Renewable and Sustainable Energy Reviews 155 (2022) 111886

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Renewable and Sustainable Energy Reviews

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

What is the energy balance of electrofuels produced through power-to-fuel

integration with biogas facilities?
Nathan Gray a, b, *, Richard O’Shea a, b, Beatrice Smyth c, Piet N.L. Lens d, Jerry D. Murphy a, b
a
MaREI Centre, Environmental Research Institute, University College Cork, Ireland
b
Discipline of Civil Engineering, School of Engineering, University College Cork, Ireland
c
School of Mechanical and Aerospace Engineering, Queen’s University Belfast, Belfast, UK
d
MaREI Centre, Ryan Institute, National University of Ireland Galway, Ireland

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

Keywords: The need to reduce the climate impact of the transport sector has led to an increasing interest in the utilisation of
Anaerobic digestion alternative fuels. Producing advanced fuels through the integration of anaerobic digestion and power-to-fuel
Electrofuel technologies may offer a solution to reduce greenhouse gas emissions from difficult to decarbonise modes of
Carbon capture and utilisation
transport, such as heavy goods vehicles, shipping, and commercial aviation, while also offering wider system
Biomethane
Methanol
benefits. This paper investigates the energy balance of power-to-fuel (power-to-methane, power-to-methanol,
Fischer-Tropsch fuels power-to-Fischer-Tropsch fuels) production integrated with a biogas facility co-digesting grass silage and dairy
slurry. Through the integration of power-to-methane with anaerobic digestion, an increase in system gross en­
ergy of 62.6% was found. Power-to-methanol integration with the biogas system increased the gross energy by
50% while power-to-Fischer-Tropsch fuels increased the gross energy yield by 32%. The parasitic energy demand
for hydrogen production was highlighted as the most significant factor for integrated biogas and power-to-fuel
facilities. Consuming electricity that would otherwise have been curtailed and optimising the anaerobic diges­
tion process were identified as key to improving the energetic efficiency of all system configurations. However,
the broad cross-sectoral benefits of the overarching cascading circular economy system, such as providing
electrical grid stability and utilising waste resources, must also be considered for a comprehensive perspective on
the integration of anaerobic digestion and power-to-fuel.

the low energy density of current battery technologies presents signifi­

cant challenges for the electrification of long-range, heavy-duty trans­
1. Introduction port such as commercial aviation, shipping and long-haul trucking [4].
There is still uncertainty surrounding the decarbonisation of these
1.1. Background modes of transport with sustainable liquid or gaseous fuels likely to be
required.
In order to meet the goal of limiting global temperature rise to 2 ◦ C, Biofuels have often been suggested as a renewable alternative to
as outlined in the Paris Climate Agreement, net emissions from human displace fossil fuel use within the transport sector [5,6]. Liquid biofuels,
activity must approach zero by 2050 [1]. The transport sector is mostly in the form of bioethanol or biodiesel, currently supply approx­
currently a major consumer of fossil fuels and a significant source of imately 4.2% of the total energy consumed by the transport sector
anthropogenic greenhouse gas emissions. In 2016, the combined emis­ worldwide [7]. However, there are several issues associated with the
sions from cars, vans, trucks, shipping and aviation accounted for 27% of production of these liquid biofuels. Firstly, the biofuel crops with the
the European Union’s (EU) total greenhouse gas (GHG) emissions – the best yields (such as sugarcane or palm oil) grow in tropical locations
most of any sector [2]. It is therefore clear that there is a need to tran­ where habitat destruction and deforestation have been associated with
sition the transport sector away from the use of fossil fuels towards the biofuel system, with a negative impact on the overall sustainability
renewable and sustainable alternatives. Increased use of electric vehi­ of the biofuel [8]. Additionally, energy crops grown in temperate cli­
cles (EVs) combined with robust public transport systems represents a mates (such as rapeseed oil or wheat) tend to produce lower yields per
pathway to decarbonise land-based passenger transport [3]. However,

* Corresponding author. MaREI Centre, Environmental Research Institute, University College Cork, Ireland.
E-mail address: [email protected] (N. Gray).

https://doi.org/10.1016/j.rser.2021.111886
Received 30 June 2021; Received in revised form 15 September 2021; Accepted 7 November 2021
Available online 25 November 2021
1364-0321/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Abbreviations kWh kilowatt hour

LCA Life cycle assessment
AD Anaerobic digestion LHV Lower heating value
AEL Alkaline electrolysis MJ Megajoule
CHP Combined heat and power NEB Net energy balance
CSTR Continuously stirred tank reactor NER Net energy ratio
DAC Direct air capture NEY Net energy yield
DS Dry solids PEM Proton exchange membrane
EROI Energy return on investment PtF Power-to-fuel
EU European Union PtX Power-to-x
EV Electric vehicle RED Renewable Energy Directive
FT Fischer-Tropsch RWGS Reverse water-gas shift
GHG Greenhouse gas SMY Specific methane yield
GJ Gigajoule SNSP System Non-Synchronous Penetration
GWP Global warming potential TJ Terajoule
ha hectare VRE Variable renewable electricity
ISO International Standards Organisation VS Volatile solids

Fig. 1. Schematic for the integration of AD and PtF.

hectare with lower ratios of energy output to energy input. For example, the terms Power-to-Fuel (PtF) or electrofuels) are also classified as
wheat ethanol has been reported as producing a gross energy of 66 advanced fuels [12].
GJ/ha/year, whereas palm oil biodiesel produces 120 GJ/ha/year [8]. PtF technologies represent a novel pathway to produce synthetic
Furthermore, when emissions from land use change are not considered, hydrocarbons from electrical power. In the PtF concept, electricity is
research indicates that the lifecycle emissions from wheat or corn used to produce hydrogen via water electrolysis. This hydrogen is then
ethanol produced in non-tropical environments can be higher than reacted with carbon dioxide (CO2) in a synthesis reactor to produce fuels
ethanol produced from sugarcane in tropical locations [9]. Moreover, such as methane, methanol or diesel [13]. The vast majority of renew­
land for crop production is a limited resource, with only 12% of global able electricity is produced from variable renewable electricity (VRE)
ice-free land devoted to crop production [10]. The use of land, that could sources, such as wind or solar [14]. The increasing share of VRE poses a
otherwise be used to grow food, to grow crops for energy purposes challenge for electrical grid operators in terms of load balancing and
further calls the sustainability of the biofuel into question, especially in grid stability. Specifically, the nature of VRE means that the net system
countries that are already utilising all available arable land. To regulate load (the difference between system demand and system generation)
the sustainability of biofuel systems, the recast EU Renewable Energy may change rapidly. Unlike traditional thermal power plants (synchro­
Directive (RED) aims for 14% of the energy in transport to come from nous generation), VRE sources (non-synchronous generation) do not
renewable sources by 2030, while also capping the contribution of food provide rotational inertia to the system. Insufficient system inertia can
crop-based biofuels at 7%. This means that there is a de facto target of cause changes in system frequency which can lead to load shedding
7% of the energy in transport to come from advanced fuels which are (blackouts) if the frequency deviation exceeds the permissible tolerances
produced from wastes, residues and by-products that do not compete for of the electrical grid [15]. Therefore, system operators generally place
land use [11]. Renewable fuels of non-biological origin (better known by upper limits on the amount of instantaneous non-synchronous electricity

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

generation. This is known as the System Non-Synchronous Penetration systems in Germany, finding that they can support higher levels of
(SNSP) limit, defined in Eq. (1) [16]: renewable electricity while also producing a flexible energy carrier [39].
Hermesmann et al. highlight PtF as a key technology for storing
Non synchronous generation + Net interconnector imports
SNSP = Eq. 1 renewable energy over long periods [14]. König et al. carried out a
System demand + Net interconnector exports
technoeconomic assessment of PtF liquid fuels, finding them to be be­
As can be seen from Eq. (1), at times when non-synchronous gener­ tween 3 and 4.4 times more expensive than current fossil fuels [40].
ation (wind or solar) is high relative to the system demand, grid oper­ Similarly, a case study of the Greek transport sector by Paris et al.
ators may be forced to dispatch down VRE power plants and hence highlights that electrofuels struggle to compete economically with fossil
“spill” or curtail renewable electricity in order to maintain grid stability fuels [41].
[17]. PtF facilities are seen as a key technology for storing excess VRE There is much less work focused on the integration of anaerobic
[18]. Furthermore, the PtF concept allows for sector-coupling, by digestion and power-to-fuel systems. Vo et al. explored both the techno-
allowing for the indirect electrification of sectors where VRE cannot economics and lifecycle impacts of integrating AD with power-to-
easily be directly used such as aviation, shipping, or road haulage methane systems [42,43], finding that the electricity GHG footprint
through the production of liquid or gaseous fuels. strongly influences the sustainability of PtF systems. Jürgensen et al.
Anaerobic digestion (AD) is a mature technology used to convert a investigated the potential for surplus wind electricity to produce
wide range of organic feedstocks (such as animal slurry, grass or hydrogen for biogas upgrading in Northern Germany, finding there is
seaweed) into an energy-rich gas mixture known as biogas (typically the potential to store 0.7 TWh of electricity in the form of synthetic
containing 60% methane and 40% carbon dioxide) [19]. While biogas natural gas [44].
has traditionally been used for electricity generation, it is possible to Furthermore, there is a scarcity of literature investigating the inte­
upgrade biogas to biomethane (~97% methane content) by gration of AD with power-to-liquid fuel production. Previous research
physio-chemical separation of the CO2 [20]. The biomethane can then has focused on either AD systems or PtF systems in isolation of each
be injected directly into the natural gas network as a replacement for other, often assessing the technoeconomic or environmental perfor­
fossil natural gas. Alternatively, the biomethane can be compressed to mance of the system. The integration of AD and PtF is an emerging area
250 bar or liquified using cryogenic technologies to be used as a trans­ of research. Peters et al. carried out a study to investigate the technical
port fuel [21], with potential for use in heavy goods vehicles (HGVs) feasibility of producing synthetic fuels at on farm biogas plants, high­
[22–24] and the shipping sector [25–27]. Expected increases in global lighting methanol as a promising pathway [45]. There is a gap in the
population and associated increase in demand for resources (food, en­ knowledge regarding the system-wide energy balance of anaerobic
ergy and water) will put significant pressure on arable land. As a result, digestion integrated with power-to-fuel systems including for liquid fuel
current commercialised AD feedstocks, such as maize, may become less production. Understanding the energy balance of advanced fuels is
viable. Nonetheless, with a greater emphasis on utilising waste feed­ necessary, as in future energy scenarios constraints on land use and
stocks and implementing circular economy principles, AD still can play a renewable electricity production mean resources must be used as effi­
critical role in future energy systems. The focus of previous research ciently as possible. To the best of the authors’ knowledge, this is the first
emphasises the many positive externalities of AD systems [28–30]. paper to perform an energy analysis from a broad system-wide
Within this context, the integration of biogas plants and PtF tech­ perspective of electrofuels (including for liquid fuels) integrated with
nology presents a promising option to produce advanced fuels (Fig. 1). AD systems.
AD is a technology which is capable of processing organic feedstocks The objectives of this paper are to:
that are typically considered to be waste streams, such as animal slurries
[31] or wastewater treatment sludge [32], to produce compressed or 1. Establish the net energy balance and net energy ratio of compressed
liquefied biomethane as a transport fuel. Biogas plants are also a source and liquefied biomethane produced from co-digestion of grass and
of concentrated biogenic CO2 for a PtF facility [33]. By integrating PtF slurry.
with AD systems, the CO2 captured during biogas upgrading is utilised to 2. Further assess the net energy balance and net energy ratio of the
produce electrofuels, creating a cascading system and obtaining greater system integrated with PtF production (power-to-methane, power-
energy yields from a fixed amount of biomass. The overarching AD-PtF to-methanol and power-to-Fischer-Tropsch fuels).
cascading circular economy system reuses by-products and waste 3. Perform a sensitivity analysis to identify key parameters affecting the
products, produces biofertilizer, improves water quality, and produces net energy balance and net energy ratio of the system to gain insights
advanced fuels to decarbonise hard-to-abate sectors such as haulage, into system optimisation.
shipping and aviation [30]. While AD facilities and PtF can operate
independently of each other, the wide-ranging benefits highlighted 2. Methodology
above would not be seen, thus integration is considered as a promising
pathway to explore. 2.1. System boundaries

1.2. Focus of paper To assess the system energy balance of PtF integrated with AD, an
example system based in Ireland was analysed. With a land area of
The focus of much previous research has been to assess anaerobic approximately 4 million hectares, grass is the most important agricul­
digestion and power-to-fuel systems in isolation of each other. Smyth tural crop in Ireland [8]. It is the main source of feed for beef, dairy and
et al. investigated the energy balance of grass biomethane [8], while sheep farming. Excess grass silage, surplus to livestock requirements, has
Korres et al. studied its lifecycle GHG impacts [34]. Blades et al. pre­ previously been identified as a feedstock for biomethane production [46,
sented a case study of a biogas plant co-digesting grass silage and dairy 47]. Mono-digestion of grass is not likely to meet the strict sustainability
slurry to produce electricity and transport fuel in a rural circular econ­ criteria of 65% GHG savings set by the EU RED for transport biofuels, as
omy [35]. Furthermore, Beausang et al. conducted a full environmental highlighted by Long and Murphy [20] and by Korres et al. [34].
assessment of a biogas facility co-digesting grass and slurry, including To improve the sustainability of the AD system, co-digestion of grass
environmental impacts such as eutrophication and acidification [31]. with animal slurries is proposed. The emissions credit (− 111.9 gCO2eq/
McDonagh et al. [36] and Gunawan et al. [37] both investigated the MJ [12]) obtained by avoiding fugitive methane emissions from open
techno-economics of hydrogen production from electrolysis. Hakawati slurry storage enhances the sustainability of the system [20]. The AD
et al. considered 49 biogas-to-energy routes, but did not evaluate inte­ system can produce advanced transport fuel in the form of compressed
gration with PtF [38]. Varone and Ferrari studied the potential of PtF or liquefied biomethane. The CO2 captured from the biogas upgrading

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Fig. 2. AD and PtF system boundaries.

2.2.2. Power-to-methanol
Table 1
Methanol is a light, volatile, colourless, flammable liquid. It is a
Advanced fuel scenarios analysed.
simple alcohol with the chemical formula CH3OH. In power-to-methanol
Scenario AD plant PtF plant facilities, hydrogen and carbon dioxide are reacted together in a ratio of
S1 Compressed biomethane n/a 3:1, according to Eq. (3) [14]. Methanol may also be produced by a
S2 Liquified biomethane n/a combination of reforming biogas and PtF methanol synthesis [53],
S3 Compressed biomethane Compressed methane
however to allow a like-for-like comparison between PtF pathways
S4 Compressed biomethane Methanol
S5 Compressed biomethane Fischer-Tropsch fuels examining this further was deemed outside the scope of this paper.
/
CO2 + 3H2 →CH3 OH + H2 O ΔH 0 = − 49.2 kJ mol Eq. 3
can then be used in an ex-situ PtF facility, where it is reacted with Direct hydrogenation of CO2 to methanol has been investigated and
hydrogen to produce further advanced transport fuels. Although a range typically takes place under temperatures of 200–270 ◦ C and pressure of
of fuels can be produced via the PtF concept, the fuels chosen for this 20–50 bar, in the presence of a Cu or Pd based catalyst [14]. Without
analysis are methane, methanol and Fischer-Tropsch fuels. A off-gas recycling, the CO2 conversion in a typical methanol synthesis
cradle-to-gate (well-to-tank) lifecycle boundary was selected for the reaction is in the range of 20–40% and carbon monoxide formation is
analysis. The boundaries and energy flows of the chosen system can be significant. Thus, there is a need to recycle unreacted gases to the feed
seen in Fig. 2. stream in order to reach nearly full CO2 conversion and high methanol
To compare the system energy balance of these advanced fuel selectivity [13]. The resulting product is a mixture of methanol and
pathways, five system configuration scenarios were assessed (Table 1). water, which must then be distilled to yield pure methanol.
Due to its importance as a chemical feedstock, a large transport and
2.2. Power-to-fuel options storage infrastructure for methanol already exists [14]. As a fuel,
methanol can be used either directly or blended with petrol in spark
2.2.1. Power-to-methane ignition (SI) engines due to its high octane rating [54]. Methanol is a
In power-to-methane technology, hydrogen and carbon dioxide are corrosive liquid, so certain modifications to engine and fuel delivery
reacted together in a ratio of 4:1 according to the Sabatier process, components must be made if high-level blends such as M85 (a blend
described by Eq. (2) [14]: containing 85% methanol and 15% petrol) are to be used. However,
/
CO2 + 4H2 →CH4 + 2H2 O ΔH 0 = − 165 kJ mol Eq. 2 low-level methanol blends are fully compatible with existing engine
technology and do not require any engine modification. Methanol has
There are two main processes for converting hydrogen and carbon also been suggested as an alternative fuel for the shipping sector as a
dioxide into methane: biological methanation or catalytic methanation replacement for heavy fuel oil (HFO) in advanced multi-fuel engines
[17]. Neither of these technologies are mature in the application to PtF. [55]. Methanol can also be dehydrated to dimethyl ether (DME, chem­
Previous work has studied both biological [48,49] and catalytic ical formula CH3OCH3), which is a promising fuel for use in diesel en­
methanation [50,51], with biological methanation being deemed more gines [56]. Furthermore, methanol can be converted to liquid
applicable to small-scale operations while catalytic methanation is hydrocarbons that function as a drop-in replacement for petrol or diesel
preferred for larger plants, as it is able to take advantage of economies of via the so-called “methanol-to-gasoline” process developed by Exxon­
scale. Mobil [57].
The Audi e-gas plant, located in the northern German town of Wertle, The George Olah plant, operated by Carbon Recycling International,
is an example of an existing power-to-methane plant. The plant operates based in Iceland, is an example of a demonstration power-to-methanol
using electricity produced from offshore wind to power three 2MWe plant. Carbon dioxide captured from a geothermal power plant is reac­
alkaline electrolysers and CO2 captured from a local biogas plant to ted with hydrogen produced using geothermal power to create low-
produce approximately 1000 tonnes of renewable methane per year carbon methanol. Operating since 2011, the plant produces 5 million
[52]. litres of renewable methanol per year [58].

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Table 2 there are plans to construct the world’s first commercial plant for pro­
Biogas feedstock characteristics and assumptions. ducing synthetic fuels in Heroya, Norway, due to start production in
Characteristic Value Reference 2023 [14].
Grass silage dry solids (DS) content 29.27% [69]
Grass silage volatile solids (VS) content 26.84% [69] 2.3. Functional units
Dairy slurry DS content 8.75% [69]
Dairy slurry VS content 6.69% [69] There are a range of metrics that are commonly used in energy LCA
Specific methane yield at a co-digestion ratio of 4:1 345 [69]
studies to assess the performance of a particular alternative fuel system.
VSgrass: VSslurry (Nm3CH4/tVS)
Biogas methane content 60% (by [19] The most common energy criteria used are [67]:
volume)
• Net Energy Yield (NEY)
• Net Energy Ratio (NER)
2.2.3. Power-to-Fischer-Tropsch fuels
Fischer-Tropsch fuels can be produced via the PtF concept according The NEY is the net energy balance of the system divided by the land
to the generic Eq. (4) [14]. area required for crop production, calculated in this paper using Eq. (6)
/
nCO2 + (3n + 1)H2 → Cn H2n+2 + 2nH2 O ΔH 0 = − 125 kJ mol Eq. 4 to Eq. (8). The energy terms used in Eq. (7) and Eq. (8) are defined in
Fig. 2. In this study, grass is used as an energy crop for AD. Although
The Fischer-Tropsch process produces a range of n-alkane products, perennial ryegrass is deemed an advanced biofuel source in the recast
from CH4 through to C30H62 and upwards. CH4 through to C4H10 are RED, it still requires land area to be grown. While energy yields can be
gaseous, C5H12 through to C20H42 are liquids and products with chain improved by co-digestion with cattle slurry and integration with PtF
lengths greater than C20 are waxes [40]. To produce advanced liquid systems, area under land is still an important metric to consider in future
transport fuels, hydrocarbons in the range C5 to C20 are of interest. The energy scenarios where land use may be constrained. A positive NEY
modified Fischer-Tropsch process proceeds in a two-step reaction, where implies that the system produces more energy in fuel than is consumed
the reverse water-gas shift (RWGS) reaction first reduces CO2 to CO, in the production process and the higher the value of NEY, the more
followed by the hydrogenation of CO to produce hydrocarbons [59,60]. efficient the system is in terms of land use.
Fe or Co-based catalysts are used to enhance the rate of reaction.
Eoutput Einput
Investigation into the addition of promoters, such as Cr-, Mn-, Cu- or NEY(GJ / ha / year) = − Eq. 6
land area land area
Zr-salts, is currently being undertaken to enhance the selectivity of
liquid hydrocarbon formation [14]. It has been reported in the literature Eoutput = EAD + EPtF Eq. 7
that although Co-based catalysts are more expensive than Fe-based
catalysts, they are more suited to the production of liquid fuels [61, Einput = Ecrop production + Etransport + Ebiogas production + Ebiogas upgrading
62]. The weight fraction of each alkane produced by the Fischer-Tropsch Eq. 8
+ Ecompression OR liquefaction + Eelectrolysis + Efuel synthesis
reaction can be modelled using the Anderson-Schulz-Flory distribution,
as seen in Eq. (5), where n is the carbon number of the alkane produced, The NER of the system is described as the ratio of the energy content
Wn is the weight fraction of that alkane and α is the chain growth in the fuel produced by the system to the energy required to produce the
probability factor [62–64]. fuel, calculated using Eq. (9). A NER of greater than one suggests the
system is a net energy producer, while if the system has a NER of less
Wn = nαn− 1 (1 − α)2 Eq. 5 than one it is an energy sink. This metric is also commonly referred to as
The value of α is dependent on a range of factors, such as operating the “energy return on investment” (EROI) in the literature [68].
temperature, and catalyst type [62]. Higher α values indicate a greater Eoutput
probability of long chained hydrocarbon formation and are thus desir­ NER = Eq. 9
Einput
able to produce liquid fuels. Cobalt based catalysts have been shown to
exhibit α values of between 0.8 and 0.94, and therefore favour the These energy metrics allow for a direct comparison of the energetic
production of liquid fuels [62,63]. The product of the Fischer-Tropsch efficiency and land use productivity amongst multiple alternative fuel
process, also known as syncrude, consists of a large variety of different production pathways. They differ in that NER is a measure of system
hydrocarbon species. The liquid fuel fractions of the syncrude are efficiency, whereas NEY measures a combination of agricultural pro­
separated using distillation, and then upgraded via hydrocracking and ductivity and system efficiency.
isomerisation to obtain the final product [58].
Fischer-Tropsch fuels act as a functional drop-in replacement for 2.4. Anaerobic digestion system
liquid fossil fuels. The use of liquid fossil fuels as transport fuels is
ubiquitous, therefore Fischer-Tropsch fuels are fully compatible with 2.4.1. Anaerobic digestion mass balance
conventional fossil fuels and therefore fully compatible with existing The processing capacity of the theoretical biogas facility analysed
engines and fuel distribution infrastructure. Fischer-Tropsch fuels do not was 53,064 t/year, consisting of 25,344 t/year of grass silage and
contain any sulphur or nitrogen [65], as such synthetic Fischer-Tropsch 27,720 t/year of dairy slurry, as per Vo et al. [43]. This ratio of feedstock
fuels offer air quality benefits in terms of lower levels of sulphur oxides is based on a ratio of volatile solids (VS) of 80% grass silage to 20% dairy
(SOx), nitrous oxides (NOx), carbon monoxide (CO) and particulate slurry and is approximately equivalent to 50:50 on a wet weight basis
matter (PM) emissions [21]. Additionally, the high energy density of (see Table 2 and Box 1). Research has shown that the specific methane
Fischer-Tropsch fuels and “drop-in” compatibility with existing infra­ yield produced from the co-digestion of grass and slurry falls as the ratio
structure mean that it is one of the few options available to decarbonise of slurry digested increases [69]. Therefore, a VS ratio of 80% grass to
the commercial aviation sector [57,66]. 20% slurry was chosen to maximise the feedstock specific methane yield
While the Fischer-Tropsch process is well established, its use in PtF while also maximising the benefit of the emissions credit for digesting
applications is still relatively new. At a pilot-plant based in Dresden, the slurry.
company Sunfire demonstrated the production of synthetic Fischer- Feedstock characteristics and assumptions made in the AD system
Tropsch fuels from CO2 captured from air and H2 produced from mass balance are outlined in Table 2. Under Irish growing conditions,
steam electrolysis. Based on the results from this demonstration plant, grass yields of 12 tonnes dry solids/ha/year can be readily achieved [8].
Therefore, using data measured by Wall et al. [69] grass is modelled

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Box 1
Grass silage and dairy slurry AD system mass balance

Annual volatile solids

For an annual input of 25,344 t/year grass and 27,720 t/year slurry.
Grass ​ silage ​ VS = 25, 344t/year ​ × 26.84% = 6, 802 ​ tVS/year
Dairy ​ slurry ​ VS = 27, 720 ​ t/year × 6.69% = 1, 854.5 ​ tVS/year
( ) ( )
6, 802 1, 854.5
VS ​ ratio ​ (grass ​ silage : dairy ​ slurry) = : ≈ 80 : 20
6, 802 + 1, 854.5 6, 802 + 1, 854.5
Annual biogas production
For a VS ratio of 80% grass and 20% dairy slurry, a specific methane yield of 345 Nm3CH4/tVS is assumed, as per Wall et al. [69]. The
produced biogas is assumed to contain 60% CH4 and 40% CO2 by volume.
(6, 802 + 1, 854.5)tVS/year × 345 ​ Nm3 CH4 /tVS
Biogas ​ production = = 4, 977, 659 ​ Nm3 biogas/year ​
60%
Biogas composition
For all density-related calculations temperature and pressure of 273.15 K and 101.325 kPa was assumed.
Biogas ​ CH4 ​ content ​ (by ​ volume) = 4, 977, 659Nm3 biogas/year × 60% = 2, 986, 595 ​ Nm3 CH4 /year
2, 986, 595 ​ Nm3 CH4 /year × 0.716 ​ kg/m3 CH4 t
Biogas ​ CH4 ​ content ​ (by ​ mass) = = 2, 138
1000 year
Biogas ​ CO2 ​ content ​ (by ​ volume) = 4, 977, 659Nm3 biogas/year × 40% = 1, 991, 063 ​ Nm3 CO2 /year
1, 991, 063 ​ Nm3 CO2 /year × 1.96kg/m3 CO2
Biogas ​ CO2 ​ content ​ (by ​ mass) = = 3, 909 ​ t/year ​
1000
Annual digestate production
Digestate ​ production = massfeedstock − massbiogas = 53, 064 ​ t/year − (2, 138 + 3, 909)t/year = 47, 017 ​ t/year
Annual biogas upgrading losses
1.5% (by volume) losses are assumed in the amine scrubbing upgrading process.
Biogas ​ losses = 4, 977, 659Nm3 biogas/year ​ × 1.5% = 74, 665 ​ Nm3 /year
Nm3 Nm3
CH4 ​ losses = 74, 665 × 60% = 44, 799 ≡ 32.07 ​ t/year
year year
3 3
Nm Nm
CO2 losses = 74, 665 × 40% = 29, 866 ≡ 58.64t/year
year year
Annual biomethane production
The upgraded biogas is assumed to have a CH4 content of 97% with 3% CO2, by volume.
(4, 977, 659 ​ Nm3 /year − 74, 665 ​ Nm3 /year) × 60%
Biomethane ​ production = = 3, 032, 780 ​ Nm3 /year
3
97% 3
Biomethane ​ CH4 ​ content = 3, 032, 780 ​ Nm /year × 97% = 2, 941, 796Nm /year ≡ 2, 106 ​ t/year
Biomethane ​ CO2 ​ content = 3, 032, 780 ​ Nm3 /year × 3% = 90, 983 ​ Nm3 /year ≡ 178.6 ​ t/year
Annual CO2 available for PtX
CO2 ​ available ​ for ​ PtX = 1, 991, 063 − (29, 866 + 90, 983) = 1, 870, 214Nm3 CO2 /year ≡ 3, 672 ​ t/year ​

with a dry solids content of 29.27%; to produce the feedstock considered 2.4.2. Anaerobic digestion gross energy yields
for this analysis (25,344 tonnes wet weight/year), 618 ha of land is From the mass balance, the gross energy of the AD system was found
required. The biogas produced from the digester is fed into an amine to be 173 GJ/ha/year (Table 3).
scrubber to upgrade to biomethane, with the CO2 removed and used in
an ex-situ PtF facility. The methodology used to calculate the mass 2.4.3. Feedstock production
balance is presented in Box 1 and a summary of the AD system mass The parasitic energy in grass production includes for the direct en­
balance is shown in Fig. 3. ergy used in planting, cultivating and harvesting the crop as well as the

Fig. 3. Summary of grass silage and dairy slurry AD system mass balance.

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Table 3 demand of 13.61 GJ/ha/year, assuming 15% heat loss [8]. The thermal
Grass silage and dairy slurry AD system gross energy yield. demand of the plant is modelled as met by combusting woodchips.
Component Value
Ethermal = Efeedstock + Eheat loss Eq. 10
3
Annual methane production (Nm CH4/year) 2,986,595
LHV methanea (MJ/Nm3CH4) 35.79 mcp ΔT
AD system gross energy yields (MJ/year) 106,883,635 Efeedstock = Eq. 11
ηboiler
Grass land take (ha) 618
AD system gross energy per ha (GJ/ha/year) 173
Eheat loss = 0.15Efeedstock Eq. 12
a
Measured at 273.15 K and 101.325 kPa.
where.
m = annual mass of feedstock (53,064 t/year).
Table 4 cp = specific heat capacity of feedstock (assumed to be similar to
AD system parasitic energy demand.
water, 4.184 MJ/t/◦ C).
Feedstock production parasitic energy demand ΔT = temperature rise (28 ◦ C).
Direct energy in agriculture (GJ/ha/year) 2.9 ηboiler = boiler efficiency (85%)
Indirect energy in agriculture (GJ/ha/year) 17.7
Total parasitic energy in feedstock production (GJ/ha/year) 20.6
The electrical demand for biogas production is reported by Wu et al.
Feedstock transport parasitic energy demand to be 10 kWhe/t feedstock [19], leading to a parasitic electrical demand
Transportation energy consumption (MJ/tkm) 0.7 of 3.09 GJ/ha/year. The source of electricity is assumed to be wind
Distance transported (km) 10 power and as such primary energy is equal to final energy and the car­
Mass feedstock transported (t/year) 53,064
bon footprint is minimised. The total parasitic energy demand for biogas
Total parasitic energy in feedstock transport (GJ/ha/year) 0.6
Biogas production parasitic energy demand production was found to be 16.7 GJ/ha/year (Table 4).
Biogas production thermal demand (GJ/ha/year) 13.61
Biogas production electrical demand (GJ/ha/year) 3.09 2.4.6. Biogas upgrading
Total parasitic energy in biogas production (GJ/ha/year) 16.7 Amine scrubbing was assumed for the removal of carbon dioxide
Biogas upgrading parasitic energy demand
Amine scrubbing thermal energy consumption (kWhth/Nm3 biogas) 0.45
from the biogas. The thermal and electrical demand of amine scrubbing
Amine scrubbing electrical energy consumption (kWhe/Nm3 biogas) 0.09 is 0.45 kWhth/Nm3 biogas input and 0.09 kWhe/Nm3 biogas input
Biogas input for upgrading (Nm3 biogas/year) 4,977,659 respectively [19]. This results in a total parasitic energy demand of
Total parasitic energy in biogas upgrading (GJ/ha/year) 15.65 15.65 GJ/ha/year for biogas upgrading (Table 4).
Biogas compression/liquefaction parasitic energy demand
Biomethane compression energy consumption (kWhe/Nm3 0.35
biomethane) 2.4.7. Biomethane compression/liquefaction
Biomethane liquefaction energy consumption (kWhe/Nm3 0.63 Energy consumption for the compression of biomethane is assumed
biomethane) to be 0.35 kWhe/Nm3 biomethane [8], while the energy consumption
Biomethane input (Nm3/year) 3,032,780 for biomethane liquefication is reported to be 0.63 kWhe/Nm3 bio­
Total parasitic energy in biomethane compression (GJ/ha/year) 6.18
Total parasitic energy in biomethane liquefaction (GJ/ha/year) 11.13
methane [21]. This results in total parasitic energy of 6.18 GJ/ha/year
for compressed biomethane and 11.13 GJ/ha/year for liquified bio­
methane (Table 4).
indirect energy used in the production of fertilizers and other inputs.
Work by Smyth et al. investigated the energy inputs in the production of
grass silage under Irish conditions, and found that 2.9 GJ/ha/year in 2.5. Power-to-fuel system
direct agricultural operations (ploughing, sowing, harrowing, rolling,
fertilizer application, lime application, herbicide application, harvesting 2.5.1. Power-to-fuel mass balance
and ensiling) and 17.7 GJ/ha/year in indirect energy (manufacture of The mass balance of the power-to-fuel system (Fig. 4) was calculated
fertilizer, seed, lime and herbicide) is required, leading to a total energy based on the amount of CO2 available for fuel synthesis (3,672,080 kg/
use in grass production of 20.6 GJ/ha/year (Table 4) [8]. As cattle slurry year) and the fuel production stoichiometric ratios (Box 2, Box 3, and
is classified as a waste, its energy inputs were not included within the Box 4). These values can be considered to be optimistic, as in reality
system boundary of the analysis. process inefficiencies mean that less than 100% of the CO2 will be
converted to fuel.
2.4.4. Feedstock transport The fuel synthesis step produces a significant amount of water
It is conservatively estimated that the silage and slurry are trans­ (Fig. 4), which can be used to meet 50%, 33% and 67% of the elec­
ported 10 km from their storage location to the biogas facility. It is trolysis water demand for the power-to-methane, power-to-methanol
assumed that the feedstock is transported to the biogas facility via diesel and power-to-Fischer-Tropsch fuel systems, respectively.
powered trucks. It is reported that transportation of goods by truck re­
quires 0.7 MJ/tkm [34]. Therefore, the transportation of 53,064 t/year 2.5.2. Power-to-fuel gross energy yields
of feedstock requires 0.6 GJ/ha/year of parasitic energy (Table 4). From the mass balances, the gross energy for the various PtF systems
was found to be 108.27 GJ/ha/year for power-to-methane, 86.07 GJ/
2.4.5. Biogas production ha/year for power-to-methanol and 54.86 GJ/ha/year for power-to-
A continuously stirred tank reactor (CSTR) set up is assumed for Fischer-Tropsch fuels (Table 5). As the aim of this paper is to assess
biogas production. CSTR reactors typically operate with a dry solids the energy balance of advanced transport fuels, only the energy con­
(DS) content of below 12% and at 38 ◦ C, in the mesophilic temperature tained in the liquid fraction of the Fischer-Tropsch process is considered,
range [8]. The desired DS content is achieved through the recirculation with gases and waxes considered by-products.
of liquid digestate. The parasitic energy required for biogas production
can be broken down into thermal and electrical energy demands. 2.5.3. Hydrogen production
The thermal demand is required to raise the temperature of the For this analysis, proton exchange membrane (PEM) electrolysis was
feedstock from an assumed initial temperature of 10 ◦ C to the required chosen as it is predicted to be the electrolyser technology of choice for
38 ◦ C and calculated using Eq. (10) to Eq. (12) to give a total thermal PtF systems in the future due to its superior efficiency and ability to
facilitate VRE when compared with alkaline electrolysis (AEL) [17].

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Fig. 4. Summary of PtF system mass balances.

Götz et al. reported that the electricity consumption of PEM electrolysis required for fuel synthesis was found to be 3.01 GJ/ha/year for
currently ranges from 4.5 to 7.5 kWhe/Nm3H2, with the potential for this power-to-methane, 4.41 GJ/ha/year for power-to-methanol and, 4.24
value to decrease to between 4.1 and 4.8 in future systems [51]. Simi­ GJ/ha/year for power-to-Fischer-Tropsch fuels (Table 6). As the gaseous
larly, Buttler et al. conclude that while the current energy consumption and wax fractions of the Fischer-Tropsch process are considered to be
of PEM electrolysis is between 5.1 and 5.4 kWhe/Nm3H2, efficiency by-products they are not included within the system boundary, with the
improvements could see values of 4.5 kWhe/Nm3H2 achieved in the parasitic energy demand for the process allocated to the liquid fuel
future [70]. Therefore, for this analysis, an electrolysis energy con­ fraction.
sumption of 4.5 kWhe/Nm3H2 was selected, which equates to 48.9
kWhe/kgH2 at conditions of 273.15 K and 101.325 kPa. 3. Results and discussion
The total parasitic energy in hydrogen production was calculated to
be 191.69 GJ/ha/year for power-to-methane, 143.76 GJ/ha/year for 3.1. Summary of system energy balance
power-to-methanol, and 143.76 GJ/ha/year for power-to-Fischer-
Tropsch fuels (Table 6). In the base case, it is assumed that the elec­ The objective of this analysis was to assess the energy balance of an
tricity for hydrogen production is supplied by renewable electricity that integrated biogas and power-to-fuel facility. A summary of the system
has not been curtailed, with a primary energy factor (PEF) of one. The net energy yields (NEYs), and net energy ratios (NERs) can be seen in
PEF connects primary and final energy. It indicates how much primary Fig. 5 and Fig. 6, which are discussed below.
energy (i.e. renewable or fossil) is used to generate a unit of electricity.

2.5.4. Power-to-methane compression 3.2. Discussion

The compression of methane produced via the power-to-methane
step (Scenario 3) was included in the analysis. The power-to-methane 3.2.1. Gross energy yields
process produces 1,338,617 kgCH4/year, which equates to 1,870,214 The gross energy of the AD system co-digesting grass silage and cattle
Nm3CH4/year under conditions of 273.15 K and 101.325 kPa. The total slurry (Scenarios 1 & 2) was 173 GJ/ha/year (Fig. 5). Through the
energy for compression was found to be 3.82 GJ/ha/year (Table 6). integration of power-to-methane (Scenario 3), the system’s gross energy
increases to 281 GJ/ha/year. This represents an approximate 63% in­
2.5.5. Fuel synthesis crease in gross energy when compared to a conventional biogas plant.
Electrical energy is required during the PtF fuel synthesis step. Billig When methanol is produced by the PtF facility (Scenario 4), greater fuel
et al. report that 1.39 MJ/kgCH4, 1.02 MJ/kgCH3OH, and 2.238 MJ/ yields in terms of mass are seen (2673 tCH3OH/year vs 1339 tCH4/
kgFTproduct is required for power-to-methane, power-to-methanol and year), although the lower LHV of methanol compared to methane (19.9
power-to-Fischer-Tropsch fuels, respectively [58]. The total energy MJ/kgCH3OH vs 50 MJ/kgCH4) results in a lower overall system gross
energy at 259 GJ/ha/year; however, this is a 50% increase over the AD

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Box 2
Power-to-methane mass balance

Stoichiometric equations
Electrolysis: 2H2 O→2H2 + O2
Power-to-methane: CO2 + 4H2 →CH4 + 2H2 O
Molar masses:
g
CO2 = 44.009
g mol
H2 = 2.016
mol g
CH4 = 16.043
mol
g
H2 O = 18.015
mol
g
O2 = 31.998
mol
Power-to-methane mass balance
3, 672, 080 ​ kg/year
No. ​ kmol ​ CO2 = = 83, 439 ​ kmol/year
44.009 ​ kg/kmol
CO2 + 4H2 →CH4 + 2H2 O
No. ​ kmol ​ H2 ​ required = 4 × 83, 439 ​ kmol/year = 333, 757 ​ kmol/year
No. ​ kmol ​ CH4 ​ produced = 1 × 83, 439 ​ kmol/year = 83, 439 ​ kmol/year
No. ​ kmol ​ H2 O ​ produced = 2 × 83, 439 ​ kmol/year = 166, 879 ​ kmol/year
Mass ​ H2 ​ required = 333, 757 ​ kmol/year ​ × 2.016 ​ kg/kmol = 672, 854 ​ kgH2 /year
Mass ​ CH4 ​ produced = 83, 439 ​ kmol/year × 16.043 ​ kg/kmol = 1, 338, 617 ​ kgCH4 /year
Mass ​ H2 O ​ produced = 166, 879 ​ kmol/year × 18.015 ​ kg/kmol = 3, 006, 318 ​ kgH2 O/year
Electrolysis mass balance
2H2 O→2H2 + O2
To produce 333,757 kmol H2, 333,757 kmol H2O is required and 166,879 kmol O2 is produced.
Mass ​ H2 O ​ required = 333, 757 ​ kmol/year × 18.015 ​ kg/kmol = 6, 012, 635 ​ kgH2 O/year
Mass ​ O2 ​ produced = 166, 879 ​ kmol ​ × 31.998 ​ kg/kmol = 5, 339, 781 ​ kgO2 /year

system alone. The selectivity towards the production of liquid fuels from electricity to a fuel, with inefficiencies along the pathway. One of
during Fischer-Tropsch synthesis (Scenario 5) results in lower fuel yields the primary reasons for making hydrogen from electricity is to store
when compared with both the production of synthetic methane and electricity that would otherwise be curtailed. Hydrogen acts as a
methanol, resulting in lower gross energy yields of 228 GJ/ha/year, chemical battery, or a means of facilitating temporal mismatches be­
although this still represents a 32% increase over the AD system in tween electricity supply and demand, and not as a means of increasing
isolation. While the gaseous and wax products of the Fischer-Tropsch energy.
process contain energy value, they were deemed outside of the system To investigate the sensitivity of the system, each parasitic energy
boundary as by-products, with the liquid fuel fraction deemed the main demand was varied by ±25% to see the effect on the NEY (Fig. 8). The
process output. parasitic energy required for hydrogen production has the most signif­
icant effect on the NEY of the system. A ±25% change in the parasitic
3.2.2. Net energy yields energy demand for hydrogen production results in a ±209% change in
The net energy yield (NEY) seen in Scenario 1, where the AD plant the system NEY. This implies that improvements in electrolysis effi­
produces compressed biomethane, was found to be 113 GJ/ha/year, ciency could significantly improve the energy balance of PtF systems.
with a net energy ratio (NER) of 2.89 (Figs. 5 and 6). In Scenario 2, Of the PtF systems assessed, power-to-methanol (Scenario 4) displays
where the AD system produces liquefied biomethane, the NEY falls to the greatest NEY, mainly due to its lower H2 demand (143.76 GJ/ha/
108 GJ/ha/year and the NER decreases to 2.67. This is accounted for by year) compared to power-to-methane (191.69 GJ/ha/year) and greater
the increased energy intensity of the liquefaction process compared to gross energy yields (259 GJ/ha/year) compared to power-to-Fischer-
compression. Tropsch fuels (228 GJ/ha/year).
Although the gross energy produced in all PtF scenarios (Scenarios 3,
4 and 5) exceeds the gross energy of the AD system in isolation (Sce­ 3.2.3. Impact of electrolysis
narios 1 and 2), the NEYs of Scenarios 3, 4 and 5 are lower at 22.94 GJ/ As the energy required for electrolysis was identified to be the most
ha/year, 51.06 GJ/ha/year and, 20.03 GJ/ha/year respectively. The significant factor in the parasitic energy of integrated AD and PtF sys­
NERs of the PtF scenarios assessed are also lower at 1.09 for power-to- tems, the source of electricity used in hydrogen production was varied to
methane, 1.25 for power-to-methanol, and 1.10 for power-to-Fischer- investigate its impact on the system’s NEY and NER. In the base case
Tropsch fuels. This is explained in particular by the very large elec­ assessed above, it was assumed that the electricity for hydrogen pro­
trical energy demand of the electrolysis process to produce hydrogen duction was sourced from renewable electricity that has not been cur­
(Fig. 7), which shows that hydrogen production accounts for 74% of the tailed (PEF = 1). In a revised analysis, electricity for electrolysis was
parasitic energy in Scenario 3 (power-to-methane). This is not unsur­ assessed when sourced from non-renewable sources (PEF = 2.3 was
prising as in essence in PtF systems we are converting an energy vector modelled which equates to an energy conversion efficiency of 43.5%,

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Box 3
Power-to-methanol mass balance

Stoichiometric equations
Electrolysis: 2H2 O→2H2 + O2
Power-to-methanol: CO2 + 3H2 →CH3 OH + H2 O
Molar masses:
g
CO2 = 44.009
g mol
H2 = 2.016
mol g
CH3 OH = 32.042
g mol
H2 O = 18.015
gmol
O2 = 31.998
mol
Power-to-methanol mass balance
3, 672, 080 ​ kg/year
No. ​ kmol ​ CO2 = = 83, 439 ​ kmol/year
44.009 ​ kg/kmol
CO2 + 3H2 →CH3 OH + H2 O
No. ​ kmol ​ H2 ​ required = 3 × 83, 439 ​ kmol/year = 250, 318 ​ kmol/year
No. ​ kmol ​ CH3 OH ​ produced = 1 × 83, 439 ​ kmol/year = 83, 439 ​ kmol/year
No. ​ kmol ​ H2 O ​ produced = 1 × 83, 439 ​ kmol/year = 83, 439 ​ kmol/year
Mass ​ H2 ​ required = 250, 318 ​ kmol/year × 2.016kg/kmol = 504, 641 ​ kgH2 /year
Mass ​ CH3 OH ​ produced = 83, 439kmol/year × 32.042 ​ kg/kmol = 2, 673, 562 ​ kgCH3 OH/year
Mass ​ H2 O ​ produced = 83, 439 ​ kmol/year × 18.015 ​ kg/kmol = 1, 503, 159 ​ kgH2 O/year
Electrolysis mass balance
2H2 O→2H2 + O2
To produce 250,318 kmol of H2, 250,318 kmol of H2O is required and 125,159 kmol of O2 is produced.
Mass ​ H2 O ​ required = 250, 318 ​ kmol/year × 18.015 ​ kg/kmol = 4, 509, 476 ​ kgH2 O/year
Mass ​ O2 ​ produced = 125, 159kmol/year × 31.998 ​ kg/kmol = 4, 004, 836 ​ kgO2 /year

typical for non-renewable sources [71]) or from electricity that would 3.2.4. Impact of biogas characteristics
otherwise have been curtailed (PEF = 0) [19]. The use of a PEF of zero To understand the effect of biogas methane content on the overall
for curtailed electricity is justified as the electrical energy would have energy balance of AD and PtF, the characteristics of the biogas were
been wasted in the absence of being used by the PtF system. varied. In a revised analysis, the methane content of the biogas was
The results of the revised analysis are displayed in Fig. 9 and Fig. 10. varied from 10% up to 100% to understand its impact on the overall
Both the NEY and NER of the system improve significantly through the system NEY (Fig. 11). It was found that if the methane content of the
use of electricity that would otherwise have been subject to curtailment. biogas is below ~55%, the system in Scenario 3 (compressed bio­
Under these conditions, the higher LHV of methane results in power-to- methane and power to methane) displays a negative NEY (with a PEF of
methane production displaying the greatest NEY and NER. Conversely, 1) due to the large amount of hydrogen required to react with the CO2
the use of non-renewable electricity to produce hydrogen has a negative removed during biogas upgrading. Biogas methane concentrations
impact on the energy balance of the PtF system, resulting in negative greater than 55% are necessary for the system in Scenario 3 to display a
NEYs and NERs of less than one, indicating the system has become an positive NEY.
energy sink. As such this would suggest that there is little merit in Similarly, the specific methane yield (SMY) of the AD feedstock was
making fuels from fossil-based electricity. varied from 300 Nm3CH4/tVS to 400 Nm3CH4/tVS to investigate the
Research by McDonagh et al. has highlighted that even in electricity effect on the system NEY (Fig. 12). As the SMY of the feedstock in­
systems with high penetrations of VRE, the resource potential for cur­ creases, the NEY of the system also increases. A 14% increase in SMY
tailed electricity may not be sufficient to economically operate a PtF from 350 Nm3CH4/tVS to 400 Nm3CH4/tVS results in a 37% increase in
system [36]. To minimise the levelised costs of hydrogen, a PtF facility the system’s NEY in Scenario 3. Both this result, and the results seen
must operate for approximately 6500 h per year to amortise the capital when varying the composition of biogas highlight the importance of
expenditure of the electrolysis system. To do this, it must engage in the current research into the optimisation of anaerobic digestion on the
electricity market as a wholesale consumer and not solely rely on sustainability of integrated AD and PtF facilities. For example in­
consuming curtailed electricity. Within the context of this paper, the novations such as the addition of conductive materials to the AD process
results seen when curtailed electricity is used for electrolysis acts as the (such as graphene or pyrochar) to enhance direct interspecies electron
“ceiling” for the system’s NEY and NER, while the use of non-renewable transfer and advanced feedstock pre-treatments (such as liquid hot
electricity acts as the “floor”. In reality, in advance of a fully deca­ water pre-treatment) can improve the biodegradability index of AD
rbonised electricity system both the NEY and NER of the system will fall feedstocks, resulting in greater SMYs and higher biogas methane con­
somewhere in between these values, and can be optimised through centrations [19,72,73]. Further research in this area will improve the
operational controls, such as using wind forecast to ensure operation of NEY and NER of integrated AD and PtF facilities.
the electrolyser at times of high wind energy [36].
3.2.5. Wider context and limitations
The NEY and NER of the integrated AD and PtF facility assessed in

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Box 4
Power-to-Fischer-Tropsch fuels mass balance

Stoichiometric equations
Electrolysis:2H2 O→2H2 + O2
Power-to-Fischer-Tropsch fuels: nCO2 + (3n + 1)H2 →Cn H2n+2 + 2nH2 O
Molar masses:
g
CO2 = 44.009
g mol
H2 = 2.016
mol g
Cn H2n+2 = 12.011n + 1.008(2n + 2)
g mol
H2 O = 18.015
mol
g
O2 = 31.998
mol
Power-to-Fischer-Tropsch fuels mass balance
3, 672, 080 ​ kg/year
No. ​ kmol ​ CO2 = = 83, 439 ​ kmol/year
44.009 ​ kg/kmol
Therefore, n = 83,439 in: nCO2 + (3n + 1)H2 →Cn H2n+2 + 2nH2 O
No. ​ kmol ​ H2 ​ required = (3 × 83, 439) + 1 = 250, 319 ​ kmol/year
No. ​ kmol ​ H2 O ​ produced = 2 × 83, 439 = 166, 879 ​ kmol/year
Mass ​ H2 ​ required = 250, 319 ​ kmol/year × 2.016 ​ kg/kmol = 504, 643 ​ kgH2 /year
Mass ​ FT ​ products = 12.011(83, 439) + 1.008((2 × 83, 439) + 2) = 1, 170, 405 ​ kgFTproduct /year ​
Mass ​ H2 O ​ produced = 166, 879 ​ kmol/year × 18.015 ​ kg/kmol = 3, 006, 318 ​ kgH2 O/year
Using the Anderson-Schulz-Flory probability distribution (see Eq. (5)), with an α value of 0.85 [21], the weight distributions of the
Fischer-Tropsch products are as follows:

Carbon number (n) Weight fraction

Gasses (n = 1 to n = 4) 0.1648
Liquid fuels (n = 5 to n = 20) 0.6802
Waxes (n = 21 plus) 0.1550

MassgaseousFTproducts = 1, 170, 405kg/year × 0.1648 = 192, 871kg/year

MassliquidFTproducts = 1, 170, 405kg/year × 0.6802 = 796, 077kg/year
MasswaxFTproducts = 1, 170, 405kg/year × 0.1550 = 181, 457kg/year
Electrolysis mass balance
2H2 O→2H2 + O2
To produce 250,319 kmol of H2, 250,319 kmol of H2O is required and 125,159 kmol of O2 is produced.
MassH2 Orequired = 250, 319kmol × 18.015kg/kmol = 4, 509, 494kgH2 O/year
MassO2 produced = 125, 159kmol × 31.998kg/kmol = 4, 004, 852kgO2 /year

of between 1.7 and 3.3 and ethanol produced from corn ranges from
Table 5 0.67 to 1.7 [74]. These values put context on the relatively high NER of
PtF system gross energy yield.
2.89 for grass and slurry biomethane (Scenario 1) found in this analysis.
Component Value The use of grass here as feedstock is beneficial in EU states as biofuels
LHV methane (MJ/kg) 50 from perennial rye grass are classified as advanced fuels in the recast
LHV methanol (MJ/kg) 19.9 RED [12] and as such there is no cap on production as there would be for
LHV diesela (MJ/kg) 42.6 first generation biofuels produced from food crops such as rapeseed
Power-to-methane production (kg/year) 1,338,616
biodiesel or corn ethanol. One of the benefits of digesting slurry is
Power-to-methanol production (kg/year) 2,673,562
Power-to-FT liquid fuel production (kg/year) 796,077 creating energy output free from agricultural land input and as such
Power-to-methane gross energy yield (GJ/ha/year) 108.27 increasing the energy output per unit of agricultural land. This effect is
Power-to-methanol gross energy yield (GJ/ha/year) 86.07 greatly enhanced by incorporating power to fuel systems with grass
Power-to-Fischer-Tropsch fuels gross energy yield (GJ/ha/year) 54.86
digestion systems; scenario 3 (compressed biomethane and
a
LHV of diesel assumed for all liquid Fischer-Tropsch fuels. power-to-methane) with a PEF of 0 (curtailed electricity) shows a NER of
4.23.
this paper are similar to values reported in the literature for conven­ While energy analysis of alternative fuel systems is useful, there are
tional gaseous or liquid biofuel production. In a review of net energy many different factors that determine the suitability of an alternative
ratios of renewable fuels, Rana et al. report that biodiesel from rapeseed fuel. Factors such as fuel costs and GHG reduction potential must also be
oil has a NER of between 1.1 and 2.6, while grass biomethane has a NER assessed. One of the limitations of energy analysis is that converting all

11
N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Table 6 sectors, reducing fugitive methane emissions from slurry) must be

PtF system parasitic energy demand. considered.
Hydrogen production parasitic energy demand
Electrolysis energy consumption (kWhe/kgH2) 48.9 4. Conclusions
Power-to-methane hydrogen required (kg/year) 672,854
Power-to-methanol hydrogen required (kg/year) 504,641
Power-to-FT fuels hydrogen required (kg/year) 504,643 The three questions that were raised in the introduction are
Power-to-methane hydrogen production parasitic energy (GJ/ha/year) 191.69 answered as below:
Power-to-methanol hydrogen production parasitic energy (GJ/ha/year) 143.76
Power-to-Fischer-Tropsch fuels hydrogen production parasitic energy (GJ/ 143.76 1. Establish the net energy balance and net energy ratio of compressed
ha/year)
Power-to-methane compression parasitic energy demand
and liquefied biomethane produced from co-digestion of grass and
Methane compression energy consumption (kWhe/Nm3 methane) 0.35 slurry
Power-to-methane production (Nm3CH4/year) 1,870,214
Power-to-methane compression parasitic energy (GJ/ha/year) 3.81 The analysis proposed in this paper examined the energy balance of
Fuel synthesis parasitic energy demand
power-to-fuel technologies integrated with biogas production. The gross
Power-to-methane fuel synthesis electrical consumption (MJ/kgCH4) 1.39
Power-to-methanol fuel synthesis electrical consumption (MJ/ 1.02 energy from a biogas facility co-digesting grass silage and slurry was
kgCH3OH) assessed as 173 GJ/ha/year. The net energy yield of producing com­
Power-to-Fischer-Tropsch fuel synthesis electrical consumption (MJ/ 2.238 pressed biomethane was assessed as 113 GJ/ha/year slightly higher
kgC15H32) than that of liquified biomethane (108 GJ/ha/year). The difference is
Power-to-methane production (kg/year) 1,338,616
Power-to-methanol production (kg/year) 2,673,562
accounted for by the greater energy demand of the liquefaction process.
Power-to-FT fuel production (kg/year) 1,170,405 The net energy ratio of compressed biomethane was calculated as 2.89
Power-to-methane fuel synthesis energy demand (GJ/ha/year) 3.01 again in excess of that of liquefied biomethane (2.67).
Power-to-methanol fuel synthesis energy demand (GJ/ha/year) 4.41
Power-to-FT fuels fuel synthesis energy demand (GJ/ha/year) 4.24
2. Further assess the net energy balance and net energy ratio of the
system integrated with PtF production (power-to-methane, power-
energy inputs and outputs into common units implicitly assume that a to-methanol and power-to-Fischer-Tropsch fuels).
joule of electricity is equivalent to a joule of diesel or a joule of methane.
This is clearly not the case, with oil and gas having a specific set of at­ When the CO2 captured from biogas upgrading was used in power-to-
tributes that set them apart from electricity. As highlighted in previous fuel production, the gross energy of the system increased: 281 GJ/ha/
work from the authors, electricity is highly unlikely to power commer­ year for power-to-methane; 259 GJ/ha/year for power-to-methanol; and
cial aviation or long-distance shipping; sustainable energy-dense fuels 228 GJ/ha/year for power-to-Fischer-Tropsch fuels. However, the net
are required to make these modes of transport climate-friendly [4]. The energy of the system decreased: 23 GJ/ha/year for power-to-methane;
value proposition of electrofuel systems is the production of 51 GJ/ha/year for power-to-methanol; and 20 GJ/ha/year for power-
energy-dense fuels to reduce emissions from difficult to decarbonise to-Fischer-Tropsch fuels. The decrease in net energy is due to the large
sectors and this is not fully captured in an energy analysis assessment. energy demand in hydrogen production for power-to-fuel scenarios,
For integrated AD and PtF systems to be sustainable, the broad which had the most significant impact on the system’s energy balance.
cross-sectoral positive externalities (such as providing electrical grid The net energy ratio for the power-to-methane system was 1.09, and the
stability, producing energy-dense fuels for difficult to decarbonise values for the power-to-methanol and for power-to-Fischer-Tropsch
fuels were 1.25 and 1.1 respectively, indicating that all system

Fig. 5. Summary of system energy balance with PEF = 1. Scenario 1: Compressed biomethane. Scenario 2: Liquified biomethane. Scenario 3: Compressed bio­
methane and power-to-methane. Scenario 4: Compressed biomethane and power-to-methanol. Scenario 5: Compressed biomethane and power-to-Fischer-
Tropsch fuels.

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Fig. 6. Summary of system net energy ratio with PEF = 1. Scenario 1: Compressed biomethane. Scenario 2: Liquified biomethane. Scenario 3: Compressed bio­
methane and power-to-methane. Scenario 4: Compressed biomethane and power-to-methanol. Scenario 5: Compressed biomethane and power-to-Fischer-
Tropsch fuels.

Fig. 7. Breakdown of parasitic energy demand for Scenario 3 (compressed biomethane and power-to-methane).

Fig. 8. Sensitivity analysis of changes in parasitic energy demand for Scenario 3 (compressed biomethane and power-to-methane).
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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Fig. 9. System net energy yield for different sources of electricity. Scenario 3: Compressed biomethane and power-to-methane. Scenario 4: Compressed biomethane
and power-to-methanol. Scenario 5: Compressed biomethane and power-to-Fischer-Tropsch fuels.

Fig. 10. System net energy ratio for different sources of electricity. Scenario 3: Compressed biomethane and power-to-methane. Scenario 4: Compressed biomethane
and power-to-methanol. Scenario 5: Compressed biomethane and power-to-Fischer-Tropsch fuels.

configurations produce more energy than they consume. rationale requires a use of a resource that would otherwise be curtailed;
in essence the electrofuel system must be seen to have a function of a
3. Perform a sensitivity analysis to identify key parameters affecting the biological battery that stores electricity in a time that there is little de­
net energy balance and net energy ratio of the system to gain insights mand for electricity and also changes the energy vector to a fuel that is
into system optimisation. available for hard to abate sectors such as haulage, shipping, or aviation.
It may be the case that the energy balance is secondary to the specifi­
The use of non-renewable or unconstrained renewable electricity cations of the fuel; for example, drop-in quality liquid fuels are essential
impacts negatively on the energy balance of an integrated anaerobic for aviation so it may be irrelevant that compressed biomethane has a
digestion and power-to-fuel system as compared to anaerobic digestion better energy yield than the Fischer-Tropsch process. However, it may
on its own. For an energy benefit it is essential that the electricity be very relevant if road haulage is considered which could avail of
consumed in the power-to-fuel process must include for electricity that compressed methane instead of Fischer-Tropsch diesel. It must be noted
would otherwise be curtailed (PEF = 0). It makes no sense to use fossil that the waxes and gases produced in the Fischer-Tropsch process were
energy in the production of electrofuels (PEF = 2.3). The energy not included in the energy output as this work is concerned with

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Fig. 11. Effect of biogas methane content on system net energy yield for Scenario 3 (power-to-methane) with a PEF of 1.

Fig. 12. Effect of feedstock specific methane yield on system net energy for Scenario 3 (power-to-methane).

advanced transport fuel able to power heavy-duty transport. These Funding

fractions, however, do have the potential to play a role in future circular
economy systems, especially waxes, offering a low-carbon alternative to This work was supported by Science Foundation Ireland (SFI)
lubricants produced form fossil fuel refining. through the MaREI Centre for Energy, Climate and Marine under Grant
The advantages of integrating anaerobic digestion and power-to-fuel No. 12/RC/2302_P2 and 16/SP/3829.
production are wide reaching, and if the system is to be viewed holis­ Richard O’Shea is funded by IDL Pernod Ricard through the MaREI
tically, the positive externalities of the overarching cascading circular Centre.
economy system that are not captured in this energy analysis must be
assessed. Besides producing fuel for hard-to-abate sectors these systems Credit author statement
have co-benefits of improved water quality, reduced fugitive methane
emissions around slurry storage, production of biofertilizer, and facili­ Nathan Gray: Conceptualisation, Formal analysis, Writing – original
tation of variable renewable electricity through reduction in curtail­ draft. Richard O’Shea: Validation, writing-reviewing and editing.
ment. While the analysis presented in this paper is specific to Ireland, the Beatrice Smyth: Validation, writing-reviewing and editing. Piet N.L.
insights gained are independent of geographic location and applicable Lens: Validation, writing-reviewing and editing. Jerry D. Murphy:
more widely. Conceptualisation, Supervision, Funding acquisition, Validation,
writing-reviewing and editing.

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N. Gray et al. Renewable and Sustainable Energy Reviews 155 (2022) 111886

Declaration of competing interest European Union. Appl Energy 2016;170:445–54. https://doi.org/10.1016/j.

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