Journal of Cleaner Production 428 (2023) 139475

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Journal of Cleaner Production

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

How sustainable and profitable are large-scale hydrogen production plants

from CH4 and H2S?
Sawsan M. Ali , Ismail I.I. Alkhatib , Ahmed AlHajaj , Lourdes F. Vega *
Research and Innovation Center on CO2 and Hydrogen (RICH), and Department of Chemical and Petroleum Engineering, Khalifa University, PO Box 127788, Abu Dhabi,
United Arab Emirates

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

Handling Editor: Panos Seferlis The large-scale production of hydrogen through mature technologies such as steam methane reforming (SMR)
has set a benchmark for emerging hydrogen production processes to gauge their economic viability for the
Keywords: hydrogen economy. In this work, we use detailed process modeling to perform a techno-economic and envi­
Hydrogen production ronmental assessments on the potential of alternative emerging hydrogen production processes based on H2S
Techno-economic assessment
utilization including H2S-methane reforming (H2SMR), and H2S pyrolysis (H2SPyrol) compared to steam
H2S-based hydrogen
methane reforming (SMR), SMR with CO2 capture, storage, and utilization (CCUS), and CH4 pyrolysis
Pyrolysis
Lifecycle assessment (CH4Pyrol). Technically, the energy intensity of these processes in terms of electrical and thermal energy con­
sumption was ranked as CH4Pyrol < SMR < SMR + CCUS < H2SMR < H2SPyrol. However, lower CH4 feedstock
and absence of direct CO2 emissions were seen for H2SMR for the same target hydrogen production. Economi­
cally, both H2S-based hydrogen production technologies were competitive with levelized cost of hydrogen
(LCOH) of $-1.000 and $3.537 per kg for H2SMR and H2SPyrol, respectively, compared to LCOH of $2.400,
$2.410, and $1.930 per kg for SMR, SMR + CCUS, and CH4Pyrol, respectively, with consideration for by-product
sales, and sensitivity analysis to their market prices and effect of carbon taxes. Environmentally, H2SMR and
H2SPyrol revealed their lower contribution to global warming, with the absence of direct CO2 emissions, qual­
ifying as low carbon hydrogen production processes. Although direct CO2 emissions are missing from CH4Pyrol,
its qualification as low carbon hydrogen producer hinges on the level of decarbonization for the electricity grid.
Conversely, the water footprint of H2S-based hydrogen production process remains to be the largest due to the
indirect consumption of cooling water required for product recovery, although not necessarily impacting water
stress, due to the lower quality of water required for cooling. In summary, transitioning from SMR wo/w CCUS to
H2SMR or CH4Pyrol seems to be potentially attractive for competing with current processes for H2 production
within the existing policies for decarbonization.

1. Introduction In the context of decarbonization and sustainable processes

Within the framework of the United Nations’ (UN) sustainable
development goals (SDGs), a transition towards a hydrogen-dependent
global energy economy is one of the solutions capable of ensuring
affordable and clean energy (SDG 7), while in parallel increasing climate
action mitigating the impacts of climate change (SDG 13) (UN, 2020).
The current dependency on fossil fuels as primary energy resources has
led to the increasing levels of CO2 emissions, associated with global
warming and climate change, mandating the search for alternative low
carbon energy sources capable of meeting net-zero emissions strategies
(Hassanpouryouzband et al., 2020, 2021).
hydrogen is promoted as an alternative clean energy carrier due to its
inherently zero direct CO2 emissions when utilized as a fuel, alongside
its capability to act as energy storage to be used in combination with
renewable energy, its role in decarbonizing the heat and power sector,
and the hard-to-abate industries such as heavy transportation, metal­
lurgy and cement industries (Griffiths et al., 2021; Hassanpouryouzband
et al., 2022; Sartbaeva et al., 2008; Staffell et al., 2019). Accordingly,
current net-zero emission scenarios project a wider application of
hydrogen for decarbonizing existing industries, with hydrogen demand
reaching 530 Mt by 2050 from its 2020 level of 90 Mt, with higher
penetration rate in industry and transportation sectors (i.e., almost 50%

* Corresponding author.
E-mail address: Lourdes.vega@ku.ac.ae (L.F. Vega).

https://doi.org/10.1016/j.jclepro.2023.139475
Received 24 July 2023; Received in revised form 29 September 2023; Accepted 22 October 2023
Available online 23 October 2023
0959-6526/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S.M. Ali et al.
of projected demand) (IEA, 2021). Despite the existing momentum for
incorporating hydrogen in the current energy nexus, the existing pro­
duction capacities are far from those required for the realization of
projected scenarios, making the next decade crucial for ensuring the
production and use of low carbon hydrogen as a needed energy vector.
This requires facilitating scaling-up production capacities and revamp­
ing current technologies in industrial sectors targeted for hydrogen
utilization.
Several technologies exist for hydrogen production, at different de­
grees of development, based on their efficiency and cost, and with
different environmental impact. Nearly 72% of the global hydrogen
production in 2020 was obtained by steam methane reforming (SMR)
from natural gas without CO2 capture, accounting for 60% of the 90 Mts
of total hydrogen production capacity (IEA, 2021). Nowadays, SMR is
the most commercially viable option, with levelized cost of hydrogen
production (LCOH) in the range of $1.03–2.16 per kg H2 (Parkinson
et al., 2019). However, at the expense of high direct CO2 emissions, with
total life cycle emissions (LCE) in the range of 10.09–17.21 kg CO2-eq
per kg grey H2 (Parkinson et al., 2019), accounting for 2.5% of CO2
emissions in 2020 (IEA, 2021).
The most promising alternative options for the commercial produc­
tion of cleaner hydrogen (low-carbon or carbon-neutral hydrogen)
include either the production of blue hydrogen via integrating SMR with
carbon capture, utilization and storage (CCUS), or green hydrogen from
water electrolysis with renewable energy (Boretti, 2021; Lee et al., 2023;
Sazali, 2020; Shiva Kumar and Lim, 2022; Zhou et al., 2022) With these
technologies resulting in LCE of 2.97–9.16 kg CO2-eq per kg blue H2
with a 90% CO2 capture rate, and 0.52–2.5 kg CO2-eq per kg green H2,
dependent on the renewable energy source (Parkinson et al., 2019).
However, the penetration of both technologies into the hydrogen pro­
duction supply chain remains insignificant, accounting for less than
0.73% of the 2020 total hydrogen production, accounting for merely
0.65 Mts of H2 (IEA, 2021). This is primarily attributed to their LCOH
with $1.93–2.26 per kg for blue H2 from the additional cost of CCUS, and
$4.61–14.87 per kg for green H2 owing to high renewable electricity and
electrolyzer costs estimated on 2016 basis (Parkinson et al., 2019).
Current political and environmental legislative pressure on actualizing
pledged policies on net zero emissions by 2050 provide sufficient
justification for adopting blue and green hydrogen supply considering
the trade-off between the high cost of hydrogen production and
low-carbon emissions, significantly dependent on the energy resource
input used in the production process (Griffiths et al., 2021; Hassan­
pouryouzband et al., 2021, 2022). This is largely seen from their pivotal
role in decarbonizing current industrial sectors, justifying the rapid in­
crease in the number of planned or under-construction blue and green
hydrogen production plants, concurrently boosting their projected share
in total hydrogen production by 2030 process (Griffiths et al., 2021).
Among the most promising alternative technologies for producing
zero CO2 hydrogen is via thermal decomposition of methane or CH4
pyrolysis (CH4Pyrol), also known as turquoise hydrogen, producing
hydrogen and solid carbon with an estimated LCOH of $1.36–3.00 per
kg of turquoise hydrogen (Diab et al., 2022; Parkinson et al., 2019;
Sánchez-Bastardo et al., 2021). Unlike SMR, CH4Pyrol is a one-step
process that does not require steam (i.e., water) as a reaction feed­
stock with almost half of the reaction enthalpy of SMR. Additionally,
CH4Pyrol has a lower contribution to global warming on account of its
58% lower methane feedstock, and five times lower CO2 emissions
compared to SMR (Keipi et al., 2016). The economics of the process can
be further improved taking into account the added-economic value of
the by-product, reaching a market price of $400–2000 per ton of carbon
black and $600 per ton of carbon nanotubes (CNTs), with an increasing
global demand due to its wide-range of industrial applications, yet
depending on the dynamics of the carbon market and its consumer
surplus (Keipi et al., 2016; Sánchez-Bastardo et al., 2021). To date,
several works have addressed the economic and environmental impacts
of CH4Pyrol, recognizing its potential as zero CO2 hydrogen (Becker
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Journal of Cleaner Production 428 (2023) 139475
et al., 2023; Diab et al., 2022; Keipi et al., 2018; Oni et al., 2022; Pruvost
et al., 2022; Zong et al., 2023).
Although energy requirement and CO2 footprint are considered in all
hydrogen production process cases, a blind spot often overlooked from
hydrogen production technology evaluation is the associated water
footprint, as most of these technologies depend on the availability of
freshwater as a feedstock. Considering that fresh water is one of the most
valuable resources, its inclusion as a feedstock for hydrogen production
is counterproductive in fulfilling some of the UN’s SDG, in particular,
ensuring the availability of clean water and sanitation (SDG 6) and
responsible consumption and production (SDG 12) (UN, 2020). This
would not add an economic burden to the hydrogen production process,
as seawater desalination merely adds $0.01–0.02 kg− 1 H2, irrespective
of the hydrogen production technology (Council, 2021; UN, 2020).
However, this has a larger social cost associated with the re-routed re­
sources for producing water for hydrogen generation rather than other
uses (van Renssen, 2020) with the water footprint for hydrogen pro­
duction being in the range of 9–18 kg water per kg of H2, from green
hydrogen production with renewable energy to blue hydrogen from
SMR + CCS (Council, 2021; UN, 2020). Indeed, this led to the emergence
of other options favoring the direct use of non-freshwater resources (i.e.,
seawater, wastewater, etc.), yet still at a low technological maturity level
for large-scale hydrogen production, or processes producing hydrogen in
the absence of water consumption such as CH4Pyrol, reducing contri­
bution to water stress. In this regard, the search for alternative hydrogen
production technologies is still underway, seeking not only technologies
producing low or neutral carbon hydrogen at low LCOH, but also
without consuming valuable resources such as water as reaction
feedstocks.
Alternatively to methane and water, hydrogen sulfide (H2S) is a
promising source of hydrogen which is an abundant by-product of the
processing and conditioning of chemical feedstock such as natural gas,
syngas, and refinery gas (Chan et al., 2023; De Crisci et al., 2019) and it
contains the same amount of hydrogen as water. The energy-intensive
Claus process, oxidizing H2S to produce elemental sulfur (S) with a
low market value of $0.04–0.24 kg− 1 S (Martínez-Salazar et al., 2019),
while consuming the hydrogen atoms in the form of low-quality steam is
the most standard process to deal with H2S in natural gas processing
plants. The high toxicity of H2S imposes stringent and expensive re­
quirements on its management in this process. Additional investments
for tail-gas treatment units are needed to process gas streams rich with
sulfur dioxide (SO2) based on imposed safety regulations on their at­
mospheric releases (Zagoruiko and Matros, 2002). The increasing de­
mand and consumption for natural gas in the current energy nexus have
forced oil and gas producers to tap into sub-quality gas reserves (i.e., CO2
and H2S content higher than 20 mol%) that were otherwise uneco­
nomical. Hence, it can be expected that significant amounts of H2S will
have to be processed and managed, while wasting valuable H2 if this
continues to be the process of choice.
A more practical solution with higher environmental and economic
benefits in line with the UN’s SDGs is through directing resources
expended on conventional H2S management toward H2 production
(Chan et al., 2023; De Crisci et al., 2019). Electrocatalytic and photo­
catalytic decomposition of H2S, analogous to H2O, are possible routes
yet at early development stages far from industrial-scale deployment
with the lack of low cost, stable, and highly active catalytic materials (Li
et al., 2021, 2022; Oladipo et al., 2020; Osasuyi et al., 2021). In a similar
analogy to SMR, methane reforming in the presence of H2S rather than
H2O (H2SMR) is another route for thermochemical H2 production that
has been explored at lab-scales using catalytic and non-catalytic routes
(Cong et al., 2016; El-Melih et al., 2016; Martínez-Salazar et al., 2015;
Spatolisano et al., 2022a). However, the up-scaling of the process can
have higher economic added value compared to SMR, as carbon disul­
fide (CS2) is the by-product rather than CO2, eliminating the need for
integrating CCUS with hydrogen production plants, thus removing the
added carbon avoidance cost (CAC) of $96.15 tons− 1 CO2 for blue
S.M. Ali et al.
hydrogen (Parkinson et al., 2019). At this stage, few works have
examined the potential of H2S-methane reforming (H2SMR) and direct
H2S pyrolysis (H2SPyrol), either through experimental investigations for
catalysis synthesis (El-Melih et al., 2016, 2017), or small-scale tech­
no-economic evaluation (Martínez-Salazar et al., 2015, 2019; Spatoli­
sano et al., 2022a, 2022b; Villasmil and Steinfeld, 2010). Nonetheless,
the large-scale technical, economic, and environmental impact of these
alternative technologies, and their potential deployment remains
unexplored.
Hence, the aim of this work to determine the technical, economic,
and environmental performance of alternative thermochemical
hydrogen production technologies employing H2S as one of the primary
feedstock through H2SMR and H2SPyrol, benchmarked with conven­
tional hydrogen production from SMR w/wo CCUS integration, and
direct CH4 pyrolysis. The goal is to assess alternative hydrogen pro­
duction technologies searching for low LCOH, and low carbon and water
footprint. The basis for the inclusion of these processes over others is
focused on thermochemical routes with direct industrial implementa­
tion by comparing H2S-based options with their CH4-based counterparts
(i.e., H2SMR vs. SMR/SMR + CCUS, and H2SPyrol vs. CH4Pyrol). To our
knowledge, this is the first comparative study examining these novel
technologies under the same large scale conditions and exploring their
technical, economic, and environmental performance.
2. Methodology
For the techno-economic analysis, steady-state mass and energy flow
data from the operations of the four hydrogen production technologies
(i.e., H2SMR, H2SPyrol, SMR, and SMR + CCUS) have been generated
using the Aspen HYSYS® process simulator (AspenTech, 2022), target­
ing a hydrogen production rate of 9.0 tons.hr− 1 (216 tons.day− 1) with a
minimum H2 purity of 99.5%, simulating a large-scale hydrogen pro­
duction plant based on an IEAGHG study for hydrogen production via
SMR (IEAGHG, 2017). The specifications for the hydrogen and CO2
by-product purity levels are included in Table S1 in the Supporting In­
formation (SI).
The techno-economic comparative analysis of these technologies was
based on key performance indicators (KPIs), accounting for non-
monetized technical KPI with specific energy consumption (SEC), and
Fig. 1. Simplified process flow diagram for the five processing sections in the five hydrogen production routes included in this work. The colors of the arrows
represent the different hydrogen production routes: SMR (grey), SMR+CCUS (blue), CH4Pyrol (turquoise), H2SMR (saffron) and H2SPyrol (orange). The dashed
orange line represents the system boundary.
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Journal of Cleaner Production 428 (2023) 139475
monetized KPI based on total annualized cost (TAC), and LCOH. Addi­
tionally, a gate-to-gate life cycle assessment (LCA), from feedstock de­
livery to process gate up to product delivery to end-user, was performed
using the LCA tool (OpenLCA®) (GreenDelta, 2022) to determine the
overall environmental impact associated with the construction and
operation of the different hydrogen production plants. The environ­
mental impacts were assessed in terms of associated process emissions
and resource consumption and their impact on global warming potential
(GWP), water footprint, and other ecological and toxicological impacts.
The process schemes for the five hydrogen production processes are
relatively similar and divided into five main stages of (1) feed pre-
heating and compression, (2) reaction stage for hydrogen production,
(3) by-product separation, (4) H2 purification, and (5) H2 compression
and delivery, as shown in Fig. 1. The primary differences among these
processes are in the reaction, and by-product processing stages due to
the differences in utilized feedstock and reaction by-products. Addi­
tionally, heat integration throughout the different processes has been
performed, whenever applicable, through direct heat exchange of pro­
cess streams to minimize operating costs, particularly in the case of SMR
and SMR + CCUS.
For the sake of simplicity, it was assumed that feedstock streams
delivered to all hydrogen production plants including methane, steam,
and H2S were readily available at the hydrogen production plant gate,
excluding upstream processing, conditioning, or pre-treatment stages
involving natural gas conditioning to sales gas specifications, and H2S
separation from sour natural gas, in a gate-to-gate approach (Durán
et al., 2020; Nikolaidis and Poullikkas, 2017); for a detailed full eco­
nomic assessment of each technology these steps and cost should be
included. Note, for all hydrogen production plants, the produced
hydrogen was compressed to 20 MPa for transportation in pressurized
I-type tube trailers (Aydin and Dincer, 2022). Additionally, in the case of
SMR + CCUS, the captured CO2 was compressed to 20 MPa suitable for
dense phase pipeline transportation for subsequent utilization.
2.1. Description of H2 production technologies
2.1.1. Hydrogen production via steam methane reforming w/wo CCUS
In conventional SMR, hydrogen is catalytically produced via two
main reactions: (1) reforming reaction, producing CO and H2 from
S.M. Ali et al.
reacting CH4 and steam in the reforming reactor at 1153 K (Eq. (1))
(Nikolaidis and Poullikkas, 2017; Sazali, 2020), followed by (2)
water-gas shift reaction, producing additional H2 through converting CO
into CO2 once reacted with steam (Eq. (2)), with the overall reaction
represented by (Eq. (3)):
Reforming : CH4 + H2 O ↔ CO + 3H2 (1)
Water − gas − shift : CO + H2 O ↔ CO2 + H2 (2)
Overall reaction : CH4 + 2H2 O ↔ CO2 + 4H2 ΔH 0 = 164.9 kJ.mol− 1
(3)
The process flowsheet for producing grey hydrogen is provided in
Fig. 2, where the numbers in red in the arrows represent the streams of
the process. The methane feedstock is compressed to 2800 kPa in a two-
stage compression train, with water pumped at the same pressure prior
to the high pressure (HP) steam generation using excess heat from the
reformer reactor outlet stream, exploiting the high endothermicity of the
reforming reaction and efficiently utilizing waste heat in the process.
The reformer feed steam-to-methane ratio was maintained at 3:1 to
ensure acceptable hydrogen yield and reactor energy requirements,
while preventing carbon deposition (Alrashed and Zahid, 2021; Durán
et al., 2020; IEAGHG, 2017).
For simplicity, the reformer reactor was modeled as an endothermic
equilibrium reactor using a nickel-based catalyst operating at 1153 K,
with feed stream pre-heating using a standalone heat exchanger rather
than a dedicated pre-heating coil inside the convective section of the
reformer’s furnace (Durán et al., 2020; Nikolaidis and Poullikkas, 2017).
Higher hydrogen yield was obtained by feeding the resulting syngas (i.e.,
H2 + CO + CO2 + CH4) from the reformer to the two-stage water-gas
shift reaction (WGSR) section with the high-temperature iron-based
catalytic shift reactor (HTS) operating at 643 K, followed by the
low-temperature copper-based catalytic shift reactor (LTS) operating at
523 K, also modeled as equilibrium reactors. Note that the choice of
catalysts is based on those utilized in industry with proven performance,
while more novel catalysts have been developed, their utilization is
outside the scope of this work (IEAGHG, 2017; Nikolaidis and Poullik­
kas, 2017). The shifted outlet gas was then routed to the pressure swing
adsorption (PSA) unit to reach the required hydrogen purity level (see
Table S1 in the SI), conditioned for pipeline transportation (i.e., 20 MPa
and 333 K) using a four-stage compression train. The separated PSA tail
gas, mainly composed of CO2 and CH4, was combusted alongside
make-up fuel gas based on the heating value of the tail gas in the radi­
ation section of the reformer reactor, modeled as an equilibrium reactor,
to provide the reformer’s heat duty. The condensed water was recycled
to the reactor’s inlet for steam generation.
The production of blue hydrogen (i.e., with CCUS integration)
Fig. 2. Process flowsheet for hydrogen production via SMR considered in this work. See text for details.
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Journal of Cleaner Production 428 (2023) 139475
follows the same SMR process scheme in Fig. 2 with an additional CO2
capture unit downstream of the WGSR section shown in Fig. 3 (Alrashed
and Zahid, 2021; Durán et al., 2020; IEAGHG, 2017). Additional
methanation stage was installed to further reduce the CO content in the
hydrogen stream recovered from the amine unit, with the exothermic
reaction (Eq. (4)) occurring over a nickel-based catalyst at 608 K using
an upstream pre-heater (Nikolaidis and Poullikkas, 2017).
Methanation : CO + 3H2 ↔ CH4 + H2 O (4)
The captured CO2 from the amine regenerator overhead was com­
pressed to 4.5 MPa through a four-stage LP compression followed by
water dehydration using triethylene glycol (TEG) to remove excess
water vapor from the captured CO2 stream, subsequently, compressed to
20 MPa in a three-stage HP compression unit for its downstream
transportation. LP steam used in the amine and water-dehydration units
was internally generated through heat integration of excess heat from
the gas-water cooler upstream the amine unit and the gas cooler
downstream the methanation reactor. Since the captured CO2 was only
from the shifted syngas, the calculated capture rate was 60%.
2.1.2. Hydrogen production via CH4 thermal decomposition
In CH4Pyrol methane is non-catalytically thermally decomposed into
hydrogen and carbon black as in (Eq. (5)). Though catalytic routes exist,
the choice of non-catalytic reactions is preferred to avoid catalyst
deactivation, coking and clogging, effectively eliminating CO2 emissions
from catalyst regeneration and carbon product contamination with
catalyst residue, aside from the reduced operating costs due to the
absence of expensive metal-based catalysts (Keipi et al., 2016; Oni et al.,
2022; Sánchez-Bastardo et al., 2021). The non-catalytic reaction (Eq.
(5)) is carried out at a low pressure of 100 kPa, and although CH4
achieves complete conversion via equilibrium at temperature above
1273 K (Sánchez-Bastardo et al., 2021), a conservative kinetic-based
conversion of 0.7 is considered with a residence time of 5 s at a
reactor temperature of 1473 K (Keipi et al., 2016, 2018). At the chosen
conditions it can be expected that the morphology of the produced
carbon would be industrial grade nanostructured carbon black with
small crystallites with a carbon content of more than 95% (Diab et al.,
2022). This grade of carbon black is used in several industrial applica­
tions such as tires, rubber plastics, toners, etc., with a 4.80% annual
growth and a $25.80 billion market value (FortuneBusinessInsight,
2023).
CH4 ↔ C + 2H2 (5)
For the CH4Pyrol process, methane feedstock is preheated in a shell
and tube heat exchanger using the excess heat from the reactor’s exit
stream. The reactor is operated at 1473 K with fuel gas combustion
S.M. Ali et al.
Fig. 3. Process flowsheet for hydrogen production via SMR + CCUS.
burners to supply and maintain heat for heat of the reaction. Different
reactor configurations have been studied in the literature including
molten salt/metal bubble reactors that facilitate carbon separation
(Keipi et al., 2016; Sánchez-Bastardo et al., 2021). For this work, a
regenerative non-catalytic heat exchanger reactor (RHER) is considered
with maximized counter-current heat transfer profile using circulated
steel bed material with high heat capacity fed from the reactor’s top
while exchanging heat with the reactor’s reactants and products. The
circulating bed material facilitates the continuous removal of carbon
that is deposited on the walls of the reactor and maintains a constant
temperature profile across the different reactor zones. CH4 feed is pre­
heated to 1273 K while the constant reaction zone temperature of 1473
K is maintained across the reaction and upper zones through the contact
with bed material. The captured carbon conveyed by the circulating bed
material is separated using an integrated cyclone that removes 80% of
the solidified carbon black from the H2 + unreacted CH4 mixture (Keipi
et al., 2018). The separated carbon black is further cooled using a
water-cooled heat exchanger to 303 K and pelletized for final dis­
patching after cooling.
The exit gas stream is further cooled to 551 K by heat exchange with
the CH4 feedstock stream followed by a water-cooled heat exchanger at
423 K to remove residual carbon through a fabric filter (Keipi et al.,
2016). The reactor product gas stream is further cooled via an air cooler
to 338 K and is compressed to 2450 kPa prior to the PSA unit, for the
recovery of unreacted CH4, circulated to the reactor’s burners. The
remaining unreacted CH4 is recycled to the reactor’s inlet and mixed
with fresh methane feedstock.
2.1.3. Hydrogen production via H2S-methane reforming
For H2S-methane reforming (H2SMR) process, methane and H2S are
reacted either catalytically or non-catalytically to produce hydrogen
alongside CS2, with the general reaction as:
CH4 + 2H2 S ↔ CS2 + 4H2 (6)
The basis for H2SMR is analogous to SMR, with the primary differ­
ences of utilizing H2S rather than steam for hydrogen production, in
addition to CS2 formation as a by-product rather than CO2. However,
H2SMR is a more endothermic than SMR (i.e., ΔH0 = 232.4 vs.164.9 kJ
mol− 1), postulating higher reaction energetic requirements for produc­
ing hydrogen at rates similar to SMR (Chan et al., 2023). An additional
by-product is produced in the form of elemental sulfur from the direct
decomposition of H2S side-reaction (see Eq (7)).
5
Journal of Cleaner Production 428 (2023) 139475
The H2SMR process flowchart is shown in Fig. 5. The process is
divided into five processing stages including: (1) feed conditioning, (2)
reaction stage for hydrogen production, (3) sulfur and CS2 separation,
(4) H2 purification, compression, and transportation, and (5) utility
recovery.
It was assumed that methane feedstock was of sales gas quality
delivered at 313 K and 100 kPa, while H2S feedstock was obtained from
the natural gas processing plant sweetening unit’s regenerator overhead
at similar operating conditions with CO2/H2S ratio below 1:15, with
negligible effect on the hydrogen yield (Spatolisano et al., 2022a).
The H2S and CH4 feed streams were mixed at a fixed ratio of 4:1 and
pre-heated to 1773 K (i.e., reaction pinch temperature) upstream of the
reactor, with the CH4 flow rate adjusted based on the amount of recycled
unreacted H2S from the downstream hydrogen purification stage in
subsequent iterations. This ratio was selected to prevent carbon laydown
from the pyrolysis reaction, along with being optimum for achieving
higher H2 yield than other feed ratios, while reducing potential oper­
ating costs for compressions, cooling, and amine-based H2S purification
units (Huang and T-Raissi, 2008; Spatolisano et al., 2022a). The H2SMR
reaction (Eq. (6)) is carried out at atmospheric pressure (i.e., 100 kPa),
as its thermodynamic equilibrium is disfavored at high operating pres­
sure resulting in low H2 yields (Huang and T-Raissi, 2008; Spatolisano
et al., 2022a).
A non-catalytic path is considered for H2SMR as a conservative basis
for the techno-economic analysis which also eliminates any potential
issues arising from catalyst poisoning with elemental sulfur (Karan et al.,
1999). The reforming reactor was modeled as an equilibrium reactor
with a conversion for the non-catalytic reaction fixed to the equilibrium
value of 68% at a reactor temperature of 1773 K, while assuming a 99%
conversion of CH4 through its decomposition above 1073 K (Huang and
T-Raissi, 2008; Spatolisano et al., 2022a, 2022b). Although higher
equilibrium conversions can be obtained at different conditions
(El-Melih et al., 2017), the detailed sensitivity analysis of the best
operating conditions is out of the scope of this work, and will be
considered in future works. The required heat duty for operating the
reformer reactor was supplied from imported methane-based fuel gas,
while heat integration was performed within the process by exploiting
flue gas from the reformer furnace for pre-heating the reformer’s reac­
tion inlet stream and water heating for the CS2 distillation column
reboiler.
The reactor effluents (i.e., H2, unreacted H2S, diatomic sulfur, and
CS2) were then sent to the by-products processing stage which involves
S.M. Ali et al.
the separation of elemental sulfur, and CS2 recovery from the produced
hydrogen. Elemental sulfur was recovered by cooling in the sulfur
condenser to 408 K to promote condensation of diatomic sulfur vapor
into liquid sulfur that was separated from the remaining reaction
products. The Sulsim® property package in Aspen HYSYS was used to
account for the thermophysical properties of the different sulfur allo­
tropes. The entrained CS2 was separated using cryogenic distillation and
extracted at its boiling point of 313 K.
The separated column overhead stream composed of H2 and
unreacted H2S at 210 K was compressed to 2450 kPa using a three-stage
compression train with intermediate cooling ahead of the H2 purifica­
tion stage using 50 wt% aqueous methyl diethanolamine (MDEA) ab­
sorption process for the removal of unreacted H2S. High-purity
hydrogen (99.68%) exiting the top of the absorber column was routed
to the downstream PSA unit for further removal of minor impurities to
reach 99.99% purity, which was subsequently conditioned for trans­
portation to 333 K and 20 MPa using a four-stage compression train with
intercooling.
The H2S-rich MDEA solvent was regenerated using atmospheric
distillation for further circulation in the process, while recovered
unreacted H2S exiting the regeneration column was cooled to 298 K and
flashed prior to being recycled back to the reformer reactor, with feed
CH4 flowrate adjusted accordingly to maintain H2S:CH4 ratio of 4:1. The
intermediate cooling and flashing steps were necessary to ensure mini­
mal water vapor carry-over (i.e., < 3 mol%) with the recycled H2S
stream into the reformer inlet, as the presence of water might compro­
mise the H2S conversion rate, H2 yield, and CS2 purity due to unfavor­
able CO formation (Spatolisano et al., 2022b).
2.1.4. Hydrogen production via H2S decomposition
In the absence of methane, the direct thermal decomposition of H2S
or H2SPyrol can be used to produce hydrogen and elemental sulfur
analogous to CH4Pyrol, represented by the reaction as:
1 mos, 2019; IEAGHG, 2017). Additional details are included in Table S4
H2 S ↔ S2 + H2
2 in the SI.
The process scheme for H2SPyrol through a non-catalytic reaction
route is shown in Fig. 6, with relatively similar general processing stages
as H2SMR for a fair comparison. The main differences are the absence of
CS2 distillation as elemental sulfur is the only by-product, and additional
compression stage upstream of the amine unit. The H2S equilibrium
conversion rate was also set to 68% at 1773 K similar to H2SMR
(El-Melih et al., 2017; Slimane et al., 2002). The excess waste heat from
the sulfur condenser was used for generating LP steam at 431 K, partially
supplementing the steam requirements for the amine reboiler, while
externally importing the remaining required steam. We note that unlike
CS2, elemental sulfur has been typically produced from H2S in tradi­
tional Claus processes, with existing industrial knowledge on its safe
handling and storing. Such details though might impact the economics
of the process, yet are not included in this work for the sake of simplicity.
2.2. Economic analysis
The economic performance of the five hydrogen production tech­
nologies was done based on the total cost associated with hydrogen
production, quantified using the monetized KPIs namely, total annual­
ized cost (TAC), and LCOH. This last indicator quantifies the minimum
hydrogen selling price to breakeven the TAC, accounting for total capital
investment (direct and indirect), and fixed operating and maintenance
cost, and variable operating cost, as:
[ ]
CAPEX×CRF FOM
+ + VOC + other costs − SR
CF CF
LCOH = (8)
QH2
where CAPEX is the total capital investment from direct and indirect
Journal of Cleaner Production 428 (2023) 139475
costs, FOM is the fixed operating and maintenance cost, VOC is the
variable operating cost, with FOM + VOC as the total operating costs
(OPEX), SR is the sales revenue generated from the sales of the by-
products, with all costs and sales reported in US $. Also, QH2 is the
annual hydrogen production rate in kg.yr− 1, CF is the capacity factor
assumed to be 0.95, and CRF is the capital recovery factor, represented
by:
i(1 + i)n
CRF = (9)
(1 + i)n − 1
where i is the discount or interest rate in % per annum set to 8%, and n is
the hydrogen production plant lifetime in years, set to 30 years. Note
that cost of land, effect of inflation, and taxes on CO2 emissions were
excluded from the economic assessment. The cost of CO2 storage and
transportation for SMR + CCUS was also included as other costs (see
Section S2 in the SI).
For estimating the CAPEX, the direct capital cost of the main
equipment (see Figs. 2–6) was calculated using the costing methodology
summarized in Section S2 in the SI to obtain the total equipment
purchase and installation costs based on the sizing from the mass and
energy balances obtained from the steady-state simulations. This was
applied to all operating units in the five hydrogen production plants,
with the exception of the PSA units for hydrogen purification, and the air
separation units (ASU) with their costs scaled based on reference
installed costs from the literature (see Table S3 in the SI) (Chisalita and
Cormos, 2019; Khojasteh Salkuyeh et al., 2017). Additional factors
accounted for in the indirect capital cost include engineering services,
contractors’ fees, and contingencies, alongside other costs, included in
Table S2 in the SI.
The OPEX were inclusive of the FOM for maintenance, labor, and
other overheads, and VOC were inclusive of utility and raw material
costs based on the results of the steady-state process simulations, and
other costs for CO2 compression and transportation (Chisalita and Cor­
(7)
2.3. Life cycle environmental assessment
The LCA assessment was conducted to complement the holistic
evaluation for the large-scale H2 production routes using H2S as a pri­
mary feedstock in order to quantify potential process improvements in
terms of cleaner and sustainable production. A gate-to-gate LCA was
implemented, accounting for emissions associated with hydrogen pro­
duction plants construction and operations, excluding emissions asso­
ciated with upstream processing and delivery of feedstock into the
plants’ gate, and downstream utilization of produced hydrogen and
other by-products (Cetinkaya et al., 2012). Accordingly, the gate-to-gate
LCA assessment considers natural gas pipeline transportation, hydrogen
production plants construction and operation with associated electrical
consumption. The LCA objective was to assess the CO2 and water foot­
prints of the five production processes in terms of amount of GHG
emissions generated, and water consumed for the construction and
operation of these processes. The LCA evaluation was done using
OpenLCA® software (GreenDelta, 2022) with publicly available agri­
balyse® and IMPACT 2002+ databases using life cycle inventory from
the mass and energy balance from the process simulations. Although
OpenLCA® possesses limited databases compared to other commercially
available software, the user is tasked with finding additional informa­
tion from complementary sources, as done in this study, sufficient for the
purpose of providing a general overview on the environmental impact of
the examined technologies. The needed datasets were complemented by
literature estimates, such as the emissions associated with plant con­
struction and natural gas pipeline transportation, including methane
fugitive emissions, proportionally estimated based on literature datasets
(Aydin and Dincer, 2022; Cetinkaya et al., 2012; Spath and Mann,
6
S.M. Ali et al.
Fig. 4. Process flowsheet for hydrogen production via CH4Pyrol. See text for details.
Fig. 5. Process flowsheet for hydrogen production via H2SMR.
2001). The key impact stressors on climate change, ecosystem quality,
and human health were computed following the default weight factors
from the software and used as the basis for the comparison among the
different processes.
For natural gas pipeline transportation, the supply chain fugitive
methane emissions were considered as 1.4% of the transported methane
(Bauer et al., 2021; Spath and Mann, 2001),with quantity of methane
transported as the sum of reaction feedstock (where applicable) and
reactor’s burner fuel gas requirements. The emissions associated with
other components in natural gas including CO, CO2, N2O, NO, benzene,
other hydrocarbons, and particulate matter, were computed on the basis
of ratio of feedstock mass flow rate used in this work relative to litera­
ture LCA data (Cetinkaya et al., 2012). The same equivalence approach
was also applied for estimating water and coal resources input flow rates
for natural gas production. Other factors for natural gas extraction
including re-compression energy associated emissions and natural gas
production plant construction were excluded from this work.
For the construction of the hydrogen production plants, the envi­
ronmental impact per 1 kg H2 functional unit was obtained from scaling
available literature data on the environmental impact for hydrogen
7
Journal of Cleaner Production 428 (2023) 139475
plant construction with production rate of 5.6 tons.day− 1 (Cetinkaya
et al., 2012), to the 9.0 tons.day− 1 production rate in this work, with
input and output flows included in Table S5 in Section S3 in the SI.
For the operation of the hydrogen production plants, all inlet feed­
stock, utilities (i.e., water for cooling or steam generation), and outlet
products, and effluents including emitted CO2/H2O from reactor flue gas
and TEG dehydration unit were considered. Internally generated utility
steam using the excess heat of the various heat exchangers was not
considered as input process flow, however, the associated water con­
sumption requirement was included in the LCA as part of the operation
phase. The input electrical requirements for the operation of the pro­
cesses were standardized using the Ecoinvent LCI cut-off dataset for
high-voltage electricity gird with an adjusted CO2 intensity of 0.275 kg
CO2-eq.kWh− 1 (Parkinson et al., 2019). Table S6 in the SI includes
detailed input and output low streams for all processes.
The LCA evaluation for H2 production processes was done based on a
1 kg H2 functional unit, examining impact categories including: (1)
global warming potential (GWP) which includes the direct and indirect
equivalent CO2, CH4, and NO2 emissions computed by the IMPACT
2002+ database (Aydin and Dincer, 2022; Spath and Mann, 2001), and
S.M. Ali et al.
Fig. 6. Process flowsheet for hydrogen production via H2SPyrol.
(2) water-footprint which indicates the degree of water consumption in
the process estimated using the available water remaining (AWARE)
database. The contribution of each life cycle stage on each impact
category was included in the assessment. The temporal impact of GHGs
was evaluated using the intergovernmental panel on climate change
(IPCC) 2007 indicators over 20- and 100-years’ time-horizons. The
significance of the 20-year timeframe is attributed to the short-lived
atmospheric impact of methane over twelve years and equivalent to
84 kg CO2-eq, while its lone-term impact is equivalent to 36 kg CO2-eq
over 100 years (Bauer et al., 2021). Additionally, other impact cate­
gories were included in the assessment, including cumulative energy
demand, and other impact categories on human health and environment
(Aydin and Dincer, 2022; Bauer et al., 2021; Spath and Mann, 2001).
3. Results & discussion
3.1. Technical process evaluation
The technical evaluation for the five hydrogen production processes
examined in this work was performed based on their material balance,
Fig. 7. Material balance of feedstock, products, and direct reaction effluents for the production routes of 9.0 tons H2 per hour of operation. TG denotes PSA tail
gas emissions.
8
Journal of Cleaner Production 428 (2023) 139475
energy requirements and their breakdown by type, along with specific
energy consumption.
Provided in Fig. 7 is the material balance for each of the five
hydrogen production processes, highlighting the main inlet feedstock
and outputs (i.e., hydrogen and by-products) along with direct effluents
from the reactions. For the hourly production of 9.0 tons H2, fixed for all
H2 production processes), H2SMR requires ~30% less CH4 feedstock
compared to SMR w/wo CCUS which highlights lower requirements for
sales gas to be drawn from transmission lines, otherwise routed for other
energy or industrial applications. Conversely, CH4Pyrol required 2.3
times the amount of CH4 feedstock compared to SMR w/wo CCUS, and
3.4 times that required for H2SMR. The required CH4 feedstock for
CH4Pyrol can be reduced by 30% through increasing reaction temper­
ature to 1773 K from the 1473 K operating temperature considered in
this work, effectively increasing the reaction conversion to 100% (Keipi
et al., 2016). However, this will be associated with additional supply of
fuel gas to the reactor’s combustion segment, compared to the case
considered herein (i.e., 1473 K), which is self-sufficient by utilizing
unreacted CH4 as a source for reactor’s energy.
Conversely, the required H2S feedstock mass rate for H2SMR is
S.M. Ali et al. Journal of Cleaner Production 428 (2023) 139475

almost two-order of magnitude to that of H2O required for the bench­ compared to SMR + CCUS is due to higher heating requirements for
mark grey and blue hydrogen, yet almost half of that required for thermal energy for the CS2 reboiler, and the amine regenerator reboiler
H2SPyrol for the same H2 production rate, owing to the latter’s lower with additional load to ensure 100% selective H2S removal from product
overall conversion rate, which would add larger stress on upstream H2 stream, as the downstream PSA unit was not conventionally designed
processing to obtain pure H2S feedstock at the required rates. A prime for H2S separation. The additional energetic load associated with
advantage of H2SMR is the absence of direct CO2 generation (emitted in H2SMR as a hydrogen production process seem acceptable compared to
SMR, or captured in SMR + CCUS), alternatively hourly producing 70.06 SMR + CCUS, given the absence of direct CO2 emissions from the
tons of CS2 and 35.00 tons of elemental sulfur, with higher marketable former, along with higher versatility in terms of generated value-added
value compared to CO2, also seen with H2SPyrol, only producing products (see Fig. 7).
elemental sulfur at an hourly rate of 143 tons. The advantage of addi­ Conversely, the energetic differences are even larger in the case of
tional marketable by-products is also seen with CH4Pyrol, producing H2SPyrol across all processing sections, given the larger H2S feedstock
solid carbon black at an hourly rate of 26.8, with no direct CO2 gener­ processing rate for the same target hydrogen production rate. H2SPyrol
ation. Surely, the absence of direct CO2 generated from the H2 produc­ required 2.54 times the specific energy for its counterpart CH4Pyrol,
tion technologies, aside from SMR, would significantly contribute to the associated with higher energy for reaction, cooling, and heating
greenness of H2S-based and CH4 pyrolysis H2 production processes, requirements.
while reducing capital investment associated with the inclusion of the Depicted in Fig. 9 is the energy consumption based on the different
CCUS value chain.
Furthermore, although H2S-based technologies have, a priori, the
potential of meeting the H2 demand with low to null CH4 consumption
compared to CH4-based technologies, several aspects need attention. On
one level, H2S is classified as a hazardous material due to its high
toxicity, requiring appropriate handling and treatment measures to
ensure occupational health and safety. This will inherently add to the
economics of the process for the installation of stringent safety measures
and monitoring systems (Chan et al., 2023). On another level, H2S is not
widely availability as a feedstock, considering that H2S is mainly found
in sour gas reservoirs in specific regions such as the Middle East, China,
Russia, and parts of South America (Chan et al., 2023). As such, the
deployment of H2S-based hydrogen production technologies would be
confined in those regions. This will open an opportunity for those re­
gions, as it is expected imminent access to highly sour gas fields
considering the high demand for natural gas, forcing oil and gas pro­
ducers to tap into these reservoirs with high H2S content.
Provided in Fig. 8 is the energy requirement mapping for the
different processes, categorized per processing section including reac­
tion, feedstock/products heating and cooling, and compression and
pumping. Interestingly, among the different technologies, CH4Pyrol had
the least energy requirements, with its low reaction enthalpy, and the
absence of thermal energy for streams heating, requiring 63% of the
thermal energy needed for the current benchmark SMR process.
Examining the alternative H2S-based processes, the energy associ­
ated with hydrogen production from H2SMR is 80% higher than SMR,
and 14% higher than SMR + CCUS. The relative similarity between
H2SMR and SMR + CCUS is due to the latter’s integration with amine- Fig. 9. Breakdown for energy consumption for the H2 production processes
based capture unit to reduce the carbon footprint of the process, with based on energy type. RXN stands for energy from the reactor and all auxiliary
amine-based absorption utilized in H2SMR for H2S selective removal heating to maintain reactor temperature, while heating refers to energy for
upstream of the PSA unit. The larger energetic consumption of H2SMR process heating apart from the reactor.

Fig. 8. Breakdown for energy requirements for the H2 production processes based on processing sections (see Fig. 1). Color code: green stands for the reaction, blue
for cooling, purple for compression and pumping, and red for heating.

9
S.M. Ali et al.
energy categories. It is observed an increase in share of thermal energy
for cooling, and reduction in the share of electrical energy requirements
from total energy consumption from conventional hydrogen processes
(i.e., SMR-based), to H2S-based processes. This is associated with the
additional by-products obtained with H2S-based hydrogen production
processes and the need for their recovery and purification with higher
cooling loads on the sulfur condenser and amine cooler for the purifying
H2S from the product H2 stream. Note that for the different H2 pro­
duction processes, similar thermal heating energy proportions are
required as heating is mostly required for the reaction section, with the
exception for CH4Pyrol (see Fig. 8). For this process, lower proportion
for thermal energy are needed compared to the other hydrogen pro­
duction technologies, primarily due to the lower reaction enthalpy,
coupled with the lack of intensive cooling demand for by-product re­
covery as seen with H2SPyrol for the sulfur condensation process, still on
the expense of higher share of electrical energy requirements for gas
compression around the PSA unit, which can impact the carbon foot­
print depending on the degree of decarbonization of the electricity grid.
The high electricity demand for CH4Pyrol compared to SMR has also
been observed in other works (Oni et al., 2022). Notwithstanding, the
higher thermal cooling energy for the H2S-based processes can be seen
as a bonus for waste heat recovery that can further reduce their overall
energetic consumption once these processes have been further refined
and optimized.
Based on the previous energy mapping of the different processes, we
opted to use the specific energy consumption (SEC) related to energy
inputs (i.e., thermal heating and electrical) as a metric allowing the
direct comparison between the different processes, and results are
shown in Fig. 10. For H2 production the SEC ranking follows the order of
CH4Pyrol < SMR < SMR + CCUS < H2SMR < H2SPyrol. Interestingly,
CH4Pyrol is found to be the least energy intensive process, even
compared to the current benchmark SMR, with the least SEC, being 18%
lower than that for SMR. Additionally, CH4Pyrol’s SEC is almost half of
that required for SMR + CCUS, the new baseline, considering the current
direction in legislations towards net zero emissions. Interestingly,
H2SMR’s SEC of 148.94 MJ kg of H2 is relatively similar to that of SMR
+ CCUS at 148.46 MJ kg of H2. Such comparable levels of energy in­
tensity support the potentiality of H2SMR given the production of CS2
and Sulfur by-products, rather than CO2 as seen with SMR + CCUS, with
the higher marketability of the former. Moreover, the pyrolysis of
methane seems to be a far more energy efficient approach compared to
that for H2S, with 2.54 times increase in SEC shifting from CH4Pyrol to
H2SPyrol, mainly on account of the latter’s energy intensive cooling
requirements. CH4Pyrol’s high energy efficiency can be attributed to its
relatively similar heating and cooling energy profiles compared to the
other processes. Hence, on a general energetic basis, it can be surmised
that methane reforming in the presence of H2S rather than water is
equally energy intensive, however, with larger versatility for value-
added products for H2S-methane reforming. This is the opposite case
for pyrolysis reaction, with methane pyrolysis being least energy
intensive, while producing a high in-demand by-product.
Fig. 10. Specific energy consumption for thermal heating and electrical energy inputs for H2 production processes per kg H2 produced.
10
Journal of Cleaner Production 428 (2023) 139475
3.2. Economic assessment
To assess the added advantage of the alternative hydrogen produc­
tion technologies, an economic analysis was performed, considering
incurred capital and operating costs, evaluated using the thermody­
namic conversion, economic assumptions and costing methodology
provided in Sections 2.2 and S2 in the SI. Hence, results should be
evaluated under these assumptions.
The first evaluated economic indicator was the TAC for each process
divided by each cost component (i.e., CAPEX, FOM, and VOC), shown in
Fig. 11. Among the different H2 production processes, SMR remains to
be the most economically feasible, with a yearly TAC of $180 MM, with
an additional $138 MM for the addition of CCUS to ensure reduced
production process carbon footprint as with SMR + CCUS. The shift in
the reaction scheme to CH4Pyrol exhibited 60% higher CAPEX and FOM
than SMR, along with larger VOC due to higher methane feedstock re­
quirements, resulting in a 43% increased TAC, yet 19% lower than SMR
+ CCUS. Interestingly, H2SMR process required an additional $75 MM
yearly investment compared to SMR for similar H2 production capacity.
Additionally, despite the higher CAPEX for H2SMR compared to SMR +
CCUS (8% higher), the total annual investment costs are 20% lower
drawing on the advantage from eliminating the need to manage direct
CO2 by-product. Considering that CO2 and CS2 separation processes are
based on the same principles, the latter has a higher added economic
value, along with lower capital investment costs (see Fig. S1 in the SI).
H2SMR process economics has the potential to significantly improve
with the inclusion of generated revenue from the sales of the produced
CS2 and Sulfur that can result in annual revenues of $320 MM and $8.1
MM, respectively, at assumed market prices of $550 per ton CS2 and $40
per ton S, still larger than the potential $136 MM revenue from CO2 sales
at a market value of $350 per ton (IndexBox, 2022). Note that this is a
conservative estimate for sulfur selling price, with higher economic
added value if considering current market price of $240 per ton
(ChemAnalyst, 2022). The required yearly investment cost is higher in
the case of H2SPyrol with $313 MM, primarily due to the larger H2S
processing scale compared to H2SMR, however, with lower potential
annual revenue of $47 MM, as sulfur is the only by-product from this
process. The economics of the pyrolysis route are more in favor for
methane over H2S, with the 18% lower annual investment requirements,
in addition to higher potential revenue with $111 MM from the sales of
carbon black at $500 per ton, with current forecasts of quadrupled
product value in the upcoming years (Sánchez-Bastardo et al., 2021).
Note that in all these cases the cost of further separation, conditioning
and transportation of the co-products, which impact the overall cost of
production, has not been considered, as they are out of the scope of this
work.
For the five processes, the variable operating costs are the largest
contributor to the yearly investment outlays, roughly 60–65% of the
TAC, for all processes except for H2SPyrol, compared to yearly CAPEX
and fixed operating costs, mainly due to the costs of reactant feedstock
and electricity, seen from the VOC breakdown in Fig. S2 in the SI. These
S.M. Ali et al.
Fig. 11. Breakdown for TAC for the H2 production processes based on cost contributors. Color code: green stands for CAPEX, blue for FOM and red for VOC.
economics and subsequent environmental impact from indirect CO2
emissions can significantly change depending on the electricity source,
with electricity from renewable energy being more expensive however,
with lower carbon footprint. Additionally, increasing yearly CAPEX
outlays are in the order of SMR < CH4Pyrol < H2SMR < SMR + CCUS <
H2SPyrol, with the breakdown based on processing sections in Fig. S1 in
the SI, with more costly reaction section for SMR and SMR + CCUS, and
more expensive H2 purification section for H2S-based processes due to
stringent limits on allowable H2S in produced H2 stream.
Based on the previous economic assessment, the minimum hydrogen
selling price captured through LCOH was calculated as an additional
economic indicator provided in Fig. 12. Note that these results exclude
the contribution from carbon pricing and consider the current market
price for the by-products. The calculated LCOH for grey H2 from SMR
was $2.400 per kg, within acceptable values to those reported in the
literature (Parkinson et al., 2019). The integration with CCUS to produce
blue H2 with appropriate CO2 management increased the H2 LCOH by
$1.840 per kg depending on the inclusion of CO2 transportation and
storage cost ($22 per ton). At the same H2 production scale and CO2
capture rate, the LCOH for SMR + CCUS obtained in this work is 18%
higher than that reported in the literature (Parkinson et al., 2019) due to
relative differences in the assumed operating conditions and number of
syngas shift and methanation process stages. Considering current di­
rection in legislation towards net-zero emissions by 2050, the govern­
mental pressure is increasing preference towards blue H2 with the
additional 76% increased H2 production price needed for partial CO2
abatement for SMR. The inclusion of economic gains from CO2 utiliza­
tion has the potential to erode this incremental increase, with a break­
even at CO2 carbon offset price of $175 per ton. Considering the current
Fig. 12. LCOH for the different H2 production technologies excluding carbon
pricing. Colored arrows denote change in LCOH with technology transition,
while black arrows denote change in LCOH with revenue from by-product sales
at their current market price.
11
Journal of Cleaner Production 428 (2023) 139475
market price for CO2 at $350 per ton, it can offset the LCOH for SMR +
CCUS to $2.410 per kg, which is almost the same as that for SMR.
Processes for SMR + CCUS and H2SMR are relatively identical with
the difference being the use of H2S rather than H2O as a feedstock, and
the functionality of the purification processing section for CS2 recovery
rather than CO2. Transitioning from SMR + CCUS to H2SMR reduced the
LCOH by 20% reaching $3.380 per kg, considering no revenue genera­
tion from by-products sales. This cuts the addition in LCOH from SMR to
another technology integrated with by-product recovery by roughly
50%, with an increase in LCOH from SMR to H2SMR by 40% instead of
80% seen with SMR + CCUS. Inclusion of added economic value from
CS2 and sulfur by-product sales, $550 and $40 per ton, respectively,
further reduces the LCOH to be within the negative range reaching $
− 1.000 per kg, indicating its potential to produce H2 at very competitive
LCOH. Inclusion of sensitivity to CS2 market price (see Fig. S3 in the SI)
with a − 50% – + 50% variation from the current market price (i.e., $550
per ton) showed null LCOH at a breakeven CS2 market price of $440 per
ton, without revenue from sales of sulfur by-product, with further
decline in market price resulting in a positive LCOH within $1.000 per
kg. As already mentioned, these values would be different if the needed
steps to conditioning the co-products, their transportation and storage
are added (out of the scope of this work); however the comparison is fair
as they all were calculated with the same gate-to-gate assumptions.
Alternatively, transition from H2SMR to H2SPyrol through changing
the governing reaction, increases the LCOH by 23%, reaching $4.170 per
kg without sulfur sales revenue, becoming more expensive than SMR by
74%, while almost matching the LCOH of SMR + CCUS without the
inclusion of revenue from CO2 sales. Its economic competitiveness be­
comes solely dependent on sulfur market price. With the sulfur selling
price considered in this work (i.e., $40 per ton), adjusted LCOH with
generated revenue reaches $3.537 per kg, 17% lower than SMR + CCUS.
Changes in market prices for Sulfur byproduct by 50% from current
market price would merely result in 9% reduction in LCOH for H2SPyrol
(see Fig. S3 in the SI). There is still room to enhance the economic
attractiveness of H2SPyrol considering improvement in current sulfur
market price in Asia, reaching $240 per ton (“ChemAnalyst,” 2022),
which as a first approximation can potentially reduce its LCOH to
$0.349 per kg. Parallel to it, the change of reactant for the pyrolysis
process with methane rather than H2S, results in a 3% increased LCOH at
$3.420 per kg, which is relatively lower than the base LCOH of SMR +
CCUS without CO2 sales revenue. Additionally, the inclusion of by-
product sales revenue has a larger impact on offsetting CH4Pyrol by
46% reduction in LCOH, compared to 15% reduced LCOH for H2SPyrol,
on account of the higher market value for carbon black, which puts
CH4Pyrol at a lower LCOH of $1.930 per kg compared to SMR, which is
in agreement with similar economic analysis (Oni et al., 2022). Further
enhancement in market prices for carbon black considering its increased
demand and market growth can potentially offset the LCOH by 38% in
case of a 50% in carbon black market price (see Fig. S3 in the SI).
S.M. Ali et al.
Lastly, the LCOH for the technologies examined in this work were
also obtained considering an average carbon tax of $100 per ton (Reu­
ters, 2023) to determine the sensitivity of the LCOH to carbon tax,
included in Table 1. In the case of SMR, the inclusion of carbon tax
increased the LCOH by 34% due to the generated CO2 emissions without
any economic gains as no byproduct is obtained from the process.
Similarly, for SMR + CCUS the inclusion of carbon tax was accompanied
by an increase in LCOH, being more noticeable when both carbon tax
and CO2 sales are accounted for, increasing the LCOH by 15% from its
$2.410 per kg H2. Similar results are seen for CH4Pyrol, H2SMR, and
H2SPyrol increasing their LCOH from the base case with byproduct sales
and without carbon tax by 16%, 20%, and 7%, respectively, showing less
sensitivity for H2SPyrol to carbon tax.
3.3. Life cycle assessment
A comprehensive LCA was conducted for the different H2 production
technologies (see Table S7 in the SI), with particular attention paid to
CO2 and water footprints of the processes, implemented in the context of
the LCA shown in Fig. 13. The results of the LCA are in agreement with
literature values for SMR in terms of GWP of 11.63 kg CO2-eq per kg H2
(Oni et al., 2022; Parkinson et al., 2019). Similarly, the GHG emissions
for SMR + CCUS at 60% capture rate of 7.70 kg CO2-eq per kg H2 and for
CH4Pyrol with 6.92 kg CO2-eq. per kg H2 are in agreement with avail­
able literature values (Oni et al., 2022; Parkinson et al., 2019), vali­
dating the reliability of our approach. However, to our knowledge, there
are not LCA available in the literature for the comparison of the two
H2S-based hydrogen technologies considered in this work, being this the
first study addressing it.
Producing H2 via H2SMR resulted in the lowest CO2-eq. emissions (i.
e., 4.50 kg CO2-eq per kg 1 to SMR, SMR + CCUS, and CH4Pyrol,
avoiding emission of 7.13, 3.20, and 2.42 kg CO2-eq. per kg H2 pro­
duced, respectively. The large departure in GWP for H2SMR compared to
SMR can be seen from the 78% lower associated GHG emissions for plant
operation (see Fig. S4 in the SI), with the former’s absence of direct CO2
emissions and lower methane feedstock requirements for the reaction
section. The emissions from H2SMR operation are associated with in­
direct CO2 emissions from fuel consumption for heating. This is also seen
with H2SPyrol’s lower associated GHG emissions compared to SMR and
SMR + CCUS, albeit being higher than H2SMR, due to its higher energy
demand for thermal heating and reaction.
Although CH4Pyrol can be seen as a CO2-free production route, with
the absence of direct CO2 emissions from the reaction section, still, the
higher methane feedstock requirements translated to higher fugitive
emissions during product delivery, with a lower extent in the other
processes utilizing methane. The impact of higher methane fugitive
emissions in CH4Pyrol contributed to its comparable IPCC-GWP-20yr to
SMR + CCUS.
Electricity consumption is another major contributor to the life cycle
emissions for all processes, with the largest seen for SMR + CCUS and
CH4Pyrol, due to their higher electricity consumption (see Fig. 9). This is
Table 1
Variation in LCOH for the five technologies considering the effect of carbon tax
($100 per ton) and byproduct sales.
LCOH SMR SMR + CH4Pyrol H2SMR H2SPyrol
CCUS
Without carbon tax or 2.400 4.240 3.420 3.380 4.170
byproduct sales
With carbon tax/ 3.220 4.590 3.730 3.730 4.400
without byproduct
sales
Without carbon tax/ 3.220 2.410 1.930 − 1.000 3.537
with byproduct sales
With carbon tax and 3.220 2.760 2.240 − 0.800 3.770
byproduct sale
12
Journal of Cleaner Production 428 (2023) 139475
largely dependent on the regional context of electricity drawn from the
grid, as different countries have varying monetary and environmental
costs associated with their energy grids. This can be seen from the
lowering of the carbon footprint for all processes by 16–30% when
basing the LCA on the decarbonized electricity grid for France with 0.04
kg CO2-eq.kWh− 1, compared to the base case used in this work for the
European Union (EU) electricity grid with an average carbon intensity of
0.275 kg CO2-eq.kWh− 1 (Parkinson et al., 2019) (see Fig. S5 in the SI).
Accordingly, H2S-based H2 production technologies carry lower nega­
tive emission related impact, with reduced direct and indirect GHG
emissions for H2 production, considering the primary purpose of pro­
ducing H2 is its cleaner combustion compared to conventional fossil
fuels. Hence, it stands to say, the low level of emissions associated with
H2SMR classifies it as low-carbon hydrogen production processes ac­
cording to EU CertifHy™ framework, with a carbon footprint lower than
4.40 kg CO2 per kg of H2, irrespective of the level of decarbonization of
the electricity grid (Griffiths et al., 2021; IEA, 2023).
Interestingly, CH4Pyrol had the least water footprint with 5.15 kg
water per kg H2 due to the absence of water as a feedstock and the low
cooling requirements. Alternatively, H2S-based hydrogen production
processes are the largest water consumers, which is rather indirect pri­
marily in the form of cooling water, with H2SMR and H2SPyrol requiring
172 and 207 kg water per kg H2 as seen from the high order of magni­
tude for thermal cooling for by-product recovery (see Fig. 8). The direct
water footprint for SMR (i.e., steam reactant) constituted 20.0% of the
total water consumption in the process, with the remainder being
directed for process cooling requirements. It can still be argued that the
alternative pathway for H2 production from H2S in addition to CH4Pyrol
are less water intensive in the sense that low quality water can be used
for stream cooling, as opposed to high quality water used as a reactant
with SMR and SMR + CCUS directly consuming ~4–5 kg H2O per kg H2
produced. As such, the water footprint of the alternative processes can
be null, helping in preserving high quality water within the UN’s SDG
goals.
4. Conclusions
In this work, the techno-economic feasibility and lifecycle environ­
mental assessment of large-scale hydrogen production through
emerging H2S-based thermal non-catalytic hydrogen production pro­
cesses (i.e., H2SMR, and H2Pyrol) were showcased compared to con­
ventional SMR and SMR+CCUS and CH4Pyrol as CH4-based processes.
Amongst all studied technologies, and with the explained assumptions,
CH4Pyrol was found to be the least energy intensive process with min­
imum water-footprint and economics comparable to SMR + CCUS, being
the most attractive technology among the five of them. H2SMR was
found to be comparable in energy consumption to SMR+CCUS, serving
as a competitive substitute for hydrogen production from H2S utiliza­
tion, while minimizing the direct CO2 emissions associated with the
hydrogen production process, qualified as a low-carbon hydrogen pro­
ducing technology. The high economic value of H2SMR by-products
including CS2 and sulfur resulted can potentially offset the investment
costs resulting in a negative LCOH of $ − 1.000 per kg compared to SMR,
SMR+CCUS, and CH4Pyrol LCOH of $2.400, $2.410, and $1.930 per kg,
respectively. Conversely, H2SPyrol is less economically profitable than
H2SMR due to the lower revenue generated from its only by-product
(sulfur) resulting in LCOH of $3.537 per kg which is yet still lower
than the LCOH of SMR+CCUS process without CO2 sales revenue, yet
not as economically advantageous as CH4Pyrol. Notwithstanding, it is
expected that the economy of scale of H2SMR will further improve under
higher actual overall H2S conversions proven by experimental analysis
and at lower reactor temperature, compared to the conservative as­
sumptions included in this work.
We stress that the results presented here depend on the stated as­
sumptions, including, for instance thermodynamic considerations for
each process used in the detailed techno-economic assessment, and will
S.M. Ali et al.
Fig. 13. CO2 emissions footprint and water footprint for producing 1 kg H2 from the different H2 production technologies investigated in this work.
vary for instance, with the inclusion of reaction kinetics and the role of
catalytic reaction routes, to be considered in future works.
From an environmental angle, the conducted gate-to-gate LCA
showed the lower contribution to global warming potential for the
alternative emerging H2SMR and H2SPyrol processes compared to SMR
and SMR + CCUS, due to the absence of direct CO2 emissions from the
hydrogen production reaction. However, the water intensity for these
processes remains relatively high, not from direct steam feedstock
consumption, but rather from the higher cooling requirements. Addi­
tionally, the absence of direct CO2 emissions from CH4Pyrol, H2SMR and
H2SPyrol also proved the added benefit of these technologies in sup­
porting the race to net-zero emissions by 2050.
The results of this work establish the larger spectrum benefits on
technical, economic, and environmental facets for deployment of large-
scale H2S-based hydrogen production processes as well as its current
limitations, with the main shift in transition from steam to H2S-based
methane reforming in regions where H2S is available. However, this is
not as advantageous when considering the pyrolysis route, with the
emerging CH4Pyr technology being highly competitive to SMR and SMR
+ CCUS, with no merits for shifting from CH4Pyrol to H2SPyrol.
CRediT authorship contribution statement
Sawsan M. Ali: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Writing – original draft. Ismail I.I.
Alkhatib: Formal analysis, Validation, Visualization, Writing – review &
editing. Ahmed AlHajaj: Formal analysis, Writing – review & editing.
Lourdes F. Vega: Conceptualization, Methodology, Project adminis­
tration, Resources, Software, Funding acquisition, Supervision, Writing
– review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work was funded by Khalifa University through project RC2-
2019-007 to the RICH Center. Computational resources from the
Research and Innovation Center on CO2 and Hydrogen (RICH Center)
and the Almesbar HPC at the Research Computing department at Khalifa
University are gratefully acknowledged. The authors also acknowledge
13
Journal of Cleaner Production 428 (2023) 139475
the useful discussion with the under-secretary of the Ministry of Energy
and Infrastructure of the United Arab Emirates, His Excellency engineer
Sharif Al Olama.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2023.139475.
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