See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/360893669

Techno-economic assessment of long-term methanol production from

natural gas and renewables

Article in Energy Conversion and Management · August 2022

DOI: 10.1016/j.enconman.2022.115785

CITATIONS READS

34 854

3 authors:

Carlos Arnaiz del Pozo Schalk Cloete

Universidad Politécnica de Madrid SINTEF
30 PUBLICATIONS 397 CITATIONS 174 PUBLICATIONS 3,077 CITATIONS

SEE PROFILE SEE PROFILE

Ángel Jiménez Álvaro

Universidad Politécnica de Madrid
39 PUBLICATIONS 353 CITATIONS

SEE PROFILE

All content following this page was uploaded by Schalk Cloete on 13 July 2022.

The user has requested enhancement of the downloaded file.

 Energy Conversion and Management 266 (2022) 115785

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Techno-economic assessment of long-term methanol production from

natural gas and renewables
Carlos Arnaiz del Pozo a, Schalk Cloete b, *, Ángel Jiménez Álvaro a
a
Universidad Politécnica de Madrid, Spain
b
SINTEF Industri, Norway

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

Keywords: Growing climate change concerns are driving interest in alternative energy carriers to fossil fuels. Methanol
Methanol (MeOH) is a promising candidate to alleviate the challenges faced by hydrogen regarding transportation and
Techno-economic assessment storage, with a developed pre-existing infrastructure and a well-known and scalable synthesis process. This study
Energy carrier
presents a techno-economic assessment of the different avenues for producing MeOH from 1) natural gas and 2)
Direct air capture
Gas switching reforming
renewable energy with direct air capture (DAC), for effective CO2 removal from the atmosphere. Under European
natural gas prices (6.5 €/GJ), state-of-the-art MeOH production from natural gas reach levelized costs as low as
268.5 €/ton, while an advanced plant using gas switching reforming attains a cost of 252.2 €/ton and approx­
imately 60% lower CO2 emissions. Middle Eastern costs can drop as low as 135.2 €/ton thanks to low natural gas
costs (2 €/GJ). In comparison, renewable MeOH with DAC reach 471.6–784.9 €/ton using technology assump­
tions representative of the year 2050, with Saudi Arabia achieving the lowest cost thanks to its outstanding solar
resource. Overall, renewable MeOH with DAC required CO2 prices of 121.4–146.7 €/ton to break even with
renewable plants using pipeline CO2, while CO2 prices in the range of 300 €/ton are required for competitiveness
against natural gas routes. Furthermore, a consistent comparison to NH3 as a carbon-free energy carrier showed
that blue and green NH3 require CO2 taxes of 49.8 and 274.3 €/ton to break even with natural gas-based MeOH,
respectively. However, NH3 is 14% cheaper than MeOH for renewable pathways, as it avoids the need for DAC.
Thus, strong policy support will be required to deploy green MeOH at scale, even in the long-term future.

intermediate energy storage medium [7]. MeOH and its derivatives are
attractive fuels for the transport sector [8], while it also has the potential
1. Introduction
to be utilized as gas turbine fuel [9] in peak electricity production, or as
a hydrogen carrier for fuel cell technology [10].
Methanol (MeOH) is an industrial commodity used as a building
The MeOH economy offers the advantage that all energy sources, of
block to produce synthetic hydrocarbons; it is employed as a solvent,
fossil and renewable origin, can be employed to produce this compound.
energy carrier or directly used as a fuel for transportation [1]. Lately,
The source of the carbon atom can be a recovered CO2 molecule origi­
due to the pressing environmental concerns related to greenhouse gas
nating from emissions of industrial and power plant sites through carbon
(GHG) emissions causing global warming [2], focus has been directed
capture utilization (CCU), while H2 can be effectively supplied by means
towards chemical energy storage systems [3] to facilitate decarbon­
of electrolysis of water with renewable power supply. This production
ization efforts. Different chemical compounds have been considered for
pathway can potentially enable effective mitigation of CO2 emissions at
this purpose, with hydrogen receiving an increasing interest as it con­
large capacities; Rivera-Tinoco et al. [11] predict MeOH costs of 891
stitutes a carbon-free energy carrier [4]. However, storage and trans­
€/ton and 5459 €/ton using proton exchange membrane (PEM) and solid
portation of this molecule presents substantial challenges in terms of
oxide (SOEC) water electrolysis, respectively. However, Ravikumar
large-scale feasibility [56], with no existing infrastructure available.
et al. [12] highlights that it is environmentally preferable to supply
MeOH, on the other hand, can be transported at ease in liquid state at
renewable electricity to the grid rather than MeOH production from
ambient temperatures through a well-developed pre-existing value
CCU, unless the grid CO2 intensity drops below 67 kgCO2/MWh. Koto­
chain, and presents low toxicity and safety hazards, showing substantial
wicz et al. [13] report an energy efficiency between 45.5% and 52.9%
potential to increase its presence in a future decarbonized economy as an

* Corresponding author.
E-mail address: [email protected] (S. Cloete).

https://doi.org/10.1016/j.enconman.2022.115785
Received 2 April 2022; Received in revised form 13 May 2022; Accepted 17 May 2022
Available online 26 May 2022
0196-8904/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Nomenclature LNG Liquefied natural gas

LP Low pressure
Acronyms OC Owners costs/Oxygen carrier
ATR Autothermal reformer PEM Proton exchange membrane
ARG Argentina PC Process contingency
ASME American Society of Mechanical Engineers PT Project contingency
ASU Air Separation Unit P/L Pipeline
BEC Bare erected cost CCU Carbon capture utilization
BWR Boiling water reactor SEA Standardized economic assessment
CCU Carbon capture & utilization SMR Steam methane reformer
CLR Chemical looping reforming SOEC Solid Oxide Electrolyte Cell
CPU Cryogenic purification unit TOC Total overnight cost
DAC Direct air capture tpd Tons per day
EPC Engineering, procurement and construction VOM Variable operating & maintenance cost
ESP Spain WGS Water gas shift
FTR Fired tubular reformer
FOM Fixed operating & maintenance costs List of symbols
GAMS General algebraic modelling system M Syngas module
GER Germany η Thermal efficiency
GHG Greenhouse gas ε Molar efficiency
GSR Gas switching reforming k Kinetic constant
HTER Heat transfer exchanger reformer Keq Equilibrium constant
IPCC Intergovernmental panel on climate change ECO2 Specific emissions
IP Intermediate pressure SC Specific consumption (GJ/ton)
LP Low pressure ṁ Mass flow (kg/s)
LCOM Levelized cost of methanol ṅ Molar flow (mol/s)
LCOP Levelized cost of product P Pressure (bar)
LHV Lower heating value Ẇ Power (kW)

for MeOH production from a wind farm and CO2 from power plants, GSR was conducted by Wassie et al. [25].
while Battaglia et al. [14] calculates costs of 846 €/ton of MeOH for Osman et al. [27] presents an experimental and process simulation
hydropower energy source and CO2 from a coal thermal plant for small study using CLR for MeOH production, revealing equivalent efficiency
scale production capacities of around 20 tpd. Alternatively, CO2 can be improvements of 5.3% relative to conventional production through
captured directly from air (DAC). This avenue was investigated by Bos autothermal reforming. In terms of economics, Spallina et al. [28] pre­
et al. [15] for a standalone 100 MW wind power MeOH process, sents a detailed techno-economic study of the dynamically operated
achieving costs of 750–800 €/ton. Much more optimistic outlooks are packed bed CLR reactors integrated with a MeOH synthesis conversion
also available such as Schorn et al. [16] predicting renewable MeOH loop, achieving cost reductions relative to conventional synthesis
costs of 370-600 €/ton for H2 prices ranging from 1.35 to 2 €/kg and CO2 pathways of 64.9 $/ton, while Labbak et al. [29] presents levelized costs
production (from DAC) at a cost of 100 €/ton, for the year 2030. as low as 242 $/ton for a CLR based MeOH production process config­
On the other hand, MeOH production through conversion of natural uration with Pressure Swing Adsorption (PSA). Other novel alternatives
gas can present an alternative means of energy storage for transportation of the syngas generation section for MeOH production include tri and
relative to liquefaction, in which case fuel efficiency, capital investment dry reforming of methane enabling a large reduction of CO2 emissions
and CO2 emissions reduction of the production process become from the plant through an enhanced CO2 conversion, relative to SMR
increasingly important. In this respect, several avenues for the configurations for syngas production and downstream CO2 addition
enhancement of the process are envisaged. New reactor technologies [30].
beyond gas phase reactors based on Cu catalysts have the potential to Due to the different economic and modelling assumptions between
increase conversion per pass of reactants achieving energy savings and literature sources, it is compelling to carry out a detailed techno-
cost reductions of the synthesis loop [17]. Liquid phase reactors can economic study of the different MeOH production pathways from a
allow a more efficient removal of the heat of reaction [18], but are consistent baseline. Such is the purpose of the present work, where the
limited by greater catalyst deactivation rates [19]. Alternatively, alternative avenues of MeOH production from natural gas using con­
membrane reactor technologies enable the withdrawal of products from ventional technologies are presented in detail and discussed, as well as a
the reaction to improve the yield and reduce investment costs [20,21]. potential advanced process based on CLR, and subsequently bench­
Cost reduction and efficiency enhancement opportunities can also be marked against renewable production by water electrolysis from
attained in the syngas generation section. One such possibility is renewable energy and DAC. Several studies considering different loca­
chemical looping reforming (CLR) [22], which can provide a suitable tions, technology costs and alternative CO2 sources (utilization of
syngas stream to the synthesis process. An alternative operation using captured CO2 from thermal power or industrial plants) for the renewable
dynamically operated fluidized beds with a valve switching mechanism case are also presented to provide a holistic perspective of the potential
[23] avoids the challenges of pressurized operation of interconnected of each synthesis route.
fluidized beds and effectively decouples the oxidation, reduction and
reforming steps undergone by the metallic oxygen carrier. Nazir et al. 1.1. Technology overview
[24] propose a gas switching reforming (GSR) concept for high effi­
ciency H2 production from natural gas with inherent CO2 capture, A brief description of the MeOH processes considered in this work is
leading to H2 costs as low as 1.83 $/kg. Experimental demonstration of depicted here, to highlight the core technological features of each

2
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

concept. A block flow diagram of the different plant configurations is Fig. 2:

shown in Fig. 1.
2.1. Natural gas MeOH plants
• Fig. 1 A) represents an SMR-ATR plant, where the syngas is produced
through steam methane reforming followed by autothermal This section provides a technical description of the MeOH plant from
reforming. This plant was studied by Blumberg et al. [31], Spallina natural gas. The key differences reside in the syngas generation route
et al. [28] and Collodi et al. [32] and it has been deployed for ca­ and process design features to attain a suitable module for the synthesis
pacities up to 5000 tpd. The key feature is that the purge stream from loop. All plants are designed adjusting the natural gas intake in each case
the synthesis loop is employed as fuel to provide heat for the to produce approximately 10,000 tpd of MeOH, which corresponds to
reforming, while the steam generation is carried out from heat re­ the largest projected production capacity achievable [34]. Detailed
covery of the ATR effluent. process diagrams and stream summaries can be found in the Supple­
• Fig. 1 B) outlines the ATR-HTER plant where syngas is produced mentary Material file attached to this work.
from autothermal reforming and a heat transfer exchanger reformer
[33] is employed to effectively recover heat from the ATR outlet for 2.1.1. SMR-ATR
conversion of a portion of the natural gas. This syngas production In the SMR-ATR plant, a fired tubular reformer (FTR) operating with
pathway is the preferred choice in modern MeOH plants for large a steam to carbon ratio of 1.8 [34] at 25 bar partially converts methane
capacities [34]. Assessments employing a single ATR for MeOH to carbon monoxide and hydrogen, after a pre-reforming and desul­
production are presented by Woods et al. [35] and Blumberg et al. phurization steps. Since the steam methane reaction produces a H2/CO
[36]. The integration of the HTER enables an improved thermal ratio of 3, the reaction is limited by a low operating temperature in the
performance, lower O2 consumption and convenient operating reformer tube outlet. The syngas effluent is then routed to an auto­
handle to adjust the syngas module for MeOH synthesis. thermal reformer (ATR) where it is partially combusted with 95%mol
• Fig. 1 C) shows the GSR concept based on chemical looping tech­ pure O2 from an air separation unit (ASU), providing heat for further
nology. It effectively integrates the synthesis loop purge stream with reforming in the catalyst section of the ATR. The outlet temperature of
the reduction step of the cluster while retrieving most of the CO2 the ATR is controlled with the oxygen intake flow to maintain a low
contained in the reduction outlet and recycling it to the reformer for methane slip, which is detrimental for the synthesis loop performance as
minimal carbon loss. Techno-economic assessments using the same it accumulates in the recycle stream and thus reduces the conversion per
syngas production principles were carried out by Labbak et al. [29], pass. On the other hand, the temperature outlet from the FTR fixes the
Spallina et al. [28] and Osman et al. [27]. module of the syngas product to the synthesis requirements (see Eq. (3)).
• Fig. 1 D) depicts the renewable MeOH concept utilizing electrolyser After the ATR, a heat exchanger network delivers HP superheated steam,
technology and direct air capture (DAC) or, alternatively, CO2 from IP reheated steam, IP water and LP steam to the steam turbine, MeOH
fossil fuel origin available from pipeline. Given the two alternative loop and purification column reboiler. After water knock out, syngas is
CO2 sources, the corresponding scope is shown in discontinuous lines compressed to 100 bar and routed to the synthesis loop. The purge
for this configuration. Concepts using DAC for MeOH synthesis have fraction from the loop recycle stream (around 4.5%) is selected to supply
been previously studied by Bos et al. [15], revealing poor competi­ sufficient heat to the FTR reformer upon combustion with close to
tive prospects relative to fossil fuel routes. stoichiometric air, fed to the system with a blower. The hot gas from the
furnace at 1010 ◦ C is used to preheat the incoming natural gas stream in
In the following sections, a comprehensive description of the three a series of heat exchangers. Since the synthesis loop contains uncon­
natural gas MeOH routes and the renewable MeOH production pathway verted CO and CO2, as well as CH4 from the reformer, the combustion of
is presented, providing details of the synthesis loop topology and reactor this stream implies generation of CO2 emissions and therefore a reduc­
model employed, common to all models. Then, the key performance tion of the carbon conversion to MeOH.
indicators from an energy and environmental perspective are defined
while the economic methodology is outlined. Subsequently, the techno- 2.1.2. ATR-HTER
economic results for all plants are shown, with appropriate sensitivity In the ATR-HTER plant configuration, syngas at 25 bar is produced
analysis to relevant economic assumptions and benchmarking between employing an autothermal reformer (ATR) fed with O2 from an ASU. The
the different production pathways. Finally, the main outcomes of the high temperature and low S/C (0.6) operation achieves a low methane
study are summarized and the core conclusions are drawn. slip and low CO2 formation. The outlet stream is routed to a heat transfer
exchanger reformer (HTER) [38] operating in parallel disposition with
2. Methodology the ATR. Namely, 20% of the natural gas input is reformed at a higher S/
C (2.7) in reformer tubes with heat provided by the ATR outlet and the
In this section, each of the plant characteristics are discussed in reformed product of the HTER. Such an arrangement facilitates a suit­
detail. Stationary power plant models were built in Unisim Design R481 able module close to 2. The mixed effluent is then cooled down by
for the natural gas-based plants and some components of the renewable preheating the inlet natural gas streams to the HTER and ATR in a
MeOH case. The Peng-Robinson equation of state (EoS) was used for recuperator. The syngas product is further cooled in a series of heat
thermodynamic property estimation in the syngas generation section as recovery exchangers to produce steam and hot water. After a final heat
recommended by the user manual for natural gas and air components rejection to ambient temperature, condensed water is knocked out and
[37]. ASME steam tables were used in the steam power cycle compo­ the syngas is compressed to 75 bar and routed to the synthesis loop. A
nents and Soave Redlich-Kwong EoS in the synthesis loop [36]. The GSR somewhat lower pressure operation is selected for the synthesis loop for
dynamic model is built in Scilab with property estimation from an in- a fixed reactor volume because the large ratio of CO/CO2 in the syngas,
house thermodynamic database from Universidad Politécnica de relative to the other models, provides a quality syngas with high reac­
Madrid (Patitug) and integrated in the stationary flowsheet through a tivity, resulting in comparatively higher conversions per pass. Further­
CAPE-OPEN unit operation. The natural gas-based plants are assessed more, since the reverse water gas shift reaction (WGS) takes place to a
using process modelling followed by an economic assessment. The small extent due to the lower presence of CO2 in the feed, there is a lower
renewable plants require optimization of the investment and hourly concentration of water in the raw MeOH product, reducing the size and
dispatch of each candidate technology to produce a constant MeOH energy demand of the purification column. The purge fraction from the
output at minimal costs from the intermittent supply of power. The synthesis loop recycle stream (4.4%) is specified to achieve sufficient
methodology of the assessment for the different cases is depicted in power generation in a steam boiler power cycle to satisfy the plant

3
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 1. Block flow diagram of the different MeOH production pathways: SMR-ATR (A), ATR-HTER (B), GSR (C), and renewable (D). Yellow, green, and red columns
in the GSR cluster represent reforming, oxidation, and reduction steps respectively. In the renewable plant, red lines represent heat flows and dashed black lines
alternative CO2 supply pathways. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

4
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 2. Methodology framework of this study.

auxiliary demand. This implies emissions arising from the combustion of and condenser. The resulting maximum temperature required in the
carbonaceous species present in the fuel. A steam extraction from the LP present model was 1030 ◦ C, in line with previous conservative as­
stage delivers sufficient steam to the purification reboiler column to sumptions for this technology from the authors [39], and similar to the
meet the demand. values reported by Spallina et al. [28]. The purge fraction (5.1%) is
specified to attain a reasonable recycle to feed ratio in the synthesis loop,
2.1.3. GSR similarly to the conventional plants. At a temperature of 1030 ◦ C, these
This work explores a MeOH production configuration based on such specifications are met while achieving sufficiently high methane con­
a syngas generation concept using a Ni-based oxygen carrier [26] and version (88.6%) to avoid a large accumulation of this component in the
reactor operating temperatures reaching a maximum value of 1030 ◦ C, a synthesis loop. Secondly, the GSR cluster is operated to minimize ingress
conservative value which strengthens the feasibility prospects of high of N2 to the reforming step outlet, avoiding undesirable presence of this
temperature gas switching valves and filters. The GSR plant features a inert species in the syngas product. Finally, the reduction outlet, con­
dynamically operated fluidized bed cluster of reactors to generate syn­ taining a relatively large concentration of N2 after water knock out
gas for the synthesis reaction. Similarly to previous work [39], steel rods (around 30%) due to mixing in the GSR, is routed to a cryogenic puri­
are placed within the reactor volume to provide thermal mass, mini­ fication unit [40], where approximately 80% of the CO2 is retrieved at a
mizing temperature fluctuations across the cycle, which increases the purity of 97%mol. This stream is repressurized to GSR pressure and
average reforming temperature leading to higher methane conversion. reheated before being mixed with the preheated natural gas and stream
The topology proposed here presents similarities to the concepts studied inlet to the reformer, allowing to adjust the module conveniently for the
by Spallina et al. [28], but incorporates several modifications. First, the synthesis reaction. By carrying out the purification prior to the recycling
maximum GSR cycle operating temperature is adjusted to close the en­ to the reformer inlet, further reductions of the N2 concentration in the
ergy balance with the purge stream heating value (employed in the GSR syngas are attained. The reforming outlet is cooled down by preheating
reduction step, Fig. 1C). All the steam produced by the MeOH reactor is the incoming streams, while LP steam and IP water for the MeOH reactor
supplied to the GSR reforming inlet, practically avoiding a steam turbine is produced in a downstream multi-stream heat exchanger. The

5
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

oxidation outlet, after expansion in a turbine, is routed to a heat more optimal energy integration of the scheme. Alternatively, electricity
exchanger further producing LP steam. The higher content of CO2 in the can be stored in batteries, while CO2 and H2 must be compressed and
syngas requires a larger separation column than in conventional plants stored in pressurized tanks.
due to the increased production of water in the synthesis. The second configuration produces MeOH without the technological
uncertainties of DAC and elevated-temperature electrolysis. In this
2.2. Renewable MeOH plant configuration, pressurized CO2 originating from CO2 capture from large
point sources is delivered via pipeline (CCU) and assigned a CO2 utili­
The renewable MeOH plant considered in this work utilizes power zation credit for avoiding additional pipeline and CO2 storage infra­
from intermittent wind and solar power resources to split water mole­ structure. In exchange for the large process simplification and
cules to oxygen and hydrogen in an electrolyser (PEM), operating with technology risk reduction of this plant, the MeOH product can no longer
an LHV efficiency of 70%, extrapolated from European targets [41], and be considered green as the CO2 would originate mainly from fossil
an H2 production pressure of 30 bar. Research and development efforts sources. However, the produced liquid fuel can still displace liquid fuel
towards higher temperature operation (150 ◦ C) [11] at pressurized from fossil origins.
conditions can improve system efficiency by reducing overvoltage losses The synthesis loop for the renewable cases is operated at 100 bar, due
[42]. The assumption that such elevated temperature electrolysis be­ to the lower reactivity of the syngas relative to that produced from
comes commercially viable in the future is important for satisfying the natural gas autothermal reforming, producing large amounts of water
process heat demand, as outlined later. On the other hand, two alter­ because of the high reaction extent of the reverse WGS. This requires a
natives are considered for recovering the CO2 for the synthesis reaction. larger distillation column to meet the purity requirements, relative to
First, a direct air capture system based on low temperature solid amine the other plants. A small backpressure steam turbine utilizing the syn­
sorbents (Fasihi et al. [43]) to produce true green MeOH. CO2 from DAC thesis heat of reaction for steam evaporation is used to produce some
is assumed to be produced at a vacuum pressure of 0.2 bar and a 99.9% electricity, while hot water to the BWR is supplied by heat recovery from
mol purity [44]. Further compression to synthesis pressure is performed the compressor intercoolers. The low-pressure steam output at 1.8 bar is
by means of a three-stage intercooled compressor. Due to the lack of used to partially satisfy the column reboiler duty. In the case with CO2
constant wind and solar power availability, storage devices of elec­ supply via pipeline, the synthesis loop is simplified by avoiding the need
tricity, hydrogen, CO2, heat and MeOH must be deployed to maintain a for CO2 compressors and buffer storage.
steady output of MeOH from the plant fixed to a value of 2300 MW. Heat
from this elevated temperature electrolysis process is effectively 2.3. Synthesis loop
employed to match the large thermal demand of the DAC regeneration
step and the MeOH purification section, by means of intermittent steam The synthesis loop employed for MeOH production is depicted in
storage [45], under the assumption that electrolyser waste heat can be Fig. 3. The system consists of an isothermal boiling water reactor [17],
used to generate low pressure steam at 150 ◦ C. Furthermore, the model where the exothermic heat of reaction is transferred across the tube
also incorporates the possibility of using excess renewable energy ca­ length to produce steam at 32 bar and 250 ◦ C. An homogeneous reactor
pacity to generate more steam through resistance heating, allowing for a model of a catalyst packed bed is employed to calculate the conversion

Fig. 3. MeOH synthesis and purification loop.

6
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

of reactants, achieving very close predictions to more involved heter­ recompression power. Formal optimization of the synthesis loop pres­
ogenous models taking into account mass and energy balances in the sure was not attempted, but the effect would likely be small due to
solid phase, as shown by De María et al. [46]. This study considers that several counterbalancing effects. For example, lowering the synthesis
the MeOH synthesis follows the reaction mechanism of CO2 hydroge­ loop pressure will decrease syngas compression costs but also reduce
nation and (reverse) water gas shift (WGS) reaction, as illustrated in Eq. conversion per pass, increasing efficiency losses related to a larger
(1) and Eq. (2). recycle and purge.
As illustrated in Fig. 3, the fresh syngas from the reforming section of
CO2 + 3H2 ↔ CH 3 OH + H2 O (1)
each plant is compressed to high pressure in an adiabatic stage and
mixed with the recirculating streams. The mixture is heated up in the
CO + H2 O ↔ H2 + CO2 (2)
recuperator prior to entering the boiling water reactor employed for
For optimal operation of the synthesis loop, it is required that the MeOH production, the effluent of which exchanges heat with the inlet.
reactants are fed at close to the stoichiometric ratio or module M of 2, This outlet stream is further cooled to ambient temperature and then
defined by Eq. (3). routed to a high pressure knock out vessel where condensed MeOH
product and water are withdrawn, together with a gaseous stream which
[H2 ] − [CO2 ]
M= ≈2 (3) is recycled to the feed point via a recompression stage to overcome the
[CO] + [CO2 ]
pressure losses of the loop. The liquid product is expanded to 2 bar and
Several kinetic models are available for industrial MeOH synthesis sent to a low-pressure vessel, after which the flashed vapours are
[47]). The kinetic expressions specified in the reactor model in this study recompressed and mixed with the feed. The liquid effluent is sent to a
were derived by [48] over a Cu/ZnO/Al2O3 catalyst, and are reflected in purification column (with changing n◦ of trays for each plant) where the
Eq. (4) and Eq. (5). These expressions are selected for their relative raw MeOH is purified to 98%mol for bulk transportation achieving
simplicity, with the pre-exponential constants and activation energies almost complete recovery. LP steam at 1.8 bar from different plant
for the kinetic constants kj,i and the equilibrium constant expressions sections (steam turbine extraction, dedicated boilers) supplies sufficient
Keq,j detailed in the aforementioned study [48]. However, kinetics heat to the reboiler, achieving approximate heat demand of 2.4–2.6 MJ/
assuming different active sites for both CO and CO2 hydrogenation are kg of MeOH, in line with Halager et al. [51], depending on the amount of
also suitable for applications with varying ratios of these molecules water in the feed to the distillation section. The column presents a
[49]). Nevertheless, the chosen kinetic model will more accurately partial condenser producing MeOH at 60 ◦ C, while the off gas is again
reflect the impact of differences in syngas composition across the plants recirculated to the feed point of the synthesis loop after recompression.
compared to an equilibrium conversion approach as used in several
large-scale technoeconomic studies (e.g.,[27,28]). Furthermore, the use 2.4. Plant performance indicators
of a kinetic model ensures that full equilibrium conversion is not ach­
ieved and that the reactor can be accurately sized for the capital cost Energy, environmental and economic performance indicators are
estimation. Further assumptions of the reactor model are provided in defined in this section to facilitate a holistic comparison between the
Table 1. different MeOH production pathways.
[ ( )]
2.4.1. Energy and environmental
1 PH2 O PCH 3 OH
k1,1 PCO2 PH2 1 − Keq,1 PCO2 PH 3

rMeOH = (
2
)3 (4) Thermal efficiency is defined as the MeOH product lower heating
value and the natural gas lower heating value input as shown in Eq. (6).
PH 2 O 0.5
1 + k1,2 PH + k1,3 PH2 + k1,4 PH2 O
The equivalent efficiency Eq. (7) accounts for electricity consumption or
2

[ ( )]
PH2 O PCO exports of the plant assuming a benchmark natural gas combined cycle
k2,1 PCO2 1 − Keq,2
rrWGS = (
PCO2 PH2
) (5) efficiency of 62.3% [52], considering that work imported to the plant
has a negative sign. The electrical efficiency is defined with the net
P
1 + k2,2 PHH2 O + k2,3 P0.5
H2 + k2,4 PH2 O
power production of the plant in Eq. (8).
2

The reactor is operated under typical industrial process conditions

[17]: the inlet feed to the reactor is set to 230 ◦ C, allowing for an ṁMeOH LHV MeOH
ηMeOH = (6)
adiabatic section where the heat of reaction elevates the temperature to ṁNG LHV NG
260 ◦ C, after which the heat transfer fluid (boiling steam) removes heat
ṁMeOH LHV MeOH
to maintain constant temperature on the reaction side thereby maxi­ ηMeOH,eq = Ẇ net
(7)
mizing conversion per pass. Such a narrow temperature range is main­ ṁNG LHV NG − ηCC

tained to ensure a long catalyst lifetime and stable operation avoiding

deactivation [50]. The loop is designed at high pressure (75–100 bar) to ηEl. =
Ẇ net
(8)
minimize recirculation of material due to incomplete conversion of the ṁNG LHV NG
reactants, ensuring a reactor inlet to fresh feed gas molar ratio of On the other hand, carbon and hydrogen efficiencies as shown in Eq.
~3.5–3.8, thereby attaining a low pressure drop per pass to reach low (9) and Eq. (10), respectively, indicate the fraction of the respective
atoms from the original fuel that are present in the final product. It gives
an understanding of the conversion efficiency of the different process
Table 1
designs:
Reactor modelling details.
Item Value Units ṅC,MeOH
εC = (9)
ṅC,NG
Inlet temperature 230 ◦
C
Outlet temperature 260 ◦
C
Pressure drop Ergun ṅH,MeOH
– εH = (10)
Catalyst density 1770 kg/m3 ṅH,NG
Catalyst particle diameter 0.005 m
Void fraction 0.4 – Complementary metrics in terms of specific consumption Eq. (11)
Tube length (adiabatic section) 1.5–2 m and specific equivalent consumption Eq. (12) are provided to reflect the
Tube length (isothermal section) 9 m energy investment required per mass unit of product, without and with
Tube diameter 0.085 m
electrical input/output in the calculation, respectively.

7
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

ṁNG LHV NG Table 3

SC = (11)
ṁMeOH Economic evaluation assumptions [35,56,57].
Capital estimation methodology
Ẇ net
ṁNG,eq LHV NG −
SCeq =
ηCC
(12) Bare Erected Cost (BEC) SEA Tool Estimate
ṁMeOH Engineering Procurement and Construction (EPC) 10% BEC
Process contingency (PC) 0–20% BEC
Environmental metrics refer to the specific CO2 emissions per unit of Project Contingency (PT) 20% (BEC + EPC + PC)
product, as reflected in Eq. (13). Owners Costs (OC) 15% (BEC + EPC + PT + PC)
Total Overnight Costs (TOC) BEC + EPC + PC + PT + OC
ṁCO2 ,emit.
ECO2 = (13)
ṁMeOH
Operating & maintenance costs
For the renewable MeOH plants, similar efficiencies are defined in Fixed
Eq. (14) to Eq. (17), but taking into account the primary energy input Maintenance 2.5 %TOC
consists of renewable electricity. Here, both the electrolyser consump­ Insurance 1 %TOC
tion and the DAC power demand (if implemented) are considered in the Labour 60,000 €/y-p
Operators 50–60 Persons
denominator, while the subsequent reactant and recycle loop compres­
Variable
sion auxiliary consumption is considered in the equivalent metric defi­ Natural gas 6.5 €/GJ
nition, taking into account this power demand of the conversion process. Electricity 60 €/MWh
Oxygen carrier 15 €/kg
ṁMeOH LHV MeOH Reformer catalyst 15 €/kg
ηMeOH = (14)
Ẇ Elect. + Ẇ DAC MeOH reactor catalyst 30 €/kg
CO2 tax 100 €/ton
ṁMeOH LHV MeOH Process water 6 €/m3
ηMeOH,eq = (15) Cooling water make-up 0.35 €/m3
Ẇ Elect. + Ẇ DAC + Ẇ SL

Ẇ Elect. + Ẇ DAC Cash flow analysis assumptions

SC = (16)
ṁMeOH 1st year capacity factor 65 %
Remaining years 85 %
Discount Rate 8 %
Ẇ Elect. + Ẇ DAC + Ẇ SL
SCeq = (17) Construction period 4 years
ṁMeOH Plant Lifetime 25 years

2.4.2. Economic
The economic assessment of the MeOH plants was conducted with
Table 4
the Standardized Economic Assessment (SEA) tool developed by the
Regional economic assumption for renewable MeOH plants.
authors [53]. The tool performs a capital cost estimation of each process
Item/Location Argentina Germany Spain Saudi Arabia
unit in the plant using cost-capacity correlations and Turton equations
(ARG) (GER) (ESP) (SA)
[54], adjusting the source to the target cost basis outlined in Table 2. A
user manual is available for download [55]. Furthermore, the tool in­ Wind capacity factor (%) 54.4 29.5 34.5 32.6
Solar capacity factor (%) 12.7 12.4 19.3 21.8
corporates location factors to account for material and labour cost dif­ Natural gas price (€/GJ) – 6.5 6.5 2
ferences in several world regions [56]. Electricity price (€/MWh) – 60 60 40
The assumptions for total overnight cost (TOC), fixed (FOM) and
variable (VOM) operating costs estimation and the cash flow analysis are
presented in Table 3. All plant units employ a process contingency factor variation partially offsetting this. On the other hand, ARG (the Patago­
of 0%, except in the advanced GSR reforming section for which a 20% is nian region) enjoys an extraordinarily high wind availability. This latter
assumed. region was not benchmarked directly with co-located natural gas-based
Several sensitivity analyses of the LCOM to key economic assump­ plants under the assumption that fuel prices will be similar to Europe.
tions are carried out for the NG-based MeOH plants including the effect Similarly to the NG-based plants, sensitivity studies to key economic
of variations in the price of natural gas, the CO2 tax imposed on emis­ assumptions were performed to the renewable MeOH plants for each
sions, electricity price, oxygen carrier cost and cash flow analysis as­ location, as reflected in Table 5. Wind, solar and electrolyser capital cost
sumptions such as discount rate and capacity factor. Each parameter is variations were considered to vary in the range of -+30%. Furthermore,
varied independently, keeping the remaining at their base reference DAC projected capital costs and thermal/electricity demand from [59]
value. for 2050 were assumed as an optimistic case while the conservative case
The natural gas MeOH plants are benchmarked against renewable employs the costs reported in that study for 2020. The base assumption
MeOH deployed in several world regions with different solar and wind taken in the present work is the average over these values, given that the
availability profiles, taken from the Renewables Ninja online tool [58]. 2050 cost forecast results in extremely low levelized costs of DAC (50
Table 4 reveals wind and solar resources in Argentina (ARG), Germany €/ton), presuming that DAC systems will become profitable technologies
(GER), Spain (ESP) and Saudi Arabia (SA). Different trends are identi­ operating in isolation, given the CO2 taxes assumed in this study of 100
fiable amongst the locations: availability is more constant in SA €/ton. Additionally, the cost difference between the base configuration
throughout the year, while the solar resources in GER vary more
strongly between winter and summer, despite complementary wind
Table 5
Sensitivity analysis ranges for the renewable MeOH plants.
Table 2 Item/Level Low High
Targe cost basis details.
Electrolysis, Wind & Solar − 30% 30%
Location Western Europe DAC* [43] (forecast 2050) [43] (forecast 2020)
Year 2020
*Includes corresponding variations in thermal (±22.7%) and electricity
Currency €
(±15.7%) demand.

8
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

and an alternative synthesis pathway with CO2 utilization from a pipe­ conversion efficiency of the scheme is approximately 6 %-points higher
line at the required hourly rate is also presented, taking into consider­ than the benchmark plant, which leads in turn to 2.6 times lower specific
ation a credit for avoiding CO2 storage of 10 €/ton. Furthermore, in the CO2 emissions. Due to the good performance of the chemical looping
suitable locations, the difference with respect to the GSR MeOH plant is system to integrate the purge heat for natural gas reforming, the
also outlined for an overall perspective. resulting hydrogen efficiency is above 100%, due to the steam present in
the feed.
3. Results Noticeably, the GSR configuration presents both a lower total
auxiliary power consumption and power generation relative to both
The results of this work are presented in two sections. First, the en­ references. This is primarily a consequence of avoiding an energy
ergy breakdown and performance of the plants attending to energy and intensive air separation unit, through the alternative steps oxidation/
environmental metrics earlier defined are presented and discussed. reduction of the oxygen carrier which indirectly supply heat for
Secondly, the economics of the different production routes is discussed, reforming. Furthermore, the GSR concept also practically avoids a bulky
providing sensitivity cases to key assumptions of the analysis. steam cycle relative to the reference plants, producing most of its elec­
trical power through the gas turbine coupled to the GSR. Finally, the
3.1. Energy and environmental results Renewable MeOH plant shown in Table 6 incorporates DAC power de­
mand to achieve a pure CO2 stream for synthesis. The results reveal a
Table 6 shows the energy and environmental results for the different relatively low electricity to MeOH efficiency, a high carbon conversion
MeOH plants. When looking at the two-reference natural gas-based (only a small amount of CO2 is vented through a small purge stream to
plants, the configuration based on ATR-HTER for syngas production prevent small amounts of N2 to accumulate in the recycle streams, with
achieves marginally better specific consumption and thermal effi­ H2 recovery through a PSA) and a low hydrogen efficiency, because of
ciencies relative to the SMR-ATR process. This results because the latter the large production of water through the reverse WGS reaction. The
has a fixed duty requirement imposed by the FTR section of the plant small CO2 stream withdrawn from the synthesis loop leads to some
which results in excess electricity production through a low efficiency emissions and effectively requires a slight oversizing of the DAC to
Rankine cycle, while the former can adjust the purge stream to produce compensate for these losses.
close to the amount required by the plant. This in turn translates to
slightly higher fuel consumption and ultimately higher specific emis­ 3.2. Economic results
sions for the SMR-ATR case. On the other hand, the GSR MeOH plant
achieves a better fuel utilization which translates to approximately 6.2 Economic results are presented in two sections. First the results for
%-points higher MeOH efficiency and 2.2 GJ/ton lower specific con­ conventional technologies and GSR using natural gas feedstock are
sumption relative to the ATR-HTER case. This attractive thermal per­ shown, with dedicated sensitivity analysis results to key process eco­
formance is somewhat offset by the electricity imports required by the nomic assumptions. Secondly, the renewable MeOH plant using
GSR plant; in terms of equivalent efficiency and specific consumption renewable power, electrolysis & alternatively DAC or CO2 from fossil
this plant still outperforms the ATR-HTER benchmark by 3.2 %-points fuel origin is presented for different locations (Germany, Spain, Saudi
and 1.2 GJ/ton respectively. However, due to the effective integration of Arabia & Argentina) and compared to the natural gas routes.
the CPU purified stream in the reforming inlet to the GSR, carbon
3.2.1. Natural gas MeOH plants
Table 6 Fig. 4 shows the specific total overnight costs for each of the MeOH
Energy and environmental results for the different natural gas based MeOH plants in k€/tpd. The ATR-HTER configuration reveals 14.2 k€/tpd
plants. (-8.9%) lower specific capital costs than the SMR-ATR plant. On the
other hand, the GSR concept achieves 21.0 k€/tpd (-13.3%) lower costs
Item/Plant Units SMR- ATR- GSR Renewable
ATR HTER (DAC) than the SMR-ATR benchmark. Relative to the ATR-HTER reference
plant, the GSR presents a cost reduction of 4.7%, mainly because
Natural gas MWth 3236.7 3171.1 2922.4 0.0
Electrolyser MWel 0.0 0.0 0.0 3709.6 avoidance of the ASU offsets the higher costs of the GSR cluster relative
duty to the ATR and HTER. The ATR-HTER plant presents the lowest costs
MeOH output kg/s 115.7 115.8 116.0 115.9 associated to the synthesis loop and purification units, due to the syngas
MeOH output MWth 2275.6 2277.2 2280.9 2279.3 quality produced in this plant that allows a lower pressure operation and
Syngas MWel 88.5 64.8 97.4 86.5
decreased reactant recirculation rates. Finally, despite the fact that GSR
compression
CO2 MWel 0.0 0.0 0.0 68.6 avoids steam cycle elements, the complex heat recovery network
compression required and gas turbine result in similar power cycle costs as the
Heat rejection MWel 3.7 3.1 3.2 0.0 reference plants. SEA tool files are available for download providing
Pumps MWel 2.9 1.4 0.9 0.4
detailed capital and operating cost estimations for each of the cases [60].
Blower MWel 6.4 1.9 0.0 0.0
ASU MWel 64.8 68.8 0.0 0.0
Regarding the operating costs for the different configurations, re­
CPU MWel 0.0 0.0 0.4 0.0 flected in Fig. 5, the large contribution of natural gas is apparent,
DAC MWel 0.0 0.0 0.0 124.3 amounting to 81.1–82.5% of the total costs. However, the GSR plant
Total MWel 166.3 140.0 101.8 279.8 achieves a 9.0% and 6.4% lower consumption relative to the SMR-ATR
Auxiliaries
and ATR-HTER configurations, respectively, although this is largely
Steam turbine MWel 185.5 138.1 4.2 36.3
Gas turbine MWel 0.0 0.0 22.1 0.0 offset by the cost of additional electricity imports. The high carbon
Net Power MWel 19.2 − 2.0 − 75.6 − 243.5 conversion efficiency of GSR is responsible for most of its operating cost
ηEl. % 0.6 − 0.1 − 2.6 – savings via low CO2 taxes (3.8% of total costs) relative to the reference
% 70.3 71.8 78.0 59.5
ηMeOH plants (9.2–10.6%). GSR also encounters higher variable operational
ηMeOH,eq % 71.0 71.7 74.9 57.7
cost due to the large quantities of oxygen carrier replacement.
εC % 86.7 88.6 94.5 98.6
εH % 90.7 92.6 100.7 67.9 The LCOM for the different MeOH plants with natural gas feedstock
SC GJ/ton 28.0 27.4 25.2 33.1 is presented in Fig. 6. The ATR-HTER reference plant is more competi­
SCeq GJ/ton 27.7 27.4 26.2 34.1 tive than the SMR-ATR configuration, achieving a cost reduction of 11.4
ECO2 kgCO2/ 235.3 198.4 76.3 19.1 €/ton (-4.2%). On the other hand, relative to the ATR-HTER benchmark,
ton
the GSR configuration achieves a 16.3 €/ton cost reduction (-6.4%).

9
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 4. Specific TOC for the different natural gas based MeOH plants.

Fig. 5. Specific operating costs for the different natural gas based MeOH plants.

These reductions are achieved through a combination of the factors of reforming units or to generate sufficient electricity in the steam cycle.
previously discussed: a better fuel utilization, reduced taxes from CO2 For the ATR-HTER reference plant, carbon efficiency could be increased
emissions and lower capital costs (which also result in comparatively if a combined cycle with a gas turbine were used to generate that power
lower FOM costs), despite the increase of VOM costs and electricity [27], due to higher efficiency electricity generation for a self-sufficient
imports. Overall, it is noteworthy to highlight the large weight of natural plant, although supply of hot water and low-pressure steam to the
gas on the levelized cost for all the cases. MeOH reactor and purification respectively might be compromised.
Finally, sensitivity analyses of the LCOM to different economic as­
sumptions are presented in Fig. 7. As expected, the cost is most sensitive 3.2.2. Renewable MeOH plants
to the natural gas price used in the economic evaluation, presenting a The renewable MeOH plants were modelled using GAMS to optimize
somewhat smaller steepness for the GSR due to the slightly higher the investment of capacity and hourly dispatch of technologies for a
thermal efficiencies achieved. The CO2 tax presents a larger effect for constant MeOH output of 2300 MW, considering different world regions
both reference plants compared to the GSR configuration, with signifi­ for renewable energy (wind and solar) availability. Detailed description
cantly lower specific emissions. At no CO2 emissions costs, the GSR of the model and assumptions are available in the Supplementary Ma­
configuration is still slightly more competitive than the benchmarks. terial file attached to this study, while a file for the results of the cases as
Both electricity price and oxygen carrier cost have influence pri­ well as the model is available online [60].
marily on the GSR configuration, although the effect is small. Finally, Fig. 8 shows the optimal capital deployment of technologies built in
the discount rate and capacity factor sensitivities show similar trends for the four regions. When comparing electricity generation, it can be seen
the three cases. The results of the sensitivity reveal the importance of that ARG depends heavily on its outstanding wind resource, both GER
maximizing natural gas conversion efficiency to the final product. This and ESP rely on a combination of wind and solar, while SA supplies
can be a challenging endeavour because some heat will inevitably be lost 100% of the power by solar PV. Since GER and ARG locations present an
because of the exothermicity of the synthesis reaction and due to the electricity production mix with an overall higher capacity factor, lower
purge requirements from the loop, either to satisfy the thermal demand electrolyser capacities are required, especially in ARG where the wind

10
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 6. LCOM for the different natural gas based MeOH plants.

capacity factor exceeds 50%. However, both wind-dominated regions Europe, natural gas pathways are 287.4 €/ton (-51.7%) and 303.6 €/ton
require larger DAC capacity and greater storage volumes of H2, CO2 and (-54.6%) cheaper than renewable MeOH from ESP with the ATR-HTER
MeOH, due to the longer variability timescales (random variations on and GSR plants, respectively. This difference is even larger in SA
weekly timescales and more regular seasonal variations) of this where the improved solar resource is outweighed by low fuel prices in
resource. SA and ESP present substantial battery storage deployment to this natural gas exporting region Specifically, the ATR-HTER and GSR
profit from their low-cost solar resources, while the H2, CO2, and MeOH plants achieve drastic cost reductions of 326.4 €/ton (-69.2%) and 336.3
storage comparatively decrease for the last two regions. €/ton (-71.3%), respectively, relative to the renewable MeOH case. The
The optimal renewable MeOH costs are compared with the natural renewable cases for ARG location are not directly benchmarked against
gas-based plants in Fig. 9. In the European locations, renewable MeOH is natural gas feedstock plants under the consideration that for this world
cheaper in ESP relative to GER by 229.1 €/ton (-29.2%), in virtue of its region, NG prices will be similar to Europe. Since its LCOM is slightly
solar resource. ESP and ARG present similar costs, being 12.0 €/ton higher than that of ESP, the comparison to NG cases will be less
(-2.1%) cheaper in the former. Thus, despite the outstanding wind favourable.
resource of ARG, the large capital cost reduction assumed for solar PV It must also be noted that these estimations present an optimistic
ensures that the moderately good solar resource in ESP achieves a lower scenario for the renewable plants, since only one year of energy source
cost of electricity inputs. Another interesting difference between ARG variability is considered for the optimization, and it is assumed that the
and ESP is the much lower electrolyser cost in the former (due to the plant can be operated with perfect foresight across regarding wind and
high wind capacity factor), partially cancelled out by larger storage costs solar power production. Furthermore, all technologies within the
(due to the longer variability timescales of wind). Owing to its renewable plants are assumed to operate with full availability, relative
outstanding solar resource, SA achieves the lowest LCOM for the to the 85% capacity factor taken for the natural gas-based plants. Given
renewable MeOH cases. the cost projection uncertainties for the different technologies consid­
For reference, the two renewable MeOH configurations with ered to the year 2050, and the possibility of alternatively utilizing CO2
different CO2 sources (DAC or CO2 pipeline) are compared in ARG. As available from pipeline, sensitivity cases outlined in Table 5 are pre­
shown in Fig. 9, the DAC plants are credited with a large CO2 revenue sented in Fig. 10 for all locations, re-running the optimization for each
(100 €/ton of CO2 or 137.5 €/ton of MeOH) for removing CO2 from the case with suitable model modifications (e.g., pipeline CCU cases do not
atmosphere, whereas the credit received by the pipeline (CO2 P/L) op­ require CO2 storage, compression etc.).
tion is much smaller (10 €/ton of CO2 for avoiding the need for CO2 GSR natural gas based MeOH plants remain far more competitive
storage). However, the cost of the DAC system outweighs the large CO2 than the renewable MeOH plants with optimistic technology assump­
credit it generates. Furthermore, the DAC configuration imposes tions for all locations. For ARG location, the GSR plant estimation for
considerably higher renewable electricity costs due to its extra elec­ Europe is represented in Fig. 10 for perspective. Also, at a CO2 tax of 100
tricity demand and the need to operate the system at a high capacity €/ton, plants with CCU are economically more attractive than invest­
factor that forces some curtailment of wind energy peaks and deploy­ ment in DAC for all locations, although this difference becomes smaller
ment of less cost-effective solar. Matching CO2 supply from DAC with H2 for SA and ESP, due to less CO2 storage and compression requirements in
supply from electrolysis also requires more storage, including CO2 tanks those regions. In general, variations between high and low levels for
and CO2 compressors. The combination of these factors makes the DAC DAC has the greatest impact on LCOM, with a greater comparative cost
case 62.8 €/ton (+11.1%) more expensive than the pipeline case, increase at the high level imposed by larger thermal and electricity
illustrating that a CO2 credit exceeding 100 €/ton will be required to auxiliary demands on the DAC, which in turn imply higher investments
justify DAC under the base case assumptions. in power and heat generation and storage. Next, changes in the capital
Fig. 9 shows that MeOH from natural gas origin is far cheaper than cost of the primary energy input have a substantial influence, particu­
that of renewable origin, despite the CO2 price/credit of 100 €/ton. In larly for those regions largely depending on their wind resource.

11
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 7. LCOM sensitivity analysis to different economic assumptions.

Electrolyser cost is less influential, although still considerable in solar- levelized cost to the a) CO2 from pipeline case and b) the NG plants.
dominated regions due to the large oversizing required to utilize daily Notably, the CO2 price also impacts both latter configurations, as the
solar production peaks. carbon conversion in the synthesis loop of each plant is below 100%,
Finally, it is clarifying to identify the break-even CO2 prices which causing some emissions. These CO2 prices are represented relative to
make the renewable MeOH plants with DAC comparable in terms of each technology and location in Fig. 11:

12
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 8. Optimal generation (above) and storage (below) capital deployment for the renewable MeOH with DAC for the different regions. The storage figure presents a
logarithmic axis due to the large differences in deployment.

As expected, huge CO2 taxes above 318.0 €/ton (ESP) are required the oxidation stage GSR outlet is added to the synthesis loop after a
for renewable MeOH with DAC to outcompete the advanced NG-based purification step. The PSA off-gas is recirculated to the GSR reduction
GSR configuration, while DAC can economically replace pipeline CO2 step, thereby capturing a CO2 stream for transport and storage after
in the renewable cases if CO2 prices reach ranges between 121.3 and water knock out and purification. On the other hand, the MeOH plant
146.7 €/ton, depending on the location. Given the larger emissions and design does not require CO2 transport and storage because most of the
relative higher cost of the ATR-HTER plant, the break-even prices of the CO2 from the GSR reduction step is fed back to the reforming step to
DAC with respect to this technology are somewhat smaller, with the maximize the carbon conversion efficiency, while the N2 stream from
lowest of 290.3 €/ton reached for ESP location. Finally, the robustness of the GSR is vented after expansion and heat recovery. For the NH3 pro­
the conclusion that NG-based MeOH is much cheaper than renewable cess using renewable power as primary energy feedstock, N2 reactant is
MeOH is verified by completing a simulation in ESP where optimistic produced from a dedicated cryogenic unit, compared to DAC in the
cost assumptions are applied to all green technologies. In this case, a CO2 MeOH counterpart for CO2, while the same electrolyser, wind, solar,
tax of 162.8 €/ton is required for renewable MeOH to outcompete MeOH battery, and H2 storage technology is assumed in both plants.
from the GSR process. Fig. 12 shows the techno-economic results for SA location on an
energy basis. This natural gas exporting region with high solar avail­
3.2.3. Comparison to NH3 as a future energy carrier ability returned the lowest costs both for renewable and natural gas
Given the growing relevance of alternative energy carriers in a routes, making it an ideal location for the export of cleaner energy
decarbonized economy, the results of this study for MeOH are compared carriers over coming decades. No CO2 tax benefit was considered in this
to a previous work that applied an identical methodology for the comparison for renewable MeOH (with DAC), considering that this en­
assessment of NH3 [39]. In this previous work, an evaluation of the GSR- ergy carrier will release the CO2 captured via DAC at the end-use,
NH3 production process was carried out for a 3000 tpd capacity, in making it directly comparable to green NH3 for energy applications.
which H2 is obtained from a PSA after a WGS unit. Additionally, N2 from The results show that, for the renewable route, ammonia is 15.3

13
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 9. LCOM comparison for the different MeOH production pathways. Total costs are indicated above the bars accounting for a 100 €/ton CO2 taxes for the
renewable plants with DAC and natural gas plants, and 10 €/ton CO2 credit for the CCU case.

€/MWh (-13.7%) cheaper than MeOH. Even though the MeOH synthesis • In terms of technical performance, the SMR-ATR configuration
loop is considerably simpler than the NH3 loop, the additional require­ achieved an equivalent specific consumption of 27.7 GJ/ton with
ment for DAC puts green MeOH at a significant cost disadvantage to electricity exports representing 0.6% of the total heat input. The
green NH3. On the other hand, when using a natural gas feedstock, ATR-HTER plant with net zero electricity demand presented 27.4
MeOH is more attractive as an energy carrier by 12.5 €/MWh (–33.6%), GJ/ton specific consumption, while the GSR requires lower equiva­
as larger production and simpler synthesis loop achieve more attractive lent specific consumption of 26.2 GJ/ton of which 4% represents
economies of scale. Nevertheless, assuming the MeOH energy carrier electricity imports. The GSR configuration also achieved low CO2
produced from natural gas is used in energy applications without CO2 emissions of 76.3 kg/ton, a 61.5% reduction relative to the ATR-
abatement, a CO2 tax of 274.3 and 49.8 €/ton would make green and HTER benchmark. Due to conversion losses in the electrolyzer,
blue ammonia an economically competitive alternative, respectively. synthesis loop, and the power consumption of the DAC facility, the
specific electricity consumption of the renewable MeOH plant was
4. Summary & conclusions higher at 34.1 GJ/ton, albeit with no CO2 emissions.
• The subsequent economic assessment revealed that the SMR-ATR
Several MeOH production pathways were analysed in this work, plant achieved a levelized cost of MeOH (LCOM) of 279.9 €/ton,
carrying out a consistent techno-economic assessment for production while the ATR-HTER plant brought a 11.4 €/ton (-4.2%) reduction
capacities of 10,000 tpd. Three natural gas-based plant models were and GSR lowered costs by an additional 16.3 €/ton (-6.4%) relative
developed. Two benchmark MeOH technologies, one employing steam to ATR-HTER. Natural gas price and CO2 tax were the most influ­
methane reforming followed by autothermal reforming (SMR-ATR) for ential economic assumptions affecting the cost of each plant.
syngas production integrating the synthesis loop purge with the • Using cost assumptions applicable to 2050 for green energy pro­
reformer, and another with an autothermal reformer operating in par­ duction and storage technology and a DAC CO2 capture credit of 100
allel with a heat transfer exchanger reformer (ATR-HTER) syngas pro­ €/ton, renewable MeOH production remained substantially more
duction section with a steam cycle boiler for combustion of the synthesis costly than natural gas-based alternatives. In Spain and Saudi Arabia,
purge. A third configuration with natural gas feedstock employing gas the GSR process is 54.6% and 71.9% cheaper than the renewable
switching reforming (GSR) was also assessed. Finally, plants based on H2 route, respectively. CO2 utilization from available fossil fuel sources
from water electrolysis with renewable electricity and CO2 from direct proved more competitive than DAC route at CO2 taxes of 100 €/ton.
air capture (DAC) or alternatively CO2 utilization from other fossil Break even CO2 taxes for renewable DAC relative to CO2 from
sources, as means to supply reactants to the synthesis loop, were also the pipeline were found to be in the range of 121.3–146.7 €/ton, while
object of this study. The main results of this study are summarized prices around 300 €/ton of CO2 are required for DAC to make com­
below: mercial sense with respect to conventional natural gas production
routes. Assuming the most optimistic cost prospects for all

14
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

Fig. 10. Sensitivity study to LCOM of technology costs and production alternatives (CO2 from pipeline, GSR) for renewable MeOH production with DAC in
different locations.

Fig. 11. Break even CO2 prices for renewable MeOH plants with DAC relative
to CO2 from pipeline and GSR configuration.
Fig. 12. LCOP in €/MWh for chemical energy carriers from renewables and
natural gas in Saudi Arabia.
technologies in the renewable MeOH plant for Spain, the break-even
CO2 tax fell to 163.6 €/ton, relative to a GSR plant.

Finally, MeOH and NH3 as future energy carriers were compared

15
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

using the same methodology, revealing that MeOH presents better [11] Rivera-Tinoco R, Farran M, Bouallou C, Auprêtre F, Valentin S, Millet P,
Ngameni JR. Investigation of power-to-methanol processes coupling electrolytic
economies of scale if produced from natural gas, while the avoidance of
hydrogen production and catalytic CO2 reduction. Int J Hydrogen Energy 2016;41
DAC makes ammonia the cheaper option for renewable routes. CO2 (8):4546–59.
taxes for emissions derived from MeOH from natural gas origin of 274.1 [12] Ravikumar D, Keoleian G, Miller S. The environmental opportunity cost of using
€/ton and 49.8 €/ton make green and blue ammonia more compelling as renewable energy for carbon capture and utilization for methanol production. Appl
Energy 2020;279.
an energy carrier respectively, assuming an identical energy-related end [13] Kotowicz J, Węcel D, Brzęczek M. Analysis of the work of a “renewable” methanol
use for such fuels. production installation based ON H2 from electrolysis and CO2 from power plants.
In conclusion, it is expected that natural gas-based MeOH production Energy 2021;221.
[14] Battaglia P, Buffo G, Ferrero D, Santarelli M, Lanzini A. Methanol synthesis through
through the state-of-the-art ATR-HTER route will remain more CO2 capture and hydrogenation: thermal integration, energy performance and
competitive than renewable synthesis based on electrolysis and direct techno-economic assessment. J CO2 Util 2021;44.
air capture or captured CO2 utilization in the long term, despite the [15] Bos MJ, Kersten SRA, Brilman DWF. Wind power to methanol: renewable methanol
production using electricity, electrolysis of water and CO2 air capture. Appl Energy
environmental attractiveness of a CO2 closed loop fuel production pro­ 2020;264.
cess that DAC route enables. Thus, strong policy support will be required [16] Schorn F, Breuer JL, Samsun RC, Schnorbus T, Heuser B, Peters R, Stolten D.
to enable the large-scale production of green MeOH, even in the long Methanol as a renewable energy carrier: An assessment of production and
transportation costs for selected global locations. Advances Appl Energy 2021;3.
term. Advanced process routes like GSR can achieve further cost re­ [17] Bozzano G, Manenti F. Efficient methanol synthesis: perspectives, technologies and
ductions relative to the ATR-HTER benchmark, but step-changes in optimization strategies. Prog Energy Combust Sci 2016;56:71–105.
natural gas-based MeOH production costs appear unlikely. GSR is better [18] Ghosh S, Seethamraju S. Process intensification with a polar solvent in liquid phase
methanol synthesis. Proc Integr Optimiz Sustainability 2021;5(4):827–42.
suited to applications like blue H2 and NH3 production where its
[19] Lee S. Methanol synthesis technology; 1989.
inherent CO2 capture ability is better utilized. [20] Gallucci F. Inorganic Membrane reactors for methanol synthesis. 2018, 493–518.
[21] Salehi M, Askarishahi M, Gallucci F, Godini HR. Selective CO2-hydrogenation
using a membrane reactor. Chem Eng Process-Process Intensif. 2021;160.
CRediT authorship contribution statement [22] Rydén M, Lyngfelt A, Mattisson T. Synthesis gas generation by chemical-looping
reforming in a continuously operating laboratory reactor. Fuel 2006;85(12):
Carlos Arnaiz del Pozo: Conceptualization, Methodology, Formal 1631–41.
[23] Zaabout A, Cloete S, Johansen ST, Van SA, Gallucci F, Amini S. Experimental
analysis, Investigation, Writing – original draft, Funding acquisition. demonstration of a novel gas switching combustion reactor for power production
Schalk Cloete: Conceptualization, Methodology, Formal analysis, with integrated CO 2 capture. Ind Eng Chem Res 2013;52(39):14241–50.
Investigation, Writing – original draft, Writing – review & editing, [24] Nazir SM, Cloete JH, Cloete S, Amini S. Pathways to low-cost clean hydrogen
production with gas switching reforming. Int J Hydrogen Energy 2020.
Funding acquisition. Ángel Jiménez Álvaro: Writing – review & edit­ [25] Wassie SA, Gallucci F, Zaabout A, Cloete S, Amini S, van Sint Annaland M.
ing, Funding acquisition. Hydrogen production with integrated CO2 capture in a novel gas switching
reforming reactor: proof-of-concept. Int J Hydrogen Energy 2017;42(21):
14367–79.
Declaration of Competing Interest [26] Abad A, Adánez J, García-Labiano F, de Diego L, Gayán P, Celaya J. Mapping of the
range of operational conditions for Cu-, Fe-, and Ni-based oxygen carriers in
The authors declare that they have no known competing financial chemical-looping combustion. Chem Eng Sci 2007;62(1–2):533–49.
[27] Osman M, Zaabout A, Cloete S, Amini S. “Pressurized chemical looping methane
interests or personal relationships that could have appeared to influence reforming to syngas for efficient methanol production: experimental and process
the work reported in this paper. simulation study. Adv Appl Energy 2021;4.
[28] Spallina V, Motamedi G, Gallucci F, van Sint Annaland M. Techno-economic
assessment of an integrated high pressure chemical-looping process with packed-
Acknowledgements bed reactors in large scale hydrogen and methanol production. Int J Greenhouse
Gas Control 2019;88:71–84.
The authors would like to acknowledge Honeywell for the free aca­ [29] Labbaf B, Tabatabaei M, Mostafavi E, Tijani M, Mahinpey N. Methanol production
via integrated methane reforming and chemical looping combustion: process
demic license of Unisim Design R481. The authors would also like to simulation and techno-economic assessment. Process Saf Environ Prot 2021;148:
acknowledge AmsterCHEM for the free academic license of the CAPE- 1346–56.
OPEN Scilab-Unisim unit operation. This work received funding from [30] Osat M, Shojaati F. Techno-economic-environmental evaluation of a combined tri
and dry reforming of methane for methanol synthesis with a high efficiency CO2
the European Union NextGenerationEU, Ministerio de Universidades utilization. Int J Hydrogen Energy 2022;47(14):9058–70.
grant RD 289/2021. [31] Blumberg T, Lee YD, Morosuk T, Tsatsaronis G. Exergoenvironmental analysis of
methanol production by steam reforming and autothermal reforming of natural
gas. Energy 2019;181:1273–84.
Appendix A. Supplementary data [32] Collodi G, Azzaro G, Ferrari N, Santos S. Demonstrating large scale industrial CCS
through CCU–a case study for methanol production. Energy Procedia 2017;114:
Supplementary data to this article can be found online at https://doi. 122–38.
[33] Wesenberg MH. Gas heated steam reformer modelling; 2006.
org/10.1016/j.enconman.2022.115785. [34] Aasberg-Petersen K, Nielsen CS, Dybkjær I, Perregaard J. Large scale methanol
production from natural gas. Haldor Topsoe 2008;22.
References [35] Woods M, Kuehn N, Shah V, Goellner JF. Baseline analysis of crude methanol
production from coal and natural gas. NETL 2014.
[36] Blumberg T, Morosuk T, Tsatsaronis G. A comparative exergoeconomic evaluation
[1] Basile A, Dalena F. Methanol: Science and Engineering; 2017.
of the synthesis routes for methanol production from natural gas. Appl Sci 2017;7
[2] Anonymous European Geosciences Union’s Reaction to IPCC Report on Global
(12):1213.
Warming of 1.5 Degrees Celsius. Targeted News Service; 2018.
[37] Honeywell, Unisim Thermo Reference Guide R480 Release; 2020.
[3] Revankar ST. Chapter Six – Chemical Energy Storage; 2019, pp. 177–227.
[38] Moriya N, Kawai T, Yagi H, Shimizu R, Morita Y. Method of heat transfer in
[4] Mazloomi K, Gomes C. Hydrogen as an energy carrier: prospects and challenges.
reformer; 1999.
Renew Sustain Energy Rev 2012;16(5):3024–33.
[39] Arnaiz del Pozo C, Cloete S. Techno-economic assessment of blue and green
[5] Schüth F. Challenges in hydrogen storage. Eur Phys J Special Topics; 2009, 176 (1),
ammonia as energy carriers in a low-carbon future. Energy Convers Manage 2022;
155–66.
255.
[6] Abdalla AM, Hossain S, Nisfindy OB, Azad AT, Dawood M, Azad AK. Hydrogen
[40] Campanari S, Mastropasqua L, Gazzani M, Chiesa P, Romano MC. Predicting the
production, storage, transportation and key challenges with applications: a review.
ultimate potential of natural gas SOFC power cycles with CO2 capture – Part A:
Energy Convers Manage 2018;165:602–27.
methodology and reference cases. J Power Sources 2016;324:598–614.
[7] Olah GA. Beyond oil and gas: the methanol economy. Angew Chem Int Ed. 2005;44
[41] FCH. State of the art and future targets for fuel cell and hydrogen applications,
(18):2636–9.
https://www.fch.europa.eu/soa-and-targets [accessed on 02.11.2021].
[8] Verhelst S, Turner JW, Sileghem L, Vancoillie J. Methanol as a fuel for internal
[42] Grigoriev SA, Porembsky VI, Fateev VN. Pure hydrogen production by PEM
combustion engines. Prog Energy Combust Sci 2019;70:43–88.
electrolysis for hydrogen energy. Int J Hydrogen Energy 2006;31(2):171–5.
[9] Tola V, Lonis F. Low CO2 emissions chemically recuperated gas turbines fed by
[43] Fasihi M, Efimova O, Breyer C. Techno-economic assessment of CO2 direct air
renewable methanol. Appl Energy 2021;298.
capture plants. J Clean Prod 2019;224:957–80.
[10] Alias MS, Kamarudin SK, Zainoodin AM, Masdar MS. Active direct methanol fuel
[44] Anonymous. https://climeworks.com/purpose. Accessed: March 2020.
cell: an overview. Int J Hydrogen Energy 2020;45(38):19620–41.

16
C. Arnaiz del Pozo et al. Energy Conversion and Management 266 (2022) 115785

[45] Kauko H, Sevault A, Beck A, Drexler-Schmid G, Schöny M. Cost-efficient thermal [52] Khan MN, Cloete S, Amini S. Efficiency improvement of chemical looping
energy storage for increased utilization of renewable energy in industrial steam combustion combined cycle power plants. Energy Technol 2019;7(11):1900567.
production – CETES. Available from: https://bit.ly/3COrgtj; 2020. [53] Carlos Arnaiz del Pozo, Schalk Cloete, and Ángel Jiménez Álvaro. Standard
[46] De María R, Díaz I, Rodríguez M, Sáiz A. Industrial methanol from syngas: kinetic Economic Assessment (SEA) Tool. Available from: https://bit.ly/3hyF1TT.
study and process simulation. Int J Chem Reactor Eng 2013;11(1):469–77. [54] Turton R, Bailie RC, Whiting WB, Shaeiwitz JA. Analysis, synthesis and design of
[47] Slotboom Y, Bos MJ, Pieper J, Vrieswijk V, Likozar B, Kersten SRA, Brilman DWF. chemical processes; 2008.
Critical assessment of steady-state kinetic models for the synthesis of methanol [55] Carlos Arnaiz del Pozo, Schalk Cloete and Ángel Jiménez Álvaro. SEA Tool User
over an industrial Cu/ZnO/Al2O3 catalyst. Chem Eng J 2020;389. Guide. Available from: https://bit.ly/3jq9Bkf.
[48] Bussche KMV, Froment GF. A steady-state kinetic model for methanol synthesis [56] Roussanaly S, Berghout N, Fout T, Garcia M, Gardarsdottir S, Nazir SM, Ramirez A,
and the water gas shift reaction on a commercial Cu/ZnO/Al2O3 catalyst. J Catal Rubin ES. Towards improved cost evaluation of carbon capture and storage from
1996;161(1):1–10. industry. Int J Greenhouse Gas Control 2021;106.
[49] Seidel C, Jörke A, Vollbrecht B, Seidel-Morgenstern A, Kienle A. Kinetic modeling [57] Anantharaman R, Bolland O, Booth N, Van Dorst E, Sanchez Fernandez E, Franco F,
of methanol synthesis from renewable resources. Chem Eng Sci 2018;175:130–8. et al., Cesar deliverable D2.4.3. European best practice guidelines for assessment of
[50] Prašnikar A, Pavlišič A, Ruiz-Zepeda F, Kovač J, Likozar B. Mechanisms of copper- Co2 capture technologies; 2018.
based catalyst deactivation during CO2 reduction to methanol. Ind Eng Chem Res [58] Pfenninger S, Staffell I. Long-term patterns of European PV output using 30 years of
2019;58(29):13021–9. validated hourly reanalysis and satellite data. Energy 2016;114:1251–65.
[51] Halager NS, Bayer C, Kirkpatrick R, Gernaey KV, Huusom JK, Udugama IA. [59] Fasihi M, Efimova O, Breyer C. Techno-economic assessment of CO2 direct air
Modelling and control of an integrated high purity methanol distillation capture plants. J Clean Prod 2019;224:957–80.
configuration. Chem Eng Process – Process Intensif 2021;169. [60] Arnaiz del Pozo C, Cloete S, Jiménez Álvaro Á. Methanol pathways: SEA tool files
and System-scale model results. Available from: https://bit.ly/3Nzdpv0; 2022.

17

View publication stats