to MeOH
conversion = 94.6%).
to MeOH
= 94.6%).The chemical conversion efficiency (ηCCE ) of the process was 82.6%, which was close
to thechemical
The maximum possible value
conversion (ηCCE,max
efficiency (𝜂 = 87.6%).
) of theWith the heat
process was integration,
82.6%, which the was
one-step
process was not only self-sufficient,
close to the maximum possible value (𝜂 , but had a heat excess that could be supplied
= 87.6%). With the heat integration, to other
processes, in agreement with the literature [21,39]. In our case, as
the one-step process was not only self-sufficient, but had a heat excess that could is commonly performed
in industrial
be supplied methanol
to other synthesis
processes, plants, the heat
in agreement withexcess was used [21,39].
the literature to generate electricity
In our case, via
as isacommonly
water Rankine cycle, reducing
performed the electricity
in industrial consumption
methanol synthesis from
plants, 47.4the
to 17.6
heatMW. excess
In Figure 7, a global exergy balance and an exergy loss distribution
was used to generate electricity via a water Rankine cycle, reducing the electricity are provided.
No distinction
consumption fromwas 47.4made between
to 17.6 MW. exergy destruction and exergy losses via side output
streams (i.e., cooling water, process
In Figure 7, a global exergy balance water, and
andflueangas). The exergy
exergy efficiency (ηExare
loss distribution ) of the
process was 76.4%, with a total exergy loss of 281.9 MW. The main losses occurred due to
provided. No distinction was made between exergy destruction and exergy losses
the exothermic chemical reactions with heat recovery at low temperatures (reactor modules:
via side output streams (i.e., cooling water, process water, and flue gas). The exergy
58.1%, fired heater: 14.8%). Additionally, exergy losses in the heat exchangers (11.1%) and
efficiency (𝜂 ) of the process was 76.4%, with a total exergy loss of 281.9 MW. The
in the column (9.0%) were also significant, mainly due to heat transfer to cooling water.
main losses occurred due to the exothermic chemical reactions with heat recovery
at low temperatures (reactor modules: 58.1%, fired heater: 14.8%). Additionally,
exergy losses in the heat exchangers (11.1%) and in the column (9.0%) were also
significant, mainly due to heat transfer to cooling water.

3.2. Three-Step Process

Processes 2022, 10, 1535 Processes 2022, 10, x FOR PEER REVIEW 15 16
of of
24 26

Processes 2022, 10, x FOR PEER REVIEW 16 of 26

Figure 7. One-step process—exergy

Figure analysis. (a) Global
7. One-step process—exergy exergy
analysis. balance.
(a) Global Total
exergy exergy
balance. input:
Total 1194.5
exergy input:MW.
1194.5
MW.
(b) Distribution of (b) Distribution
exergy of exergy
losses (total losses
= 281.9 MW). (total = 281.9 MW).

3.2.
a) Three-Step Process
CO2 single-pass conversion (%) b) Feed excess (%)
53.2.1. 5
Three-Step Process—Selecting Key Parameters 6
65
The three-step process was successfully implemented in Matlab. In Figure5 8, CO2
4 4
Purge fraction (%)

Purge fraction (%)

single-pass conversion (XCO2 ,SP ) (Figure

62 8a), the required feed excess (Figure 8b), the
4
optimal temperature (Figure 8c), and the total recycle stream (Figure 8d) are described as
3 59 3
a function of the number of reactor modules and the purge fraction. Since this3 process
considers three reaction steps
Figure 7. with
One-step intermediate
process—exergy cooling,
analysis. the
(a) Global simulations
exergy balance. Totalwere
exergylimited to
input: 1194.5
2 56 2 2
multiples of three MW.
as the total number
(b) Distribution of reactor
of exergy modules.
losses (total = 281.9 MW).

53 1
1 a) CO2 single-pass conversion (%) 1 b) Feed excess (%)
5 5 60
3 6 9 12 5065 3 6 9 12
5
Number
4 of reactor modules 4 Number of reactor modules
Purge fraction (%)

(%) fraction (%)

62
c) Optimal cooling fluid temperature (°C) d) 4
Total recycle stream (kmol·h −1
)
5 3 59 53
260 40,000
3

255
Purge fractionPurge

2 56 42 2
4 34,000
Purge fraction (%)

250
53 1
1 31 28,000
3
245 0
3 6 9 12 50 3 6 9 12 22,000
2 Number of reactor modules 240 2
Number of reactor modules
c) Optimal cooling fluid temperature
235 (°C) d) 16,000
Total recycle stream (kmol·h −1
)
1 5 15
260 40,000
230 10,000
3 6 9 12 255 3 6 9 12
4 4 34,000
Purge fraction (%)
Purge fraction (%)

Number of reactor modules Number of reactor modules

250
3 3 28,000
Figure 8. Three-step process—CO2 single-pass conversion (a), required feed excess (b), optimal
245
temperature (c), and total recycle stream (d) as a function of the number of reactor modules and the
22,000
2 purge fraction. 240 2

235 16,000
1 1
230 10,000
3 6 9 12 3 6 9 12
Number of reactor modules Number of reactor modules

Figure 8. Three-stepFigure 8. Three-step single-pass

process—CO process—CO2 conversion
single-pass conversion (a), required
(a), required feed feed excess
excess (b),(b),optimal
optimal
2
temperature (c), and total recycle stream (d) as a function of the number of reactor modules and the
temperature (c), andpurge
totalfraction.
recycle stream (d) as a function of the number of reactor modules and the
purge fraction.
Processes 2022, 10, 1535 16 of 24

A significant improvement was seen in the three-step process in relation to the one-step
approach. For similar conditions (i.e., the same total number of reactor modules and purge
stream fraction), CO2 single-pass conversion had approximately doubled, the required
feed excess decreased by 60–70%, and the total recycle stream decreased by 50–70%. The
optimal values for the reactor cooling fluid remained close to the ones of the first approach
(between 230 and 260 ◦ C).
Similarly to the one-step process, a purge fraction equal to 2% was chosen here, having
a good compromise between minimizing the feed requirements and minimizing the total
recycle stream. With this fixed purge fraction, a number of reactor modules equal to three
was selected, as further increasing this amount gave limited improvement in the required
feed excess and the total recycle stream, while considerably increasing equipment and
catalyst costs.
When analyzing different scenarios in Matlab, the same cooling fluid temperature
(Tw ) was considered for all reactors. A further optimization was possible by allowing this
temperature to be independently operated in each reactor. This possibility was checked
for the chosen condition (2% purge fraction, three reactor modules), but only a marginal
improvement was obtained (see Table 3), probably not justifying the increase in plant
complexity. Therefore, in the detailed analysis, the cooling fluid temperature of all the
reactors was set to 258.5 ◦ C.
Table 3. Three-step synthesis—Performance indicators for two process approaches: same cooling
fluid temperature in all reactors, and independent optimization of the cooling fluid temperature in
each reactor.

Tw,R1 Tw,R2 Tw,R3 XCO2 ,SP Feed Total Recycle

Approach
(◦ C) (◦ C) (◦ C) (%) Excess (%) Stream (kmol·h−1 )
Same Tw 258.5 258.5 258.5 54.1 2.42 23,038
Varying Tw 264.6 259.9 249.4 54.6 2.35 22,464

Similarly to the one-step process, the average heat transfer coefficients were obtained
for each reactor and given to Aspen Plus: U1 = 327 W·m−2 ·K−1 , U2 = 285 W·m−2 ·K−1 ,
U3 = 246 W·m−2 ·K−1 . The decrease in the coefficient values is associated with a decrease
in total flow, due to intermediate product removal. Still, the heat transfer coefficients were
higher than in the one-step process (155 W·m−2 ·K−1 ), which had lower flows for each
reactor module because of parallel operation.

3.2.2. Three-Step Process—Detailed Plant Simulation and Process Analysis

A detailed flowsheet of the three-step process presented in Figure 4 was implemented
in Aspen Plus, considering a 2% purge fraction, three reactor modules working in series
with intermediate product condensation, and the previously optimized temperature of the
reactor cooling fluid (Tw = 258.5 ◦ C). A detailed plant description, stream properties, and a
picture of the flowsheet in Aspen Plus are provided in the Supplementary Material (Section F).
In Figure 9, the concentration of the products along the length of the three reactors is
shown, as well as the product removal through the intermediate condensation steps. In
Reactor 1, CO entered at a low concentration (1.3% mol/mol), peaked at z = 2.5 m, and
left the reactor with a higher concentration (2.7% mol/mol). This CO production through
R ,out
the rWGSR increased the water concentration (y H12 O = 5.6% mol/mol) and slowed down
R ,out
1
methanol production (y MeOH = 4.7% mol/mol).
In Reactors 2 and 3, the CO inlet concentration was significantly higher (3.0% mol/mol
for both cases), causing its concentration peak to come much sooner (at 1.8 m and 1.25 m,
respectively). After that, the WGSR was faster than its reverse reaction and the CO con-
centration decreased, leaving both reactors with an overall positive CO consumption.
Therefore, the water concentration in Reactors 2 and 3 was maintained at lower levels
R3 ,out
(y RH22,out
O = 4.7% mol/mol, y H2 O = 4.5% mol/mol), enhancing the final methanol concentra-
R ,out
tion (y RMeOH
2 ,out 3
= 5.6% mol/mol, y MeOH = 5.8% mol/mol).
Processes 2022, 10, x FOR PEER REVIEW 18 of 26
Processes 2022, 10, 1535 17 of 24

Figure9.9.Three-step
Figure Three-stepprocess—methanol,
process—methanol, water,
water, andand CO concentration
CO concentration alongalong the length
the length of each of each
reactor,
reactor, as well as in the intermediate condensation steps (C1
as well as in the intermediate condensation steps (C1 and C2). and C2).

In Reactors
Water is known2 and 3, the CO
to accelerate theinlet concentration
deactivation was significantly
of Cu-based catalysts [67].higher (3.0%
Therefore,
mol/mol
the lowerfor bothconcentration
water cases), causing of its
theconcentration peak to
three-step process in come much
relation sooner
to the (at 1.8process
one-step m and
1s,out
1.25 m, respectively). After that, the WGSR was faster than its reverse reaction and the CO
(y H2 O = 7.2%) should not only benefit the reaction rates, but also the catalyst lifetime.
concentration
In Table 4,decreased,
the operating leaving both reactors
conditions with
and split an overall
ratios positive CO consumption.
of the intermediate condensation
Therefore,
steps the water
are provided, concentration
while the reactor in Reactors 2isand
information 3 was maintained
summarized in Table 5.at lower levels
Methanol and
, ,
( 𝑦 were
water = almost fully removed
4.7% mol/mol, 𝑦 from= the gas mol/mol),
4.5% phase, but at the cost ofthe
enhancing ca. 9–13% CO2 con-
final methanol
densation. split, ratios
The(𝑦 of CO ,
concentration = 5.6% 2 and methanol
mol/mol, 𝑦 =were
5.8%strongly
mol/mol).dependent on temperature,
with the chosen values (T = 45 ◦ C, T = 30 ◦ C) being derived from a sensitivity analysis.
Water is known to accelerate
1 the
2 deactivation of Cu-based catalysts [67]. Therefore,
the lower water concentration of the three-step process in relation to the one-step process
Table, 4. Three-step process—operating conditions and split ratios of the intermediate condensation steps.
(𝑦 = 7.2%) should not only benefit the reaction rates, but also the catalyst lifetime.
Cond.
In Table 4, Pres.conditions and split ratios of the Split
the operating
Temp. Ratio
intermediate condensation
Step ◦ C) Phase
( (Bar) CO (%) MeOH
steps are provided, while the reactor information is 2summarized in Table (%) 5. Methanol
H2 O (%)
and
water were almost fully removed Gas
from the gas 90.66
phase, but at the5.31
cost of ca. 1.17 CO
9–13%
#1 45 69.25 2
Liquid 9.34 94.69 98.83
condensation. The split ratios of CO 2 and methanol were strongly dependent on
Gas 87.36 2.46 0.52
#2
temperature, with 68.50 values (𝑇 = 45 °C, 𝑇 = 30 °C) being derived from a
30 the chosen
Liquid 12.64 97.54 99.48
sensitivity analysis.
Table 5. Three-step process—heat transfer, inlet mole flow, mole fractions, and methanol production
Table 4. Three-step process—operating conditions and split ratios of the intermediate condensation
in the reactor modules.
steps.

Cond. Reactor
. Temp. Pres. #1 #2 Split Ratio #3
Phase
−18.5 −25.7 −22.7
Step . Q (MW)
(°C)
−1
(Bar) CO2 (%) MeOH (%) H2O (%)
nin (kmol·h ) 40,833 33,209 26,366
#1y H2 ,in (% mol/mol)
45 69.25 69.1Gas 90.66
69.0 5.31 69.51.17
yCO,in (% mol/mol) Liquid
1.3 9.343.0 94.69 3.098.83
yCO2 ,in (% mol/mol) 20.6Gas 17.3
87.36 2.46 14.40.52
y#2 30
MeOH,out (% mol/mol)
68.50 4.7
Liquid 12.645.6 97.54 5.899.48
y H2 O,out (% mol/mol) 5.6 4.7 4.5
.
∆n MeOH (kmol·h−1 ) 1616 1589 1325
The methanol production was similar in Reactors 1 and 2 (1616 and 1589 kmol·h−1,
respectively), while it was 18% lower in Reactor 3 (1325 kmol·h−1). This shows the positive
effectThe
of amethanol production
higher CO was similar
concentration in Reactors
in the reactor feed,1despite
and 2 (1616 and 1589
the lower totalkmol h−1 ,
feed ·flow
respectively), − 1
·hReactor
and CO2 inletwhile it was 18%
concentration oflower in Reactor
Reactors 2 and 33in
(1325 kmolto
relation ). This1.shows the positive
effect of a higher CO concentration in the reactor feed, despite the lower total feed flow
The CO2 single-pass conversion (𝑋 , ) was 53.9%, with a selectivity to methanol
and CO2 inlet concentration of Reactors 2 and 3 in relation to Reactor 1.
of 99.8% and a selectivity to CO of 0.2%. The feed excess was 2.35%, leading to an overall
The CO2 single-pass conversion (XCO2 ,SP ) was 53.9%, with a selectivity to methanol
conversion of CO2 to methanol of 97.7%. These values are in agreement with the Matlab
of 99.8% and a selectivity to CO of 0.2%. The feed excess was 2.35%, leading to an overall
simulations (𝑋 , = 54.1%, 𝐸𝑥𝑐 = 2.42%, overall CO2 conversion to MeOH = 97.6%).
conversion of CO2 to methanol of 97.7%. These values are in agreement with the Matlab
The three-step approach was significantly superior to the one-step process, even
simulations (XCO2 ,SP = 54.1%, Exc = 2.42%, overall CO2 conversion to MeOH = 97.6%).
using only half the number of reactor modules (three vs. six). This superiority is clear
The three-step approach was significantly superior to the one-step process, even using
only half the number of reactor modules (three vs. six). This superiority is clear when
 when looking at the CO2 single-pass conversion (53.9% vs. 28.5%), leading to a
considerably higher overall conversion to methanol (97.7% vs. 94.3%).

Table 5. Three-step process—heat transfer, inlet mole flow, mole fractions, and methanol
production in the reactor modules.

Reactor #1 #2 #3
Processes 2022, 10, 1535 𝑸 (MW) −18.5 −25.7 −22.7 18 of 24
𝒏𝒊𝒏 (kmol·h )−1 40,833 33,209 26,366
𝒚𝑯𝟐 ,𝒊𝒏 (% mol/mol) 69.1 69.0 69.5
𝒚𝑪𝑶,𝒊𝒏 (% mol/mol) 1.3 3.0 3.0
looking at the CO single-pass conversion
𝒚𝑪𝑶2𝟐 ,𝒊𝒏 (% mol/mol) 20.6
(53.9% vs. 28.5%),
17.3
leading to a14.4considerably
higher overall conversion to methanol
𝒚𝑴𝒆𝑶𝑯,𝒐𝒖𝒕 (% mol/mol) (97.7%
4.7 vs. 94.3%). 5.6 5.8
With the heat integration,
𝒚𝑯𝟐 𝑶,𝒐𝒖𝒕 (% mol/mol)the three-step
5.6 process was also 4.7 self-sufficient in
4.5 heat, while
∆𝒏𝑴𝒆𝑶𝑯 (kmol·h
electricity was produced through−1) a water1616
Rankine cycle, reducing
1589 the total power
1325 consump-
tion from 42.7 to 21.8 MW. The chemical conversion efficiency was ηCCE 3s = 85.6%, which
With the heat integration, the three-step process
1s was also self-sufficient in heat, while
was higher than the value of the one-step process (ηCCE = 82.3%) and, therefore, even closer
electricity was produced through a water Rankine cycle, reducing the total power
to the maximum possible value
consumption from 42.7(ηCCE,max = 87.6%).
to 21.8 MW. The chemical conversion efficiency was 𝜼𝟑𝒔 𝑪𝑪𝑬 =
In Figure 10, an exergy analysis of the process
85.6%, which was higher than the value of theisone-step
presented.
processThe(𝜼𝟏𝒔
exergy
𝑪𝑪𝑬 = 82.3%)efficiency
and,
3s therefore, even closer to the maximum possible value (𝜼𝑪𝑪𝑬,𝒎𝒂𝒙
was ηEx = 78.8%, an improvement from the previous approach (ηEx = 76.4%), with the = 87.6%).
1s
In Figure 10, an exergy analysis of the process is presented. The exergy efficiency was
total exergy losses
𝜼𝟑𝒔 decreasing in 13% (245.3 vs. 281.9 MW). Although 𝟏𝒔 the total power
𝑬𝒙 = 78.8%, an improvement from the previous approach (𝜼𝑬𝒙 = 76.4%), with the total
consumption decreased
exergy losses (42.7 vs. 47.4inMW),
decreasing the netvs.power
13% (245.3 consumption
281.9 MW). Although increased slightly
the total power
consumption
(21.8 vs. 17.6 MW). decreasedbecause
This occurred (42.7 vs. 47.4 MW),generation
power the net powerwasconsumption increased
significantly slightly
lower in the
(21.8 vs. 17.6 MW). This occurred because power generation was significantly lower in the
three-step approach (20.8 vs. 29.8 MW) due to the much lower heat duty of
three-step approach (20.8 vs. 29.8 MW) due to the much lower heat duty of the firedthe fired heater,
as less reactantheater,
was lost inreactant
as less the purge streams.
was lost in the purge streams.

Figureprocess—exergy
Figure 10. Three-step 10. Three-step process—exergy analysis.
analysis. (a) Global (a) Global
exergy exergy
balance balance
(total (total
exergy exergy
input input MW).
= 1157.5 =
1157.5 MW). (b) Distribution of exergy losses (total = 245.3 MW).
(b) Distribution of exergy losses (total = 245.3 MW).
Chemical reactions with heat recovery at low temperatures was also the main cause
Chemical ofreactions withinheat
exergy losses recoveryapproach
the three-step at low temperatures
(reactor modules: was alsofired
66.0%, theheater:
main 6.0%).
cause of
exergy losses inBoth
theprocesses
three-steplostapproach (reactor
approximately modules:
the same exergy66.0%, fired heater:
in the reactor modules6.0%).
and theBoth
distillation column.the
processes lost approximately Thesame
main improvement
exergy in thein relation
reactorto the one-step and
modules processthewas a much
distillation
lower exergy loss in the fired heater (14.7 vs. 41.4 MW), as the total purge stream flow
column. The main improvement in relation to the one-step process was a much lower exergy
decreased by 59% (455 against 1100 kmol·h−1). Despite the higher number of cooling and
loss in the firedwarming
heater operations
(14.7 vs. 41.4 MW),
and the higherastotal
theheat
total purge
transfer stream
duty flow decreased
in the three-step by 59%
process (357.1
(455 against 1100 kmol·h−1 ). Despite the higher number of cooling and warming operations
and the higher total heat transfer duty in the three-step process (357.1 vs. 310.2 MW),
the exergy losses in the heat exchangers were slightly lower for the three-step process
(29.4 vs. 31.4 MW). Finally, moderate improvements were also seen in the compressors and
pump (8.2 vs. 9.1 MW) and in the valves and turbine (5.0 vs. 7.4 MW).
In Table 6, the data comparing both processes is summarized, once again emphasizing
the superior performance of the three-step approach.

Table 6. Data comparison between the one-step and the three-step approach.

Item One-Step Three-Step

Total methanol production (kmol·h−1 ) 4527 4525
CO2 single-pass conversion (%) 28.5 53.9
Overall CO2 conversion to methanol (%) 94.3 97.7
Feed excess (%) 6.05 2.35
Methanol selectivity (%) 99.5 99.8
Total recycle stream flow (kmol·h−1 ) 54,290 22,581
Maximum water concentration (% mol/mol) 7.2 5.6
Total exergy loss (MW) 281.9 245.3
Exergy efficiency (%) 76.4 78.8
 Overall CO2 conversion to methanol (%) 94.3 97.7
Feed excess (%) 6.05 2.35
Methanol selectivity (%) 99.5 99.8
Total recycle stream flow (kmol·h−1) 54,290 22,581
Maximum water concentration (% mol/mol) 7.2 5.6
Processes 2022, 10, 1535 Total exergy loss (MW) 281.9 245.3 19 of 24
Exergy efficiency (%) 76.4 78.8

3.3.
3.3. Techno-EconomicAnalysis
Techno-Economic Analysis

InInFigure
Figure11a,
11a, the
the distribution
distribution ofof the
theequipment
equipmentcosts costs(𝐸𝐶)
(EC)is presented, withwith
is presented, the the
reactor modules and the compressors representing the majority of the costs (>75%). The
reactor modules and the compressors representing the majority of the costs (>75%). The
total EC was 85.5 and 66.1 M€ for the one-step and the three-step approach, respectively.
total EC was 85.5 and 66.1 M€ for the one-step and the three-step approach, respectively.
This significant improvement of the three-step process was a consequence of the
This significant improvement of the three-step process was a consequence of the inter-
intermediate condensation steps, requiring a lower total reactor volume (due to an
mediate condensation steps, requiring a lower total reactor volume (due to an enhanced
enhanced reaction velocity), lower compressor size (due to a lower recycle flow), and
reaction velocity),
lower furnace, lower
turbine, andcompressor size(due
generator size (dueto atolower
a lower
purgerecycle
flow). flow),
The costand lower fur-
reduction
nace, turbine, and generator size (due to a lower purge flow). The cost reduction
in the aforementioned equipment was significantly higher than the additional costs of the in the
aforementioned
heat exchangersequipment was significantly
and flash drums higher thancondensation
from the intermediate the additional costs
units. of total
The the heat
exchangers and
fixed capital flash drums
investment (𝐹𝐶𝐼)from
was the
415.9intermediate
and 321.4 M€ condensation units.
for the one-step andThe total fixed
three-step
capital investment
approach, (FCI) The
respectively. was detailed
415.9 and 321.4 M€
estimated for the and
capacity one-step
price and three-step
of each equipmentapproach,
is
respectively.
presented inThe
the detailed estimated
Supplementary capacity
Material andH).
(Section price of each equipment is presented in
the Supplementary Material (Section H).

(a) (b)
Figure 11. Distribution of the costs. (a) Equipment Costs (EC). (b) Net Production Costs (NPC).
Figure 11. Distribution of the costs. (a) Equipment Costs (EC). (b) Net Production Costs (NPC).

InInFigure
Figure11b,
11b,the
thedistribution
distribution of
of the
thenet
netproduction
productioncosts (𝑁𝑃𝐶)
costs (NPC)is detailed. The The
is detailed. mainmain
operating costs were the reactant expenses (78–80% of 𝑁𝑃𝐶 ), with 𝐴𝐶𝐶 contributing
operating costs were the reactant expenses (78–80% of NPC), with ACC contributing with
with only 4–5%, while the catalysts and electricity consisted of less than 3% of the 𝑁𝑃𝐶.
only 4–5%, while the catalysts and electricity consisted of less than 3% of the NPC. Due
to the higher overall CO2 conversion to methanol, the NPC of the three-step process was
5.7% lower than the one-step approach. The detailed OPEX costs are presented in the
Supplementary Material (Section H).
In Table 7, a summary of the overall costs is presented. The NPC was 920 and 868
€·ton−1 for the one-step and the three-step process, respectively, corresponding to an
improvement of 5.7% for the new process. Besides the hydrogen and carbon dioxide costs,
the fixed capital investment (FCI) and the discount rate were the most sensitive parameters
to the methanol selling price, as shown in the tornado analysis (see Figure 12).

Table 7. Summary of the costs of the one-step and the three-step process.

Costs
Item Decrease (%)
One-Step Three-Step
Equipment Costs ( EC ) 85.5 M€ 66.1 M€ 22.7
Fixed capital investment ( FCI ) 415.9 M€ 321.4 M€ 22.7
Working capital (WC ) 46.2 M€ 35.7 M€ 22.7
Total CAPEX 462.1 M€ 357.1 M€ 22.7
Annual Capital Costs ( ACC ) 53.5 M€·a−1 41.3 M€·a−1 22.7
Direct OPEX 874.9 M€·a−1 839.6 M€·a−1 4.0
Indirect OPEX 143.4 M€·a−1 129.6 M€·a−1 9.6
Total OPEX 1018.3 M€·a−1 969.3 M€·a−1 4.8
Net Production Costs ( NPC ) 1071.8 M€·a−1 1010.6 M€·a−1 5.7
 Direct 𝑶𝑷𝑬𝑿 874.9 M€·a−1 839.6 M€·a−1 4.0
Indirect 𝑶𝑷𝑬𝑿 143.4 M€·a−1 129.6 M€·a−1 9.6
Total 𝑶𝑷𝑬𝑿 1018.3 M€·a−1 969.3 M€·a−1 4.8
Net Production Costs (𝑵𝑷𝑪) 1071.8 M€·a−1 1010.6 M€·a−1 5.7
Processes 2022, 10, 1535 20 of 24

H2 H2
FCI FCI
CO2 CO2
−20% Interest rate +20% −20% Interest rate +20%
Catalyst Catalyst
Electricity Electricity
Operating Labor Operating Labor
700 800 900 1000 1100 700 800 900 1000 1100
Net production costs (€·ton−1) Net production costs (€·ton−1)

(a) (b)
Figure
Figure 12.
12. Sensitivity
Sensitivityanalysis
analysisof
ofthe
themain
maincost
costfactors
factorsin
inrelation
relationto
tothe
thenet
netproduction
productioncosts
costs(NPC).
(NPC).
Variation of ± 20% in each factor. (a) One-step process. (b) Three-step process.
Variation of ± 20% in each factor. (a) One-step process. (b) Three-step process.

Processes 2022, 10, x FOR PEER REVIEW In Figure13,

In Figure 13,the
the
netnet production
production costscosts are plotted
are plotted againstagainst the hydrogen
the hydrogen 22 price.
price. Although
of 26
Although
the methanol market price in Europe was still significantly below the values (495 €values
the methanol market price in Europe was still significantly below the ·ton−1
(495 €·ton−1 in
in February February
2022), [68,69]2022), [68,69]
the green the green
methanol methanol
produced from produced from process
the proposed the proposed
would
process
become economically competitive if the green hydrogen price reached 1468 €·ton . 1468
would become economically competitive if the green hydrogen price reached
− 1
€·ton−1.
1250
Current green
Net production costs (€·ton- 1)

H2 price
1000

Current methanol
750 market price

500

250
One-Step
Three-Step
0
0 1000 2000 3000 4000
Green hydrogen price (€·ton- 1)
Figure13.
Figure Netproduction
13.Net productioncosts
costsofofmethanol
methanolasasa afunction
functionofofgreen
greenhydrogen
hydrogenprice.
price.

4. Conclusions
4. Conclusions
A detailed study of a methanol synthesis plant from H2 and CO2 with intermediate con-
A detailed study of a methanol synthesis plant from H2 and CO2 with intermediate
densation units (the three-step process) is presented and compared with the conventional
condensation
approach (theunits (theprocess).
one-step three-stepThe process) is presented
total production was fixed andat compared
1.16 Mton MeOH with ·the
a−1 .
conventional approach (the one-step process). The total production was
The processes were first implemented in Matlab in order to critically analyze the number fixed at 1.16 Mton
MeOH·a
of reactor. The
−1 processes
modules, were first
the purge implemented
fraction, in Matlab
and the reactor in order
operating to criticallyUsing
temperature. analyzethe
the number
most suitableof reactor
processmodules,
parameters,the purge fraction,
detailed plantsand the reactor
of both operating
approaches weretemperature.
implemented
Using the most
in Aspen suitable process
Plus, including parameters,
heat integration anddetailed
a waterplants
Rankine of cycle
both toapproaches
make use were of the
implemented in Aspen Plus, including heat integration and a water
reaction enthalpy. Finally, techno-economic analyses were applied. Both processes Rankine cycle to offered
make
use of theofreaction
an excess enthalpy.
heat, which was used Finally, techno-economic
to generate electricity in ouranalyses were
work, but applied.
could Both
alternatively
processes offered an excess of heat, which was used to generate
supply other plants (e.g., CCU, OME synthesis) in a larger process integration. electricity in our work,
but could
It wasalternatively
demonstrated supply
that other plants (e.g.,conversion
CO2 single-pass CCU, OMEalmost synthesis) in a when
doubled largerincluding
process
integration.
intermediate condensation steps (53.9 vs. 28.5%), resulting in a significantly higher overall
It was demonstrated
conversion that CO
to methanol (97.7 single-pass
vs.2 94.3%) conversion
and in almost efficiency
a higher exergy doubled when (78.8 including
vs. 76.4%).
intermediate condensation steps (53.9 vs. 28.5%), resulting in
Because of the enhanced conversion, the new process required lower recycle a significantly higherandoverall
feed
conversion to methanol
streams, decreasing (97.7
net vs. 94.3%)costs
production and byin a61.2
higher −
M€·exergy 1
a (5.7%).efficiency (78.8 vs.
Although 76.4%).
additional
Because
equipmentof the enhanced
(i.e., conversion,
heat exchangers andthe new process
gas–liquid required
separators) lower recycle
is necessary, the and feed
improved
streams, decreasing net production costs by 61.2 M€·a−1 (5.7%). Although additional
equipment (i.e., heat exchangers and gas–liquid separators) is necessary, the improved
process was significantly more efficient than the conventional approach, requiring lower
sizes of the main equipment (e.g., compressors, reactors, fired heater). Consequently,
according to our analysis, the total investment costs were 94.5 M€ (22.7%) lower than for
Processes 2022, 10, 1535 21 of 24

process was significantly more efficient than the conventional approach, requiring lower
sizes of the main equipment (e.g., compressors, reactors, fired heater). Consequently,
according to our analysis, the total investment costs were 94.5 M€ (22.7%) lower than for
the conventional process.
Intermediate condensation steps are therefore highly recommended for methanol
production from H2 /CO2 , reducing costs by improving CO2 equilibrium conversion to
methanol while using commercially proven technology. Besides, since water accelerates the
deactivation of Cu-based catalysts, product intermediate removal should increase catalyst
lifetime, as the average water concentration in the reactor is significantly lower than in the
conventional process.
With our proposed process, the methanol net production costs amounted to 868 €·ton−1 ,
which are still significantly higher than the current market price (495 €·ton−1 ) but is believed
to become economically viable with an effective reduction in the price of green hydrogen.

Supplementary Materials: The following supporting information can be downloaded at: https://
www.mdpi.com/article/10.3390/pr10081535/s1, Figure S1: One-step process—Aspen Plus flowsheet;
Figure S2: Three-step process—Aspen Plus flowsheet; Table S1: Parameters for the estimation of
the specific heat capacity and specific enthalpy of selected components in the gas phase; Table S2:
Liquid and gas fractions (% mol/mol) of the phase separation via flash drums and the separation
via the distillation column in the one-step process. Values taken from Aspen Plus calculations and
used for the Matlab simulations; Table S3: Liquid and gas fractions (% mol/mol) of the phase
separation via flash drums and the separation via the distillation column in the three-step process.
Values taken from Aspen Plus calculations and used for the Matlab simulations; Table S4: Aspen
kinetic factor and Model-6p corresponding expressions; Table S5: Coefficients of the driving force
constant and the corresponding expressions from Model-6p; Table S6: Concentration exponents (υ j )
of the driving force expression; Table S7: Adsorption constants and the corresponding expression of
Model-6p; Table S8: Concentration exponents and the corresponding values of Model-6p; Table S9:
Properties of the streams from the one-step process; Table S10: Molar composition (% mol/mol)
of the streams from the one-step process; Table S11: Properties of the streams from the three-step
process; Table S12: Molar composition (% mol/mol) of the streams from the three-step process;
Table S13: Dimension of the flash drums of the one-step and the three-step processes; Table S14:
Global heat transfer coefficients, heat transfer duty, and estimated surface area of the heat exchangers
of the one-step and the three-step process; Table S15: Calculation of the Capital Expenses (CAPEX)
depending on the total equipment costs (EC); Table S16: Estimation of indirect operating expenses
(OPEXind ); Table S17: Equipment characteristic dimensions and equipment costs (EC) of the one-step
approach. All equipment was built with carbon steel. All equipment reference prices were taken from
Peters et al., except for the power generator, whose ref. price was taken from Henning and Haase;
Table S18: Equipment characteristic dimensions and equipment costs (EC) of the three-step approach.
All equipment was built with carbon steel, and the costs included 10% delivery costs. All equipment
reference prices were taken from Peters et al., except for the power generator, whose ref. price was
taken from Henning and Haase; Table S19: Detailed operating expenditures (OPEX) of the one-step
and the three-step approach.
Author Contributions: Conceptualization, B.L.d.O.C. and J.S.; methodology, B.L.d.O.C., K.J. and P.B.;
software, B.L.d.O.C., K.J. and P.B.; formal analysis, B.L.d.O.C.; writing—original draft preparation,
B.L.d.O.C.; writing—review and editing, K.J., P.B., K.H.D., S.P., N.D. and J.S.; visualization, B.L.d.O.C.
and P.B.; supervision, K.H.D., S.P., N.D. and J.S.; funding acquisition, K.H.D., S.P., and J.S. All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior (CAPES) (process number: 88881.174609/2018-01) and by the Helmholtz Research Program
“Materials and Technologies for the Energy Transition (MTET), Topic 3: Chemical Energy Carriers”.
We also acknowledge the support from the KIT-Publication Fund of the Karlsruhe Institute of
Technology.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
in the decision to publish the results.
Processes 2022, 10, 1535 22 of 24

References
1. Our World in Data. Renewable Energy. Available online: https://ourworldindata.org/renewable-energy (accessed on 4 April 2022).
2. Daiyan, R.; MacGill, I.; Amal, R. Opportunities and challenges for renewable power-to-X. ACS Energy Lett. 2020, 5, 3843–3847.
[CrossRef]
3. Younas, M.; Shafique, S.; Hafeez, A.; Javed, F.; Rehman, F. An overview of hydrogen production: Current status, potential, and
challenges. Fuel 2022, 316, 123317. [CrossRef]
4. Chisholm, G.; Zhao, T.; Cronin, L. 24—Hydrogen from water electrolysis. In Storing Energy, 2nd ed.; Letcher, T.M., Ed.; Elsevier:
Amsterdam, The Netherlands, 2022; pp. 559–591. [CrossRef]
5. Artz, J.; Müller, T.E.; Thenert, K.; Kleinekorte, J.; Meys, R.; Sternberg, A.; Bardow, A.; Leitner, W. Sustainable conversion of carbon
dioxide: An integrated review of catalysis and life cycle assessment. Chem. Rev. 2018, 118, 434–504. [CrossRef] [PubMed]
6. Wang, L.; Chen, M.; Küngas, R.; Lin, T.-E.; Diethelm, S.; Maréchal, F.; Van Herle, J. Power-to-fuels via solid-oxide electrolyzer:
Operating window and techno-economics. Renew. Sustain. Energy Rev. 2019, 110, 174–187. [CrossRef]
7. Bongartz, D.; Burre, J.; Ziegler, A.L.; Mitsos, A. Power-to-OME1 via direct oxidation of methanol: Process design and global
flowsheet optimization. In Computer Aided Chemical Engineering; Türkay, M., Gani, R., Eds.; Elsevier: Amsterdam, The Netherlands,
2021; Volume 50, pp. 273–278.
8. Schmidt, P.; Batteiger, V.; Roth, A.; Weindorf, W.; Raksha, T. Power-to-liquids as renewable fuel option for aviation: A review.
Chem. Ing. Tech. 2018, 90, 127–140. [CrossRef]
9. Methanol Institute—Methanol Fuel in China 2020. Available online: https://www.methanol.org/methanol-fuel-in-china-full-
report/ (accessed on 5 July 2022).
10. Global Data—Methanol Market Capacity 2021. Available online: https://www.globaldata.com/store/report/methanol-market-
analysis/ (accessed on 27 June 2022).
11. Bozzano, G.; Manenti, F. Efficient methanol synthesis: Perspectives, technologies and optimization strategies. Prog. Energy
Combust. Sci. 2016, 56, 71–105. [CrossRef]
12. Freepik. Flaticon Icons. Available online: https://www.flaticon.com/authors/freepik (accessed on 27 June 2022).
13. Ott, J.; Gronemann, V.; Pontzen, F.; Fiedler, E.; Grossmann, G.; Kersebohm, D.B.; Weiss, G.; Witte, C. Methanol. In Ullmann’s
Encyclopedia of Industrial Chemistry; Wiley: New York, NY, USA, 2012. [CrossRef]
14. Toyo Engineering. G-Methanol. Available online: https://www.toyo-eng.com/jp/en/solution/g-methanol/ (accessed on 9 May 2022).
15. Lacerda de Oliveira Campos, B.; Herrera Delgado, K.; Wild, S.; Studt, F.; Pitter, S.; Sauer, J. Surface reaction kinetics of the
methanol synthesis and the water gas shift reaction on Cu/ZnO/Al2 O3 . React. Chem. Eng. 2021, 6, 868–887. [CrossRef]
16. Studt, F.; Behrens, M.; Kunkes, E.L.; Thomas, N.; Zander, S.; Tarasov, A.; Schumann, J.; Frei, E.; Varley, J.B.; Abild-Pedersen,
F.; et al. The mechanism of CO and CO2 hydrogenation to methanol over Cu-based catalysts. ChemCatChem 2015, 7, 1105–1111.
[CrossRef]
17. Bussche, K.M.V.; Froment, G.F. A steady-state kinetic model for methanol synthesis and the water gas shift reaction on a
commercial Cu/ZnO/Al2 O3 Catalyst. J. Catal. 1996, 161, 1–10. [CrossRef]
18. Slotboom, Y.; Bos, M.J.; Pieper, J.; Vrieswijk, V.; Likozar, B.; Kersten, S.R.A.; Brilman, D.W.F. Critical assessment of steady-state
kinetic models for the synthesis of methanol over an industrial Cu/ZnO/Al2 O3 catalyst. Chem. Eng. J. 2020, 389, 124181.
[CrossRef]
19. Lacerda de Oliveira Campos, B.; Herrera Delgado, K.; Pitter, S.; Sauer, J. Development of consistent kinetic models derived from a
microkinetic model of the methanol synthesis. Ind. Eng. Chem. Res. 2021, 60, 15074–15086. [CrossRef]
20. Pérez-Fortes, M.; Schöneberger, J.C.; Boulamanti, A.; Tzimas, E. Methanol synthesis using captured CO2 as raw material:
Techno-economic and environmental assessment. Appl. Energy 2016, 161, 718–732. [CrossRef]
21. Szima, S.; Cormos, C.-C. Improving methanol synthesis from carbon-free H2 and captured CO2 : A techno-economic and
environmental evaluation. J. CO2 Util. 2018, 24, 555–563. [CrossRef]
22. Cordero-Lanzac, T.; Ramirez, A.; Navajas, A.; Gevers, L.; Brunialti, S.; Gandía, L.M.; Aguayo, A.T.; Mani Sarathy, S.; Gascon, J. A
techno-economic and life cycle assessment for the production of green methanol from CO2 : Catalyst and process bottlenecks.
J. Energy Chem. 2022, 68, 255–266. [CrossRef]
23. FFE München. Electrolysis, the Key Technology for Power-to-X. Available online: https://www.ffe.de/veroeffentlichungen/
elektrolyse-die-schluesseltechnologie-fuer-power-to-x/ (accessed on 4 April 2022).
24. Fasihi, M.; Efimova, O.; Breyer, C. Techno-economic assessment of CO2 direct air capture plants. J. Clean. Prod. 2019, 224, 957–980.
[CrossRef]
25. Carbon Recycling International. Renewable Methanol from Carbon Dioxide. Available online: https://www.carbonrecycling.is/
(accessed on 4 April 2022).
26. Siemens Energy. The Haru Oni Hydrogen Plant. Available online: https://www.siemens-energy.com/global/en/news/
magazine/2021/haru-oni.html (accessed on 1 February 2022).
27. van Bennekom, J.G.; Venderbosch, R.H.; Winkelman, J.G.M.; Wilbers, E.; Assink, D.; Lemmens, K.P.J.; Heeres, H.J. Methanol
synthesis beyond chemical equilibrium. Chem. Eng. Sci. 2013, 87, 204–208. [CrossRef]
28. Bos, M.J.; Brilman, D.W.F. A novel condensation reactor for efficient CO2 to methanol conversion for storage of renewable electric
energy. Chem. Eng. J. 2015, 278, 527–532. [CrossRef]
Processes 2022, 10, 1535 23 of 24

29. Seshimo, M.; Liu, B.; Lee, H.R.; Yogo, K.; Yamaguchi, Y.; Shigaki, N.; Mogi, Y.; Kita, H.; Nakao, S.-i. Membrane reactor for
methanol synthesis using Si-Rich LTA Zeolite Membrane. Membranes 2021, 11, 505. [CrossRef]
30. Johnson Mattey. Methanol Synthesis Technology. Available online: https://matthey.com/en/products-and-services/chemical-
processes/core-technologies/synthesis (accessed on 9 May 2022).
31. Guo, Y.; Li, G.; Zhou, J.; Liu, Y. Comparison between hydrogen production by alkaline water electrolysis and hydrogen production
by PEM electrolysis. IOP Conf. Ser. Earth Environ. Sci. 2019, 371, 042022. [CrossRef]
32. Porter, R.T.J.; Fairweather, M.; Kolster, C.; Mac Dowell, N.; Shah, N.; Woolley, R.M. Cost and performance of some carbon capture
technology options for producing different quality CO2 product streams. Int. J. Greenh. Gas Control. 2017, 57, 185–195. [CrossRef]
33. Bennekom, J.G.v.; Winkelman, J.G.M.; Venderbosch, R.H.; Nieland, S.D.G.B.; Heeres, H.J. Modeling and experimental studies on
phase and chemical equilibria in high-pressure methanol synthesis. Ind. Eng. Chem. Res. 2012, 51, 12233–12243. [CrossRef]
34. Gaikwad, R.; Bansode, A.; Urakawa, A. High-pressure advantages in stoichiometric hydrogenation of carbon dioxide to methanol.
J. Catal. 2016, 343, 127–132. [CrossRef]
35. Süd-Chemie AG. Safety Data Sheet—MegaMax 700. 2006.
36. Zhu, J.; Araya, S.S.; Cui, X.; Sahlin, S.L.; Kær, S.K. Modeling and design of a multi-tubular packed-bed reactor for methanol steam
reforming over a Cu/ZnO/Al2 O3 Catalyst. Energies 2020, 13, 610. [CrossRef]
37. Van-Dal, É.S.; Bouallou, C. Design and simulation of a methanol production plant from CO2 hydrogenation. J. Clean. Prod. 2013,
57, 38–45. [CrossRef]
38. Pontzen, F.; Liebner, W.; Gronemann, V.; Rothaemel, M.; Ahlers, B. CO2 -based methanol and DME—Efficient technologies for
industrial scale production. Catal. Today 2011, 171, 242–250. [CrossRef]
39. Bongartz, D.; Burre, J.; Mitsos, A. Production of oxymethylene dimethyl ethers from hydrogen and carbon dioxide—Part I:
Modeling and analysis for OME1. Ind. Eng. Chem. Res. 2019, 58, 4881–4889. [CrossRef]
40. Burners for Fired Heaters in General Refinery Services. In Reference Practice (RP) 535, 3rd ed.; American Petroleum Institute (API):
Washington, DC, USA, 2014.
41. Goos, E.; Burcat, A.; Ruscic, B. New NASA Thermodynamic Polynomials Database. Available online: http://garfield.chem.elte.
hu/Burcat/THERM.DAT (accessed on 4 March 2022).
42. Gruber, M. Detaillierte Untersuchung des Wärme und Stofftransports in einem Festbett-Methanisierungsreaktor für Power-to-Gas
Anwendungen. Ph.D. Thesis, Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany, 2019; 275p.
43. VDI Heat Atlas, 2nd ed.; Springer: Berlin-Heidelberg, Germany, 2010; p. 1585.
44. Seidel, C.; Jörke, A.; Vollbrecht, B.; Seidel-Morgenstern, A.; Kienle, A. Kinetic modeling of methanol synthesis from renewable
resources. Chem. Eng. Sci. 2018, 175, 130–138. [CrossRef]
45. Peng, D.-Y.; Robinson, D.B. A new two-constant equation of State. Ind. Eng. Chem. Fundam. 1976, 15, 59–64. [CrossRef]
46. Meng, L.; Duan, Y.-Y.; Wang, X.-D. Binary interaction parameter kij for calculating the second cross-virial coefficients of mixtures.
Fluid Phase Equilibria 2007, 260, 354–358. [CrossRef]
47. Meng, L.; Duan, Y.-Y. Prediction of the second cross virial coefficients of nonpolar binary mixtures. Fluid Phase Equilibria 2005, 238,
229–238. [CrossRef]
48. Deiters, U.K. Comments on the modeling of hydrogen and hydrogen-containing mixtures with cubic equations of state. Fluid
Phase Equilibria 2013, 352, 93–96. [CrossRef]
49. Kuld, S.; Thorhauge, M.; Falsig, H.; Elkjær, C.F.; Helveg, S.; Chorkendorff, I.; Sehested, J. Quantifying the promotion of Cu
catalysts by ZnO for methanol synthesis. Science 2016, 352, 969–974. [CrossRef] [PubMed]
50. CLARIANT. Catalysts for Methanol Synthesis, Product Data Sheet. 2017. Available online: https://www.clariant.com/-/media/Files/
Solutions/Products/Additional-Files/M/18/Clariant-Brochure-Methanol-Synthesis-201711-EN.pdf (accessed on 4 April 2022).
51. Saito, M.; Murata, K. Development of high performance Cu/ZnO-based catalysts for methanol synthesis and the water-gas shift
reaction. Catal. Surv. Asia 2004, 8, 285–294. [CrossRef]
52. Campos Fraga, M.M.; Lacerda de Oliveira Campos, B.; Lisboa, M.S.; Almeida, T.B.; Costa, A.O.S.; Lins, V.F.C. Analysis of a
Brazilian thermal plant operation applying energetic and exergetic balances. Braz. J. Chem. Eng. 2018, 35, 1395–1403. [CrossRef]
53. Nitzsche, R.; Budzinski, M.; Gröngröft, A. Techno-economic assessment of a wood-based biorefinery concept for the production
of polymer-grade ethylene, organosolv lignin and fuel. Bioresour. Technol. 2016, 200, 928–939. [CrossRef] [PubMed]
54. Green, D.W.; Southard, M.Z. Perry’s Chemical Engineers’ Handbook, 9th ed.; McGraw Hill: New York, NY, USA, 2018.
55. König, D.H.; Baucks, N.; Dietrich, R.-U.; Wörner, A. Simulation and evaluation of a process concept for the generation of synthetic
fuel from CO2 and H2 . Energy 2015, 91, 833–841. [CrossRef]
56. Albrecht, F.G.; König, D.H.; Baucks, N.; Dietrich, R.-U. A standardized methodology for the techno-economic evaluation of
alternative fuels—A case study. Fuel 2017, 194, 511–526. [CrossRef]
57. Peters, M.S.; Timmerhaus, K.D.; West, R.E. Plant Design and Economics for Chemical Engineers, 5th ed.; McGraw-Hill Education Ltd.:
Boston, MA, USA, 2002; p. 1008.
58. Hennig, M.; Haase, M. Techno-economic analysis of hydrogen enhanced methanol to gasoline process from biomass-derived
synthesis gas. Fuel Processing Technol. 2021, 216, 106776. [CrossRef]
59. Travelex. Worldwide Money. Available online: https://www.travelex.com/currency/currency-pairs/usd-to-eur (accessed on
4 April 2022).
Processes 2022, 10, 1535 24 of 24

60. Towler, G.; Sinnott, R. Chemical Engineering Design—Principles, Practice and Economics of Plant and Process Design, 2nd ed.; Elsevier:
Amsterdam, The Netherlands, 2013.
61. Aden, A.; Ruth, M.; Ibsen, K.; Jechura, J.; Neeves, K.; Sheehan, J.; Wallace, B.; Montague, L.; Slayton, A.; Lukas, J. Lignocellulosic
Biomass to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn
Stover; National Renewable Energy Laboratory: Golden, CO, USA, 2002; 154p.
62. Cheremisinoff, N.P. Clean Electricity Through Advanced Coal Technologies; Elsevier: Amsterdam, The Netherlands, 2012. [CrossRef]
63. Bustillo-Lecompte, C.F.; Mehrvar, M.; Quiñones-Bolaños, E. Cost-effectiveness analysis of TOC removal from slaughterhouse
wastewater using combined anaerobic–aerobic and UV/H2 O2 processes. J. Environ. Manag. 2014, 134, 145–152. [CrossRef]
64. Tan, E.C.; Talmadge, M.; Dutta, A.; Hensley, J.; Snowden-Swan, L.J.; Humbird, D.; Schaidle, J.; Biddy, M. Conceptual process
design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through
methanol/dimethyl ether intermediates. Biofuels Bioprod. Biorefining 2016, 10, 17–35. [CrossRef]
65. Ashraf, M.T.; Schmidt, J.E. Process simulation and economic assessment of hydrothermal pretreatment and enzymatic hydrolysis
of multi-feedstock lignocellulose—Separate vs. combined processing. Bioresour. Technol. 2018, 249, 835–843. [CrossRef] [PubMed]
66. Granjo, J.F.O.; Oliveira, N.M.C. Process simulation and techno-economic analysis of the production of sodium methoxide. Ind.
Eng. Chem. Res. 2016, 55, 156–167. [CrossRef]
67. Prašnikar, A.; Pavlišič, A.; Ruiz-Zepeda, F.; Kovač, J.; Likozar, B. Mechanisms of copper-based catalyst deactivation during CO2
reduction to methanol. Ind. Eng. Chem. Res. 2019, 58, 13021–13029. [CrossRef]
68. Argus Media. European Methanol Spot and Contract Prices. Available online: https://www.argusmedia.com/en/blog/2022
/february/4/european-methanol-spot-and-contract-prices (accessed on 4 April 2022).
69. Methanol Institute—Methanol Prices, Supply and Demand. Available online: https://www.methanol.org/methanol-price-
supply-demand/ (accessed on 4 April 2022).