Applied Energy 284 (2021) 116401

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

Techno-economic comparison of 100% renewable urea

production processes
Hanfei Zhang a, *, Ligang Wang b, c, *, Jan Van herle d, François Maréchal e, Umberto Desideri a, *
a
Department of Energy, Systems, Territory and Constructions Engineering, University of Pisa, Pisa, Italy
b
Innovation Research Institute of Energy and Power, North China Electric Power University, Beijing, China
c
Key Laboratory of Power Station Energy Transfer Conversion and System (North China Electric Power University), Ministry of Education, China
d
Group of Energy Materials, Swiss Federal Institute of Technology in Lausanne (EPFL), Sion, Switzerland
e
Industrial Process and Energy Systems Engineering, Swiss Federal Institute of Technology in Lausanne (EPFL), Sion, Switzerland

H I G H L I G H T S

• Two renewable urea production processes are investigated techno-economically.

• The overall system efficiency of biomass-to-urea may reach 39%.
• Integrated biomass- and power-to-urea achieves a higher overall efficiency of 53%.
• Integrated biomass- and power-to-urea enables continuous, highly-flexible operation.
• Integrated biomass- and power-to-urea shows a high levelized cost of the urea.

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

Keywords: Urea is widely used in agriculture, industry, and food, while it is also a potential fuel. Large-scale urea production
Renewable urea relies on fossil fuels, thus there is a strong need for green urea given the increasing penetration of renewable
Methane-to-urea energy sources. A potential alternative is biomass-to-urea; however, it cannot fully convert the biomass carbon
Biomass-to-urea
into urea. To achieve full carbon conversion, innovative integrated biomass- and power-to-urea processes are
Power-to-urea
Power-to-hydrogen
designed conceptually. The two green urea production processes are evaluated techno-economically and
Solid-oxide electrolyzer compared with state-of-the-art methane-to-urea. The results show that the methane-to-urea achieves a system
efficiency of 58% (LHV), while biomass-to-urea only has 39% (LHV) with unconverted biomass carbon of up to
60%. The integrated power- and biomass-to-urea has outstanding heat integration performance which fixes all
biomass carbon into urea, with an efficiency enhanced up to 53%. Due to the electricity demand, the levelized
cost of the urea of integrated biomass- and power-to-urea is 15 – 38 and 58 – 87% points higher than those of the
biomass-to-urea and methane-to-urea for the scale of 10 – 60 MWth urea production. The available annual hours
and electricity price of renewable electricity have a significant impact on the levelized cost of the urea. When the
available annual hours decrease from 7200 to 3600 with an electricity price of 73 $/MWh, the levelized cost of
urea increases on average by 13% from 51 $/GJ with the plant capacity being 10 – 60 MWth urea. However,
when electricity price is reduced from 73 $/MWh to 35 $/MWh with available annual hours of 3600, the lev­
elized cost decreases on average by 15% from 59 $/GJ with the same plant capacity.

urea produced is used as fertilizer in agriculture [3], and the remaining

1. Introduction
Urea ((NH2)2CO) is one of the most produced organic chemicals
worldwide with its global capacity growing at a rate of 3 – 4% [1] and
expected to reach 226 million tonnes in 2023 [2]. More than 80% of the
is used (1) in selective catalytic reduction systems to reduce NOx
emissions in fossil-fueled power plants and diesel engines in the light
and heavy transport sectors [4], (2) as a raw material for important
chemicals like plastics and waterproof glue for marine plywood [5,6],
(3) in petroleum refining to produce jet aviation fuel and de-wax

* Corresponding authors at: Department of Energy, Systems, Territory and Constructions Engineering, University of Pisa, Pisa, Italy (H.zhang, and U. Desideri) .
Corresponding authors at: North China Electric Power University, Beijing, China (L. Wang)
E-mail addresses: zhf19860822@163.com (H. Zhang), ligang.wang@ncepu.edu.cn (L. Wang), umberto.desideri@unipi.it (U. Desideri).

https://doi.org/10.1016/j.apenergy.2020.116401
Received 21 July 2020; Received in revised form 10 December 2020; Accepted 25 December 2020
Available online 12 January 2021
0306-2619/© 2021 Elsevier Ltd. All rights reserved.
H. Zhang et al. Applied Energy 284 (2021) 116401

Nomenclature SMR steam methane reforming

SoA state-of-the-art
Abbreviations SOE solid-oxide electrolysis
AAHs available annual hours SR secondary reformer
AE alkaline electrolyzer STN steam turbine network
AGR acid gas removal WGSR water–gas-shift reaction
ASU air separation unit $ US dollar
ATR autothermal reformer € euro
BtA biomass-to-ammonia
BtU biomass-to-urea Greek Symbols
BPtU biomass- and power-to-urea η energy efficiency
COP coefficient of performance Mathematical Symbols
CEPS centre for European policy studies CAPEX capital expenditure
EFG entrained flow gasifier Cdep depreciation cost
HTSR high-temperature water–gas shift reactor Cinv investment cost
HEN heat exchanger network Copt operational cost
HHV higher heating value
Cbyp by-product revenue
ICE internal combustion engines rev
i annual interest rate
LHV lower heating value
LCOU levelized cost of the urea
LTSR low-temperature water–gas shift reactor
MUSP minimum urea selling price
MEA monoethanolamine
ΔĖ net electric power input
+
MtA methane-to-ammonia
ΔĖ net electric power output
−
MtU methane-to-urea
1
PEME polymer electrolyte membrane electrolyzer ΔH298K standard enthalpy of formation, kJ mol−
PR primary reformer OPEX operational expenditure
PtA power-to-ammonia T temperature, K
PtH power-to-hydrogen

lubricant oils [6], and (4) as food and animal feed additive [6]. The
energy density of urea (11.89 MJ/m3) is higher than compressed or
liquid hydrogen (4.93 MJ/m3 at 700 bar and 8.94 MJ/m3 at liquid
form). The non-flammable, non-toxic, easy-to-store and -transport fea­
tures enable it as an ideal hydrogen carrier and fuel for fuel cells [7,8].
For example, alkaline membrane electrolyte-based fuel cells can directly
convert urea to electricity [8]. Urea as a fuel in solid oxide fuel cell
(SOFC)-based power system can achieve an overall efficiency of 55% at
800 ℃ and fuel utilization of 0.8 [4]. The direct urea SOFC integrated
with the gas turbine power cycle can achieve an overall energy system
efficiency of up to 56.8% at 800℃ and fuel utilization of 0.85 [9].
Large-scale commercial urea production plants use the Basarov re­
action through the synthesis of ammonia and carbon dioxide at 170 –
220 ℃ and 125 – 250 bar [10]. The ammonia is mainly synthesized by
the hydrogen derived from fossil fuels (natural gas and coal), while
carbon dioxide mainly comes from the acid gas removal (AGR) process
in the ammonia synthesis [11]. According to the IEA report [11], urea is
the largest-volume derivative of ammonia, which consumes more than
half of the annual production of ammonia. Due to the ammonia supply,
urea is thus mostly produced using natural gas globally, while in China
97% of the ammonia feedstock is via coal gasification [12]. Producing a
tonne of urea requires a minimum of 0.73 tCO2, and nearly 130 MtCO2 is
utilised for urea production annually, but the bulk is released down­
stream in the agriculture sector, sometimes only days later [11]. These
emissions accounted for about 9% of CO2 emissions (1.4 GtCO2) in the
chemical sector in 2019 [13]. Therefore, green urea production is
important for mitigating climate change, and approaching net-zero
emissions in the latter half of this century to achieve the Paris Agree­
ment’s goal of limiting the global temperature rise to “well below 2 ℃”.
To reduce fossil fuel consumption and greenhouse-gas emissions,
green ammonia, derived from renewable energy sources, particularly
biomass and renewable power via biomass-to-ammonia (BtA) and
power-to-ammonia (PtA) [14], should be promoted for green urea.
There are few studies about the green urea synthesis process. Ref. [15]
reported a series of cases based on biomass gasification and PV
electrolysis process to synthesize green urea, which proposed a green
urea production strategy by considering the future cost development of
technologies and feedstock price for each technology in the three de­
cades from 2020 to 2050. The results showed that the biomass gasifi­
cation process is preferable from 2020 to 2035 and the combined
biomass gasification-PV electrolysis without battery is the optimum
from 2040 to 2050. Ref. [16] compared the biomass gasification using
oxygen-only and steam-only gasifying agents to produce high-grade
Fisher-Tropsch liquids, methanol, urea, and power. The results showed
the methanol generation option with oxygen-only gasification demon­
strated a minimum selling price of around 375 $/tonne of methanol
whereas the urea process demonstrated no positive breakeven point. A
municipal solid waste-to-urea case with gasification process is analyzed
in Ref. [17] and compared with a conventional natural gas-to-urea
process. The overall material balance for a 500 tonne/day urea plant
was studied, for which approximately 700 tonne/day of residual-derived
fuel are used as feedstock leading to a 450 tonne/day CO2 emission. The
estimated cost was 135 €/tonne of urea for an Italian site. The natural
gas-to-urea process with the same urea yield required 191 tonne/day of
CH4 and excess 2 tonne/day of NH3. However, all the above studies did
not provide a detailed conceptual process design, thermodynamic per­
formance evaluation, and economic performance comparison of the
green urea processes. Therefore, to overcome these gaps, this paper aims
at proposing a comprehensive consistent comparison framework for
investigating techno-economically the 100% renewable urea production
processes using the same calculation methodology, tools and
assumptions.
The BtA process provides not only ammonia but also a source of CO2
for synthetic urea and the amount of CO2 produced in BtA is much
higher than required [15]. To convert all the CO2 generated in BtA into
urea, it is feasible to integrate PtA into BtU to form the so-called inte­
grated biomass- and power-to-urea (BPtU). Biomass gasification and
electrolysis technologies have been detailed reviewed and analyzed by
the authors in previous studies [14,18], where the entrained-flow
gasifier (EFG) and solid-oxide electrolyzer (SOE) technologies are

2
H. Zhang et al. Applied Energy 284 (2021) 116401

Fig. 1. Schematic of the SoA MtU plant. The heat exchanger network (HEN) is not explicitly designed, but its performance is estimated via the classical chemical
engineering approach described in Ref. [44]. In the ammonia synthesis loop, only the MtA case has a primary reformer furnace, while in other cases, a heat-recovery
boiler is placed. The Rankine cycle, represented by steam turbine network (STN), is not presented in the figure as well, but it is sized and optimized for heat recovery
of the overall system.

integrated for ammonia production. As a follow-up, this paper further
evaluates the techno-economic feasibility of 100% renewable urea
production. Two green urea production processes (BtU and BPtU) are
designed conceptually and compared with the state-of-the-art (SoA)
methane-to-urea (MtU) in terms of (1) the overall system efficiency, (2)
system-level heat integration, and (3) economic performance. A signif­
icant benefit of using urea as a hydrogen carrier is that it can be stored as
a solid or liquid, which is not dangerous and is commonly distributed
and used in industry and more recently in transportation. Although
energy is needed in the solidification and in the further liquefaction of
urea the advantages of transporting a solid hydrogen carrier are very
high. On the other hand, it is important to note that urea is not carbon-
free, and its carbon should be made available from carbon capture or
renewable sources and should not be an addition to the natural carbon
present in the atmosphere.
The rest of the paper is organized as follows: The basis of ammonia
and urea synthesis is briefly introduced in Section 2. All processes, i.e.,
BtU, MtU and BPtU, are then described in Section 3. In Section 4, the
modeling details and analysis methodology is introduced with defined
performance indicators. Afterward, the thermodynamic and economic
performances of the studied cases are discussed comprehensively in
Section 5 to support the practical design of such systems. The conclu­
sions are drawn in Section 6.

3
H. Zhang et al.
Fig. 2. Schematic of the BtU plant with EFG. The ammonia synthesis, urea synthesis, the Rankine cycle and the heat exchanger network are treated the same as
described in the capture of Fig. 1.
2. Ammonia and urea synthesis
The commercial ammonia synthesis is based on the Haber-Bosch
process and the chemical reaction shown in (Eq. 1) [19]:
N2 + 3H2 ↔ 2NH3 ΔH298K = − 92.44 kJ/mol
The ammonia synthesis is limited by thermodynamic equilibrium
and can only achieve a low single-pass conversion efficiency of 25 – 35%
[19]. A more detailed description of ammonia synthesis can be found in
previous publication by the authors [14].
The commercial urea synthesis is based on the Basarov reaction [10]
(Eq. 2) at 125 – 250 bar and 170 – 220 ℃ with two reactions [5,10,20]:
the formation of ammonium carbamate (NH2 COONH4 ) (Eq. 3) and the
dehydration of ammonium carbamate to generate urea (CO(NH2 )2 ) (Eq.
4).
2NH3 + CO2 ↔ CO(NH2 )2 + H2 O
2NH3 + CO2 ↔ NH2 COONH4 ΔH298K = − 136.2 kJ/mol
NH2 COONH4 ↔ CO(NH2 )2 + H2 ΔH298K = +17.6 kJ/mol
The overall urea synthesis process is exothermic; however, the
dehydration of ammonium carbamate is slightly endothermic, indi­
cating a slow reaction and thus requiring a high reactor.
3. Process description
The methane-to-ammonia (MtA), biomass-to-ammonia (BtA), and
power-to-ammonia (PtA) synthesis processes, have been described in
detail in Ref. [14]. However, for a better understanding of the systems,
the MtA, BtA, and PtA processes are explained below and further
adapted for the urea production.
3.1. State-of-the-art methane-to-urea (MtU)
The SoA MtU plant process is illustrated in Fig. 1. The natural gas
feedstock (1) is first divided into two flows: stream (3) is fed to the
primary reformer furnace to provide heat for the steam-methane
reformer (SMR); while stream (2) is mixed with steam (7) with a
steam-to-carbon ratio of 3 and sent to a primary endothermic reformer
(PR), an indirectly heated tube filled with nickel-contained reforming
catalyst. The methane content at the reformer outlet is controlled at
Applied Energy 284 (2021) 116401
around 10 vol%. Then, the reformed gas is fed to a secondary auto­
thermal reformer (SR), whose heat requirement is satisfied by partial
oxidation of the gas mixture (9) with air (12). The gas mixture passes
through the nickel catalyst layer adiabatically to attain an H2/N2 mole
ratio of around 2.5. The SR outlet temperature is about 1000 ℃ to ensure
(1)
a small residual methane content of less than 0.5 vol%. The reformed
syngas (13) is cooled and then enters successively a high-temperature
(HTSR) and a low-temperature water–gas-shift reactor (LTSR) to in­
crease the H2 fraction for a desired H2/N2 mole ratio of 3 (stream 17).
Afterward, the CO2 presented in the gas mixture (17) is separated via
monoethanolamine-based chemical absorption as a carbon source for
the urea synthesis. The reformed gas (19) then enters the final purifi­
cation stage with a methanator to remove any trace of CO and CO2.
The raw gas mixture for ammonia synthesis (23) is then compressed
and fed into the synthesis reactor, i.e., a 3-bed quench converter that
divides the inlet gas into three parts: the mainstream (29), the first
(2)
quench flow (30), and the second quench flow (31). The mainstream
(29) of gas passes through a preheater before it enters the two beds with
(3)
a subsequent quench after each bed. The product gas from the third bed,
(4) the raw ammonia (32), is chilled in the refrigeration station and then
purified in a high- and medium-pressure separators to obtain pure
ammonia (37). The purge gas (42) and flash gas of the medium pressure
separator (47) are converted inside the primary reformer furnace for
energy recovery.
The urea synthesis adopts a mature CO2 stripping process. The
ammonia solution (38) is heated to 9 ℃ and fed into the cold ammonia
tank. The extra ammonia (38a) can be sold as a by-product. The
ammonia (40) that leaves the cold ammonia tank is heated to 25 ℃ and
fed into the hot ammonia tank. The hot ammonia (42) is pumped to 160
bar using a volumetric high-pressure liquid ammonia transfer pump and
mixed with stream (44) using an HP ejector before being fed (45) into
the HP carbamate condenser. The CO2 (18) from the AGR is compressed
to 141 bar and heated to 100 ℃, and then sent to the CO2 stripper to strip
the urea solution from the urea reactor. In the stripper, the urea solution
falls in the tubes, which is countercurrent with the rising CO2 stripping
gas. The unreacted ammonium carbamate decomposes, liberating more
NH3 and CO2 to be stripped out. The vapor stream from the top of the
stripper enters the HP carbamate condenser with liquid ammonia (45)
(molar ratio of inlet NH3/CO2 of 3.1). Part of the NH3 and CO2 are
condensed to form ammonium carbamate (exothermic reaction) in the
condenser. The vapor–liquid mixture (50) goes to the bottom of the
adiabatic urea synthesis reactor, where the remaining NH3 and CO2
4
H. Zhang et al.
Fig. 3. Schematic of the BPtU process. The ammonia synthesis, urea synthesis, the Rankine cycle and the heat exchanger network are treated the same as those
described in Fig. 1.
condense and generate ammonium carbamate to provide heat for the
slightly endothermic reaction of ammonium carbamate dehydration to
urea. The unreacted gases (58) are discharged from the top of the urea
reactor to the HP Scrubber, where the NH3 and CO2 create ammonium
carbamate (44), which is mixed with the liquid ammonia stream
through the HP ejector, and then recirculated to the urea reactor via the
HP carbamate condenser and converted into urea. Meanwhile, the inert
gases of O2, N2, and others (59) vent out from the top. The bottom
stream (53) from the stripper is relieved to 4.5 bar and enters the LP
distillation column, where a circulating heater maintains the tempera­
ture at 135 ℃ to decompose the ammonium carbamate into NH3 and
CO2. This mixture (55) is sent to the LP carbamate condenser again to
compound ammonium carbamate (56), which is further cooled and
passes through an HP ammonium carbamate circulating pump into the
HP Scrubber eventually into the urea reactor to complete the loop. The
urea-rich liquid (60) from the LP distillation column is sent to the flash
drum, finally obtaining a urea solution of 77 wt%.
3.2. Biomass-to-urea (BtU)
The BtU plant with EFG is illustrated in Fig. 2 based on the BtA
process [14]. The biomass feedstock (9) is first fed into an EFG using
pure oxygen (5) supplied by the ASU as an oxidant agent. The gasifi­
cation produces raw syngas that passes through a gas conditioning
process similar to that described in Fig. 1: After filtering, the raw syngas
(11) enters the high-temperature (HTSR) and low-temperature water­
–gas-shift reactor (LTSR) to increase the H2 fraction. Afterward, the CO2
5
Applied Energy 284 (2021) 116401
present in the syngas is capture via monoethanolamine-based chemical
absorption as a carbon source (15a) for urea synthesis with the extra as a
by-product (15b). At the final purification stage, a methanator is
employed to remove any trace of CO and CO2. The H2 (21) mixed with
the N2 (22) is then compressed and fed to the ammonia synthesis and
urea synthesis loops, which are the same as the MtU case.
3.3. Integrated biomass- and power-to-urea (BPtU)
The BPtU case (Fig. 3) integrates BtU with the SOE-based PtA pro­
cess, which has been investigated in detail in Ref. [14]. The PtA process
is sized by the available CO2 captured from the syngas (14) out of the
water–gas-shift reactor to ensure the full conversion of the CO2. Thus, an
ASU unit will be needed to provide N2 for both BtU and PtU. The by-
products O2 from ASU (5) and SOE (38) are supplied to the EFG as
gasification agents, while the extra O2 (7) is for off-site sales. For the
steam electrolysis by the SOE, the demineralized water (25) is heated
and sent to the cathode to produce H2 (33) with part of the cathode
outlet recirculated (33a) to maintain the reduction atmosphere of the
cathode. The O2 flows across the electrolyte and is swept out as a by-
product. To increase the operating current density, a certain amount
of oxygen (35) is recirculated for the thermal management of the stack
[21,22,32]. Hydrogen (33) is then mixed with N2 (41) with an H2/N2
ratio of 3 and sent to the ammonia synthesis loop. Such a system can
realize the full carbon conversion compared with the BtU case and
enhance the flexibility of the whole plant: When renewable electricity is
not available, the plant can still work with water–gas-shift reactor and
H. Zhang et al. Applied Energy 284 (2021) 116401

Table 1 Other important components to be modeled for the processes

Comparison of the simulation and industrial practice. described in Section 2.1 have been developed and discussed in detail in
Industry Simulation Error, Refs. [14,18], including (1) the primary and secondary methane re­
% formers, (2) the EFG, (3) the WGSR, (4) the AGR, (5) the methanator, (6)
Input NH3/CO2 ratio, mol/ mol 2.0 2.0 0 the ASU, (7) the SOE, and (8) the ammonia synthesis process. The key
HP carbamate condenser inlet NH3/CO2 ratio, 3.08 3.12 1.2 technical specifications of these components, such as the operating
mol/ mol temperature and pressure, are selected referring to the optimization
HP carbamate condenser temperature, ℃ 179 167 6.7 results of the previous study [14] with the values shown in Figs. 1-3. The
HP carbamate condenser pressure, bar 144.2 141 2.2
Urea reactor outlet temperature, ℃ 185 183 1.1
operating parameters of the SOE stack are shown in Table 2. The com­
Urea reactor operating pressure, bar 141 141 0 positions of the biomass (wood) are given in Table 3. Besides, the per­
Single-pass carbon conversiona, % 51.3 52.3 2.1 formance of the heat exchanger network (HTN) is estimated via heat
Urea concentration, wt% 72 77 6.4 cascade calculation, as described elsewhere in Refs. [25,26,27]. The
a
. Single-pass carbon conversion: ratio of carbon at the inlet of the HP steam turbine network (STN) is employed for heat recovery and
carbamate condenser to urea formulated as described in Refs. [28,29].

4.2. Performance indicators

Table 2
Practical stack operating point at 750 ℃ and 2.2 bar. The stack power corre­
sponds to 5120 cm2 active cell area.
Operating variable Value
Average current density 0.95
Average voltage 1.32
Cathode feed H2O 8.0
Reactant utilization 80
Anode feed 0.13
Outlet temp. 864
Stack power 6.49
CO2 removal (the BtU mode) with the captured CO2 stored for the period
with available renewable electricity. Similarly, when renewable elec­
tricity is available, excess oxygen can be partially stored and supplied to
the gasifier for the period with SOE disconnected from the system. The
storage capacity of CO2 and O2 is considered based on the amount of the
system operating at full load for 24 h. When the SOE is disconnected
over 24 h, the system will operate under a partial load of the BtU mode
according to the amount of oxygen provided by the ASU.
4. Methodology
4.1. Process modeling
For the urea synthesis process, the model is developed based on
ASPEN PLUS urea process package [23] referring to an actual industrial
plant in China [24]. The adiabatic urea reactor is modeled via an Rplug
reactor under 141 bar outlet 183℃, where the carbamate reaction and
urea formation reaction take place with thermal self-sufficiency. The HP
carbamate condenser is modeled with a Rstoic reactor under 141 bar
and 167 ℃. The outlet temperature of the urea reactor is controlled by
adjusting the extent of the carbamate reaction in the HP carbamate
condenser. The CO2 stripper and HP scrubber are modeled with the
RadFrac model under 141 bar. The LP distillation column is represented
simply by a Rstoic reactor and separator model under 4.5 bar and 115
℃, and its heat demand represents the energy consumption of the
circulating heater at the bottom of the LP distillation column. The
ammonium carbamate decomposes into NH3 and CO2 in Rstoic, and then
the separator is used to separate the gas and liquid phases. The LP
carbamate condenser is modeled as a RGibbs reactor under 4.5 bar and
115 ℃. The simulation agrees well with the reference data provided by
an existing industrial plant in China, as shown in Table 1.
The techno-economic evaluation is carried out using the OSMOSE
platform developed by the Group of Industrial Process and Energy Sys­
Unit tems Engineering at École Polytechnique Fédérale de Lausanne. The
A/cm2 platform can integrate readily the Aspen models developed and perform
V plant-wise heat integration to close the energy balance of the overall
sccm/cm2
system. The platform has been employed for the optimal design of
%
sccm/cm2 various complex systems, e.g., Refs. [14,18,26,30,32]. The detailed
℃ workflow has been illustrated in detail in Refs. [18,31]. In this paper, the
kW thermodynamic and economic performances are evaluated with the key
performance indicators given below.
(1) System efficiency
The overall energy efficiency (η) is defined as
Ṁ product ∙LHV product + ΔE−
η= ∙100 (4)
Ṁ fuel ∙LHV fuel + ΔE+
where Ṁ is the mass flowrate (kg/s). The product represents urea for
the BtU and BPtU, but urea and ammonia for the MtU. The subscript fuel
represents biomass or natural gas. The superscripts – and + refer,
respectively, to the net power produced and consumed with ΔE =
|E− − E+ |, either the net electric power input (ΔE− ) or output (ΔE+ ) of
the process is considered since only the overall balance is of interest
[32].
(2) Levelized cost of the urea production
Based on the capital expenditure (CAPEX) and operating expenditure
(OPEX), the levelized cost of urea (LCOU) ($/GJ) is calculated according
to Ref. [33]:
byp
Copt + Cdep − Crev
LCOU = (5)
Purea
where Purea is the capacity of urea production (GJ/year), Cbyp rev is
byproduct revenues ($/year) from the sale of exported electricity, oxy­
gen, nitrogen, carbon dioxide, and ammonia, Cdep is the depreciation
cost ($/year). The Cdep can be calculated by:
i × (i + 1)n
Cdep = Cinv × (6)
(i + 1)n − 1
where Cinv is the investment cost ($), i is the annual interest rate, and
n is the plant lifetime (year).
The capital investment of the key components is estimated according
to [21] using the capacity factor method and pressure and material
factor method. More information about CAPEX and OPEX is given in

Table 3
The compositions of biomass.
Material Ultimate analysis (air-dried, wt%) Proximate analysis (air-dried, wt%) Heating value (kJ/kg)

C H O N S Moisture Ash Volatile Fixed carbon LHV

Biomass [18] 48.88 6.29 33.59 1.7 0.06 4.79 4.69 72.29 18.23 18,313

6
H. Zhang et al.
Fig. 4. The system energy efficiency (LHV) of urea production processes.
Part A of the Appendix. The reference economic assumptions include a
plant lifetime of 25 years [34], an interest rate of 10% [34], annual
operating hours (AoHs) of 7200 h [35], an electricity price of 73 $/MWh
[35], a biomass price of 5.1 $/GJ [36], and a natural gas price of 17.7
$/MWh [37]. The stack lifetime of 48,000 h [38] is considered, thus 3
replacements will be needed to finish the plant lifetime with the
replacement cost included in capital investment [14]. The sensitivity of
the most influential factors is also discussed in the following section.
5. Results and discussion
The three cases of urea production described in Section 3 are eval­
uated techno-economically and compared with the same urea yield of
10–50 MW in sections 5.1 and 5.2.
Fig. 5. The overall energy and material flows of (a) the MtU case, (b) the BtU case, and (c) the BPtU case.
7
Applied Energy 284 (2021) 116401
5.1. Thermodynamic performance
5.1.1. System energy efficiency
The overall system energy efficiency (LHV) for all three cases are
given in Fig. 4. Without heat recovery of STN, the BPtU case (BtU in­
tegrated with PtA) achieves a system efficiency of 49%, similar with that
of the SOA MtU (48%). The BtU case only reaches an efficiency of 36%.
The integration of STN to recover excess process heat can improve the
efficiency by 3 – 10% points. Particularly, the efficiency of the SoA MtU
case is enhanced by 10% points.
The overall energy and material flows of the three cases with refer­
ence to urea production of 1 MW are shown in Fig. 5 considering the
integration of STN. For the MtU case (Fig. 5a), all of the CO2 produced is
converted into urea by over 90% of total ammonia produced, with the
remaining ammonia and additional electricity (equivalent to 15% of the
urea production) as a by-product. Since no external electricity is
required, the overall energy efficiency can reach as high as 58%. For the
BtU case (Fig. 5b) with urea synthesis following BtA, only 40% of the
CO2 captured is converted into urea and a small amount of electricity is
needed to drive the auxiliaries. The BPtU realizes full carbon conversion
and reduces significantly the biomass consumed to produce the same
amount of urea, only 40% of that of the BtU case.
5.1.2. System-level heat integration
The integrated composite curves concerning the Rankine cycle for
recovering excess process heat are compared in Fig. 6. The corre­
sponding integrated Carnot composite curves are reported in Fig. B1 of
the Appendix Part B. The pressure levels and corresponding super­
heating temperatures are optimized, as listed in Table B1 of the Ap­
pendix, to maximize heat cascade utilization to enhance the system
H. Zhang et al. Applied Energy 284 (2021) 116401

Fig. 6. The integrated composite curves of the urea processes: (a) MtU, (b) BtU, and (c) BPtU.

8
H. Zhang et al. Applied Energy 284 (2021) 116401

Fig. 7. Cost breakdown of all three cases with 50 MW urea production: (a) investment costs, (b) operating costs and revenues.

efficiency. In the urea synthesis subprocess, the heat-releasing compo­ b). Above 300 ℃, the heat released by the gasification subsystem (the
nents are the HP, LP carbamate condensers and the HP Scrubber, while gasifier, the recovery boiler, the syngas and flue gas cooling), the SOE
the heat absorbing component is the circulating heater of the LP distil­ outlets, the ammonia synthesis reactor outlet, and HTSR is recovered by
lation column. The heat integration characteristics of other sub­ the Rankine cycle. Since the sizes of the HTSR and AGR are significantly
processes, i.e., methane-to-ammonia, biomass-to-ammonia, and power- reduced, the cascade utilization level of heat below 300 ℃ is high. The
to-ammonia, have been studied in detail in our previous work [14]. heat released from the hot process stream (200 – 300 ℃) and the 1st
In the MtU case (Fig. 6 a), a primary reformer furnace burning nat­ steam extraction is used for the HTSR steam generation. The heat
ural gas is required as hot utility to provide enough heat for the high- released from the HP carbamate condenser meets the major heat de­
temperature endothermic primary reformer (SMR). The primary mand of the AGR. The HP scrubber and the 2nd steam extraction can
reformer furnace consumes roughly 30% of the total natural gas feed. meet the heat demand of the circulating heater of the LP distillation
There is a large energy pocket between 200 ℃ to 775 ℃, in which a column and the steam generation for the SOE. Similar to the BtU, part of
great amount of heat is released from the high-temperature flue gas, the the heat released from the LP carbamate condenser is recovered by the
secondary reformer, the ammonia synthesis reactor, and HTSR. The heat Rankine cycle. In addition, the integrated composite curve of the SOE is
released is partly utilized by the process itself, e.g., the steam generation also reported in Fig. B2 of the Appendix Part B.
of the primary reformer, while the excess is recovered by the Rankine
cycle. The cascade utilization of the process heat is enhanced below 200
5.2. Economic performance
℃, mainly because (1) a large amount of heat from the HP carbamate
condenser is used by AGR (solvent regeneration); (2) the heat demand of
The cost breakdown of the three cases with 50 MW urea production
the circulating heater of the LP distillation column is satisfied by the
is compared in Fig. 7. The total investment of the BtU (324 M$) is the
heat released from the HP scrubber; and (3) the heat released from the
highest due to the large size of the gasification subprocess, followed by
LP carbamate condenser is recovered by LP steam generation of the
the BPtU (295 M$) and the MtU (222 M$), as shown in Fig. 7a. For the
Rankine cycle.
MtU case, the major investment cost comes from the heat exchangers
The BtU process (Fig. 6 b) does not need additional high-temperature
(44%), ammonia synthesis (20%), the STN (9%), urea synthesis (6%)
hot utility due to the heat released of the EFG. The overall process is
and the reformers (13%). For the BtU case, the investment cost is further
strongly exothermic, due to the recovery boiler, the syngas and flue gas
increased by the gasifier and ASU. The heat exchangers contribute the
cooling, HTSR, the ammonia synthesis reactor, the carbamate con­
most (39%) to the total investment, followed by EFG (20%), ammonia
densers and the HP Scrubber. However, to produce the same amount of
synthesis (16%), ASU (9%), urea synthesis (4%), and the STN (5%). For
ammonia, the biomass gasification pathway needs to supply more steam
the BPtU case, due to the integration of PtA, the contribution of WGSR,
for the HTSR and to remove more CO2 than the MtU case, which require
AGR, EFG, and ASU is up to 19%, lower than that of the BtU system
an enormous amount of heat and limits the available heat that could be
(36%). The major contributions come from the heat exchangers (32%),
recovered by the Rankine cycle. A large amount of heat from the HP
ammonia synthesis (21%), the EFG (12%), the SOE stacks (17%) and
carbamate condenser and steam extraction of the Rankine cycle is used
urea synthesis (5%).
by the AGR (solvent regeneration), while the heat demand of the
The breakdown of the operating costs and by-product revenues of the
circulating heater of the LP distillation column is met by the heat
three cases are compared in Fig. 7b, where the positive and negative
released from the HP scrubber. Most of the heat released from the LP
values indicate the operating costs and by-product revenues, respec­
carbamate condenser is recovered by the Rankine cycle.
tively. The costs of natural gas, biomass, and renewable electricity are
The BPtU process (Fig. 6 c) has an overall smaller heat load for the
the main contribution. Due to the low efficiency, the operating cost of
same urea production, because of the integration of an efficient PtA
the BtU is 1.4 times of that of the MtU case. Although the biomass cost of
process. The biomass used in the BPtU is only 40% of that of BtU (Fig. 6
the BPtU is only 40% of that of BtU, the operating cost of BPtU reaches

Fig. 8. The variation of economic indicators with plant capacity.

9
H. Zhang et al.
Fig. 9. The variation of economic indicators of the BPtU case with AAHs and electricity price: (a) impacts of AAHs (1800 – 7200 h) on the specific CAPEX, (b)
impacts of the electricity purchase price (0 – 73 $/MWh) and AAHs (1800 – 7200 h) on the LCOU.
1.5 times of that of the BtU due to the electricity demand (70% of the
total). The economic performance can be improved by the by-product
sales revenues: (1) ammonia and electricity for the MtU, (2) N2 and
CO2 for the BtU, and (3) high purity O2 for the BPtU.
The economic indicators (specific CAPEX and LCOU) of the investi­
gated cases are shown in Fig. 8 with a sensitivity of urea production
within 10 – 60 MW. The increase in the plant capacity will reduce the
specific investment cost of the plant (Fig. 8 a). The BtU case results in the
highest specific CAPEX of 10,000 – 6000 $/kW urea, followed by BPtU
(8500 – 5700 $/kW urea) and MtU (6800 – 4300 $/kW urea). The
variation of the LCOU with plant capacity is similar to that of the specific
CAPEX (Fig. 8 b). The MtU case has the lowest LCOU, followed by the
BtU and BPtU. The detailed LCOP in terms of energy is 38 – 23 $/GJ for
MtU, 52 – 31 $/GJ for BtU, and 60 – 43 $/GJ for BPtU. Given a payback
time of 7 years, the minimum urea selling price is also computed ac­
cording to Ref. [31] and is given in Fig. B3 of the Appendix Part B.
Compared with the BtU, the BPtU realizes efficient renewable urea
production with the LCOU 15 – 38% higher. The SOE-based BPtU case
needs to import a large amount of renewable electricity to drive the SOE,
thus both the renewable electricity price and available annual hours
(AAHs) have a significant impact on its economic feasibility. When
renewable electricity is not available, the SOE needs to be kept as hot
stand-by, and the system will be operated under the BtU mode with the
excess CO2 stored for the periods with available renewable electricity.
Therefore, when AAHs are smaller than AOHs, the system needs to store
CO2 and O2 that is easier than the storage of hydrogen and electricity.
Besides, to convert all the CO2 captured, the size of the SOE equipped will
be enlarged by AAHs/AOHs, and the sizes of ammonia and urea synthesis
also need to be expanded. The variation of the specific BPtU CAPEX with
the AAHs is shown in Fig. 9 a. When the AAHs decrease from 7200 to 3600,
the specific CAPEX increases by around 25%. When AAHs decrease from
7200 to 1800, the specific CAPEX increases by around 60%. The variation
of BPtU LCOU with AAHs and electricity price is shown in Fig. 9 b. If AAHs
decrease from 7200 to 3600 and 1800 with the electricity price being 73
$/MWh, the BPtU LCOU will increase by around 13% and 35%. When the
electricity price is reduced from 73 to 35 and 0 $/MWh with AAHs of 3600,
the LCOU will be decreased in average by 15% and 33% and becomes
lower than the LCOU with AAHs 7200 and electricity price 73 $/MWh. For
a payback time of 7 years, the variation of MUSP of the BPtU case with
AAHs and electricity price are given in Fig. B4 of the Appendix Part B.
6. Conclusions
In this paper, two green urea production processes (biomass-to-urea
and integrated biomass- and power-to-urea) are studied to systematically
evaluate the technical feasibility from thermodynamic and economic
performances in comparison with the state-of-the-art methane-to-urea.
The biomass-to-urea is achieved by integrating the green ammonia and
CO2 produced by the biomass-to-ammonia but the CO2 captured cannot
be fully converted into urea. For full carbon conversion to urea, the in­
tegrated biomass- and power-to-urea is made possible by solid-oxide
electrolyzer. The performance indicators are evaluated with heat
10
Applied Energy 284 (2021) 116401
cascade utilization to close energy balance and the Rankine cycle to
recover excess heat. A sensitivity analysis of the economic assumptions on
the economic indicators is also performed. The major conclusions include:
• With the optimal integration of Rankine cycles, the biomass-to-urea
efficiency only reaches 39% with a carbon loss of up to 60%, whereas
the state-of-the-art methane-to-urea efficiency can achieve 58%. The
proposed biomass- and power-to-urea can realize full carbon con­
version to urea with the system efficiency enhanced to 53% and the
capacity to store large-scale renewable electricity. The biomass
consumption is reduced by 60%, compared to the biomass-to-urea.
• Biomass-to-urea is more exothermic because of the gasification. Due
to the biomass C-H-O composition, the CO2 removal and steam
generation of HTSR is required, whose heat requirements reduce the
heat recovery and power produced by the steam cycles. The level of
heat cascade utilization becomes higher below 300 ℃ due to the heat
consumption of CO2 removal and HTSR processes.
• Due to the large electricity demand, the levelized cost of urea of the
integrated biomass- and power-to-urea is 43 – 60 $/GJ, which is
increased by 15 – 38 and 58 – 87 points compared to biomass-to-urea
and methane-to-urea, with 10 – 60 MW urea. The annual available
hours and price of renewable electricity have a significant impact on
the levelized cost of urea. If it decreases from 7200 to 3600 and 1800
with an electricity price of 73 $/MWh, the levelized cost of urea in­
creases in average by 13% and 35% from 51 $/GJ. When the electricity
price is reduced from 73 $/MWh to 35 and 0 $/MWh with annual
available hours of renewable electricity being 3600, the levelized cost
of urea decreases in average by 15% and 33% from 59 $/GJ.
• Compared with the biomass-to-urea process, the integrated biomass-
and power-to-urea concept can generally achieve a higher overall
energy efficiency, indicating a promising technical route for 100%
green urea production. Nevertheless, there is still a long way ahead
from commercial application since the higher levelized cost of urea.
In the future, more efforts should be invested into: (1) SOE tech­
nology development in terms of lifetime extension, single stack
power enhancement, mass production, and facilitation of the matu­
rity and commercialization; (2) market-oriented or government-
guided policies to maximize the available hours of renewable elec­
tricity and minimize the price of renewable electricity.
CRediT authorship contribution statement
Hanfei Zhang: Conceptualization, Methodology, Software, Valida­
tion, Investigation, Data curation, Writing - original draft, Visualization.
Ligang Wang: Methodology, Software, Review and Editing, Supervi­
sion. Jan Van herle: Methodology. François Maréchal: Methodology,
Supervision. Umberto Desideri: Conceptualization, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
H. Zhang et al. Applied Energy 284 (2021) 116401

Fig. B1. The integrated Carnot composite curves for the steam Rankine cycle: (a) MtU, (b) BtU, (c) BPtU.

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H. Zhang et al. Applied Energy 284 (2021) 116401

Fig. B2. The integrated composite curve for SOE in BPtU case.

Fig. B3. The trends of MUSP for different cases along with plant capacity.

Fig. B4. Impacts of the electricity purchase price (0 – 73 $/MWh) and AAHs (1800 – 7200 h) on the MUSP.

12
H. Zhang et al. Applied Energy 284 (2021) 116401

the work reported in this paper. Scholarship Council, China, for the PhD scholarship of Mr. Hanfei Zhang
and scholarship (borsa di ricerca) of the University of Pisa, Italy. Hanfei
Acknowledgments Zhang special thanks the Group of Industrial Process and Energy Sys­
tems Engineering at EPFL for their support.
The research leading to the above results was funded by China

Appendix

Part a economic modeling

(1) The capital investment

The economic evaluation mainly estimates the capital expenditure (CAPEX) [33]. To estimate the total investment cost of the equipment, the first
step is to estimate the purchase cost, Cp , of the equipment with the following procedure, given in Ref. [21].
The purchase cost of the equipment, operating at reference pressure and made of carbon steel, C0p , can be expressed in the following equation Eq.
(I).

log10 Cp0 = K1 + K2 ∙log10 A + K3 ∙(log10 A)2 (I)

where A is the capacity or sizing parameter (for example the power of a turbine or the surface area for a heat exchanger), while K1 ,K2 , and K3 are
the parameters fitted from market studies.
As the cost of equipment increases with operating pressure and material grades increase, Eq. (I) is no longer applicable. The additional pressure and
material-factors will be employed to account for the changes in operating pressure and the materials used. The revised equipment price is defined as
“Bare Module Cost”, as given in Eq. (II).
CBM = Cp0 FBM = Cp0 (B1 + B2 FM FP ) (II)

where CBM is the bare module cost of equipment, FBM is the bare module cost factor, B1 , B2 are factors depending on the type of equipment. The FM
and FP are pressure and material factors.
The best estimate of the purchase cost of major equipment is to use the reference cost data from previously purchased equipment of the same type,
as listed in Table 4. The bare module cost of the equipment can be estimated by Eq. (III).
A m
0
CBM = Cp,ref ∙( ) (III)
A0ref

where C0p,ref and A0ref refer to the base cost and reference size or capacity of equipment from literature. The cost exponent m is assumed to be 0.65 to
0.85 in this study.
When the equipment cost data comes from records or literature for price information, it should be converted into the present time by Eq. (IV).
Iindex
Cpt = Cp0 ∙( ) (IV)
Iref index
where the C is purchased cost, subscript t refers to the time when the cost is desired, subscript 0 refers to the reference time when the cost is known.
Iindex and Iref index are cost index of desired and reference time, e.g., the Marshall and Swift Equipment cost index.
Total module cost CTM refers to the cost of making small to moderate expansions or alterations to an existing facility. The CTM is composed of CBM
and “contingency and fee costs”. The latter is included in the cost in the evaluation of the cost as a protection against oversights and faulty information.
Unless otherwise stated, values of 15% and 3% of the bare module cost are assumed for contingency costs and fees, respectively. The CTM can be
evaluated by Eq. (V).
CTM = 1.18∙CBM (V)
A completely-new facility to be constructed on essentially undeveloped land is defined as Grass Roots CGR . The CGR is composed of CTM and
auxiliary facilities costs. The auxiliary facilities costs include costs for site development, auxiliary buildings, and off-sites and utilities. Unless
otherwise stated, the auxiliary facilities costs are assumed to be equal to 50% of the CBM for the base case conditions. The grassroots cost can be
evaluated by the Eq. (VI).
CGR = CTM + 0.5∙CBM (VI)

Table 4
Parameters to estimate the investment of major equipment. (Reference year 2017)
Unit Base cost C0p.ref (M$) BaseA0ref Base unit Base year m Ref.

a -3
SOE single stack 2.36 × 10 – – – – –
EF gasifier (gasifier, lock hopper, water quench) 63.4 2000 ton/d 2007 0.65 [40]
ASU 29.5 432 ton/dO2 2009 0.65 [41]
AGR 18.1 1227 kmol/hrCO2 2009 0.65 [42]
Steam Turbine system 5.9 10.3 MW 2002 0.65 [42]
a
. The SOE stack is taken as around 2,000 €/stack [43] with a lifetime of about 48,000 h [39].

13
H. Zhang et al. Applied Energy 284 (2021) 116401

For the compressor purchase cost, when the power of the compressor is less than 75 kW, the pressure- and material-factored method is employed;
while when the power of the compressor is more than 75 kW, another method is employed by Gavin Towler [39], as shown in Eq. (VII).
CBM = a + bSn (VII)
where a, b are the cost constants. S is the sizing parameter (driver power of compressor).
(2) The operating cost
The cost of operating labor is estimated base on Turton et al. [21]. The operating labor requirement for chemical processing plants can be evaluated
by the equation Eq. (XVI) and (XVII).

NOL = (6.29 + 31.7∙P2 + 0.23∙Nnp )0.5 (XVI)

where NOL is the number of operators per shift, P is the number of processing steps involving the handling of particulate solids, such as trans­
portation and distribution, particulate size control, and particulate removal. The handling of particulate solids is not considered in this study, and the
value of P was assumed as zero, because we considered this as an external service that is quite sensitive to the location of the plant and the availability
of biomass. Nnp is the number of equipment, such as compressors, towers, heater exchangers.
The value of NOL in Eq. (XVI) is the number of operators required to run the process unit per shift. The total number of operators can be estimated
according to the following equation Eq. (XVII).
Operatinglabor = 4.5 × NOL (XVII)
The cost of operating labor can be calculated by operating labor multiplied by operator salary. The salary per operator is assumed to be 52,900
$/year in this study.
With the calculated investment cost, the depreciation cost can be computed by Eq. (XVIII) [34]
i × (i + 1)n
Cdep = Cinv × (XVIII)
(i + 1)n − 1
where Cinv is investment cost, i is annual interest rate and n is plant lifetime (year). the levelized cost of product LCOP ($/GJ) can be computed by
Eq. (XIX):
byp
Copt + Cdep − Crev
LCOP = (XIX)
Purea
where Purea is the capacity of urea production (GJ/year), Cbyp
rev is byproduct revenues ($/year), Cdep is the depreciation cost ($/year).
When the payback time τ is determined, the minimum urea selling price MUSP ($/GJ) can be computed according to Eq.(XX) [34]:
byp
Cinv − τ × (Crev − Copt )
MUSP = , (XX)
τ × Purea
where Copt is operational cost includes labor, biomass, catalysts and imported electricity ($/year).
The assumptions for economic evaluation are listed in Table A1.
Part B
(See Table B1)

Table A1
Assumptions for evaluating the operating costs.
Economic data value unit Ref.

Plant lifetime 25 year [35]

Interest rate 10 % [34]
Annual operating hours 7200 hours/year [35]
Currency exchange rate (€ to$) 1.18 – [45]
Electricity price 73 $/MWh [36]
Natural gas price 17.7 $MWh [38]
Biomass price 6 $/GJ [37]
Ammonia price 514 $/ton [46]
Catalyst (primary reformer) 10 $/kg [47]
Catalyst lifetime (primary reformer) a 5 year –
Catalyst (secondary reformer) 15 $/kg [47]
a
Catalyst lifetime (secondary reformer) 7 year –
Catalyst (ammonia reactor) 23 $/kg [48]
Catalyst lifetime (ammonia reactor) 14 year [49]
Catalyst (HTSR) 17.64 $/kg [50]
Catalyst lifetime (HTSR) 4 year [50]
Catalyst (LTSR) 21.36 $/kg [51]
Catalyst lifetime (LTSR) 4 year [51]
Catalyst (methanation)a 17.7 $/kg –
Catalyst lifetime (methanation) a 4 year –
Nitrogen price 50 $/ton [35]
Oxygen price 177 $ /ton [52]
Carbon dioxide 30 $ /ton [53]
MEA price 1250 $/ton [54]
Process water price 0.4756 $/ton [46]
Operator salary 52,900 $/year [21]
a
. From manufacturer

14
H. Zhang et al. Applied Energy 284 (2021) 116401

Table B1
Key parameters of the optimal Rankine cycle.
Unit MtU BtU BPtU

Steam turbine Live steam 1 bar/℃ 120/573 120/575 120/574

Live steam 2 bar/℃ 110/568 6.5/295 28/474
Live steam 3 bar/℃ 1.3/356 6.4/294 3.5/156
Exhaust bar/℃ 0.05/33 0.05/33 0.05/33

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