Computers and Chemical Engineering 165 (2022) 107948

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Computers and Chemical Engineering

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

Power-to-X: A review and perspective

Matthew J. Palys, Prodromos Daoutidis ∗
Department of Chemical Engineering and Materials Science, University of Minnesota, Twin Cities, Minneapolis, MN 55455, United States of America

ARTICLE INFO ABSTRACT

Keywords: In the past decade, producing chemicals from renewable energy for use as fuel has gained considerable interest.
Power-to-x Renewable hydrogen production (PtH) is the backbone of this power-to-x concept, while further conversion
Energy storage to methanol (PtM) or ammonia (PtA) serves to increase energy density. In this article, we review production
Systems engineering
and utilization technologies for PtH, PtM, and PtA in the context of the energy and transportation sectors.
Hydrogen
Specifically, each technology’s basic operating principals, state of development, energy efficiency, dynamic
Methanol
Ammonia
flexibility, and deployment outlook is discussed. We also review recent process systems engineering research
of PtH, PtM, and PtA. At the process level, this research largely aims to improve economics through optimal
synthesis and design of novel processes as well as coupled real-time optimization and control for dynamic
operation. At the facility or supply chain level, combined capacity planning and scheduling to optimally use
intermittent renewable resources is the major focus.

1. Introduction
Since the beginning of the 21st century, development of renewable
electricity generation technologies has been extensive, with a view
on decoupling energy supply from fossil fuels. In the last 10 years,
deployment of these technologies, primarily wind turbines and PV
arrays, has increased seven-fold (International Energy Agency, 2022a).
A renewables-dominant energy supply for power, heat, and cooling is
critical in keeping global warming below 1.5 ◦ C to avoid the worst
impacts of anthropogenic climate change identified by the IPCC (In-
tergovernmental Panel on Climate Change, 2018). The energy supply
sector is the single largest source of global CO2 emissions, responsible
for 35% in 2018 (Intergovernmental Panel on Climate Change, 2018).
Furthermore, it has been the largest contributor to emissions growth
since 2010, largely due to coal combustion in developing countries (In-
tergovernmental Panel on Climate Change, 2018). Replacing coal with
renewables could ensure continued energy access and the associated
quality of life without negative climate effects. Alone, decarbonizing
energy supply will not be sufficient for meeting the 1.5 ◦ C goal. Using
renewables to electrify transportation has widespread implications to
this end as this sector is responsible for 25% of global emissions (Inter-
governmental Panel on Climate Change, 2018). Electric vehicles (EVs)
are one way to facilitate this. Their global deployment has risen from
20,000 in 2010 to 7.2 million today (International Energy Agency,
2021).
The global momentum towards renewable energy supply and trans-
portation electrification is undeniable, but significant progress still
needs to be made. Despite considerable growth over the last decade,
wind and solar generation together meet roughly 10% of global elec-
tricity demand (International Energy Agency, 2022a) while EVs make
up only 1% of the global civilian vehicle fleet (International Energy
Agency, 2021), with even smaller market penetrations for heavier
transportation such as trucks, trains, or ships. The intermittent nature
of renewables is a major barrier to more widespread implementa-
tion. Wind and solar generation outputs can vary on wide range of
timescales, from nearly instantaneous to seasonal. In a renewables-
dominant energy mix, this generation must be balanced with demands
across these different timescales using energy storage systems (ESS).
Batteries are well-suited to short-term generation-demand balanc-
ing, specifically within a day, and make up the majority of globally
deployed energy storage (Sivaram et al., 2018). However, battery ESS
have relatively low energy densities (kWh/kg) and thus high energy
capacity costs of at least $250/kWh, resulting in large and expensive
systems for energy storage over longer durations (Guerra, 2021). Other
common energy storage technologies include those classified as thermal
(e.g. molten salts) or mechanical (e.g. pumped hydro, compressed
air) storage. Each of these technologies has their own advantages
and drawbacks and generally offer energy capacity costs in the $100-
250/kWh range (Guerra, 2021). Broadly, these costs are still prohibitive
for high capacity, long durtion storage applications (Sepulveda et al.,
2021). Technologies for decarbonizing transportation have largely been

∗ Corresponding author.
E-mail address: daout001@umn.edu (P. Daoutidis).

https://doi.org/10.1016/j.compchemeng.2022.107948
Received 2 March 2022; Received in revised form 18 June 2022; Accepted 29 July 2022
Available online 11 August 2022
0098-1354/© 2022 Elsevier Ltd. All rights reserved.
M.J. Palys and P. Daoutidis
Table 1
Comparison of hydrogen, methanol, and ammonia energy properties (Dias et al., 2020).
Energy density (kWh/kg)
Boiling point at 1 bar (◦ C)
Storage pressure at 25 ◦ C (bar)
Volumetric energy density (kWh/L)
a
Hydrogen can be stored as a high pressure gas or as a cryogenic liquid, resulting in a range of energy
densities. This is discussed in SubSection 2.2.
limited to batteries. However, their low energy density limits the full-
charge driving distance (range) in battery electric vehicles (BEVs) while
precluding long-haul trucking or shipping almost entirely.
Producing fuels from renewable electricity which can later be used
for stationary energy production or transportation is one approach
to overcoming the limitations of electrical energy storage. This idea
was termed ‘‘power-to-x’’ in Germany in the early 2010s (Sterner and
Specht, 2021). Practically, power-to-hydrogen (PtH) is the backbone
of the power-to-x concept (Siemens, 2020). Hydrogen can be produced
from renewable energy via electrolysis with water as the only feedstock,
making its deployment quite geographically flexible. On a weight basis,
hydrogen is very energy dense (see Table 1). Hydrogen can be used
directly as fuel for stationary energy generation or transportation, pro-
ducing only water as byproduct when used as fuel in well-designed fuel
cell or combustion systems. As a result, hydrogen has received extensive
attention from academic, corporate, and governmental perspectives at
a global scale in the context of energy and transportation (Solomon and
Banerjee, 2006; Bockris, 2013). Hydrogen can also be further processed
to other fuels to improve storage or utilization characteristics. Power-
to-methanol (PtM) and power-to-ammonia (PtA) are two promising
examples of such processing routes which are largely motivated by
improving volumetric energy densities (see Table 1). PtM involves
combining electrolytic hydrogen with carbon dioxide (CO2 ). This CO2
can be obtained from a variety of sources and electrically-powered pro-
cesses, either as an industrial byproduct or captured directly from air.
PtM is thus well-suited for coupling with carbon capture installations,
though subsequent use of this methanol to produce energy would emit
CO2 as a byproduct. Considerable past exploration has been devoted to
methanol as a fuel for both fuel cell and combustion systems (Hagen,
1977; Bromberg and Chang, 2010). PtA involves combining electrolytic
hydrogen with nitrogen electrically separated from air. Ammonia does
not emit carbon when used to produce energy, instead releasing water
along with nitrogen-containing molecules, some of which must be
abated. Further, PtA relies only on water and air as feedstock, giving
it similar geographical versatility as PtH. For these reasons, PtA in
energy applications has recently gained traction (Giddey et al., 2017;
Valera-Medina et al., 2018).
In this paper, we review PtH, PtM, and PtA in the context of energy
supply and transportation. Specifically, we describe technologies for
production of these chemicals using renewables and for their subse-
quent use in energy supply or transportation applications. Hydrogen
storage methods are also specifically reviewed. This discussion focuses
on each technology’s state of development as well as their relative ad-
vantages and drawbacks in power-to-x systems. Detailed reviews have
previously been conducted for specific technologies in PtH (Schmidt
et al., 2017; Acar et al., 2021; Yue et al., 2021), PtM (Dieterich et al.,
2020; Mbatha et al., 2021), and PtA (Valera-Medina et al., 2021; Afif
et al., 2016; Yapicioglu and Dincer, 2019) systems. The goal of this
paper is to synthesize information about power-to-x production and
utilization processes and analyze them in a comparative context.
Economic considerations are a main barrier to competitive power-
to-x adoption, particularly the high associated capital investment.
These elevated costs arise because power-to-x systems using intermit-
tent wind and solar resources cannot operate at steady state. These
systems instead require time-varying operation of at least some subset
of oversized process units, additional energy storage units, or a combi-
nation of both to meet production targets with intermittently available
Computers and Chemical Engineering 165 (2022) 107948
Hydrogen Methanol Ammonia
33.3 5.6 5.2
−252.8 64.7 −33.3
300–700a 1 10
0.5-2.3a 4.6 4.3
energy. For instance, since solar energy from PV arrays is not produced
overnight, a solar-based power-to-x project could accommodate this by
only operating chemical production while solar energy is available and
oversizing the involved chemical processes to meet production targets
(e.g., installing double the capacity and operating half of the time) or
by using batteries or other direct electrical energy storage which are
charged during the day and discharged overnight to allow for steady-
state chemical production. These design considerations inevitably lead
to higher capital intensities compared to traditional chemical manu-
facturing which operates with continuously available feedstock at high
capacity factors to minimize capital intensity ($/product).
Thus, efforts to reduce individual process costs and to optimize
the sizing of each process in power-to-x systems are both of utmost
importance. The viability of power-to-x projects can also be affected
by the energy efficiency of each involved process, but improving this
efficiency can often be in conflict with reducing capital cost. At the
systems level, sizing each involved process is non-trivial as is illustrated
even in the simple example in the previous paragraph. The lowest
cost system design will depend on a number of factors, including the
location and scale of the project, the types of renewable energy to be
used, and the costs of each involved processes. Operational aspects of
power-to-x must also be carefully considered. Some existing processes
which could theoretically be used for power-to-x are not well-suited
to frequent and/or large changes in their production rates for safety,
efficiency, or performance degradation reasons. Such processes must
thus be re-designed or retrofitted with dynamic flexibility as a key
consideration or otherwise must be deployed in systems which can ac-
commodate these limitations. Process systems engineering is uniquely
suited to systematically address these challenges across multiple tempo-
ral and spatial scales with a view on economic competitiveness. Thus, in
addition to discussing relevant technologies, we review the literature on
optimal design, scheduling, and control of PtH, PtM, and PtA processes,
systems, and networks for energy and transportation.
The rest of this article is structured as follows. Sections 2 through 4
respectively describe the enabling technologies and recent systems
engineering research for PtH, PtM, and PtA. Section 5 describes recent
investigations into integrated power-to-x systems which combine en-
ergy vectors and/or use cases to exploit synergies and reduce costs.
Section 6 summarizes the state of development of each power-to-x
pathway and provides important directions for future research.
2. Power to hydrogen
PtH relies on the use of electrical energy to power electrolysis, sep-
arating water into its constituent hydrogen and oxygen molecules. This
hydrogen can be stored as a high pressure gas, a cryogenic liquid, or in
metal hydrides and then fed to fuel cells or combustion technologies for
energy generation. Further, PtH serves as the precursor to electrifying
the production of chemicals such as methanol and ammonia as dis-
cussed respectively in Sections 3 and 4. Fig. 1 outlines the PtH-relevant
technologies described in this section and the interconnections between
them. Detailed descriptions of these hydrogen production, storage, and
utilization technologies are provided in Sections 2.1 through 2.3.
2
M.J. Palys and P. Daoutidis
Fig. 1. Conceptual technology outline for electrified hydrogen production and utilization in energy and transportation.
Table 2
Comparison of electrolysis technology investment costs.
AEC PEMEC
Present-day ($/kW) 850 1,000
Projected 2030 ($/kW) 500 600
2.1. Hydrogen production technology: Electrolysis
Electrolysis uses an electrical current to separate water:
2H2 O → 2H2 + O2 𝛥𝐻 = 571.66 kJ∕mol
Electrolysis cells consist of an anode and a cathode separated by an
electrolyte. The oxidation and reduction half reactions respectively
occurring at the anode and cathode depend on the specific electrol-
ysis technology. Three main classes of electrolysis are used for PtH:
alkaline (AEC), proton electrolyte membrane (PEMEC), and solid oxide
(SOEC) (Schmidt et al., 2017). Table 2 provides estimated present-day
and 2030 capital costs for each electrolysis technology. At present, AEC
is the most widely deployed (International Energy Agency, 2022b).
Both AEC and PEMEC operate at 50–80 ◦ C and can achieve efficiencies
as high as 85% based on the lower heating value (LHV) of hydrogen.
In AEC, OH− anions pass through an aqueous alkaline hydroxide elec-
trolyte, most commonly potassium hydroxide (KOH). Nickel or nickel
alloys are used in both the cathode and anode (Zeng and Zhang,
2010). AEC has the lowest associated present-day capital cost due
to its high technical maturity, avoidance of expensive noble metals,
operating lifetimes of up to 90,000 h (Bertuccioli et al., 2014). The
main drawback of AEC is limited dynamic flexibility, with an operating
lower bound of 10%–40% of installed capacity and more detrimentally,
startup times on the order of 60 min (Lehner et al., 2014).
PEMEC achieves similar efficiencies as AEC while offering consid-
erably better dynamic response characteristics, with a lower operating
bound of 0%–10%, millisecond response times, and startup times less
than 20 min (Carmo et al., 2013). PEMEC can also operate at pressures
up to 200 bar, making it well suited for gaseous hydrogen storage or
other high pressure applications. PEMEC uses a solid polymer mem-
brane electrolyte such as Nafion through which protons (H+ ) flow
from anode to cathode. PEMEC anodes use platinum (Pt) or platinum–
palladium (Pt–Pd) while cathodes employ ruthenium oxide or iridium
oxide. The use of these rare earth metals leads the capital cost of
PEMEC to be approximately double that of AEC. At present, PEMEC
has shorter operating lifetimes than AEC, specifically in the range of
20,000–60,000 h. However, PEMEC’s flexibility and resultant ability to
better couple with intermittent renewables has driven industrial efforts
to reduce cost and increase lifetime. At present, PEMEC makes up a
Computers and Chemical Engineering 165 (2022) 107948
moderate share of electrolysis deployment, with some predictions that
PEMEC will be the dominant technology by 2030 (Schmidt et al., 2017).
SOEC SOEC is at a much earlier stage of development and has mostly been
3,500 limited to demonstration efforts (Zhang et al., 2015). These systems
1,900
operate at temperatures of 650–1000 ◦ C and can achieve efficiencies
as high as 100% of hydrogen LHV (Laguna-Bercero, 2012). SOEC
uses ceramics such as Yttria stabilized Zirconia (YSZ) as electrolyte
through which O2− ions flow from a Ni on YSZ cathode to Perovskite-
type lanthanum strontium (LSM) on YSZ anode. The capital cost of
these systems is currently quite high, but reductions are expected with
their continued development (Kilner et al., 2012). However, high tem-
(1) perature operation presents a number of challenges. Primarily, SOEC
materials degrade faster than in AEC or PEMEC, leading to lifetimes less
than 10,000 h. Furthermore, the dynamic flexibility of SOEC is similar
to or worse than AEC, with operating lower bounds above 30% and
startup times of up to an hour (Hauch et al., 2020).
2.2. Hydrogen storage technology
Hydrogen storage is of key importance for the viability of PtH.
At ambient conditions, hydrogen is the least dense of all elements at
0.89 kg H2 /m3 ; the resultant low energy density is untenable. Storage
technologies primarily serve to increase this volumetric energy density.
The key technological considerations are the cost of the storage system
and the energy required to transform hydrogen into its stored form.
In transportation applications, the weight of the storage system is
also crucial. This section focuses on three types of hydrogen storage
technologies: compressed gas, cryogenic liquid, and metal hydrides.
The key characteristics of each are summarized in Table 3. Hydrogen
can also be ‘‘stored’’ in the form of chemical bonds — its use as a
reactant for methanol and ammonia synthesis is respectively discussed
in the subsequent Sections 3 and 4.
Compressed gas is the most developed form of hydrogen storage.
Practically, this entails ambient temperature hydrogen compressed to at
least 200 bar and up to 1000 bar, with many storage vessels for energy
and transportation applications rated at 700 bar (Barthélémy et al.,
2017). Compressing hydrogen to 700 bar consumes approximately 10%
of the contained energy (based on LHV). State-of-the-art high pressure
vessels rely on two separate components. They generally use (i) a
composite shell of carbon or glass fiber embedded in resin to provide
mechanical integrity without excessive thickness or weight and (ii) a
metal or polymer liner in contact with the gas to act as a hydrogen
permeation barrier (Tzimas et al., 2021). Compressed hydrogen storage
investment costs are $10–15/kWh based on LHV (James and Houchins,
2016). State-of-the-art hydrogen-fueled passenger vehicles store 5–7 kg
H2 in a full tank at 700 bar to give a maximum driving distance (range)
3
M.J. Palys and P. Daoutidis
Table 3
Comparison of hydrogen storage technologies.
Compressed
Pressure (bar) 200–1,000
Temperature (◦ C) 25
Energy density (kWh/L) 0.5–1.8
Energy lossb (%) 10
Storage cost ($/kWh) 10–20
a
In a storage context, energy loss refers to the additional energy required on a percentage basis to store a
given quantity of hydrogen.
b
Metal hydride storage materials require decreased pressure and increased temperature to release the stored
hydrogen.
of 400–600 km (Lipman et al., 2018). Salt caverns can be used for
stationary storage at larger scales. Salt is inert with respect to hydrogen
and thus limits its diffusion from storage. Salt cavern storage generally
occurs at pressures up to 200 bar, thus requiring less energy for hydro-
gen compression (Ozarslan, 2012). This storage method becomes more
economical than vessel-based storage if more than 20 ton H2 are to be
stored and the specific investment is roughly an order of magnitude
lower ($1–1.5/kWh) over 100 ton H2 storage volume (Ahluwalia et al.,
2010). The main drawback of salt cavern storage is their geographical
limitation in that these caverns may not exist in desirable areas for
PtH. Further, hydrogen transportation to and from these caverns is
nontrivial, generally making their use uneconomical for even moderate
distances between the caverns and production/utilization sites.
Cryogenic liquid storage involves cooling to −253◦ with mild com-
pression to about 4 bar (Barthélémy et al., 2017). This allows for
energy density twice that of compressed gas while avoiding safety
concerns associated with high pressure. However, storage at these con-
ditions consumes approximately 35% LHV of the contained hydrogen.
More recent efforts have utilized temperatures of −238 ◦ C to −163 ◦ C
and pressures of 50–700 bar to achieved so-called ‘‘cyro-compressed’’
storage (Yanxing et al., 2019). This can reduce storage energy con-
sumption to roughly 25% of LHV but at additional compression cost.
Ultimately, liquid or cyro-compressed hydrogen storage is not well
suited to stationary energy applications. Few hydrogen-fueled vehicles
employ cryogenic storage either due to the requirement of advanced
onboard cooling/insulation systems which add additional cost. Overall,
the most likely applications for cryogenic storage are the ones in which
high volumetric densities are of utmost importance, even at the expense
of energy losses.
Reversible storage in metal hydrides is based on the exothermic
hydrogen dissociation onto a metal surface and subsequent absorption
into the metal (Barthélémy et al., 2017). Then, the absorbed hydro-
gen is endothermically released by increasing the temperature. The
suitability of metals for hydride storage depends largely on thermody-
namics, both in terms of the required absorption-release temperature
swing, which dictates the energy penalty for storage, and the maximum
amount of hydrogen which can be stored, which determines the total
weight of the storage system. Magnesium hydride (MgH2 ) has been
identified as a promising storage candidate. Mg can store more than
7% hydrogen by weight, about three times the amount stored in
typical metal hydrides (Motyka, 2015). This storage can be achieved
at pressures of below 20 bar and is inexpensive from a raw materials
perspective, resulting in investment costs below $1/kWh (Eigen et al.,
2007). Micron-scale Mg powders doped with approximately 1 mol%
catalyst can enable charge and discharge on the order of minutes (Leng
et al., 2006), and cyclic stability has been demonstrated for over 2000
cycles (Luo et al., 2019). The main drawback of MgH2 storage is the
heat required to achieve release temperatures of 200–300 ◦ C (Sakin-
tuna et al., 2007). Onboard vehicle use of metal hydrides is unlikely due
to these high temperatures as well as high total storage system weight
and the resulting detriment to fuel economy. However, their ability to
store hydrogen at lower pressures makes their use at fueling stations
intriguing from a safety perspective.
4
Computers and Chemical Engineering 165 (2022) 107948
Cryogenic Metal hydride
4 20 (Releasea : 1–5)
−253 25 (Releasea : 200–300)
2.3 1.4–1.8
35–40 15
5 1
Table 4
Comparison of fuel cell investment costs.
AFC PEMFC SOFC PAFC
Present-day ($/kW) 700 1,600 2,200 2,900
Projected 2030 ($/kW) 400 950 1,200 2,500
2.3. Hydrogen utilization technology
Fuel cells are the most commonly considered technology for produc-
ing energy from hydrogen. As with electrolysis discussed in Section 2.1,
fuel cells consist of an anode and a cathode with an ion-permeable
electrolyte between them. Hydrogen is delivered to the anode, oxygen
(generally air-contained) is delivered to the cathode, and electrons
which are abstracted at either the anode of cathode (depending on
the technology used) flow through an external circuit to generate
electricity while producing water as a byproduct. Water formation is
an exothermic reaction which can be exploited in combined heat and
power (CHP) applications. Conceptually, fuel cell reactions are the
reverse of those taking place in electrolysis. As such, many of the
major types of hydrogen fuel cells fall under the same classification as
the electrolysis technologies discussed in Section 2.1, namely alkaline
(AFC), proton electrolyte membrane (PEMFC), and solid oxide (SOFC).
The reader is thus directed to that Subsection for detailed discussion
of the anode, cathode, and electrolyte materials along with the elec-
trochemistry basics. The discussion here focuses on operational aspects
of these fuel cell technologies, especially in comparison to each other.
Phosphoric acid fuel cells (PAFC) are also introduced and discussed in
this section. Table 4 provides estimated present-day and 2030 capital
costs for each hydrogen fuel cell technology discussed in this section.
AFC operates at 70–100 ◦ C and can achieve state-of-the-art electri-
cal efficiency around 60% and CHP efficiencies of approximately 80%.
As with electrolysis, alkaline technologies require the least investment
due to technical maturity and low cost materials, but suffer from
limited dynamic operating range and slower startup. PEMFC achieves
similar electrical efficiencies of 50%–60% but CHP efficiencies up to
90%. These systems operate either in a 80–100 ◦ C low-temperature
regime or a 200 ◦ C high-temperature regime (Yue et al., 2021). Higher
operating temperatures can increase CHP efficiency and simplify the
management of water product which will vaporize over 100 ◦ C. How-
ever, this vaporization also causes membrane dehydration, increasing
degradation rates and decreasing lifetime (Mekhilef et al., 2012). Low
temperature PEMFCs are also better suited to dynamic operation owing
to faster startup. The main drawback of PEMFC is the expensive materi-
als used in the anode and cathode. Both AFC and PEMFC are best suited
to small-scale stationary applications. Their maximum single module
outputs are approximately 100 kW and 250 kW respectively (Mekhilef
et al., 2012). If their desired total output is higher, ‘‘numbering up’’
to increase total capacity does allow for some economies of volume
cost savings on balance of plant components. PEMFC are the most
commonly considered technology for fuel cell vehicles due to their
availability in outputs below 1 kW, low temperatures, lightweight
components, and dynamic operating capabilities (Wang et al., 2005).
M.J. Palys and P. Daoutidis
PAFCs employ a phosphoric acid electrolyte held inside a porous
matrix through which protons (H+ ) travel, with both anode and cath-
ode using Pt coated on carbon microfibers (Kirubakaran et al., 2009).
PAFC operate between 180–200 ◦ C, with electrical and CHP efficiencies
of 40%–45% and 80% respectively. PAFCs have been mostly considered
for energy generation, with maximum single module power output in
the range of 400–1000 kW; economies of scale enable lower per kW
capital investment than PEMFC (Mekhilef et al., 2012). However, the
use of expensive Pt in the anode and cathode still results in higher
capital investment than for AFC. Dynamic flexibility is also major draw-
back of PAFC, with startup times as long as 4 h because considerable
preheating is required before operation (Acar et al., 2021). Nonetheless,
PAFCs are commercially available, though interest in them has waned
with the continued development of AFC and PEMFC.
SOFCs involve considerably higher temperatures than the previously
discussed fuel cell systems, operating in the range of 600–1000 ◦ C. Elec-
trical and CHP efficiencies are 35%–45% and up to 90% respectively.
High temperature operation leads to a number of distinct advantages
and drawbacks. High temperature waste heat makes these fuel cell
technologies especially attractive in CHP applications. Further, SOFCs
can operate reversibly in both electrolysis and fuel cell modes (Mo-
gensen et al., 2019); this could enable further cost savings in stationary
energy applications by reducing the number of required process units.
However, high temperatures accelerate degradation of cell compo-
nents which worsens performance and/or shortens lifetime (Acar et al.,
2021). High temperature operation also limits dynamic flexibility, as it
results in startup and shutdown times on the order of hours (Oryshchyn
et al., 2018). SOFC are available in large modules, with maximum sizes
of 1000 kW (Mekhilef et al., 2012). This makes them well suited to
large scale energy supply applications or perhaps in long haul trucking
or marine shipping settings where startup times, system size/weight,
and high temperatures are less detrimental than in passenger vehicles.
Hydrogen can also be combusted for energy supply or transporta-
tion applications. Conventional combustion systems must be modified
for use with hydrogen due to its higher flame speed and resulting
higher combustion temperature than conventional fuels (Ilbas et al.,
2006). These high temperatures increase formation of nitrous oxide
from nitrogen in the air used for combustion. Mitigating these NOx
emissions is essential for local air quality and because on a mass basis
NOx is at least 250 times more potent than CO2 as a greenhouse
gas (U.S. Environmental Protection Agency, 2022). Design alterations
such as the use of advanced hydrogen-mixing devices (Cappelletti and
Martelli, 2017) or sequential combustion chambers with intermediate
temperature control (Bothien et al., 2019) have been investigated to
this end. Higher temperatures coupled with the increased amount of
steam in the combustion products can also result in increased corrosion
and degradation of system components, though this can be mitigated
through material changes to system components (Stefan et al., 2021).
Turbines are the state-of-the-art for large scale power generation with
fossil fuels. These generate power by converting kinetic energy from
a moving gas, either steam raised in a boiler using the fuel’s heat
of combustion or the combustion product gases themselves. Turbines
using pure hydrogen as fuel have demonstrated electrical efficiencies
of 35% (Cappelletti and Martelli, 2017; Goldmeer, 2019), comparable
that of simple combustion turbine systems. Combined cycle gas turbines
(CCGT) achieve electrical efficiencies as high as 60% by using waste
heat from a direct combustion turbine to drive a secondary steam-
powered turbine. Major manufacturers have set a 2030 target to deliver
100% hydrogen-fed CCGTs, with investment costs projected to be 10%
higher than conventionally fueled systems (European Turbine Network,
2019; Bothien et al., 2020).
Internal combustion engine (ICE) generators can also be used for
energy supply as well as transportation. In a stationary context, they are
generally used as ‘‘peaking’’ plants in grid operations during periods of
high demand or for emergency backup or remote power applications.
ICE generators startup times are much less than turbines. However,
5
Computers and Chemical Engineering 165 (2022) 107948
ICE generators are less efficient than turbines and have higher per
unit capital costs. Gasoline-fueled ICE is the ubiquitous passenger ve-
hicle engine concept, so hypothetically these could be retrofitted or
replaced with hydrogen-fed engines with the appropriate modifications
as discussed above. Hydrogen-fed ICE or ICE generators are about 80%–
85% as efficient as gasoline ICE or diesel generators (White et al.,
2006), but these power losses can be mitigated by using higher engine
compression ratios (Akal et al., 2020). Hydrogen ICE have considerably
lower efficiency than fuel cells, resulting in higher fuel consumption
and lower range in a vehicle context (Candelaresi et al., 2021).
2.4. Control and real-time operation
A major focus of recent systems engineering research in PtH systems
is control and real-time operation of hydrogen production, storage,
and (potentially) utilization processes in the face of intermittent re-
newables. The operational decision-making for these systems must
account for the dynamics of each constituent technology as they inter-
act with intermittent renewable availability. Torreglosa et al. (2014)
proposed a two-layer hierarchical control strategy for a standalone
wind-PV power system which uses both batteries and hydrogen for
energy storage. In their formulation, the primary control layer deter-
mines the cost optimal storage charge and discharge states based on
renewable generation, power demand, and the current states of each
storage technology relative to their operating limits. The dispatch cost
calculation accounts for the effects of charge/discharge cycling and
operating hours on storage technology lifetime. The secondary layer
uses cascade control with individual PI controllers for electrolysis,
fuel cells, and batteries. Case studies for 25 years of operation using
one hour sampling for primary control showed both prolonged battery
and fuel cell lifetimes and effective setpoint tracking and disturbance
rejection. Garcia et al. (2013) proposed a parallel control strategy for
a hybrid battery-hydrogen system. A utilization cost optimization layer
was used to determine battery or hydrogen storage dispatch for charg-
ing or discharging while considering degradation of each component.
The cost layer did not explicitly account for battery state-of-charge
(SOC) and hydrogen storage inventory. This was accomplished through
fuzzy logic control which overrode the utilization cost layer to ensure
allowable storage operation. The fuzzy logic controller used the battery
SOC, hydrogen inventory, and net power (generation–demand) as input
with three, three, and five membership functions respectively. A set
of rules for each permutation of these membership functions then
determined which control mode was active and then implemented
charge/discharge if fuzzy logic control was chosen. Compared with a
binary fully rule-based control strategy via a 25 year hourly resolution
simulation, the proposed fuzzy logic approach enabled close to 30%
reduction in utilization cost and enables zero renewable curtailment.
Trifkovic et al. (2013) proposed a multilevel control architecture
for hydrogen ESS consisting of a supervisory layer which determines
binary operation modes and set-points for electrolysis/hydrogen com-
pression and fuel cells and model predictive control (MPC) for each unit
based on linearized state–space models. Two MPCs were designed for
each unit, specifically with linearization at 10% and 90% rated power
operating points, to account for their highly nonlinear behavior. This
allowed for the mitigation of controller-model mismatch by selecting
the MPC closer to the setpoint from supervisory control. Case studies
performed for 1 kW order of magnitude residential demands showed
that this dual MPC strategy significantly improved electrolysis and fuel
cell efficiency while also reducing electrolysis startup and shutdown
cycling. Trifkovic et al. (2014) then used this multilevel control
formulation as the basis for proactive energy management strategy
based on real time optimization (RTO). The RTO level determined
unit commitments and setpoints to maximize renewable utilization and
hydrogen production while minimizing electrolysis startups over a daily
receding horizon with hourly resolution. Forecasts for power demand,
wind speed, solar irradiance as well as current unit states were used
M.J. Palys and P. Daoutidis
as RTO input data. The optimal setpoints were then achieved using the
dual MPC formulation proposed in their previous work (Trifkovic et al.,
2013). A notable feature of the 2014 work of Trifkovic et al. was the
inclusion of a battery and the ability to adjust its operation at the unit
control level to resolve the difference in forecasted and realized de-
mand and renewable availability. This proactive strategy was simulated
for a year of energy system operation. The optimal control strategy
favored consecutive hours of electrolysis and fuel cell operation to mini-
mize their cycling, charging or discharging the batteries to achieve this.
Torreglosa et al. (2015) used MPC to improve upon their previous work
by replacing the PI controllers (Torreglosa et al., 2014). They employed
a centralized (linear/nonlinear) MPC formulation which determined
power charge and discharge for battery and hydrogen storage options
based on net power availability. This strategy achieved 15% higher sys-
tem efficiencies compared to the use of individual PI controllers. Nair
and Costa-Castelló (2020) also used MPC for control islanded energy
storage system which included batteries, a reversible hydrogen-fed fuel
cell, and a dispatchable fossil fueled generator. They formulated the
MPC problem as a mixed integer quadratic programming (MIQP) to
penalize battery and fuel cell cycling. They used 5 min control intervals
in a receding horizon and performed case studies for horizon lengths
ranging from 3 h to 24 h. Prediction horizons longer than 6 h only
marginally improved control performance while drastically increasing
computational time. Their MIQP MPC formulation outperformed a
heuristic power management scheme based on fuzzy logic, providing
less battery degradation due to less time at SOC above 80%, smoother
reversible fuel cell setpoint variation, less curtailed PV power, and less
dispatchable fossil generation
Recent research has also used economic model predictive control (E-
MPC) for in the context of PtH and hydrogen ESS. Pereira et al. (2015)
used such a formulation for a PV-battery-hydrogen (in metal hydride)
system for diurnal energy storage that could exchange energy with the
neighboring utility. The economic objective was to maximize the profit
from this exchange and included the cost of deviating from day-ahead
energy bids (the quantity and duration of which were parameters in
their work) as well as degradation costs for ESS components. They
used a linear state–space model for battery and hydrogen storage
dynamics based on the average step response over 300 simulations of a
nonlinear process model they developed previously. The initial state
of the system was left as a free variable, and they instead imposed
periodic constraints. They simulated E-MPC implementation on the
original nonlinear model for five days of operation, using a 30 min
sampling time over a 24 h receding horizon. Each set of optimal
control actions were computed in less than 4 min and convergence to
optimal periodic trajectories was observed even in the face of changing
economic parameters, for example, if energy sale was no longer allowed
after 48 h of operation. Mendes et al. (2016) developed a two layer
control formulation for a wind-PV-battery-hydrogen (in metal hydride)
system using both E-MPC and MPC. The E-MPC layer determined opti-
mal control actions every five minutes, while the MPC layer ensured
real-time setpoint tracking. The control problems were formulated
as mixed integer linear programs (MILPs), with constraints limiting
electrolysis and battery switching included in the E-MPC model. Com-
putational experiments were performed for ‘‘sunny’’, ‘‘cloudy’’, and
‘‘windy’’ representative days, with the optimal results in each requiring
two electrolysis-fuel cell cycles to mitigate degradation of these units.
Garcia-Torres and Bordons (2015) used a four level cascade E-MPC
formulation for a grid-connected wind-PV-hydrogen-battery ESS to link
market operations over different timescales. The considered markets
(with relevant control resolutions/horizons) were daily (1 h/24 h),
interday (1 h/24→9 h), deviation management (1 h/24→5 h), and
regulation service (10min/3 h), where the interday and deviation man-
agement market horizons shrank throughout the day. Each E-MPC layer
was formulated as an MIQP to account for battery, electrolysis, and fuel
cell degradation costs. An implementation case study showed shifting
optimal battery SOC and hydrogen storage levels in response to price
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Computers and Chemical Engineering 165 (2022) 107948
signals from the different markets; the value of energy became higher
at later stages, so corrective action through the cascade improved
economics. They also compared the MIQP and MILP formulations and
found similar grid economics but found that accounting for degradation
resulted in less battery and hydrogen storage cycling.
Cau et al. (2014) used an E-MPC framework to manage uncertainty
in renewable generation and demand forecasts. They used scenario
trees with multi-hour to describe the evolution of this uncertainty
over a day. The E-MPC was formulated as a MILP, using piecewise
linear functions to describe the efficiency of batteries, electrolysis, and
fuel cells. They performed case studies for a representative week from
each season, using a 24 h receding horizon with hourly resolution.
For each representative week, a tree with 15 scenarios was obtained
using scenario reduction technique. Compared to a binary rule-based
formulation, E-MPC resulted in cost savings through more efficient
hydrogen utilization. However, the time required to solve the E-MPC
approached an hour in many instances; this temporal proximity to
the decision resolution could cause problems with implementation.
Cano et al. (2015) used fuzzy logic control for power management
under uncertainty in a wind-PV-battery-hydrogen ESS. They described
net load (renewable generation–demand) as a stochastic process and
used the current value, forecasted difference in successive periods,
and forecasted variance in the next period along with the current
battery state-of-charge as input variables to the fuzzy controller. The
controller output was the electrolysis power consumption or fuel cell
power generation. Triangular and trapezoidal membership functions
were used for the input–output mapping. They applied this framework
to case studies for the same hourly resolution representative weeks
as Cau et al. (2014), and found their approach resulted in fewer
electrolysis startups and less fuel cell degradation with much faster
computation.
2.5. Capacity planning
There has been extensive research on capacity planning of PtH sys-
tems which both produce and use hydrogen for energy storage. In this
review, we classify capacity planning for power-to-x systems as prob-
lems in which multiple process units are sized simultaneously. These
problems often incorporate unit scheduling decisions at the design stage
as to allow unit sizing to explicitly account for temporal variability
in renewable generation. Much of the earlier PtH capacity planning
work focused on optimization of standalone (most generally) wind-
PV-electrolysis-storage-fuel cells systems with case studies for single
locations (Garcia and Weisser, 2006; Dufo-López and Bernal-Agustín,
2008; Zhou et al., 2008; Kaviani et al., 2009; Shabani et al., 2010;
Erdinc and Uzunoglu, 2012; Jallouli and Krichen, 2012; Castaneda
et al., 2013; Vasallo et al., 2013; Lacko et al., 2014; Kalinci et al.,
2015; Bakhtiari and Naghizadeh, 2018; Zhang et al., 2018). Most of
these efforts used heuristic power management rules parameterized on
input data to reduce the decision space (Garcia and Weisser, 2006;
Zhou et al., 2008; Shabani et al., 2010; Erdinc and Uzunoglu, 2012;
Castaneda et al., 2013). Other research has used meta-heuristic algo-
rithms (e.g particle swarm optimization or simulated annealing (Dufo-
López and Bernal-Agustín, 2008; Kaviani et al., 2009; Bakhtiari and
Naghizadeh, 2018; Zhang et al., 2018) or parallel simulation of many
fixed design alternatives (Lacko et al., 2014; Vasallo et al., 2013; Kalinci
et al., 2015) for computational tractability. The solution approaches
applied in these works enabled high scheduling resolution, for example,
a yearlong horizon with hourly granularity. One notable recent work
is that of Rullo et al. (2019) who used a genetic algorithm solu-
tion approach for a bilevel MINLP which combined capacity planning
with scheduling based on E-MPC over a 12 h receding horizon. This
approach allowed for explicit accounting of process dynamics during
scheduling and resulted in 10% reduction in levelized cost of energy
compared to heuristic power management rules (Rullo et al., 2019).
M.J. Palys and P. Daoutidis
Research conducted since 2018 has used MILP optimization to
solve these capacity planning problems. Mallapragada et al. (2020)
performed a U.S. national survey of optimal PV-based hydrogen produc-
tion costs, determining the size and schedules of PV arrays, batteries,
electrolysis, and high pressure storage to meet continuous hydrogen
production targets. They found that hydrogen production costs below
$2.5/kg H2 were best met through over-sized electrolysis which dy-
namically tracks solar generation, minimizing local battery capacity.
These designs were most favorable with a reduction in electrolysis
capital cost as well as low cost salt cavern hydrogen storage. Marocco
et al. (2021) and Kotzur et al. (2018) applied MILP capacity planning
respectively to wind- and solar-based isolated hydrogen energy storage
systems, determining optimal sizing of this renewable generation along
with batteries, hydrogen production, storage, and fuel cell technolo-
gies. Both found renewable generation investment to be the main cost
drivers of these energy systems. Additionally, optimal hydrogen storage
capacity was an order of magnitude higher than battery capacity,
indicating its suitability for longer storage durations. Mehrjerdi (2020)
and Gabrielli et al. (2019) incorporated solar generation and energy
demand uncertainty in their capacity planning for PV-hydrogen sys-
tems, with Gabrielli et al. focusing on CHP supply. Mehrjerdi employed
a stochastic MILP formulation using 10 scenarios for the PV capac-
ity factor and power demand, using four season-representative days
with hourly resolution for operating decisions (96 scheduling periods).
Gabrielli et al. instead used robust optimization, sampling over 1000
input data scenarios to find temporal profiles which gave the highest
annual electrical and thermal demands and the lowest solar availability.
They subsequently used these worst-case input data to optimize sizing
and dispatch, employing a scheduling decision partitioning approach
where binary operating decisions were made over 48 hourly resolution
representative design days and these were linked via constraints to
continuous operating decisions made for every hour in the selected
‘‘robust’’ representative years.
Given the extensive state of capacity planning research for single-
location hydrogen systems, recent investigations have also incorpo-
rated a spatial element to enable the design of PtH networks. Ogbe
et al. (2019) considered the augmentation of existing natural gas
supply chains with renewable hydrogen, optimizing the locations of
electrolysis-based hydrogen production and injection into the existing
pipeline under maximum hydrogen concentration constraints. They
used a tractable stochastic formulation with 16 scenarios to account
for uncertainty in the purity of hydrogen produced via electrolysis and
the total gas demand. The author-identified limitation of this study was
not considering temporal variability in energy availability for hydro-
gen production due to the limitations on tractability inherent to the
stochastic formulation. He et al. (2021) optimized design and operation
of a network of hydrogen production with truck and pipeline trans-
portation to demand sites, with these trucks and pipeline potentially
acting as storage in addition to stationary high pressure vessels. They
performed a case study for a six zone network in the Northeast U.S.
using 20 representative weeks for operation. They found that the ability
to flexibly use hydrogen transportation as storage reduces stationary
hydrogen storage capacity by approximately 60% and hydrogen supply
costs by $0.2/kg H2 . Heras and Martín (2021) used a time-invariant
hydrogen energy network model employing magnesium for low cost
hydrogen storage. Since the use of Mg for low cost hydrogen storage is
a novel concept, Heras and Martin first performed detailed nonlinear
optimization of the storage and discharge processes in their work. They
then optimized the location and scale of these technologies along with
wind and solar generation, hydrogen production via electrolysis, and
fuel cells for power generation across the country of Spain. Optimized
electricity costs were found to be as low as $0.1/kWh if byproduct heat
and O2 from the hydrogen storage process can be sold. Samsatli and
Samsatli (2019) developed a hydrogen-based heating network MILP
model for Great Britain. This model optimized the addition of new
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Computers and Chemical Engineering 165 (2022) 107948
onshore and offshore wind generation as well as installation and oper-
ation of electrolysis, high pressure and underground hydrogen storage,
hydrogen and direct electric boilers at both industrial and distribution
scales, and transmission and distribution infrastructure for power, heat,
and hydrogen. They performed a case study where great Britain was
divided into 16 characteristic zones and employed a hierarchical, non-
uniform time aggregation approach with variable-length multi-hour
periods per season to efficiently represent the hourly resolution yearly
input data. They found that hydrogen was the key to the profitability
of this network in reducing the cost of seasonal heat storage.
3. Power to methanol
PtM extends the PtH concept discussed in Section 2 by combining
hydrogen with CO2 to synthesize methanol. Methanol is easily stored
as liquid and can be used to produce energy via decomposition to
hydrogen, direct use in fuel cells, or combustion. Fig. 2 outlines the
PtM-relevant technologies described in this section and the intercon-
nections between them. The CO2 for PtM can be obtained from a variety
of sources. It can be almost pure as an industrial byproduct, captured
from combustion flue gas, or directly captured from air. CO2 capture
technologies are not discussed in this paper; for more information, the
reader is referred to a recent review by Bui et al. (2018). Detailed
descriptions of these methanol production and utilization technologies
are provided in Sections 3.1 and 3.2.
3.1. Methanol production technology
Catalytic methanol synthesis was invented in the 1920s (Kastens
et al., 1948) and is the prevailing industrial approach today. It uses
a feedstock which contains hydrogen, CO, and CO2 (termed ‘‘syngas’’)
to produce methanol in the following network of reactions (Klier et al.,
1982; Sahibzada et al., 1998):
2H2 + CO ⇌ CH3 OH 𝛥𝐻 = −90.6 kJ∕mol (2)
3H2 + CO2 ⇌ CH3 OH + H2 O 𝛥𝐻 = −49.4 kJ∕mol (3)
2H + CO2 ⇌ H2 O + CO 𝛥𝐻 = 41.6 kJ∕mol (4)
The state-of-the-art process pressure and temperature ranges are
50–100 bar and 200–300 ◦ C respectively (Haid and Koss, 2001). The
primary reactor design consideration is economically removing the heat
formed by this exothermic synthesis reaction to enable high equilibrium
conversion to methanol while avoiding formation of unwanted side
products which are promoted by higher temperatures (Mbatha et al.,
2021). The dominant and technically well-established reactor configu-
ration is a multi-tubular bed which operates close-to-isothermally via
cooling through vaporizing water. Other configurations include a coil
wound heat exchanger with catalyst on the shell side, radial flow reac-
tors, or multi-stage adiabatic reactors with inter-bed cooling (Bozzano
and Manenti, 2016). Slurry, trickle bed, and fluidized bed reactors
have been proposed as means to mitigate mass and heat transport
limitations, but have not been implemented at appreciable production
scales (Hansen and Hojlund, 2008). Single pass conversions tend to
be in the 35%–60% range; reactor effluent is cooled and separated
so that unreacted syngas can be recycled. After synthesis, methanol
must be separated and purified. The product of the above-described
synthesis approaches is generally termed ‘‘raw’’ or ‘‘crude’’ methanol.
Purification of this raw methanol generally first employs flash sep-
aration at 5–10 bar to remove any dissolved light gases, and then
one or more distillation columns depending on the intended methanol
use. Energy or fuel grade methanol requires only a single column
with methanol as the distillate and higher boiling point components as
the bottoms (Bertau et al., 2014). Methanol synthesis process depends
M.J. Palys and P. Daoutidis
Fig. 2. Conceptual technology outline for electrified methanol production and utilization in energy and transportation.
strongly on economies of scale, with its estimated capital investment
being (Demirhan et al., 2020):
𝑥 to mitigate cathode oxidation (Cinti et al., 2016). This hydrogen can
𝐶𝐴𝑃 𝐸𝑋(𝑀𝑀$) = 1.8( 𝑀𝑒𝑂𝐻 )0.65 (5)
1000
where 𝑥𝑀𝑒𝑂𝐻 is the ton/y nameplate capacity of the CO hydrogenation
methanol synthesis process. From an energy perspective, this process
requires approximately 0.25–0.5 MWh/ton MeOH.
Process intensification has been used in an attempt to reduce this
cost and/or energy consumption. Membrane (Gorbe et al., 2018) and
sorption-enhanced (Terreni et al., 2019) reactors have been inves-
tigated with a view on removing methanol from the reaction zone
and thus mitigating equilibrium limitations on conversion. Reactive
distillation has also been investigated for methanol production as an
intensified solution to reduce investment (Ghosh and Seethamraju,
2019).
The commercial synthesis catalysts use copper oxide (CuO) or zinc
oxide (ZnO) supported on alumina (Al2 O3 ). Equilibrium conversions
using syngas feed are considerably higher than for direct hydrogenation
of CO2 (see Eq. (3).1) (Pontzen et al., 2011). As such, two stage
processes for PtM have been developed for CO2 abatement where
CO2 is first converted at least partially to CO and then the methanol
synthesis proceeds as described in the previous paragraph. One such
approach is to use the water gas shift (WGS) reaction (see Eq. (3).1)
for this CO2 transformation. This entails the use of an auxiliary iron
catalyst bed operating at around 10 bar and 600–700 ◦ C (Joo et al.,
1999), with these high temperatures favoring CO formation because
WGS is endothermic. The resultant water is separated and additional
hydrogen can be added to achieve conventional syngas compositions
before methanol synthesis. Co-electrolysis is an alternative which is less
developed than the combination of electrolysis to produce hydrogen
coupled with water gas shift, but offers promise with respect to energy
efficiency and overall process cost reduction by eliminating the WGS
reactor (Andika et al., 2018). In a co-electrolysis cell, water and CO2 are
fed to the cathode where they are reduced to hydrogen and CO to give
the desired syngas composition. The resulting O2− ions pass through
a solid oxide electrolyte where they combine to O2 at the anode. Co-
electrolysis systems operate at 600–1000 ◦ C and use a Ni/YSZ cathode,
a LSM/YSZ anode, and a YSZ electrolyte (Zheng et al., 2017), similar
8
Computers and Chemical Engineering 165 (2022) 107948
to SOEC for hydrogen production. Practical operation of co-electrolysis
requires 5–10 mol% hydrogen co-feeding with water and CO2 in order
be obtained through recycle from methanol production or a separate
smaller electrolysis unit.
Considerable research has also been dedicated to developing cata-
lysts and processes uniquely suited to direct CO2 hydrogenation. Cata-
lysts for CO2 hydrogenation tend to consist of multiple components,
for example promoting CuO-ZnO-Al2 O3 with zirconium, gallium, or
yttrium. These catalysts are tuned to maximize CO2 conversion and mit-
igate water formation (Dang et al., 2019; Guil-López et al., 2019). The
emergence of these multi-component catalysts has enabled methanol
synthesis from direct CO2 hydrogenation with higher selectivity and
fewer impurities than methanol production from syngas (Pontzen et al.,
2011). The less exothermic nature of CO2 hydrogenation relative to
methanol production from syngas potentially allows for simpler reactor
and process designs from a heat transfer/integration perspective — this
is promising both from a capital cost perspective and for the dynamic
flexibility of CO2 hydrogenation.
3.2. Methanol utilization technology
Methanol can be reformed to hydrogen for use in fuel cells or
combustion technologies as discussed in Section 2.3. It is worth not-
ing that PAFCs can effectively handle more impurities in the feed;
historically, this was a main driver in their development for use with
hydrogen sourced from hydrocarbons, and in present day would allow
for less stringent pre-reforming for use with MtP compared to PEMFC
and AFC. Hydrogen for use in more established fuel cell technologies
can be produced from methanol via four routes: steam reforming
(MSR), partial oxidation (POM), autothermal reforming (ATRM), and
decomposition (MD). The first three are analogous to routes used for
hydrogen production from methane. This paper provides a high level
overview of hydrogen production from methanol. A review by Garcia
et al. (2021) provides a more detailed discussion. Producing hydrogen
from methanol results in CO and/or CO2 byproducts. In a hydrogen fuel
cell context, CO must be separated from reactor effluent to avoid cell
degradation. CO can also be used to obtain additional hydrogen via
WGS, but this adds cost. SMR produces considerably lower CO than
M.J. Palys and P. Daoutidis
the other three routes, which makes coupling with fuel cells attrac-
tive (Iulianelli et al., 2014). It is also the most well-established and
having the highest specific yields since both methanol and water pro-
duce hydrogen. However, this endothermic process requires heating for
both isothermal operation and steam generation. This results in higher
energy consumption and slower process dynamics. POM and ATRM
offer more dynamic flexibility and are respectively heat producing
and thermo-neutral with the aforementioned drawback of additional
CO production. POM entails exothermic methanol combustion with
well-below stoichiometric amounts of O2 ; this ratio can be adjusted
for dynamic operation. ATRM combines the MSR and POM reactions,
adjusting feed water and oxygen flowrates to balance their endothermic
and exothermic heats of reaction. MD requires no additional feed and
can give complete conversion into hydrogen and CO. As with SMR, this
is an endothermic reaction. It has thus been suggested to spatially and
temporally integrate MSR or MD and hydrogen combustion systems to
provide this required heat Wilson (2009).
Low temperature direct methanol fuel cells (DMFC) are specifically
designed for methanol-based energy generation (Demirci, 2007; Ku-
likovsky, 2008). DMFC systems operate at 30–100 ◦ C and, similar to
PEMFC, use polymer membranes as a proton conducting electrolyte and
operate at 30–100 ◦ C. These systems are fed with a liquid mixture of
methanol and water rather than H2 and O2 . DMFCs can achieve electri-
cal efficiencies 40% and CHP efficiencies of 80%, while offering better
dynamic flexibility than other direct-fed fuel cells due to their lower
operating temperature. The investment cost and capacity availability of
DMFC are similar to that of PEMFC (Müller and Stolten, 2011), without
considering the cost of methanol reforming needed for use with PEMFC.
Thus, DMFC are superior for methanol fueling in small stationary or
portable energy applications as well as for passenger vehicles. However,
direct methanol fueling of vehicles would result in highly spatially
dispersed CO2 emissions. Methanol can also be directly fed to SOFC due
to their high operating temperatures, which enable internal reforming
of methanol to H2 . Molten carbonate fuel cells (MCFC) also enable
internal reforming. These systems operate at 600–700 ◦ C and can
achieve electrical and CHP efficiencies up to 50% and 85% respectively.
MCFC systems use an electrolyte of sodium, potassium and/or lithium
molten carbonates suspended in a ceramic matrix. The electrolyte-
traversing anion is CO2− 3
(Sundén, 2019). MCFCs must in fact be used
with carbon-based fuels such as methanol because they require the
presence of CO2 to this CO2− 3
ion. The anode and cathode both use
nickel, avoiding expensive precious metals. At present, MCFCs are more
established than SOFC and require roughly 40%–50% less investment,
but their respective capital costs are projected to reach parity in the
future (International Energy Agency, 2022b). However, MCFCs have
shorter lifetime due to the corrosive nature of electrolyte (Acar et al.,
2021). As discussed in Section 2.3, high temperature operation limits
dynamic flexibility which restricts deployment of SOFC and MCFC to
certain stationary or long haul transportation applications. Nonetheless,
their large available module sizes above 1000 kW and, for MCFC,
mature state of development makes them attractive.
Methanol is also suitable for direct combustion and this has been
an active topic of research since the 1980s (Von KleinSmid et al.,
1981; Weir et al., 1981; GE, 2001). Methanol can be used for power
generation in turbines, wherein the differences between methanol and
methane necessitate a number of modifications to system design and/or
operation (Murray and Furlonge, 2009). Methanol contains 60% less
energy than CH4 on a mass basis, so more fuel and larger fuel feed
infrastructure are required for a given energy demand. Methanol is
more viscous, so either additional engine lubricants are required or
components like fuel pumps need to be constructed from specific ma-
terials. Methanol also has a higher auto-ignition temperature, so either
combustion enhancing additives are needed or advanced combustion
strategies like exhaust gas scavenging or fuel boiling can be used. Well-
designed methanol combustion turbines can actually achieve higher
electrical and CHP efficiencies than those use methane (Räuchle et al.,
9
Computers and Chemical Engineering 165 (2022) 107948
2016). Additionally, retrofitting existing combustion systems to be com-
patible with methanol generally only requires small investment (A.D.I.
Analytics, 2017). Long-term methanol turbine operation has also been
successfully demonstrated at the 50 MW scale (Chudnovsky et al.,
2015).
ICE technologies can also be made compatible with methanol (Ver-
helst et al., 2019). The engine components must be used to mitigate the
corrosive nature of methanol relative to other non-alcohol fuels (Yuen
et al., 2010). methanol’s lower LHV, higher heat of vaporization, and
higher autoignition temperature also makes engine startup more dif-
ficult. To overcome this, electrical heating can be used to increase
fuel temperature (Bergström et al., 2007) or high pressure injection
ports can be used improve fuel atomization. For stationary power
generation, methanol ICE gensets have been commercialized (Shmuli,
2021) but fuel cells are more widely considered due to their higher
efficiency. Pure methanol-fueled vehicles have been developed with
higher demonstrated efficiency than gasoline engines (Nguyen et al.,
2018). Additionally, methanol offers a lower flammability risk than
gasoline. Methanol has also gained considerable interest as a marine
fuel as it can enable fewer CO2 and sulfur emissions than the currently
used heavy fuel oils while also being easier and less costly to store and
handle than liquefied natural gas (Svanberg et al., 2018). The promise
of methanol as a marine fuel has led to a number of demonstration
projects in recent years (Hobson and Marquez, 2018).
3.3. Process design and operation
One focus of recent research relevant to PtM has been intensification
and optimal design of syngas-fed methanol synthesis. Arora et al.
(2018) proposed a sorption-enhanced methanol production process to
counter equilibrium limitations. A dynamic model was developed for
this process which is inherently transient due to the four-step periodic
operation of the reaction–sorption column. This model was used for
constrained grey-box multi-objective optimization for methanol syn-
thesis process retrofit, that is, augmenting catalyst with sorbent in
an existing reaction vessel. This enabled up to an 8% increase in
methanol yield and decrease in raw material consumption at similar
production costs. Monjur and Hasan (2021) proposed a methanol
production process based on a membrane reactor which served to
mitigate equilibrium while also allowing for steady-state production.
The process model used detailed reaction kinetics and surrogate models
for reaction and membrane thermodynamics. The lowest cost process
design was determined using an NLP formulation, with the optimally
designed reactor operating at lower temperature and pressure than
the conventional synthesis process. Overall, the use of a membrane
reactor was shown to reduce compression investment and electricity
consumption by approximately 65% each.
There has also been recent research into processes inherently better
suited to PtM, specifically direct CO2 hydrogenation and co-electrolysis.
Borisut and Nuchitprasittichai (2020) analyzed multiple flowsheet con-
figurations for CO2 hydrogenation via optimization of neural networks.
The training data for these networks was obtained via latin hypercube
sampling of flowsheet results from different reactor-recycle configura-
tions simulated over a range of operating conditions. Ultimately, the
lowest cost configuration used two CO2 hydrogenation reactors in series
to maximize methanol yield without the additional energy consumed
by recycle. Kenkel et al. (2021) used superstructure optimization for
CO2 hydrogenation flowsheets, considering multiple alternative CO2
sources and electrolysis technologies. Their model was formulated as
a MILP with piece-wise linearization for equipment costs. The lowest
cost solution captured CO2 from refinery fluegas and used low pressure
alkaline electrolysis. The maximum carbon removal design addition-
ally powered CO2 direct air capture using methanol waste heat. This
increased methanol production costs by 10%.
Much of the process design research for co-electrolysis has focused
on energy optimization. Léonard et al. (2016) and Chaniago et al.
M.J. Palys and P. Daoutidis
(2019) developed simulation models for methanol production based on
co-electrolysis. These models used detailed kinetic and thermodynamic
models for the co-electrolysis, methanol synthesis reactors, and distilla-
tion. Léonard et al. (2016) used pinch analysis to reduce process heat
consumption by 55% and improve energy efficiency by 12%. Chaniago
et al. (2019) included heat recuperators before the co-electrolysis unit
and methanol synthesis reactors in their process flowsheet to further
reduce energy consumption. They employed a vortex search optimiza-
tion algorithm for optimal process design and by doing so, improved
overall energy efficiency by 16%. Al-Kalbani et al. (2016) performed
an energy optimization-based comparative assessment of CO2 hydro-
genation and solid oxide co-electrolysis. They developed flowsheet
models for both processes and optimized operating conditions and heat
integration configurations to maximize energy efficiency. They found
the overall energy efficiency of the co-electrolysis process to be double
that of the hydrogenation process. However, the co-electrolysis process
did require more heat due to its high operating temperature, so the
methanol production setting which informs the heating method (steam
vs. electrical) could affect process selection. Zhang and Desideri (2020)
developed a heat integrated flowsheet model for methanol production
based on co-electrolysis and used it for multi-objective optimization to
minimize methanol production cost and maximize energy efficiency.
They used a MINLP formulation to determine optimal process operating
conditions and to select and size the hot and cold utilities. The pareto-
optimal multi-objective solution achieved minimum production cost
and maximum LHV energy efficiencies of $530/ton methanol and 72%
respectively, with co-electrolysis investment and operation being the
main cost driver.
Lonis et al. (2019) examined together methanol production and
energy utilization via reversible solid oxide cells (R-SOFC). They devel-
oped detailed steady-state process models for the R-SOFC in both elec-
trolysis and fuel cell modes, a CO2 hydrogenation-based methanol syn-
thesis reactor, a distillation column for methanol purification, and ther-
mal storage to integrate methanol production and utilization modes.
Thermal storage was modeled as an isothermal phase change material
which was melted by the heat generated by power generation in fuel
cell mode and then solidified when heat was withdrawn for electrolysis
and methanol synthesis. They assumed production-utilization mode
switching every 6 h; methanol and thermal storage units were sized
accordingly. Whole-system energy optimization via pinch analysis gave
roundtrip power-to-power efficiency of 33%.
Recent work has also focused on better understanding and quanti-
fying the dynamics of methanol synthesis based on CO2 hydrogenation.
Varela et al. (2020) developed a detailed dynamic model for CO2
hydrogenation to understand the effect of feed flow variations caused
by renewable intermittency. This analysis focused only on a reactor-
flash separation process, the end product of which is ‘‘crude’’ methanol.
They studied independently the effect of changes in H2 and CO2 con-
centrations and found an operating window with up to 20% and 5%
respective step changes in these concentrations allowed new steady
states to be reached within 90 s. Cui et al. (2022) performed detailed
dynamic simulations of renewable methanol production to understand
process performance characteristics with production rates reduced to
50% of installed capacity over ramp times of 15 min to 2 h. They
specifically developed detailed dynamic models of methanol synthe-
sis and distillation with PI controllers tuned via Ziegler–Nichols and
Tyreus–Luyben rules to adjust production based on feed rate changes.
Steady-state energy efficiencies at full and half capacity operation were
found to be within 2%, with slower ramping reducing the magnitude
of temporal efficiency fluctuations. The detailed simulation results were
used to develop nonlinear autoregressive exogenous surrogate models.
Huesman (2020) analyzed the effect of PtM dynamics on solar
methanol production costs through an optimal control lens. They mod-
eled electrolysis, methanol synthesis, and methanol distillation each
as a first order process, giving the overall methanol production pro-
cess third order dynamics. This process model was used in an E-MPC
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Computers and Chemical Engineering 165 (2022) 107948
formulation which minimized methanol production costs over a four
representative day operating period using 5 min control intervals.
This control approach was used to compare steady-state methanol
production enabled by batteries and dynamic methanol production.
Oversized and dynamically operated methanol production resulted in
lower methanol production costs by avoiding large battery installations.
For the dynamically flexible approach to be viable, a partial capacity
operation lower bound and maximum ramp rate of 25% and 25%/h
respectively were identified.
3.4. Capacity planning
Capacity planning and scheduling for PtM is less well-explored than
that for PtH. PtM systems are a newer topic of study and furthermore,
capacity planning for these systems can be more computationally dif-
ficult because of the additional processes involved and the complex
dynamics of methanol synthesis and distillation-based separation. As
such, much of the work-to-date in this area uses simplifying assump-
tions to reduce the decision space. Rivarolo et al. (2016) considered
steady-state methanol production enabled by hydrogen buffer storage
and grid power purchases, thus only scheduling the hydroelectric,
wind, and solar power generation as well as electrolysis. They for-
mulated sizing optimization as an NLP and linked this to a genetic
algorithm for hourly energy management via a penalty function. Chen
et al. (2021) performed similar analysis, parameterizing wind, solar,
and external power import fractions to study their effect on methanol
production costs. They considered steady-state methanol production
and developed a high throughput NLP capacity planning model with
heuristic power and hydrogen management algorithms based on renew-
able power availability. Case studies for Kramer Junction (CA), USA
and Norderney, Germany showed lowest cost methanol production with
solar and wind dominant power supply respectively. The results also in-
dicated that interday hydrogen storage capacities (with approximately
18 h duration) optimized the tradeoff between high hydrogen storage
costs and lessening the dependency on external power purchases.
Martín and Grossmann (2017) developed a multi-period MINLP
flowsheet optimization model for methanol production using variable
wind and solar energy and CO2 from algae growth. For computational
tractability, extensive operating decisions (e.g. material and energy
flows) were optimized with monthly resolution based on wind and solar
availability whereas intensive decisions (e.g. temperature, pressure)
were optimized once for a given design and assumed to be constant over
each month. In their work, hydrogen and methanol production rates
were coupled, so their installed capacities could be treated as a single
decision. They found that using PV arrays for power generation gave
the lowest methanol production costs. They (Martín, 2016) extended
this optimization approach to a two-stage MILP stochastic model to
determine optimal capacity planning and dispatch of combined wind-
and solar-powered methanol production using CO2 from local power
plants. The capacity decisions were the number of wind turbines, PV
arrays, and electrolysis units. Surrogate models developed using results
from (Martín and Grossmann, 2017) defined the size of methanol syn-
thesis units as a function of the number of electrolysis units installed as
well as optimal intensive operating variables. Dispatch decisions were
again made with monthly resolution and 27 scenarios were considered
each month cumulatively for uncertainty in wind generation, solar
generation, and the sale price of excess generated power.
Chen and Yang (2021) more explicitly analyzed the effects of
methanol production flexibility by optimizing system operation with
higher resolution. They developed a capacity planning and scheduling
model which enables (in general) decoupled operation of electrolysis,
methanol synthesis, and methanol distillation. Storage for H2 and
raw (pre-purified) methanol could be installed to accommodate the
varying dynamic ranges and ramping capabilities of each process unit.
Further, they included a hydrogen-fed fuel cell for backup power
M.J. Palys and P. Daoutidis
Fig. 3. Conceptual technology outline for electrified ammonia production and utilization in energy and transportation.
generation. They formulated this model as an LP to enable a full year,
hourly resolution horizon for scheduling decisions. This formulation
was enabled by considering fully flexible electrolysis and a 10% lower
operating bound for methanol synthesis while methanol distillation was
constrained to operate at steady-state. They found that combining over-
sized and dynamically operated electrolysis and methanol synthesis
processes reduced methanol production costs by up to 35%.
Bique et al. (2018) and d’Amore and Bezzo (2020) used time
invariant capacity planning models to analyze PtM from a supply chain
perspective, and formulated MILPs to determine the optimal location
and sizing of carbon capture to provide CO2 , electrolysis for hydro-
gen production from curtailed renewables, and CO2 hydrogenation
processes for methanol production. Bique et al. (2018) performed
a case study for northwest Germany where they considered 18 can-
didate production sites for methanol or its feedstocks. They found
that economically optimal supply chains co-located electrolysis and
methanol production at sites of highest curtailed renewable availability
while transporting CO2 from the power plants at which it is captured.
d’Amore and Bezzo (2020) considered the entirety of Europe in a
future scenario with 50% emissions reduction through a combination
of CO2 utilization and sequestration. In their work, the optimal sup-
ply chain configuration transported CO2 captured at many nodes to
few hydrogen-methanol production sites selected based on their low
electricity costs. The ability to produce methanol for use in the energy
sector decreased overall supply chain costs by 4% relative to CO2
sequestration alone.
Tso et al. (2019) compared methanol to hydrogen as an energy
carrier. They formulated a time-invariant MILP supply chain model
which minimized the levelized cost of energy (LCOE) for fixed storage
durations by determining the optimal location and capacity of wind
and solar generation, hydrogen or methanol production, hydrogen- or
methanol-to-power technologies and, in the case of methanol produc-
tion, pipelines to provide CO2 from industrial sources. For a one month
storage duration, the LCOE using hydrogen was 35% less than that
using methanol because hydrogen’s higher roundtrip efficiency resulted
in less required investment in renewable generation and because CO2
transportation costs were avoided. When energy must be stored for
three months, the economic advantage of hydrogen was reduced to 14%
because higher energy capacity costs are incurred. However, hydrogen
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Computers and Chemical Engineering 165 (2022) 107948
was still less expensive to use than methanol because it does not require
CO2 transportation.
4. Power to ammonia
PtA is another extension of PtH which involves combining hydrogen
with nitrogen separated from air. As with methanol, ammonia can
easily be stored as liquid and then used to generate power and/or
heat via fuel cells or combustion technologies. Fig. 3 outlines the PtA-
relevant technologies described in this section and the interconnections
between them. Detailed descriptions of these ammonia production and
utilization technologies are provided in Sections 4.1 and 4.2.
4.1. Ammonia production technology
Synthetic ammonia production currently relies on the Haber–Bosch
(HB) process, which has been in operation since the 1920s (Smith et al.,
2020). The process combines hydrogen and nitrogen in a 3:1 molar
ratio to produce ammonia in an exothermic reaction:
3H2 + N2 ⇌ NH3 𝛥𝐻 = −91.8 kJ∕mol (6)
This synthesis reaction occurs at high pressures and temperatures
of 150–250 bar and 350–450 ◦ C respectively. Reaction equilibrium
limits single pass conversion of ammonia to 15%–20%, so unreacted
hydrogen and nitrogen are recycled after being separated from the
ammonia product via condensation which occurs at synthesis pressure
and temperatures below 0 ◦ C. State-of-the-art implementations of the
HB process tend to use multiple catalyst beds in series with inter-
cooling to improve reaction conversion and reduce the amount of gas
being recycled, ultimately to mitigate synthesis loop pressure drop and
reduce refrigeration requirements for condensation. This is achieved
either through indirect cooling with a heat exchange network inter-
twined with the beds or direct quench cooling where low temperature
feed gases are partitioned between each bed’s inlet, which addition-
ally serves to increase synthesis rates by reducing ammonia concen-
tration (Khademi and Sabbaghi, 2017). As with methanol produc-
tion, economies of scale affect the capital investment required for the
HB synthesis process (Bartels, 2008; Morgan, 2013; Bañares-Alcántara
et al., 2015):
𝑥
𝐶𝐴𝑃 𝐸𝑋(𝑀𝑀$) = 3.4( 𝑁𝐻3 )0.6 (7)
1000
M.J. Palys and P. Daoutidis
where 𝑥𝑁𝐻3 is the ton/y nameplate capacity of the HB synthesis
process. Electric implementations of the HB process – those which
are not energy integrated with upstream SMR-based H2 production
– consume approximately 0.5–0.75 MWh/ton NH3 (Morgan, 2013;
Bañares-Alcántara et al., 2015).
The first synthesis catalysts were composed primarily of iron (Fe)
(Liu, 2014), with promoted iron (specifically magnetite or wustite) now
the industrial standard. Over the last 25 years, promoted ruthenium
catalysts with appreciably high kinetic rates at lower temperatures
and pressures have been developed (Rosowski et al., 1997). Lower
temperature shifts the synthesis reaction equilibrium toward the am-
monia product, potentially allowing higher single pass conversion to
ammonia. Lower pressure can reduce capital costs and energy required
for feed compression. However, lower pressure synthesis has limited
utility when paired with condenser-based separation, which relies on
high pressures in addition to cryogenic temperatures for ammonia
liquefaction. A desire for lower pressure ammonia production has
led to the development of alternative separations. One approach is
direct replacement of the condenser with a bed of adsorbent such
as a zeolite (Beach et al., 2018; Lucero et al., 2021) or supported
metal halides for chemisorption (Malmali et al., 2016; Wagner et al.,
2017). This direct replacement enables comparable ammonia produc-
tion rates to condenser-based HB with an order of magnitude reduction
in synthesis pressure down to 10–30 bar and separation at ambient
temperatures or even higher. Well-designed ammonia production at
these milder operating conditions can reduce capital costs relative to
HB synthesis because high pressure and low temperature separation
are the major cost drivers of that process. Some very recent work has
analyzed intensified ammonia synthesis-separation processes such as a
catalytic membrane reactor (Zhang et al., 2021) or a sorption-enhanced
reactor (Smith and Torrente-Murciano, 2021). Intensified synthesis and
separation may lead to further lowering of capital intensity by reducing
the number of required process units, but inherent loss in design
degrees of freedom necessitates additional investigation, for example,
to ensure adequate conversion to ammonia or energy efficiencies.
Electrochemical ammonia synthesis (electrosynthesis) which re-
places the HB process and instead produces ammonia directly from
water and nitrogen at ambient pressure is a more ambitious alternative
that has also been an active topic of recent research. These processes
produce ammonia at the cathode of an electrosynthesis cell, with
the specific nitrogen reduction reaction and accompanying oxidation
reaction at the cathode depending on the electrolyte (Shipman and
Symes, 2017). Aqueous electrolytes have been used, but both ammonia
synthesis rates and selectivity are too low to be practical at this
stage, largely due to a competing hydrogen evolution reaction (HER)
accelerated by the water contained in the electrolyte (Suryanto et al.,
2019). Hydrophobic ionic liquid electrolytes have also been studied
with a view on improving ammonia selectivity by minimizing HER.
Their associated energy efficiencies are as high as 60% but they are
limited by low synthesis rates (Zhou et al., 2017; Suryanto et al.,
2018). On the other hand, high temperature (200–500 ◦ C) molten salt
electrolytes improve synthesis rates by two orders of magnitude but
suffer from energy efficiencies below 35% (Licht et al., 2014; Yang
et al., 2020). Solid-state proton conducting membrane electrolytes are
promising, being able to achieve the highest recorded electrosynthesis
rates while operating below 100 ◦ C (Garagounis et al., 2014). However,
these membranes can degrade over time when in contact with ammonia
due to their acidic nature (Hongsirikarn et al., 2010), so strategies
are needed to mitigate this. Anode and cathode material selection is
far from consensus at the current stage of development, but systems
studied in the literature have used a host of different metals (Ni, Fe,
Pt, Pd, Ru, Re, Rh). Ultimate material selection will partially depend
on electrolyte compatibility while also requiring resolution of a trade-
off between cost and productivity, especially if precious metals are to
be used. The potential benefits of this approach are plentiful (MacFar-
lane et al., 2020). Ambient pressure and low temperatures (for some
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Computers and Chemical Engineering 165 (2022) 107948
electrolytes) can reduce capital costs. Additionally, the modular nature
of electrosynthesis cells enables production scale flexibility without
higher capital intensity. Further, these systems are more resilient to
O2 or water impurities than catalytic ammonia synthesis. Overall,
electrosynthesis is likely a decade from commercialization (MacFarlane
et al., 2020).
4.1.1. Nitrogen production technology
Nitrogen for PtA can be obtained from technologies which are
extensively used in the air separation business. Three different types
of processes are generally used: cryogenic distillation (CRD), pressure
swing adsorption (PSA), and membranes. Each is reviewed briefly here.
Cryogenic distillation produces nitrogen as distillate and O2 as bottoms,
relying on the difference in their respective boiling points of −196 ◦ C
and −183 ◦ C. The process operates at a temperature slightly below the
boiling point of O2 and uses at least two columns in series operating at
descending pressures from 6 bar to 1.5 bar to obtain ultra high nitrogen
purity above 99.9% (Bocker et al., 2013). Cryogenic distillation is
tightly heat integrated to achieve energy consumption around 0.11
MWh/ton N2 , less than PSA or membranes, despite its operation at
very low temperatures (Bocker et al., 2013). Unfortunately, this heat
integration also limits process dynamic flexibility. It requires hours
for startup and has a fairly narrow dynamic range, with operating
lower bounds above 60% of installed capacity (Miller et al., 2008).
Nonetheless, this process is the industrial standard for large scale air
separation at scales above 150,000 ton N2 /year. In fact, the Linde
Ammonia Concept already uses cryogenic distillation to obtain nitrogen
feedstock (Pattabathula and Richardson, 2016).
PSA is a cyclic separation process which uses at least two beds of
O2 -selective carbon molecular sieve absorbent (Step and Petrovichev,
2002). PSA operates isothermally at ambient temperature with pressure
cycling between 6–8 bar for adsorption and 1 bar for desorption. PSA
units are compact and inherently modular, so from a cost perspective
they are well-suited for small production scales below 7500 ton N2 /day.
They also have good dynamic flexibility, with startup times less than
an hour and a lower operating bound around 30% (Ivanova and Lewis,
2012). The main drawbacks of PSA relative to cryogenic distillation are
more expensive scale-up for larger production targets, lower nitrogen
purity around 99.8%, and higher energy consumption of 0.22–0.31
MWh/ton N2 (Bocker et al., 2013).
Membrane-based air separation uses O2 -permeable polysulfone hol-
low fiber (Lababidi, 2000) or carbon molecular sieve (Campo et al.,
2010) membranes. This separation process occurs at ambient temper-
ature and is driven by a pressure difference between the feed and the
permeate, which respectively operate at 6 to 25 bar and atmospheric
pressure. Membranes for nitrogen production are a less developed
technology than cryogenic distillation or pressure swing adsorption.
This process offers better dynamic flexibility than cryogenic distillation
and simpler operation than PSA because it is continuous in nature.
However, increased pressure is required to achieve nitrogen purity
above 99.5%, which can result in energy consumption as high as 0.65
MWh/ton N2 (Bocker et al., 2013). Post-membrane separation is also
required due to the presence of argon. Additionally, the investment cost
of this process depends almost linearly on the quantity of membrane
required and thus the production scale; this lack of economies of scale
means that membranes may only be well-suited to nitrogen production
below 750 ton N2 /day (Smith and Klosek, 2001).
4.2. Ammonia utilization technology
Ammonia can be decomposed to hydrogen and nitrogen in the
reverse of the synthesis reaction. This can produce hydrogen to feed the
fuel cell technologies discussed in Section 2.3. Ammonia concentrations
on the order of 1 ppm can cause irreversible damage to alkaline or
PEM fuel cells, resulting in efficiency loss and shorter lifetimes (Halseid
et al., 2006), so decomposition and/or purification must be complete.
M.J. Palys and P. Daoutidis
The endothermic ammonia decomposition reaction occurs at or near
atmospheric pressure and requires high temperatures of 500–700 ◦ C.
Reactors for ammonia decomposition are still actively being designed;
concepts include fixed bed reactors with membranes for hydrogen
removal (Abashar, 2018), or catalytic microchannel reactors (Chiuta
and Bessarabov, 2018). Heat integrating ammonia decomposition with
waste heat from hydrogen-fed power generation (Kim and Kwon, 2011)
or other co-located processes is crucial for energy efficiency. The most
well-studied decomposition catalysts are composed of supported Ni and
Pt (Chellappa et al., 2002), while Ru has been identified as the most
active (Lamb et al., 2019). Efforts to reduce cost of decomposition
catalysts have led a move away from use of transition metals to
sodium (David et al., 2014) or lithium (Hunter et al., 2016).
Ammonia can also be internally reformed in SOFC (Farhad and
Hamdullahpur, 2010) to allow for its direct use, as previously discussed
for methanol. Ammonia-fed SOFC can achieve comparable efficiencies
to use with other fuels, and this has been demonstrated with over
1000 h of operation (Okanishi et al., 2017; Siddiqui and Dincer, 2018).
Direct ammonia fuel cells (DAFC) have increasingly gained attention as
their lower operating temperatures of 80–120 ◦ C potentially make them
better suited to dynamic operation (Zhao et al., 2019). These are largely
still at the experimental stage, but the most promising recently studied
cells use a Pt-based anode and a precious metal-free cathode where
ammonia and air are respectively fed and a OH− exchange membrane
electrolyte (Gottesfeld, 2018). This DAFC system achieved ammonia-to-
power efficiencies as high as 40% with expected capital cost reduction
due to the absence of precious metals in the cathode.
Power and heat can also be generated from ammonia combus-
tion, though fundamental differences relative to carbon-based fuels
necessitate system design and operational changes. Ammonia suffers
from lower flame speed and a higher auto-ignition temperature than
other fuels. This can be alleviated through addition of a combus-
tion promoter (Frigo and Gentili, 2013). Ammonia blended with 5%–
10% hydrogen has been shown to maximize efficiency without added
emissions (Mørch et al., 2011). Pure ammonia mixtures can also be
preheated via exothermic combustion to reduce or eliminate the need
for blending during continuous, non-startup operation (Chen et al.,
2022). Another challenge is that ammonia combustion dramatically
increases NOx emissions. These can be removed via post-combustion
selective catalytic reduction (SCR) of NOx with ammonia, which react
to form nitrogen and water. The SCR unit adds cost to the combustion
system. Further, the additional use of ammonia, while not requiring
storage of other chemicals, decreases the macroscopic ammonia-to-
power efficiency (Boretti, 2012). Combustion-based power generation
using ammonia has been studied and demonstrated using both gas
turbines (Tsujimura and Iki, 2016; Kobayashi et al., 2019) and ICE
systems (Reiter and Kong, 2011; Patil et al., 2014; Kane and Northrop,
2021).
4.3. Process design and operation
There has been research focused on process design and/or synthesis,
which is generally characterized by complex nonlinear models for
steady-state or minimally time-varying (for example, monthly) ammo-
nia production. Some of this work considered conventional condenser-
based ammonia synthesis and focused on optimization of its design and
operating conditions as well as design and/or selection of precursor
hydrogen and nitrogen production. Demirhan et al. (2019) developed a
MINLP model for superstructure optimization of ammonia production,
considering as feedstock a combination of renewable electricity (with
constant availability), biomass, and natural gas and multiple competing
technologies for hydrogen production (e.g. PEMEC and AEC). They
optimized the ammonia cost over a range of production scales, loca-
tions, and GHG emissions restrictions. They found present day PtA to
be approximately two times more expensive than ammonia produced
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Computers and Chemical Engineering 165 (2022) 107948
from biomass. Sánchez and Martín (2018a) developed an NLP model
for optimal design of a wind- and solar-power PtA facility using alkaline
electrolysis, cryogenic distillation for nitrogen production, and both
direct and indirect cooling synthesis reactor configurations. They found
lowest renewable ammonia production costs of roughly $1000/ton NH3
which used PV arrays and direct reactor cooling, with main cost drivers
being PV arrays and electrolysis. They also extended this analysis to
account for modular availability of electrolysis and nitrogen production
at small scale (Sánchez and Martín, 2018b), modeling and selecting
between CRD, PSA and membrane separation for nitrogen production,
and ultimately determining the production scale ranges over which
each technology was optimal. Wang et al. (2020) analyzed a PtA
system which used a battery and hydrogen buffer storage to modulate
short-term variability in renewable generation, notably developing a
combined optimal design and control methodology which included a
proportional load tracking strategy for electrolysis and P or PI temper-
ature control on cryogenic distillation which produces nitrogen and the
ammonia synthesis reactor. Optimal design was performed considering
four representative days of wind generation parameterized into 100
control intervals.
In our previous work (Palys et al., 2018), we developed a dynamic
model of the inherently transient absorbent-enhanced ammonia synthe-
sis process discussed in Section 4.1 to enable MINLP optimal design
to minimize synthesis costs. We found that this alternative process
required less investment than traditional process at production scales
up to 75,000 ton NH3 /year and was increasingly advantageous at small
production scales, but used 3x more energy due to endothermic desorp-
tion of ammonia. These results were motivation for continued discovery
of absorbent cycling conditions which were less energy intensive. Lin
et al. (2020) performed similar comparative analysis for the condenser
and absorbent processes at a production scale of 20,000 ton NH3 /year.
They pursued heat integration of the exothermic ammonia synthesis
reaction and absorption, and endothermic desorption which ultimately
brought synthesis loop energy consumption to comparable levels as the
condenser process.
There have also been similar efforts to analyze and optimize pro-
cesses which use ammonia for energy production. Chachuat et al.
(2005) developed a detailed steady-state model for a system with
an ammonia decomposition reactor followed by hydrogen-fed SOFC
and used a MINLP formulation to optimize its design, achieving a
maximum energy densities above 1 MWh/ton NH3 while meeting a
nominal power demand. Wang et al. (2017) considered a 100 MW
PtA system which employed a reversible SOFC which can operate in
both electrolysis and fuel cell modes along with dedicated ammonia
synthesis and decomposition reaction systems. Energy integration of
the constituent processes in this system was pursued; exothermic heat
from ammonia synthesis was used to heat steam for the SOFC in
ammonia production or ‘‘charging’’ mode while the heat required for
endothermic ammonia decomposition was obtained from the SOFC
effluent in power generation or ‘‘discharging’’ mode. Optimal design of
this system at the 100 MW scale enabled overall efficiencies as high as
72% and levelized cost of energy as low as $0.24/kWh. Sánchez et al.
(2021a) solved several NLPs to optimally design ammonia-to-power
process alternatives. Potential constituent processes included a cat-
alytic membrane reactor for ammonia decomposition, nitrogen/argon
recovery to monetize these combustion inerts, gas turbines, selective
catalytic reduction to remove NOx produced by ammonia combustion,
and either secondary hydrogen combustion or recovery and recycle
using a membrane. They determined ammonia-to-power efficiencies in
the range of 30 to 45% and levelized power costs as low as $0.23/kWh
at the 100 MW scale.
Another key topic of recent research on PtA is determining how to
operate its constituent subsystems in the face of renewable intermit-
tency and variable energy demands. To date, this topic has received
less focus. Allman and Daoutidis (2018) formulated a MILP optimal
M.J. Palys and P. Daoutidis
scheduling model for dynamic ammonia production to minimize op-
erating costs based on a 24-hour receding horizon. They considered
power sourced from both wind generation and a utility with time-of-use
pricing. Dynamic flexibility was enabled through oversized hydrogen
and nitrogen production with buffer storage as well as the oversized
ammonia synthesis to enable some turn-down, though conservative
partial operation and ramp constraints were enforced. The iterative
use of this scheduling formulation over representative weather years
allowed for a survey of different U.S. Midwest locations, ammonia
production scales, and degrees of nitrogen and hydrogen oversizing to
determine which factors had the largest impact on production costs. Xu
et al. (2020) developed a 24-hour optimal scheduling model for PtA-
based energy storage in a CHP microgrid setting. Dynamic flexibility
was enabled through a battery, hydrogen buffer storage, and ammonia
storage, and the process models included degradation effects to assess
the trade-off between dynamic production and component lifetime.
This model was formulated as a MINLP, but practically decomposed
into NLP and MIQP subproblems for computational tractability. Ac-
counting for degradation during scheduling resulted in less frequent
charge/discharge and on/off cycling for the battery and electrolysis
respectively by using more ammonia for CHP.
4.4. Capacity planning
PtA capacity planning is inevitably more computationally intensive
than for PtH because of the additional process units for nitrogen and
ammonia production as well as the possibility of decoupling hydrogen
and ammonia production by using hydrogen buffer storage. As such
these models rely on less detailed descriptive models for operational
characteristics (e.g. energy consumption, dynamic lower bounds, and
ramping capabilities) of process units than in Section 4.3 so that
generally these problems can incorporate unit scheduling to account
for variable renewable power availability or time-varying electricity
prices, as discussed in more detail in Section 2.5. Beerbühl et al.
(2015) reduced the design decision space in the context of PtA from
grid power by assuming that electrolysis was fully dynamically flexi-
ble while ammonia synthesis must run throughout the year. Further,
ammonia synthesis capacity was fixed in their work as was nitrogen
production capacity because no nitrogen buffer is assumed, so sizing
decisions were only made for electrolysis and hydrogen buffer storage.
This simplification allowed them to formulate a tractable convex NLP
which accounted for partial load operation effects on the efficiency
of electrolysis and ammonia synthesis. Nayak-Luke et al. (2018) and
Armijo and Philibert (2020) did consider sizing of ammonia synthe-
sis, along with electrolysis and hydrogen buffer storage as well as
other units specific to their individual work. Both of their capacity
planning formulations used scheduling heuristics for computational
tractability. Nayak-Luke et al. (2018) additionally optimized sizing
of fuel cells for backup power and considered power purchases from
existing renewable generation. They developed electrical power and
hydrogen management algorithms which consisted of a set of decision
rules depending on renewable availability from existing wind and solar
generation. They performed case studies for Lewrick, Scotland using
five years of historical hourly resolution data to determine the effect of
wind/solar generation fractions, renewable electricity costs, and ammo-
nia synthesis partial operation lower bound and ramping capabilities on
optimized ammonia production costs. They found that partial operation
lower bounds and ramp rates of 20% and 6%/hour respectively are
needed for cost competitive renewable ammonia. Armijo and Philibert
(2020) additionally determined optimal sizing of PV arrays and wind
turbines while also scheduling the purchase of ‘‘firming’’ power from
the local utility. They used a simulation-based optimization approach
where they calculated ammonia production costs over a range of solar-,
wind-, and synthesis-to-electrolysis ratios. The size of hydrogen buffer
storage was computed during simulation from this relative oversizing
and the ‘‘optimal’’ configuration was identified as the one which gave
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Computers and Chemical Engineering 165 (2022) 107948
lowest production costs. They found that renewable ammonia produced
at the 35,000 ton NH3 /year scale can be cost competitive in four
high renewable potential South America locations if ammonia synthesis
can operate at 20% partial loads. Allman et al. (2019) overcame
computational tractability limitations by embedding their previously
developed scheduling framework from Allman and Daoutidis (2018) in
a PtA capacity planning model. Specifically, they first determined opti-
mal schedules for many fixed feasible designs and developed surrogate
models to describe annual operating costs based on these scheduling
results. These surrogates were used to inform a much smaller time-
invariant NLP design model, enabling computational tractability while
incorporating this more complex scheduling formulation.
Nayak-Luke et al. (2018) extended their previous capacity planning
analysis with rule-based scheduling to determine optimal renewable
ammonia production costs for 534 locations using hourly resolution
wind and solar availability data in each and optimizes the power
generation fractions in addition to system design. They found lowest
global renewable ammonia production costs of $473/ton NH3 today
and $310/ton NH3 in 2030. Fasihi et al. (2021) performed a similar
global renewable ammonia production study, creating an optimal cost
atlas over a 0.45◦ by 0.45◦ spatial grid. They formulated a capacity
planning model which sized every technology in the PtA system and
considered dynamic flexibility in the form of batteries, hydrogen buffer
storage, hydrogen-fed gas turbines and dynamic ammonia production.
Their scheduling model was formulated as a LP, with fully flexible
operation assumed for all processes except ammonia synthesis which
was constrained to run at or above 50% partial capacity and with
hourly ramp up and down limits of 2% and 20% respectively. Their LP
scheduling formulation allowed the use of representative year data with
hourly time steps. They also solved their model using technology cost
projections from today to 2050, finding lowest global ammonia produc-
tion costs of $440/ton NH3 today and $260/ton NH3 in 2050, with the
cost reduction stemming from less expensive renewable generation and
electrolysis.
More recently, MILP formulations have been used for PtA capacity
planning. Osman et al. (2020) considered continuous ammonia produc-
tion and optimized the selection, sizing, and scheduling of the upstream
electrical and thermal energy, hydrogen, and nitrogen production and
storage infrastructure to enable this constant operation when powered
with solar, both through PV arrays and concentrated solar power.
They used a full year of hourly resolution data as input to the ca-
pacity planning model. They found present-day LCOA of $718/ton
NH3 , with future LCOA of $450/ton NH3 through projected technology
cost reductions. Wang et al. (2021a) performed a first of its kind
capacity planning study for ammonia production using offshore wind.
Their model allowed for a high degree of design flexibility, considering
decoupled hydrogen and nitrogen production with buffer storage as
well as batteries, hydrogen fuel cells, and ammonia ICE generators for
local energy storage. They formulated this model as a MILP and aggre-
gated wind speed input data into one hourly resolution representative
week for each month (2016 total scheduling periods) for computational
tractability. They compared onshore ammonia production connected
to offshore wind by underwater power cables with offshore ammonia
production, and found offshore production to be less expensive. They
also found that optimal designs used both hydrogen and nitrogen buffer
storage as well as hydrogen fuel cells to balance wind generation with
synthesis energy demands.
Less work has focused on explicit capacity planning for systems
which both produce and use ammonia for energy. As with methanol,
Tso et al. (2019) comparatively analyzed ammonia energy storage to
hydrogen using a time-invariant supply chain optimization model. They
found that hydrogen storage gave 40% lower LCOE for 1 month dura-
tions due its higher roundtrip efficiency while ammonia and hydrogen
are roughly equivalent for 3 month durations due to hydrogen’s higher
storage cost. In our previous work (Palys and Daoutidis, 2020), we
M.J. Palys and P. Daoutidis
compared the economics of using ammonia for standalone renewable
energy storage to those of using hydrogen. We developed a MILP ca-
pacity planning model to minimize the levelized cost of energy supply
by determining the size and schedule of each unit in the full power-
to-x-to-power system including renewable generation, and considered
both hydrogen and nitrogen buffer storage in ammonia production. For
computational tractability, we aggregated hourly resolution input data
into 672 variable length optimal scheduling periods. We performed
case studies for 15 U.S. cities which comprehensively represent climate-
demand regions throughout the country and found that using hydrogen
gave slightly lower LCOE in locations with high solar potential and/or
less seasonal generation-demand mismatch, while ammonia provided
up to 30% LCOE reduction in locations with high wind potential and
larger seasonal storage requirements.
5. Integrated power-to-x systems
The potential of power-to-x can be improved by exploring the pos-
sibility of systems which consider parallel power-to-x processes and/or
demands arising from different sectors. The synergies offered by such
integration can be exploited to improve the economics and thus likeli-
hood of adoption. Optimization is a powerful tool to aid in maximizing
this economic benefit, especially with the increased decision space that
comes with more constituent processes and demands. Further, certain
synergies may not be readily apparent or may even counteract physical
intuition. For this reason, rigorous MI(N)LP formulations are preferable
to intuition-based approaches that use decision rules which are speci-
fied a priori or other heuristics. In this section, we review recent work
on integrated power-to-x systems falling under two categories: Hybrid
energy systems and sector coupling.
5.1. Hybrid energy systems
Recent work on renewable energy storage facilities has considered
co-optimization of power-to-x pathways. In our previous work on com-
paring the optimal economics of hydrogen and ammonia for electrical
energy storage (Palys and Daoutidis, 2020), we also optimized their
synergistic use in the 15 studied U.S. locations. We found that systems
which use both outperform those which use only one storage option,
taking advantage of the more efficient hydrogen storage for short-term
balancing and ammonia’s lower cost for seasonal storage. Sánchez et al.
(2022) performed a similar analysis for 14 different regions of Spain
with batteries, hydrogen, and ammonia available as energy storage
media. They developed a MILP capacity planning and scheduling using
one hourly resolution representative week per season. The optimized
fully renewable ESS in each region used all three storage technologies
to achieve the best overall tradeoff between efficiency and storage
cost in balancing intermittent wind and solar resources with demand.
Demirhan et al. (2020) proposed to optimize connected energy facilities
in high renewable resource and high demand regions, considering
liquefied hydrogen, methanol, and ammonia to enable a low cost
interconnection. They formulated a combined capacity planning and
scheduling MILP and aggregated input data into 12 season-representing
hourly resolution days which are repeated a variable number of times.
They performed a case study analyzing the coupling of Texas and
New York City (NYC), looking to replace 10% of NYC’s annual power
demand. They found that using chemicals for energy transportation
reduces overall costs by up to 50% compared to segregated systems and
that using both hydrogen and methanol or hydrogen and ammonia as
energy carriers gives 10% cost reduction than using hydrogen alone.
We more recently extended our hydrogen–ammonia electrical energy
systems analysis to renewable CHP systems in remote locations (Palys
et al., 2021). These locations are characterized by high conventional
energy costs. We considered fully renewable energy systems which
could produce hydrogen and ammonia and use them for power gen-
eration with heat cogeneration or dedicated heat production in boilers.
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Computers and Chemical Engineering 165 (2022) 107948
Optimal use of hydrogen and ammonia for renewable CHP resulted in
energy supply costs only 3% more expensive than those at historically
low conventional prices in both Mahaka, Hawaii and Northwest Arctic
Borough, Alaska. From a methodological point-of-view, Allen et al.
(2021) proposed a solution acceleration strategy for these types of ca-
pacity planning and scheduling problems based on linear programming
relaxation. This approach was shown to reduce computational time
by two orders of magnitude, potentially making complex formulations
tractable in the future, for example, those with less time aggregation
or more competing technologies.
From a supply chain perspective, the previously described work of
Tso et al. (2019) considered simultaneous use of hydrogen, methanol,
and ammonia as energy carriers in Texas. In the optimal supply chain
for three month storage duration, all three carriers are used, with
spatial synergies resulting in 26% LCOE reduction compared to using
ammonia alone, the best case for a single carrier. Some hydrogen was
produced since it provides the highest roundtrip efficiency, but only
in areas of the highest PV generation potential because solar’s strong
diurnal (rather than seasonal) characteristic mitigates hydrogen storage
volumes. Methanol was produced near CO2 sources because PtM is
more efficient than PtA while ammonia was produced in other locations
to reduce total CO2 transportation costs. Sánchez et al. (2021b) also
analyzed renewable energy storage supply chains which used methanol
and ammonia. They optimized these supply chains through a decompo-
sition technique which first optimized the supply chain configuration
and technology selection using monthly variation for wind and solar
generation and then optimized the capacity and scheduling of the
chosen processes using an hourly resolution representative week per
season. They performed case studies for the Leon province of Spain.
Their results corroborate those of Tso et al. (2019), with methanol
produced only near CO2 sources and renewable ammonia produced
elsewhere since it only requires air and water as raw materials. Han
and Kim (2019) studied a transportation energy system which supplies
carbon-containing fuels for ICE vehicles, power for electrical vehicles,
and hydrogen for fuel cell vehicles in 15 regions in South Korea. They
developed a MILP model for capacity planning and monthly schedul-
ing with multiple investment intervals to reflect changes in vehicle
mix. This optimization revealed a spatial synergy in that renewable
hydrogen produced in every region was used for fuel supply, while also
being transported to centralized CO2 -to-fuel facility in regions with the
cheapest land.
5.2. Sector coupling
Sector coupling is well-suited to power-to-x due the utilization
versatility of its products. Hydrogen and methanol both have strong
demands in the chemical production sector, while ammonia is tradi-
tionally used as fertilizer. Combining these sectors with energy supply
can reduce costs and make more complete use of renewable energy
because, in general, chemical commodities inherently have monthly
or seasonal demand resolution, in contrast to energy demands which
are pseudo-instantaneous. This means that chemicals can largely be
produced when renewable generation exceeds energy demands. Recent
work has explored this possibility. Bødal et al. (2020) analyzed cou-
pling the electrical power and fuel cell vehicle sectors using renewable
hydrogen. They used an LP model for capacity planning and schedul-
ing across multiple generation and demand nodes with transmission
between them. They performed a case study for Texas and found that
the dynamic flexibility of PEM electrolysis reduced energy prices by
acting as demand response in its hydrogen fuel production schedule.
Further, some power generated via hydrogen fuel cells acted as a
means of longer duration energy storage than batteries. Hydrogen also
allowed spatial balancing of power and fuel demands via transportation
pipelines, with electrolysis mostly occurring at nodes with high renew-
able potential. Allen et al. (2022) considered a similar Texas-based
M.J. Palys and P. Daoutidis
system, with the major difference that they considered sector-agnostic
cryogenic hydrogen demand. They formulated a planning and schedul-
ing MILP in which investment decisions were made every five years and
proposed a graph-based approach to solve optimal scheduling. Their
results showed that liquified hydrogen was produced almost exclusively
with renewable energy that would otherwise be curtailed. Andika et al.
(2019) analyzed a wind and solar energy supply system which could
also produce and export methanol to improve its economic viability.
Their considered system included batteries for demand balancing and
methanol synthesis based on CO2 hydrogenation. They used an NLP
capacity planning and scheduling model with two years of hourly reso-
lution renewable generation and demand data. They found that PtM is
able to monetize otherwise curtailed renewable energy, decreasing total
system costs without affecting ability to meet power demands. Salmon
and Bañares-Alcántara (2021) considered ammonia production with
coupled use of variable renewable electricity and variable-priced grid
electricity as well as the possibility of selling excess generated renew-
able power to the grid. They used a MILP capacity planning model with
one year of representative hourly resolution wind availability, solar
availability, and electricity price data to perform case studies for six
Australian states. They found that renewable ammonia production with
consumer–supplier grid interaction gave 5% average LCOA reduction
across Australia, while also reducing grid power supply emissions in
four of the six states.
Some recent work has examined coupling the energy supply and
agriculture sectors. We conceived of a farm-scale system which used
only renewable energy to meet power demands and make hydrogen
and ammonia for use as fertilizer, tractor fuel, and energy storage (Palys
et al., 2019). We optimized the design of this system using a MILP for-
mulation with optimal scheduling for hourly resolution representative
week per month. As in other previously described results, hydrogen
and ammonia were used synergistically for energy storage. Further,
combining energy and agriculture demands led to an increase in hy-
drogen and ammonia production capacity factors, ultimately giving
better utilization of capital investment and lower overall costs than
considering energy and agriculture systems separately. Wang et al.
(2021b) extended this system to include explicit nitrogen and water
management with a view on decreasing nitrogen pollution in surround
bodies of water. They also considered urea production from renewable
ammonia and captured CO2 , which has less propensity for leaching
than ammonia. They developed surrogate models to describe inherently
nonlinear soil water and nitrogen dynamics, and embedded these in
a capacity planning and scheduling model in which input renewable
generation, demand, and precipitation data was aggregate into five
hourly resolution representative weeks repeated a variable number of
times. They found that nitrogen pollution can be decreased by 57%
with only an 8% increase in net present cost. Ikäheimo et al. (2018)
considered a much larger spatial scale, determining the optimal design
of energy and fertilizer supply networks in Northern Europe which
only used renewable energy. They performed capacity planning and
scheduling with hourly resolution for yearlong horizon with tractability
enabled by an LP formulation. In their results, renewable ammonia was
used as a fertilizer as well as to store and transport energy. Further, they
found shared use of ammonia pipelines for both fertilizer and energy
carrier purposes depending on the time of year, as fertilizer demands
are seasonal.
6. Conclusions
This article provides a review of power-to-hydrogen (PtH), power-
to-methanol (PtM), and power-to-ammonia (PtA) through the lens of
decarbonizing the energy supply and transportation sectors. Collec-
tively, power-to-x provides a path to reducing the cost of balancing
intermittent renewable energy generation with demands, especially
storing such energy over long durations. Power-to-x also provides an
16
Computers and Chemical Engineering 165 (2022) 107948
alternative to battery electric vehicles in electrifying the transportation
sector, especially for long haul or heavy transportation. PtH offers the
highest roundtrip efficiency and it the most well-developed pathway of
the three discussed in this review. Hydrogen production via electrolysis
requires only water as feedstock and its costs are expected to fall
as demand for electrolysis units increases in the coming decade. On
the utilization side, flexible PEM fuel cells are still expensive and
combustion technologies that can use 100% hydrogen are not yet
available at commercial scale. As with electrolysis, high demand for
these technologies should reduce costs and enable the overcoming
of operational challenges with additional research and development.
However, the high cost of hydrogen storage resulting from its low
energy density at ambient conditions is a barrier with a less clear
solution.
The promise of PtM and PtA lies in decreasing these storage costs via
liquid storage at moderate conditions. Methanol can be stored as liquid
at ambient pressure and temperature. Furthermore, its production in
a PtM setting sequesters CO2 . To this end, direct CO2 hydrogenation
and co-electrolysis processes are still being developed to improve en-
ergy efficiency and reduce capital costs. From a utilization standpoint,
methanol decomposition to hydrogen, combustion, or use in fuel cells
is well established, but the feasibility of mitigating CO2 emissions
in distributed use cases (e.g. passenger vehicles, ships) is an open
question. Ammonia also offers high energy density without the burden
of CO2 emissions upon use. It can be produced using only water to
supply hydrogen and air for nitrogen. Interest in PtA has led to the de-
velopment of new synthesis processes with the aim of lowering capital
investment and improving dynamic flexibility. Ammonia lags behind
hydrogen and methanol from a utilization standpoint. Decomposition
technologies for hydrogen production or direct-use fuel cells are far
from being commercially available. Ammonia combustion seems to
have the shortest path to commercialization, with ongoing development
of techniques to overcome ammonia’s undesirable low flame speed and
high auto-ignition temperature while also mitigating NOx emissions.
Increased development and deployment of power-to-x technologies
should lead to cost reductions via multiple avenues. One such avenue
is the development of specific methanol and ammonia synthesis tech-
nologies well-suited to using intermittent renewables, namely direct
CO2 hydrogenation and low pressure ammonia synthesis processes with
dynamic flexibility in the near term and electrochemical synthesis pro-
cesses in the longer term. The inherent design and operational features
of these processes should enable lower cost implementations in specific
power-to-x settings than the current state-of-the-art CO hydrogenation
and HB synthesis processes. Along a different vein, continued deploy-
ment of existing technologies such as electrolysis and fuel cells should
reduce capital intensity through economies of volume. Electrolysis and
fuel cells are inherently modular. Their cell stacks and much of the
required auxiliary equipment (e.g. power electronics) are fabricated in
an optimized manufacturing environment and then transported to the
location of their intended use. This results in potential advantages such
as increased efficiency of labor, for example, as well as better use of ma-
terials of construction when many modules are being fabricated at once
before deployment. The per-module capital cost can be reduced via
this manufacturing approach. This concept is well suited to power-to-
x systems which use spatially distributed renewable resources because
cost savings are still achieved by cumulative capacity increases across
multiple locations, in contrast to the economies of scale traditionally
observed in the chemical production industries.
7. Process systems engineering perspective
Process systems engineering has an important role to play in the
economic viability of power-to-x, wherein the involved processes face
challenges that conventional chemical production does not. The in-
termittency of the input renewable energy necessitates time-varying
M.J. Palys and P. Daoutidis Computers and Chemical Engineering 165 (2022) 107948

chemical production which can lead to operational challenges as well Notation

as oversizing to meet production targets leading to higher capital
AEC Alkaline electrolysis cell
intensity. The cited work in this review has made strides in alleviating
AFC Alkaline fuel cell
these challenges through design of alternative methanol and ammonia ATRM Autothermal reforming of methanol
production processes, development of coupled scheduling and control (B)EV (Battery) electric vehicle
approaches for dynamic operation, and capacity planning of whole CCGT Combined cycle gas turbine
power-to-x systems or supply chains that use intermittent renewables. CHP Combined heat and power
However, a number of vistas for future research into these processes CRD Cryogenic distillation
and systems remain. DAFC Direct ammonia fuel cell
DMFC Direct methanol fuel cell
At the process level, continued work in optimal design of methanol E-MPC Economic model predictive control
and ammonia synthesis is needed. For methanol, the research-to- ESS Energy storage system
date indicates that a continued focus on CO2 hydrogenation or co- HB Haber–Bosch
electrolysis processes is prudent, specifically analyzing and optimizing HER Hydrogen evolution reaction
their investment costs and balancing this with their promising energy ICE Internal combustion engine
efficiency characteristics. For ammonia, a focus on electrochemical LCOE Levelized cost of energy
LHV Lower heating value
synthesis processes will aid in determining cost- and energy-optimal
LSM Lanthanum strontium
material selection and operating condition regimes with the aim of
MCFC Molten carbonate fuel cell
accelerating their economical deployment. Methanol and ammonia MD Methanol decomposition
synthesis processes, both the existing state-of-the-art and the novel ones MI(N)LP Mixed integer (non)linear program
mentioned above, have complex nonlinear dynamics that can manifest MIQP Mixed integer quadratic program
themselves unintuitively during time-varying operation. These must MD Methanol decomposition
be understood so as to quantify dynamic flexibility limitations, effects MPC Model predictive control
MSR Methanol steam reforming
on energy efficiency, and long term catalyst performance. As such,
PAFC Phosphoric acid fuel cell
dynamic characterization studies like those by Varela et al. (2020)
PEMEC Proton electrolyte membrane electrolysis
and Cui et al. (2022) for methanol synthesis by CO2 hydrogenation PEMEC Proton electrolyte membrane fuel cell
should be continued and expanded to methanol production based on POM Partial Oxidation of Methanol
co-electrolysis. Such studies should also be conducted for condenser- R-SOFC Reversible Solid Oxide Fuel Cell
based, separation-enhanced, and electrochemical ammonia synthesis PSA Pressure Swing Adsorption
approaches. Better understanding of synthesis process dynamics will PtA Power-to-Ammonia
then enable studies on real-time operation and control of PtM and PtA, PtH Power-to-Hydrogen
PtM Power-to-Methanol
especially under uncertainty; such research can be in part inspired by
RTO Real Time Optimization
the existing work of that kind for PtH (Torreglosa et al., 2014)-(Cano
SCR Selective Catalytic Reduction
et al., 2015), though considering methanol or ammonia synthesis in SOC State of Charge
addition to electrolysis in PtM or PtA systems will undoubtedly add SOEC Solid Oxide Electrolysis
complexity. SOFC Solid Oxide Fuel Cell
At the systems level, capacity planning models that simultaneously WGS Water Gas Shift
YSZ Yttrium Stabilized Zirconia
optimize the facilities or supply chains that both produce and use
methanol and/or ammonia should continue to be developed, especially CRediT authorship contribution statement
integrating these with hydrogen and other technologies better suited
for short duration storage. These models should consider multiple can- Matthew J. Palys: Conceptualization, Investigation, Writing – orig-
didate technologies for the same function (i.e. conventional vs. novel inal draft, Writing – review & editing. Prodromos Daoutidis: Supervi-
synthesis, fuel cells vs. combustion) to contextualize the benefits and sion, Conceptualization, Writing – review & editing, Funding acquisi-
drawbacks of each. Another interesting consideration is that of fuel- tion.
flexible operation, for example, allowing time-varying composition of
Declaration of competing interest
methanol–hydrogen or ammonia–hydrogen mixtures fed to compati-
ble fuel cells or combustion systems in the scheduling optimization. The authors declare the following financial interests/personal rela-
Future research should also attempt to incorporate multiple years of tionships which may be considered as potential competing interests:
renewable generation data in capacity planning formulations in or- Matthew J. Palys reports financial support was provided by Xcel Energy
der to better understand the true value of long duration storage to Inc.
mitigate year-over-year changes in renewable energy availability. For
Acknowledgments
power-to-x sector coupling studies, optimization models with multiple
decision-makers will be crucial for realistic representation of tradi-
This work was funded by a generous gift from Xcel Energy.
tionally separate entities (e.g. utilities, chemical producers) acting in
their own self-interest. Capacity planning models incorporating the References
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