Fuel 253 (2019) 1071–1079

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Full Length Article

P2G movable modular plant operation on synthetic methane production T

from CO2 and hydrogen from renewables sources
Claudia Bassanoa, , Paolo Deianaa, Luca Liettib, Carlo Giorgio Viscontib
⁎

a
ENEA, Italian Agency for New Technologies, Energy and Sustainable Economic Development, Via Anguillarese 301, 00123 Rome, Italy
b
Politecnico Di Milano, Dipartimento di Energia, Milano, 20156, Italy

ARTICLE INFO ABSTRACT

Keywords: Renewables are steadily growing becoming a significant part of the global energy mix, in particular in the power
Power to Gas sector. An attractive solution could be represented by Power to Gas (PtG), an energy storage strategy. In the PtG
CO2 methanation process renewable or excess electric energy is used for water electrolysis to produce hydrogen that is then
Fixed bed reactor combined with CO2 and converted into methane (synthetic or substitute natural gas, SNG) through the Sabatier
Ruthenium base catalyst
reaction. SNG is particularly interesting because leads to an easily transportable (in the existing infrastructures)
Biogas upgrading
fuel with a wide proven market for power, thermal and mobility final use applications. The key issue consist on
putting together green hydrogen produced by electrolysis fed by renewables with high content CO2 gases sup-
plied from different sources (e.g. syngas from gasification, biogas, geothermic fields, soil gas and gas wells). In
this work the CO2 hydrogenation process, coupled with renewables, has been study in a modular, moveable,
skidable plant, in the scale of 0.2–1 Nm3/h of produced SNG. The pilot plant is equipped with a methanation unit
constituted by a multi-tubular fixed bed reactor able to work in cooled or adiabatic conditions; water produced is
separated by a plate&shell condenser. Several sensors, an online gas analysis system and a data acquisition
system allow monitoring continuous experimental tests. The methanation facility is able to work in the range of
1–5 bars. The paper reports the results of first experimental activities related to SNG production with Ru based
supported catalyst. The experimental activity was carried out in order to check the operability of all components
and to improve the knowledge on methanation process in different conditions relevant to Power-to-Gas appli-
cations. Different weighted hourly space velocity (WHSV), gas inlet composition, reagent mixture, H2/CO2 ratio,
temperature and pressure conditions have been investigated. Increasing pressure drives CH4 production as CO2
conversion is kinetically boosted by raising pressure. Results show that a decreasing trend of XCO2 is observed by
increasing WHSV. Results indicate high CO2 per pass conversion with CO2/H2 concentrate feed using Ru based
catalyst. Finally the effect of CH4 in the feed was studied emulating two reactors in series. Biogas representative
CO2/H2/CH4 mixtures were tested in order to study direct methanation as a biogas upgrading technology.

1. Introduction
The increasing penetration of vRES (variable Renewable Energy
Sources), essential for the achievement of the ambitious objectives set
by the recent Paris agreement (COP21-2015), poses significant chal-
lenges for the sustainability of the electricity grid, due to non-pro-
grammability of the Renewable Energy Sources. In the Renewables
2017 report [1], the International Energy Agency (IEA) predicts that on
global scenario RES generation will reach 8000 TWh by 2022, an
amount equivalent to the combined consumption of China, India and
Germany. EU's energy and climate goals for 2030 introduce a new re-
newable energy target of at least 27% of final energy consumption in
the EU by 2030. Europe adopted the Energy Union Strategy which
foresees to reach a share of renewables of 20% final energy consump-
tion from renewable sources by 2020.
In Europe is recently evident that large deployments of renewable
power resources often produce excess power that out strips demand so
the need for grid scale energy storage is necessary to manage renewable
energy intermittency and over generation. Energy Storage Technologies
can contribute in renewable energy peak shaving avoiding temporal

Abbreviations: AEL, Alkaline Electrolysis; CAPEX, CAPital Expenditure; CCS, Carbon Capture Storage; GHSV, Gas Hourly Space Velocity; LHV, Low Heating Value;
PEM, Polymer Electrolyte Membrane Electrolysis; PtG, Power to Gas; PtM, Power to Methane; RWGS, Reverse Water Gas Shift; SNG, Synthetic Natural Gas; SOEC,
Solid Oxide Electrolysis Cell.; TRL, Technology Readiness Level; vRES, variable Renewable Energy Sources; WHSV, Weighted Hourly Space Velocity
⁎
Corresponding author.
E-mail address: claudia.bassano@enea.it (C. Bassano).

https://doi.org/10.1016/j.fuel.2019.05.074
Received 15 October 2018; Received in revised form 8 May 2019; Accepted 14 May 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
C. Bassano, et al. Fuel 253 (2019) 1071–1079

energy or cost effort [3]. Capturing CO2 from power and industry sec-
Nomenclature
tors is, up to now, an energy intensive process. The use of Carbon
Capture Storage (CCS) technologies can reduce CO2 emissions by
nCO2in inlet CO2 mole stream
80–90% in energy intensive industry and in power plant, although with
nCO2out oulet CO2 mole stream
a significant reduction in efficiency of about 8 to 12 percentage points.
p pressure
Typically for power plants global net efficiency falls from 38 to 28% in
T Temperature
coal-fired plants and from 50 to 42.8% in plants fed by natural gas [4].
U overall heat transfer coefficient
The typical cost of applying CCS technology in power plants is esti-
XCO2 CO2 conversion
mated among 30–130 $/tCO2.
The PtM can be considered as a solution capable of achieving carbon
neutrality and climate resilience. Contributing to the circular economy
fluctuation that can cause shortage or surplus in energy supply. The
concept as captured CO2 is converted to a re-usable energy source in-
EU's energy and climate goals for 2030 introduces a new renewable
stead to be emitted in the atmosphere consequently, PtM contributes to
energy target of at least 27% of final energy consumption in the EU by
the reduction of greenhouse gas emissions [3].
2030. The proposal for a revised Renewable Energy Directive aims to
The features of this technology allow the connection of electrical
make the EU a global leader in renewable energy. One of the priorities
and gas networks in a single energy system introducing high flexibility
inside the EU Energy strategy is to identify Energy Storage Technologies
in the balance of the grid [5]. The advantage of this approach is that it
able to remedy to renewable energy source intermittence by a more
is relatively easy to store large quantities of gas as consequence of the
resilient power system.
large storage capacity of the natural gas network and the connected gas
For managing renewable power intermittency and over generation
storage systems. For example in Germany the natural gas grid has a
Power to Gas (PtG) technology represents one potential tool. PtG is
storage capacity of about 220 TWh while the German electricity grid
considered to be an enabling technology, to support the integration of
has a storage capacity of about 0.4 TWh [6].
renewables with the electrical energy system [2]. The key issue consists
The efficiencies of the process are in the order of 25–60%LHV basis
on putting together green hydrogen produced by electrolysis fed by
according to [7]. Wide range is related to the final use: the low value
renewables with high content CO2 gases supplied from different sources
represents the round trip efficiency (reconversion into electricity) de-
to produce methane in Power to Methane (PtM) system. This concept
spite the high value is related to the production of SNG from power.
allows storing exceeding renewable power production balancing offer
Generally, the efficiency of Power to Gas systems with production of
and demand over time on the grid. Among the various technologies, the
SNG increases when the released heat is used, for example for district
power to gas allows to exploit the enormous potentiality of methane for
heating or in nearby industrial plants for the regeneration of amines.
electric energy and heat production and transportation, using the ex-
Further R&I efforts are required to reduce technology and non-
isting natural gas infrastructures and local grid.
technology costs, to improve performances and to promote technology
Fig. 1 provides a simplified scheme of the PtM concept. CO2 con-
deployment to market.
version to methane finds the key to overcome the limited fossil natural
gas sources and to the uncontrolled CO2 emitted in to the atmosphere
Synthetic natural gas has got the possibility of being used in widely 1.1. Electrolysis technologies for hydrogen production
available means on the market and has favorable chance to be in-
troduced into existing transport/storage infrastructures. The main water electrolysis technologies are classified in: Alkaline
However, the production of synthetic natural gas requires the pre- Electrolysis (AEL), Polymer Electrolyte Membrane Electrolysis (PEM)
sence of a CO2 source which therefore limits the location of the plant. and solid oxide electrolysis cell (SOEC). A recent review [8] on current
Possible CO2 feedings come from different gaseous streams as: captured status of water electrolysis for energy storage compares electrolysis
CO2 in energy intensive industry, gasification syngas, biogas, geo- technologies in terms of available capacity, nominal and part-load
thermic fields, soil gas and gas wells. performance, flexibility lifetime and investment costs. Alkaline elec-
The biogas upgrading and bioethanol production plants emit CO2 trolysis is the most mature technology with lowest specific investment
gases ready for use in the methanation process without additional and maintenance costs and offer single-stack capacities up to 6 MWe.
The minimum load of AEL is limited to 10–40% of nominal hydrogen

Fig. 1. Power to Gas concept simplified scheme.

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C. Bassano, et al.
production while in the PEM electrolyser the hydrogen production rate
can be varied over the full load range. Other advantages that PEMs offer
compared to alkaline are: compact design and pressurized operation.
Between the water electrolysis technologies, SOEC presents highest
efficiencies, with a specific electrical energy consumption value of
3 kWh/Nm3 compared to the values of 4.2–4.8 kWh/Nm3 for AEL and
4.4–5 kWh/Nm3 for PEM. The SOEC furthermore allows reversible
operation, allowing for operating range from −100 to 100%. An ad-
ditional feature of the SOEC is the production of syngas in co-electro-
lysis. However, SOEC is still at the pre-commercial stage with low TRL.
Current capital costs, reported on [9], are around 1000
€/kWel–1200 €/kWe for AEL and 1800–2300 €/kWe for PEM systems
(1 MWe size). Cost estimates lie above 2000 €/kWe for SOEC with high
level of uncertainty due to the pre-commercial status of the technology.
In the future, a cost reduction is expected and as reported by Schmidt
et al. [9] capital costs can be reduced by 0–24%. Increasing funding for
research and development and production growing would lead to a
17–30% reduction in the capital cost.
1.2. CO2 methanation
The reduction of carbon dioxide with hydrogen is a subject studied
by Sabatier since the beginning of the last century. The CO2 hydro-
genation reaction requires for each mole of carbon dioxide four moles
of hydrogen to produce one mole of methane (Eq. (1)):
CO2 + 4H2 CH4 + 2H2 O H°298 = 165 kJ/mol
CO2 methanation is an equilibrium highly exothermic reaction. CO2
methanation is a combination of the CO methanation (2) and the Re-
verse Water Gas Shift reaction (RWGS) (3).
CO + 3H2 CH4 + H2 O H°298 = 206 kJ/mol
CO2 + H2 CO + H2 O H°298 = 41 kJ/mol
Thermodynamically, the CO2 conversion decreases with increasing
temperature and increases with the pressure [10]. Analysis of CO2
equilibrium conversion using the Gibbs free energy minimization
method is given in Fig. 2. The minimum Gibbs free energy was calcu-
lated by Aspen Plus software using the Soave–Redlich–Kwong (SRK)
equation of state as performed by Gao et al.[11]. The plot shows the
effects of pressure and temperature on CO2 methanation.
In theory, the hydrogenation of CO2 is favored at low temperatures,
where the conversion of CO2 and selectivity to CH4 can reach almost
100%. Conversely, the kinetics and therefore the reaction rate increase
with the temperature. The effect of pressure depends on the tempera-
ture. In the typical temperature range of 200–600 °C, the increase in
pressure is effective up to a certain point and the further increase in
pressure is less effective, consequently a pressure of 10 to 30 atm is
considered the most suitable in terms of stress on the catalyst. High
operating pressure is not economical and low operating temperature
does not promote the kinetic and requires a sufficiently high active
Fig. 2. Effects of pressure and temperature on CO2 conversion using AspenPlus,
H2/CO2 molar ratio = 4.
Fuel 253 (2019) 1071–1079
catalyst, therefore, a technical-economic compromise must be identi-
fied [3].
The electron reduction of CO2 to CH4 by hydrogen is characterized
by a high kinetic barrier; consequently to proceed at acceptable rate a
suitable heterogeneous catalyst with a high activity is necessary espe-
cially at low temperature.
Several metals for CO2 methanation may be used as catalyst, all
metals of groups 8–10 have been used and have shown a catalytic ac-
tivity [12]. The catalytic activity order can be summarized, only for
metals that have been considered. “Important for methanation cata-
lysts…”, as follow Ru > Ni > Co > Fe > Mo and noble metal pro-
portions might increase the productivity [13,14].
A recent review on catalysts used for CO2 methanation was made by
Aziz et al. [15], the review provides current comprehension of the
catalytic performance and insight into the reaction mechanism over
heterogeneous catalysts. The main mechanism that contributes to the
deactivation of methanation catalysts can be classified according to
Rönsch et al. [16] into: poisoning (chemisorption of species on catalytic
sites, chemisorption of sulfur e.g. H2S), thermal degradation (thermally
induced loss of active surface area as thermal sintering), fouling (carbon
or coke deposition onto the catalytic surface), attrition (loss of catalytic
material in fluidized-bed reactors due to abrasion) and crushing
(breakup of catalyst particles due thermal stress caused by reactor
startup/shutdown or mechanical stress produced by pressure varia-
tions). For Nickel moreover, at temperatures below 230 °C, nickel car-
bonyls are formed in the presence of CO [16].
(1)
1.3. Reactor conceptual design
The CO2 methanation is a highly exothermic reaction as a con-
sequence an important issue in the design of a methanation reactor is to
(2) realize a good temperature control in order to avoid temperature in-
(3) crease inside the catalyst bed and to prevent thermodynamic limit.
Improper heat removal can cause hot spots, construction material stress
and sintering of the catalyst. The higher outlet temperature restricts the
CO2 conversion caused by the thermodynamic equilibrium and the
outlet gas composition does not meet the natural gas grid specifications.
For this reason, to remedy this issue different plant configurations
and reactor concepts have been developed, namely these can be sum-
marized as follows: cascades of fixed bed reactors with intercooling,
cooled fixed-bed reactors, fluidized-bed reactors, structured reactors
and three-phase reactors [16]. In the PtM applications, catalytic me-
thanation reactors are typically operated at temperatures between 200
and 550 °C and at pressures ranging from 1 to 20 bar. The process of
methanation is currently applied in the industrial production of am-
monia and, after the oil crises of 70 s, for the production of SNG from
synthesis gas [17]. However, the application in the Power to Gas pro-
cess is more complex, due to small size of the plant and intermittent or
dynamic operation [18].
Fixed-bed reactors can operate in adiabatic or cooled condition and
are mainly used. The adiabatic fixed bed reactor configuration is de-
signed as a series of adiabatic reactors with intercooling and gas re-
circulation or steam addition in order to avoid temperature increase
and local hot spot. These reactors are simple and economical compared
to the other types, moreover steam can be produced. Drawbacks are
possible as hot spot and poor flexibility respect to the load [19,16].
Processes using adiabatic fixed bed reactors are all realized with at least
two stages [20].The maximum operating GHSV (Gas Hourly Space
Velocity) of adiabatic fixed-bed reactors, assumed for technical plants,
is normally in the range of 2000–5000 h−1 as reported by Gotz et al.
[18].
The cooled fixed bed reactors are cooled tube bundle reactors or
cooled plates reactors, the advantages of this reactor concept is a lower
temperature gradient with lower outlet exit temperature and a high
conversion rate with respect to adiabatic reactor. Cooled fixed-bed re-
actors and structured reactors have a hot spot temperature near the gas
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C. Bassano, et al.
inlet in the reactor. However in comparison to adiabatic reactors this
reactor concept has a lower temperature increase, allowing high con-
version rates with respect to thermodynamic restriction. Conversely
cooled fixed bed reactors are more expensive. Due to the thermo-
dynamic limit generally more reactors are used in series and the pur-
pose is to manage the heat in particular in the first reactor, in order to
avoid local hot spots. For this reason different measures are possible to
optimize fixed-bed systems (both adiabatic and cooled concept) in a
way that can be summarized as follows: recycling part of the product
gas or diluting the inlet gas with steam, partial feeding of the product
gas at different stage along reactor, splitting of the overall inlet CO2
flow at different reactors in series [21], diluting catalyst bed.
Fixed bed reactor technologies are available on the market: MAN
proposes a cooled fixed-bed reactor with molten salt cooling, Outetec
proposes a staged fixed-bed reactor with intermediate cooling and
Etogas uses fixed-bed reactor or plate reactor with steam cooling [16].
Structured fixed bed reactors are technologies under development to
overcome the drawbacks of adiabatic fixed-bed reactors, such as tem-
perature hot spots and high pressure drops. These structured reactors
and micro-reactors have limitations such as high manufacturing price
and scale-up challenges. Examples of these reactors are: honeycomb,
microchannel, sorption-enhanced and membrane reactors [16]. A fixed-
bed membrane reactor has been modeled by Schlereth et al. [22], in the
study authors investigate how the temperature control improves by
separate and controlled feeding of CO2 and H2, allowing for attaining
near-equilibrium gas compositions. The sorption-enhanced methana-
tion reactor concept is based on water adsorption on the catalyst sup-
port [23]. Consequently, the produced H2O is removed and the ther-
modynamic limit of the conversion of CO or CO2 is reduced. Monolithic
reactors have the advantages of a relatively high specific catalytic-
surface, small pressure losses and short response times despite dis-
advantages are a non-uniform gas distribution and scale-up limitation
[3]. Bengaouer et al. [24] proposed an experimental comparison of a
fixed-bed reactor, a millistructured reactor, and a metallic foam reactor
with the same nickel-alumina catalyst for CO2 methanation. The paper
presents the advantages of the millistructured reactor that shows a
higher methane space-time yield and volumetric productivity than the
other reactors, but a significant catalyst temperature elevation.
Research activities generally focus on an improvement of tempera-
ture control, efficiency and methanation process flexibility and a re-
duction in the cost. More details on different reactors concept can be
found in [16,3].
1.4. Conditioning and upgrading
The legal framework of the acceptable H2 level for hydrogen in-
jection in the pipeline is typically specified by national legislation.
Research studies have suggested that H2 volume fractions up to 20%
could be tolerated without many modifications of the infrastructure.
However, end use appliances for natural gas often show lower hydrogen
(H2) tolerances, which is the reason why most European standards are
below 5%. For example, the CO2 and hydrogen content has to be lower
than 2.5 and 6% in France, lower than 6 and 5% in Germany while in
Italy the limit for H2 content is 0.5% vol.. To accomplish the require-
ments of the natural gas grid, the product gas must generally achieve a
CH4 content of 96 vol%. Consequently, if the gas does not comply with
the requirements for feeding into the grid, upgrading must be carried
out and CH4 rich gas from methanation must be fed to an upgrading
unit, to separate remaining H2 and CO2 and to remove the water.
Usually, this is done by pressure swing adsorption, water scrubbing,
amine scrubbing or membranes [25]. Membranes are a promising op-
tion for small to mid-sized plants (< 250 m3/h). Using membranes of-
fers some advantages compared to other state of the art technologies
[26], like flexibility and suitability for scale up due to their modular
design. In polyimide membrane systems the cleaned methane remains
in pressurized form on the permeate side while the permeate stream,
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Fuel 253 (2019) 1071–1079
composed of CO2 and H2, is recycled to the methanation reactor [26].
1.5. Economic feasibility of power-to-gas
In an innovative and experimental perspective PtG is a technolo-
gical solution with high potential for application for alternative uses of
existing gas transportation infrastructures and, if integrated with re-
newables, can be configured as an energy storage technology sup-
porting national energy networks. The interest on Power-to-gas is in-
creasing, since it allows to utilize the existing natural gas infrastructure
as storage medium reducing capital investments and facilitating its
deployment.
From the economic point of view this kind of systems are not able to
compete with conventional gas production systems when only selling
hydrogen and SNG. Alternative revenues are to be considered in the
economic analysis. Different studies consider to give a value to heat and
oxygen sale. Moreover, electric grid balancing services and green cer-
tificates that take into account environmental benefits (CO2 emissions
quotes, biogas feed in tariffs) could help the whole economic perfor-
mance. A typical construction of revenue mechanism sums different
types of benefits [27]. Total levelised costs are calculated as sum of
capital and operational expenditure actualized for the lifecycle of the
plant. The yearly cash flow is driven by the difference between rev-
enues and the sum of capital and operational costs that refers to the
main components (electrolizer, methanation reactor and general bop)
and to the related operation and maintenance that comprises costs for
electricity supply. The levelised cost and the levelised value of energy
storage are one of the most representative parameters for the economic
analysis. They are calculated as ratio between costs and stored energy
or between revenues and stored energy. Also the internal rate of return,
compared to the rate of discount, is always given as a measure of
profitability. Another crucial factor that drives economics is the scale.
As a matter of facts sizes larger than 1 MW are required to create an
economically profitable case [28]. The relatively high cost of PEM
stacks (1000 $/kW compared to 500 $/kw typical of the alkaline tech-
nology) is not the main barrier.
Many uncertainties still exist in the determination of future PtG
plant capital costs, since its operating costs strongly depend on the local
electricity tariff, plant efficiency, utilization factor, CO2 cost and must
be assessed case by case. Concerning the methanation investment costs
there is a lot of uncertainty due to lack of demonstration facilities with
long operating experience. The most significant contributor to the total
CAPEX is the electrolysis. Electrolysis investment is in the range of
approximately 800–3000 €/kWe and methanation investment is in the
range of approximately 500–3000 €/kWCH4 [29]. Specific production
costs are strongly dependent on the price of electricity and the number
of annual operating hours. Generation costs of SNG produced via PtG,
are in the range of values of 8–60 c€/kWhSNG [18]. Still far from the
specific cost of natural gas that is in the range of 3–8 c€/kWhCH4 in-
cluding tax (Eurostat 2017). The PtG technology is currently at its early
stages and has a high specific cost and low efficiency [7] therefore the
role of incentives becomes important to allow the technology devel-
opment and its deployment to the market.
1.6. Status of power to methane projects
In Europe, since 2012, there has been a strong increase in the
number of demonstration plants of PtG technology, both for the pro-
duction of hydrogen and methane. Germany is the leading nation in
Europe. Currently there are about 45 PtG projects in Europe with a
strong research or demonstration character [30]. A large number of
demonstration sites have been and are being erected to showcase the
potential of Power to Methane (e.g. STORE&GO, Windgas Falkenhagen,
Energiepark Mainz, PTG-BioCat Project, HELMET project, etc.).
A review of Power to Gas projects (laboratory, pilot and demo
plants) which investigate methanation through the application of
C. Bassano, et al.
renewable hydrogen is presented by Bailera et al. [31]. In the review
about 40 plants are described, reporting the technical parameters of
both catalytic and biological methanation. Catalytic methanation re-
actors are mostly fixed bed type with tube reactors with gas recycling or
steam cooled plate reactors [16]. In STORE&GO project new catalytic
reactors concept will be tested, the demonstration site of Falkenhagen is
equipped with two catalytic honeycomb and structured wall reactors
for methanation while the site of Troia (Italy) is equipped with a
modular millistructured catalytic methanation reactors.
ETOGAS-Audi e-gas plant is the largest PtM industrial plant in the
world (6MWe). It has been running since 2013 and is located in Werlte
(Germany). It is based on the catalytic reaction of pure H2 and CO2 in a
single fixed bed isothermal reactor cooled by molten salt. Hydrogen
comes from three alkaline electrolyzers powered by an offshore wind
farm. The plant, co-financed by Audi AG and a regional power com-
pany, is fed by CO2 captured from biogas by amine absorption.
A recent Horizon 2020 project on CO2 to CH4 chemical conversion,
is the HELMETH project, that is based on a SOEC system and a multi-
stage methanation module, both the conversion units being thermally
integrated. The electrolyzers have a capacity of 15 kW and operates at
800 °C and 15 bar. The methanation reactor concept is composed by
two reactors in series with a possible third reactor fed by split CO2. The
multistep reactor module operates in the pressure range of 10–30 bar,
using boiling water as refrigerant medium.
Different commercial and new concept of nickel-based catalysts
have been tested, among all them the new Ni-Al hydrotalcite catalyst
shows a good catalytic performance over time [32]. The efficiency of
the PtG process with methane production it is in the order of 30–50%
[18].
Jupiter 1000 is a French project of industrial demonstration of PtG
technology that aims to identify the technical and economic issues, as
well as to analyze the regulatory barriers regarding also future pro-
duction and injection standards over the gas network. The excess
electricity present in the network will be converted into hydrogen by
two electrolysers (alkaline and PEM) and subsequently in methane
using CO2 captured by a neighboring industrial process. The size is
1 MWe with a production of around 100 Nm3/h of H2 and 25 Nm3/h of
CH4. The methanation reactor is a structured reactor developed by CEA
Fig. 3. Pilot plant details at ENEA Research Center.
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Fuel 253 (2019) 1071–1079
& ATMOSTAT. The Jupiter 1000 project was co-funded by the
European Union in the context of European regional development
funds, by national funds through the French Energy Agency (Ademe)
and the Provence-Alpes-Côte d'Azur Region.
2. Moveable plant description
A pilot scale experimental facility dedicated to study and test the
methanation process has been built at ENEA Casaccia Research Center
(Fig. 3). The pilot plant is equipped with a methanation unit constituted
by a multi-tubular fixed bed reactor able to work in cooled or adiabatic
conditions.
The reactor is “shell-and-tube” type to guarantee the correct heat
transfer between the reagent gas and the refrigerant; the catalyst bed
consists of seven tubes filled with pellets and inert material, while in the
shell the coolant circulation takes place. The catalyst bed diameter is
about 15 mm while the maximum length can reach 400 mm. Tube
diameters 15 mm allow better dispersion of radial heat produced by
shorter transport distances and higher Reynolds numbers. The reactor is
cooled by CO2 or N2 circulation. The cooling fluid circulates in coun-
tercurrent in the reactor and rises upwards in the shell side. The flow
during the tests has been maintained in the range of 2–8 kg/h. The
countercurrent flow in the reactor tends to lowers the temperature in
the first catalyst layer. The refrigerant circuit is equipped with a heat
exchanger which, by heating the fluid, allows the reactor to be heated
in the startup phase; the exchanger is bypassed during normal plant
operation. Next step and improvement of the plant will be the em-
ployment of diathermic oil and a close circuit that will allow to heat up
the reactor in the startup phase and to cool it in the test phase.
Using oil as a medium allows very good cooling capability since the
overall heat transfer coefficient U for oil flowing in tubes at the outside
of the tube can be very high, 1000–1700 W/(m2K) for example. Instead,
the use of gas as a cooling medium has lower U values equal to
30–200 W/(m2K) and may require considerable flow rates. Generally,
the correct choose of the coolant contributes strongly to the thermal
inertia of the system and makes the fixed-bed methanation reactor more
suitable for intermittent operation.
The system is able to work in the range of 1–5 bar using a back
C. Bassano, et al.
pressure control valve. The feed gas is obtained by mixing pure gases
from cylinders with the help of four mass flow controllers (MFC) en-
abling the emulation of different gas mixtures entering into reactive
section. Before entering into the reactor, the inlet gas is heated up to
250 °C in an electric heater. The temperature can be set up to better
address the operating start up conditions required for the methanation
reaction. All auxiliaries are included in the facility. Pressure drops in
the reactor is measured by two pressure gauges positioned upstream
and downstream of the reactor.
Moreover the plant is equipped with several sensors and a data
acquisition system. The composition of flowing gas, in each section, is
measured by online gas analysis system. The multichannel gas analyser
(ABB) allows the measurement of CO2, CO, CH4 concentration with an
infrared sensor (NDIR) and the measurement of H2 concentration with a
thermal conductivity detector (TCD). The nominal methane flow is in
the range of 0.25 to 1 Nm3/h.
Downstream water is separated in a condenser and the dry gas is
sent to flare. The condenser is a plate & shell type. The exchanger
consists of circular plates, inserted in a tubular shell. The circular
plates, thanks to the corrugation of the surfaces, allow reaching high
coefficients of thermal exchange in turbulent conditions. This design
makes these exchangers particularly suitable for operating in severe
mechanical and thermal conditions with minimal overall dimensions.
Water is collected and measured. The reactor was equipped with
different K-type thermocouples inserted on the reactor shell and in the
middle high of each tube filled with catalyst. In this way it is possible to
acquire temperature values inside the reactor during the test.
The pilot plant is equipped with a data acquisition system to
monitor the main operating parameters and control the process. Input
and output variables are elaborated by a PLC (programmable logic
control) system. The software architecture allows controlling the
parameters of interest and permits the application of appropriate ad-
justments in both manual and automatic way during the pilot plant
activities, the startup and the shut-down phase. The data acquisition
system is also equipped with alarms to block the process in case of
malfunctions. Synoptic scheme indicating the main plant sections and
plant instrumentation is shown in Fig. 4.
The whole system is installed on a skid that is movable on site. In
this research facility is possible: to test different real or mixed feeding
Fig. 4. Pilot plant scheme at ENEA Research Center.
1076
Fuel 253 (2019) 1071–1079
gases, to test different methanation catalysts and intensified reactors
and finally is possible also to test SNG upgrading methodologies (e.g.
membranes).
The movable modular plant operation on synthetic methane pro-
duction will have to produce SNG to grid specifications (CH4 > 96%
vol.); consequently it will be equipped with other reactor steps with
condenser (for water separation between the steps) and reheating. The
plant will also be equipped for the final polishing with a dehydration
system and a membrane system that will allow the purification of CH4
from the remaining amounts of H2O, H2 and CO2.
3. Methodology and experimental activities
The experimental activity was carried out in order to check the
operability of all components and to improve the knowledge on me-
thanation process in different conditions relevant to Power-to Gas ap-
plications. The test procedure includes: a heating phase of the catalytic
bed, a hydrogen reduction step, an experimental operative phase and
finally a shutdown phase in inert atmosphere. In the hydrogen reduc-
tion step catalyst was activated by reduction at atmospheric pressure
using H2 (WHSV = 1800 Ncm3/(gcat*h)) at 400 °C.
Different weighted hourly space velocity (WHSV), gas inlet com-
position, reagent mixture, H2/CO2 ratio, temperature and pressure
conditions have been investigated.
In this study flow rates and WHSV data are calculated and assumed
as:
WHSV
Nm3
=
Normalised volumeric gas flow ( )
Nm3
h
g h catalyst bed weight (g ) (4)
In order to prevent hot spot phenomena and to distribute the heat
produced by the reaction along the reactor axis and to facilitate the
disposal of heat, a 1 to 1 volumetric dilution of catalyst with inert glass
was selected.
About 160 g of a commercial methanation catalyst (Ru 0.5% wt. on
Al2O3) was used in the present work. The catalytic material has a cy-
lindrical shape with a characteristic length (defined as volume to sur-
face ratio) of 3.2 mm. Further details regarding the characteristics of
the catalyst used can be found in Falbo et al. [33].
C. Bassano, et al. Fuel 253 (2019) 1071–1079

This choice is alternative to the most common used cheaper Ni

based catalyst. The basic idea is to overcome the main disadvantage of
Ni and its high tendency to oxidize like the other non-noble metals (Fe
and Co). As reported in the literature, ruthenium catalysts, in contrast
to nickel catalysts, show better stability when operating over a wide
range of temperatures; the Ni instead, could presents problems of de-
activation at low temperatures [15,14]. Moreover Ru is noble metals
and offers positive characteristics such as high activity, CH4 selectivity
(also at low temperatures) and high resistance to oxidizing atmospheres
[3].
However Ru is more expensive than Ni and actually it is not used for
industrial-scale SNG production. In perspective, ruthenium could be Fig. 5. Carbon dioxide conversion in function of pressure WHSV = 7000 Ncm3/
used more because the high cost would be offset by high yields in (gcat*h), H2/CO2 = 4.5 Tbed medium = 290–320 °C; Cooled reactor.
methane especially at low temperatures [15]. One of the most re-
presentative scientific work related to the kinetics of Sabatier's reaction
low CO2 conversion is measured and low CH4 volumetric concentration
on Ru-based catalysts is the one of Peter Lunde and Frank Kester [34].
gas is produced. By increasing the pressure the CO2 conversion grows
The work describes the experimental tests carried out in a cooled tube
up to the value of 0.92 at 5 barg and the volumetric CH4 concentration
reactor without dilution at atmospheric pressure and in isothermal
passes from to 38% vol. to 60% vol.
conditions on a ruthenium-based catalyst (0.5% by weight of Ru sup-
ported on γ-alumina) with different inlet H2/CO2 ratio gas mixtures.
Results indicate a CO2 conversion rate of 86% with a low GHSV of 4.2. Effect of WHSV
526 h−1 at a pressure of 0.1 MPa.
Experimental results are reported as carbon dioxide conversion XCO2 The effect of WHSV on CO2 conversion has been investigated
calculated as follows: (Fig. 6). Results show that by increasing WHSV from 6500 to
nCO2 (in) nCO2 (out ) 11,500 Ncm3/(h*gcat), XCO2 decreases from 0.94 to 0.87. These results
XCO2 = are in line with what reported in the literature: Lange et al. [35] in-
nCO2 (in) (5)
vestigated the carbon dioxide to methane hydrogenation using RuNi
where nCO2 is: inlet and outlet of CO2 mole stream. bimetallic catalysts. In this study the increase in space velocities
CO2 conversion data were collected in the following ranges of process showed only a small decline in carbon dioxide conversion. Also Janke
conditions: Tgas inlet = 250 °C, P = 1–5 bar, WHSV = 6000–11500 Ncm3/ et al. [36] investigated the CO2 hydrogenation at 1 bar and H2/CO2 = 4
(gcat*h), H2/CO2 inlet ratio = 4–4.5 molH2/molCO2. The spatial velocities over a 10% Ru/γ-Al2O3 catalyst and demonstrates an excellent se-
used in the present experimental work refer to a catalyst with a low per- lectivity to methane and CO2 conversions under low space-velocity
centage of metal, therefore expressing them with respect to the active metal conditions. A decreasing trend in CO2 conversion is also observed
(0.5% Ru) the values used were the following WHSVRu changing the H2/CO2 molar inlet ratio. Table 2 indicates results of the
3
basis = 120000–220000 Ncm /(gruthenium*h). Each effect was studied WHSV variation.
keeping constant all the other process conditions at the central values and According to that, experimental results indicate a slight increase in
varying the desired one by one. Pressure drop during all tests were in the the CO2 conversion when H2/CO2 ratio varies from 4.3 to 4.5.
order of 8–11 mbar. Table 1 shows main test parameters. Fig. 7 indicates SNG composition and WHSV trend during a test.
High methane concentration values (up to 67%) have been achieved in
4. Results once through configuration with temperatures in the range of 300–330 °C
and pressure of 5 barg. During this experimental test the temperature on
In this section experimental results are described. reactor tube side remain quite constant meaning good thermal distributions
in the catalyst bed and consequently good process control.
4.1. Effect of pressure

Sabatier's reaction is favoured by pressure, so the effect of pressure

on the process, in the range 1–5 bar, was studied. Considering the
pressure effect on thermodynamics, it is reported that the performance
of PtM technology may be optimized if the CO2 methanation reactor is
operated with a pressure in the 5–20 atm range [18].
Fig. 5 shows the effect of pressure on catalyst activity. The effect of
pressure on XCO2 is evident because at 290 °C–320 °C the catalyst works
far from the thermodynamic equilibrium conditions. Moreover, an in-
crease of pressure drives CH4 production as CO2 conversion is kineti-
cally boosted by raising pressure. At the operating pressure of 1 bar(g)
Fig. 6. Effect of WHSV and H2/CO2 inlet ratio on CO2 conversion.
Table 1
Main Test Parameters.
Table 2
Catalysts Ru 0.5% wt. Effect of WHSV Variation on CO2 conversion.
Support Al2O3 pellets
Temperature range 250–350 °C WHSV Ncm3/(g*h) 6500 7200 11,500
Pressure range 1–5 bar H2/CO2 – 4.5 4.5 4.5
Feed gas mix T in 250 °C p barg 5 5 5
WHSV 6000–11000 Ncm3/(gcat*h) T internal medium value °C 290 280 290
(3000 h−1–6000 h−1) CO2 conversion XCO2 0.94 0.92 0.89
Reactor condition Cooled/Adiabatic multitube Reactor concept cooled cooled cooled

1077
C. Bassano, et al.
Fig. 7. Composition and WHSV trend during a test P = 5 bar, H2/
CO2 = 4.5 Tbed medium = 290–320 °C, cooled reactor.
Fig. 8 shows the trend of temperatures in the seven catalyst beds during
a test indicating a gas distribution in the catalyst beds constant. During the
test the outlet gas leaves the reactor at the temperature of 150 °C.
4.3. Effect of CH4 in the feed and biogas upgrading
The effect of CH4 in the feed has also been studied and showed in
Fig. 9a,b. Using a single reactor in a single pass does not meet the re-
quirements for the injection into the gas grid, so a second reactor was
emulated to increase the methane content. The main conditions, in
these tests, were: pressure 5 barg, H2/CO2 ratio 4.4 and cooled reactor
type. The resulting temperatures inside the seven catalytic beds have
been constant in the range of 310–330 °C. The emulation of the two
cooled reactors in series has allowed obtaining higher CH4 content into
out coming gas produced. Results show a content of CH4 of about 80%
Fig. 8. Temperature trend on reactor tube side.
Fig. 9a. Effect of CH4 in the feed-emulating two reactor a) First reactor
P = 5 bar, H2/CO2 = 4.4 Tbed medium = 310–330 °C, cooled reactor.
1078
Fuel 253 (2019) 1071–1079
Fig. 9b. Effect of CH4 in the feed-emulating two reactor b) Second reactor
P = 5 bar, H2/CO2 = 4.4 Tbed medium = 310–330 °C, cooled reactor.
vol. after the second reactor. As shown in the figure, the second reactor
has a lower CO2 conversion due to the presence of CH4 in the feed that
decreases the thermodynamically achievable conversion.
Also some biogas representative CO2/H2/CH4 mixtures have been
tested in order to evaluate the feasibility to use CO2 methanation pro-
cess as biogas upgrading technologies. Direct methanation of biogas
could be an alternative solution to conventional upgrading technolo-
gies, if renewable H2 is available. Therefore a representative mixture of
a biogas plant was emulated and H2 was added in a ratio equivalent to
5 molH2/molCO2. Fig. 10a,b shows the results of experimental test, main
conditions have been: pressure of 5 bar and cooled reactor concept.
In two reactor steps it was possible to upgrade the biogas to a gas
with a content of about 86% vol. of CH4.
Fig. 10a. Biogas emulating feed a) First reactor P = 5 bar, H2/CO2 = 5 in the
1st reactor, Tbed medium = 340–360 °C, cooled reactor.
Fig. 10b. Biogas emulating feed b) Second reactor P = 5 bar, H2/CO2 = 5 in
the 2st reactor, Tbed medium = 340–360 °C, cooled reactor.
C. Bassano, et al.
5. Conclusions
A new moveable, modular, skidable plant dedicated to CO2 hydro-
genation to CH4 has been designed and built at Enea Casaccia Research
Center. First experimental tests were carried out in order to check the
operability of all components and to improve the knowledge on me-
thanation in the different phase of start-up, steady operation and shut
down. In this work the CO2 hydrogenation process, coupled with re-
newables, has been study in the scale of 0.2–1 Nm3/h of produced SNG.
The paper reports the results of first experimental activities related to
SNG production with Ru based supported catalyst. A first character-
ization of the process was performed and the modalities and key
parameters to achieve standard operating conditions were identified.
The experimental activity was carried out in order to check the oper-
ability of all components and to improve the knowledge on methana-
tion process in different conditions relevant to Power-to-Gas applica-
tions. Different weighted hourly space velocity (WHSV), gas inlet
composition, reagent mixture, H2/CO2 ratio, temperature and pressure
conditions have been investigated. Results indicate that increasing
pressure drives CH4 production as CO2 conversion is kinetically boosted
by raising pressure. Results show that a decreasing trend of XCO2 is
observed by increasing WHSV. High methane concentration values (up
to 67%) using Ru based catalyst has been achieved in once through
configuration with CO2 and H2 concentrate feeds and with tempera-
tures in the range of 300–330 °C and pressure of 5 barg. The effect of
CH4 in the feed has been also studied to better simulate a second or a
third reactor in order to meet the requirements for SNG injection into
the gas grid. Gas with up to 80% vol CH4 has been generated after the
second reactor. Finally a biogas representative CO2/H2/CH4 mixture
has been tested in order to study direct methanation as a biogas up-
grading technology. After the first experimental sessions, different on-
going activities are running and many future developments are in
progress. Future activities include tests with different catalysts, dif-
ferent feeding mixtures in steady and dynamic tests. Also the adoption
of a diathermic oil circuit and the augmentation of the number of re-
actors is foreseen.
Acknowledgment
This work was developed into the RdS Research Program on
Electrical Grid funded by the Italian Ministry of Sustainable Economic
Development.
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