Journal of CO2 Utilization 58 (2022) 101911

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Electrified methane reforming decarbonises methanol synthesis

Anna Mion a, Federico Galli b, *, Paolo Mocellin a, Simone Guffanti c, Gianluca Pauletto c, *
a
Università degli Studi di Padova, Dipartimento di Ingegneria Industriale, Via Marzolo 9, Padova 35131, Italy
b
Université de Sherbrooke, Départment de Génie Chimique et de Génie Biotechnologique, 2500, boul. de l′ Université, Sherbrooke, QC J1K 2R1, Canada
c
SYPOX, Department of Chemistry, Technical University of Munich, Garching 85747, Germany

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

Keywords: Power-to-X processes convert free electrons stemming from renewable energy into chemical bonds. In this
Direct electrification framework, electrochemical processes drastically increase energy demand. Differently, directly electrified ther­
Syngas decarbonisation mochemical processes, such as electrically heated methane reforming, minimise renewable energy requirements
Methanol synthesis
and achieve high decarbonisation levels. In the case of electrically heated methane reforming carbon dioxide
Electrically heated reforming
Process simulations
emission from the stuck of the firebox is avoided. In this work, we report two innovative process configurations
for methanol production that involve an electrically heated methane reformer for syngas generation. Reforming
of methane and carbon dioxide containing gas streams into syngas coupled with methanol synthesis can achieve
negative carbon dioxide balance without requiring carbon capture and sequestration. Increasing the amount of
reformed carbon dioxide, it is possible to increase its consumption. Integration of an electrolyser is required
when syngas with a hydrogen/carbon monoxide below 2 is generated. It results that the integration of an
electrically heated reformer in a methanol plant makes it possible to convert respectively 0.3 t and 0.93 t of
carbon dioxide per ton of methanol produced. The consumption of renewable electricity is 2.3 MWh and 7.1
MWh per ton of methanol produced.

1. Introduction renewable energy is abundant and is efficiently harvested. Methanol,

Almost 80% of the global CO2 emissions in 2019 (35 billion tons) was
related to the chemical industry and the energy sector. This results in an
increasing pressure on the chemical industry that is currently focusing
on the development of low emitting process configurations [1,2]. These
include electrochemical and electrically heated processes, where
renewable electricity is used as source of energy within endothermic
chemical reactors. Both these unit operations are Power-to-X (P2X)
technologies as they convert free electrons into energy that is stored into
chemical bonds. In the case of electrified steam methane reformers
(e-SMR), the demand of renewable electricity necessary to produce 1 kg
of H2 is less than one third compared to the one used by electrolysers (14
kWh vs 50 kWh). Additionally, the e-SMR has shown ground-breaking
improvement and huge process intensification potentials coming from
the minimisation of the characteristic length scale of heat transfer [3].
Methanol is an essential building block within the chemical industry
that can be used to produce formaldehyde, dimethyl ether, methyl tert-
butyl ether, acetic acid, hydrocarbons, and olefins. Methanol is also an
energy carrier that enable to transport energy from locations where
differently than liquid H2, has twice higher energy density: 5 kWh L− 1 vs
2.5 kWh L− 1 [4,5]. The annual methanol demand grew to an annual
compounded growth rate of 4.6% between 2016 and 2021 [6]. If this
constant additional methanol demand will be produced following
traditional processes, that have average emission of 0.35 kg CO2 per kg
of MeOH, this will lead to an emission of 54 Mt y− 1 of additional CO2 [7,
8]. Currently, methanol is produced via a two-step process that involves
syngas generation and downstream high-pressure methanol synthesis. In
the European and North America context, most of the syngas is gener­
ated from natural gas. On the other side China privileges carbon gasi­
fication as this raw material is much cheaper. The syngas generation
step, based on natural gas, requires approximately 60% of the overall
capital expenses (CAPEX) [9]. Most of the CO2 produced in these plants
is connected to the combustion of fuels in the firebox where the syngas is
generated. In this equipment fuels are used to supply the energy
required to compensate for the high endothermicity of the reforming
reaction. Downstream, methanol is produced via exothermic COx hy­
drogenation. Here accurate control of the reaction temperature is
necessary to avoid hotspots that could lead to secondary products

* Corresponding authors.
E-mail addresses: federico.galli@usherbrooke.ca (F. Galli), gianluca.pauletto@sypox.eu (G. Pauletto).

https://doi.org/10.1016/j.jcou.2022.101911
Received 6 November 2021; Received in revised form 2 January 2022; Accepted 23 January 2022
Available online 3 February 2022
2212-9820/© 2022 Elsevier Ltd. All rights reserved.
A. Mion et al. Journal of CO2 Utilization 58 (2022) 101911

(methane production) and catalyst deactivation. Industrial plants use REquil reactor to simulate respectively the reformer and the methanol
boiling water reactors (BWR) as a technological solution to control the reactor [20,21]. Both reactors operate at conditions of commercially
temperature and to remove the heat. Configurations with series of available catalysts.
adiabatic reactors and interstage cooling or quench are also used [10, The initial syngas generation section is mainly driven by the
11]. reactions:
Depending on the productivity, traditional methanol installations
involve either a fired steam methane reformer or an autothermal CH4 + H2O ⇌ 3H2 + CO (1)
reformer (ATR) or a combination of these two. While the first option CH4 + CO2 ⇌ 2H2 + 2CO (2)
requires CO2 co-feed, the second needs pure oxygen. As ATR involves an
air separation unit (ASU), this solution is selected only for plants that Increasing the amount of CO2 used to produce syngas, it is possible to
produce more than 5000 t d− 1 of methanol [10,11]. preferentially follow steam reforming (1) (H2/CO = 3) or dry methane
The latest advancements on the syngas generation starting from reforming reaction (2) (H2/CO = 1). By modulating the CO2 co-feed, it is
methane-containing-gas stream are the short contact time catalytic possible to tune the H2/CO ratio. The final goal is to have the SN ratio
partial oxidation, the ATR that operates at pressures close to 70 bar, and (H2-CO2)/(CO+CO2), methanol module, that is within the interval 2 –
the combination of a SMR and adiabatic reverse water gas shift reactor 2.05 (Table 1).
[12]. These solutions significantly reduce CAPEX and operating ex­ When the reformer relies preferentially on dry reforming, we have
penses (OPEX) but have limited impact on the CO2 emission reductions used additional H2 produced using an electrolyser.
[13]. The main differences of the herein reported process schemes,
The International Renewable Energy Agency (IRENA) estimates that compared to the traditional methanol production processes, relies on the
with the right policies and incentives, renewable methanol could be integrating of the electrified reformer (e-SMR or electrified dry methane
competitive by 2050 or even earlier [14]. reformer: e-DMR) that is, in one case, coupled with an electrolyser. In
In recent years, extensive research has been dedicated to the direct this way, the process scheme is drastically modified as no convective
hydrogenation of CO2 into methanol through carbon capture and uti­ section of the reformer is involved. At the same time the CO2 balances
lisation technologies (CCU) [4,15,16]. The main existing drawbacks are become negative as CO2 is used rather than being produced.
related to the thermodynamic limitation on the CO2 conversion together
with the limited activity and stability of the methanol synthesis catalyst
2.1. Configuration A and B
[4,11,17,18]. On the other side, Haldor-Topsoe is demonstrating CO2
neutral methanol production starting from biogas that is reformed in an
Both reformers operate at 900 ◦ C and 20 bar even if typically, the
electrified steam reformer [19].
operating pressure of the reformer in a methanol plant varies from 25
Additionally, except for a limited number of geographical locations,
bar to 30 bar. Here we have decided to decrease the operating pressure
direct CO2 hydrogenation is extremely expensive as the required H2
to 20 bar for the following reasons:
involves energy-intensive water electrolysis. A direct CO2 hydrogena­
tion plant producing 1500 t d− 1 of methanol would require approxi­
- lower thermodynamic carbon forming potentials particularly rele­
mately 11700 kg h− 1 of H2, thus an electrolyser that requires
vant when reforming CH4, H2O and CO2 mixtures (Fig. 1);
approximately 560 MW of renewable electricity. Additionally, only for
- higher methane conversion;
electricity prices below 30 € MWh− 1 and remuneration on CO2 uti­
- possibility to directly integrate H2 produced by a water electrolyser
lisation above 255 € t− 1, it is possible to produce methanol economically
without requiring a dedicated H2 compressor.
via direct CO2 hydrogenation [15].
The electrification of chemical processes however needs a tech­
The mixture of CH4, H2O, and CO2 is fed to the electrified reformer
noeconomic assessment as cost of energy, methane prices and taxation
after being preheated. Commercially available nickel-based catalysts
on the carbon emission may outplay the technology especially in
have been selected as they can operate under the selected operating
countries with an energy production mix heavily dependent on fossil
conditions [9,13,22,23].
fuels.
In the first layout, configuration A (Fig. 2), the electrified reformer
Here we report two innovative process configurations that involve
(R-01) operates at steam to methane ratio (S/C) equal to 2. CO2 is added
electrically heated methane reformers. In both cases, the source of car­
only in small amounts, CO2/CH4 = 0.28, to enhance the CO production
bon converted into methanol consists in a mixture of CH4 and CO2.
that decreases the H2/CO ratio. In this way, we avoid the production of
Additionally, increasing the usage of CO2 in the reformer, thus shifting
H2 excess. The syngas leaving the reformer is cooled to 40 ◦ C, and after
from steam to dry reforming conditions, we can boost the level of
water removal, it is compressed before entering the methanol section.
decarbonisation. An electrically heated dry reformer generates an excess
The second scheme, configuration B (Fig. 3), operates with S/C = 1
of carbon monoxide, H2/CO ratio close to 1, thus it requires the inte­
and CO2/CH4 = 2. In this case, the e-DMR (R-01) produces syngas CO-
gration of an electrolyser that adjusts the syngas composition. In this
rich that needs an additional input of H2. Here, before cooling and
work, for the first time, we i) propose two new process configuration
removing the water, additional H2 is mixed with the CO-rich syngas and
that integrates an electrified steam or dry reformer and an electrolysis
then it is compressed and fed to the downstream methanol section.
unit to adjust the hydrogen to CO ratio to synthesise methanol, ii) we
Electrolytic H2 could also be introduced downstream the two-phase
study the sensitivity of the parameters and we clearly outline in which
separator with minor modifications of the process scheme. The uti­
economic scenario one configuration is better than the other and iii) in
lisation of CO2 is higher than configuration A as in e-DMR CO2 is the
the best configuration we demonstrate that this new process consumes 1
main co-reactant during operation. We named the reactor either e-SMR
ton of carbon dioxide of 0.93 t per ton methanol.
or e-DMR to identify the main reaction occurring inside the reformer.

2. Methods
Table 1
Parameters related to the composition of processed syngas.
The two process schemes rely on three main plant sections (Eq 1 and
Indicator Optimal range Reference stream
Eq 2): initial syngas generation, downstream syngas conditioning/
compression, and methanol production. AspenPlus solved the mass and SN (H2-CO2)/(CO+CO2) 2.0–2.05 Make-up syngas [11]
energy balances using Peng-Robinson with the Boston-Mathias alpha COR CO/(CO+CO2) < 0.6 Make-up syngas [19]
CO2, concentration % 1.5–12 MeOH reactor inlet [32]
function as a thermodynamic model. We have used the R-Gibbs and the

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A. Mion et al.
Fig. 1. Carbon limit diagram of CH4, H2O and CO2 mixtures. The region in grey
identifies thermodynamic conditions favourable to carbon formation. The red
line represents the feed condition to obtain 95% conversion of methane at
20 bar and 900 ◦ C (see inset). All the data reported in this figure were obtained
using a Gibbs Reactor and the Peng-Robinson with the Boston-Mathias alpha
function as a thermodynamic model.
2.1.1. e-Reformer
In existing fired reformers, combustion of fresh methane, off-gases
coming from the pressure swing absorption (PSA) and the methanol
section provides the heat for the strong reaction endothermicity. Even if
the energy required by the reforming reaction is approximately 1.2 kWh
per Nm3 of H2 produced, fuel firing generates from 2.2 kWh to 2.4 kWh
per Nm3 of H2. Consequently, the efficiency of reforming furnaces is
approximately 50% [13,23]. This imposes extensive heat recovery from
low-pressure flue gases within the convective section as well as process
integration that involves expensive equipment for steam raising,
super-heating, and feedstock preheating. Within the firebox, more than
90% of the heat is transferred via radiation, achieving average heat flux
at the external surface of the reforming tube of approximately
100 kW m− 2 [9].
Nowadays, as renewable electricity prices continue to decrease,
direct electrification of endothermic reactors is strongly encouraged due
to cost-saving and GHG emission reduction [24,25]. The electrification
of methane reformers decuples the performance of the reactor from the
Fig. 2. Block flow diagram of Configuration A. Electrified reformer (R-01) followed by syngas conditioning, syngas compression (C-01), methanol reactor (R-02), and
product-reactants separation.
3
Journal of CO2 Utilization 58 (2022) 101911
heat flux at the reforming tubes that is the existing crucial design
parameter. An electrified reformer avoids the emission of CO2 produced
while generating the heat required to drive the reaction. Thus, when
integrating an electrified reformer into a methanol production plant, it is
possible to entirely avoid CO2 emissions if the syngas composition sat­
isfies the SN ratio (Table 1). Finally, the thermal efficiency of the elec­
trified reformer is above 90% if the heating is provide using resistive
heating elements. Additionally, electrically heated reformers optimise
the temperature profile minimising temperature gradients thus mini­
mise the carbon forming potentials, extremely relevant when reforming
CO2 CH4 mixture as low S/C.
2.1.2. Electrolyser
Electrolysis is a green production pathway that produces hydrogen
starting from water and electricity following an electrochemical process.
Currently, only 4% of the total H2 production comes from this route,
mainly due to the limited availability of renewable electricity [26]. This
process is energy-intensive and requires exclusively renewable elec­
tricity to be carbon-neutral. If electricity with an associated CO2 emis­
sion equal to 0.2 kgCO2 kWh− 1 is used, the electrolyzer emits the same
amount of carbon dioxide of a traditional fired reformer: 10 kgCO2
kgH2− 1.
Here we assumed to have an alkaline electrolyser as this is the most
mature technology currently deployable at hundreds of megawatt en­
ergy power. This unit typically consumes 50 kWh kg− 1 of H2 with an
efficiency of approximately 70% [11,27].
2.1.3. Methanol section
The methanol synthesis section is unchanged when compared to a
traditional commercial plant. Methanol catalyst requires removal of
excess steam from the syngas to avoid sintering and deactivation [28].
The reactor operates isothermally at 250 ◦ C and 50 bar when using
traditional Cu-based (CuO/ZnO/Al2O3) catalysts [11,29]. We have
selected a boiling water reactor (BWR) as this generates steam while
recovering the heat produced by the exothermic methanol synthesis.
Steam is used as heating medium within both configuration A and B.
Next to the SN ratio, the CO/CO2 ratio (Table 1) was tuned to optimise
both syngas utilisation and single-pass conversion. We implemented the
methanol reactor as a REquil with a temperature approach to equilib­
rium for the reactions.
CO + 2H2 ⇌ CH3OH (3)
CO2 + H2 ⇌ CO + H2O (4)
A. Mion et al. Journal of CO2 Utilization 58 (2022) 101911

Fig. 3. Block flow diagram of Configuration B. Electrified reformer (R-01) followed by syngas conditioning, electrolyser (R-03), syngas compression (C-01), methanol
reactor (R-02), and product-reactants separation.

The temperature approach to equilibrium for both reaction (3) and

(4) have been used to account for the difference in the real single pass 1 - (CO + CO2)purge + liq⋅product / (CO + CO2)syngas (8)
conversion that characterizes industrial reactors and thermodynamic
equilibrium. In this way, we reproduced the performance of real meth­
anol reactor [30].
The used temperatures approach to equilibrium are:

- Configuration A (Fig. 2): 7 ◦ C and 0 ◦ C for Eqs. (3) and (4) - Energy consumed per ton of methanol produced, including both the
respectively; feed’s energy content and the electricity used as energy input, in GJ
- Configuration B (Fig. 3): 20 ◦ C and − 10 ◦ C for Eqs. (3) and (4) t− 1 of MeOH.
respectively. - CO2 consumption:

CO2 in - CO2 out (9)

These values vary as the CO/CO2 ratio changes between case A and
B.
After cooling, a two-phase separator removes incondensable gases
from liquid methanol and water. The gaseous outlet stream of unreacted
compounds and inert methane is almost entirely recycled. Respectively,
1.5% for configuration A and 2% for configuration B of the gas stream - Overall process efficiency, calculated as
leaving the two-phase separators are purged to avoid accumulation of (energy content of produced methanol) / (energy content of fed
inert CH4. The overall conversion of CO and CO2 is almost complete as it methane + electricity input).
is in traditional methanol processes [31].

2.2. Key performance indicators 2.3. Economic assessment

The most important indices (Table 1) are related to the composition We assessed capital (CAPEX) and operating expenditures (OPEX) to
of the syngas that enters into the methanol synthesis. estimate the production cost of methanol before purification. We have
A limited percentage of CO2 in the feed to the methanol synthesis assumed the following hypothesis:
section is beneficial because it enhances CO hydrogenation. On the other
side, compositions above 12% decrease the reaction rate and lead to - 8000 operating hours per year,
excess water production with a consequent decrease in catalyst lifetime - 15-year plant lifetime,
[19]. - Chemical Engineering Plant Cost Index, CEPCI: 607.5 (2019)
Additional parameters have been used to compare the performances - Exchange rate 1 € = 1.2 $
of existing processes with the traditional ones. These are: Capital costs have been calculated from scale-up factors, data re­
ported in the scientific literature, and personal information within
- methane conversion in reforming unit (R-01, Eq 5) the authors. The simplified techno-economic analysis included the
costs of the most expensive unit operations such as:
(CH4 IN - CH4 OUT) / CH4 IN (5) - e-SMR where the cost is evaluated on an energy consumption basis
and consists of multiple 3 MW-modules installed in parallel. Each
- CO and CO2 per pass conversions related to the methanol reactor: module costs approximately 1.7 M€ resulting in a total cost of the
electrically heated reformer equal to the price of the traditional fired
(CO IN - CO OUT) / CO IN (6) configuration [33].
- Methanol synthesis reactor (BWR): capacity scaling calculation
(CO2 IN - CO2 OUT) / CO2 IN (7)
Ci = Cref,i (Si/Sref,i)n (CEPCI2019 / CEPCIref,i) (10)

- Total carbon conversion of the methanol loop (Eq 8) where Ci is the calculated cost, and Cref,i the cost of the reference

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A. Mion et al. Journal of CO2 Utilization 58 (2022) 101911

equipment; Si and Sref,i are the sizing parameters, i.e. the capacities of Table 3
the methanol reactor [34,35]. Type of heat exchanger and Global heat transfer coefficient, configuration B.
From the sizing perspective, the approach follows Turton et al. Unit Description U, W m− 2 ◦
C− 1

considering that the BWR is a shell and tubes heat exchanger [36].
HX-01 (WHB) MULTIPLE PIPE 300
- Compressor, heat exchangers, and process vessels costs are calcu­ HX-02 FLAT PLATE 150
lated according to the following approach [36]: HX-03 FLAT PLATE 150
HX-04 MULTIPLE PIPE 1100
C–– CBM (CEPCI 2019/CEPCI 2001) (11) HX-05 FLAT PLATE 150
CBM is the bare module cost calculated on the reference year and HX-06 MULTIPLE PIPE 300
depending on a different sizing factor based on the type of equipment, HX-07 MULTIPLE PIPE 1100

the construction material, and the operating pressure.

- The sizing parameter is the exchanging area for heat exchangers HX-i Table 4
(general sizing equation A = Q/U * ΔTLM) (Tables 2 and 3). Syngas Price of consumables and reactants for the base case (reference date: early
enters the waste heat boiler (WHB), HX-01, at approximately 900 ◦ C. 2021).
CBM of the compressor is a function of power requirement while
Chemical Price Reference
flashing tanks are assimilated to process vessels, with the volume
Natural gas 6 € GJ− 1 [38]
corrected at the operating pressure and calculated assuming a fixed
Demineralised 0,7 € m− 3 (“Brumar prodotti chimici per l′ industria Treviso
residence time [37]. water Silea, descrizione prodotti, articoli, unità di
misura,” 2021)
- H-01 in Fig. 2 is electrically powered, and the equipment cost is CO2 0 € kg− 1 [33]
evaluated by considering that the heater consists of 3 MW-modules Green electricity 80 € [25]
MWh− 1
assembled in parallel each having a price of 400 k€.
- The electrolyser cost is calculated according to the power con­
sumption, 900 € kW− 1 is the selected price [11]. 1445 t d− 1.
The syngas fed to the methanol synthesis section has always the
The prices of consumables and reactants (Table 4) refer to early 2021 proper composition required in the traditional methanol synthesis pro­
for the base case. Green electricity is the only considered utility, cesses (Table 7).
neglecting the cost of cooling water. In the base case, remuneration on The low purge fractions of the unreacted mixture imposed according
CO2 utilisation has also been neglected. to Section 2.2.3 provide a recycle ratio, as the volumetric flow of the
Catalyst cost is assumed 1.8 M€ y− 1. Other fixed costs, including recycle over the syngas, of 6.5 and 4.7, respectively.
overhead, administrative, and labour have been considered as 5% of the
total plant cost, i.e., the cost related to capital expenditure. 3.2. Energy balance
From the base case, a sensitivity analysis on OPEX has been
completed varying the natural gas price from 4 € GJ− 1 to 14 € GJ− 1 and The e-SMR in Configuration A consumes approximately 1.2 kWh
the electricity from 20 € MWh− 1 to 80 € MWh− 1. These ranges are Nm− 3 H2 (Table 8), and e-DMR in Configuration B requires 2.3 kWh
consistent with the current market trends with increasing natural gas Nm− 3 H2 (Table 9). This is due to the higher endothermicity of the dry
and decreasing renewable electricity costs. The remuneration from tax reforming reaction and the different H2 productivity achieved by con­
credit on CO2 consumption has been limited to the range of − 200 € t− 1 verting the same amount of CH4.
to 0 € t− 1. The cost of methanol produced via fired reforming has been The energy consumption for preheating is low, thus not relevant, but
used for comparison. a more accurate heat integration would possibly avoid extra electricity
usage. Most of the electrical energy consumption in configuration A
3. Results relates to R-01 (e-SMR), H-01, and C-01. In configuration B the e-DMR
and the C-01 are the main responsible. The total electricity demands is
3.1. Mass balances respectively 142 MW and 430 MW.
The electrolyser is the most energy-intensive unit within configura­
The mass balances of process Configuration A (Fig. 2) and Configu­ tion B and absorbs approximately 84% of the total electricity input.
ration B (Fig. 3) are reported in Tables 5 and 6.
Configuration A consumes 65000 kg h− 1 water, 40000 Nm3 h− 1 of 3.3. Thermal integration
methane and 22500 kg h− 1 of CO2 to produce 1470 t d− 1 of methanol.
Configuration B consumes 13000 kg h− 1 of water, 16000 Nm3 h− 1 of A waste heat boiler (WHB) is always placed after the reformer to
methane, 62000 kg h− 1 of CO2, and 7200 kg h− 1 of H2 produced via generate the steam while cooling down the hot synthesis gas (Figs. 2 and
water electrolysis (Table 6). With this addition, we modify the SN from 3). The larger amount of H2O in configuration A requires primary pre­
0.27 to 2.04. The final productivity of methanol is, in this case, equal to heating in HX-04 before vaporisation in the WHB (HX-01).
HX-07 and HX-06 in configurations A and B, use the high-pressure
Table 2 steam generated in the MeOH reactor (BWR) to preheat the reactor
Type of heat exchanger and Global heat transfer coefficient, configuration A. inlet at 240 ◦ C.
Unit Description U, W m− 2 ◦
C− 1
Even before optimisation, the thermal efficiency of configurations A
HX-01 (WHB) MULTIPLE PIPE 300 and B is comparable to the heavily integrated traditional methanol
HX-02 FLAT PLATE 150 plants that involve fired SMR or ATR. This is possible thanks to huge
HX-03 FLAT PLATE 150 simplification related to the simple integration of electrically heated
HX-04 MULTIPLE PIPE 300
reactors.
HX-05 MULTIPLE PIPE 1100
HX-06 FLAT PLATE 150
HX-07 MULTIPLE PIPE 300 3.4. Key performance indicators
HX-08 MULTIPLE PIPE 1100
H-01 Electrical module
Table 10 summarises the key performance indicators of
–

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A. Mion et al. Journal of CO2 Utilization 58 (2022) 101911

Table 5
Configuration A. Resulting mass balances.
Process stream

10 11 18 22 24 27 28 29 30

Temperature, ◦ C 550 900 40 240 250 40 40 40 40

Pressure, bar 20 20 20 50 50 50 50 50 50
Mole Flow, kmol h− 1 5910 8981 6954 52139 48298 2424 45874 688 45186
Mass Flow, kg h− 1 116177 116177 79655 625787 625787 71339 554449 8317 546132
Volume Flow, m3 h− 1 20134 43941 9058 44963 42293 104 23399 351 23048
1
Composition, mol mol−
H2O 0.61 0.23 0.00 0.00 0.01 0.19 0.00 0.00 0.00
CO2 0.09 0.06 0.08 0.08 0.08 0.01 0.08 0.08 0.08
CH4 0.30 0.03 0.04 0.32 0.34 0.01 0.36 0.36 0.36
H2 0.00 0.51 0.66 0.52 0.47 0.00 0.50 0.50 0.50
CO 0.00 0.17 0.22 0.07 0.05 0.00 0.05 0.05 0.05
CH3OH 0.00 0.00 0.00 0.01 0.05 0.79 0.01 0.01 0.01

Table 6
Configuration B. Resulting mass balances.
Process stream

8 9 14 15 18 22 24 27 28 29 30

Temperature, ◦ C 550 900 80 173 40 240 250 40 40 40 40

Pressure, bar 20 20 20 20 20 50 50 50 50 50 50
Mole Flow, kmol h− 1 2800 4091 3600 7691 6937 39391 35623 2508 33115 662 32453
Mass Flow, kg h− 1 85454 85454 7257 92712 79151 395696 395696 72682 323014 6460 316544
Volume Flow, m3 h− 1 9597 20026 5321 14278 9034 34021 31221 105 17188 344 16844
1
Composition, mol mol−
H2O 0.25 0.19 0.00 0.10 0.00 0.00 0.02 0.23 0.00 0.00 0.00
CO2 0.50 0.17 0.00 0.09 0.10 0.12 0.11 0.02 0.12 0.12 0.12
CH4 0.25 0.01 0.00 0.01 0.01 0.07 0.07 0.00 0.08 0.08 0.08
H2 0.00 0.30 1.00 0.63 0.69 0.73 0.69 0.00 0.74 0.74 0.74
CO 0.00 0.33 0.00 0.18 0.20 0.08 0.05 0.00 0.05 0.05 0.05
CH3OH 0.00 0.00 0.00 0,.00 0.00 0.01 0.06 0.75 0.01 0.01 0.01

Table 7 Table 9
Performance of the configuration analysed. Energy balance of configuration B.
Configuration A Configuration B Process Unit Energy demand, MW

S/C (H2O/CH4) 2 1 HX-01 (WHB) 10

CO2/CH4 0.28 2 HX-02 10
SN (H2 – CO2)/(CO + CO2) 2.02 2.04 HX-03 7
COR (CO)/(CO + CO2) 0.26 0.33 R-01 (e-DMR) 62.5
CO2 Methanol reactor inlet 8.2% 11.7% R-03 (Electrolyser) 360.3
CH4 conversion 85% 92% HX-04 -18
Per pass conversion of CO(Eq. 6) 40% 44% C-01 7.7
Per pass conversion of CO2(Eq. 7) 9.9% 11.9% HX-05 49
Total (CO + CO2) conversion 94% 92% HX-06 13
R-02 (MeOH) -42
HX-07 -48
Tot electricity cons. 430
Table 8
Energy balance of configuration A.
Process Unit Energy demand, MW Table 10
R-1 (e-SMR) 127 Key performance indicator of Configuration A and B.
HX-01 (WHB) 40
Configuration A Configuration B
HX-02 14
− 1
HX-03 7 CO2 spec. consump., t t MeOH 0.3 0.93
HX-04 12 CH4 Feed specific consump., GJ t− 1MeOH 20.1 8.6
H-01 8.2 Total electricity consump., MWh t− 1MeOH 2.3 7.1
HX-05 -25 Total energy consump., GJ t− 1MeOH 28 34
C-01 7.3
HX-06 59
R-02 (MeOH) -43 is required because a considerable fraction of the carbon contained in
HX-07 37
the produced methanol comes from CO2. The specific CO2 consumption
HX-08 -71
Tot electricity cons. 142
is equal to 0.93 t of CO2 per t of methanol produced. Both configurations
achieve a negative CO2 balance, if we neglect the use of methanol as
fuel. The traditional emission that characterises natural gas to methanol
configurations A and B. plants is approximately equal to 0.35 t of CO2 per t MeOH [8].
The productivity of the two configurations is equal to 1470 t d− 1 and The increasing consumption of CO2 in the two process schemes fol­
1445 t d− 1 of methanol. In Configuration B, a much lower methane feed lows a trend similar to the energy consumption. In Configuration B the

6
A. Mion et al. Journal of CO2 Utilization 58 (2022) 101911

usage of electricity and CO2 is much higher because an electrolyser is for Configuration A and B.
used (Table 10). In Configuration B, a total electricity consumption of 430 MW is
In both configurations, the energy consumption per ton of methanol required to supply the heat of the reformer and the energy used by the
produced (Table 10) approaches the overall energy efficiency of the electrolyser. If methane and electricity cost respectively 6 € GJ− 1 and 80
process. € MWh− 1 the methanol production price given by the configuration B is
The energy consumption of both process schemes is similar current equal to 0.63 € kg− 1 (Table 4). This makes this solution economically
industrial processes: unattractive as current methanol production cost in traditional plants is
0.27 € kg− 1.
1. Johnson-Matthey/Devy Process, where a conventional SMR gener­ OPEX is responsible for 93% and 91% of total costs, i.e. the cost of
ates syngas, and a quench reactor synthesises methanol: 32.6 GJ production is much more sensitive to the variation of the OPEX
ton− 1 MeOH. compared to the CAPEX. For this reason, we completed a sensitivity
2. A Haldor Topsoe methanol synthesis process via a two-step reform­ analysis based on the natural gas and electricity prices (Section 4.2).
ing and three adiabatic reactors with intermediate cooling: 28.3 GJ
ton− 1 MeOH. 4.2. Sensitivity analysis
3. A large-scale Haldor Topsoe methanol plant that adopts a two-step
reforming and a boiling water reactor (BWR): 28.8 GJ ton− 1 MeOH. When investigating the effect of the variation on the natural gas
price, we have assumed that electricity costs 80 € MWh− 1 and CO2 0 €
Although an e-SMR has a much higher efficiency than a traditional ton− 1. Under these assumptions, Configuration B is never profitable
fired unit, the overall thermal efficiencies are similar. On the other side, (Fig. 5). On the other side, the slope of the curve related to configuration
the process integration is entirely different as the amount of recovered B is lower compared to configuration A as the natural gas consumption
heat [9,11,39]. per ton of methanol produced is much lower.
While maintaining constant the natural gas price at 6 € GJ− 1 and the
4. Economic analysis CO2 cost at 0 € ton− 1, the sensitivity analysis shows that configuration A
achieves lower production costs even with an electricity price equal to
4.1. Base case 75 € MWh− 1 (Fig. 6). If we maintain the natural gas and electricity prices
at 6 € GJ− 1 and 80 € MWh− 1, and we change the compensation related to
The estimated CAPEX for Configuration A that involves an e-SMR the CO2 consumption, configuration B is not attractive (Fig. 7).
operating at 20 bar and 900 ◦ C is about 158 M€ (Fig. 4). This configu­
ration produces approximately 1,00,000 Nm3 h− 1 of H2 and requires 5. Conclusions
127 MW. Configuration B has a CAPEX of 444 M€. In this second case,
the costs are much higher due to the presence of the electrolyser that The present study focuses on two innovative process configurations
produces 7200 kg h− 1 of H2 from 64,800 kg h− 1 of H2O consuming for methanol production involving an electrically heated methane
360 MW of electricity. The electrolyser capital cost is equal to 324 M€
(Fig. 4). Table 11
Configuration A has a specific cost of 0.02 € kg− 1 MeOH, configu­ OPEX of Configurations A and B.
ration B 0.06 € kg− 1 MeOH.
A B
In Configuration B, approximately 72% of CAPEX is related to the
− 1 1
purchase of the electrolyser. ITEM € kg MeOH € kg− MeOH
Methane cost 0.11 0.05
The operating costs are calculated according to Section 2.4, and the Water 0 0
results are reported in Table 11. For both the configurations, the cost of Power 0.19 0.57
the process water and the catalyst are negligible. The total specific OPEX Catalyst 0 0
costs amount to 0.30 € kg− 1 MeOH and 0.63 € kg− 1 MeOH respectively OPEX 0.30 0.63

Fig. 4. Capital expenses for Configurations A and B, allocated per main unit operations.

7
A. Mion et al.
Fig. 5. Effect of the natural gas price on the profitability of electri­
fied processes.
Fig. 6. Effect of the electricity price on the profitability of electrified processes.
Fig. 7. Effect of the income from CO2 remuneration on the profitability of
electrified processes.
reformer, more competitive and at a higher technology readiness level
compared to plasma technologies [40]. The processes refer to
medium-scale methanol production: Configuration A produces 1470 t
8
Journal of CO2 Utilization 58 (2022) 101911
d− 1 and Configuration B 1445 t d− 1. Both the configurations still relate
to the utilisation of natural gas, which is the fossil material expected to
be avoided progressively. The specific consumption of Configurations A
and B is 20.1 GJ CH4 t− 1 and 8.6 GJ CH4 t− 1 of methanol, respectively.
From an environmental point of view, Configuration B is the most
effective with a specific consumption of carbon dioxide of 0.93 t per ton
methanol. Configuration A limits this consumption to 0.3 t. However,
Configuration B has a high specific electricity consumption of 7.1 MWh
t− 1, while Configuration A requires only 2.3 MWh t− 1 MeOH.
We assumed to employ commercial catalyst for the process, however
new catalyst formulation may be more indicated to operate methane
conversion due to the non-standard feedstock composition.
The described e-SMR Configuration A is the best one when consid­
ering the overall production costs of 0.32 € kg− 1 MeOH, when natural
gas price is 6 € GJ− 1, and the electricity price is 80 € MWh− 1. At the same
conditions, Configuration B allows a production cost of 0.69 € kg− 1
MeOH. The first configuration will become more attractive than a
traditional process as the green electricity cost decreases below 75 €
MWh− 1.
Configuration B gains interest only when the electricity price sta­
bilises under 25 € MWh− 1.
CRediT authorship contribution statement
Anna Mion: Methodology, Software, Data curation, Writing – orig­
inal draft. Federico Galli: Visualization, Writing – review & editing.
Paolo Mocellin: Supervision, Writing – review & editing. Simone
Guffanti: Software, Validation, Revision. Gianluca Pauletto: Concep­
tualization, Methodology, Data curation Writing – original draft,
Supervision.
Declaration of Competing Interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Gianluca Pauletto and Simone Guffanti currently works for a company
that develops electrified unit operations (SYPOX GmbH i.g.). However,
the data reported in the paper are based on commodity prices, economic
models, or manufacturer quotes and therefore the results are not
affected by any bias.
Acknowledgements
The work was supported thanks to the grant 03EFQBY237: SYPOX
Exist Forschungstransfer from the German Ministry of Economic Affairs
and Energy (BMWi) and the European Social Fund (ESF).
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