1 s2.0 S1364032124002405 Main

Renewable and Sustainable Energy Reviews 199 (2024) 114517
Contents lists available at ScienceDirect
Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Green ammonia production using current and emerging

electrolysis technologies
Hossein Nami a, b, *, Peter Vang Hendriksen a, Henrik Lund Frandsen a
a
Department of Energy Conversion and Storage, Technical University of Denmark (DTU), Building 310, Fysikvej, DK-2800, Lyngby, Denmark
b
SDU Life Cycle Engineering, Department of Green Technology, University of Southern Denmark, Campusvej 55, 5230, Odense M, Denmark
A R T I C L E I N F O A B S T R A C T
Keywords: This study investigates utilizing hydrogen produced via water electrolysis to produce green ammonia. Routes are
Green ammonia benchmarked based on employing either alkaline electrolysis (AEC) or solid oxide electrolysis (SOEC). Both
Blue ammonia existing and possible improvements are modeled for the AEC and SOEC technologies coupled with the Haber-
Green hydrogen
Bosch process to synthesize ammonia. The cost of green ammonia is estimated considering the cost of electro
Power-to-ammonia
Pressurized SOEC
lyzers for both today and future projections and are compared with that of "fossil" ammonia synthesized from
High-temperature alkaline electrolyzer natural gas. Threshold CO2 taxes required to achieve cost parity between green and "fossil" ammonia are
determined based on the price of natural gas and the levelized cost of electricity. It is found that whereas the
green ammonia produced from a system based on AEC is cheaper today, SOEC shows to be more cost-effective,
when basing the comparison on the projected future cost of the electrolyzers. Green ammonia from an SOEC-
based plant is estimated to have accost of 495 €/t by 2050 with an assumed electricity price of 30 €/MWh. In
the SOEC-based ammonia plants, approximately 57 % and 31 % of the steam needed for the electrolyzers can be
generated through heat integration between the electrolyzer and Haber-Bosch process, for low-pressure and
high-pressure electrolyzers, respectively. A good fraction of the heat can also be covered by the intercoolers of
the compressors. With the projected cost for SOEC, reducing the levelized cost of electricity from 60 to 10
€/MWh would decrease the cost of green ammonia from 690 to 340 €/t by 2050.
interest in green ammonia production. Compared with hydrogen,

ammonia has some advantages. It is much easier to liquefy and store at
1. Introduction
higher temperatures (− 33 vs. − 253 ◦ C at ambient pressure) and its
transport is at least three times cheaper than hydrogen [4]. Besides,
The chemical industry and the transportation sector will have to
ammonia can be used in internal combustion engines [5] and gas tur
transition to green routes to produce high-demand chemicals like
bines [6] with modest modifications of the core technology. The lev
ammonia to align with climate policy targets. Ammonia is an extremely
elized cost of electricity (LCOE) from green ammonia in large-scale
important chemical used in the fertilizer industry. It has also garnered
power plants (combustion in combined cycle gas turbines) is forecasted
interest as a green fuel for shipping [1], as well as an energy storage
by Cesaro et al. [7]. They found that at power plant capacity factors
medium capable of overcoming hydrogen storage challenges [2]. Green
below 25 % (increasingly common in electricity sectors with high var
ammonia production is not a new concept, as it has been implemented
iable renewable electricity), the cost of ammonia should be below 400
since the late 1920s until the 1990s in Norway, utilizing AEC as a green
USD/tNH3 to effectively compete with other dispatchable, low or
hydrogen pathway powered by hydropower [3]. However, the economic
zero-carbon technologies, including gas, bioenergy, or coal-fired power
attractiveness of fossil hydrogen produced from natural gas through
plants equipped with CCS. In addition, published research works in the
steam methane reforming (SMR) has made it a preferred choice for
last years suggest ammonia as the future marine fuel [8,9]. Many in
ammonia production in most locations and for volume production.
vestigations exist in the literature addressing the green ammonia econ
Nonetheless, the mounting environmental concerns, advancements in
omy and technology readiness. Some of the relevant published works are
water electrolysis technologies, and the significant cost reduction in
reviewed hereunder.
renewable electricity over the past decade have reignited substantial
* Corresponding author. Department of Energy Conversion and Storage, Technical University of Denmark (DTU), Building 310, Fysikvej, DK-2800, Lyngby,
Denmark.
E-mail address: hon@igt.sdu.dk (H. Nami).
https://doi.org/10.1016/j.rser.2024.114517
Received 11 September 2023; Received in revised form 26 April 2024; Accepted 1 May 2024
Available online 10 May 2024
1364-0321/© 2024 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
H. Nami et al. Renewable and Sustainable Energy Reviews 199 (2024) 114517
Nomenclature M molar mass (kg/kmol)

ṁ mass flow rate (kg/s)
Abbreviationss n number of electrons
AEC alkaline electrolysis ṅ mol flow rate (kmol/s)
ASU air separation unit N number
Comp compressor P pressure (bar)
Cond condenser Pr compressor pressure ratio
Dist distillation column Q̇ heat transfer rate (kW)
ELH electrical heater R gas constant (kJ/kmol K)
HBL Haber-bosch loop s entropy (kJ/kmol K)
HEX heat exchanger SUF steam utilization factor
HT-SOEC high-temperature atmospheric SOEC T temperature (K)
HTP-AEC high-temperature pressurized AEC Ẇ power (kW)
LT-SOEC low-temperature atmospheric SOEC
LTP-AEC low-temperature pressurized AEC Greek letters
MIX mixer η overpotential (V)
SOEC solid oxide electrolysis δ thickness (m)
SPL splitter γ pre-exponential factor (1/s)
ψ resistivity (Ω)
Latin letters
A heat transfer area Subscripts
EL economic life a anode
CAPEX capital investment cost ($) act activation
CF capacity factor c cathode
CRF capital recovery factor conc concentration
Deff effective diffusion coefficient (m2/s) cv control volume
e specific physical exergy (kJ/kmol) D destruction
E potential (V) e electrolyte
Ė exergy rate (kW) hf hot flow
F Faraday constant (C/mol) i inlet
G Gibbs free energy (kJ/mol) o outlet
h specific enthalpy (kJ/kmol) ohm ohmic
H enthalpy (kJ) ph physical
i interest rate (%) r reversible
J current density (A/m2) ref reference
J0 exchange current density (A/m2) tn thermo-neutral
LCOE levelized cost of electricity 0 ambient conditions
Campion et al. [10] conducted a techno-economic assessment of kgCO2/kgNH3 when natural gas, syngas and biogas are used as feed
green ammonia production, considering diverse wind and solar poten stock, respectively. Biomass-based ammonia can be considered carbon
tials, weather profiles, and electrolyzer technologies. Optimization neutral due to the renewable character of the feedstock. However, it is
findings indicated that employing a semi-islanded configuration stands important to be aware that biomass availability may become limited in
out as the most cost-effective choice, potentially resulting in cost re future energy systems [13].
ductions of up to 23 % when compared to off-grid systems. However, it is Zhang et al. [14] investigated and compared various ammonia pro
found that this approach leads to greenhouse gas emissions comparable duction routes, including power-to-ammonia, biomass-to-ammonia, and
to those of using fossil fuels for ammonia production when considering methane-to-ammonia. The study concludes that power-to-ammonia
the current electricity mix. When evaluating off-grid systems, the represents the most efficient route, boosting LHV-based efficiency to
practice of estimating costs based on the levelized cost of electricity and 74 % (Mass flow Total
rate of produced ammonia×LHVNH3
) but it is currently not econom
consumed electricity
capacity factors for solar or wind sources (which in turn determines ically attractive due to the high cost of electrolyzer stacks and high
operating hours) resulted in an overestimation of costs by as much as 30 electricity prices. Nevertheless, it has the potential to become
%. The most economical off-grid setup has attained a production cost of cost-competitive if the stack cost can be reduced to 920 $/m2. Bicer and
842. €/tNH3. Islanded green ammonia and hydrogen production and Dincer [15] compared the feasibility of nuclear-driven SOEC and
export from Saudi Arabia is optimized by Florez et al. [11]. Their results copper-chlorine cycle as green hydrogen routes to produce ammonia. It
showed that plant optimization can lead to production costs of ammonia was found that employing electrolyzers has a lower environmental
of 383 USD/tNH3, while the single largest cost driver is the electricity impact than the copper-chlorine cycle (460 vs. 580 tCO2 eq per tNH3).
cost, representing 60–70 % of the total project cost. Ammonia as a hydrogen storage carrier was studied by Al-Zareer
Frattini et al. [12] evaluated three distinct pathways for green et al. [16]. The hydrogen storage system was proposed to chemically
ammonia production. These routes were benchmarked against the pro store hydrogen as ammonia, which was pressurized in a multistage
duction of fossil ammonia through steam methane reforming and ammonia production system. The produced ammonia was stored in a
involved the utilization of renewable hydrogen obtained through SOEC, novel conceptual design of an ammonia tanker truck equipped with an
biomass gasification, and biogas reforming. They found that all the ammonia electrolyzer for the transportation and delivery of the stored
systems have the same energy consumption of 14–15 MW/tNH3. The hydrogen. It has been assumed that the tanker truck can either provide
CO2 equivalent emissions are estimated to be 2.05, 3.82 and 3.59 the ammonia to end-users who decompose the ammonia later when they
2
need the hydrogen or deliver hydrogen directly produced from ammonia that the addition of tidal stream capacity to wind capacity decreases the
decomposition. The proposed system demonstrated energy and exergy hydrogen storage requirement by 96 % and reduces the cost of ammonia
efficiencies of 72.3 % and 71.8 %, respectively. by 12 %.
SOEC-based green ammonia production using nitrogen generated via Table 1 summarizes the rest of the reviewed works, all dealing with
a series of solid electrolyte oxygen pumps was studied by Nowicki et al. different electrolysis options and different sources of renewable
[17]. Solid electrolyte oxygen pumps are devices that leverage the electricity.
movement of oxide ions within dense electrolyte materials to achieve The literature review highlights the extensive research on techno-
the separation of oxygen from gas mixtures (here air). The specific en economic assessment conducted on various aspects of green ammonia
ergy consumption was found to be 9.9 kWh/kgNH3 (efficiency of 52.1 production, particularly concerning existing technologies. However, it is
%). Scaling options for the trade of green ammonia are studied by Egerer crucial to acknowledge the rapid advancements in electrolysis and
et al. [18] assuming the import of ammonia from Australia to Germany ongoing investigations into modifying existing technologies. Conse
in 2030 as the case study. With the production costs of 30.43 €/MWh quently, considering the projected future cost developments is of para
electricity supply in Australia, the levelized cost for green ammonia at mount importance for effective energy planning and policy-making.
the German harbor is calculated to be 109.39 €/MWh (566.64 €/t). They In this work, the existing AEC and SOEC technologies are compared
concluded that green ammonia could achieve cost parity with natural at their current maturity level, addressing projections for future de
gas-based ammonia, even at moderate gas prices (around 30 €/MWh), velopments through a comprehensive thermodynamic and techno-
given a sufficiently high CO2 tax (approximately 180 €/tCO2). They also economic analysis of green ammonia plants designed based on these
indicated that cracking ammonia to generate pure hydrogen introduces two technologies. To investigate the effect of various potential techno
a 45 % cost increase per MWh at the destination. The impact of climate logical advancements for both AEC and SOEC, high-pressure AEC is
change on the cost of production of green ammonia from offshore wind modeled in both low-temperature (LTP-AEC) and high-temperature
at four locations in the UK was studied by Hattonet al. [19]. Using an (HTP-AEC) versions, and SOEC is modeled considering both low-
islanded green ammonia production model, the achievable cost of pressure (LP-SOEC) and high-pressure (HP-SOEC) technologies.
ammonia was evaluated to range between 935 and 1696 USD/tNH3. Furthermore, an estimation of the future cost of green ammonia,
Driscoll et al. [20] evaluated offshore green ammonia production using incorporating the current and projected capital expenditure (CAPEX)
tidal and wind energy from techno-economic perspective. They found values of electrolysis technologies is included considering different
Table 1
Literature review of green ammonia production.
Reference Energy source H2 route LCOE (Min) ammonia (Max) System Remarks on main findings and key assumptions
cost efficiency (%)
[21] Solar + Wind AEC Solar: 26.7 500 $/t na Green power variability is the major cost driver for green NH3
$/MWh production.
Wind: 35.8 The estimated near-term ammonia price (below 500 $/t) is
$/MWh comparable with the market price of 300–600 $/t of imported NH3
from SMR in Chile.
[22] Solar PEMECa na na 26b,d The system has a capacity of 0.22 kg/s ammonia production from
0.04 kg/s H2 and 0.18 kg/s N2
The electrolyzer is the most exergy-destructive unit of the integrated
system.
[23] Solar + Wind + PEMEC 18 €/MWh – na A sensitivity analysis is carried out concerning electricity price, plant
hydraulic dams operating hours, size of the system, estimated CAPEX, and ammonia
market price.
A payback period of 7.6 years is estimated.
NH3 production in Chile and transferring to Japan as an H2 carrier
solution would be profitable and technically viable.
[24] Solar AEC & na 718 $/t 37.4 Energy consumption of 10.43 kWh/kgNH3 is reported.
PEMEC Further reductions in the cost of ammonia are postulated under the
expected technical advancements reaching 450 $/ton
[25] Solar PEMEC na na 16d During the low demand period, extra power produced by the
photovoltaic is utilized to synthesize ammonia and during the peak
demand period, the ammonia is fed to the fuel cell to generate power
[14] na SOEC 73 $/MWh >550 $/t 74 % It is concluded that power-to-ammonia is currently not competitive
with biomass-to-ammonia routes.
[26] Solar + Wind + PEMEC na 431-528 €/t na Power-to-ammonia technology can be cost-competitive if the natural
hydropower gas price or CO2 tax increases to 0.07 €/kWh or 200 €/tCO2,
respectively.
[27] Solar PECc na 840 $/t 5–9.6d The cost of electricity is estimated to be 60 $/MWh.
(exergy A 10 % increase in operating capacity factor and a 10 % decrease in
efficiency) total CAPEX decreases the ammonia cost by 80 and 20 $/t,
respectively.
[28] na AEC/ 0-60 174-1000 $/t na Fixed values of 61.0, 64.4, and 42.6 kWh/kgH2 are assumed for AEC,
PEMEC/ $/MWh PEMEC, and SOEC, respectively.
SOEC
[29] PV + Onshore PEMEC PV: 31–46 723 €/t for na India’s green ammonia potential can supply global ammonia demand
wind €/MWh domestic usage in Currently, a CO2 tax of 224–335 €/tCO2 is required to compete with
Wind: India conventional fossil ammonia
66–233 765 €/t for export
€/MWh
a
Proton Exchange Membrane Electrolyzer.
b
with solar radiation of 0.2 kW/m.2.
c
photoelectrochemical water splitting.
d
This is solar energy to ammonia efficiency.
3
OPEX values based on LCOE-estimates for the powering technologies. (ohmic, activation and concentration) balances the heat needed for the
This analysis not only offers insights into anticipated costs but also water splitting reaction. Part of the thermal energy required to produce
provides a valuable tool for comparing the advantages of different steam (at the stack operating temperature) can be supplied from the
technology improvements. The main findings of this study are related to HBL. Maximizing the heat integration between SOEC and HBL mini
the electrolyzers’ technical characteristics, the implications of which are mizes electricity consumption by the electrical heaters and increases the
reflected in the economic analysis of green ammonia production. It is overall power-to-ammonia efficiency.
important to note that while this study provides general insights, a more To consider the possibility of selling the oxygen as a by-product and
detailed economic analysis tailored to specific locations and their to protect the electrode through start-up and thermally managing the
respective local conditions (such as LCOE and capacity factors) is stack, part of the generated oxygen is recirculated with an outgoing
necessary to achieve solid results on green ammonia cost and conditions bleed instead of sweeping air [32]. However, the recirculation of hot
where it can become cost-competitive. These site-specific considerations pure oxygen is a safety challenge that has to be addressed (requiring
may alter some of the economic conclusions presented here, and the industrial protocols to be developed). It imposes stringent material re
economic assessments presented here should be considered as guidance quirements on the construction materials used in the oxygen loop. It
rather than definitive conclusions. The technical results presented here should be noted that this assumption has a minimal impact on the
can of course be transferred to an economic analysis for a specific site. assessed efficiencies and costs, as the power consumption of an alter
native air blower would be extremely low compared with other
2. Theoretical analysis and model description components.
The chemical reactions at the fuel (cathode), at the oxygen (anode)
2.1. System development and mathematic modeling electrodes of the cell, and the overall reaction are as follows:
Cathode:
The main units of the proposed green ammonia production systems H2 O + 2e− → H2 + O− −
(1)
are the electrolyzer (SOEC or AEC), the Haber-Bosch loop (HBL), and the
air separation unit (ASU). Each unit is described and modeled individ Anode:
ually at the component level, except the ASU for which data reported in
O2− → 0.5O2 + 2e− (2)
the literature is used [26]. Based on Morgan [30], an energy consump
tion of 108 kWh/tN2 is assumed for the ASU, delivering pure N2 at 8 bar. Overall:
H2 O → H2 + 0.5O2 (3)
2.1.1. Electrolysis technologies
The electrolysis systems examined in this study, all based on AEC and The cell voltage, ESOEC, can be calculated as follows [33]:
SOEC technologies, are detailed in Table 2 in terms of operating con ( )
ESOEC = Er − ηact,a + ηact,c + ηconc,a + ηconc,c + ηohm (4)
ditions. While these technologies are known, certain extensions pro
posed in this study surpass the current state-of-the-art for scalable
where, the reversible potential, Er , can be obtained by the Nernst
systems. Notably, HTP-AEC, validated at technology readiness level 3,
equation [34]. ηohm , ηconc , and ηact are the ohmic overpotential, con
and HP-SOEC, demonstrated at technology readiness level 4–5, exem
centration overpotential, and activation overpotential, respectively.
plify advancements beyond conventional applications [31].
Table 3 lists the equations utilized to calculate these quantities. More
details about SOEC modeling and cell performance validation can be
2.1.1.1. Solid oxide electrolysis (SOEC). SOEC performs efficiently
found in the Appendix.
compared with other available electrolyzers, especially when there is a
Finally, the generated hydrogen, (ṅH2 )SOEC , and SOEC power con
heat integration between the electrolyzer and HBL. Part of the required
sumption, ẆSOEC , can be written as:
external heat for water splitting can be supplied from waste heat sources
available in the HBL to increase the overall system efficiency. J
(ṅH2 )SOEC = (5)
A schematic diagram of a stand-alone SOEC is shown in Fig. 1. The 2F
system utilizes two heat exchangers, HEX1 and HEX2, to effectively J is the current density and ṅH2 the hydrogen production rate per cell
recover the waste heat from the stack off-gas. However, to achieve the cross-sectional area.
desired stack inlet temperature and provide the necessary external heat
during startup, auxiliary electrical heaters, ELH1 and ELH2, are ẆSOEC = ESOEC JAcell Ncell (6)
employed. To maintain a hydrogen mole fraction of 10 % in the inlet
flow, a portion of the cathode off-gas is recirculated, while the where, Acell and Ncell are the active cell area and number of the cells in a
remaining flow passes through HEX1 and enters the condenser, COND, stack, respectively.
where it undergoes cooling and water separation. The resulting pure
hydrogen can then be combined with nitrogen and supplied to the HBL. 2.1.1.2. Alkaline electrolysis (AEC). Currently, AEC is the primarily
The stack is assumed to be operating at the thermoneutral point. The employed technology for large-scale green hydrogen production, as it is
thermo-neutral point is where the current density is raised to the extent the most developed and mature electrolysis technology [41]. However,
that the internal resistive heating from various internal resistances relatively high internal cell resistance decreases the overall efficiency of
the system. For AEC, the optimum operating point can be determined
Table 2 through a balance between CAPEX and OPEX, as shown in Ref. [31].
Different electrolysis systems modeled in this study. This study investigates two AEC technologies. Currently, high-
Technology Naming Operating conditions
pressure low temperature (~80 ◦ C) AEC is being commercialized and
scaled up. Operation at high pressure improves the efficiency, as bubble
AEC LTP-AEC Stack is operating at 80 ◦ C
formation is retarded and the internal resistance in this way can be kept
Hydrogen is produced at 30 bar
HTP-AEC Stack is operating at 200 ◦ C down [42,43]. Bubble formation and transportation results in extra
Hydrogen is produced at 30 bar losses [42]. Not only the gas dissolution but also the blocking of the
SOEC LP-SOEC Hydrogen is produced at 1 bar reaction site with the gas phase between the electrolyte and electrodes
Stack is operating at 700–800 ◦ C leads to increased resistance. The oxygen evolution process, however,
HP-SOEC Hydrogen is produced at 30 bar
Stack is operating at 700–800 ◦ C
still causes high internal resistance. Increasing the temperature to
4
Fig. 1. Schematic diagram of SOEC system.
Table 3
SOEC modeling equations.
Description Governing equation
( )
Open-circuit voltage (OCV) ΔG RT PH2 P0.5
O2
[35] Er = + ln
nF nF PH2O Po.5
ref
Gibbs free energy [36] ΔG = − 0.0031T2 − 49119T + 244778
[ ( ) (
Butler-Volmer (BV) [37] nFηact,a/c (
J = J0,a/c exp − αa/c − exp − 1 −
RT
)]
) nFηact,a/c
αa/c
RT
( ) ( )
Anode exchange current PO2 m − Eact,a
J0,a = γa exp
density [37] Pref RT
Cathode exchange current ( ) ( ) ( )
PH2 a PH2O b − Eact,c
density [37] J0,c = γc exp
Pref Pref RT
(( )0.5 )
Anode concentration RT xIO2
overpotential [38] ηconc,a = ln
2F x0O2
( I 0 )
Cathode concentration RT xH2 xH2O
ηconc,c = ln 0 I
overpotential [38] 2F xH2 xH2O
( )
Ohmic overpotential [37] T Eact,ohm
ηohm = J exp
Bohm RT
Dusty-gas model (DGM) fluxes N1 x2 N1 − x1 N2 1
+ = − (P∇x1 + x1 ∇P + x1 ∇
[39] D
eff
D
eff RT
1K 12
kP
P) eff
D1K μ
N2 x1 N2 − x2 N1 1
+ = − (P∇x2 + x2 ∇P + x2 ∇
eff
D1K D12
eff RT
Fig. 2. Schematic diagram of a simplified AEC system.
kP
P) eff
D2K μ
Binary diffusion coefficient 0.00143T1.75 2
Chemical reactions in the cathode and anode sides of the cell and the
Dij = )2 ; Mij = − overall reaction are as follows:
[40] (
1/3 Mi 1 + M−j 1
Vi 1/3 + Vj
PM0.5
ij
√̅̅̅̅̅̅̅̅̅ Cathode:
Knudsen diffusion coefficient dp 8RT
[36] Dik = 2H2 O + 2e− → H2 + 2OH− (7)
3 π Mi
Effective diffusion coefficient eff,a/c
Dij
a/c
= kD,eff Dij
a/c
Anode:
2OH− → 0.5O2 + H2 O + 2e− (8)
150-200 C can significantly lower the overpotential needed for this.
◦
Overall:
This is done in the high temperature, high-pressure alkaline technology
(HTP-AEC). H2 O → H2 + 0.5O2 (9)
The operating load current density for both AEC technologies is
The required cell voltage for this electrochemical reaction can be
assumed to be around 0.5 A/cm2, which is higher than the thermo
determined by the cell thermodynamics as follows:
neutral point for the current technologies. Therefore, both LTP-AEC and
HTP-AEC operate under exothermic conditions. ΔG = ΔH- TΔS (10)
Fig. 2 illustrates the flow diagram of AEC. HEX1 and HEX2 are used
for cooling to keep the stack inlet temperature fixed at the operating here, ΔG is the change in Gibs free energy of the reaction, ΔH the
temperature. reaction enthalpy and ΔS the reaction entropy.
5
In this research, the polarization curve reported by Green Hydrogen Table 4

Systems [44] is used to represent the state-of-the-art performance of a Input data and assumptions considered to model the HBL [47].
LTP-AEC system. For HTP-AEC, in-house data from the EEEHy project Parameter Value Parameter Value
[45] have been used. More details about the data utilized for both LTP-
First bed inlet temperature 310 First bed inlet temperature ( C)
◦
380
and HTP-AEC modeling can be found in Ref. [31]. (◦ C)
The rate of produced hydrogen and power consumption by the AEC Reactor operating pressure 200 Compressor isentropic efficiency 80
are as follows: (bar) (%)
First bed conversion (%) 20.7 Reactor pressure drop (bar) 1.5
J Second bed conversion (%) 6.5 Minimum temperature approach 10
(ṅH2 )AEC = (11)
2F (◦ C)
Third bed conversion (%) 7.2 Separator operating temperature 40
ẆAEC = EAEC JAcell Ncell (12) (◦ C)
Feed stream H2:N2 molar 3:1 Heat exchanger effectiveness (%) ≤90
ratio
Where J is the current density running through the electrolyzer, EAEC the
cell potential, Acell the cell area and Ncell the number of cells.
k1 = 1.79 × 104 e− 87090/RT

(15)
2.1.2. Haber-Bosch loop (HBL)
Haber-Bosch loop is the primarily used industrial process of k2 = 2.75 × 1016 e− 198464/RT
(16)
ammonia production, which utilizes a mixture of hydrogen and nitrogen
as feedstock to synthesize ammonia at temperatures around 450–600 ◦ C where P is the partial pressure of the compound (bar), R the universal
and pressures higher than 100 bar [46]. gas constant (J/mol K), ρcat the catalyst density (kg/m3), f a correction
Fig. 3 shows the flow diagram of the HBL at the system level. In this factor (4.75), k1 and k-1 the pre-exponential factors for the forward and
research, the HBL was modeled based on the study performed by Flórez- reverse reaction paths, respectively. KMR 111 is assumed as a pre-
Orrego et al. [47] for large-scale ammonia production. As the figure reduced iron-based ammonia synthesis catalyst with a density of
shows, the ammonia synthesis plant consists of a three-bed reactor 2474 kg/m3 [48].
equipped with a heat exchanger to transfer heat between the first bed
inlet and outlet flows and two heat recovery steam generators (HRSG) 2.2. System efficiency
after the second and third beds to produce steam. In addition, the waste
heat of the compressor intercoolers is utilized to produce steam or The LHV-based efficiency of the entire system can be written as:
preheat the feed water for electrolysis. The inlet temperature of each bed
should be high enough for the reaction to proceed fast but not to the ṁNH3 LHVNH3
η= (17)
point where the conversion is limited by equilibrium. Flórez-Orrego Ẇtotal
et al. [47] have optimized the performance of the HBL by tuning the
inlet bed temperature of each bed for the specific syngas compositions. where ṁNH3 is the produced green ammonia mass flow rate (kg/s),
To achieve a higher ammonia conversion per pass, they divided the LHVNH3 is the lower heating value of ammonia (kJ/kg) and Ẇtotal is the
reactor into three sequential catalyst beds with intercooler. Table 4 total consumed power by the system (kW), including electrolyzer, air
outlines the assumptions and input data considered in the HBL separation unit, electrical heaters, compressors and pumps.
modeling.
The following reaction, which occurs at higher temperatures 3. Techno-economic analysis
(~300–600 ◦ C) in the presence of appropriate catalysts, describes the
ammonia synthesis: To conduct the economic analysis, the required initial investment
/ cost; as the capital expenditure (CAPEX) of each individual component is
1 3
N2 + H2 → NH3 ΔH0 = − 45.64 kJ mol (13) estimated together with maintenance and manufacturing costs.
2 2
Manufacturing costs are the costs incurred during the production of a
The reaction rate of ammonia synthesis over a catalyst can be product. These costs include direct (labor costs, direct supervisory and
expressed as follows [14]: clerical labor and laboratory charges) fixed (local taxes and plant
( ) overhead) and general (distribution, R&D and administration)
2f PN2 P1.5 PNH3 manufacturing costs. The most frequently utilized cost functions in the
rNH3 = k1 H2
− k− 1 1.5 (14)
ρcat PNH3 PH2 literature are considered for the employed components to estimate the
Fig. 3. Flow diagram of the HBL.
6
overall system CAPEX, as detailed below.

amortized CAPEX = CRF × (CAPEX + PVSRC ) (19)
Different expenses can be found in the literature for electrolyzers.
Common is, however, that the electrolysis stack cost is expected to drop CRF is the capital recovery factor and is defined as:
significantly over the years. This is due to the expected development of
electrolysis technologies and, in particular, the expected cost reductions i(1 + i)EL
CRF = (20)
from mass manufacturing. SOEC with the lowest maturity is expected to (1 + i)EL − 1
experience the highest relative cost reduction [49]. It is generally
assumed that the HBL plant and ASU are mature technologies and are where, EL is the system economic lifetime.
not expected to undergo significant changes in terms of CAPEX in the In addition to estimating the amortized CAPEX, it is necessary to
foreseeable future. estimate the OPEX of the system in terms of €/year. This should include
Here, literature values are used to estimate the cost of AEC and SOEC costs related to electricity consumption, maintenance of the entire sys
in 2020, 2030, and 2050. The chosen base case values are listed in tem, and manufacturing costs. The annual maintenance cost is assumed
Table 5. More details about the CAPEX estimation for AEC and SOEC and to be 2 % of the whole system CAPEX [21]. Manufacturing costs are
their stack replacement cost can be found in Ref. [31]. adopted from Reference [53], consisting of direct, fixed and general
Also, it is assumed that the entire CAPEX of a HP-SOEC is 20 % higher manufacturing costs. Direct manufacturing cost mainly depends on the
than a LP-SOEC [31]. The reason is that more robust pipes and vessels number of operators per shift (NOL) which is a function of the number of
will be used to withstand the higher pressures. processing steps involving the handling of particulate solids and the
No cost prediction is available for HTP-AEC by 2020, as this tech number of nonparticulate processing steps. More details can be found in
nology is not yet established. However, it is assumed that this technol Reference [53]. Details of manufacturing costs and the rest of the inputs
ogy will be developed by 2030 and follow the same CAPEX trend as the utilized in the techno-economic assessment are listed in Table 6. The
SOEC technology. Both technologies rely on ceramic cells, and coatings evaluated CAPEX for electrolyzers encompasses comprehensive
and special steels are needed to withstand the corrosive environments. turn-key prices, including manufacturing, engineering, piping, pro
After estimating the CAPEX of the entire system, the present value curement, construction, contingencies, financing, and other relevant
(PV) of future monetary transactions, specifically the cost of stack factors. Consequently, the electrolyzer CAPEX is subtracted from the
replacement, is calculated as follows [52]: overall gross initial cost (CAPEXtotal in Table 6) to estimate the
manufacturing expenses.
SRC Once the amortized CAPEX and annual OPEX of the system have
PVSRC = (18)
(1 + i)m been estimated, the cost of green ammonia can be determined using the
following equation:
where SRC is the stack replacement cost at the end of the mth year and i
is the annual interest rate. In this way, the present value of stack amortized CAPEX + OPEX = (annually produced NH3) × cost of
replacement cost can be calculated and considered as part of the initial NH3 (21)
CAPEX for the electrolyzer.
After estimating the required CAPEX for the entire system and the
present value of the stack replacement cost, the amortized CAPEX can be
expressed in terms of €/year as follows:
Table 5
Table 6
Cost functions of the main components. The costs of the electrolysis units are
Input data for the economic analysis.
“tun key” estimates at plant level and includes thus balance of plant components
and additional costs as outlined in Ref. [31]. Parameter Value
Component CAPEX [unit] Condition Reference SOEC stack replacement cost (% CAPEX) [31] 2020: 23.5
2030: 13.5
LP-SOEC 2020: CAPEXSOEC = 2.770 For a reference [31] 2050: 9.5
[M€/MW] load current AEC stack replacement cost (% CAPEX) [31] 2020: 50
2030: CAPEXSOEC = 1.140 density of J = Jtn 2030: 48
[M€/MW] (ca. 0.96 A/cm2 for 2050: 44
2050: CAPEXSOEC = 0.400 LP-SOEC and 1.25 SOEC Stack lifetime (year) [31] 5
[M€/MW] A/cm2 for HP- AEC Stack lifetime (year) [31] 10
SOEC) LCOE (€/MWh) 10–60
LTP-AEC 2020: CAPEXAEC = 0.840 For a reference [31] EL (year) 25
[M€/MW] load current Plant capacity factor (plant operation hours in 8760 h) (%) 50
2030: CAPEXAEC = 0.700 density of J = 0.5 Average € to $ exchange rate 1.12
[M€/MW] A/cm2 i (%) 8
2050: CAPEXAEC = 0.300 Manufacturing cost [53]:
[M€/MW] Direct manufacturing cost (€/year):
HEX
( ) – [50]
AHEX 0.78 - Labor cost (COL) 68000 × 4.5 × NOL
CAPEXHEX = C1 [€]
0.093 (NOL is the number of
C1 = 110
€ operators per shift)
0.78
(m2 ) - Direct supervisory and clerical labor 0.18 × COL
HBL CAPEXHBL = 3 [M€/(tNH3/h)] – [26] - Laboratory charges 0.15 × COL
ASU CAPEXASU = 1.45 [M€/(tN2/h)] – [26] Fixed manufacturing cost (€/year):
Cond CAPEXCOND = C2 ṁhf [€] – [51] - Local taxes 0.032 × CAPEXtotal
€ - Plant overhead 0.708 × COL + 0.036
C2 = 1500
(kg/s) × CAPEXtotal
Comp C3 ṁg ηis = 0.8 [52] General manufacturing cost (€/year):
CAPEXCOMP = rp ln(rP )
C4 − ηis - Distribution 0.11 × COL
[€] - R&D 0.05 × COL
€ - Administration 0.177 × COL + 0.009
C3 = 60 & C4 = 0.9
(kg/s) × CAPEXtotal
7
4. Results and discussion difference. One could also operate with the oxygen at the same pressure
as the H2, but this case was not treated here.
4.1. System layouts The electrical heater 1 (ELH1) vaporizes the remaining feed water
and/or superheats the generated steam up to electrolyzer operating
Figs. 4 and 5 show the green ammonia producing systems designed temperature. Although the SOEC plant operates at the thermoneutral
based on AEC and SOEC, respectively. Current densities of 0.5 A/cm2 point, ELH1 and ELH2 are needed to compensate for the slight amount of
and the one corresponding to the thermoneutral point are assumed for heat that is lost in waste heat recovery from SOEC off-gas. For start-up
AEC and SOEC, respectively. The operating conditions and the technical conditions, ELH1 supplies all the required energy to produce steam
parameters of the HBL and ASU are the same for all systems. This and heat up the system.
baseline enables a consistent comparison between the different routes
for hydrogen generation of each process concept. 4.2. Thermodynamic results
In Fig. 4, the AEC and HBL are connected such that the produced
hydrogen is combined with nitrogen and sent to the HBL. A multi-stage An overview of the technical results obtained from the detailed
compressor (COMP1) equipped with intercoolers is modeled to pres thermodynamic analysis of each system is shown in Table 7. The systems
surize the HBL feedstock. During steady-state operation, the HTP-AEC are designed to produce 430 kton green ammonia per year under steady-
operates under exothermic conditions and there is no need for heat state conditions. In Table 7, the results are normalized to be per pro
integration (rather, there is a need for cooling or extracting waste heat to duced ton of ammonia, as no non-linear scaling effects enter the models.
be sold if possible). Referring to this table, the system equipped with HTP-AEC performs
Fig. 5 shows the layout of the SOEC-based green ammonia plant. The more efficiently than the system designed based on LTP-AEC. The ben
main difference with the AEC-based plant is that here there is a heat efits of HTP-AEC compared with LTP-AEC include enhancing the rates of
integration between SOEC and the HBL. The following couplings have electrochemical reactions at the electrode surfaces and increasing the
been made. ionic conductivity of the electrolyte, which results in low power con
sumption by the electrolyzer and higher system efficiency.
• Waste heat from the multi-stage compressor (COMP1) intercoolers is SOEC is more efficient than AEC, but especially the heat integration
utilized to generate steam for the LP-SOEC system in the preheater between SOEC and HBL leads to efficiency improvement.
(PH). However, the heat from the intercoolers will only be able to Increasing SOEC pressure decreases the heat generated by the com
preheat the feed water (without vaporizing it) for the HP-SOEC pressors and, as a result, the heat from the intercoolers. Thus, ELH1
system, as evaporation occurs at 234 ◦ C (saturated steam at 30 bar). requires more power (0.21 MWh/tNH3 more power than the system
• The heat content in the reactor off-gas (REAC2 and REAC3) is also designed based on LP-SOEC), which is counted in the operation of the
used to evaporate part of the feed water using the heat recovery electrolyzer unit. Thus, the electrolyzer appears less efficient in Table 7.
steam generator 1 and 2 (HRSG1 and HRSG2). However, the needed power for the HBL feedstock pressurization is
• Furthermore, the heat content in the SOEC plant off-gas is utilized to reduced by 0.29 MWh/tNH3 compared to the LP-SOEC system. Thus,
vaporize any remaining water in the feed and to superheat the these two have “opposing” effects on the entire system’s efficiency.
generated steam if possible. Eventually, the system designed based on HP-SOEC has slightly higher
efficiency than that designed based on LP-SOEC.
For the pressurization, it should be noticed that the cathode (or fuel) Results from the modeling reveal that in the systems designed based
side of the SOEC in this study is pressurized to obtain a lower open on LP-SOEC and HP-SOEC, around 57 % and 31 % of the required steam
circuit voltage as compared to pressurizing both oxygen and fuel sides. could be produced by heat integration with the HBL; 1.43 and 0.77 ton
As reported in Ref. [54], there is little difference between single-sided of steam at SOEC operating pressure per ton of produced ammonia,
and double-sided pressurization as the single-sided mode hinders the respectively.
OCV increase and reduces the ASR. This would eventually lead to a more
efficient system, as the generated oxygen is not pressurized and hence 4.3. Cost breakdown results
there is no efficiency penalty via an increased electromotive force (EMF)
of the cell. It is assumed that the stacks can tolerate the imposed pressure It is worth noting that the results associated with techno-economic
Fig. 4. AEC-based green ammonia plant.
8
Fig. 5. SOEC-based green ammonia plant.
analysis only estimate green ammonia cost now and in the future under decrease due to operating efficiently and the anticipated CAPEX
specific assumptions and cannot be easily generalized to different lo reduction for SOEC, mainly due to technology development and scaling
cations in the world with different LCOE and capacity factors. The sys up of production volumes. The cost benefits of incorporating SOEC in
tems should be assessed for specific sites using real wind and solar green ammonia systems are further discussed later by calculating the
profile data to calculate a close-to-real green ammonia cost see e.g. LCOEs and needed capacity factors to ensure economic competitiveness.
Ref. [10]. However, a sensitivity analysis is presented next which elu Comparing the cost of ammonia produced using low- and high-
cidates the effects of different LCOEs and capacity factors in the pressure SOEC technologies, the latter is the more cost-efficient. The
following. lower internal resistance at high pressure increases the current density
In addition, the main aim of this work is to assess the economic at the thermo-neutral operation, resulting in the need for fewer cells and
impact of the possible technical developments under identical and thus lower CAPEX. Besides, employing HP-SOEC reduces electricity
conceivable conditions. As hydrogen storage is expensive at small scale, expenses for the HBL feedstock compression. These advantages of using
it is assumed in this analysis, that the produced green hydrogen will be HP-SOEC almost overcome the effect of the assumed 20 % higher CAPEX
directly converted to ammonia; no storage facilities are considered. for a pressurized system and reduced heat integration between the
It is assumed that the systems operate 50 % of the year (4380 h) electrolyzer and the HBL. By 2050, the expenditures related to plant
when green electricity from wind and sun is available. Therefore, the CAPEX will have a lower share than the OPEX in the cost breakdown.
systems are intentionally oversized by a factor of 2 to meet the desired Therefore, the only significant advantage of utilizing HP-SOEC here is
annual production of green ammonia. the reduced power required for feedstock compression.
The cost breakdown of green ammonia production based on AEC and In 2030, employing high-temperature alkaline electrolysis becomes
SOEC technologies is illustrated in Fig. 6, considering the years 2020, less attractive because of the estimated higher CAPEX than low-
2030 and 2050, with a capacity factor of 50 % and a LCOE of 30 €/MWh. temperature alkaline. However, by 2050, employing HTP-AEC could
In this figure, "other CAPEX" refers to the capital expenditures of the become cost-effective under the projected cost developments compared
entire system except for the electrolyzer. Since HTP-AEC and HP-SOEC to LTP-AEC. These estimates rely on the assumption of the rate of
are not commercially available, the cost of ammonia produced based upscaling to mass manufacture, which depends on the willingness for
on these technologies is not included in the year 2020. investment. It is more accurate to state that, even with a higher CAPEX,
As can be seen, by 2020, the AEC-based system leads to the most cost- the up-scaled HTP-AEC is expected to eventually outperform the LTP-
effective ammonia production. However, by 2030 and 2050, the cost of AEC technology.
ammonia produced using SOEC is expected to experience a considerable In 2050, the cheapest projected ammonia cost is 495 €/ton, which
9
Table 7 approximately 2 % of worldwide fossil fuel consumption and approxi

Technical results of the systems thermodynamic modeling (LHV of 120 and 18.6 mately 1.8 % of global CO2 emissions [55]. However, it is hard to
MJ/kg are considered for hydrogen and ammonia, respectively). determine the specific CO2 emitted from fossil ammonia plants, since it
Electrolysis system AEC SOEC highly depends on the utilized fuel in the plant (natural gas, coal, oil or
LTP- HTP- LP-SOEC HP-
naphtha). Besides, some ammonia plants operate more efficiently
AEC AEC SOEC and/or less polluting than others. The average value of CO2 emissions of
ammonia production is estimated to be 2.4 tCO2/tNH3 [1], while
System capacity (ktNH3/year) 430 430 430 430
Power consumed by the 8.81 7.47 6.07 + 6.07 + ranging between 1.6 and 2.7 for major regions [56]. The modern
electrolysis unit (MWh/tNH3) 0.70*+0.29** 0.91* NG-based sites in the Asia Pacific region are responsible for the lower
Power consumed by the ASU 0.13 0.13 0.13 0.13 value of this range; coal-based plants widespread in China can be
(MWh//tNH3) considered the most CO2-intensive production route with almost triple
Power consumed by the HBL 0.23 0.23 0.23 0.23
(MWh/tNH3)
emissions, i.e., 4.4 tCO2/tNH3 [57]. It should be highlighted that the
Total consumed power (MWh/ 9.17 7.83 7.4 7.3 impacts of any possible methane leaks associated with the process are
tNH3) not considered in these assessments.
Generated steam from – – 1.43 0.77
intercoolers waste heat and
4.4.2. Cost of grey ammonia and threshold CO2 taxes
HBL steam generators (tH2O/
tNH3) Ammonia produced from NG is here referred to as grey ammonia. It
Thermal heat integration – – 1.08 0.86 is responsible for considerable CO2 emissions worldwide today. The cost
between electrolyzer and HBL of grey ammonia is mainly a function of fossil feedstock price. The steam
(MWh/tNH3) methane reforming (SMR) process is the most mature conventional fossil
LHV-based electrolyzer 66.7 78.6 83.1 84.1
efficiency (%)
hydrogen production technology. Based on Yadav et al. [58], the in
LHV-based overall efficiency (%) 56.4 66.0 69.7 70.4 dustrial SMR process emits 10.6 kg CO2 per kg of hydrogen. Also, the
power production from natural gas resources releases 443 gCO2/kWh
* 0.70 and 0.91 MWh/tNH3 are the consumed electricity by ELH1 in the systems
emissions [59].
designed based on LP-SOEC and HP-SOEC, respectively. 6.07 MWh/tNH3 is the
consumed electricity by the stacks and is the same for both cases.
To estimate the cost of grey ammonia in this study, the cost of grey
** 0.29 MWh/tNH3 is the extra consumed power for the extra pressurization of hydrogen is first obtained via the following correlation [58]:
the hydrogen after the LP-SOEC. Consumed power for feedstock pressurization CH2,SMR = 5.08CCH4 + 0.3918 (22)
for the HBL is 0.29 MWh/tNH3 higher for the system designed based on LP-
SOEC.
where CH2, SMR and CCH4 are the cost of fossil hydrogen and natural gas
(NG) in terms of $/kg and $/Nm3, respectively. After calculating the cost
could be achieved with the system that utilizes HP-SOEC as the source of of grey hydrogen, the cost of grey ammonia is estimated in the same way
the green hydrogen. as for green ammonia.
During the last ten years before COVID 19, the NG price has been
4.4. Fossil-based ammonia relatively stable in Europe, ranging from 10 to 30 €/MWh [60]. How
ever, when drafting this investigation, the NG price in Europe has
4.4.1. Emissions experienced a wide fluctuation. In 2020, it dropped below 10 €/MWh.
Ammonia, the second most produced chemical, is responsible for Then, it increased by a factor of almost 7–8 compared with the
Fig. 6. Cost breakdown of green ammonia production via different electrolysis technology (LCOE = 30 €/MWh, capacity factor of 50 % and a current density of 0.5
A/cm2 for AEC and thermo-neutral value for the SOEC (ca. 0.96 A/cm2 for LP-SOEC and 1.25 A/cm2 for HP-SOEC)).
10
maximum price before COVID due to Russian-Ukraine conflict in 2022. currently not captured. The potential for significant attention towards
Although it is difficult to estimate the NG price for the future, this blue ammonia hinges on two factors: rapid scalability and the pace of cost
analysis assumes that it will remain in the pre-COVID situation range by reduction in renewable electricity sources. Although not sustainable, this
2030 and 2050. route can be considered a relatively environmentally friendly alternative
Table 8 represents the estimated cost of fossil hydrogen and to grey ammonia. The lack of industry standards for proven permanence
ammonia without CO2 tax, while LCOE is assumed to be 30 €/MWh. The of carbon capture and storage (CCS) and mitigation of upstream methane
cost of grey ammonia is estimated to be 275–450 €/tNH3, changing the emissions are serious challenges impeding blue ammonia.
natural gas price from 10 to 30 €/MWh. Implementing a CO2 tax will The cost of blue ammonia mainly depends on NG price and the cost
increase the cost of fossil ammonia. The cost of grey ammonia is re of CCS. The CO2 already captured is more than 60 % of the CO2 from a
ported to be 385 €/tNH3 by Pozo and Cloete [61] for the conventional NG-based ammonia plant, but handling and storage will still add costs.
plants at European energy prices (60 €/MWh electricity and 6.5 €/GJ ∼ However, the reformers are also powered by fossils (typically NG as
23.4 €/MWh natural gas). well), resulting in CO2 emissions [63]. The CO2 coming from the re
For green ammonia to reach cost parity with grey ammonia, a CO2 formers of Yara’s ammonia plant in Porsgrunn, Norway, is around 415
tax would need to be imposed. To estimate the threshold CO2 tax, the life ktCO2 out of the overall CO2 emission of 1 Mt per year at full capacity
cycle greenhouse gas emission of e-ammonia is assumed to be 10 gCO2/ [64]. In this work, it is assumed that 40 % of produced CO2 stems from
MJ (0.186 tCO2/tNH3). This assumption is based on reported figures of the dilute flue gas, which requires adding a CCS unit for capturing. It is
approximately 5 and 15 gCO2/MJ (only electricity-based emissions) for possible to supply the heat for the steam methane reforming by elec
wind- and solar-driven e-ammonia plants, respectively, in the IEA report tricity rather than by burning natural gas (referred to as “e-SMR”),
[62]. whereby only half the amount of CO2 needs to be captured. This will
Fig. 7 depicts the estimated threshold CO2 taxes for different LCOE reduce the overall cost of the CCS plant but add cost compared to
and natural gas prices for today and estimated green ammonia costs for NG-fired reforming. This approach, albeit promising, is not analysed
the future, assuming a capacity factor of 50 % for the green ammonia further here, since detailed process costs are not available in literature.
plant. The obtained thresholds are thus the difference between the grey Table 9 outlines the estimated cost of blue ammonia for 2020, 2030
and green ammonia costs that need to be balanced by a CO2 tax to and 2050 without imposing a CO2 tax. It is assumed that the NG price
incentivize the transition. will remain 10-30 €/MWh until 2050. The cost of blue ammonia is the
Fig. 7 shows that since the cost of green ammonia is 2–4 times higher cost of grey ammonia, outlined in Table 8, plus costs related to CCS.
than grey ammonia for 2020, relatively high CO2 taxes are required to Also, it is supposed that from 2020 to 2050, CCS cost will reduce from
reach parity. The lowest taxes relate to the LTP-AEC case. Assuming a 133 to 87 €/tCO2 [65]. As can be seen, currently, CCS cost constitutes
LCOE of 30 €/MWh and a NG price of 30 €/MWh, a CO2 tax of 115 22–32 % of blue ammonia cost depending on NG price.
€/tCO2 (~275 €/tNH3) is required for cost parity. Assuming a NG price of 30 €/MWh, the following points can be seen
By 2030 and 2050, lower CO2 taxes will lead to cost parity due to a from the obtained results.
reduction in the cost of green ammonia, mainly because of the lower
CAPEX assumed for electrolyzers and technology improvement (high- • By 2020, only AEC-based green ammonia can compete with blue
temperature for AEC technology and high-pressure for SOEC ammonia when considering a “low” value of 15 €/MWh as LCOE.
technology). • By 2030, the cost of green ammonia (based on both AEC and SOEC
By 2030 and LCOE values of higher than 20 €/MWh, green ammonia technologies) will be lower than that of blue ammonia when
produced via SOEC-based system reaches cost parity with grey ammonia considering LCOEs below 15 €/MWh.
at lower CO2 taxes compared with the AEC-based system. This is because • By 2050, SOEC-based green ammonia is economically favorable
the cost of green ammonia from SOEC-based systems will be lower than compared with blue ammonia for LCOEs below 35 €/MWh.
that of AEC-based systems for LCOEs higher than 20 €/MWh by 2030.
By 2050, with 30 €/MWh as the projected natural gas price, imple 4.5. Sensitivity analysis
menting a CO2 tax of 110 €/tCO2 (~265 €/tNH3) would make SOEC-
based green ammonia cost-competitive even at a LCOE as high as 60 4.5.1. Effects of levelized cost of electricity (LCOE)
€/MWh. In 2020, despite the disruptions imposed by COVID, the trend in cost
decrease continued for wind and solar power. Compared to 2019, the
4.4.3. Cost of blue ammonia global weighted-average LCOE from new capacity additions of concen
Blue ammonia is produced the same way as grey ammonia, while trating solar power, offshore wind, onshore wind and utility-scale PVs
85–95 % of the produced CO2 is assumed to be captured and stored declined by 16, 9, 13 and 7 %, respectively [66].
downstream. Blue ammonia is often promoted as an alternative to green At the time of writing this work, the LCOE for wind farms across the
ammonia, as much of the CO2 from fossil fuel utilization can be captured. world ranges from 29 (Denmark) to 896 €/MWh (Italy), while for solar
Most of the CO2 is already captured after the SMR to separate it from the plants varies from 34 (France) to 275 €/MWh (Italy) [67]. However, for
hydrogen in the current ammonia plants, it is however vented into the the plants with a capacity of higher than 100 MW, LCOE from wind en
atmosphere. Only the part CO2 from the NG used for heating the SMR is ergy span from 31 (Norway) to 200 €/MWh (Japan) and for solar plants
ranges between 35 and 142 €/MWh in the United States of America [67].
The trend shows that these costs must be expected to keep decreasing
Table 8
onwards. Norway and Algeria are among the countries with the lowest
Cost of grey hydrogen and ammonia produced from natural gas as a function of
natural gas price (LCOE = 30 €/MWh). LCOE for industries; ~43 and ~19 €/MWh, respectively [68,69].
However, estimating future cost levels of electricity is not trivial as
NG price (€/MWh) 10 (~0.115 30 (~0.345
this highly depends on technological and societal developments and
$/Nm3) $/Nm3)
adopted policies. This factor could be the primary source of uncertainty in
Cost related to grey H2 (€/tNH3) 155 330
projecting future ammonia prices. Some attempts to predict the expected
Other CAPEX (€/tNH3) 50
Maintenance (€/tNH3) 10 electricity costs can be found in the literature [70,71]. From the analyses
Electricity (€/tNH3) 10 presented by Campion et al. [70], it seems that LCOE levels around 20–30
Manufacturing cost (€/tNH3) 50 €/MWh could likely be achieved in several places in the world with good
Cost of NH3 (without CO2 penalty) 275 450 wind and sun potential, even when counting in some purchases from the
(€/tNH3)
grid to enable around 7000 h of operation per year [70].
11
Fig. 7. The threshold CO2 tax that leads to the cost parity of grey and green ammonia (capacity factor of 50 % for green ammonia plant and current density of 0.5 A/
cm2 for AEC and thermo-neutral value for the SOEC (ca. 0.96 A/cm2 for LP-SOEC and 1.25 A/cm2 for HP-SOEC)).
12
Table 9
Cost of blue ammonia (LCOE = 30 €/MWh).
NG price (€/MWh) 10 (~0.115 $/Nm3) 30 (~0.345 $/Nm3)
Year 2020 2030 2050 2020 2030 2050

CCS cost (€/tCO2) [65] 133 107 87 133 107 87
CCS cost (€/tNH3) 128 103 84 128 103 84
Share of CCS cost in the cost of 32 27 23 22 19 16
blue ammonia (%)
Cost of grey ammonia without 275 275 275 450 450 450
CO2 tax (€/tNH3) (see
Table 8)
Cost of blue ammonia without 403 378 359 578 553 534
CO2 tax (€/tNH3)
To generalize the obtained results, a sensitivity analysis is conducted

to see the effects of changing LCOE on the estimated cost of green
ammonia. Changing LCOE will change the share of electricity cost in the
total cost of green ammonia, while the other costs remain constant.
Fig. 8 shows the costs related to the consumed power by the entire
system based on different electrolysis technologies for LCOE values of
10–60 €/MWh. The two vertical lines show the current LCOE for in
dustries in Algeria and Norway - representing locations with the lowest
LCOE for the industry in the world and Europe, respectively. Referring to
this figure, the cost associated with the consumed electricity is almost
the same for the systems that employ LP-SOEC and HP-SOEC. Both high-
and low-pressure SOECs operate under thermo-neutral operating con
ditions. So, although the HP-SOEC uses less power for feed gas
compression, additional heat must be added to the HP-SOEC system
elsewhere to make the SOEC unit run thermo-neutral. Electric heaters
will supply this additional heat.
As seen in Fig. 9(a), the system designed based on AEC will produce
cheaper ammonia than the SOEC-based system, by 2020, due to its lower
CAPEX. Also, it should be noted that maintenance costs in these esti
mates highly depend on the estimated CAPEX for the entire system.
By 2030, the CAPEX of the SOEC-based system is expected to be
considerably lower, which here results in the cheapest green hydrogen
route for ammonia synthesis. Although similar cost is assumed for the
HTP-AEC and the LP-SOEC, this is still not economically competitive
compared with LTP-AEC for LCOE below 50 €/MWh, as the efficiency is
still lower than the SOEC. So, although HTP-AEC has better efficiency
than LTP-AEC, the CAPEX is still too high.
By 2050, the CAPEX of all the electrolysis technologies is estimated
to have dropped significantly, so OPEX will have a higher impact on the
cost of the produced ammonia. Therefore, the HTP-AEC will be more
competitive than the LTP-AEC, while the SOEC-based plants are superior
to both.
Fig. 9. Cost of green ammonia produced with different electrolysis technology

vs. LCOE (capacity factor of 50 % for green ammonia plant and current density
of 0.5 A/cm2 for AEC and thermo-neutral value for the SOEC (ca. 0.96 A/cm2
for LP-SOEC and 1.25 A/cm2 for HP-SOEC)).
Interestingly, the HP-SOEC only yields slightly cheaper ammonia

than the LP-SOEC with the assumed 20 % higher CAPEX. Referring to
Fig. 8, the cost related to the consumed power by the entire system is
Fig. 8. Costs associated with electricity consumption via different electrolysis approximately the same for both systems operating with LP- and HP-
vs. LCOE. SOEC. However, the electrolyzer CAPEX is lower for HP-SOEC (per
13
produced amount of hydrogen). Consequently, the system equipped

with HP-SOEC has slightly better economic performance.
Fig. 9(c) also compares the estimated cost of grey and blue ammonia,
assuming modest price development of these fuels. By 2050, assuming a
NG price of 30 €/MWh, the cost of green ammonia will be lower than
that of blue ammonia if a LCOE of 35–40 €/MWh can be achieved. Also,
assuming a NG price of 30 €/MWh, green ammonia will be cost-
competitive to grey ammonia for LCOE lower than 20–25 €/MWh.
4.5.2. Effects of capacity factor

All results presented and discussed up to this point assume a capacity
factor of 50 %; thus, the green electricity is available at the LCOE for 50
% of the year. Under the base case conditions, all the systems were
scaled to produce 430 ktNH3 per year with a capacity factor of 50 %. It is
assumed that operating with different capacity factors does not affect
the stack replacement time and system economic life.
Fig. 10 presents the effects of the availability of low-price renewable
electricity on the cost of green ammonia. Here, the capacity factor is the
ratio of system equivalent full-load operating hours to the maximum
possible operating hours in a year (8760). For instance, a capacity factor
of 50 % means that the system should be scaled up by a factor of 2 to
produce 430 ktNH3 per year.
Operating with lower capacity factors resulting from a lower amount
of available renewable electricity will make the green ammonia more
costly due to the depreciation of the capital investment – the plant has
now to be oversized to reach the same amount of product annually. The
CAPEX refers to a significant share of the green ammonia cost. Thus, as
can be seen in Fig. 10(a), the cost of green ammonia is extremely high for
lower capacity factors, especially for SOEC-based system. The system
OPEX per produced amount of ammonia remains constant, and the
CAPEX per produced amount of ammonia increases.
Referring to Fig. 10 (b), by 2030, cost of green ammonia produced
from the system based on HTP-AEC is the same as that produced from
the system based on LTP-AEC. Although HTP-AEC performs efficiently
compared with LTP-AEC, CAPEX depreciation significantly affects the
cost of green ammonia. For SOEC-based systems, efficiency improve
ment due to heat integration between electrolyzer and HBL compensates
for CAPEX depreciation.
By 2050, the share of electrolyzer CAPEX will be low and system
efficiency (OPEX) has a higher impact on the cost of green ammonia.
Therefore, employing SOEC to produce green ammonia is the best
choice, followed by HTP-AEC.
The method here applied assuming a certain LCOE and capacity
factors of higher than 50 % will underestimate the ammonia costs, as
green electricity is only available at these capacity factors in few but
highly relevant places in the world. If based on solar or wind sources, the
capacity factors would range from 25 to 50 % and hence running the
plant more than 50 % of the time would require that the electricity from
the grid is also purchased at times of no wind and sun. This electricity
would generally not be green.
Accounting for different capacity factors provides the results in the
plots in Fig. 10. However, this overestimates the economical penalty of
reducing the annual number of operation hours, as possibilities of
storing H2 or electricity from times of low electricity costs to periods
with little production are neglected.
4.5.3. Effects of the estimated CAPEX

Since SOEC technology is currently in the initial commercialization
phase, its future performance, scalability and consequent economic Fig. 10. Cost of green ammonia produced with different electrolysis technology
assessment are uncertain. Besides, the electrolyzer CAPEX is estimated vs. capacity factor (LCOE = 30 €/MWh and current density of 0.5 A/cm2 for
to be decreased significantly in the long term. Consequently, a ±50 % AEC and thermo-neutral value for the SOEC (ca. 0.6 A/cm2 for LP-SOEC and
uncertainty is considered for the estimated CAPEX of the electrolyzers in 0.86 A/cm2 for HP-SOEC)).
the long term, as shown in Fig. 11.
Referring to this figure, by 2050, for a capacity factor of 50 %, the ammonia cost and this is even more so at higher capacity factors. This is
costs associated with the consumed electricity will be so high that a ±50 rather interesting, as it highlights that CAPEX will be a parameter for
% change in the electrolyzer CAPEX does not considerably affect the competition, but the ability to heat integration (to reduce the OPEX)
14
even more so. Both the systems are modeled at the components level, and it was
As shown in Fig. 11(a), in 2050, assuming a capacity factor of 50 % found that.
and for LCOE values of higher than 40 €/MWh, the system designed
based on LP-SOEC produces cheaper ammonia, even assuming 50 % • The overall efficiency of 56.4, 66.0, 72.5 and 73.4 % is obtained for
more CAPEX (600 €/kW) for LP-SOEC and 50 % less CAPEX for LTP-AEC the system designed based on LTP-AEC, HTP-AEC, LP-SOEC and HP-
(150 €/kW). SOEC, respectively.
Fig. 11(b) compares the cost of green ammonia produced based on
HP-SOEC and HTP-AEC as emerging technologies for green hydrogen. The possibility of supplying cheaper renewable electricity is studied,
As the figure shows, for higher LCOEs like 60 €/MWh, the system and the cost of green ammonia is estimated considering the current and
designed based on HP-SOEC produces cheaper ammonia, even assuming currently projected electrolyzer CAPEX. It was found that.
50 % more CAPEX (720 €/kW) for HP-SOEC and 50 % less CAPEX for
HTP-AEC (200 €/kW). • Although SOEC performs efficiently compared with AEC, employing
this technology to produce green ammonia is not economically
5. Conclusion favorable before the cost of SOEC is decreased to 1500 €/kW
(assuming a capacity factor of 50 %, LCOE of 30 €/MWh and AEC
In this work, various green ammonia producing systems based on CAPEX of 830 €/kW) through, e.g., upscaled manufacturing.
electrolytic hydrogen from AEC or SOEC have been modeled under • By 2030 and 2050, upscaled manufacturing and technology im
steady-state operating conditions. To investigate the effect of different provements are expected to decrease the cost of the SOEC. Therefore,
potential technological improvements for both AEC and SOEC, pres employing SOEC in a green ammonia producing system appears to be
surized AEC is modeled in both low-temperature (80 ◦ C) and high- economically favorable to the AEC in this analysis.
temperature (200 ◦ C) operating modes and SOEC is also modeled • By 2050, assuming a LCOE of 30 €/MWh and a capacity factor of 50
considering both low-pressure (atmospheric) and high-pressure (30 bar) %, a green ammonia cost of 495 €/ton is projected, produced with a
modes. pressurized SOEC-based system.
Fig. 11. Effect of a change in LCOE and estimated electrolyzers CAPEX on the cost of green ammonia by 2050 (capacity factor of 50 % for green ammonia plant and
current density of 0.5 A/cm2 for AEC and thermo-neutral value for the SOEC (ca. 0.6 A/cm2 for LP-SOEC and 0.86 A/cm2 for HP-SOEC)).
15
The cost of green ammonia is compared with grey and blue detailed economic analysis should be undertaken at specific sites with
ammonia. The threshold CO2 tax that would bring green ammonia on distinct weather profiles, as these factors may influence the economic
par with grey ammonia is estimated for different years, assuming NG conclusions presented herein. Therefore, these economic assessments
prices of 10–30 €/MWh and a wide range of LCOE values. The main should be regarded only as guidelines. The potential error in this
findings of this are. investigation might arise from the projected 2030 and 2050 CAPEX
values for emerging electrolysis technologies. However, it is noteworthy
• With a LCOE of 30 €/MWh, a capacity factor of 50 % and a NG price that since the cost of consumed electricity largely determines the green
of 30 €/MWh, a CO2 tax of 105 €/tCO2 (~250 €/tNH3) is required for ammonia price, this factor may not significantly alter the economic
green ammonia to be cost comparable with grey ammonia. conclusions presented in this research.
• By 2050, with 30 €/MWh as the projected NG price, implementing a
CO2 tax of 100 €/tCO2 (~240 €/tNH3) would make SOEC-based CRediT authorship contribution statement
green ammonia cost-competitive even for a LCOE value as high as
60 €/MWh. Hossein Nami: Conceptualization, Methodology, Study design,
• By 2050, assuming a projected NG price of 30 €/MWh and a capacity Software, Validation, Formal analysis, Investigation, Data curation,
factor of 50 % for green ammonia plant, the cost of green ammonia Writing – original draft, Writing – review & editing. Peter Vang Hen
produced with the SOEC-based system will be competitive with grey driksen: Conceptualization, Methodology, Study design, Investigation,
and blue ammonia for LCOE values lower than 25 and 40 €/MWh, Resources, Writing – original draft, Writing – review & editing, Visual
respectively. ization, Supervision, Project administration, Funding acquisition. Hen
rik Lund Frandsen: Conceptualization, Methodology, Study design,
A sensitivity analysis is carried out to assess the effects of LCOE, Investigation, Resources, Writing – original draft, Writing – review &
capacity factor and estimated CAPEX on the cost of ammonia. It was editing, Visualization, Supervision, Project administration, Funding
found that. acquisition.
• By 2050, for LCOE values of higher than 40 €/MWh, the (LP-SOEC)- Declaration of competing interest
based system produces cheaper ammonia, even assuming 50 %
higher CAPEX (600 €/kW) for LP-SOEC and 50 % lower CAPEX for The authors declare that they have no known competing financial
LTP-AEC (150 €/kW) compared to the base case values. interests or personal relationships that could have appeared to influence
• By 2050, increasing the capacity factor from 30 to 90 % decreases the the work reported in this paper.
cost of green ammonia by almost 80 %.
Data availability
Ammonia serves as a hydrogen carrier and is likely to be traded
internationally to leverage global collaboration for cost minimization. Data will be made available on request.
The practical implications of this study for industry and policymakers
involve utilizing emerging electrolysis technologies for green ammonia Acknowledgments
production, projecting future ammonia prices, and determining the
necessary CO2 tax for fossil ammonia to achieve cost parity between Support from the Danish Maritime fund within the project, MarE-
green and fossil ammonia. These implications address efficiency fuel; sustainable maritime fuels is thankfully acknowledged. The authors
improvement, cost considerations, and climate impact, respectively. would like to express their sincere gratitude to Nicolas Campion, Marie
This research is conducted with the understanding that a more Münster, and Giacomo Butera for their valuable support.
Appendix. Cell model for the SOEC
The operating conditions and geometric and modeling parameters used for the SOEC model are given in Table A1.
Table A.1
Parameters utilized in SOEC modeling
Parameter Value
Operating temperature [72] (ᵒC) 750

Operating pressure [72] (bar) 0.4, 3, and 10 for validation
1 and 30 (pressure increase is just assumed for the cathode side) in the this research
Hydrogen mole fraction at the cathode inlet [72] 0.5
Oxygen mole fraction at the anode inlet [72] 1
Height of the anode electrode (m) 4 × 10-5
Height of the cathode electrode (m) 3.5 × 10-4
Mean pore diameter of the anode electrode [36] (m) 3.06 × 10-7
Mean pore diameter of the cathode electrode [36] (m) 6.41 × 10-7
Number of exchanged electrons in the reactions [37] 2
Permeability of the electrodes [36] (m2) 10–13
Load current densities are considered as knowns/inputs to solve for their corresponding cell voltages. Calculating the ohmic and concentration
overpotentials is straightforward as they are explicit functions of the current density. Since the activation overpotentials are implicit functions of the
current density, the “fsolve” function is used to solve for them through solving a system of nonlinear equations with two equations and two unknowns.
The governing equations presented for SOEC modeling listed in Table 3 have 13 free parameters, which are given in Table A. 2, which can be
adjusted by fitting the model polarization curves to the experimental ones. The genetic algorithm with a population size of 104 is used to find the
optimum values of the parameters that minimize the errors between the cell voltages from the model and the experimental data:
16
nj
np ∑
∑ ( )2
fob = ESOEC,exp − ESOEC,sim (A.1)
i=1 k=1
here, fob is the objective function, np and nj are numbers of the operating pressures and load current densities, respectively, and abbreviations exp
and sim denote the experimental and simulation data, respectively. Operating pressures of 0.4, 3, and 10 bar are considered [72], and 28 load current
densities between − 0.5 and 0.85 A/cm2 with a fixed step size of 0.05 A/cm2 are used. It should be noted that the experimental data are interpolated
over these current densities so that the operating points are the same as those used in the simulation for calculating the error between the experimental
and simulation data, Eq. (A.1).
Table A.2 lists the optimum values of the fitting parameters evaluated by the genetic algorithm for the old and new cells produced and used for the
experiments in DTU-Energy. The label “old cell” is used for the cells used over a decade ago, and their experimental data are used due to their available
high-pressure operation data [72]. Nonetheless, the fitting parameters are adjusted for updated cells with improved performance, especially of the air
electrodes, which have been used by Sun et al. [73]. Unfortunately, the high-pressure operation experiments have not been performed on the new
cells; thus, the fitting is done just for their atmospheric operations. All the operating conditions, except the operating pressures, are the same for the
experimental data from both old and new cells used for the fitting here.
Table A.2
Optimum values of the fitting parameters
Parameter Value – old cell Value – new cell
Constant of the prefactor used for the anode exchange current density (γ0,a ) 1.2236 × 108 A m− 2 K− 1
2.4341 × 108 A m− 2 K− 1
Constant of the prefactor used for the cathode exchange current density (γ0,c ) 5.6601 × 106 A m− 2 K− 1
8.9977 × 106 A m− 2 K− 1
Activation energy used for the anode exchange current density (Eact,a ) 1.4916 × 105 J mol− 1 1.4814 × 105 J mol− 1
Activation energy used for the cathode exchange current density (Eact,c ) 1.2491 × 105 J mol− 1 1.2055 × 105 J mol− 1
Charge transfer coefficient of the anode reaction (αa ) 0.6573 0.8303
Charge transfer coefficient of the cathode reaction (αc ) 0.5000 0.7725
Power of the oxygen partial pressure used for the anode exchange current density (m) 0. 1853 0.1825
Power of the hydrogen partial pressure used for the cathode exchange current density (a) − 0.2154 − 0.0583
Power of the steam partial pressure used for the cathode exchange current density (b) 0. 3143 0.4881
Correction factor for the diffusion coefficients of the species in the anode porous media (kaD,eff ) 0.0995 0.1996
Correction factor for the diffusion coefficients of the species in the cathode porous media (kcD,eff ) 0.0201 0.1695
Material-specific constant used for the ohmic overpotential (Bohm ) 8.2598 × 1012 S K m− 2 7.8247 × 1011 S K m− 2
Activation energy used for the ohmic overpotential (Eact,ohm ) 1.2055 × 105 J mol− 1 8.0022 × 104 J mol− 1
Fig. A.1 compares the polarization curves from the experimental data and the developed model for the optimum values of the fitting parameters
given in Table A.2. A good match is seen between the polarization curves for all operating pressures. One can see better performance if the material
parameter identified for the newer cells are used to simulate the high-pressure operation. The latter is used in the onwards simulations. The higher
open circuit voltage (OCV) and lower ASR for higher operating pressures and higher pressure effects for lower operating pressures are consistent with
the trends reported in the literature, e.g. Refs. [74,75].
Fig. A.1. Comparisons of the polarization curves from the experimental data and the model for different operating pressures. The abbreviations exp and sim denote
the experimental and simulation data, respectively.
17
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Renewable and Sustainable Energy Reviews 199 (2024) 114517

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Green ammonia production using current and emerging

interest in green ammonia production. Compared with hydrogen,

Nomenclature M molar mass (kg/kmol)

Fig. 1. Schematic diagram of SOEC system.

In this research, the polarization curve reported by Green Hydrogen Table 4

k1 = 1.79 × 104 e− 87090/RT

Fig. 3. Flow diagram of the HBL.

overall system CAPEX, as detailed below.

Fig. 4. AEC-based green ammonia plant.

Fig. 5. SOEC-based green ammonia plant.

Table 7 approximately 2 % of worldwide fossil fuel consumption and approxi­

Year 2020 2030 2050 2020 2030 2050

To generalize the obtained results, a sensitivity analysis is conducted

Fig. 9. Cost of green ammonia produced with different electrolysis technology

Interestingly, the HP-SOEC only yields slightly cheaper ammonia

produced amount of hydrogen). Consequently, the system equipped

4.5.2. Effects of capacity factor

4.5.3. Effects of the estimated CAPEX

Appendix. Cell model for the SOEC

Operating temperature [72] (ᵒC) 750

Parameter Value – old cell Value – new cell

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Table 7 approximately 2 % of worldwide fossil fuel consumption and approxi