Applied Energy 260 (2020) 114249

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Production of synthetic natural gas from industrial carbon dioxide T

a b c b a,⁎
Remi Chauvy , Lionel Dubois , Paul Lybaert , Diane Thomas , Guy De Weireld
a
Thermodynamics and Mathematical Physics Unit, University of Mons, 20 Place du Parc, 7000 Mons, Belgium
b
Chemical and Biochemical Process Engineering Unit, University of Mons, 20 Place du Parc, 7000 Mons, Belgium
c
Thermal Engineering and Combustion Unit, University of Mons, 20 Place du Parc, 7000 Mons, Belgium

HIGHLIGHTS

• Power-to-gas has a strong potential in the transition to a renewable network.

• Advanced CO capture process allows to reduce the energy consumption.
• Heat
2
integration improves the competitiveness of the global Power-to-Gas chain.
• Attractiveness of Power-to-gas is economically sensitive to electricity cost.

ARTICLE INFO ABSTRACT

Keywords: The Power-to-Gas strategy has become a mainstream topic for decarbonization and development of renewables
Carbon capture and utilization and flexibility in energy systems. One of the key arguments for decarbonizing the gas network is to take ad-
Power-to-gas vantage of existing network infrastructure, gradually transitioning to lower fossil carbon sources of methane
Process simulation from Power-to-Gas.
Techno-economic evaluation
This work proposes the techno-economic investigation of an integrated system considering an advanced CO2
Heat integration
capture process, in terms of solvent and process configuration, to treat about 10% of a cement plant’s flue gas
and convert the captured CO2 into synthetic natural gas using renewable hydrogen generated from a large-scale
wind powered electrolyzer. An optimized heat recovery system is proposed, drastically decreasing the external
hot utility demand of the CO2 capture unit. In addition, it leads to the production of complementary electricity
(about 1.06 MW), reducing thus also the electrical demand of the integrated process.
The synthetic natural gas produced has a composition (CH4 92.9 mol.%, CO2 3.7 mol.%, and H2 3.4 mol.%)
and a Wobbe index (46.72 MJ/m3), corresponding to specification for gas grid injection at 50 bar in Germany.
With an overall system efficiency of 72.6%, the process produces 0.40 ton synthetic natural gas per ton of
captured CO2. The cost of the synthetic natural gas produced is higher when compared to the present natural gas
market price, but cost reductions and possible commercial use of coproducts like oxygen, represent a likely
alternative. Costs are mainly driven by high capital investments (the electrolyzer), and the price of renewable
electricity, which is expected to decrease in the coming years.

1. Introduction are therefore considering these two families of technologies, such as

Following the 2016 Paris Agreement (COP 21) to keep warming
below 2 °C above pre-industrial levels, pursuing efforts to limit the
temperature increase to 1.5° C, above pre- industrial levels, the
European Union (EU) reaffirmed its goal to reduce greenhouse gas
emissions by 80–95% compared to 1990 levels by 2050. In order to
achieve these goals, large-scale implementation of low-carbon tech-
nologies, such as renewable energy sources (RES), and carbon capture
utilization and storage (CCUS), are necessary. Numerous EU countries
Norway, Germany, and Denmark. Zappa et al. recently conducted a
study investigating whether a 100% renewable European power system
would be feasible by 2050 [1]. They concluded that a 100% renewable
power system would still require significant flexible zero-carbon sto-
rage capacity to balance variable renewable energy generation, and
CCUS may still be required to achieved the EU’s ambitious climate
objective.
Nowadays, global wind power capacity is growing continuously
(310 TWh per year in 2015 in European countries with an installed

⁎
Corresponding author.
E-mail address: guy.deweireld@umons.ac.be (G. De Weireld).

https://doi.org/10.1016/j.apenergy.2019.114249
Received 29 July 2019; Received in revised form 21 November 2019; Accepted 23 November 2019
Available online 18 December 2019
0306-2619/ © 2019 Elsevier Ltd. All rights reserved.
R. Chauvy, et al.
capacity of 136 GW [1]) as the cost of producing renewable electricity
is sometimes even lower than the cost obtained from fossil fuels. Pe-
netration of wind power in the electricity market is already high in
several EU countries such as Denmark (51%), and Ireland (24%). Ger-
many also denotes a high share of solar-based electricity (6%) [2].
However, the penetration of renewable sources into the energy system
is often limited by the energy storage capability, mainly due to high
costs. Therefore, for continuous availability and reliability, develop-
ment of other efficient grid storage alternatives is needed.
In this context, the Power-to-Gas (PtG) strategy is of growing in-
terest for decarbonization and increasing development of renewables
and flexibility in energy systems [3]. In PtG applications, when abun-
dant renewable energy is available, mainly (but not necessarily ex-
clusively) excess electricity can be used to produce a storable gas, such
as hydrogen produced by water electrolysis. Currently, only 4% of
hydrogen is produced by water electrolysis (overwhelmingly by steam
reforming), where the total hydrogen production around the world is
about 500 bill·Nm3/year [4,5]. This renewable hydrogen is either used
directly in industrial applications or in fuel cells [6]. Direct injection of
hydrogen into the natural gas grid (up to 10%) or conversion into
synthetic natural gas (SNG) by methanation and subsequent injection
into the gas grid are widely considered in the literature [2,7,8,9]. In
addition to maintain the high heating value of the gas, methanation
denotes several advantages, as it avoids adaptation in the gas grid
equipment necessary for higher hydrogen contents. Furthermore,
compared to pure hydrogen, SNG (87–97 wt% methane) has fewer
barriers to implementation, as it is safer, easier to transport and store,
and more suitable for industrial applications [10]. It overcomes the
facility and energy density issues related to the use of hydrogen, while
providing other services [11]. It has to be noticed that the conversion is
limited in the term ‘Power-to-Gas’ to the production of hydrogen and
methane, the later in the form of SNG. Other converting forms of
electrical energy to liquid energy carriers (hydrocarbons such as me-
thanol, dimethyl ether, and Fischer-Tropsch products) are more likely
to associate the term ‘Power-to-Fuel’ or ‘Power-to-Liquid’ [12]. Even
though hydrocarbons denote a higher volumetric density in comparison
to gases, PtG allows the use of the existing natural gas infrastructure as
transport and storage medium, offering a market availability of all the
system-relevant components. Furthermore, wind-to-SNG offers an en-
ergy storage medium for the intermittent wind resource, where the
electricity generated by the renewable energy is merged into the grid
providing a more constant renewable energy supply, avoiding over-
supplying power grids with high production from renewable energy.
Concurrently, many industrial processes look for possibilities to
decrease their CO2 emissions, where CCUS is considered. Accounting
for 2–2.5 GtCO2 per year (5–7% of the total anthropogenic CO2 emis-
sions) [13,14], the cement sector is investigating ways to cut its emis-
sions through different levers such as modern dry-process technology,
clinker substitution, free-carbon alternative fuels and CCUS. It is esti-
mated that only about one third of the CO2 released is due to com-
bustion, and this makes the cement industry a specific case compared
with other combustion industries. Clinker, main constituent of the ce-
ment, is made by heating a homogeneous mixture of raw materials at
minimum temperature of 1450 °C. Two thirds of these released emis-
sions, i.e. 550 kgCO2 per ton of clinker, come from the limestone cal-
cination during the decarbonation step in the clinker burning process,
and are then necessarily emitted [15,16]. Hence, the capture of CO2
from cement plant’s flue gas and its conversion are key issues. This CO2
can be a source for methanation.
Several technologies at different levels of maturity and perfor-
mances can be envisaged for capturing the CO2 from cement kilns (e.g.
oxy-fuel combustion, chilled ammonia technology, adsorptive pro-
cesses, calcium looping, etc.) [17–20]. The most mature technology is
the absorption-regeneration amine-based process, which reached a TRL
(Technology Readiness Level) of 9 compared to the lower TRLs of all
other technologies. More precisely, a recent study from the IEA
2
Applied Energy 260 (2020) 114249
Greenhouse Gas R&D Programme [21] pointed out that among the
different liquid absorbents that can be used for capturing CO2 (e.g.
aqueous amine (TRL 6–9), amino acid or mixed salts (TRL 6), ionic
liquids (TRL 4), water-lean absorbents (TRL 5), precipitating and de-
mixing solvents (TRL 4–6), etc.), aqueous solutions composed of amine
blends (e.g. piperazine (PZ) mixed with another amine such 2-amino-2-
methyl-1-propanol (AMP) or methyldiethanolamine (MDEA)) can be
considered as the new reference solvents in place of monoethanolamine
(MEA), long time considered as benchmark for such CO2 capture pro-
cesses [21]. These amines blends and especially activated solutions
allow to reduce significantly the energy demand of the system. Re-
garding the other post-combustion CO2 capture technologies, mem-
brane systems (TRL 5–6) and solid sorbent processes (TRL 6) (e.g. Va-
cuum Pressure-Swing Adsorption (VPSA), calcium looping, etc.) have
also received a growing interest [22–24]. The widespread deployment
of pilot and demonstration plants, including both large-scale demon-
stration projects and commercial size amines-based post-combustion
worldwide installations, such as Boundary Dam (Canada), Petra Nova
(USA), and Shengli (China), were reviewed by Idem et al. [25].
In the case of the post-combustion CO2 capture by absorption–re-
generation processes applied in a cement plant, the CO2 is separated
from the exhaust gases of the system by adding a unit to the tail-end of
the clinker process. While this end-of- pipe mature technology achieves
high absorption efficiency (usually 90%), the main disadvantage is the
high energy demand for the scrubbing liquid regeneration (e.g. from
3.2 GJ/t CO2 to around 3.8 GJ/t CO2 with MEA 30 wt% as solvent
[26]). Nevertheless, the development of new solvents (new solutions or
blends) [21,27], and new process configurations [28,29] are allowing
the global performances of the absorption-regeneration technology to
reduce its energy consumption to be improved, so that this technology
remains attractive and competitive.
The Power-to-Gas process chain was first proposed in Japan in the
late 1980 s. Recently, a growing interest dealing with this technology
has begun, especially in Europe. In a detailed review, Rönsch et al. give
an overview of methanation technology and research, focusing on
projects with methane as a product [30]. Chauvy et al. maintain that
PtG is one of the best alternative processes for CO2 utilization among
examined cases in the sensitivity analysis [31]. The interest is mainly
driven by the increasing share of renewable energy (wind and solar
power), where PtG may provide large-scale and long-term energy sto-
rage [32]. Other field of applications include services to balance the
loads in electricity networks, a substantial source of fuel for heating and
transportation, and a significant contribution to emission reduction
targets [33]. Pilot plants are under construction, or even in operation,
in several countries, including Germany, Switzerland, Denmark, France,
and Japan. In particular, the European Power-to-Gas Platform contains
a database of past, current and planned PtG projects in Europe [34].
Numerous reviews of PtG projects present lab, pilot and demo plants for
storing renewable energy and CO2 [7,35,36]. Quarton and Samsatli is
particularly recommended for more detail on real-life PtG projects,
economic assessments and systems modeling [7]. Bailera et al. detail
worldwide existing projects and present basic information together
with qualitative descriptions of the plants, technical data, budget and
project partners [35]. Wulf et al. reference about 130 demonstration
projects in operation or planning in Europe (63 projects were in op-
eration by end of May 2018), about 40% of which were developed in
Germany [36].
One example project that illustrates the concept of PtG is the e-Gas
Project (Werlte, Germany) [8,35]. It demonstrates how renewable en-
ergy could be efficiently stored in the existing natural gas network. It
consists of methanation combined to an organic waste biogas plant,
which produces about 1 kton methane-rich gas from concentrated CO2
and renewable H2. Three alkaline electrolyzer stacks of 2 MW supplied
from a 14.4 MW capacity offshore wind park generate the H2. The
annual SNG injection to the grid from this process is approximately 3
million Nm3.
R. Chauvy, et al.
Raw materials
Cement kiln
Fuel
Flue gas
Cement
Excess RE H2
Electrolysis
H2O
O2
Fig. 1. Conceptual Flowsheet of the interconnected PtG system comprising (A) CO2 capture unit; (B) CO2 methanation unit.
In the meantime, many studies focus on thermodynamic con-
siderations, the development of new catalysts, the characterization of
the reaction kinetics and mechanisms of CO2 methanation [37,38]. For
instance, Su et al. proposed a review on the advances in catalytic CO2
hydrogenation to methane, discussing the structure of the catalysts, the
preparation methods, the pre-treatment conditions and their compo-
nents in detail [37].
In addition, Eveloy and Gebreegziabher recently reviewed projected
PtG deployment scenarios at regional and distributed scales [39]. They
highlighted that even though many types of PtG energy/material in-
tegrations are possible, few of them have been incorporated into PtG
deployment modelling works. Furthermore, they identified that heat
recycling from catalytic methanation reaction products, feed compres-
sion trains, and condensed water integrated with CO2 capture from
cement production and/or water electrolysis requirements have re-
ceived limited attention. This lack of experience with the whole PtG
system was also highlighted by Quarton and Samsatli [7], Ghaib and
Ben-Fares [8], and Thema et al. [40]. It has to be pointed out that the
development of PtG technology is also subject to fundamental energy
and climate policy decisions.
Therefore, only a few studies attempt to evaluate large-scale in-
tegrated PtG process performances, showing a large potential for im-
provement, which helps the decision makers to justify their choices.
Becker et al. recently proposed a detailed SNG plant study case where
the synergies between large-scale reactors, thermal management and
techno-economic considerations were provided [41]. Morosanu et al.
proposed a concept based on water electrolysis to produce hydrogen,
CO2 capture from ambient air using solid adsorption materials, catalytic
CO2 methanation, gas separation, and a single mixed refrigerant (SMR)
methane liquefaction process, where mass and energy balances at de-
monstration scale were provided [42].
To this extent, in-depth modelling and economic analysis of PtG
systems are addressed in this paper. The integration of SNG production
with an advanced CO2 capture process, mainly in terms of solvent and
process configuration, and considering an optimized heat recovery
leading to a complementary electricity production, are especially in-
novative and correspond to the purpose of the present study. The sug-
gested PtG technology is flexible, easily up/down-scalable and modular
in order to allow an adjustment to any specific boundary conditions of a
distinct application, such as end-product, source of CO2, use of potential
by-products, and main purpose of the system (utilization of excess re-
newable energy, storage, etc.).
2. Materials and methods
The present PtG integrated process plant was developed to convert a
Applied Energy 260 (2020) 114249
Other CCUS route(s)
A
CO2-separation unit
Depleted flue gas
Amine scrubbing
Scrubbing liquid
regeneration
CO2 Heat Excess heat for other
application
B
Methanation
CO2/H2 Raw SNG
H2O
Gas upgrading Grid injection
SNG
part of CO2 coming from a cement plant into SNG, and comprises four
implementation steps: (i) an operational cement plant equipped with
the Best Available Technique (BAT), where an advanced CO2 separating
unit for scrubbing CO2 contained in the flue gas was considered; (ii) an
electrolysis unit for splitting water by electrolysis to produce renewable
H2 and O2; (iii) a methanation unit for converting the CO2 and the
renewable H2 by a methanation reaction to a methane rich gas (SNG);
and (iv) a SNG upgrading unit to fulfil the requirements for further
injection into the gas grid. Finally, the possibility of heat integration
through systematic process-to-process analysis is investigated to reach
high energy efficiency and minimize utility costs. It is worth noting that
the produced SNG can also be converted into compressed renewable
natural gas or liquefied renewable natural gas to serve as a transport
fuel.
The size of the PtG process is based on a 90 MW large-scale wind-
based electrolyzer, generating 40 ton of renewable H2 per day. The flue
gas to be treated comes from a conventional BAT cement plant pro-
ducing 3000 tons of clinker per day. It corresponds to a total flow rate
of 250,000 m3/h, at 1.20 bar and 40 °C after conditioning (after de-
sulfurization, denitrification, dedusting and cooling), with a CO2 con-
tent of 20 mol.%, generating 2475 ton of CO2 per day [43]. Therefore,
9.8% of the cement plant flue gas is treated where 90% of the CO2 is
captured, representing a CO2 production of about 219 ton per day. The
CO2 capture unit can be upscaled in order to treat the entire cement
plant’s flue gas, where the captured CO2 can be geologically stored or
converted into other products.
Fig. 1 illustrates the conceptual flowsheet of this interconnected PtG
system.
2.1. Process modeling and design
2.1.1. Thermodynamics models and simulation tools
The units investigated in this study were implemented in
AspenTech’s software. Concerning the CO2 capture unit, it was simu-
lated using the Acid Gas Property Package in Aspen Hysys™ v10.0
software. More precisely, the thermodynamic models implemented in
such package are the Electrolyte Non-Random Two-Liquid (eNRTL)
activity coefficient model for electrolyte thermodynamics in the liquid
phase [44] and the Peng-Robinson equation of state for the vapor phase
[45]. The Acid Gas Package also includes the physicochemical prop-
erties of acid gases (CO2 and H2S), water, amines alone (e.g. MEA, DEA,
MDEA, PZ, etc.) as well as several mixtures (e.g. MDEA + PZ,
DEA + PZ, etc.). The CO2 capture modelling is based on a rate-based
calculation model and comprises a makeup unit operation to auto-
matically compensate water and amine losses, which was validated by
Laribi et al. [46].
3
R. Chauvy, et al.
Aspen Plus™ v10.0 was used for both the CO2 methanation and gas
upgrading units considering the Peng Robinson equation of state for the
calculation of gaseous properties. Estimates were considered to model
the block unit for hydrogen generation.
2.1.2. Renewable H2 production unit
Water electrolysis is mainly characterized by the source of elec-
tricity, i.e. high temperature steam, solar or wind-based electrolysis,
and the solution used as electrolyte, i.e. alkaline (AE), proton exchange
membrane (PEM) or solid oxide (SOEC) electrolyzers.
An essential block for PtG, electrolyzers need to fulfil some special
requirements, including dynamic behavior to follow fluctuating power
inputs, high efficiency to avoid energy losses, elevated pressure to re-
duce compressor costs, as well as long lifetimes. Even though alkaline
electrolyzer technology is fully mature, PEM water wind-based elec-
trolysis, which is currently close to commercial deployment, was
chosen in this work as it is more compact and best suited to the dynamic
load balancing of electricity grids needed with use of intermittent re-
newable energy. Traditional alkaline electrolyzers, on the other hand,
are typically used for continuous steady-state industrial production of
hydrogen [47,48]. The comparison of electrolyzer technologies is sum
up in the Supporting Information (see SI.2). PEM electrolyzer produces
hydrogen at 30 bar with a high purity level of 99.9 vol%, whilst the
operating temperature is typically low (50–100 °C) [49]. The specific
electrical power of these electrolyzers is estimated at 5 kWh per Nm3,
approximately 55.6 kWh per kg H2. A production cost of 4–5 € per kg
H2, and a total system cost, including power supply and installation
costs, of 1200 € per kW with an operation lifetime of 20 years are
considered [41,49]. The oxygen stream from the water electrolysis is
produced in high purity, and may be further used in the calcination
process to increase the CO2 partial pressure which facilitates CO2 se-
paration (partial oxy-combustion) [17,19,46]. This high purity by-
product can also be traded for many high-tech applications.
The electrolyzers are assumed to be co-located with the sources of
renewable electricity and CO2, neglecting de facto the efforts to in-
tegrate the different units, such as infrastructures, and avoid transport
needs.
2.1.3. CO2 capture unit
The implemented CO2 capture process was based on the works of
Dubois and Thomas [29,50] considering a Rich Vapor Compression
(RVC) process combined with an Inter-Cooled Absorber (ICA) and two
Water-Wash (WW) sections, and the use of a MDEA 10 wt% + PZ 30 wt
% blend as the solvent. The selection of the configuration and the sol-
vent, specifically the use of PZ as absorption activator in comparison
with other ones (e.g. (piperazinyl-1)-2-ethylamine – PZEA), based on
reaction mechanisms differences leading to different absorption-re-
generation performances, are derived from previous simulation results
(see Supporting Information for more details). Fig. 2 presents the im-
plemented flow sheet.
The installation was designed taking the pilot unit used in the
CASTOR/CESAR European Projects as Ref. [51]. The CASTOR/CESAR
unit was selected as a reference since all the design and operating
parameters in relation with the installation are available in literature
[51]. In the current study, this unit was upscaled (columns diameter) in
order to treat 24,660 m3/h of flue gas with a CO2 absorption ratio of
90 mol.%, corresponding to a production of 219 ton per day of CO2
(98 mol.% purity). The upscaling was performed to keep the same gas
and liquid velocities, 1.29 m/s and 6.70 10−3 m/s, respectively, such as
the optimum value for the (L/G) vol ratio, namely around 5.19 10−3 m3/
m3.
The dimensions of the absorber and the stripper, and the operating
conditions for each column are provided in Table 1. Note that Tabs
corresponds to the absorption temperature, at the top of the absorption
column, while Tregen refers to the regeneration temperature, at the
bottom of the stripper. PZ-based solvents being conventionally
4
Applied Energy 260 (2020) 114249
regenerated at higher temperature for optimal performances [29], a
regeneration pressure (Pbottom of the stripper) of 5 bar was considered,
leading to a regeneration temperature of 140.8 °C, in contrast to a
temperature Tregen of around 120 °C with a conventional MEA 30 wt%
solvent.
The RVC configuration (applied to the rich solution, i.e. after the
absorption step) uses a heat pump effect. As described by Le Moullec
et al., the purpose of the RVC process modification is to increase the
heat quality provided to the system by enabling the valorization of heat
available at a lower quality level or when increasing the quality level is
energetically interesting [28]. Thanks to the flashing of the solvent, a
gaseous stream mainly composed of CO2 and H2O is produced. This
stream is compressed and sent back to the regeneration column in order
to reduce the steam demand at the reboiler. At the same time, with the
vapor coming from the compressor following the flash tank being quite
hot (which could lead to hot spot and degradation problems in the
stripper’s bottom if it is reinjected at such temperature level), a second
internal heat exchanger is added in order to cool this vapor down to the
same temperature level at the bottom of the regeneration column
(Tregen ). Such an operation also has the advantage of improving the
preheating of the rich solution before entering the stripper.
Concerning Intercooling, this is a well-described technique which
has already been applied in several pilot or industrial units. It can also
be considered in the “absorption enhancement” process modification
category. The principle of intercooling is to withdraw the solvent
(partially or totally) flowing in the absorber, at a stage n , to cool it
down and to send it back to the absorber at the stage n 1. Such a
method enables a shift in the thermodynamic gas–liquid equilibrium,
and consequently increases the rich loading at the absorber bottom (at a
same liquid flow rate) [28]. However, a lower temperature in the ab-
sorber leads to reduced chemical kinetics and diffusivities which is
mostly compensated by the increase of CO2 solubility leading globally
to very little change to the overall mass transfer coefficient. Globally,
such a technical option is expected to decrease the reboiler duty, as
highlighted by Le Moullec et al. [28].
Regarding the water-wash sections, as described in the IEAGHG
report prepared by CSIRO (Australia) [52], scrubbers are used for ex-
tracting condensable or soluble vapor from gases. Amine vapors and
their degradation products are conventionally captured by water wash
or a scrubbing stage, or several stages with demineralized water, acidic
water or with special reagents. In the present work, and in accordance
with the CASTOR/CESAR pilot unit considered as a reference, two
water-wash sections were added to the simulation flow sheet in com-
parison with the previous model described by Dubois and Thomas [29].
As such, one water-wash section was used at the top of the absorber,
consisting of a packed column composed of three-stages of 1 m height
per stage, and another wash section was used directly inside the top of
the stripper consisting of three stages of packing (same dimensional
parameters as for the main column section) below the condenser and
above the rich solution inlet, in which the vapor coming from the re-
generation meets the liquid coming from the condensation. In the ab-
sorber water-wash section, a freshwater make-up is added and also
serves as water make-up for the global flow sheet. Only a small com-
plement is added into the make-up unit.
It is assumed that the pre-treated flue gas (after de-SOx, de-NOx, de-
dusting and cooling) entering the CO2 capture process (composition in
Table 2) consists primarily of CO2, H2O, N2 and O2. This composition is
based on average values coming from the Brevik Cement plant (Norcem
company) in Norway. It is important to note that the amount of CO2 in
the gas to be treated was maintained at 20.4% for all the simulated
cases. Nevertheless, the influence of the inlet gas CO2 content on the
absorption–regeneration performances has been discussed in previous
works [29,53].
A summary of the simulation results of the implemented process
highlighting its energetical benefit in comparison with the conventional
process using MEA 30 wt% as solvent, is provided in the Supporting
R. Chauvy, et al. Applied Energy 260 (2020) 114249

Fig. 2. Aspen Hysys™ flow sheet of the RVC + ICA + WW configuration with MDEA + PZ as solvent.

Table 1 High pressure and low temperature enhance the CO2 methanation
Main process data equipment for the CO2 capture unit. process performance, as denoted in Fig. 3. Below 600 °C, only species
Parameter Absorber Stripper involved in the Sabatier reaction (see Eq.(1)) are present, with CO ap-
pearing only for higher temperatures (see SI.3.1). Gao et al. underline
Diameter (m) 2.6 2.6 that carbon deposition is not observed under these simulation condi-
Packing height 17 (17 × 1 m) 10 (10 × 1 m) tions for a H2/CO2 stoichiometric ratio of 4, as the water produced
(m)
Packing type Random packing IMTP Norton Metal 50 mm MELLAPACK,
during the methanation process reacts with solid carbon [55]. In this
SULZER, Standard, 125× (for the water wash section) work, operating conditions are chosen in such a way that CO and solid
Tabs (°C) 40 – C are not produced. In addition, this would allow the simplification of
Tregen (°C) – 140.8 the following gas upgrading step before injection into the grid [56].
Pbottom (bar) 1.2 5 The main detailed kinetic law was developed in 1989 by Xu and
Froment on the Ni/MgAl2O4 (Ni 15 wt%) commercial catalyst, defined
for temperatures between 300 and 400 °C and pressures between 3 and
Table 2
10 bar without dilution gas that is closer to the industrial im-
Composition of the conditioned gas to be treated
plementation of CO2 methanation [57]. A lower temperature (below
(G = 24,660 m3/h, 1.20 bar, 40 °C).
about 200 °C) may cause the formation of nickel carbonyl, while a high
Component mol frac. temperature above 500–650 °C may cause carbon deposition (coking),
N2 64.7%
which will deactivate the catalyst [58]. Modelling catalyst reactions in
CO2 20.4% a series of catalytic reactors has been considered, as it avoids the coking
O2 8.6% and sintering of the catalyst. At least two adiabatic reactors have to be
H2O 6.2% connected in series for a good control of the reaction temperature [59];
CO 1330 ppm
the usual approach relying typically on a series of two to five reactors
SO2 111 ppm
NO 474 ppm [60]. In this work, the methanation unit consists of four adiabatic multi-
NO2 2 ppm tube fixed bed reactors, featuring a multi-stage cooling system and gas
recirculation, allowing the outlet specifications to be achieved while
minimizing costs. The Gas Hourly Space Velocity (GHSV) was main-
Information, where the reactions that are included in the Acid Gas tained close to 4000 h−1.
Package for PZ and MDEA solvents reacting with CO2 are also presented The corresponding rate equations are therefore given by Eqs.
(see SI.1). (4)–(7), where the kinetic parameters and their implementation are
discussed in the Supporting Information (see SI.3.2).
2.1.4. CO2 methanation unit
4 ×p
Thermodynamics and kinetics. Methane production by catalytic pCH4 × pH22 O
pH
2 CO 2
k1
CO2 hydrogenation (Sabatier reaction) has been used since the begin- r1 = 3.5 ×
K1

ning of the 20th century. The reaction scheme is given by [54]: pH2 DEN 2 (4)

CO2 + 4H2 CH 4 + 2H2 O H0298 = 165 kJ/mol (1)

p H2 × pCO 2
k2 pCO × p H2 O K2
CO2 + H2 CO + H2 O 0
H298 = + 41 kJ/mol (2) r2 = ×
p H2 DEN 2 (5)
CO + 3H2 CH 4 + H2 O H0298 = 206 kJ/mol (3)

5
R. Chauvy, et al. Applied Energy 260 (2020) 114249

1.0 100%

0.8 80%

Molar composition
H₂

CH4 yield (%)

0.6 60% CO₂
H₂O
0.4 40% CH₄
CO

0.2 20% CH₄ yield (10 bar)

CH₄ yield (1 bar)

0.0 0%
200 300 400 500 600 700 800
Temperature (°C)
Fig. 3. Molar concentrations of CO2, H2, H2O, CH4 and CO at stoichiometric ratio H2/CO2 = 4, P = 10 bar, and CH4 yield at P = 1 and 10 bar).

3 ×p
pH CO
2 electrolysis, considering the stoichiometric ratio H2/CO2 of 4. A single-
k3 pCH4 × p H2 O
r3 = 2.5 ×
K3 stage CO2 compression step is considered technically appropriate to
pH2 DEN 2 (6) reach the working pressure of 10 bar, while hydrogen is brought to the
same pressure. They are then mixed with the recycle stream derived
where from the upgrading unit and pre-heated to 350 °C before feeding the
K H2 O p H2 O first adiabatic reactor (REA-1) where the methanation reactions occur.
DEN = 1 + K CO pCO + K H2 p H2 + K CH4 pCH4 + A fraction of the effluent, set at 0.7, is recycled to the inlet of REA-1 to
p H2 (7) lower the temperature below 650 °C in order to avoid catalyst sintering
and with ri referring to the rate of reactions i (reactions (1)–(3), re- [61]. Heat removal is ensured to counteract thermodynamic limitations
spectively), k1, k3, the rate coefficients of reactions (1) and (3) (kmol of the reaction as well as to prevent the catalyst bed from sintering the
bar1/2/kgcat h), respectively, k2 the rate coefficient of reaction (2) methanation reactors. The reaction mixture is therefore cooled down to
(kmol/bar kgcat h), K1, K3 the equilibrium constant of reactions (1) and 350 °C after each reactor to obtain high CO2 conversion. The heat of the
(3) (bar2), respectively, K2 the equilibrium constant of reaction (2), methanation reactions can be partly used to produce steam to re-
K CH4 , K CO , and K H2 the adsorption constants of reaction for CH4, CO and generate the scrubbing liquid in the CO2 capture unit. After methana-
H2 (bar−1), respectively, K H2 O the desorption constant of H2O, and p tion, water vapor has to be separated from the product gas. The outlet
the partial pressure (bar). of the last reactor (REA-4) is therefore cooled to a temperature of 25 °C
Process modelling. Fig. 4 shows the process flow sheet of the CO2 to condense the water. A purity of 99.99 vol% is then achieved in the
methanation unit including the upgrading section. H2O stream.
The CO2 coming from the CO2 capture unit is fed at 5 bar with Table 3 presents the main process data equipment for the CO2 me-
hydrogen coming at 30 bar from the PEM water wind-based thanation unit, while Table 4 introduces the specifications for the four

Fig. 4. Aspen Plus™ flow sheet of the CO2 methanation unit including the upgrading section.

6
R. Chauvy, et al.
Table 3
Main process data equipment for the CO2 methanation unit.
Parameter Specification
Reactor operating Pressure (bar) 10
Pressure Loss (%) 2 CO2
Reactor operating Inlet Temperature (°C) 350
Catalyst Ni/MgAl2O4
Catalyst density (kg/m3) 2350
Bed density (kg/m3) 790
Bed porosity 0.44
Table 4
Main specifications for the four multi- tubular adiabatic reactors at a GHSV of
4000 h−1.
Parameter REA-1 REA-2 REA-3 REA-4
3
Reactor volume (m ) 15.60 8.32 7.71 7.47
Mass of catalyst (ton) 22.00 5.87 5.44 5.27
multi- tubular adiabatic reactors.
2.1.5. SNG upgrading unit
The raw-SNG, containing methane, CO2, water vapor and H2, is then
upgraded to be injected into the grid where it can be stored, trans-
ported, or used as fuel (e.g. for CNG cars). Even though the flash unit
removed most of the water (see Fig. 4), the raw-SNG must be further
dehydrated to comply with the water dew point requirements of the
pipelines, to control corrosion and prevent formation of solid hydro-
carbon/water hydrates. Currently, glycol dehydrators are widely used
for natural gas dehydration. Despite their advantages, the system op-
eration is complex and requires solvent storage, replacement and dis-
posal. Moreover, the vent streams from the dehydrators are a source of
emissions of volatile organic compounds. According to Lin et al.,
membrane technology appears to be an attractive alternative for nat-
ural gas dehydration [62]. To this extent, a commercial Pebax®-based
membrane (poly ethylene oxide- based block copolymer) was con-
sidered to dry the raw-SNG [63,64]. The performance is based on lit-
erature values, using an estimated normalized permeability constant of
1000 GPU (1 GPU being 3.35 10−10 mol/m2 s Pa) [62,65], to determine
the size required using Eq.(8). In the Aspen Plus™ model, only the re-
tentate/permeate pressures are specified for given feed conditions, as
well as the split fractions of one of the stream.
The feed gas mixture is compressed in a multi-stage raw-SNG
compression step to reach a pressure of 35 bar. A small one-stage
system removes 90% of the water in the feed gas, producing a low-
pressure permeate gas representing 5–6% of the initial gas flow [66].
The permeate pressure containing the water is set to 1.1 bar [62,65].
permeate flow rate
Amemb =
permeance × driving force
where the permeate molar flux (mol/s) through the membrane is driven
by the partial pressure difference (Pa) of the component of interest H2O,
namely the driving force, and the permeance is expressed as the ratio of
the permeability with the thickness of membrane, leading to the nor-
malized permeability constant (mol/m2 s Pa) taken to be a measure of
the membrane’s ability to permeate gas.
In addition, excess hydrogen also has to be separated in a gas up-
grading downstream of the dehydration membrane, and then fed back
to the methanation reaction. A commercial membrane technology
(polysolfone-based membrane) for hydrogen separation was chosen to
achieve a 90% hydrogen separation [67]. An estimated normalized
permeability constant of 100 GPU [66] was considered to approximate
the performance and determine the size required using Eq. (8). The
stream is therefore expanded to reach a working pressure of 20 bar. The
permeate pressure containing the component of interest H2 was set to
Applied Energy 260 (2020) 114249
Table 5
Gas specification for gas grid injection in Germany [56,69,70].
Parameter Specification
3
Wobbe Index (MJ/m ) 37.8–56.5
< 6 vol%
H2 < 5 vol%
Dust Technically free
water Traces (ppm)
1 bar. Almost all H2 along with a certain amount of methane transport
across the membrane, was recirculated back to the reactor. The large
amount of methane not crossing the membrane forms the retentate at
the identical pressure as the feed stream.
The product stream SNG was then supplied to the natural gas grid
usually at elevated pressures from 4 to 70 bar, by using a multistage
compressor [68]. The number of stages was determined by a pressure
ratio of 4, with equal pressure ratio among all stages. The isentropic
efficiency of each stage of 75%, and the inter-stage cooling temperature
was set at 40 °C. In the frame of this study, it was assumed that the SNG
was delivered at 50 bar. Gas specification for gas grid injection in
Germany is presented in Table 5. The Wobbe index represents the in-
terchangeability of fuel gases with respect to natural gas, which is
usually used to compare the combustion energy output of different
composition fuels.
2.1.6. Heat recovery and utilities
Systematic process-to-process heat recovery through data evalua-
tion, pinch analysis, and optimized heat exchanger network were per-
formed on the system to reach high energy efficiency and minimize
utility costs. Appropriate heat exchangers areas were designed using
Aspen Plus™.
According to the present design, HX-1 was fed with pressurized
boiled feed water at 110 °C and 125 bar. HX-2 was placed to extract
heat from the outlet of the first reactor (REA-1). The steam temperature
and pressure at the outlet of HX-2 was 505 °C and 125 bar, respectively.
A steam turbine unit was used to generate process power to cover a
portion of the electrical demand. This was expanded to 10 bar with an
isentropic efficiency of 0.85, generating 1055 kWe . After the exit of the
turbine, the steam was fed to the condenser, where it released heat and
was condensed to 110 °C. The condensate returned to the system with a
flow rate equal to 7.5 t/h.
As previously mentioned, five additional heat exchangers (from HX-
3 to HX-7) were implemented to cool down the outlet of each reactor to
the working temperature of 350 °C, to obtain high CO2 conversion.
They were fed with boiled feed water at 110 °C and 8 bar, to generate a
medium-pressured steam at 170 °C and 8 bar. This was done so that it
could be brought to the reboiler heat duty of the CO2 capture unit,
which requires heat at 140 °C and 5 bar.
(8)
2.2. Techno-economic analysis
2.2.1. Technical analysis
Technical indicators, including the mass balance of individual in-
puts and outputs, and the utilities demand (mainly heat and electricity
duties), are direct results from the process modelling using the software
Aspen Hysys™ and Aspen Plus™.
In addition, the methanation efficiency is calculated according to
Eq. (9) using the general approach suggested by Salomone et al. [9]:
× XCO2 × MCH4 × LHVCH4
CH4
CH4 =
H2 × MH2 × LHVH2 (9)
where XCO2 is the conversion of CO2 within the methanation unit, MCH4
and MH2 are the CH4 and H2 molar weights (kg/kmol), LHVCH4 and
LHVH2 are the CH4 and H2 lower heating values (MJ/kg), CH4 and H2
are the CH4 and H2 stoichiometric parameters, respectively. The
7
R. Chauvy, et al. Applied Energy 260 (2020) 114249

conversion of CO2 within the methanation unit is assumed to be su- The total product cost (TPC ) is calculated by Eq.(14).
perior to 98.9% to achieve the SNG quality [9]. n
To evaluate the process efficiency of the PtG plant, the PEM elec- TPC =
j=1
Cj
(14)
trolyzer, methanation unit, compressors, and heater are considered,
according to Eq. (10) [9]: with Cj the cost of item j based on Table 7.
nCH4 × MCH4 × LHVCH4
=
PtG
EPEM + Ecomp + Eheat (10) 3. Results and discussions

where EPEM is the electrical energy used by the electrolyzer (MJ), Ecomp
the energy spent for the compression (MJ), and Eheat represents the total
required heat (MJ).
Finally, the overall energy utilization factor is calculated with Eq.
(11).
Eheat
=1
PtG
EPEM + Ecomp
The following parameters are also required for the produced SNG
stream: (i) composition, essential to achieve the gas requirements for
injection into the networks (i.e. percentage of hydrogen); (ii) the Low
Heating Value (LHV) and/or High Heating Value (HHV); and (iii) the
Wobbe index.
2.2.2. Economic analysis
Both operating and investment costs were evaluated. Most of the
capital investment for the equipment was generated directly via
AspenTech Economic Analyzer™. In addition, the cost of several in-
dividual pieces of equipment was approximated when the cost of a si-
milar item of a different size or capacity was known, using expression
(12). The costs were estimated with a nominal accuracy of ± 30%.
S
C = C0
S0
where the incremental cost C decreases with larger capacities S , C0 and
S0 being the reference characteristics values. The exponent takes the
economy of scale effect into account, which is often approximated to
0.6. The results were then updated from the original cost index to the
year 2018 using the annual chemical engineering plant cost index
CEPCI (CEPCI2018 = 603.1) to account for the price development effect
(Chemical Engineering magazine for latest values).
The total capital investment (TCI ) was determined using the fac-
torial methodology, according to the recommended ratio factors for
fluid processing plant by Peter and Timmerhaus [71], and the capital
investment (IE ) of the equipment (see Eq. (13)).
( )
n
TCI = IE × 1 +
i=1
RFi
3.1. Process performances
3.1.1. CO2 capture unit results
Table 8 summarizes the CO2 capture unit simulation results in terms
of gas phase compositions.
An absorption ratio of 90 mol.% leads to the production of 211
(11) kmol/h of CO2 (9.16 t/h) with 98 mol.% purity. In addition to nitrogen
(123 ppm) and oxygen (29 ppm), the produced CO2 flow still contains
some water (around 2 mol.%) and some other components initially
present in the flue gas, namely SO2 (< 50 ppm), NO (< 5 ppm), NO2
(1 ppm) and CO (< 0.5 ppm). As a result of the water-wash sections,
the amines (MDEA and PZ) are only present as traces in the washed-gas
and the produced CO2 flow.
Concerning the energy consumptions, the main energy consuming
unit is the reboiler of the regeneration column (5.75 MWth ), while the
other thermal demands are for cooling (mainly condenser cooling en-
ergy, −1.45 MWth , and lean solution cooling, −2.80 MWth ). The
cooling energy of the absorber intercooling is less significant (−0.72
MWth ) and the water-wash cooling energy is very low (−0.01 MWth ).
Regarding the electrical demands, while the total pumping energy is
low (0.04 MWe ), the electrical consumption of the compressor used in
the RVC configuration is not negligible (0.91 MWe ). These results were
obtained for the optimum operating parameters given in Table 9, where
(12) the specific energy consumption per ton of captured CO2 is also pro-
vided.
The specific solvent regeneration energy (2.28 GJ/tCO2) is drasti-
cally reduced in comparison with conventional CO2 capture processes
using MEA 30 wt% as a solvent (generally estimated around 3.5 GJ/
tCO2 [26] and being precisely calculated at 3.36 GJ/tCO2 using the
present simulation model), which highlights the interest of using an
advanced CO2 capture process such as the one considered in the present
study. All the simulation results in relation with the optimization of the
CO2 capture unit are provided in the Supporting Information (see SI.1),
where comparisons are also performed in terms of equivalent works and
utilities costs both for conventional process configurations (without
ICA) and for three different solvents (MEA 30 wt%, PZ 40 wt% and
(13) MDEA 10 wt% + PZ 30 wt%).

where RF is the ratio factor for direct, indirect and working capital, i
being the items summarized in Table 6. 3.1.2. CO2 methanation and SNG upgrading units’ results
The CO2 methanation unit simulation results in terms of outlet gas
Table 6 compositions are summarized in Table 10.
Estimation of the total capital investment (TCI ) [71,72]. Based on the simulations and the present process design, material
and energy streams were estimated and summarized in Table 11.
Type Item (i ) Ratio Factor (RF )
In order to meet the pipeline quality standards, the CH4 mole
Direct cost 1 Purchased equipment (delivered) 1.00 fraction in the raw SNG of about 70% has to be increased to more than
2 Purchased equipment installation 0.47 90% in order to meet the natural gas grid requirements. Table 12
3 Piping 0.36 presents the technical features of the utilized membranes.
4 Instrumentation and Controls 0.68
A membrane’s size of 62 m2 was therefore required to achieve a
5 Electrical systems 0.11
6 Buildings (including services) 0.18 90% water separation, using Eq. (8). To achieve a 90% H2 separation,
7 Yard improvements 0.10 the size of the second membrane was estimated to 244 m2. The elec-
8 Service facilities 0.70 trical consumption of the compressor used to reach the working pres-
Indirect cost 9 Engineering and supervision 0.33 sure of the dehydration membrane is of importance (0.36 MWe ).
10 Construction expenses 0.41 In addition, the SNG was brought to 50 bar to meet the pressure
11 Legal expenses 0.04 pipelines, leading to a consumption of 0.25 MWe . It is worth mentioning
12 Contractor’s fee 0.22
that for some local or regional grid injections, this elevated pressure is
13 Contingency 0.44
14 Working Capital 0.89 not necessary, as these pipelines mostly operate in the pressure range of
4 to 40 bar.

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R. Chauvy, et al. Applied Energy 260 (2020) 114249

Table 7
Economic assumptions for operating cost estimation (TPC ).
Item ( j ) Assumptions

1 Raw material
2 Utilities
3 Operation and
maintenance
4 Depreciation
5 General expenses
Operating labor and supervisory
labor
Maintenance and repairs
Operating supplies
Laboratory charges
Solvent: 1 €/kg(1); Catalyst: 90 €/kg(2); Process water: 1 €/ton(3); Demineralized water: 3 €/ton(4); Renewable
H2: onsite production(5); SNG selling price: 21 €/ton(6); O2 selling price: 87.4 €/ton(7); CO2 credit tax: 25.2
€/ton(8)
Cooling water: 0.025 €/ton(9); Electricity: 40 €/MWh(10); Steam: self-produced(11)
60 labors/shift, 3 shift/day, 54,000 € per labor per year(12) + 20% of operating labor
6% of capital investment
15% of Maintenance and repairs
15% of operating labor
Annual depreciation cost, with an assumption of a 20-year recovery period and 0 € salvage value, linear
15% of total product cost

(1)
Amine solvent considered: PZ 30% + MDEA 10% (+60% water): 2.16 €/kg PZ × 0.3 + 1.7 €/kg MDEA × 0.1 + 0.001 €/kg H2O × 0.6 = 0.818 €/kg ≈ 1
€/kg solvent cost estimated from de Medeiros et al. [73].
(2)
Catalyst cost considered from own estimation.
(3)
Process water cost considered from Michailos et al. [74].
(4)
Demineralized water cost considered from Li et al. [75].
(5)
Renewable H2 considered produced onsite. Only the cost of demineralized water is taken into account in the calculation of TPC .
(6)
SNG selling price estimated from natural gas price (≈ 4.56 €/1000 ft3 in April 2019).
(7)
Oxygen selling price from Michailos et al. [74].
(8)
CO2 credit tax (€/ton) in April 2019, according to European Emission Allowances (EUA).
(9)
Cooling water cost considered from Michailos et al. [74].
(10)
Electricity considered from renewable energy (wind power). Cost considered from Glenk and Reichelstein [76] supported by www.eex.com.
(11)
Steam considered self-produced. Only the cost of process water is taken into account in the calculation of TPC .
(12)
Operating labor and supervisory labor costs considered from Zhang et al. [72].

Table 8 Table 10
Composition of the gas to be treated, washed-gas and produced CO2 (mol frac. Composition of the outlet streams (mol frac. Basis).
basis).
Component Inlet REA-1 REA-2 REA-3 REA-4 Raw-SNG SNG
Component Gas to be treated Washed-gas Produced CO2
CO2 19.9% 7.5% 4.3% 2.4% 1.5% 3.7% 3.7%
N2 64.7% 69.9% 123 ppm H2 79.9% 31.8% 19.0% 11.5% 8.1% 21.3% 3.4%
CO2 20.4% 2.2% 98.0% H2O 0.2% 40.5% 51.1% 57.4% 60.3% 0.3% Traces
O2 8.6% 9.3% 29 ppm CH4 0% 20.2% 25.6% 28.7% 30.2% 74.8% 92.9%
H2O 6.2% 18.5% 1.98% CO 0% Traces – – – – –
CO 1330 ppm 100 ppm 0.4 ppm
Total mol 1038.12 745.23 692.67 664.94 653.05 268.54 214.22
SO2 111 ppm 112 ppm 43 ppm
flow
NO 474 ppm 512 ppm 3 ppm
(kmol/
NO2 2 ppm 2 ppm 1 ppm
h)
MDEA 0 Traces Traces
Total mass 10.84 10.79 10.79 10.79 10.79 3.78 3.60
PZ 0 Traces Traces
flow (t/
Total mol flow (kmol/h) 1124 1040 211 h)
Total mass flow (t/h) 34.85 27.90 9.16

Table 11
Table 9 Material and energy consumptions of the PtG plant.
Optimum operating parameters and specific energy consumptions of the CO2
Indicator Specification Value
capture unit.
Indicator Specification Value CO2 methanation inputs H2 (t/h) 1.65
CO2 (t/h) 9.09
Operating conditions (L/G) vol,opt (m3/m3) 5.19 10−3 Energy consumptions CO2 compressor (MWe ) 0.14
Recycle compressors (MWe ) 0.19
L opt (m3/h) 128
Membrane compressor (MWe ) 0.36
Intercooling temp. (°C) 40
SNG compressor (MWe ) 0.25
Intercooling stage 8
Pump (MWe ) 0.07
Flash p (bar) 4
Turbine (MWe ) −1.06
CO 2, rich (mol/mol) 0.98
CO 2, lean (mol/mol) 0.33 PtG outputs SNG (t/h) 3.60
SNG Wobbe Index (MJ/m3) 46.72
Energy consumption Eregen (GJ/tCO2) 2.28 Total Output HHV (MW) 50.4

Efficiency Methanation efficiency ( CH4 ) 83.4

PtG plant HHV ( PtG ) 72.6
3.1.3. Process integration results
Overall energy utilization factor ( PtG ) 75.7
The methanation efficiency was estimated at 83.4%, while the
process efficiency of the PtG plant ( PtG ) equaled 65.5% (72.6% on HHV
basis), based on Eq.(9) and (10), respectively, with a comprehensive Table 5). These results are summarized in Table 11.
usage of excess heat and technical assumptions. The overall energy Stream data (temperature, composition, heat capacities, etc.) com-
utilization factor ( PtG ) reached 75.7%. A Wobbe Index of 46.72 MJ/m3 puted by Aspen Plus™ are available in the Supporting Information (see
was calculated, which is in the range of Wobbe Indices in Germany (see SI.4). A minimum pinch point temperature of 30 °C was defined for the

9
R. Chauvy, et al. Applied Energy 260 (2020) 114249

Table 12 the total product cost, it was estimated at 61.60 M€ per year. Fig. 6
Technical features of the membranes system. displays the operational expenses distribution, based on the previously
Parameter Dehydration membrane H2 separation membrane mentioned assumptions (see Table 7). The expected indirect revenues
were 407.9 € per ton SNG, considering SNG, oxygen and CO2 trading.
At present, the estimated cost of SNG is therefore 1587 €/ton SNG,
2
Membrane area (m ) 62 244
Feed pressure (bar) 35 20
about 115 €/MWh, which is in the cost range evaluated by Guilera et al.
Permeate pressure (bar) 1.1 1
Temperature (°C) 40 90
[2]. It is about 3.5 times higher than fossil natural gas (33 €/MWh in
Permeance (GPU) 1000 100 Germany [2]). The annual operating costs amount to around 7% of the
Compressor (MWe ) 0.36 – investment, which is in accordance with the values reported for cata-
lytic processes [78]. It is worth noting that the amortized CAPEX of the
electrolyzers is taken into account in “Hydrogen production”.
600 A sensitivity analysis was carried out regarding the parameters that
500
most influence the SNG cost, derived from Table 15. One input variable
at a time was changed to its low or high value, while the other variables
Temperature (°C)

400 were maintained at their base values. Fig. 7 illustrates the sensitivity
300 analysis.
The electricity price therefore has a huge influence on the cost of
200
SNG, especially due to the fact that H2 production derived directly from
100 it, represents about 70% of the cost of SNG. The additional expenses
and CAPEX, the electrolyzer efficiency, and the O2 selling price have an
0
0 2 4 6 8 10 12 14 influence higher than 10% on the final SNG cost. In particular, the in-
Heat load (MW) come obtained from the sale of oxygen in the PtG plant represents an
Hot composite curve Cold composite curve interesting economic incentive, especially in the current context of low
prices for carbon emissions trading (CO2 credit tax) that have an almost
Fig. 5. Hot and cold composite curves. negligible effect.

heat exchanger with gaseous streams [77]. 4. Conclusion and outlook

The total recovered heat from the plant amounts to about 13.25
MWth , which is available between 25 and 615 °C (see Fig. 5). A fraction The present work has assessed the production of SNG from in-
of the heat recovered at 170 °C can be brought to the reboiler of the CO2 dustrial CO2 in the context of PtG technology. The PtG plant was im-
capture unit, accounting for 5.75 MWth , so that the heat integration plemented in AspenTech’s software, both in Aspen HYSYS™ and Aspen
compensates the hot utility requirement of the CO2 capture unit. Plus™, to extract mass and energy balances in order to investigate its
In addition, the electricity produced in the steam turbine was used economic viability. An advanced CO2 capture process was proposed to
to cover internal demand (see Table 11). Thus, no external electrical treat 10% of a BAT cement plant’s flue gas. Together with renewable
requirement was required for both the CO2 methanation and SNG up- H2, they were converted to SNG through methanation reaction, pro-
grading units. The total external electrical requirement of the whole ducing 0.40 ton SNG per ton of captured CO2. In the suggested process
suggested process designed is therefore linked to the compressor used in design, a dry methane mole fraction of 92.9 mol.% in the final SNG was
the RVC configuration, equal to 0.90 MWe . achieved, together with a CO2 and H2 content of 3.7 mol.% and 3.4 mol.
%, respectively, which are the most critical aspects of the SNG quality
and compatibility.
3.2. Economic performances Systematic process-to-process analysis was investigated to reach
high energy efficiency and minimize utility costs. Thermal integration
Based on the simulation results, the capital investment and oper- led to an overall system HHV-based efficiency equal to 72.6%.
ating costs of the integrated process plant were evaluated. Table 13 lists As seen in this work, SNG is currently not competitive with natural
the estimated capital investment for the equipment. gas. The estimated cost of SNG was about 115 €/MWh, about 3.5 times
Table 14 presents the main costs for all the units. higher than fossil natural gas. Costs are mainly driven by the high initial
The TCI of the integrated process was therefore evaluated to investment costs, as well as the production of H2, which depends di-
166.85 M€ (excluding the capital investment of H2 production), where rectly on the price of renewable electricity. Thus, a reduction of the
the CO2 conversion unit itself represents 58%, mainly due to the electrolyzer investment costs combined with a higher electrolyzer ef-
complex network of heat exchangers that had been implemented to ficiency and higher revenues, could result in a profitable business case
integrate the heat. The final TCI was estimated at 804.92 M€, where for large-scale deployment of this PtG technology. In future scenarios,
about 79% was dedicated to the renewable production of H2. Regarding the cost of SNG can be therefore reduced. Specific costs for PEM tech-
nologies are for instance expected to fall from about 1200 €/kW in
Table 13 2017 to 500 €/kW in 2050 [40]. Furthermore, when applying a time-of-
Cost estimation of main equipment (M€). use retail electricity price of approximately 10 €/MWh, the costs of SNG
Main equipment CO2 Capture CO2 methanation Gas Upgrading decrease to about 40 €/MWh, which is really close to the current price
of fossil natural gas. Several studies also point out that with ongoing
Columns (absorber/stripper) 1.24 – – trends in 10–20 years, PtG might be economically profitable [33].
Reactors – 3.50 –
Moreover, in regions where a natural gas infrastructure exists, the ex-
Compressors 3.36 2.28 3.91
Turbine – 0.45 – isting network for grid gas injection is a major advantage of the PtG
Heat Exchangers (heaters/ 2.40 9.35 0.15 technology. By utilizing excess energy to produce hydrogen via water
coolers) electrolysis, energy can be stored and distributed in the existing system
Flash tanks 0.18 0.09 – for use when and where it is needed. Despite the fact that the use of
Membranes – – 0.68
(excess) renewable energy introduces a seasonal and daily component
Total Purchased equipment 7.18 16.22 4.74
cost (delivered) into H2 production, Gahleitner highlighted that the use of such fluctu-
ating power sources is satisfying, and is currently in use in a lot of PtG

10
R. Chauvy, et al. Applied Energy 260 (2020) 114249

Table 14
Estimation of the total capital investment (M€).
Main cost H2 production CO2 Capture CO2 methanation Gas Upgrading

(1)
Total Direct Cost 387.36 25.84 58.40 17.05
Total Indirect Cost 154.94 10.34 23.36 6.82
Fixed Capital Investment (FCI ) 542.30 36.17 81.76 23.88
Total Capital Investment (TCI ) 638.07 42.56 96.20 28.09

(1)
Calculation based on specific electrical power of approximatively 55.6 kWh per kg H2 and an investment cost of 1200 € per kW (installed) for the production of
40 ton per day of renewable H2 [49,76], and Table 6 to estimate the Total Direct Cost.

Fig. 6. Operational expenses in € per ton SNG.

Table 15 targets, and high renewable energy availability and penetration in the
Input variable for the sensitivity analysis. market. Additionally, several actions could be taken to foster the de-
Input variables Low value Base value High value
ployment of PtG technologies. A key action is the development and
deployment of cheap low carbon electricity, which is necessary to re-
(1)
Electricity price (€/MWh) 0 40 120 duce the costs for PtG. The transition to low-carbon depends on the cost
Electrolyser efficiency(2) (%) 65 75 85 for conventional fossil choices, such as the gas price. Thus, additional
Additional expenses & CAPEX(3) −30% Nominal +30%
taxes on fossil resources could promote a shift to PtG technologies.
CO2 credit tax(4) (€/ton) 0 25.2 50.4
Oxygen price(5) (€/ton) 43.7 87.4 131.1 Direct subsides is also a measure that can be used to improve the
business case for private investors. Creating a green hydrogen market
(1)
Electricity ranging from 0 €/MWh (free renewable electricity) to 120 would also be necessary, giving a premium in the selling price of hy-
€/MWh (own assumption). drogen. Finally, to overcome the seasonal component of PtG, nuclear,
(2)
Electrolyser efficiency commonly considered in the literature [74,76]. geothermal, biomass, and hydro energy are necessary, also increasing
(3)
Additional expenses and CAPEX accuracy with a ± 30% fluctuation. the flexibility of the whole system.
(4)
Electricity considered CO2 credit tax in April 2019, according to European
By applying these actions, combined with a policy penalizing new
Emission Allowances (EUA).
(5) investment in industries using fossil resources, the suggested process
Oxygen selling price from Michailos et al. [74], with a ± 50% fluctuation.
will likely play a certain role for the transition to a renewable network,
integrating large fractions of renewables that require balancing power
Electricity price
and seasonal energy storage, and introducing considerable flexibility
Additonal expenses & CAPEX into the energy system. Furthermore, additional energy and environ-
mental policy challenges can be solved by the enlargement of the per-
Electrolyser efficiency
centage of alternative fuels in the mobility or heating sector. In a
O₂ selling price longer-term perspective, with markets characterized by cheap elec-
CO₂ credit tax tricity and high fuel prices, PtG shall gradually eliminate fossil fuels,
transitioning to a low carbon economy. PtG may also have higher ac-
0 50 100 150 200 250 300 ceptance in society, denoting advantages over the existing alternative
SNG cost (€/MWh) storage technologies as well as over network expansion, representing a
non-negligible component in the future prospects of the technology.
Low value High value

Fig. 7. Sensitivity analysis on the cost of SNG in €/MWh (base cost 115 €/MWh
CRediT authorship contribution statement
SNG).

Remi Chauvy: Conceptualization, Methodology, Investigation,

pilot plants [79]. Validation, Writing - original draft, Writing - review & editing,
In the context of CCUS, the main drivers for methanation deploy- Visualization. Lionel Dubois: Methodology, Investigation, Validation,
ment are limited and/or unwanted CO2 storage, high CO2 reduction Writing - original draft, Writing - review & editing. Paul Lybaert:

11
R. Chauvy, et al.
Resources, Validation. Diane Thomas: Writing - review & editing,
Supervision. Guy De Weireld: Validation, Writing - review & editing,
Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge the European Cement Research
Academy (ECRA) for its technical and financial support. The authors
thank Marc Frère for his help and scientific guidance.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apenergy.2019.114249.
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