Sustainable Production and Consumption 43 (2023) 124–139

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Sustainable Production and Consumption

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

Towards ethylene production from carbon dioxide: Economic and global

warming potential assessment
Grazia Leonzio a, b, *, Benoit Chachuat a, Nilay Shah a
a
Sargent Centre for Process Systems Engineering, Department of Chemical Engineering, Imperial College London, London SW7 2AZ, UK
b
Department of Mechanical, Chemical and Materials Engineering, University of Cagliari, via Marengo 2, 09123 Cagliari, Italy

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

Editor: Prof. Rafiqul Gani Currently, ethylene is the most important chemical with the largest global demand: it is mainly produced by
ethane or naphtha cracking but, this is characterized by significant carbon dioxide emissions. For this reason,
Keywords: starting from carbon dioxide and water, different routes for ethylene production have been proposed and
Carbon dioxide electroreduction investigated in the literature but a complete comparative analysis is missing.
Methanol-to-olefin plant
In this research, we analyze ethylene production via carbon dioxide electroreduction and methanol-to-olefin
Ethylene
process, with methanol obtained in several ways. After the modelling of these systems, economic and environ­
Life cycle assessment
Modelling mental (in term of global warming potential) analyses are conducted to develop a comparison among the
Economic analysis investigated processes and a conventional one based on naphtha cracking.
Results, located in the UK, show that the tandem process could be economically competitive (with the lowest
production cost of $ 1.34 per kg of ethylene), while the methanol-to-olefin process with methanol obtained from
syngas (produced through carbon dioxide-water co-electrolysis) has the best advantage for carbon dioxide
emissions (with the lowest impact of − 3.08 kg of CO2eq per kg of ethylene). Moreover, the most preferred energy
source for the electricity supply is the nuclear one with a small-scale plant because, economic and greenhouse gas
emission advantages are provided while, worse conditions are obtained when solar energy is used.
Our main finding is that electrochemical processes are likely to play an important role in the future when
performance improvements are realized.

and industrial precursors such as plastics, textiles, composites (poly­

ethylene, ethylene dichloride, ethylene oxide, ethylbenzene, vinyl ace­
1. Introduction
tate, co-polymers, etc.), end products (food packaging, film, toys, food
containers, bottles, pipes, antifreeze, carpets, insulation, housewares,
Globally, carbon dioxide (CO2) emissions were about 34.81 billion
etc.) (Berkelaar et al., 2022; Emerson, 2022). It is evident that ethylene
tonnes in 2020, hence there is an urgency to reduce these emissions to
is one of the most important organic materials: it is expected that its
avoid negative phenomena such as global warming and climate change
production will increase in the next future (the worldwide production of
(Our World in data, 2022; Wyndorps et al., 2021). The European Union
ethylene increased by over 15% in 2021 in comparison with 2018
(EU), in this context, aims to reduce 80% of CO2 emissions by 2050
(Statista, 2022)).
(COM, 2011). To achieve this aim, greenhouse gases (GHGs) must be
Currently, ethylene is mainly produced by the steam cracking of
reduced in all sectors including the chemical industry which contributes
naphtha (Europe and Asia corresponding to more than 80% of total
about 6% to global CO2 emissions (Our World in Data, 2021). Therefore,
ethylene production) and natural-gas-derived ethane (North America).
low-carbon technologies reusing CO2 to produce chemicals have to be
However, both conventional routes have both high energy requirements
developed according to circular economy principles. Among these
(up to 40 GJ heat per ton of ethylene) and CO2 emissions (1.8–2 kg of
chemicals, methanol and ethylene have the largest global market with
CO2 per kg of ethylene): it has been estimated that about 0.26 GtCO2eq
production capacities respectively of 145 million ton per year and 185
were emitted to satisfy the 2021 production, accounting for about 30%
million ton per year in 2018 (Global Data Petrochemical, n.d.). As shown
of the total energy required by the chemical industry (Sisler et al., 2021;
by these data, ethylene is the product with the highest demand in the
Haribal et al., 2018; Worrell et al., 2020). For these reasons, other
world as it is a building block used to produce pharmaceutical products

* Corresponding author at: Department of Mechanical, Chemical and Materials Engineering, University of Cagliari, via Marengo 2, 09123 Cagliari, Italy
E-mail address: g.leonzio20@imperial.ac.uk (G. Leonzio).

https://doi.org/10.1016/j.spc.2023.10.015
Received 24 June 2023; Received in revised form 18 October 2023; Accepted 22 October 2023
Available online 24 October 2023
2352-5509/© 2023 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
G. Leonzio et al. Sustainable Production and Consumption 43 (2023) 124–139

Nomenclature MTO methanol to olefin

NRTL non-random two liquids
AEM anion-exchange membrane OPEX operating cost
APEA aspen process economic analyzer PEM proton exchange membrane
AEL alkaline cell PSA pressure swing adsorption
BAU businesses as usual ROI return of investment
BoP balance of plant SRK soave-redlich kwong
CAPEX capital cost SOEC solid oxide electrolytic cell
CRF capital recovery factor TRL technology readiness level
DAC direct air capture
GHG greenhouse gas emission Symbols
GWP global warming potential H annual operating time of the plant (h per year)
LCA life cycle assessment Ee production energy consumption (kWh per kg of H2)
LCI life cycle inventory QH annual production capacity of the plant (kg of H2 per year)
LCIA life cycle impact assessment α technical learning rate (%)
MEA membrane electrode assembly

ethylene production routes have been investigated and suggested, being value of Return of Investment (ROI) is obtained for the same ethylene
based either on CO2 utilization in an electrolytic cell or via methanol to price in the range between $ 0.5 and $ 0.9 per Ib) than the oxidative
be used in a methanol-to-olefin (MTO) process (Jouny et al., 2018; Chen coupling of methane (OCM) process. However, the MTO is worse from
et al., 2021). This allows the decarbonization of feedstocks and energy an environmental point of view even though improved performance
sources. could be achieved by changing some process variables such as the
For CO2 utilization in an electrolytic cell, known also as the CO2 recycle ratio in the methanol reactor. The economic advantages of a new
electrochemical reduction (CO2ER) system, CO2 is directly reduced to MTO plant based on absorption technology in the recovery section are
ethylene at the cathode side and, water is oxidised at the anode side. An reported in Reyniers et al. (2017): the suggested scheme has capital costs
economic analysis of this process has been conducted in the literature by up to 14% and operating costs up to 9% lower compared to the tradi­
Pappijn et al. (2020) and Orella et al. (2020) finding a production cost tional cryogenic configuration. Another economic analysis is conducted
higher than that of the current market price, when using specific con­ in the work of Chen et al. (2021) finding that the MTO plant is
ditions for selectivity and conversion. However, an ethylene production economically profitable with a methanol price between 150 and 200 $
cost lower than that of the market price has been reported in the work of per ton for which the ROI is respectively 66% and 28.7%. For a methanol
Kibria et al. (2019), De Luna et al. (2019) and Jouny et al. (2018). In price of $ 250 per ton the ROI is negative (− 8.6%).
Kibria et al. (2019), a Faradaic efficiency of 90%, a current density of Electrochemical and MTO processes for ethylene production are
500 mA/cm2 and an electricity cost of $ 0.02 per kWh are assumed. The compared in Berkelaar et al. (2022) and Ioannou et al. (2020). In Ber­
same value of Faradaic efficiency is considered in the work of De Luna kelaar et al. (2022) the direct CO2ER to ethylene route, MTO plant with
et al. (2019), obtaining a production cost of 1100 $ per ton compared to methanol from direct CO2ER, CO2 hydrogenation, syngas (obtained
current prices which are in the range between $ 600 and $ 1300 per ton. from CO2-H2O co-electrolysis) and Fischer-Tropsch process are
In Jouny et al. (2018) the process for ethylene production is economi­ compared. The conducted analysis shows that the MTO plant with
cally feasible (net present value is positive) when optimistic conditions methanol from syngas produced from CO2-H2O co-electrolysis is the best
are taken into account (current density of 300 mA/cm2, selectivity of one based on efficiency, selectivity, process complexity and thermody­
90%, electricity price of $ 0.03 per kWh). namic limitations. The authors find also that electricity and CO2 costs
The environmental analysis of the direct CO2ER route has been re­ are critical for the economic analysis. As a similar work, in Ioannou et al.
ported in the literature in addition to the economic analysis. Even (2020) the following routes for ethylene production are analyzed and
though for Nabil et al. (2021), the electrochemical production of compared: the direct CO2ER to ethylene, MTO plant with methanol from
ethylene from CO2 is one of the most compelling product in terms of CO2 hydrogenation (green and blue hydrogen) and syngas from natural
global warming potential (GWP), in Pappijn et al. (2020) only the use of gas, naphtha cracking. These processes are classified as electro-route,
green electricity allows having an overall negative net CO2 balance. On thermo-route and fossil-route. Results show that under the current sce­
the other hand, in the cradle-to-gate analysis of Khoo et al. (2020) the nario, CO2-based alternative solutions for ethylene production, due to
value of GWP for a large-scale model is between 0.65 and 3 ton of CO2eq high electrical energy consumption, are not economically competitive
per ton of ethylene. with the fossil-based production routes, although they are more envi­
Another electrochemical process for CO2 reduction has been pro­ ronmentally friendly. The authors suggest the hybridization of CO2
posed by Sisler et al. (2021) considering a tandem scheme for CO2 utilization with fossil technologies in order to combine environmental
reduction to carbon monoxide (CO) in the first stage (in a solid oxide and economic benefits.
electrolytic cell (SOEC)) and CO reduction to ethylene in the second It is possible to see that comparative studies on ethylene production
stage (in a neutral membrane electrode assembly (MEA) or alkaline flow via alternative solutions are scarce in the existing literature. In partic­
cell). The solution avoids CO2 losses due to crossover in neutral MEAs ular, as point of weakness, all possible processes for ethylene production
and carbonate formation in alkaline flow cells and with an electrical are not taken into account and compared together. Moreover, economic
energy efficiency (evaluated as Faradaic efficiency×(Thermodynamic and environmental results of the electrochemical path depend on fixed
cell voltage/Cell voltage)) of about 52% can produce ethylene at $ 1000 assumptions and hence, a deeper analysis is required.
per ton. In this research, different and new alternative paths for ethylene
For the MTO process, economic and environmental analyses have production, mainly based on CO2 and H2O as raw materials, are inves­
been conducted in the literature. In Ortiz-Espinoza et al. (2017) it is tigated considering different CO2 and power sources: the electro­
reported that this process (where methanol is obtained from syngas chemical process (including the tandem process proposed by Sisler et al.
produced by methane steam reforming) is more profitable (a higher (2021) and the direct CO2ER to ethylene), MTO plant with methanol

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G. Leonzio et al. Sustainable Production and Consumption 43 (2023) 124–139

obtained from CO2 hydrogenation with blue and green hydrogen and Table 1
from CO2ER, and an MTO process with methanol obtained from syngas Assumption for the Tandem process (Sisler et al., 2021).
produced in a SOEC for the CO2-H2O co-electrolysis. After the modelling Solid oxide electrolytic cell Alkaline flow cell
of these processes, ethylene production cost and global warming po­
Cell voltage (V) 1.3 1.8
tential are evaluated and compared together and with the businesses as Faradaic efficiency (%) 100 90
usual (BAU) process, based on naphtha cracking. Current density (mA/cm2) 1000 1000
Single pass conversion (%) 60 53
2. Materials and methods
inherent difference in the technology that follows different reactions
In the following sections, the models used for the analyzed processes
although they produce ethylene at the end so that the same optimistic
(classified into three main routes such as the electrochemical production
conditions could not be taken into account. In any case, in each refer­
routes, the MTO plant with methanol produced from catalytic or elec­
ence, each optimistic condition is well supported. For the direct CO2ER
trochemical reactions and the MTO plant with methanol produced from
scheme, in Jouny et al. (2018) a current density of 300 mA/cm2 was
CO2-H2O co-electrolysis) are described. The methodology for economic
assumed at cell voltage of 2 V, because fell within the range of com­
and greenhouse gas emission analyses is also reported.
mercial water electrolyzers. Faradaic efficiencies of 90% have been
demonstrated for numerous CO2 reduction products, such as CO, formic
2.1. Process modelling acid, and methanol, and were assumed for the analysis. Regarding CO2
conversion, a value up to 35% has been reported in the literature (mostly
2.1.1. Electrochemical routes for ethylene production for batch and single pass cells) so that a better electrolyzer design at a
The tandem process and the single electrolyser cell are analyzed for large scale and an optimistic forecast could potentially boost the CO2
the electrochemical production of ethylene from CO2. The tandem conversion to well over 50%. For the tandem process, in Sisler et al.
process has been proposed by Sisler et al. (2021), as in Fig. 1: CO2 is at (2021), the SOEC can already operate with very high energy efficiency,
first reduced to CO in a solid-oxide electrolyser cell and then the pro­ so that many of its optimistic performance metrics have been measured.
duced CO is reduced to ethylene in an alkaline flow cell in a second step, For the alkaline flow cell, the same comparison with alkaline anion-
avoiding CO2 losses, according to the following reactions respectively exchange membrane (AEM) water electrolyzers was used to obtain the
for the cathode and anode side (see Eqs. (1) and (2)): optimistic current density. However, compared to the reference system,
2CO + 8e− + 6H2 O→C2 H4 + 8OH − (1) due to the limited pH gradients in the alkaline environment and the
lower thermodynamic voltage of the reaction an optimistic cell voltage
4OH − →2H2 O + 4e− + O2 (2) of 1.8 V was considered. The optimistic Faradaic efficiency was
increased to 90% because recent demonstrations of CO reduction to­
A gas separation unit based on pressure swing adsorption (PSA) is
wards ethylene have reached a value of up to 72% while the conversion
present after each electrolytic cell, allowing the separation of CO, H2 and
was increased of 10% (for the same reason discussed for the CO2ER
ethylene. The unconverted CO is recycled so that the external CO in the
scheme). The consideration of optimistic data helps to reduce costs up to
feed is lower than the stoichiometric amount. Simple material and en­
about 15% for the direct CO2ER and up to 60% for the tandem process.
ergy balances for an electrochemical process, as reported in the Sup­
plementary Materials, are used to model this overall system with the
2.1.2. Ethylene production with a MTO plant with methanol produced from
optimistic assumptions reported in Table 1 (Sisler et al., 2021).
catalytic or electrochemical reactions
A schematic diagram of the direct process reducing electrochemi­
The MTO plant is taken into account for ethylene production, with
cally CO2 to ethylene is reported in Fig. 2 (Jouny et al., 2018). The single
methanol obtained from a catalytic reaction between CO2 and green or
electrolyser cell for the direct CO2 electro-reduction to ethylene is
blue H2 and from CO2 electrochemical reduction, as in Figs. 3, 4 and 5.
modelled using the material and energy balances, as reported in the
All these sections are modelled in Aspen Plus except water and CO2
Supplementary materials, for an electrochemical process with the
electrolytic cells that are analyzed through material balances and in­
following optimistic assumptions: current density of 300 mA/cm2, cell
ventory data.
voltage of 2 V, Faradaic efficiency of 90%, CO2 conversion of 50%
The blue H2 is obtained from the methane steam reforming plant,
(Jouny et al., 2018). The cell works under alkaline conditions, because
reproduced in Aspen Plus as the work of Ciuchi (2019). The plant is
they are used by the best bench scale CO2 electrolyser and this allows the
composed of three main sections: the H2 production (reformer reactor,
use of non-precious metals at the anode, making the comparison with
high and low temperature water gas shift reactors and pressure swing
alkaline water electrolysis appropriate. A gas separation unit, based on
adsorption columns), CO2 capture (absorption with monoethanolamine
PSA, is present after the electrolytic cell.
(MEA) and stripper columns) and heat production parts. Soave-Redlich-
Optimistic conditions, and not lab data, are assumed for both elec­
Kwong (SRK) is used as the thermodynamic model.
trochemical processes because we aim to evaluate ethylene production
The green H2 is obtained from a proton exchange membrane (PEM)
at a large scale. Each technology is evaluated differently due to the

Fig. 1. Scheme diagram of tandem process (Sisler et al., 2021).

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Fig. 2. Scheme diagram of the CO2 electrochemical reduction to ethylene process (Jouny et al., 2018).

Fig. 3. Scheme diagram of ethylene production through a MTO plant with methanol from a catalytic reaction between CO2 and blue H2 (MTO = methanol to olefin).

cell and alkaline (AEL) electrolysis process, considering the inventory ethylene and propylene. In the recovery section, in addition to ethylene
data reported in Fan et al. (2022), as in Table 2. other products such as light gas products, ethane, propylene, propane,
The methanol plant based on CO2 hydrogenation using a highly 4 and C5 are separated. The Peng-Robinson equation of state ther­
C+ +

active catalyst is modelled in Aspen Plus as the work of Kiss et al. (2016). modynamic model is used.
Three sections are present: the methanol reactor with the recycle of CO,
CO2 and H2, a stripping column for water removal from the H2 stream 2.1.3. Ethylene production with a MTO process with methanol produced
and the distillation column for methanol purification. The SRK ther­ from CO2-H2O co-electrolysis
modynamic model is used for the modelling of the first two sections In this case study, the MTO process produces ethylene from methanol
while, the Non-Random Two Liquids (NRTL) is used for the distillation obtained by the syngas of a SOEC cell, based on CO2-H2O co-electrolysis,
column. The Graaf kinetic model is taken into account for the methanol as shown in Fig. 6. As mentioned, methanol is here produced by syngas
reactor (Graaf et al., 1988), characterized by the amount of catalyst while in the previous schemes, methanol is obtained via CO2ER or CO2
(865 kg) and tube (810 with a length of 12 m) as in Kiss et al. (2016). hydrogenation distinguishing the scheme from the others. The SOEC cell
The methanol production based on CO2 electrochemical reduction is is modelled in Aspen Plus as in the work of Freire Ordonez et al. (2021),
modelled with material balances for an electrochemical process as in by adjusting the CO2 flow rate in order to have syngas with a stoichio­
Jouny et al. (2018) with optimistic conditions such as: a current density metric number S equal to 2.03 which is suitable for the methanol syn­
of 300 mA/cm2, cell voltage of 2 V, Faradaic efficiency 90%, CO2 con­ thesis as in Zhang and Desideri (2020).
version 50% (as stated before, optimistic conditions are considered The methanol process using syngas in the feed and simulated in
because a large-scale production is investigated). As for the electrolytic Aspen Plus, is based on the separation of methanol and water (from
cell reducing CO2 to ethylene, alkaline conditions are used here with unreacted gases) by condensation and on the recycle of unconverted
non-precious metals as catalysts at the anode side. A distillation unit is gases (Leonzio and Foscolo, 2020). The methanol reactor is modelled as
present at the downstream for the recovery of methanol. in the work of Kiss et al. (2016).
The MTO plant is modelled in Aspen Plus reproducing the work of The used MTO plant is reproduced in Aspen Plus as described in
Chen et al. (2021), considering two main sections: the reaction and Section 2.1.2.
conditioning section and the product separation and recovery section. In
the first section the SAPO-34 catalyst is used to achieve a nearly com­
plete methanol conversion with about 80% of carbon selectivity to

Fig. 4. Scheme diagram of ethylene production through a MTO plant with methanol from a catalytic reaction between CO2 and green H2 (MTO = methanol to olefin;
MeOH = methanol).

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G. Leonzio et al. Sustainable Production and Consumption 43 (2023) 124–139

Fig. 5. Scheme diagram of ethylene production through a MTO plant with methanol from the electrochemical reduction of CO2 (MTO = methanol to olefin).

2.2. Economic analysis cost $ 1067 and 300 per kW respectively (Sisler et al., 2021). In the
SOEC, the CAPEX includes the electrolyzer, gas separation unit for the
The economic analysis is conducted assuming that all plants are cathode side and catalyst/membrane costs with their installation and
located in the UK with different CO2 sources (natural gas processing/ balance of plant (BoP) costs. For the gas separation unit, the reference
coal to chemicals, ammonia/bioethanol/ethylene oxide, methane steam capital cost, reference capacity and scaling factor are respectively $
reforming, iron and steel, cement, power generation and direct air 1,990,000, 1000 m3/h and 0.7 (Sisler et al., 2021). The catalyst/mem­
capture (DAC) with a respective cost of $ 23.7, 35.6, 77.1, 83, 106, 88.9 brane cost is 5% of electrolyser capital cost while, the BoP is 50% of total
and 325 per ton of CO2 (IEA, 2022)) and electricity (solar, wind, nuclear capital (Sisler et al., 2021). The installation cost is obtained by the
energy including a small modular reactor and large scale plant with a capital cost with a Lang Factor of 1 (Sisler et al., 2021). The OPEX in­
respective cost of $ 0.14, 0.09, 0.049 and 0.059 per kWh (IRENA, 2019, cludes the electricity cost for electrolyser and PSA units (consuming 0.25
NAMRC, 2022; Beis, 2016) sources. Assumptions for the economic kWh/m3 of gases (Sisler et al., 2021)), the cost of CO2 raw material and
analysis that are used in our work are the same proposed by the other additional operating costs related to the electrolyzer that are
respective literature work taken as reference. If some assumptions are estimated as 10% of electricity cost (Sisler et al., 2021). For the alkaline
missed in the literature, we consider the most suggested and used value flow cell, the same economic scheme of the SOEC is used for the eval­
in other research. Regarding the analysis method, for electrolytic cells uation of CAPEX and OPEX but, considering in addition the cost of the
we use the same method proposed by the respective literature work with anolyte solution (500 $ per ton) and water raw material ($ 1.5 per ton
our contribution if a shortfall is present. For plants simulated in Aspen (Thameswaer, 2022)) feed at the anode side. The system lifetime is 20
Plus (methanol, MTO, methane steam reforming) we use the economic years while, for the catalyst/membrane and electrolyte the lifetime is
tool of this software to have capital (CAPEX) and operating (OPEX) respectively 5 and 1 year. The overall ethylene production cost is eval­
costs. An overview of the used methodology is reported in the Supple­ uated as the sum of specific CAPEX and OPEX.
mentary material. For the direct electrochemical process, the economic analysis is
conducted based on the work of Jouny et al. (2018) where the electro­
2.2.1. Electrochemical routes for ethylene production lyser is assumed to cost 919.7 $/m2. The overall CAPEX is provided by
The economic analysis of the two routes based on electrosynthesis is the sum of capital cost for the electrolytic cell, BoP (53% of electrolyser
conducted considering the production of 100 ton/day of ethylene. capital cost) and capital cost for the PSA unit evaluated as described in
CAPEX and OPEX costs are evaluated. the tandem process (Jouny et al., 2018). A shortfall is present in the
In the tandem process, these two terms are evaluated as reported in evaluation of operating cost in Jouny et al. (2018) so that the OPEX is
Sisler et al. (2021). It is assumed that the SOEC and alkaline flow cells obtained as the sum of direct production costs and total fixed production
costs, as reported by Peters and Timmerhaus (1991), considering CO2
Table 2 and H2O as raw materials and the electricity consumption for the elec­
Assumptions for alkaline and proton exchange membrane cells for water elec­ trolyser and gas separation equipment as utilities. For the evaluation of
trolysis in green H2 production (Fan et al., 2022). the total levelized production cost these correlations are used (see Eqs.
Alkaline cell Proton exchange
(3)–(6)), assuming an interest rate of 10%, the plant lifetime of 20 years,
membrane cell an utilization of 95.2% and an annual production in ton per year
(Moreno-Gonzalez et al., 2021).
Outlet pressure (bar) 1 30
Electricity consumption (kWh per kg of H2) 51 58 CAPEX × CRF
Water consumption (kg per kg of H2) 10 10 Levelized CAPEX = (3)
Electrolyte (KOH) (gr per kg of H2) 1.9 0
Annual production × Utilization
Steam (kg per kg of H2) 0.11 0
Nitrogen (gr per kg of H2) 0.29 0

Fig. 6. Scheme diagram of ethylene production through a MTO plant with methanol from syngas obtained from CO2-H2O co-electrolysis (MTO = methanol to olefin;
MeOH = methanol).

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G. Leonzio et al. Sustainable Production and Consumption 43 (2023) 124–139

interest rate × (1 + interest rate)plant lifetime distillation capital costs. For the electrolyser, BoP and PSA the as­
CRF = (4) sumptions reported for the CO2 electrochemical reduction to ethylene
(1 + interest rate)plant lifetime − 1
are considered. For the distillation unit, the product-rich electrolyte is
OPEX recycled until a steady-state volume concentration of 10% methanol is
Levelized OPEX = (5) reached, hence quantifying the electrolyte flow rate used for the capital
Annual production × Utilization
cost of distillation. Assuming an electrolyte reference capacity of 1000
Total Levelized Production Cost = Levelized CAPEX + Levelized OPEX L/m, the distillation reference cost is $ 4,514,670 with a capacity scaling
(6) factor of 0.7 (Jouny et al., 2018). The OPEX is evaluated as reported for
the electrochemical system reducing CO2 to ethylene and discussed in
2.2.2. Ethylene production with a MTO plant with methanol produced from Section 2.2.1 but, by adding the utility cost for the distillation section
catalytic or electrochemical reactions (the reference cost is $ 11,508.1 per day with a reference electrolyte
The economic analysis of H2 production by water electrolysis is flow rate of 1000 L/min (Jouny et al., 2018)). The total levelized cost of
conducted according to the work of Fan et al. (2022) evaluating CAPEX methanol production is obtained from Eqs. (1)–(4).
and OPEX. The CAPEX is obtained by the following correlation (see Eq. The APEA tool is used to find the levelized cost of ethylene in the
(7)) (Fan et al., 2022): MTO plant, producing 46.4 ton of ethylene per h (Chen et al., 2021), in
addition to the allocation by mass procedure for the specific cost.
CAPEX = Electrolyser cost × e− 3×α
× Cap (7)
2.2.3. Ethylene production with a MTO plant with methanol produced from
where the electrolyser capital cost is equal to $ 742 and 1187 per kW
CO2-H2O co-electrolysis
respectively for AEL and PEM, α is the technical learning rate (that
For the economic analysis of an SOEC system, the specific electricity
considers that fact that technological progress might reduce the in­
consumption is evaluated from the work of Freire Ordonez et al. (2021)
vestment cost) equal to 12% and Cap is provided by Eq. (8) (Fan et al.,
and it is equal to 6.38 MWh per ton of syngas. This enables evaluation of
2022):
the electricity consumption of the simulated electrolyser cell producing
QH × Ee 18.9 ton of syngas per h (Zhang and Desideri, 2020). The electrolyser
Cap = (8)
H cost is based on Freire Ordonez et al. (2021) considering a reference cost
of $ 1.48×106 per MW, a reference size of 1 MW and a scaling factor of
with QH the annual production capacity of the plant (kg of H2 per year), 0.65. As a shortfall is present in the reference work, CAPEX and OPEX
Ee the production energy consumption (kWh per kg H2) and H the are obtained according to the methodology suggested by Peters and
annual operating time of the plant. The OPEX is obtained considering Timmerhaus, 1991.
the annual consumption of water, electricity, other raw materials (as in The economic analysis of methanol and MTO plants is carried out
Table 2), as well as operation and maintenance cost (4% of total in­ through the APEA tool in Aspen Plus and already discussed.
vestment cost) (Fan et al., 2022). The H2 production cost is provided as
the sum of specific OPEX and CAPEX (assumed a lifetime of 20 years and 2.3. Life cycle of greenhouse gas emissions
an interest rate of 10% for the CRF evaluation).
The economic analysis of blue H2 production by methane steam The analysis of greenhouse gas (GHG) emissions of processes pro­
reforming is carried out by the Aspen Process Economic Analyzer ducing ethylene is conducted according to the principles of Life Cycle
(APEA) providing the values of CAPEX and OPEX while, Eqs. (1)–(4) are Assessment (LCA) with the following standard phases as suggested by
used for the levelized cost. The lifetime of the plant is assumed to be 20 the ISO 14040: goal and scope definition, life cycle inventory (LCI), life
years with 8000 h/year as operating time (Ciuchi, 2019). The cost of cycle impact assessment (LCIA) and interpretation (ISO 14040, 2009;
electricity grid is assumed to be $ 0.251 per kWh (GlobalPetrolPrice, ISO 14044, 2006).
2022) while, the production rate is 7.27 ton of H2 per h (Ciuchi, 2019). Regarding the first phase of LCA, the aim of the analysis is to evaluate
The economic evaluation of the methanol plant based on CO2 hy­ and compare GHG emissions of the proposed ethylene production routes
drogenation is conducted by APEA tool assuming an operating time of at different CO2 and electricity sources. In view of this, the LCA is
8000 h/year (as the most used data in the literature) and a production of conducted considering 1 kg of ethylene as the functional unit (the
11.2 ton of MeOH per h (Kiss et al., 2016). The levelized cost of meth­ reference to which all inputs and outputs of the specific process are
anol is evaluated with Eqs. (1)–(4). related) and cradle-to-gate system boundaries (the use of ethylene is not
The analysis of methanol production cost through CO2 electro­ taken into account during the evaluation of the environmental burden
chemical reduction is carried out according to the procedure reported in but, only all processes from raw material extraction up to the production
Jouny et al. (2018), supposing a production rate of 100 ton/day and an of ethylene are considered). An allocation by mass is assumed in pro­
operating time of 8400 h/year, as proposed by the same authors. The cesses (MTO and tandem) where ethylene is not the unique product and
CAPEX is obtained by the sum of electrolyser capital cost, BoP, PSA and the geographical location was chosen as UK.
In the second phase of LCA, inventory data are evaluated. The in­
ventory data (consisting of material and energy balances based on 1 kg
Table 3
of produced ethylene) for all investigated processes are reported in the
Inventory data for the SOEC electrolyser in tandem process (all heating in the
Tables 3–13 and are obtained from modelling studies as described in
process can be provided by recycled heat of up and down stream processes and
Section 2.1, since these are unavailable in Ecoinvent.
for this reason an external heat in the input is not considered in the inventory
data. This explains the fact that the electricity consumption for the electrolyser is These foreground inventories are combined with data collected from
lower than the heating value of CO (10 GJ/ton)) (Sisler et al., 2021). Ecoinvent for the background process in order to quantify the LCIs of
each production process. At this stage, carbon footprints of CO2 from
Inputs
different sources are taken from Muller et al. (2020) where in the mul­
CO2 1.57 ton per ton of CO tifunctionality this parameter for the CO2 feedstock is evaluated through
Electricity-electrolyser 8.96 GJ per ton of CO
Electricity-PSA 1.31 GJ per ton of CO
the substitution method, keeping the carbon footprint of the main
product of the CO2 source unchanged. In this way all emission re­
Outputs
ductions are credited to the CO2 feedstock. As a result, the CO2 feedstock
CO 1 ton has negative carbon footprints even for fossil CO2. In their work (Muller
CO2 emissions 0.62 ton per ton of CO et al., 2020), having conducted a cradle-to-gate analysis, a negative

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Table 4 Table 8
Inventory data for the alkaline flow cell in tandem process (Sisler et al., 2021). Inventory data for the MTO plant simulated in Aspen Plus (Chen et al., 2021).
Inputs Inputs

CO 1.06 ton per ton of ethylene MeOH 6.04 ton per ton of ethylene
H2O 2.57 ton per ton of ethylene Steam-raw material 1.51 ton per ton of ethylene
Electricity-electrolyser 55.13 GJ per ton of ethylene Electricity 0.00025 kWh per ton of ethylene
Electricity-PSA 2.53 GJ per ton of ethylene Cooling water 797 ton per ton of ethylene
Steam LP 2.14 ton per ton of ethylene
Outputs
Steam MP 0.07 ton per ton of ethylene
Ethylene 1 ton
Outputs
H2 0.032 ton per ton of ethylene
Ethylene 1 ton
CO2 emissions 0.0018 ton per ton of ethylene
Table 5 By-products 1.63 ton per ton of ethylene
Inventory data for the direct CO2ER route (Jouny et al., 2018).
Inputs Table 9
CO2 6.27 ton per ton of ethylene Inventory data for hydrogen production through water electrolysis (Fan et al.,
H2O 2.52 ton per ton of ethylene 2022).
Electricity electrolyser 25.73 MWh per ton of ethylene
Electrolyser AEL PEM
Electricity PSA 750 kWh per ton of ethylene
Inputs
Outputs
Electricity (kWh per ton of H2) 0.051 0.048
Ethylene 1 ton
Water (ton per ton of H2) 10 10
H2 0.046 ton per ton of ethylene
Electrolyte (KOH) (gr per ton of H2) 0.0019 0
CO2 emissions 3.13 ton per ton of ethylene
Steam (ton per ton of H2) 0.11 0
Nitrogen (gr per ton of H2) 0.00029 0

value of carbon footprints means a reduction of emissions and not their Outputs
removal. However, the substitution method is neither applicable nor Hydrogen (ton) 1 1
needed for CO2 from a direct capture system because other products
besides CO2 feedstock are not produced.
In the following phase of LCA, i.e. LCIA, the global warming poten­ investigated in future studies.
tial (GWP) is evaluated through two different steps: classification and In the last stage of LCA, i.e. the interpretation, results obtained in the
characterization. In these steps, the LCI results are generated and previous phase are discussed and compared together and with the
organized into the impact category and then into the impact indicator at literature.
the midpoint level using the Environmental Footprint 2.0 method, rec­
ommended by the European Commission’s Joint Research Centre (Eu­ 3. Results and discussion
ropean Commission, 2018) by using SimaPro software (version 9.1.1.7)
interfaced with the Ecoinvent database. At this first level of study, we are 3.1. Results of process modelling
neglecting the analysis of other impact categories which could be
All simulations in Aspen Plus are validated by respective references
in the literature (Ciuchi (2019) for the methane steam reforming plant,
Table 6 Kiss et al. (2016) for the methanol plant with CO2 hydrogenation, Chen
Inventory data for the hydrogen production through the methane steam et al. (2021) for the MTO plant and Leonzio and Foscolo (2020) for the
reforming plant simulated in Aspen Plus (Ciuchi, 2019). methanol plant with syngas as feed). After the validation of the models,
Inputs from the modelling of each process, material and energy balances are
Natural gas 3.12 ton per ton of H2 determined. Table 14 reports the overall material and energy balances
Water 8.76 ton per ton of H2 (classified as raw materials, utilities and outputs relative to 1 ton of
Electricity 0.00346 kWh per ton of H2 ethylene production) of the investigated processes. It is clear that the
Cooling water 1742 ton per ton of H2
major differences in the mass and energy balances come from the used
Steam LP 2.11 ton per ton of H2
Steam MP 10.00 ton per ton of H2 technology for ethylene production.
Fuel 0.0008 ton per ton of H2 CO2 and process water are the two main important raw materials to
Outputs
be considered. The process with the highest CO2 consumption for 1 ton
of ethylene production (16.55 ton of CO2 per ton of ethylene) is the MTO
CO2 emissions 3.79 ton per ton of H2
with methanol from the CO2ER system. On the other hand, the tandem
Hydrogen 1 ton
process consumes only 1.66 ton of CO2 per ton of ethylene, the lowest
value among all studied processes. Another process with a significant
Table 7 CO2 consumption is the MTO plant with methanol from CO2-H2O co-
Inventory data for methanol production through carbon dioxide hydrogenation electrolysis: in this case CO2 is transformed to syngas and after that
with blue hydrogen simulated in Aspen Plus (Kiss et al., 2016). into methanol for ethylene production. Regarding water consumption,
Inputs MTO plants have values higher than those of electroreduction routes
(the lowest value equal to 2.52 ton of H2O per ton of ethylene is for the
CO2 1.53 ton per ton of MeOH
H2 0.21 ton per ton of MeOH pure CO2ER process).
Electricity 0.00029 kWh per ton of MeOH Other raw materials are steam, methane, electrolyte (KOH) and ni­
Cooling water 458 ton per ton of MeOH trogen, all used in the MTO plant options. However, it is evident that
Steam LP 0.95 ton per ton of MeOH
electrochemical routes (tandem and direct CO2ER), based only on CO2
Outputs and water, have lower consumptions of raw materials compared to MTO
MeOH 1 ton processes, despite higher amounts of electricity consumption. In fact, the

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Table 10 between $ 2.11 and 8.18 per kg of ethylene. The higher range cost ob­
Inventory data for methanol production through carbon dioxide hydrogenation tained for the direct CO2ER route is due to the higher CO2 flow rate
with green hydrogen simulated in Aspen Plus (Kiss et al., 2016) (Differences are needed in the feed (6.27 ton per ton of ethylene) and overall electricity
due to the pressure level of H2 from the cells). consumption (95.33 GJ per ton of ethylene) as already reported in
Inputs Table 14. In fact, these two factors contribute to the increase of oper­
H2 source AEL PEM ating costs. Although the direct CO2ER process has a lower CAPEX
CO2 (ton per ton of MeOH) 1.41 1.53 compared to the tandem process ($ 154 per ton of ethylene vs $ 270 per
H2 (ton per ton of MeOH) 0.19 0.21 ton of ethylene), OPEX are higher and influences the total cost in a
Electricity (kWh per ton of MeOH) 0.00054 0.00013 significant way. More optimization studies should be conducted in order
Cooling water (ton per ton of MeOH) 502 434
Steam LP (ton per ton of MeOH) 0.8 0.91
to optimize the direct electrochemical conversion in order to reduce
operating costs.
Outputs
In both study cases, the lowest price is obtained when CO2 comes
MeOH (ton) 1 from natural gas processing/coal to chemicals source while using a small
modular nuclear reactor as an electricity source. The highest price, on
the other hand, is produced with CO2 from a DAC system while using
Table 11
solar energy for electricity.
Inventory data for methanol production through carbon dioxide electrochemical
reduction (Jouny et al., 2018). Fig. 8 shows the ethylene production cost using a MTO plant with
methanol from the catalytic reaction between CO2 and blue H2 at
Inputs
different CO2 sources and with electricity from the UK grid. The cost has
CO2 2.74 ton per ton of MeOH values between $ 3.19 and 4.81 per kg of ethylene when CO2 comes from
H2O 1.10 ton per ton of MeOH
natural gas processing/coal to chemicals sources and DAC processes
Electricity electrolyser 11.53 MWh per ton of MeOH
Electricity PSA 236 kWh per ton of MeOH
respectively.
Fig. 9 reports the ethylene production cost when the MTO plant is
Outputs
used and with methanol from the catalytic reaction between CO2 and
MeOH 1 ton green H2 (obtained in PEM and AEL electrolysers) (Fig. 9a), from the
H2 0.02 ton per ton of MeOH
direct electrochemical reaction of CO2 and syngas produced in a SOEC
CO2 emissions 1.37 ton per ton of MeOH
for CO2 and H2O co-electrolysis (Fig. 9b). The cost is evaluated at
different CO2 and electricity sources. Among these processes, the cost
highest value of electricity consumption is for the direct CO2ER route range is between $ 3.25 and 8.64 per kg of ethylene for the MTO plant
(95.33 GJ per ton of ethylene) while, the lowest value of electricity using methanol from hydrogenation with green H2 produced in AEL
consumption is for the MTO plant using blue H2 (0.02 GJ per ton of electrolysers. Here, the lowest cost is obtained when CO2 is captured
ethylene). The highest value of the electricity consumption for the from natural gas processing/coal to chemicals sources and electricity is
electrochemical route is due to the fact that electricity is the only driver extracted from small modular nuclear reactors. On the other hand, the
in this route that is based on a non-spontaneous reaction so that more highest cost is when CO2 is obtained from DAC plants and solar energy is
energy in input is required. In any case, the order of magnitude of the exploited for electricity. In a similar process but, with H2 from a PEM
electricity consumption ratio between electrochemical and MTO routes water electrolyser, the specific cost to produce ethylene ranges between
is the same of that suggested by Ioannou et al. (2020). On the other $ 4.17 (CO2 from natural gas processing/coal to chemicals sources and
hand, MTO plants have other utilities as inputs, such as cooling water, electricity from small nuclear plants) and 8.89 per kg of ethylene (CO2
steam at medium pressure (MP), steam at low pressure (LP), steam at from DAC plant and electricity from solar energy). The higher range cost
high pressure (HP) and fuel. obtained for the MTO plant with methanol produced by CO2 hydroge­
CO2 emissions are present for all analyzed processes with the highest nation with PEM is due to the higher OPEX compared to the same system
and lowest value respectively for the MTO plant with methanol from but using the AEL. In fact, as shown in Table 14, the process based on
CO2ER (8.27 ton of CO2 per ton of ethylene) and other MTO plants
(0.0018 ton of CO2 per ton of ethylene). In the tandem process, 0.66 ton Table 12
of CO2 per ton of ethylene (0.62 ton of CO2 per ton of CO) are emitted Inventory data for the SOEC cell for carbon dioxide water co-electrolysis simu­
because in the SOEC the CO2 conversion is not total but it is set to 40 % lated in Aspen Plus (Freire Ordonez et al., 2021; Zhang and Desideri, 2020).
(Sisler et al., 2021).
Inputs
For future research, it is suggested to consider the recycle of the
CO2 1.30 ton per ton of syngas
emitted CO2 in these processes with a once-through scheme and verify
H2O 1.62 ton per ton of syngas
how this influences on the results. In addition to CO2 emissions and the Electricity 0.00639 kWh per ton of syngas
main product, by-products are present as outputs. Hydrogen (in tandem
Outputs
and direct CO2ER processes respectively of 0.032 and 0.046 ton per ton
of ethylene) and other by-products (for the MTO plant equal to 1.63 ton Syngas 1 ton
per ton of ethylene and including ethane, propylene, propane, C+ 4 and
C+5 ) are obtained.
Table 13
Inventory data for methanol production from syngas simulated in Aspen Plus
3.2. Results of economic analysis (Leonzio and Foscolo, 2020).
Inputs
In the economic analysis the levelized production cost of ethylene for
all analyzed routes is evaluated as reported in Figs. 7, 8 and 9 for Syngas 1.60 ton per ton of MeOH
Electricity 0.00016 kWh per ton of MeOH
different CO2 and electricity sources.
Cooling water 233 ton per ton of MeOH
Among these, Fig. 7 shows the ethylene production cost for the Steam LP 1.07 ton per ton of MeOH
electrochemical routes (tandem and direct CO2ER processes): lower Steam HP 0.60 ton per ton of MeOH
costs are determined for the tandem system with values in a range be­ Outputs
tween $ 1.34 and 3.74 per kg of ethylene. On the other hand, for the
MeOH 1 ton
direct electrochemical reduction of CO2 to ethylene the cost ranges

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Table 14
Overall material and energy balances for the investigated processes (CO2ER = CO2 electrochemical reduction; MTO = methanol to olefin; MeOH = methanol; AEL = alkaline cell; PEM = proton exchange membrane cell;
LP = low pressure; MP = medium pressure; HP = high pressure).
Tandem Direct CO2ER MTO with MeOH MTO with MeOH MTO with MeOH from green H2 (AEL) MTO with MeOH MTO with MeOH from
to ethylene from blue H2 from green H2 (PEM) from CO2ER CO2-H2O co-electrolysis

Raw material CO2 (ton per ton of ethylene) 1.66 6.27 9.24 9.24 8.52 16.55 12.56
Water (ton per ton of ethylene) 2.57 2.52 11.11 12.68 11.48 6.64 15.66
Steam (ton per ton of ethylene) 0 0 1.51 1.51 1.51 1.51 1.51
CH4 (ton per ton of ethylene) 0 0 3.96 0 0 0 0
Electrolyte (KOH) (kg per ton of ethylene) 0 0 0 0 2.18 0 0
Nitrogen (kg per ton of ethylene) 0 0 0 0 0.33 0 0
Utilities Electricity (GJ per ton of ethylene) 68.55 95.33 0.02 0.22 0.22 0.26 0.23
Cooling water (ton per ton of ethylene) 0 0 5773 3418 3829 797 2204
Steam LP (ton per ton of ethylene) 0 0 10.55 7.64 7.10 2.14 8.60
Steam MP (ton per ton of ethylene) 0 0 12.75 0.07 0.07 0.07 0.07
132

Steam HP (ton per ton of ethylene) 0 0 0 0 0 0 3.62

Fuel (ton per ton of ethylene) 0 0 0.001 0 0 0 0
Output Ethylene (ton) 1 1 1 1 1 1 1
H2 by-product (ton per ton of ethylene) 0.032 0.046 0 0 0 0 0
CO2 emissions (ton per ton of ethylene) 0.66 3.13 4.8 0.0018 0.0018 8.27 0.0018
Other by-products (ton per ton of ethylene) 0 0 1.63 1.63 1.63 1.63 1.63

Sustainable Production and Consumption 43 (2023) 124–139

G. Leonzio et al. Sustainable Production and Consumption 43 (2023) 124–139

Fig. 7. Ethylene production cost for the electrochemical routes at different CO2 and electricity sources and comparison with the BAU process (BAU = business
as usual).

Fig. 8. Ethylene production cost for the MTO plant with methanol from blue H2 and comparison with the BAU process (BAU = business as usual).

PEM has higher CO2 (9.24 ton per ton of ethylene), water (12.68 ton per and electricity from small modular reactors). Comparing these last two
ton of ethylene) and steam LP (7.64 ton per ton of ethylene) processes, the MTO plant with methanol from syngas has a higher OPEX
consumptions. that increase the overall ethylene production cost. A higher OPEX is due
A wider range exists for the production cost of ethylene in MTO plant to a higher consumption of water, cooling water and steam, despite of
with methanol from the electrochemical reduction of CO2: $ 3.24 and the lower CO2 consumption.
9.08 per kg of ethylene, for the same electricity and CO2 sources Overall, the results show that in order to decrease the production
considered in the previous processes. cost, CO2 should be captured from natural gas processing/coal to
The highest production cost, equal to $ 10.02 per kg of ethylene, in chemicals sources while electricity should be produced in small scale
Fig. 9b is for the MTO plant with methanol obtained by syngas (pro­ nuclear plants, due to the very convenient price of CO2 and electricity
duced with CO2-H2O co-electrolysis). This cost is incurred when CO2 is (although the GWP is much higher compared other cases) (IEA, 2022;
captured from the atmosphere and the electricity is from solar energy. NAMRC, 2022). The DAC process and solar energy both have still higher
For the same process, the lowest production cost is $ 4.06 per kg of costs (Ioannou et al., 2020; IRENA., 2019; Leonzio et al., 2022a, 2022b).
ethylene (CO2 from natural gas processing/coal to chemicals sources A conventional process for ethylene production is naphtha cracking

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Fig. 9. Ethylene production cost for the MTO process with methanol from, a) CO2 hydrogenation with green H2 (PEM and AEL), b) CO2ER and CO2-H2O co-
electrolysis and comparison with the BAU process (BAU = business as usual; MTO = methanol to olefin; MeOH = methanol; CO2ER = CO2 electro­
chemical reduction).

with a cost of $ 1.29 per kg of ethylene (Ioannou et al., 2020; ICIS, emissions) and that based on MTO with methanol from syngas. The
2022). The market price of ethylene fluctuates with time, but in this economic profitability of ethylene production via the tandem route has
analysis a reference price of $ 1.29 per kg of ethylene is considered and been demonstrated by Sisler et al. (2021), suggesting that it has more
all costs of ethylene will be compared to this reference cost. promise for producing low-cost ethylene due to its efficient use of energy
A secondary process that could be considered as reference for and CO2. Other process schemes for ethylene production that are
ethylene production is that based on MTO plant with methanol obtained analyzed in this research and based on MTO plant with methanol from
from syngas produced by methane steam reforming. CO2 hydrogenation of green H2 have a cost higher compared to that of
Table 15 reports the discussed cost ranges for each process and a the current production, as already found by Ioannou et al. (2020). The
comparison with both naphtha cracking process and the second refer­ costs of the of CO2ER to ethylene route in comparison current prices are
ence process (here the simulation for the MTO plant and the market in line with the work of Pappijn et al. (2020), Ioannou et al. (2020) and
methanol price (Methanex, 2023) are considered). It is evident that, Orella et al. (2020). For other systems producing ethylene a comparison
considering uncertainties in the economic analysis, only the tandem with market prices has not been presented in the literature.
process in cases with lower costs is competitive with the traditional
method of ethylene production (in the absence of high costs for CO2

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3.3. Results of GHG emission analysis from nuclear energy (small modular reactors) while 1.04 kg of CO2eq per
kg of ethylene are produced by using CO2 from a DAC system and
The global warming potential impact category is evaluated for the electricity from solar energy. For the same process but, with H2 pro­
analyzed processes, as shown in Figs. 10, 11 and 12. duced in an AEL cell, the climate change is between − 2.07 kg of CO2eq
Among these Figures, in Fig. 10 results for the two electrochemical per kg of ethylene (CO2 from a methane steam reforming plant and
routes are reported for different CO2 and electricity sources: the direct electricity from small-scale nuclear plant) and 1.09 kg of CO2eq per kg of
and tandem CO2ER to ethylene system enables negative values of global ethylene (CO2 from DAC plants and electricity from solar energy).
warming potential meaning a mitigation of CO2 because, a cradle-to- Comparing the results for these two last processes with those of the
gate analysis is conducted. In fact, for the direct process, the lowest MTO plant with methanol from syngas, it is possible to see that better
achieved value is − 2.52 kg of CO2eq per kg of ethylene when CO2 is performances are for the second mentioned system: for the same amount
captured from a methane steam reforming plant and electricity is ob­ of CO2 emitted, a higher amount of CO2 feedstock ensures better envi­
tained by nuclear energy (small nuclear reactors). On the other hand, for ronmental conditions.
the same process, the highest value is 1.78 kg of CO2eq per kg of ethylene Overall, results show that the lowest GWP impact is ensured by using
obtained from CO2 captured in a DAC system and electricity from solar CO2 captured from a methane steam reforming plant and electricity
energy. In addition to the pure CO2ER, the GWP of the tandem process is produced by nuclear energy, in particular small modular reactors. On
shown in Fig. 10: it has overall a higher environmental impact (in term the other hand, the highest GWP impact is caused by using CO2 from a
of CO2 emissions) compared to the direct CO2 electrochemical reduction DAC plant and electricity from solar energy. These results are techni­
to ethylene with a range of GWP between − 0.771 kg of CO2eq per kg of cally in agreement with the work of Muller et al. (2020) finding that the
ethylene (when CO2 is captured from a methane steam reforming plant CO2 capture from ammonia plant (then from a methane steam reforming
and electricity is obtained by small nuclear reactors) and 1.35 kg of plant) leads to the lowest carbon footprint of the CO2 feedstock. How­
CO2eq per kg of ethylene (CO2 from DAC with electricity from solar ever, this result does not agree from the point of view of the European
energy). The better performance of the direct CO2ER is due to the higher Union legislation because other CO2 sources are preferred for fuel syn­
CO2 consumption, as already discussed, resulting in a more negative thesis (McQuillen et al., 2022).
carbon footprint of the feedstock compared to the other system. It is Table 16 shows the GWP range for the investigated processes and the
evident that in this case the feed has the highest influence on GWP. comparison with the GWP impact of the conventional process based on
As shown in Fig. 11, higher values of GWP are obtained for the MTO naphtha cracking which is equal to 1.6 kg of CO2eq per kg of ethylene
plant with methanol produced by CO2 hydrogenation with blue H2: 3.97 (Ioannou et al., 2020) and that based on MTO plant with methanol from
kg of CO2eq per kg of ethylene are when CO2 is captured from the at­ methane steam reforming with a GWP of 2.15 kg of CO2eq per kg of
mosphere and UK electricity grid is used. For this process, the lowest ethylene (obtained from SimaPro considering the new defined MTO
value of GWP is 2.73 kg of CO2eq per kg of ethylene, by capturing CO2 plant and the conventional methanol flow rate as in the Ecoinvent
from a methane steam reforming plant. database).
In Fig. 12, results for the other MTO plants are shown: it is evident Considering the lowest value of GWP in that range, all processes for
that the lowest GWP impact is for the MTO with methanol obtained by ethylene production except the MTO plant with methanol from blue
CO2-H2O co-electrolysis (Fig. 12b). Here the GWP is in a range between hydrogen are more environmentally friendly compared to the tradi­
− 3.08 kg of CO2eq per kg of ethylene (CO2 from methane steam tional one and the process based on MTO with methanol from methane
reforming plant and electricity from a small-scale nuclear plant) and steam reforming. The environmental benefit of the CO2ER to ethylene
0.655 kg of CO2eq per kg of ethylene (CO2 from a DAC system and route has been also reported by Pappijn et al. (2020), especially when
electricity from solar energy). On the other hand, the highest value of renewable energies are used for electricity generation. In Ioannou et al.
GWP in Fig. 12b is for the MTO plant with methanol from CO2ER that (2020), a better performance of the direct electrochemical reduction
incurs 2.2 kg of CO2eq per kg of ethylene with CO2 captured from the route and the MTO plant with methanol from green H2 is achieved
atmosphere and electricity from solar energy. For the same process, the compared to the naphtha cracking. For the other alternative plants, a
lowest GWP impact of − 2.24 kg of CO2eq per kg of ethylene is obtained comparison with the BAU has not been conducted in the literature so far.
with CO2 captured from methane steam reforming plant and electricity In any case, in our results, the best process with the lowest value of
from small modular reactors. Despite of a higher CO2 consumption GWP value is the MTO plant with methanol obtained from syngas from
(16.55 ton per ton of ethylene) in the feed for the MTO plant with CO2-H2O co-electrolysis in a SOEC. Another competitive process is the
methanol produced via CO2ER, a higher CO2 emission (8.27 ton per ton direct CO2ER for which a proper optimization could ensure good per­
of ethylene) causes a higher environmental impact compared to the formances as well the best process. An optimization of the operating
MTO plant with methanol from syngas. conditions (increase of CO2 conversion and consumption with a recycle
− 2.3 and 1.04 kg of CO2eq per kg of ethylene is the GWP range for the of emissions and reduction of consumed electrical energy) must be
MTO plant using methanol from the CO2 hydrogenation with green H2 focused on later studies. Negative values of GWP can be achieved by all
(PEM). In this range, − 2.3 kg of CO2eq per kg of ethylene are for the case investigated processes but not by the tandem system and MTO plant
in which CO2 is from a methane steam reforming plant and electricity is using blue hydrogen that should be optimized in future research in order

Table 15
Comparison between the ethylene production cost of proposed and conventional routes (CO2ER = CO2 electrochemical reduction;
MTO = methanol to olefin; MeOH = methanol; AEL = alkaline cell; PEM = proton exchange membrane cell).
Process Min production cost ($ per kg of ethylene) Max production cost ($ per kg of ethylene)

Tandem 1.34 3.74

Direct CO2ER to ethylene 2.11 8.18
MTO with MeOH from blue H2 3.19 4.81
MTO with MeOH from green H2 (PEM) 3.25 8.64
MTO with MeOH from green H2 (AEL) 4.17 8.89
MTO with MeOH from CO2ER 3.24 9.08
MTO with MeOH from CO2-H2O co-electrolysis 4.06 10.02
Naphtha cracking 1.29 1.29
MTO with MeOH from methane steam reforming 1.48 1.48

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Fig. 10. Global warming potential for the electrochemical routes at different CO2 and electricity sources and comparison with the BAU process (BAU = business as
usual; CO2ER = CO2 electrochemical reduction).

Fig. 11. Global warming potential for the MTO plant with methanol from blue H2 and comparison with the BAU process (BAU = business as usual; MTO = methanol
to olefin; MeOH = methanol).

to reduce their environmental burden. only 1.66 ton of CO2 per ton of ethylene are required by this process
reducing in this way the OPEX (in particular the expenditure for raw
3.4. Best ethylene production routes materials) in comparison with other investigated routes characterized
by higher CO2 consumptions.
From the above results it is determined that the best process for Regarding the MTO plant integrated into a SOEC, it can be supposed
ethylene production from an economic point of view is the tandem one. that a relative high CO2 consumption in the feed and the lowest value of
On the other hand, the MTO plant with methanol obtained from syngas CO2 emissions make the process the best one in the GHG emission
from CO2-H2O co-electrolysis is the best process for a GWP point of view. analysis. It can be underlined that the MTO plant with methanol from
It can be supposed that the use of only electrical energy and the high CO2ER has the highest CO2 consumption (16.55 tonCO2/tonEthylene) but
electrical energy efficiency make the tandem process the most favorable in this case a relative high emission of CO2 (8.27 ton of CO2 per ton of
in the economic analysis (a lower value of OPEX is ensured). Moreover, ethylene) is present making the process not favorable for the GWP point

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Fig. 12. Global warming potential for the MTO process with methanol from a) CO2 hydrogenation with green H2 (PEM and AEL), b) CO2ER and CO2-H2O co-
electrolysis and comparison with the BAU process (BAU = business as usual; MTO = methanol to olefin; MeOH = methanol; CO2ER = CO2 electrochemical
reduction; AEL = alkaline cell; PEM = proton exchange membrane cell).

of view. 4. Conclusions
Results suggest that these new technologies could be competitive and
better compared to the conventional thermos-routes in the next future. The research introduces a comparative analysis of all ethylene pro­
CO2 consumption and emission and energy consumptions as well are duction routes investigated in the literature. The alternative production
important factors able to provide economic and GWP benefits. It is paths, starting from two important molecules such as CO2 and H2O, are
convenient to have low values for CO2 emissions and energy consump­ based on CO2 electroreduction (direct and tandem processes) and on
tion in order to have low costs and GHG emission burdens. On the other MTO plant (with methanol from different production ways such as CO2
hand, for CO2 consumption a trade-off should be achieved: a high value hydrogenation, syngas and CO2ER), while the fossil-based ethylene
causes a high OPEX but a low value of global warming potential if the production based on naphtha cracking is taken as a reference.
overall process is efficient from an environmental point of view. Future In the first stage, the modelling of each process according to the
research should be conducted on electrochemical reduction routes tak­ literature is carried out considering the optimistic conditions for elec­
ing into account these factors influencing costs and impact on the trochemical processes although, electrolytic cells for CO2 reduction are
environment. currently characterized by a low value of technology readiness level
(TRL). In the second stage, the economic profitability in terms of

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Table 16
Comparison between the global warming potential of proposed and conventional routes for ethylene production (CO2ER = CO2 electrochemical reduction; MTO =
methanol to olefin; MeOH = methanol; AEL = alkaline cell; PEM = proton exchange membrane cell).
Process Min global warming potential (kg of CO2eq per kg of ethylene) Max global warming potential (kg of CO2eq per kg of ethylene)

Direct CO2ER to ethylene − 2.5 1.8

Tandem 0.8 2.3
MTO with MeOH from blue H2 2.7 4.0
MTO with MeOH from green H2 (PEM) − 2.3 1.0
MTO with MeOH from green H2 (AEL) − 2.1 1.1
MTO with MeOH from CO2ER − 2.2 2.2
MTO with MeOH from CO2-H2O co-electrolysis − 3.1 0.7
Naphtha cracking 1.6 1.6
MTO with MeOH from methane steam reforming 2.15 2.15

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