To cite : DOI: 10.1016/j.icou.2021.

101488

1 1 Introduction
2
3 Growing concerns about global climate change have recently received great attention, leading to
4 scientific consensus that anthropogenic greenhouse gases have significantly affected the world's climate.
5 Research reports of the Intergovernmental Panel on Climate Change (IPCC) highlight that limiting
6 warming to 1.5 °C by 2100 remains possible, even though significant CO2 and other greenhouse gases
7 emissions reductions are essential [1]. CO2 is one of the highest greenhouse gases in terms of tonnage,
8 with an estimated 37 GtCO2 generated per year [2], It arises from a wide range of sources, from both
9 stationary (including industrial ones, such as power plant, cement manufacturing, iron and steel making,
10 and chemicals industries), and non-stationary systems (e.g. automobile). Alongside with other
11 mitigation strategies such as alternative resource use, recycling, electrification and efficiency increases,
12 Carbon Capture Utilization and Storage (CCUS) has been proposed to achieve the climate change
13 mitigation goals [1], Captured CO2 can be geologically stored, either permanently or over geological
14 time scales, in saline aquifer, oil and gas reservoirs, or potentially in unmineable coal seams [3,4],
15 Alternatively, captured CO2 can be either directly used or after in a commercial application. These
16 technologies need to be developed in parallel.
17 CCUS not only reduces CO2 emissions but can also produce marketable CO2-based compounds,
18 i.e. valuable fuels and chemicals such as methane, methanol, carbonates, hydrocarbons, and formic acid
19 [5]. In particular, CCUS technology is critical for deployment of low-carbon hydrogen, as natural gas
20 can be reformed to hydrogen with a CO2 capture system, supporting thus the decarbonization of heating,
21 transport, and power generation sectors.
22
23 Thus, an industrial plant, with a commitment to CO2 allowances, can implement a power-to-gas
24 (PtG) process to capture CO2 and convert it to synthetic natural gas (SNG), replacing fossil resources
25 with renewable sources, and reducing the costs of the otherwise emitted CO2 in the CO2 allowances
26 scheme. Ghaib and Ben-Fares indicate that the most relevant CO2 sources candidates for PtG are these
27 from cement manufacturing, iron and steel making, and chemical processes, such as in the process of
28 ethylene production, denoting higher CO2 partial pressure [6] . Responsible for 5 to 7% of the global
29 anthropogenic CO2 emissions, cement manufacturing is expected to grow with industrialization and
30 increased urbanization in all parts of the world [7], The cement manufacturing process has already been
31 optimized with regards to economic and environmental considerations, these improvements being
32 summarized in the Best Available Techniques (BAT) to be used to produce cement [8,9]. However, two-
33 thirds of the CO2 emissions are related to the decarbonation reaction of limestone occurring in the clinker
34 manufacturing process leading to the production of lime, while the remaining is mainly due to
35 combustion for providing necessary heat [10]. To this extent, the cement sector is a good candidate to
36 implement such CCUS and PtG integrated system.
37
38 A PtG system consists of the core unit electrolyzer and a methanation unit both with their peripheral
39 systems, to produce synthetic natural gas [11], SNG is thus generated out of electrical energy, which is
40 used to generate renewable hydrogen, and out of carbon dioxide captured from industrial flue gas.
41 Electrical energy is used from renewable energy source, mainly produced in excess hours from wind
42 power and stored afterwards in the SNG. Recently, studies on application of PtG are receiving increased
43 attention. Several identifiable benefits are usually described in the context of PtG technologies [12].
44 Indeed, PtG is often seen to provide a long-term electrical energy storage, improving the management
45 of volatile electricity production, especially from renewable sources [13]. Due to the intermittent and
46 fluctuating characteristic of renewable energy and load, PtG can absorb excess renewable energy, which
47 can then be supplied or stored in off seasons, providing more flexibility within the system [14-16]. PtG
48 allows also to raise the share of renewable energy in the transport sector, as well as the shift of the
49 energy-transport from the power system to the gas system [17-20]. Finally, combined with the use of
50 captured carbon dioxide from flue gas, PtG may result in a possible reduction of emission certificates
51 and an increase of resource utilization [21,22], and creates self-sufficient energy solutions combining
52 relevant energy segment, namely electricity, heat and transport [23],
53
54 In a comprehensive review of projected PtG deployment scenarios, Eveloy and Gebreegziabher
55 indicate that many types of PtG energy-material integrations are possible [24]. These integrations

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 To cite : DOI: 10.1016/i.icou.2021. 101488

1 include the use of low-temperature electrolysis heat losses for district and building heat supply, the use
2 of methanation heat for high-temperature electrolysis, steam production, and thermal power generation,
3 as well as CO? capture for methanation from oil refining, iron and steel manufacturing, and cement
4 production. However, they highlight that not all of them have been incorporated in PtG deployment
5 modelling works, or have only been applied in a limited number of deployment scenarios [24]. Bassano
6 et al. also highlight the lack of data regarding the integration of CCUS and PtG system, while
7 investigating the synergies between these two processes considering coal and biomass gasification, SNG
8 cleaning, methanation and CO? compression and storage [21], As concurred by Romeo and Bailera, only
9 in a limited number of works the catalytic methanation heat energy is used for carbon capture [25], They
10 also point out that such integration would contribute to reduce the global impact and CO? emissions of
11 PtG system.
12
13 In this context, this paper investigates the simulation of a complete material and energy integration
14 of an advanced carbon capture process and a catalytic methanation process, avoiding the use of external
15 thermal energy. The CO? source considered comes from the flue gas of a cement plant equipped with
16 the best available technology, as it has been demonstrated its feasibility of using this CO? for catalytic
17 PtG [6], A techno-economic study is carried out and the environmental performance of the suggested
18 integrated plant is also investigated through a cradle-to-gate life cycle analysis, considering several
19 scenarios.

20 2 Material and methods

21 2.1 Technical development and analysis of an integrated power-to-gas system
22
23 In general, a PtG process combined with a CCUS technology comprises several units for water
24 electrolysis to generate renewable hydrogen, CO? capture, compression, CO? methanation, SNG product
25 separation and purification, as illustrated in Fig. 1 . As there are various technologies to upgrade a gas
26 mixture containing CO?, H?, CH4 and additional impurities, which are currently commercially available
T1 [26], the SNG product upgrading section is excluded from this work, an example of a two-stages
28 membranes-based SNG upgrading process being proposed by Chauvy et al. [27]. Moreover, Raw-SNG
29 can be used directly in an industrial plant without the need to feed it into the gas grid first [28,29], This
30 can lead to several advantages, such as (i) reducing the use of fossil-based sources, (ii) reducing the
31 lifecycle duration of the product, (iii) lowering the investment and operative costs related to the
32 upgrading before eventual grid injection, and (iv) using the Raw-SNG directly in a plant that is equipped
33 with a CO? capture unit, which would not be necessarily the case in other applications leading to a CO?
34 release potentially without capture possibilities.
35
o2 h2o

Cement Non-captured flue gas Depleted flue gas CO2 to storage and/or other applications
36
37 Fig, 1. Conceptual Power-to-gas system combined with a CCUS technology

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To cite : DOI: 10.1016Zi.icou.2021. 101488

For the modelling of the plant, a polymer electrolyte membrane electrolysis (PEM) with a 30-bar
operation pressure is assumed, as it is suited under dynamic load balancing of electricity grids needed
with use of intermittent renewable energy [6,31], PEM stacks have typical capacities of up to 2 MW
[32], Multiple electrolyzer stacks are installed, achieving the overall electrolysis capacities of 10 MW,
connected to a nearby 15 MW wind park [32,33], The H2 production rate is 180 kg/h; the specific oxygen
production being 8 kg O2 per kg H2.

The conditioned flue gas to be treated enters the post-combustion CO? capture unit with a flow rate
of 5600 kg/h, at 1.20 bar and 146.4 °C. It is composed of N2 (64.7 mol.%) CO2(20.4 mol.%), O2 (8.6
mol.%) and H2O (6.3 mol.%), based on average values coming from the Brevik Cement plant (Norcem
company) in Norway. The capture unit is based on the configuration previously developed in Aspen
Hysys™ software by Chauvy et al. [27], It includes a Rich Vapor Compression (RVC) unit, an Inter-
Cooled Absorber (1CA) and two Water-Wash (WW) sections at the top of the absorber and of the
stripper; the stripper’s water wash being included inside the column to create a contact between the
vapor coming from the regeneration and the liquid coming from the condensation. The solvent is a blend
composed of MDEA 10 wt.% + PZ 30 wt.%. It is worth noting that the CO? capture performances
comparison between the selected solvent (MDEA+PZ) and configuration (RVC+ICA) and other ones
(both in terms of other solvents like MEA and process configurations), have been investigated in
previous works [27,30], The thermodynamic solution model considered is Electrolyte Non-Random
Two-Liquid (eNRTL) for the liquid phase [34] with Redlich-Kwong as equation of state for the gas
phase [35], The reactions for PZ and MDEA solvents reacting with CO2, as well as all the simulation
parameters, are given in the Supporting Information (see SI.l). It also features a Direct Contact Cooler
(DCC) unit, allowing to reduce the pre-treated flue gas temperature to 50 °C thanks to a contact with
fresh water which also saturates the gas with water. The flow rates of the freshwater input (40 kg/h),
namely DCC make-up in Fig. 2, and of the total liquid entering the DCC column (3730 kg/h) are adjusted
in order to reach the desired flue gas temperature. In order to treat 5600 kg/h of flue gas with a CO2
absorption ratio of 90 mol.%, corresponding to a production of about 1620 kg/h of CO? (98 mol.%
purity), the columns diameter are fixed to 0.95 m and the solvent flow rate to 29,472 kg/h, leading to a
(L/G)voi ratio equal to 6.6 10'3 m3/m3. The DCC unit is designed as an 8 meter-height column with the
same packing and diameter as for the absorber. The global water balance of the process is ensured by
the water inputs in the DCC and absorber-WW units. Other dimensioning and operating parameters are
similar as the ones described in Chauvy et al. [27], and summarized in the Supporting Information (see
SI.l). In particular, the material and energy balances, giving the temperature, pressure, flow rate, and
stream composition of the main streams, are presented in Table SI. 4 (see SI.l).

The captured CO? and renewable H2 are then fed together in the methanation unit, considering a
stoichiometric H2/CO2 ratio of 4. Three main reactions are involved, i.e. the exothermic catalytic CO2
methanation (Sabatier reaction, Eq.( 1)), the Reverse water gas shift, Eq.(2), and the CO methanation,
Eq.(3).

CO2 + 4H2 CH4 + 2H2O — —165 kJ /mol (1)

CO2 + h2 CO + H2O = +41 kJ /mol (2)
CO + 3//2 ch^h2o = —206 kJ /mol (3)

The methanation unit consists of a series of four adiabatic multi-tube fixed bed reactors. To reduce
the temperature in the first reactor related to the heat released of the methanation reaction (Eq.(l)), a
fraction of the reactor’s outlet gas stream is recirculated. Additionally, intermediate gas cooling steps
are implemented, maintaining the subsequent reactor’s inlet gas stream temperature to 350 °C. This
configuration allows a good control of the reaction temperature to avoid the coking and sintering of the
commercial catalyst Ni/MgAbO4 (Ni 15 wt.%), and achieve the outlet specifications [36-38]. The
process stream leaving the last methanation reactor is then cooled and dried in a flash unit. In all reactors,
the Gas Hourly Space Velocity (GHSV) is maintained close to 4000 h'1 [38,39]. The thermodynamic

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To cite : DOI: 10.1016Zi.icou.2021. 101488

^Raw-SNG + E excess heat

EpEM + ECOmp+Eaux+ Eheai (4)

^Raw-SNG 's the energy content associated with Raw-SNG on a LHV-basis, and equals to
mRaw-sNG x LHVRaw-SNG, where TnRaw_SNG is the amount of produced Raw-SNG, and
LHVRaw —sng is 'ts lower heating value calculated considering both methane and hydrogen as fuel
(MJ/kg), as a result of the process simulation. Finally, Epem is the electrical energy used by the
electrolyzer (MJ), Ecomp the energy spent for the compression (MJ), Eaux the energy required by the
auxiliaries, i.e. pumps (MJ) and Eheat represents the total required external heat (MJ), while Eexcess heat
is the excess heat that can be recovered from the CO2 methanation unit. It is worth noting that in the
present case Eheat is equal to zero thanks to the heat integration.

This efficiency is calculated under the assumption that the Raw-SNG produced is not purified,
excess H2 being then not recycled. PtG efficiencies have been reported in the range of 65 to 90%,
according to Blanco et al. [43],

2.2.1.2 Capital expenditure and operative costs

Both capital expenditure and annual operative cost are used to evaluate the feasibility of the
concept. The CAPEX includes all required costs for the plant facilities, comprising the fixed capital
investment (FCI) and working capital. FCI includes direct costs, such as purchasing and installing the
equipment, as well as cost of piping, electrical system, instrumentation and building and service
facilities, and indirect costs, such as cost of engineering and supervision, legal expenses, construction
expenses, contractor’s fees and contingency. In this work, the direct costs are directly derived from
process modelling, using the Aspen Process Economic Analyzer (APEA) feature. A ratio factor of 1.44
is applied across the direct purchased equipment cost for the indirect costs [44,45], The cost for working
capital is typically around 10-20% of the FCI [44]; a value of 15% being considered in this work.
The operative costs are mainly composed by variable costs, including the consumption of raw
materials and energy (electricity) costs, and fixed costs, such as operation and maintenance, as tabulated
in Table 1. The cost of working personnel, supervisors, laboratory work and patents are not included in
this cost analysis.

Additionally, the capital expenditures CAPEXannuity are calculated based on the mentioned
assumed lifetime a and the interest’s rate i (straight-line depreciation), as given in Eq.(5).

CAPEXannuity = CAPEX X (5)

It is worth noting that all costs are adjusted to the year 2019, using the Chemical Engineering Plant
Cost Index (CEPCI2019 = 618.7, see the Chemical Engineering magazine for latest values). Costs that
are reported in U.S. dollars are first standardized to 2019 using CEPCI, then a year-average currency
conversion rate for the year 2019 is applied (1$ = 0.8931 €).

Table 1 presents the assumptions (base case, upper and lower boundaries) for all cost parameters
included in this work.

Table 1. Base case assumptions and upper and lower boundaries for all cost parameters

Upper Lower
Item Base case Reference
boundary boundary
Electricity (€/MWh) 40 70 25 [46,47]
Steam (€/ton) Self-produced - - -
PEM Electrolysis specific cost (incl.
785 1200 500 [33]
installation & design costs) (€/kW)

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 Total fossil depletion

Fig. 9. Contribution analysis on fossil depletion (kg oil-eq per FU)

4 Conclusion and outlook

The present work addressed the techno-economic and environmental evaluations of an integrated
CO2 capture and catalytic conversion process to produce Synthetic Natural Gas (SNG). An advanced
CO? capture process was designed, both in terms of configuration (namely Rich Vapor Compression
and InterCooling) and solvent (MDEA+PZ). The heat released by the CO2 conversion process was
recovered for the solvent regeneration step in order to maximize the amount of captured CO2, i.e. more
CO2 than just the quantity required for the conversion was recovered. The additional captured CO? can
be used for other applications and/or stored. The plant was designed in order to convert 10 MW
renewable energy into H2, and to produce SNG using captured CO2 from a cement plant.

Both economic and environmental interests of an integrated CCUS process in comparison with a
reference scenario (without any CO2 capture and conversion to SNG) were shown. The global CAPEX
of the installation was estimated, and it was shown that while the capture and the methanation units have
quite similar contributions, the CAPEX related to heat integration is very low (around 2% of the total
CAPEX). It was also highlighted that thermal energy self-sufficiency is possible thanks to an optimized
integration between the CO2 capture and conversion units, avoiding also steam importation for the
solvent regeneration, and related costs and environmental impacts. Additionally, the overall energy
efficiency of the global PtG plant reached 89.5% on a LHV basis, which is particularly high for such
CO2 conversion system. Even though the process is not currently economically viable, with the total
cost of production being about 2.7 times the expected revenue (without considering CO2 certificate
trading), its economic breakthrough occurs for PEM electrolysis specific costs down to 500 €/kW, which
is expected in 2050 [33]. Regarding the environmental assessment, three scenarios were defined
considering the application to a cement plant flue gas and the production of renewable hydrogen. A 71%
reduction in terms of net CO2 emissions in comparison with the reference scenario was denoted for the
integrated CO2 capture and conversion to SNG. An even more drastic reduction was observed for the
fossil depletion, with a decrease of 81% in comparison with the reference scenario. The more captured
CO2 was used to produce synthetic natural gas, the more it replaces fossil-based natural gas and
consequently reduce the fossil depletion.

In terms of perspectives, the CO2 capture unit could be designed considering technology
improvements (e.g. new solvents such as demixing ones) or other techniques (e.g. thermal swing
adsorption processes, membranes, etc.) with the objective of further reduce its specific energy

20