i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

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Review Article

Hydrogen from hydrogen sulfide: towards a more

sustainable hydrogen economy

Antonio G. De Crisci*, Armin Moniri, Yuming Xu

Department of Natural Resources Canada, CanmetENERGY in Devon, 1 Oil Patch Drive, Devon, Alberta, T9G 1A8,
Canada

article info abstract

Article history: The decomposition of hydrogen sulfide (H2S) with simultaneous hydrogen (H2) generation
Received 31 July 2018 offers a sustainable energy production option and an environmental pollution abatement
Received in revised form strategy. H2S is both naturally occurring and human-made. In the future, H2S production is
3 October 2018 expected to increase due to increased heavy oil refining. Currently, H2S is largely converted
Accepted 5 October 2018 to sulfur and water using industrial processes such as the Claus process, however, it would
Available online 14 December 2018 be more useful and economical to convert H2S to sulfur and H2 instead. H2 currently comes
from the steam reforming of natural gas, which is an energy-intensive process. Because H2
Keywords: is a valued commodity and global consumption is expected to increase, alternative sources
Hydrogen sulfide of H2 and hydrogen conservation have become topics of active research. Alberta is an
Hydrogen production especially large consumer of H2 due to its oil sands processing. H2 from petroleum-based
H2S decomposition H2S sources could be reused in petroleum upgrading, as a partial replacement of steam
Oil sands methane reforming. This review paper highlights some of the methods of H2S utilization,
Petroleum upgrading such as partial oxidation, reformation and decomposition techniques and approaches that
H2S utilization convert H2S to sulfur, water and, more importantly, H2. To date, almost no technologies
exist that are suitable for converting H2S to sulfur and H2 for industrial-scale applications.
Here, we survey the literature to identify the most promising approach.
Crown Copyright © 2018 Published by Elsevier Ltd on behalf of Hydrogen Energy Publica-
tions LLC. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1300
H2S sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1300
Hydrogen use from H2S sources in oil sands processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1301
H2S utilization processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1302
H2S partial oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1303
H2S reformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1305
H2S decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1305
Thermodynamic considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1305

* Corresponding author.
E-mail address: antonio.decrisci@canada.ca (A.G. De Crisci).
https://doi.org/10.1016/j.ijhydene.2018.10.035
0360-3199/Crown Copyright © 2018 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. All rights reserved.
1300 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Thermal, catalytic and membrane-assisted decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1306

Photocatalytic decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1308
Direct decomposition using non-thermal plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1313
Thermochemical decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1315
Electrolysis decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1317
Biological decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1319
Technological assessment overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1319
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1321
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1321
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1321

enable the recovery and recycling of H2, significantly reducing

Introduction
Hydrogen sulfide (H2S) is a toxic [1] and corrosive substance
which is present either naturally in aqueous form (e.g. the
Black Sea) or gas form (e.g. natural gas wells and gas hydrates),
or can be generated by industrial processes (e.g. petroleum
industry). Along with its characteristic foul odour of rotten
eggs, harmful effects of H2S on life are seen at air concentra-
tions of 10 ppm. In human exposure it can cause eye damage
at 50 ppm, and death at 320 ppm. Considered a broad spec-
trum poison, it quickly binds with iron-containing complexes
in the body, preventing normal cellular respiration. H2S has
been implicated in many biological processes and has even
influenced evolution [2]. Despite its toxicity, H2S has a variety
of industrial uses, from metallurgy to manufacturing,
including the pulp and paper industry, the production of
elemental sulfur and sulfuric acid. Worldwide, H2S production
(from both petroleum and natural sources) has reached 10
million tons per year and is expected to increase further.
Most H2S is currently oxidized and converted to sulfur and
water [3,4] via a sulfur dioxide (SO2) intermediate from the
Claus process. In some processes, SO2 can be made directly by
oxidative desulfurization using ozonized air in straight-run
residual fuel oil [5]. Now used on a commercial scale, the
Claus process involves a non-catalytic combustion step,
which is highly exothermic and produces SO2, which then
reacts with more H2S in the presence of catalyst to produce
elemental sulfur, a more environmentally friendly and less
hazardous product than H2S. In some cases, up to 99.9% pure
elemental sulfur can be achieved [6]. However efficient the
Claus process may be, it has two major drawbacks. One is that
one of the products is water, not hydrogen (H2), H2 being
preferred because it is a higly desirable commodity with a
wide range of applications, especially in the energy and
chemicals industry. The second drawback is that the Claus
process requires a further step in which H2S and unconverted
impurities are burned to form SO2 which requires additional
energy input and emits sulfur in the tail gas even at the
highest recovery efficiencies.
Alberta, Canada is a large producer and consumer of H2
[7,8] generated from steam reforming of natural gas. During
the upgrading and refining of sour crudes, H2S is generated as
a by-product from hydrotreating processes. Creating H2 from
the H2S generated from these industrial processes, may
the need to acquire new H2 sources and reducing costs. Global
H2 consumption is estimated at around 680 billion normal
cubic meters (Nm3) [9], largely due to oil refining. In addition,
H2 has the potential of being integrated into the fuel cycle for
energy storage carriers, resulting in no emissions of air pol-
lutants [10]. H2S and natural gas (a very abundant, ubiquitous
resource) have been discussed as potential feedstocks in a
solid oxide fuel cell for energy generation [11]. More broadly,
various techniques exist for splitting H2S into sulfur and H2,
two valuable commodities with wide applicability [12]. How-
ever, large-scale H2 production processes from H2S have not
yet been developed, likely for economic or technical reasons
[7,13,236]. Therefore, H2S utilization has been a topic of
increasing research interest [14e19].
This review is written to inform readers of some of the
progress that has occurred or is occurring in the field of H2S
utilization, with emphasis on H2 production from H2S decom-
position. Topics include H2S sources, H2 use from H2S, and H2S
utilization. H2S utilization is discussed in three sections, 1) H2S
partial oxidation, 2) H2S reforming, and finally 3) H2S decom-
position. The latter section has seen the most efforts to date
and includes decomposition techniques such as thermal (cat-
alytic/membrane-assisted), photocatalytic, non-thermal
plasma, thermochemical, electrolysis, and biological pro-
cesses. Our aim is to inform the readers of this review of the
most promising method(s) for H2 production from H2S.
H2S sources
The chemistry of H2S has been studied since the 1600s, and
production of H2 from H2S has been known since at least the
19th century [20]. Petrus Johannes Kipp was a Dutch phar-
macist who invented an apparatus, coined the Kipp gener-
ator, which can produce H2S or H2, depending on the
reactants used [21]. Natural sources of H2S include
geothermal sources, [20], marine sediments, [22], agricultural
waste sectors, [23], and coal seams [24] and are mainly
derived from bacterial activity involving redox reactions of
biochemically active microorganisms in deeply buried oil and
gas reserves [25e27]. The Black Sea has been a location of
interest for decades because of its H2S content [28e30]. It
contains a large anoxic zone and is considered 90% anaerobic.
H2S concentration steadily increases from the anoxic
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
interface, reaching a value of 300 mM at 1000 m, increasing to
400 mM at 1900 m, where the concentration of H2S remains
unchanged. It is estimated that the total sulfide production
from the sediments in the Black Sea is 10,000,000 kg/day and
the H2S content is increasing because the sea has not yet
reached a steady state [28]. In some parts of the world, natural
sources of H2S can poison nearby workers; for example,
landfills emit H2S and its concentration levels depend directly
on the rate of municipal solid waste degradation and the
vertical distribution of sulfide, in addition to microbial ac-
tivities related to sulfur, nitrogen (N2), and iron [26,27,31e33].
Other H2S sources include those related to oil and gas pro-
duction, and petroleum upgrading and refining. A large vol-
ume of H2S is also produced along with natural gas
production. H2S is generated by aquathermolysis and ther-
molysis of heavy oil under thermal recovery conditions such
as SAGD (steam-assisted gravity drainage) or CSS (cyclic
steam stimulation) [34]. H2S is a by-product from the sweet-
ening of heavy oil, bitumen, and coal, [35], and can be a sig-
nificant component of oil and gas upstream production.
Heavy oils tend to contain more impurities than their
lighter counterparts, and thus heavy oils require extra refining
resources. Hydrodesulfurization (HDS) of crude is one of the
major catalytic processes utilized to remove sulfur from pe-
troleum products. The Athabasca deposit of northern Alberta
contains 1.8 trillion barrels of oil [36] and many of the heavy
oils have high sulfur contents (‘sour’ oils) with an estimated
amount greater than 2 wt% [37] resulting from the generation
and concentration of organic sulfur compounds during
biodegradation [38]. Extra heavy crude oil, such as bitumen
from the oil sands of Alberta, Canada, can be upgraded (before
it is refined) to obtain synthetic crude oil (SCO). Upgrading
typically occurs in two stages: primary upgrading and sec-
ondary upgrading. Fig. 1 (a) and (b) show two pathways for
Alberta's diluted bitumen and a generic process flow diagram
for a typical bitumen upgrader, respectively.
The classes of compounds responsible for H2S formation in
crude oil refining and upgrading are thiols, thioethers, disul-
phides, and heterocyclic sulfides (e.g. thiophenes, dibenzo-
thiophenes, etc.). It is estimated that there are over 3000
different sulfur-containing compounds in crude oils [25] all of
which are amenable to the H2S-forming hydrodesulfurization
(HDS) process. Eqs. (1)e(4) show the stoichiometry of some
HDS reactions;
R-SH þ H2 / ReH þ H2S
R1-S-S-R2 þ 2H2 / R1-R2 þ 2H2S
R1-S-R2 þ H2 / R1-R2 þ H2S
C4H4S þ 4H2 / C4H10 þ H2S
During upgrading, carbon rejection is one method used to
increase the H2-to-carbon ratio of bitumen. The rejected car-
bon can be used as fuel for gasification [40]. Asphaltenes are a
component of bitumen and represent about one-third of the
vacuum residue. Despite the fact that these carbon-rich
asphaltenes are liquid at operating temperatures, they are
1301
very problematic in bitumen upgrading facilities because they
are highly aromatic and contain substantial quantities of coke
precursors, metals, sulfur, and nitrogen, making them diffi-
cult to handle and can result in refinery upsets and fouling
[41]. Asphaltenes can be separated from bitumen by treating
the bitumen with low-boiling-point alkanes in a solvent
deasphalting unit, causing the insoluble components to pre-
cipitate out. The separated asphaltenes can be gasified by
pyrolysis [40]. The by-products of this process are soot and
H2S.
Technologies which convert H2S to valuable products, can
be beneficial to the oil and gas industry from both an envi-
ronmental and economic perspective.
Hydrogen use from H2S sources in oil sands
processes
The transformation of Canadian oil sands resources into
marketable products is very energy-intensive. In particular,
producing the large amount of H2 required to upgrade and
refine bitumen is a major contributor to Canada's overall GHG
emissions [42]. In oil sands upgrading, primary upgrading
cracks the larger molecules into smaller ones (thermal
cracking and hydrocracking), and the bitumen is then further
treated (hydrotreating) to remove sulfur, nitrogen, and other
non-hydrocarbon-based impurities. This process purifies the
hydrocarbon product by converting the sulfur-containing
components to hydrocarbons and H2S in the presence of H2.
Most of the H2 used in this process comes from steam
reforming of natural gas, a significant carbon dioxide (CO2)
emitting process.
Coal gasification is another source of H2 that is seen by
some as a more reliable alternative to natural gas due to its
lower and less volatile pricing [43]. Globally, coal gasification is
increasing, especially in China, largely due to coal's global
availability [43,44]. However, the environmental conse-
quences of this process have led to the development of plants
with CO2 capture, and even co-storage with H2S. With steam
reforming accounting for roughly 48% of H2 production (30%
coming from oil, 18% from coal, and further 4% from elec-
trolysis [45]), it is evident that current commercial methods of
obtaining H2 are energy-intensive and can be considered
environmentally challenging.
A case study of H2SeH2O-splitting cycle in oil sands
(1) bitumen upgrading for H2 production: With the average sulfur
content in Canadian oil sand bitumen ranging from 3.5 to
(2) 5.5 wt.% [46,47], it is considered a sour crude that is a signifi-
cant source of sulfur or sulfur-containing components. In
(3) Alberta alone, sulfur production was 4.4 million tonnes in
2012, with 40% from natural gas and 60% from oil sand
(4) upgrading [48]. For example, in order to process 1.5 million
bbl/day of bitumen, 16.5 million m3/day of H2 is needed to
remove (or convert) the sulfur- and N2-containing species.
This results in the production of about 10,600 tons/day of H2S
[49,50], which is converted to sulfur and water in the Claus
process. Converting the captured (or native) H2S back into H2
would be a convenient source of H2. The amount of H2 that
could be recovered from H2S produced in a typical oil sand
1302 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Fig. 1 e (a) From bitumen production to the refinery: two pathways for Alberta's diluted bitumen (b) A generic process flow
diagram of a typical bitumen upgrader. Figure used with permission from Oil Sands Magazine [39].

upgrading plant can be estimated [51,52]: Assume a plant ca-
pacity of 120  103 bbl/day bitumen which produces approx-
imately 425  103 tonnes/year or 12.5  109 mol/year of H2S. If
the technology to create H2 from H2S is based on the H2SeH2O-
splitting scheme, then 2 moles of H2 are produced from 2
moles of water and 1 mol of H2S (refer to the three-step closed
cycle with iodine, sulfuric acid and elemental sulfur oxidation
in Section Thermochemical decomposition). This would
create 25  109 mol/year of H2 (or 560  106 m3/year) and
12.5  109 mol/year of H2SO4 at standard temperature and
pressure. The recovered H2 could be re-used at the same site
for oil sands upgrading or delivered to other processes
requiring H2, such as refining, treating metals, food processing
or energy generation.
The following section describes methods of H2S utilization
with a focus on H2S decomposition.
H2S utilization processes
There are three main methods at various maturity levels
which utilize H2S in some form or another. Ranging from
bench scale, pilot scale and commercial scale, the methods; 1)
partial oxidation (Eq. (5)), 2) reformation (Eq. (6)) and 3)
decomposition (Eq. (7)), and their associated technologies will
be reviewed, with a focus on H2S decomposition leading to H2
production. The basic chemistry of these methods can be
summarized as follows.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
Partial oxidation: H2S þ 0.5O2 / H2O þ SY
Reformation: 2H2S þ CH4 / 4H2 þ CS2
Decomposition: H2S / H2 þ SY
The most important commercially available partial oxida-
tion technology for processing H2S is called the Claus process
where H2S is first thermally oxidized to SO2 and then is cata-
lytically oxidized to produce elemental sulfur and water
(described in Section H2S Partial Oxidation H2S Partial Oxida-
tion). In the H2S partial oxidation process (DH0298K ¼ 265.2 kJ/
mol), only elemental sulfur and heat can be generated, and
direct H2 production is not possible [53e55].
Reformation of methane with H2S is an unconventional
method that has recently received great attention. As seen in
Eq. (6), 4 moles of H2 and 1 mol of CS2 are produced from
2 moles of H2S and 1 mol of CH4. [53e55] H2S reformation is an
energy intensive process (DH0298K ¼ 232.4 kJ/mol) suitable for
systems with high concentrations of H2S. This technology will
be briefly reviewed in Section H2S Reformation .
H2S decomposition (splitting) to produce H2 (Eq. (7)) is an
endothermic reaction. Methods of this nature have been
extensively researched and will be discussed in Section H2S
Decomposition . At the time of this writing, no commercial-
scale technologies have been reported based on this method.
Processes such as thermal (catalytic/membrane-assisted),
photochemical, non-thermal plasma, thermochemical, elec-
trolysis and biological methods will be discussed, including an
exploration as to possible reasons for the lack of commercial-
scale decomposition technologies.
H2S partial oxidation
Current industrial practices to treat sour streams include
processes where H2S is converted to elemental sulfur. Tradi-
tional sulfur recovery units (SRUs) involve amine separation
where the acid gas (H2S and CO2) is separated from feed gas
(e.g. methane), then CO2 is usually vented out while the H2S
stream is converted to elemental sulfur and water through the
Claus process. The Claus process can only achieve a sulfur
recovery yield of up to 97%. Therefore, tail gas treatment is
necessary in all SRUs. In the following sections, amine
extraction, Claus reaction, and all available tail gas treatment
processes are discussed.
Amine Extraction: Amine gas treating, also known as
amine scrubbing, or gas sweetening, refers to a group of pro-
cesses that use aqueous solutions of various alkylamines such
as monoethanolamine (MEA), diethanolamine (DEA), meth-
yldiethanolamine (MDEA), diisopropylamine (DIPA), or digly-
colamine (DGA). These solvents remove H2S and CO2 from
sour gas in an amine unit (Fig. 2), and are commonly used in
refineries, petrochemical, and natural gas processing plants.
The main sections of a plant include an absorber, a regener-
ator, plus all accessory equipment [56]. The extracted acid gas
is passed to the Claus unit for sulfur recovery.
Claus thermal and catalytic stages: The Claus process
converts H2S to elemental sulfur and H2O, and is responsible
1303
(5)
(6)
(7)
Fig. 2 e Flow diagram of a typical amine treating process
used in industrial sulfur recovery plants [56].
for most of the sulfur production worldwide [57]. The two-step
process is described in Eqs. (8) and (9), where Eq. (10) is the
overall reaction.
H2S þ 1.5O2 4 H2O þ SO2 (8)
2H2S þ SO2 4 3SY þ 2H2O (9)
2H2S þ O2 / 2SY þ 2H2O (10)
The Claus process combines thermal and multiple catalytic
steps as shown in Fig. 3 [25,56,58]: H2S is oxidized in air (Eq. (8))
to give SO2 at 823 K in the thermal step (approximately one-
third of the H2S is converted), and the remaining H2S reacts
further with the SO2 in the presence of an alumina- or tita-
nium dioxide-based catalyst to give elemental sulfur and
water in the catalytic steps (Eq. (9)) [59]. However, because the
second equation is equilibrium limited, not all of the H2S is
converted. Therefore, tail gas treatment is essential to meet
environmental regulations.
Tail gas treatment: Almost all medium to large refinery
plants require a recovery of more than 99% of the sulfur from
SRUs to meet the stringent SOX emission regulations. Even
with three catalytic reactors, the Claus process can only ach-
ieve a sulfur recovery of 97%. Therefore, tail gas treatment is
essential regardless of the plant capacity. Three main
methods of tail gas treatment are available at commercial
scale: 1) sub dew point (low-temperature), 2) selective or direct
catalytic oxidation and 3) reduction-absorption [60]. Table 1
shows the relative capital cost and recovery ranges in
various sulfur recovery processes of tail gas treatment. The
sub dew point process utilizes a special alumina-based cata-
lyst to further process H2S and SO2 in the tail gas from the
Claus reactor at or below sulfur dew point in a liquid system.
This way more elemental sulfur is produced. However the
catalyst is subject to deactivation due to liquid elemental
sulfur deposition on its surface and so has to be replaced
1304 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Fig. 3 e Typical arrangement of a Claus unit [56].

periodically [58]. The catalytic reduction-absorption process is followed by oxidation of a redox pair by air or oxygen (O2) as
a two-step process where all sulfur compounds are first shown in the following equations.
catalytically hydrogenated to give H2S, followed by a selective
absorption with methyldiethanolamine (MDEA) solution. The 2Fe3þ (aq) þ H2S (g) / 2Fe2þ (aq) þ SY þ 2Hþ (aq) (14)
desorbed H2S is finally recycled back to the Claus unit for 2Fe2þ (aq) þ 0.5O2 (g) þ H2O (l) / 2Fe3þ (aq) þ 2OH (aq) (15)
further sulfur recovery using the Shell Claus Off-Gas treating
process. This process has the capacity to capture the Typical anions for the above reactions include Cl and
maximum amount of sulfur from the feed gas [58]. The H2S- SO2
4 , organic reagents, chelates, cyanide, etc. [53]. Here, SO2
selective catalytic oxidation process includes the following formation is avoided as in the conventional Claus process,
irreversible reactions where Eq. (11) is the main reaction, and thereby reducing costs for tail-gas treatment. However, this
Eqs. (12) and (13) are the side reactions. method does not appear to have been developed further.
A superadibiatic process has been discussed recently [61],
H2S þ 0.5O2 / 1/n Sn þ H2O (11) where, a non-conventional combustion process is achieved
from the addition of O2 in a superadiabtic combustion reactor
1/n Sn þ O2 / SO2 (12) (SAC). This creates a highly exothermic environment, enough
to decompose H2S thermally via excess enthalpy, compared to
H2S þ 1.5O2 / SO2 þ H2O (13) open-air combustion. For instance, by partially oxidizing
1 mol of H2S in a SAC reactor, 10 more moles of H2S are
The H2S-selective catalytic oxidation process is a highly thermally decomposed. One of the most interesting aspects of
promising approach because it is thermodynamically this method is that it allows combustion of very rich or very
favourable and as such, has been researched extensively in lean fuel mixtures that would not support a flame under
recent decades. A comprehensive paper has reviewed the normal conditions and more importantly, CO2 is not created,
most widely-used catalysts (metal oxide-based, carbon-based despite the use of a stream of O2. The basic equations gov-
and clay-supported) and processes (MODOP, Super-Claus, and erning this method are shown in Eqs. (16) and (17):
Euro-Claus) for this sulfur removal method [58].
In addition to the conventional Claus process, an uncon- H2S þ 0.5O2 / H2O þ S (16)
ventional partial oxidation process for H2S has been reported
based on an aqueous redox system [53]. A two-step process H2S þ heat / H2 þ SY (17)
(Eqs. (14) and (15)), where H2S is oxidized to elemental sulfur,
New H2S partial oxidation methods are still emerging.
Despite the Claus process being a very well-established
technique that continues to be improved [62], it has draw-
Table 1 e Comparison of relative capital cost of the claus backs; about half of the H2S handling costs are related to the
tail gas treatment methods [60]. tail gas treatment, which largely consists of N2 from the air
Process Recovery Relative and, more importantly, the conversion of H2 into low-value
capital cost water [63]. This is quite wasteful especially from a thermo-
dynamic point of view, considering that the dissociation
2 stage Claus 94e95 1.0
3 stage Claus 96e97 1.2 energy of H2S is only 0.2 eV per molecule compared to water
3 stage Claus þ1 stage 98.8e99 1.4 at 2.9 eV per molecule [64]. Therefore, with all improve-
H2S-selective catalytic oxidation ments and modifications to reach high sulfur recovery effi-
1 stage Claus þ2 sub dew 98e99.5 1.35e1.45 ciency, modified Claus processes still impose a very high
point process capital cost to the process economy. H2S-selective catalytic
2 Stage Claus þ catalytic 99.5e99.95 1.8e2.2
oxidation has great potential as the most cost-effective
reduction-absorption
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
alternative for tail gas treatment; however the challenges for
this reaction are the reverse Claus reaction and deep
oxidation of elemental sulfur to SO2. In addition, since
catalysis is the biggest core element for this method, the tail
gas treatment process must be developed according to the
particular catalyst. Systematic research on catalytic devel-
opment plays a crucial role in increasing process efficiency
and decreasing the capital cost of tail gas treatment for
almost all modified Claus processes.
H2S reformation
H2S gas is often found in natural gas reserves, and its con-
centration varies from trace to 90%, making separation of H2S
difficult [53,65]. Hydrogen sulfide reformation of methane
(HSRM) may be a viable approach if the natural gas is sour and
of subpar quality. Reformation of H2S and CH4 mixtures,
similar to the already well-established methane steam
reforming process, can generate 2 moles of H2 and 0.5 mol of
CS2 per 1 mol of H2S reacted with 0.5 mol of CH4 (see Eq. (6)). CS2
is a liquid used as a precursor for several industrial processes,
and therefore may provide incentive for further research into
this process. No CO2 is formed unlike the traditional methane
steam reforming techniques [53,66]. Few experimental studies
have been performed exploring this approach. A very recent
study [66] investigated temperature impacts on H2 production
and found that H2 and CS2 concentrations increased at higher
reactor temperatures. The H radical played a significant role in
the decomposition of both CH4 and H2S, while the HS radical
played an important role in CS2 formation. The experiments
were conducted in a plug-flow reactor at residence times of
1.2 s with a temperature range of 1273e1673 K. A numerical
and experimental study was also performed in a plug flow
reactor [67]. The effects of temperature and residence time on
the amounts of H2 produced were investigated over the same
temperatures range. Presence of methane increased H2S con-
version and 95% H2 recovery was achieved. The qualitative
agreement between the experimental and theoretical results
revealed a high potential for further development of this
technology. In the same context, two series of catalysts were
designed to form ceramic phases (ZrO2-SBA15 and ZrO2e
La2O3) and refractory metals (Mo and Cr) to reform methane
with H2S for H2 production [68]. High yield, 64% H2, in the
1073e1123 K temperatures range was achieved. Mixtures of
sulfides and carbides were observed during the reaction, such
as MoS2, ZrS2 and the carbides MoC, Mo3C2. The authors
identified the best catalysts to be CrMo/La2O3eZrO2 and Mo/
La2O3eZrO2 systems. CH4 and H2S conversion rates were
identified to be dependent on temperature and catalyst
composition. However, to achieve high activity and selectivity,
the development of crystalline phases at high temperatures
seemed to be essential.
In another technique for H2S reformation, a modified
version of the sulfur-iodine water-splitting cycle, called the
sulfur-sulfur cycle, was proposed to tackle technical diffi-
culties encountered in the HI decomposition step to avoid
formation of HIeH2O azeotropic mixture [69]. The key step of
this cycle was steam reformation of H2S which was investi-
gated over a variety of catalytic and non-catalytic settings in a
quartz tube reactor [70]. Satisfactory results were achieved
1305
with a molybdenum catalyst, leading to increasing conversion
over non-catalytic trials.
A recent study presented a detailed kinetic and mechanism
study of the decomposition under dilute conditions. To pre-
dict H2 production and conversion of H2S and CH4 accurately
by investigating the effects of temperature and initial H2S/CH4
ratio, a tubular furnace reactor was utilized and the system
was kinetically analyzed using CHEMKIN software. Temper-
ature had a positive impact on conversion of both H2S and
CH4, with increased H2 and CS2 yields, and decreased S2 yields.
Adjusting the initial H2SeCH4 ratio at 1373 K resulted in an H2S
conversion of almost 50%, CH4 around 40%, with H2 produc-
tion at 8%, and CS2 at 0.5% [71].
H2S reformation seems to have great potential for further
development and has recently attracted significant attention.
However, endothermicity of H2S reformation is the biggest
barrier for process development as it makes the economics of
this technology unfeasible. For instance, at temperatures
lower than 1273 K, H2S is essentially an inert gas in this system
[55]. Side reactions, lack of active and selective catalysts, and
the necessity of using high H2S concentrations, are also im-
pediments to commercial deployment.
H2S decomposition
This section surveys literature pertaining to H2S decomposition
to produce H2. Most of the technologies described here are in
early stages of research and quite far from commercialization.
Active fundamental and applied research is still required to in-
crease technology readiness levels (TRLs) [72]. The methods that
are reviewed include thermal (catalytic/membrane-assisted),
photochemical, non-thermal plasma, thermochemical, elec-
trolysis, and biological. There have been some breakthroughs,
especially novel catalysts discoveries for each method, but we
are not aware of any successful demonstration-scale tests at the
time of writing this review.
Thermodynamic considerations
From a molecular point of view, converting H2S to sulfur and
H2 should not readily occur. Being a diprotic acid, H2S has pKa
values of 7.0 and 11.96 in water [73]. Under basic conditions
(e.g. in 0.5 M KOH at pH 13.5), the H2S is dissociated to form
hydrosulfide HS and sulfide S2 [74]. However, the minimum
dissociation energy of H2S (into H2 and sulfur) is only 0.2 eV
per molecule. Such a low energy requirement of dissociation
of H2S into sulfur and H2 provides a foundation for developing
an implementable commercial process. Free energies and
enthalpies have been determined under various conditions
[75e79]. In the gas phase, the formation of H2 from H2S has
been reported to occur at 873 K as a homogenous reaction, and
the calculated DHrxn was 167.4 kJ/mol [75]. The standard Gibbs
free energy and enthalpy of dissociation for H2S are:
DG0 ¼ 33.0 kJ/mol and DH0 ¼ 20.4 kJ/mol, respectively [76e78].
The enthalpy of decomposition of 20.4 kJ/mol for H2S is less
than that for the decomposition of water (286 kJ/mol) or
methane (75 kJ/mol) [20,21]. Despite low dissociation energy
compared to water, the reaction is highly endothermic and
conversions are very poor at low temperatures [35,80]. For
example, thermodynamic equilibria calculations give 20%
conversion at 1273 K; temperatures above 1648 K are required
1306 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
to obtain H2S conversion above 50%. At 1133 K the conversion
is less than 10% and above this temperature, the advantage of
using catalysts decreases since thermally-driven reactions
become a major competitor at high temperatures. Varying the
temperature has a direct influence on the nature of the poly-
atomic sulfur species produced (including sulfanes): diatomic
sulfur is the major sulfur species (91%) above 1023 K [35,81,82].
On the other hand, higher conversions can be achieved at
lower H2S pressures [75]. In some cases, membranes can be
used to separate the H2 product from the sulfur species [83,84]
and influence the equilibrium of products and reactants; this
will be discussed in the next section.
Thermal, catalytic and membrane-assisted decomposition
Considering the thermodynamic implications for H2S
decomposition in the gas phase, we will now discuss methods
that utilize thermal means to decompose H2S to H2 and sulfur,
with and without the use of catalysts. Membrane reactors can
also assist thermal processes by enabling better control of
process conditions and a more effective use of the catalyst.
Thermal Methods (non-catalytic): Thermal decomposition
of H2S to H2 and sulfur has not always been the method of
choice because it is very energy-intensive. However, it may be
preferred because it is simple and direct. Studies have shown
that varying the temperature and pressure has a significant
influence on the molecular composition of the resulting sulfur
products. For example, Torres et al. [75] reported that in the
temperature range of 973e1123 K and pressure range of
1e4 atm, sulfur exists in a diatomic state for more than 99.8%
of the time. The rate of thermal decomposition at tempera-
tures over 1223 K reaches that of catalyzed reactions; how-
ever, at moderate temperatures, the equilibrium H2 yield is
very low. Thermal decomposition at temperatures between
1273 and 1473 K was also investigated [75], and at 1473 K and
1 atm, H2S conversion was a mere 35.6% (97.5% of its ther-
modynamic limit) when a steady gas flow rate of 50 mL/min
was achieved with a 48 s residence time. In one report [13], a
detailed reaction mechanism study using theoretical and
experimentally derived data, determined that when a small
amount of O2 is added to the H2S stream, H2 yields increased;
however, higher O2 concentration led to the oxidation of H2.
The increase in H2 production was postulated to be the result
of increased radical intermediates under the reaction condi-
tions. Higher-temperature thermoelectric reactors capable of
achieving temperatures of 2173 K have been proposed
whereby the systems recover waste heat to preheat the H2S
stream before reaction [85]. A key point to maximize H2 yield
for thermal reactions is to rapidly quench the reaction prod-
ucts [79].
To decrease the high temperature requirements for the
above methods, catalytic processes have been investigated,
and are described in the next section.
Catalytic Methods: The requirement for unreasonably high
temperatures for thermal decomposition has led to continued
efforts to create H2S-splitting processes with catalysts [13].
Low-temperature operations have been reported with the use
of MoS2-based catalysts, resulting in 95% conversion to H2 at
773 K [86e88]. Mechanistic studies reveal open coordination
sites over MoS2 created a reactive 4-coordinate molybdenum
on the surface-active site [86]. In some systems, H2 and S2
were formed at room temperature. However, conversion of
H2S was low at these temperatures [89]. Room temperature
H2S activation became of interest when researchers discov-
ered that metal sulfides such as Ni3S2 and CoS2 can oxidatively
add H2 at room temperature as part of the active component in
HDS catalytic systems [90,91]. The metal ions achieve their
stable d6 electron configuration as the unoccupied 3dz2 and
3dxz metal orbitals interact effectively with the anti-bonding
orbitals of H2S [92]. However, in the absence of occluded H2,
the H2S molecule is not adsorbed by the metal catalyst when
in their d7 electronic configuration since the 3dz2 orbital is
filled [90,92]. Although H2S dissociation is an endothermic
process in the gas phase, calculations indicate that on the
surface of sulfide catalysts it is an exothermic process
accompanied by a decrease in Gibbs free energy (by about
16.6 kcal/mol from surface adsorbed H2S), yielding H2 and
adsorbed solid singlet sulfur [90]. The surface process is irre-
versible because its products are spatially separated and the
H2 molecule leaves the catalyst surface. A reaction coordinate
is shown in Fig. 4.
Other metals that have an affinity for sulfur have been
investigated, including oxides of alumina [93,94], cobalt sul-
fides [95], nickel [96], zinc [97], gold [98] and rhodium [99]. The
copper sulfides Cu2S, Cu9S5, and CuS were found to be inef-
fective for the thermal decomposition of H2S. However, in the
same study, the catalyst containing Cr2S3, MoS2, WS2, and
MoS2 were found to be most effective above 873 K, but below
873 K both Cr2S3 and WS2 gave higher H2 yields than MoS2
[100]. A catalyst that performed better than MoS2 was
discovered when a V2S3 precursor was used in thermal
diffusion column reactors between 673 and 1073 K; here, the
mixed system, V2S3/Cu9S5 formed from Cu3VS4 at elevated
temperatures in a closed circulating system using a quartz
reactor [101] and V2S3/Al2O3 in a Pyrex® tube reactors resulted
in 70% conversion at 873 K for 23 s residence time at a 5e10 wt.
% V2S3/Al2O3 catalyst loading [102]. Iron- and nickel-based
systems on inert supports were also investigated in a similar
manner using column reactors [103]. In this study, the thermal
diffusion columns were connected in series and H2 concen-
tration was greater than 90% at the top of the upper column
using Mo and FeS2 on alumina supports, thus providing
excellent separation of H2 and sulfur [103]. Further, perovskite
oxides in quartz tubular reactors have recently been employed
for the thermal decomposition of H2S. This pioneering study
found H2S conversions at 1223 K were 37.7%, 36%, and 34.7%
for LaSr0.5V0.5O3, LaSr0.5Mo0.5O3, and LaMoO3, respectively,
about four times of those in non-catalyzed (thermal) systems
[104].
H2 production can be more economically feasible using
concentrated solar radiation (heat) than the Claus process.
Solar H2 could be produced at costs ranging from 6.1 to 8.6
cents/kW∙h, leading to an annual savings of 45% using a solar-
only approach from solar towers [105]. The cost can be further
reduced to 5.8 cents/kW∙h by using a natural gas/solar plant
hybrid design unit working continuously. Concentrated solar
radiation is used with an Al2O3-based, honeycomb structre
absorber for the heat transfer flow to reactants. When natural
gas is used and combusted in an adiabatic burner, the tem-
perature can reach nearly 1700 K in the reactor. This reactor
unit, however, would negate the economic advantage owing
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
Fig. 4 e Computed free energy reaction coordinate (room-temperature) for H2S decomposition on a catalyst surface. Image
used with permission from Springer [90].
to CO2 emissions, determined to be 0.42 kg/kW∙h compared to
a solar-only approach. In another study, the activation energy
of the catalyzed decomposition of H2S over alumina NieMo
and CoeMo sulfide was calculated to be between 14.15 and
18.08 kcal/mol using concentrated solar energy at 1043 K with
16% H2 production [106].
Due to the high temperature requirements of pure thermal
processes (i.e. non-catalytic), to obtain a reasonable yield and
conversion significant capital cost would be required if such a
process could be made practical. In addition, a recycle feed-
back loop would be required to use the other unreacted H2S,
along with a purification step for the separation of H2S from
H2. Therefore, thermal processes involving catalysts (thermal
catalytic) would create simpler reactor designs and be ideal for
commercial development. Alexeeva [107] provides a short
review on thermocatalytic processes. Table 2 lists some
thermal catalytic processes along with their operating
conditions.
Membrane-Assisted: The equilibrium nature of the ther-
mal catalytic decomposition of H2S has led to studies on the
use of membranes in membrane reactors to remove compo-
nents from the reaction [80]. By removing components of the
reaction, thermodynamic and kinetic barriers can be made to
favour product formation. This innovative technology can
lead to improvement of reactor performance, compactness,
and cost-effectiveness because of the removal of a product or
component of the reactant feed. If the membrane removes a
product, the thermodynamic threshold related to conven-
tional reactors is overcome because the reaction never rea-
ches equilibrium and is not limited by thermodynamics.
However, reactor complexity increases due to the introduc-
tion of selective and permeable membranes [111]. Thus, in
recent years published works in membrane-assisted pro-
cesses involving H2S have decreased. Highlighted below are
some of the more promising studies in membrane reactor
technologies for H2S decomposition.
Experimental studies performed on palladium- and
vanadium-based membrane systems revealed that the
vanadium-based systems are similar in terms of cost and
1307
performance to the costly palladium-based systems [112].
Glass (or silica) [113] and alumina-based membrane reactors
were shown to double the conversion due to the selective
permeation for H2 in the reactor from the decomposed H2S via
a MoS2 catalyst. Sulfur permeation was low; the glass was
made of Vycor with a porosity of 0.79. The membrane was
surrounded by a stainless steel shell and protected by the
alumina [7,83]. Durability of the glass membrane held up to
1073 K and diminished with further temperature increase.
Control experiments revealed that the glass itself possessed
no catalytic activity. When an alumina membrane was used,
permeability was higher but separation was poorer [7,83]. A
composite membrane made of silicone dioxide, vanadium,
and a coating of platinum on the feed side of the reactor was
investigated and H2S conversion of 99.4% was achieved at
973 K, with only H2 and sulfur present in the products; no
sulfur oxides were detected [112]. The results highlight the
advantages of vanadium over palladium, especially since the
latter suffers from H2 embrittlement. In addition, conversion
is typically much lower under similar thermal conditions
without a membrane, highlighting the advantages of metal-
based membrane reactors. In another study, simulations
were investigated using palladium and ceramic-based mem-
branes in plug-flow type reactors using isothermal, one-
dimensional models [114]. The characteristic features of the
reactors were evaluated with respect to dimensionless pa-
rameters relating to reaction coefficients, reactor geometry,
membrane properties, and operating conditions. This pro-
vided guidelines to define the system boundaries and design
parameters and help identify areas for further development
[20]. Other models with Knudsen diffusion characteristics are
reported by Ohashi et al. [115]. In general, membrane tech-
nologies are still under development and membranes for
high-H2S concentration stream applications are not
commercially available yet. Polyamide-based membranes
have shown good performance but cannot currently handle
more than 10% H2S. Ceramic-based membranes, operating via
Knudsen diffusion, still do not have sufficient separation
factors. A membrane based on surface diffusion is under
1308 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
Table 2 e Details on selected thermal catalytic processes.
Catalyst Comments
V2O5/Al2O3 (to create V2S4) Two-step system, to create V2S4 from
V2O5 and H2S, followed by
decomposition of V3S4 to VS4 to
liberate S and H2
Perovskites, LaMO3 (M: Ce, Co, Cr, Cu, Various perovskite catalysts were
Mo, Sr, V) tested and compared to non-catalyzed
LaSr0.5V0.5O3, LaSr0.5Mo0.5O3 and H2S decompositions
LaMoO3
MoS2 and WS2 Requires continuous removal of sulfur
and intermittent separation of H2
Carbon fiber-based supports with Ti Using Ti-based coatings on activated
carbon fibers
Fe7S8, Fe7S8/MoS2 or Fe7S8/NiS1.20 on Thermal diffusion columns used as
alumina support the reactor and effective separator for
H2 and H2S
development and offers some promise for this application
[61].
Pressure swing adsorption (PSA) is a technique that ach-
ieves a similar outcome to that of membrane-assisted sys-
tems. In PSA, gas separation in mixtures is achieved by
selectively adsorbing a component on a microporous-
mesoporous solid adsorbent at a relatively high pressure
through contact on a solid surface, in order to produce a gas
stream enriched in the less strongly adsorbed components of
the feed gas [116]. The adsorbed components are then
removed from the solid by lowering their superincumbent
gas-phase partial pressures inside the column so that the
adsorbent can be reused with no external heat required. When
this method is applied to the decomposition of H2S to sulfur
and H2, one can achieve the same beneficial results as in
membrane reactors by shifting the equilibrium to the product
side. This method was applied to separate H2 and sulfur from
the decomposition of H2S as shown in Fig. 5. The investigators
reported that, after condensation of sulfur from the decom-
position of H2S, the gas mixture containing 25% H2 and 75%
H2S was then enriched to 98% H2 after a single-pass process
using PSA on zeolite or carbon molecular sieves [117]. The H2S
can be fed back to the decomposition reactor and the process
can be repeated until the desired conversion is achieved.
To conclude, for thermal methods to be adopted, more
efficient catalysts are required to lower operating tempera-
tures and increase H2 production. Innovations of such mem-
brane reactor technology, with increased selectivity, flow
properties, and durability can help. Utilization of heat from
direct solar methods would take advantage of renewable en-
ergy but the capital costs for the creation of solar farms should
be considered.
The use of (sun) light photochemically is another way to
incorporate renewable energy and is discussed in the next
section.
Photocatalytic decomposition
Photocatalytic reactions (photochemical reactions) in the
presence of catalyst utilize the well-known photoexcited state
Temperature (K) Reference
and yield or conversion (%)
~64% H2 at 873 K at 180 min (5% V2O5/ [102,108]
Al2O3)
~62% H2 at 873 K at 180 min (5% V2S3/
Al2O3)
LaCrO3 at 1023 K, 14% H2S conversion [104,109,110]
La2SrOx at 1223 K, 37% H2S conversion
LaSr0.5Mo0.5O3 at 1073 K, 16% H2S
conversion
Non-catalytic conversion at 1073 K,
3.3% H2S conversion
95% H2S conversion from 773 to 1073 K [88]
(using MoS2)
90% H2S conversion to H2 and sulfur [107]
was observed at 973e1023 K
90% H2 concentration (enrichment) [100,103]
achieved at top of column at 773e973 K
properties of a semiconductor. H2 production from photo-
chemical water-splitting has been a long-standing topic of
intense interest [118]. However, like H2O systems, commercial
processes for H2 production from H2S [119] are not well
developed. Nevertheless, H2S decomposition has a lower free
energy of reaction than that of water with DG0 ¼ 33.33 kJ/mol
vs 237.19 kJ/mol [120]. Therefore, using photolysis to decom-
pose H2S to H2 has been a topic of interest and a recent review
article provides an extensive description of this technology
[74]. For a chemical reaction to be driven by light, semi-
conductor materials should possess photocatalytic properties
that can be activated in the UV/visible region, which is the
most suitable for H2S photodissociation. In particular, CdS,
CdSe- and ZnS/CdS-based catalysts have proved to be partic-
ularly useful since they possess band-gaps in the visible re-
gion of light [25]. The basic principles of light-excited
materials are as follows: when light energy is absorbed by a
semiconductor an electron is promoted from the highest level
of the valence band to the lowest energy level in the conduc-
tion band. This creates an electron (e) hole (hþ) pair. A va-
cancy or hole (hþ) is an electron-acceptor and is responsible
for oxidizing substrates on the surface of the semiconductor,
while an e acts as a reducing agent for those species that
capture it. In the photodecomposition of H2S, sulfur behaves
as the ‘hole’ to make disulfide and radical-based in-
termediates [121]. The light source must be at a wavelength
less than or equal to the equivalent band gap energy, assumed
to be constant in the bulk material.
We will now discuss photocatalysts which operate in
the liquid phase (Section Photocatalytic decomposition in
liquid phase) and the gas phase (Section Photocatalytic
decomposition in gas phase ).
Photocatalytic decomposition in liquid phase. The photo-
generated electron-hole pair has a number of competing
pathways and these can be controlled through surface modi-
fications and addition of electrolytes or reactive redox species
[74] such as H2S intermediates. In liquid phase under basic
conditions, acid dissociation occurs yielding HS and S2 ions
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
Fig. 5 e Recovery process for H2 by thermal decomposition of H2S in conjunction with a pressure swing adsorption for the
separation of H2S and H2. Image used with permission from Elsevier [117].
in equilibrium; when the band gap in the photocatalyst is
excited (Eq. (18)), hþ oxidizes S2 (Eq. (19)) and HS ions (Eq.

(20)) to disulfide ions S2
2 , releasing a proton from HS and the
electron from the conduction band reduces a proton to give
molecular H2 (Eq. (21)). The reactions are summarized in Eqs.
(18)e(21) [25,74,122]. A typical liquid-phase setup used for H2S
photochemical decomposition is shown in Fig. 6; details are
given by Preethi and Kanmani [74].
hy þ (photocatalyst) / hþ þ e (18)
2S2 þ 2hþ / S2
2 (19)
2SHe þ 2hþ / S2
2 þ 2H
þ
(20)
2Hþ þ 2e / H2 (21)
To date, various types of semiconductors and supports
have been established as active photocatalysts for H2 pro-
duction in a liquid phase [74]. A very thorough review has been
published on photocatalysts for H2 generation from water-
splitting and H2S-splitting. It includes, but not limited to,
semiconductor-based photocatalysts, a number of synthetic
and modification techniques for adjusting the band gap to
harvest visible light and improve the charge separation in
photocatalysis [123].
TiO2 is the most studied semiconductor because of its
nontoxicity, low cost, and high stability [124]. Other widely
studied semiconductors for photocatalysts are metal oxides
(binary and ternary) and metal sulfides. The metal oxides
include d0 metal oxides (i.e. SrTiO3, ZrO2, Nb2O5, Ta2O5, or
Bi2W2O9), d10 metal oxides (i.e. ZnO, or In2O3), and f0 metal
oxides (i.e. CeO2). The metal sulfides include CdS, ZnS, CuInS2,
AgIn2S2, and their solid solutions [125], of which CdS was of
widest interest due to its responsibility to visible light (with a
direct band gap of 2.4 eV). Most of the catalysts operate in the
1309
UV light range, which makes them less than ideal for sunlight
applications. Metal sulfide semiconductors such as CdS, RuS2,
and mixed Zn-Cu-S can produce H2 in visible light but must
operate with a sacrificial electron donor or hole scavengers.
Sacrificial agents are necessary because they promote H2 pro-
duction by reacting with the photo-generated holes and pre-
vent charge recombination between photo-generated electrons
and holes. Table 3 lists some common semiconductor photo-
catalysts for H2S/water-splitting under visible-light irradiation.
Supports which increase the surface area of the catalyst usually
lead to an increase in photocatalytic activity and stability [126].
For example, CdS nanoparticles formed in the pores of an HY-
zeolite resulted in an H2 production rate increase of 5.23
times compared to that of bulk CdS in the photodecomposition
of H2S [127].
Increasing H2 evolution rates have been observed from the
addition of RuO2 in the form of TiO2/RuO2 to a CdS system.
Although this led to an increase in H2 production rates, it was
also dependent on catalyst preparation [128] as the crystal-
linity and particle size of the catalyst changed depending on
the method used [74]. Doping the photocatalysts is another
approach for improving catalyst efficiency [129]. These
methods include doping metals (i.e. Ni or Cu) and main group
elements (i.e. N, C, or S), which adjust the band gap energy of
the metal catalyst. Composite photocatalysts made from ZnO/
ZnS and CdS/TiO2 produce more H2 than ZnO and CdS
[130,131]. The manner in which the CdS catalyst is prepared,
has an influence on its photocatalytic H2 production rates
[132]. The composite materials exhibit smaller bandgaps
compared to their component materials, leading to improved
efficiency in the visible region. H2 production rates of the
composite catalyst have been reported to be as high as
4.96 mmol h1 g1 compared to 4.1 mmol h1 g1 for the
nonporous CdS catalyst. The mechanism is thought to operate
by the activation of CdS by visible light and promotes an
electron into the conduction band of TiO2 rather than the
1310 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Fig. 6 e Liquid-phase reactor setup of H2S-splitting to produce H2. Image used with permission from Elsevier [74].

direct excitation from TiO2 [131,133]. N-doped TiO2 catalysts
have shown even higher H2 producing activities of up to
8.8 mmol h1 g1 [134]. The structures of these highly active
catalysts were shown to possess marigold-type morphology,
making their activity higher than that of other known N-doped
TiO2 systems.
Main group metals, such as bismuth, also show promise
for converting H2S to sulfur and H2 photochemically. For
example, when polycrystalline Bi2S3 thin films were placed
onto Pt and Bi substrates and used as a photoanode with
sulfide as redox couple, the yields of 2.13  102 mL/mg of H2
was obtained after 4 h of irradiation with the visible output of
a 500-W halogen lamp [135]. Perovskite-based photocatalysts
[136] have been investigated and the layered morphology has
been shown to be particularly well suited for H2 production
[74]. A conversion efficiency of 13.5% for H2 evolution reac-
tion (HER) with noble-metal-free catalysts, such as
molybdenumetungsten phosphide (Mo-W-P), was shown to
efficiently split H2S with the aid of graphite carbon media-
tors. Compared to water-splitting, this device consumed
43.3% less energy when making an equivalent amount of H2
[137]. An aqueous-based system using core-shell nano-
particles based on TiO2-cores and CdS-ZnS-shells was re-
ported for the photocatalytic activity of H2 generation [138].
H2 production rates of 29 mL/h were achieved from water
containing dissolved H2S. Under optimized conditions, a
conversion rate of 30% was observed. A recent article offers a
more comprehensive overview of the different types of
photocatalysts [74]. Polymer-supported photocatalysts have
also been investigated for their H2S-splitting capabilities. The
polymer-supported catalysts have several advantages
compared to unsupported catalysts, including easy removal
of the (regenerable) catalyst and simplified coagulation. The
polymer can participate in the process and polymers that
have active centers (i.e. ion exchange) can promote catalytic
activity as was found in one study [139]. When CdS is co-
precipitated with finely dispersed group VIII metals, a
considerable enhancement of reaction rates and longer
catalyst life is observed.
One challenge often encountered with alkaline sulfide so-
lutions in liquid phase is by-product interference [122]. As the
concentrations of yellowish disulfide and polysulfide ions

Table 3 e Common semiconductor photocatalysts for H2S/water-splitting under visible-light irradiation.

Photocatalyst Light source Aqueous reaction H2 activity Quantum yield (%) Ref.
solution mmol.h1.g1
CdS/HY-zeolite 250 W Hg, >400 nm H2S þ NaOH/Na2O3 24000 e [127], [122]
Nb2Zr6O17-xNx 450 W Xe, >420 nm H2S þ KOH 8566 13.5 (550 nm) [140], [122]
CuGa2O4 450 W Xe, >420 nm H2S þ KOH 3212 5.3 (550 nm) [141], [122]
FeGaO3 450 W Xe, >420 nm H2S þ KOH 4730 7.5 (550 nm) [142], [122]
N-doped TiO2 300 W Xe, >420 nm H2S þ KOH 8800 e [134], [122]
Bi2S3 (Pt/Bi2S3) 500 W halogen KOH þ Na2S 237 0.19 [135]
Na14In17Cu3S35 $ xH2O 300-W Xe, >420 nm Na2S 18 3.7 (420 nm) [143], [123]
CdS 300-W Xe, >420 nm Na2S þ Na2SO3 27333 60 (420 nm) [144], [123]
CdSeZnS 350-W Xe, >430 nm Na2S þ Na2SO3 900 10.2 (420 nm) [145], [123]
CdIn2S4 450 W Xe, >420 nm H2S þ KOH 6960 17.1 (500 nm) [146], [123]
CdS (PtePdS) 300-W Xe, >420 nm Na2S þ Na2SO3 29233 93 (420 nm) [147], [123]
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7 1311

increase, the sulfides may act as optical filters, which affect

the photon-absorbing properties of the cell. Eqs. (22)e(24) 
1.5S2O2e 2
3 þ 3OH þ 2hv / 2SO3 þ S
2
þ 1.5H2O (27)
demonstrate the chemistry of polysulfide formation in
solution.
If a system contains both photocatalytic H2 generation (Eq.
(26)) and sulfite generation (Eq. (27)), the overall process (Eq.
S2 þ 2hþ / S (22)
(28)) leads to the production of 3 mol of H2 from 1 mol of H2S
S2 þ S / S2
2 (23) and 1.5 mol of water, as follows [7,122,150]:

S2 2
2 þ 2S / S4 (24) S2 þ 1.5H2O / SO2
3 þ 3H2 (28)

Addition of sulphite ions (SO2

3 ) to the solution counteracts
To date, no one has reported whether this method is
this phenomenon by making colorless thiosulfate, S2O2 3 (Eq.
feasible and it is not clear if the efficiencies of the two half
(25)) [7,25,148,149]. cycles could match each other effectively [122]. A schematic
illustration of the S2/SO2 2
3 /S2O3 redox system is shown in

S2 2 2e 2
2 þ SO3 / S2O3 þ S
This gives rise to a different method wherein H2S is
decomposed via a S2/SO2 2
3 /S2O3 redox system. The overall
reaction of this process is shown in Eq. (26) [7,122,150,151].
 exploited the limited acid stability of complex sulfur species,
S2 þ SO2 2e
3 þ 2H2O þ 2hn / S2O3 þ 2OH þ H2
S2/SO23 has been widely studied as one of the most well-
known sacrificial donors under basic conditions for metal
sulfide photocatalysis, which can also effectively inhibit
photocatalytic instability of metal sulfides [122]. Almost all the
catalysts have shown quantum yields less than 50% for this
process except one reported by Li et al. [147] over a visible-
light-driven Pt-PdS/CdS catalyst, a quantum yield of 93% was
achieved at 420 nm in the presence of S2/SO2 3 in solution; no
deactivation was observed during an illumination period of
100 h [147]. PdS and Pt were believed to be contributing factors
to extremely high quantum efficiency.
The absence of accumulation of either sulfur or thiosulfate
by-products makes the H2S decomposition process very effi-
cient [7]. Borgallero et al. proposed a two-compartment pho-
tocleavage system for H2S in the presence of sulfite ions where
H2 was produced in the CdS/RuO2 containing half cell and S2
was concurrently oxidized to S2O2 3 [7,122,150]. Then, the
produced S2O2 3 was transferred to a second half cell con-
taining TiO2 particles where light-driven dismutation of S2O2 3
occurred as shown in Eq. (27).
Fig. 7.
(25)
Another method to remove thiosulfate from the reactor
outlet was first reported by Linkous et al. where various
platinized cadmium sulfide preparations (powder suspen-
sions, colloids, sedimentary dispersions and immobilized
particle beds) were used as the catalysts [152]. This approach
(26)
by extracting elemental sulfur when H2S contacted the sulfur
solution from the reactor outlet causing a decrease in pH, as
shown in Eq. (29) and Eq. (30) [122].
 
S2O2
3 þ H2S / S þ HS þ HSO3 (29)
S2
2 þ H2S / S þ 2HS
e
(30)
Implementation required a circulating system consisting
of a scrubber tower and a photo reactor (Fig. 8) in order to
decompose H2S and to separate elemental sulfur and H2 [152].
In a typical run after the reaction a mixture of SO2 2
3 , S2O3 and
2
S from the reactor outlet contacted H2S in the scrubber and
elemental sulfur was precipitated. Then, the enriched HS
and HSO 3 were returned to the photo reactor once the pH of
the solution reached 4.2 or lower. This was the requirement
for thiosulfate to decompose, which turned out to be a big
hurdle for the reaction kinetics. In this pH range, the solution
mostly consisted of dissolved H2S in the scrubber, which
remained unreacted in the photo reactor and eventually was
carried out with the produced H2. The slow kinetics imposed
longer residence time for the sulfide in the reactor and

Fig. 7 e Illustration of S2¡/SO2¡ 2¡

3 /S2O3 redox system for H2 production. Image used with permission from IntechOpen [122].
1312 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
Fig. 8 e Schematic illustration of light-driven H2S decomposition using an immobilized photocatalyst. Image used with
permission from IntechOpen [122].
promoted polysulfide formation which was against pH > 10
criterion for an S2/SO23 system. To overcome this problem,
SO2
3 was excluded from the reaction feed, but it was neces-
sary to keep the solution depth to less than 1 cm in the reactor
to minimize light absorption by polysulfide. The authors
noted that none of the catalyst configurations showed clear
superiority over the others and all had their positive and
negative attributes. It was noted that the suspension system
may be the best because of the reasonable photoactivity,
mainly due to; three-dimensionality of the catalyst surface,
ease of separation from the sulfur-enriched solution in a
settling tank, and operability in a thin-layer flow system.
Commercial-scale photo reactors that are compatible with
the photocatalytic conditions required for the reaction are a
necessity to implement the use of the photocatalysts on an
industrial scale [74]. Simulations have provided some insight
in this regard. Simulations of fluidized bed reactors for the
photocatalytic decomposition of H2S were carried out using
computational fluid dynamics calculations and solid particle
dynamics calculations. The light-adsorbing characteristics
were modeled by Monte Carlo methods [153]. The fluidizing
process of the photocatalyst particles and the fluidizing time
to reach homogenous (uniform) suspension were investigated
and optimal operating conditions were reported. It was found
that the light energy adsorption along the radial direction
decayed exponentially with the homogenous conditions, but
for the heterogeneous conditions (i.e. catalyst particles were
not uniformly distributed throughout the reaction space), the
absorption of light was influenced by the non-uniform dis-
tribution of catalyst particles. The authors claimed that a
fluidized-bed annular photocatalytic reactor irradiated by a
UV lamp located along the axis could be a feasible approach to
creating large-scale photocatalytic reactors [153]. Based on
numerical studies, a fluidized bed photocatalytic reactor was
subsequently constructed, and pure H2S was used as the gas
for catalyst suspension. The experimental study was carried
out under various reaction conditions and the results were
compared to those for a batch reactor. It was concluded that
the activity of the reaction in the fluidized bed reactor (H2S
bubbling) was higher than that in the batch reactor in Na2S/
Na2SO3 solution [154].
Another commercial application of a photo reactor system
was reported recently [155]. The thermodynamic performance
of a water gas shift membrane reactor (WGSMR) was investi-
gated with an integrated coal gasification unit, a carbon cap-
ture unit, and a system for direct splitting of H2S utilizing
Aspen Plus software as the simulator. The purpose of this
study was to determine whether the integration of the pro-
posed systems was beneficial in terms of thermodynamic
performance. The results were compared with experimental
values from open literature. However, the effect of the
photochemical splitting of H2S to H2 and sulfur utilizing a CdS
based photocatalyst on the overall efficiency of the system
was found to be negligible for both types of coal that were
used, due to a very low conversion percentage of H2S to H2 and
sulfur and very small amounts of the H2S present in the syn-
gas. Although, the resulting flow rate of H2 produced by H2S
direct splitting was less than 0.1% of the H2 produced by the
WGSMR, the authors highlighted the importance of H2S
elimination because of the environmental benefits.
Rapid progress has been made in the field of photochem-
ical H2S-splitting reaction in the liquid phase in terms of
fundamental mechanistic studies, efficiency calculations, and
catalyst development, although only a very limited number of
high efficiency catalysts have been reported. Amongst them is
the previously described catalyst reported by Li et al. [147].
However, more research in this field is needed before these
technologies are viable at other than a bench-scale.
Photocatalytic decomposition in gas phase. Few reports have
been published on photocatalytic H2S-splitting in the gas
phase. The main problem was catalyst deactivation at high
concentrations of H2S caused by adsorption of by-products on
the catalyst surface [156]. Canela et al. conducted
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
photocatalytic splitting of H2S using TiO2 as a catalyst and a
black light lamp as the light source in the gas phase [156]. They
observed deactivation of the catalyst at concentrations of H2S
higher than 600 ppmv. Kataoka et al. performed similar ex-
periments using in situ FT-IR analysis and concluded that H2S
was oxidized to SO2 4 without producing significant gaseous
intermediates such as SO2, SO and SO2 [157]. Degradation of
gaseous sulfur compounds, such as H2S and methyl-
mercaptan (CH3SH) was reported by Kato et al. [158] over
silver-deposited titanium dioxide (Ag-PCF). The photocatalytic
degradation rates of H2S and methylmercaptan by Ag-PCF
were 7 times and 14 times larger, respectively, than those by
conventional photocatalytic filter. The authors noted that the
deposited silver may act as a co-catalyst which enhanced the
photocatalytic oxidation of sulfur compounds.
A kinetic analysis on heterogeneous photocatalytic degra-
dation of gaseous acetaldehyde, ammonia and H2S
was performed under UV irradiation over highly active
nanostructured-anatase and rutile films [159]. The anatase
film showed a higher photocatalytic activity than the rutile
film and the magnitude of the difference decreased in the
order of ammonia > acetaldehyde > hydrogen sulfide. By
analyzing the adsorption characteristics and the kinetics of
photocatalytic degradation of the three reactants, it was
realized that H2S adsorbed more strongly on rutile than on
anatase. It was concluded that the kinetics of the photoreac-
tion of H2S is mostly governed by the adsorption characteris-
tics of the catalyst.
H2S elimination with initial concentration 15 ppm in gas
phase was investigated over heterogeneous photocatalysts
[160]. The main hurdle for practical applications was due to
the nature of the reaction products, as during the process SO24
accumulated on the photocatalyst surface, leading to deacti-
vation. As a result, two strategies were suggested to mitigate
the effects of sulfur poisoning for the catalyst. First, porous
and SO2-selective photocatalysts were synthesised by the sol-
gel method with the help of surfactants to increase conversion
and more importantly to mitigate deactivation by retaining
SO2 by-products. Secondly, to improve adsorption capacity of
the photocatalysts, hybrid TiO2-SiMgOx composites were
synthesized to avoid SO2 release and to increase the stability
of the catalyst. With fresh composite, an H2S conversion of
40% was achieved without SO2 formation; however, a steady
decrease in activity was observed during a 72 h reaction
period. To regenerate the photocatalysts, a 1 M KOH basic
solution was used to wash the catalyst. The wash process not
only recovered the catalyst, but also increased the photo-
catalytic activity. H2S conversion rate reached near 100% due
to the incorporation of basic sites that favoured H2S
adsorption.
Photocatalytic splitting of H2S was investigated in the gas
phase for H2 production in an anaerobic environment by
Gujun et al. over semiconductor photocatalysts including
TiO2, CdS, ZnS, ZnO, and ZnIn2S4 [161]. ZnS showed the
highest rate of H2 production, and the addition of Cu2þ
enhanced its activity during the ZnS preparation. Loading Ir
was also effective for promoting H2 production.
Most recently, Baldovi et al. [162] reported photo-splitting
of H2S in the absence of catalysts or photocatalysts at near
room temperature. They observed that, upon irradiation at
1313
254 nm in the gas phase, H2S split into stoichiometric amounts
of H2 and S with a quantum efficiency close to 50%. This
research demonstrated an economically promising route for
photo-splitting of H2S.
Numerous research studies have been conducted on pho-
tocatalytic H2S decomposition for H2 production either in gas
or aqueous phase by investigating different variables such as
pH [163,164], various semiconductors [165], aqueous solutions
and their combinations [166], and preparation techniques [7].
Despite significant progress in terms of catalyst development,
photocatalytic processes are far from commercialization. Lack
of industrial-scale applications can be mainly attributed to
reactant consumption, back reactions of products, and cata-
lyst deactivation. The impacts of first two factors could be
mitigated significantly by utilizing a well-designed continuous
reactor, efficient product separation, and recycling methods
for non-consumed reactants [151]. To avoid catalyst deacti-
vation, catalysts that respond to visible light and contain
optimized structure designs such as morphology, band
structure, surface area, etc. are still required to meet indus-
trial requirements. In addition, for practical purposes, selec-
tive heterogeneous catalysts are essential to tolerate the high
H2S concentrations in the gas phase to prevent deactivation.
Direct decomposition using non-thermal plasma
In general, thermal decomposition and decomposition using
plasma systems may have provided more promising results
for H2S splitting because of their more direct and cleaner
approach. However, as already mentioned, the equilibrium of
the thermal decomposition of H2S, low conversions and
various forms of sulfur, S8 or S2, produced even at tempera-
tures near 1250 K, can complicate separation of H2. Ideally, a
non-equilibrium system is required.
Plasma is often considered the fourth state of matter,
having properties like no other phases; it is an ionized gas,
produced by a number of different methods including com-
bustion, explosion, furnaces, electrical discharge including
coronas, sparks, glows, arcs, plasma jets or shocks that are
electrically, chemically, or magnetically induced [7]. Plasma-
based chemical reactions can operate at temperatures of up
to 20,000 K (thermal plasma) and pressures of 10e109 Pa,
allowing for high conversions of thermodynamically unfav-
ourable reactions. The various methods are often evaluated by
their specific energy requirement (SER), which determines the
efficiency of a plasma system for the production (or destruc-
tion) of a specific chemical substance, such as SER for H2
production, and can be used for thermal and non-thermal
plasma systems [63]. SER is calculated from measured or
computed parameters using Eq. (31).
ε ¼ W=Q i (31)
where ε is SER in eV/molecule, W is total power input and Qi is
the flow rate of substance of interest.
High pressures alone may not yield desirable outcomes.
Theoretical studies indicate that although solid H2S is stable
below 43 GPa, at elevated pressures it decomposes into H3S
and sulfur [167]. Other species include H4S, H5S, and H6S, but
they were found to be unstable. Plasma dissociation of H2S
was studied extensively by scientists from the former Soviet
1314 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Union using microwave and radio frequency discharges with
minimum dissociation energies of 0.76 eV per H2 molecule.
Pilot plants were constructed based on their experimental
results [7,168e173], and results showed that plasma dissoci-
ation of 1 m3 of H2S gave 1 m3 H2 and 1.4 kg sulfur at a cost of
0.6e1.2 kW∙h/m3 to operate [168,169]. However, safety and
economic reasons have hampered its practical use. In addi-
tion, an effective quenching system must be achieved to
control the chemical reaction. The quenching system is typi-
cally in the form of direct water injection, surface heat ex-
change, or expansion through a nozzle or fluidized bed [7].
Plasma systems can generate extremely high tempera-
tures, which are considered excessive for H2S dissociation
and lead to waste and increased costs. However, warm
plasma systems which operate at cooler temperatures
(2000e4000 K), may be more suitable [174]. The elevated
temperatures produce by plasma systems compared to con-
ventional thermal H2S-splitting methods, can be beneficial
for the prevention of sulfur condensation on reactor walls,
and may allow for the easier separation of sulfur species via
condensation. Non-thermal plasma sources include those
based on light applications and have been used for living
tissue treatments [64]. Other non-thermal methods including
dielectric barrier, rotating glow, corona, microwave, and
radio frequency discharge are compared in Table 4
[64,173,175e186]. However, most of these studies dilute
their H2S stream and have high energy costs associated with
its conversion to H2 (>50 eV per H2) and thus are not suitable
for industrial-scale applications [7]. Diluting the H2S source
with another gas of lower dielectric strength (e.g. Ar, He, N2,
or H2) is used because it lowers breakdown voltage as was
observed with a pulsed corona discharge reactor (PCDR) [181].
Energy consumption is higher when H2 is used as a diluent
versus N2, presumably due to the molecular size mismatch,
H2 being 1.86 [119] times smaller than N2 causing a lower rate
of electron collisions and more energy dissipation reactions
with H2 [181]. The authors noted that, despite observing lower
breakdown voltages with the mixed gas systems, further in-
creases in efficiency are needed.
In another study, a novel reactor design employing a wire-
in-tube configuration allowed for view ports to obtain a visual
of the corona along the length of the reactor containing an
equimolar mixture of Ar and N2 (4.9 eV/H2S) at constant power
[187]. The combination of plasma discharges with catalytic
systems has led to achieving energy consumption for H2
production as low as 1.6 eV per molecule [188,189]. The system
consists of a novel type of dielectric barrier discharge (DBD)
tubular reactor with inner electrodes made of either copper
wire or aluminum foil, coated with metal catalyst fibers (sin-
tered metal fibers) or silver paste. Residence time, discharge
gap, and energy input were varied to determine the effect on
yield/conversion, and specific input energy (SIE). Increasing
the energy input increased conversion and residence time
also influenced H2S conversion; however, energy consump-
tion increased as well. At the gas residence time of 6 s, 40% H2S
conversion was achieved leading to the observed 1.6 eV per
molecule.
Gliding arc plasma technologies have shown promise for
fuel conversion because they are considered a ‘warm’ plasma
with sufficiently high temperatures for chemical trans-
formation but also advantageous for energy and cost saving
[64]. Gliding arc in Tornado (GAT) was developed to improve
the gas contact geometry of classical gliding arc technologies
for the partial oxidation of natural gas. One study involving
GAT for H2S dissociation found that it was quite economical to
achieve a dissociation energy of 1.2 eV per H2 molecule at
atmospheric pressure, much lower than most other applica-
tions, and more suitable for commercial and industrial ap-
plications [64]. Other investigators found that adding O2 (20%)
with the GAT plasma technology reduced energy costs for H2
production while increasing H2S decomposition to 65%
without decreasing the production of H2 or the production of
SO2. Here, the specific energy requirement for H2 was deter-
mined to be 1.0 eV per molecule H2, largely due to the O2eH2S
gas mixture [190]. Various plasma technologies were also
conducted in a plug-flow reactor [63]. Four different plasmas
were tested, namely AC corona, dielectric barrier, streamer,
and contracted glow discharge. SER levels of 2.4 eV per
molecule were measured in a contracted glow discharge
arrangement; it was concluded that further SER reduction was
not possible in a plug-flow reactor design due to the absence of
energy recovery mechanisms. However, all SER values were
higher than for typical GAT plasma methods. It was postu-
lated that the reaction mechanism involved an initial direct
electron impact to H2S and that thermal dissociation was a
key factor for lowering SER values [63]. Earlier attempts
involving plasma discharges having varying degrees of suc-
cess are discussed elsewhere [7].
Plasma systems may have more potential than other H2S-
splitting approaches because of their lower energy

Table 4 e Various plasma methods reported by specific energy requirement (SER) number.
Plasma method type Comments SER value Reference
(eV/molecule)
Microwave Reactor Low Pressure (76 Torr) 0.76 [184,185]
Gliding Arc in Tornado (GAT) Pressure, 250 Torr 1.2 [64]
Gliding Arc in Plasmatraon (GAP) 50e60% H2 yield in single pass 2.64 to 4 [192]
AC corona discharge Constant flow rate (0.22 L/min), pressure (265 Torr) and power supply 26.6 [63,174,191]
(2.1 W) at room temperature
Dielectric Barrier Discharge 18.5% H2S dissociation occurred and was constant between 300 and 700 K 12 [63,191]
Streamer Discharge Constant flow rate (0.15 L/min) at 150 Torr, 10 ns pulse at 30 kV between 10 14 [63]
and 160 Hz
Contracted Normal Glow 1 L/min flow rate, 50 mA, 150 Torr, 15.4% H2 production 2.35 [63] [176]
Discharge
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
consumption [63]. Thermodynamic equilibrium modelling
reveals that H2S dissociation into gaseous products including
H2, requires a minimum SER of 1.8e2.1 eV/molecule of H2
produced under ideal conditions [64,191,192]. SER values
lower than this value may indicate non-trivial and non-
equilibrium effects are contributing and require further
investigation. Table 4 compares various plasma-based pro-
cesses with calculated SER values.
Thermochemical decomposition
In this section, three thermochemical methods will be dis-
cussed. The first method is a two-step closed cycle which in-
volves use of metals and their affinity towards sulfides to
produce H2 and sulfur. The second method is a closed three-
step cycle with iodine and sulfuric acid called the H2S-split-
ting cycle. A modified version of this method called H2SeH2O-
splitting cycle will also be described. The third method is a
two-step closed cycle with iodine called the iodine thermo-
chemical cycle.
Two-step closed cycle with metals or metal sulfides. This
closed cycle includes the adsorption or affinity of H2S
[193e196] on metals and/or other inorganic components. The
method involves two-step reactions using metal or metal
sulfide as a substrate to capture sulfur from H2S while H2 is
liberated (Eq. (32) and Eq. (33)) [7]. The metal sulfide is subse-
quently converted into sulfur and the original metal or metal
sulfide.
(xM or MxSy) þ zH2S / (MxSz or MxSyþz) þ zH2
(MxSz or MxSyþz) / (xM or MxSy) þ zS_
The overall reaction is shown in Eq. (34).
zH2S / zH2 þ zS_
Kiuchi et al. claimed that Ag and other metals such as Cu,
Co, Fe, Ni, V, and Mo decompose H2S and may form higher
oxide products such as sulfates, which could affect the
reversibility of the reaction [197]. Other metals such as Ti, Zr,
and Hf have also been investigated for direct reaction with
H2S. Theoretical studies reveal that the direct insertion of the
metal into the S-H bond results in an H2MS complex that could
liberate H2 [198]. A comprehensive report on H2S- splitting
processes has reviewed this method [7]. Based on this review,
the sulfiding reaction (Eq. (32)) usually occurred in the range of
673e823 K under reduced pressure while decomposition (Eq.
(33)) occurred at higher temperatures (1023e1123 K) and
reduced pressure [7]. When FeS, chalcopyrite (CuFeS2-x) and
pentlandite (Ni4.5Fe4.5S8) were the sources of sulfide, no
satisfactory results were observed. For instance, only 30% H2
was evolved and no FeS was restored to its original form.
When Ni3S2 was used, H2 evolution decreased over time, due
to sintering or partial diffusion of sulfides. We could not find
recent reports on this method. We suspect research activities
on this process may have been abandoned due to technical
issues.
Three-step closed cycle with iodine and sulfuric acid: This
process is also known as the H2S-splitting cycle, was initially
proposed by Goldstein et al., and based on the multistep
1315
sulfur-iodine water-splitting thermochemical process [199].
This method was adapted by researchers from the University
of Saskatchewan as a means of efficiently converting H2S into
H2 and S (Eqs. (35)e(37)). Theoretically, all components except
H2, S, and H2S are recycled, resulting in the net H2S-splitting
cycle (Eq. (38)) [51].
H2S Oxidation: H2S þ H2SO4 / SY þ SO2 þ 2H2O (35)
Bunsen Reaction: 2H2O þ I2 þ SO2 / H2SO4 þ 2HI (36)
HI Decomposition: 2HI / H2 þ I2 (37)
The overall reaction is shown in Eq. (38).
H2S / H2 þ SY (38)
A working concept of the process is shown in Fig. 9 where
the acid gas is injected as a mixture of CO2 and H2S from
feedstocks in gas plants [51]. As a result of further elemental
sulfur oxidation (Eq. (40)), this process produces twice the
amount of recycling agents and eventually H2 (Eqs. (41) and
(42)), thus giving rise to another new cycle called the H2Se
H2O-splitting cycle, represented by the following reactions
[51]. A case study was presented in Section Hydrogen use from
H2S sources in oil sands processes .
H2S þ H2SO4 / SY þ SO2 þ 2H2O (39)
(32)
O2 þ SY / SO2 (40)
(33)
2SO2 þ 4H2O þ 2I2 / 4HI þ 2H2SO4 (41)
4HI / 2H2 þ 2I2 (42)
(34)
The overall reaction is shown in Eq. (43).
H2S þ O2 þ 2H2O / H2SO4 þ 2H2 (43)
The same research group from the University of Sas-
katchewan proposed other theorized routes to produce SO2
to feed the Bunsen reaction for the H2S-splitting cycle, by
performing a comprehensive exergy analysis. It was found
that the first reaction of the original H2S-splitting cycle had
the least destructed exergy, while H2S direct oxidation of the
Claus process (Eq. (8)) had the greatest irreversibility [200].
The Bunsen reaction, is a moderately exothermic reaction,
which is believed to be the most crucial part of both H2S-
splitting and sulfur-iodine water splitting cycles because it
links H2S oxidation (Eq. (35)) and hydroiodic decomposition
(Eq. (37)) of the H2S-splitting cycle and also connects the
sulfur and the iodine loops of the sulfur-iodine water-split-
ting cycle. A company called General Atomics (GA) exten-
sively investigated this reaction in order to optimize the
conditions under which the two produced acids have the
highest degree of separation. GA concluded that both acids
are not separated by any thermal means without reversing
the equilibria unless excess amounts of water and iodine are
used [201]. The stoichiometry originally proposed by GA is
shown in Eq. (44).
1316 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Fig. 9 e The H2S-splitting cycle for H2 production. Image used with permission from Elsevier [51].

researchers investigated the effect of operating parameters

such as liquid volume, toluene/water volume ratio, and
SO2 þ 16H2O þ 9I2 / (2HI þ 10H2O þ 8I2)HIx
agitation speed on the apparent SO2 absorption/reaction rate
phase þ (H2SO4 þ 4H2O)Sulfuric acid phase (44)
in a closed system of a volume-fixed batch reactor [206]. The
comparison of the rate of SO2 absorption in the liquids of
The stoichiometry requires considerable amounts of iodine
different compositions, such as toluene, toluene and water, or
(9 mol) and water (16 mol) to drive the splitting of the acids
I2-toluene solution and water, indicated that the SO2-dis-
through a spontaneous phase separation process. The relative
solving-in-liquid phase was the rate-controlling step if the gas
amounts of water and iodine create two immiscible phases: a
phase resistance was negligible. Given the small activation
light H2SO4/H2O and a heavy HI/I2/H2O phase, which must be
energy (6.02 kJ/mol), it was concluded that in order to increase
concentrated before each is sent for decomposition. The
the reaction rate, improving the contact between reactants in
separation steps would become a huge burden later in the
the multiphase system became crucial. Therefore, Corning®
downstream sections as the diluted streams need to be
Advanced-Flow™ Reactors (AFR-LF and AFR-G1) were chosen
further concentrated and purified [201].
to test this due to excellent resistance to corrosion, and
To tackle the technical challenges of the GA method for the
improved mixing efficiency of multiphase fluids. With these
Bunsen reaction, Wang et al. [49] proposed a low-temperature
advanced flow reactors, the overall mass transfer coefficients
process, where toluene was used to dissolve iodine such that
were calculated for binary systems (SO2-water and SO2-
the Bunsen reaction could be carried out continuously at room
toluene) and the effects of operating conditions such as gas
temperature and technical difficulties of GA Bunsen reaction
and liquid flow rates, the water to toluene ratio, and the
can be avoided. In their version of the H2S-splitting cycle, H2S
temperature on the absorption rates of SO2 and the I2 reaction
was first oxidized with concentrated sulfuric acid (94e98 wt%)
rate were studied. The results showed seamless scaling-up of
(Eq. (35)). Details can be found in the following references
the method using the Corning reactors when the flow rates
[202e205]. Then, the produced SO2 was reacted with stoi-
were increased twenty times [201].
chiometric amounts of iodine dissolved in toluene and water
Two-step closed cycle with iodine: With the goal of
at room temperature (Eq. (36)), which resulted in a gas-liquid-
replacing the Claus process, another theorized cycle called the
liquid multiphase system [206]. Finally, the product acids from
iodine thermochemical cycle was introduced. H2 production,
the Bunsen reaction, including some unreacted iodine dis-
as shown in the following two reaction steps (Eq. (45) and Eq.
solved in toluene and sulfuric acid, were electrolyzed during
(46)), was investigated using process modelling [7,208].
which HI was decomposed to H2 and I2 in the electrolysis unit
at room temperature (Eq. (37)) [207]. To date, all the reaction
H2S þ I2 / 2HI þ 1/8S8 (45)
sections in the H2S-splitting cycle have been investigated
separately, but no integration between the three reaction
2HI / H2 þ I2 (46)
sections, including unit operations such as purification and
upgrading steps, have been performed.
To date, the detailed mechanism of Eq. (45) is not well-
In order to understand the kinetics of the Bunsen reaction
known. The authors noted that the solvation of hydroiodic
of the described gas-liquid-liquid multiphase system per-
acid in iodine must occur in the aqueous phase [208]. The value
taining to the H2S-splitting cycle, the apparent reaction rate
of DGrxn of 71.6 kJ/mol for Eq. (45) implies that the reaction for
was studied where toluene was used as the I2 solvent. The
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
consumption of H2S in water phase is spontaneous. In this
cycle, Eq. (46) is not new: it is basically HI decomposition re-
action of sulfur-iodine water-splitting. This is one of the most
challenging steps for water-splitting due to the presence of an
azeotropic point in the HIx mixture which prevents simple
distillation. Isopropyl alcohol can be used as a solvent to miti-
gate costs from vaporization of the aqueous phase. However, it
was later determined that fundamental issues such as vapor-
ization and condensation of solvent made the process un-
competitive both economically and environmentally. The side
reactions of the iodine with water and iodide were also a
concern. Despite this, process modelling suggested that the
iodine thermochemical cycle could be comparable in cost and
superior in GHG emission to current industrial practices.
Despite rigorous feasibility studies of thermochemical
methods such as H2S-splitting and iodine thermochemical
cycles, unit operations may be a significant source of cost for
these processes such as circulation, vaporization, purification
and condensation of the solvents: the authors have mainly
focused on the feasibility of the reaction steps and the inte-
gration of different sections has never been performed
experimentally. Therefore, a more comprehensive experi-
mental design, modelling, and economic analysis is required
after the integration of all the separate reaction sections, with
their relevant separation steps, to develop a more realistic flow
sheet for scale up.
Electrolysis decomposition
Electrolysis has been investigated as a means of obtaining H2
from H2S using electrochemical technologies that decompose
H2S and/or SOx's to H2 and S [12]. Typically, 3 types of elec-
trolysis methods are utilized; 1) direct, 2) indirect, and 3) other
methods.
Direct Methods: The direct electrochemical decomposition
of H2S is described by the following half-reactions, Eqs. (47)
and (48) [209].
H2S / 2Hþ þ 2e þ S E0 ¼ 0.19 V at 423 K (anode)
2Hþ þ 2e / H2 (cathode)
Direct methods are generally preferred, however the major
obstacle faced by this method is sulfur passivation of the
anode electrode. Sulfur is highly soluble in alkaline media
forming polysulfides, but their solubility can be easily excee-
ded, leading to precipitation from solution which can interfere
with H2 production. Therefore, various systems were devel-
oped, such as the incorporation of solvent, membranes and
compartments to minimize sulfur-related issues. Fetzer first
showed that electrolysis of sodium sulfide (i.e. a deprotonated
version of H2S) led to the complete loss of current due to
electrode passivation by sulfur [210,211]. This has led to in-
direct routes that avoid the passivation of the electrode by
chemically oxidizing sulfur, followed by subsequent reduction
of the oxidizer via electrochemical means at the anode to
generate H2. This completes the catalytic cycle and avoids the
formation of sulfur at the electrode [211]. However, the pro-
cess was not efficient due to the high voltages required and
more direct approaches were therefore developed. The cor-
rosive nature of H2S also limits the type of anode material
1317
[212]. Table 5 list some common direct electrolysis methods.
As can be seen, various remedies to eliminate sulfur passiv-
ation on the anode have been investigated. Techniques
include porous electrodes, solvent addition to remove sulfur,
mechanical removal (stirring) and, high temperature methods
(increased corrosion). All of these have limited scalability due
to the complex nature of the system. Therefore, although the
direct methods are more energy efficient, the production of
sulfur creates separation and electrode contamination issues,
and with the introduction of high-temperature electro-
chemical methods, undesirable secondary reactions occur
[213].
Indirect Methods. Indirect methods typically involve the
use of a chemical co-oxidant (e.g. iodide, metal-oxides or ha-
lides), and while they offer advantages, high voltages are
required to run the electrochemical reactions as compared to
the direct approaches.
A vanadium dioxide (VO2)þ/(VO)2þ couple system has been
studied as an indirect approach to create H2 from H2S. Here, in
an acidic medium, the very stable and soluble (VO2)þ/(VO)2þ
couple, can oxidize sulfide to elemental sulfur but not to
higher oxidation states [213]. The overall reaction scheme is
shown below through Eqs. (49)e(52):
2Hþ þ 2(VO2)þ þ H2S / 2(VO)2þ þ SY þ 2H2O (adsorption
reaction) (49)
2(VO)2þ þ 2H2O / 2(VO2)þ þ 4Hþ þ 2e (anode) (50)
2Hþ þ 2e / H2 (cathode) (51)
H2S / H2 þ SY (overall) (52)
The simultaneous oxidation of (VO)2þ to form (VO2)þ and
reduction of Hþ to yield H2 was carried out in a dual fluid cell
separated by a membrane. In this system, H2S adsorption
(47) increased to 90% at 323 K, with a current efficiency of 97%.
Another indirect electrolysis process called the “FeeCl
(48) hybrid process” was developed by Idemitsu Kosan Co. (IKC). It
consists of adsorbing H2S gas in aqueous solution using an
inexpensive FeCl3 catalyst followed by electrolysis of FeCl2.
This process was proposed in 1991 as a way of decomposing
H2S to H2 and S [214]. A simplified flow diagram is shown in
Fig. 10. H2S absorption was found to be almost 100% at 348 K
with satisfactorily low electrolysis voltage (0.7 V) and current
densities of 100 mA cm2 at 343 K. A bench-scale plant was
developed with a production capacity of 2.1 Nm3 of H2 gas per
day and 3 kg of sulfur per day with the operation (intermittent)
of the bench-scale plant for 1000 h [215]. A process simulation
study of this process revealed that the IKC process was able to
replace the Claus process when modeled and validated
against sulfur recovery plants in Abu Dhabi [216]. Cost anal-
ysis revealed that operating the process at high ferric con-
centrations was more beneficial than high solution flow rates.
In another study, H2S was electrolyzed at 423 K, which was
warm enough to allow sulfur to run off the electrode surface.
Electrode testing revealed that using an anode catalyst
composed of ruthenium (IV) oxide/p-dichlorobenzene/cesium
hydrogen sulfate/platinum black and cathode catalyst
1318 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7

Table 5 e A sample of various electrochemical methods for H2S electrolysis.

Electrochemical Comments Conversion/yield (%) or end result Reference(s)
method type
Direct - Stepwise, compartmentalization method using Unwanted side reactions are eliminated, with [211,223]
aqueous NaOH and NaHS as analyte with continuous sulfur precipitation occurring in the bulk solution
application minimizing electrode passivation, with yields
greater than 95% for both H2 and crystalline
sulfur, at 353 K
- Use of organic vapour (C6H6, C6H5CH3, cycloparaffins, Current densities of up to 50 amp/ft2 of electrode [16]
CS2, NH3, or (NH4)2S) introduced in H2S stream to surface at cell voltages of 0.3e0.7 V with
remove sulfur accumulation on electrode surface efficiencies as high as 50% were obtained
- Addition of toluene or benzene to remove sulfur from 60% conversion efficiency was achieved with 95% [224]
the electrode surface in a continuous-stirred tank sulfur purity. A volume flow rate of 10e66 mL/h at
electrochemical reactor (CSTER) 293e333 K, and applied voltage 1.8e4.8 V was
investigated
- Use of Nafion membranes to separate the anodic and NaHS solution at 358 K at 0.5 V at 100 mA/cm2 [225], [7]
cathodic compartments produce high purity sulfur with high faradaic
efficiencies for H and S production. Membrane
effectiveness decreased over time
- Use of a filter press electrolyser to recycle sulfur and Produces sulfur at the anode and H2 at the [226]
H2 in a sodium carbonate solution cathode At 348 K, 85% sulfide conversion was
containing H2S observed
Indirect - Use of iodide as co-oxidant in acidic solutions Lead to 99.3% sulfur recovery (after purification) [227,228]
and concurrent H2 production, and high current
densities and efficiencies
- Metal oxide, (VO2)þ/(VO)2þ electrochemical couple Adsorption efficiency of H2S increased with [213]
under acidic conditions capable of oxidizing sulfide to (VO2)þ concentration and temperature then
elemental sulfur plateauing (90% adsorption at 323 K) and current
efficiencies reached 97%. Limiting mass transfer
requires better reactor design
- Aqueous FeCl3 used for H2S adsorption followed by Tested on bench scale for 1000 h to create 3 kg of [214]
subsequent formation of FeCl2 is thought responsible sulfur and 2.1 N m3 of H2 per day
for H2S decomposition
Other methods - Electrochemical reduction of H2S from coal or natural H2 is evolved at the cathode and sulfur is [229], [7]
gas removed from a molten salt electrolyte suspected
in ceramic matrix

composed of black/p-dichloromethane gave the most prom- modification of catalytic activity (NEMCA) effect [218]. Modi-
ising results [217]. fying the electrode surface by supplying oxygen anions in a
The electrochemical decomposition of H2S in the gas phase predictable manner creates a super reactive surface and
has been exploited by the non-Faradaic electrochemical electrochemical promotion that results in increased chemical

Fig. 10 e Simplified flow diagram of the FeeCl hybrid process. Image used with permission from Elsevier [216].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
rate. These phenomena can reduce the need for harsh reac-
tion conditions, allowing the use of reduced pressures and
temperatures. For example, the electrocatalytic decomposi-
tion of H2S to H2 and S2 over Pt electrodes was investigated at
873e1023 K and 1 atm pressure. Upon applying a potential to
Pt supported on an O2-conducting yttria-stabilized zirconia
disk, the decomposition of H2S rate significantly increased by
up to a factor of 11 at 873 K [219]. Although NEMCA is a
promising electrochemical process, the technology is still not
mature [220]. A sample of indirect electrochemical methods
are also summarized in Table 5.
Other Methods: High temperature processes reduce the
sulfur deposition issue, however, corrosion of the cell archi-
tecture and other components becomes a new challenge. At-
tempts to incorporate renewable energy into H2S electrolysis,
has been invested by some research groups. For example,
modelling of H2 production from H2S in geothermal power
plants using electrolysis methods was proposed [221]. This
study had three fundamental steps 1) removal of mercury by
chemical absorption 2) selective catalytic oxidation of H2S to
SO2, and 3) SO2 scrubbing by geothermal water. This approach
can be used as a lower energy strategy for H2S electrolysis. In
another study, modelling was also used for the economic
analysis and energy production determination from biogas-
based electricity and sewage sludge derived H2S. The study
investigated various electrochemical methods and scenarios
with the aim to determine the most effective wastewater
treatment method [222]. H2S was present in only 1e2% of the
stream, however, it had an economic advantage for H2 pro-
duction because of the lower Gibbs free energy compared to
water, at the same temperature.
Electrolysis has not been the most active field for H2S
research recently, however, the recent studies on the incor-
poration of a renewable source of energy, may provide a new
direction for H2S electrolysis. In addition, indirect methods
can be promising with higher conversion rates and low
voltage potentials.
Biological decomposition
Biological processes can be a new alternative to decompose
H2S for H2 production, considering that using microorganisms
to create H2 may be an attractive option to costly industrial
methods. Microorganisms can evolve H2 from various sources
including organic material and water, making it a worthwhile
approach for H2 producing alternatives. Fermenters or bio-
reactors with immobilized cells are used for H2 production in
the dark and are an essential part of biohydrogen production
[230e232]. Markov reviewed H2 production using bioreactors,
including detailed descriptions of the methods [231].
Green sulfur bacteria known as obligate photoautotrophic
bacteria can produce H2 from H2S [232]. The pathway includes
H2S as a reducing agent that donates electrons to nitrogenase
for H2 production, coupled with N2 fixation (Fig. 11). However,
very few studies have been performed on green gliding bac-
teria for the production of H2.
Sulfur-oxidizing bacteria, Thiobacillus thioparus, were
immobilized on Mavicell B support and used as part of a
micro-aerobic biotrickling filter reactor to form synthetic (bio)
gas to help develop efficient gas purification processes for
biogas technology [233]. When a supply of O2 was provided,
1319
Fig. 11 e H2 production from green sulfur bacteria. Image
used with permission from Elsevier [232].
the bioreactor removed 100% of the H2S. However, when the
O2 level decreased, the performance also decreased.
In another study, a mixed system of sulfate reducing bac-
teria, Rhodobacter sphaeroides and Desulfomicrobium bacu-
latum in a synthetic medium was examined for its H2
producing properties [234]. Bacteria that can produce H2 in the
presence of other bacteria and under non-sterile conditions
will have great implications for the scale up and commercial
implementation of bio-reactors for the generation of H2 from
H2S. However, to date, very few live biochemical systems exist
that can create H2 from H2S, a field that requires further
research, and has the potential to boost renewable energy
incorporation.
Technological assessment overview
This review highlights some of the potential and emerging
research that can lead to technologies for H2S utilization,
especially H2S decomposition. The different technologies
discussed here range from bench scale to commercial scale,
all with the intention to convert H2S to marketable
commodities.
Criteria to consider for any H2S utilization process include
technical viability, technical maturity, economics, and market
constraints [235]. More importantly, environmental impacts
should be considered for any H2S utilization and removal
methods, such as the handling of hazardous streams with
typical contaminants (e.g. green house gas emissions, hydro-
carbons, solvents, amines, water, and ammonia). Common
problems frequently observed during any H2S utilization re-
action is elemental sulfur extraction which can result in
plugging, precipitation, and corrosion. In addition, proper
material selection for selected operating conditions, and
correctly addressing safety hazards due to the high concen-
trations of H2S gas streams, and H2 will be crucial. From a
technical point of view, recombination of products or by-
products with H2S and/or other molecules present in reac-
tion environment, competing reaction pathways, fouling or
poisoning of catalytic and/or electrolytic systems, catalyst life
cycle costs and regeneration, have to be overcome for any
commercial applications. Other factors must also be
1320 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
considered in order to seamlessly deploy a new H2S utilization
technology, such as meeting stringent sulfur recovery regu-
lations, sufficient funding for novel technology developments
and scale-up, overall economics analysis and process model-
ling and more importantly, appropriate competition strategies
Table 6 e Summary of H2S utilization methods described in this review. TRL ¼ technology readiness level; from 1
(theoretical studies) to 10 (full-scale commercial).
Utilization TRL Pros
methods [72]
Partial Oxidation
Claus Process 9þ - Very well-known process
- The cost of retrofitting existing units
is minimal
Superadiabatic 5 - Good thermal efficiency
Combustion (SAC) - No CO2 generation from combustion
- Modest cost compared to Claus
process
- Compatible with rich and lean H2S
streams
H2S Reformation 6 - Valorizes methane and H2S at the
same time
- High yield of H2: 2 moles of H2 is
produced per 1 mol of H2S
H2S Decomposition
Thermal 4 - Direct route to create H2 and S from
H2S
- Catalysts not required for pure
thermal methods
- With catalysts, temperatures as low
as 673 K can produce H2
- 99.4% conversion of H2S can be
achieved at 973 K over a Pt-based
membrane
Photocatalytic 3 - Potential for renewable energy
integration
- Lower CO2 footprint
- High technical viability
Non-Thermal 5e6 - No catalyst required
Plasma - direct route to create H2 and S from plasma type and reactor design
H2S
- Separation process is easier
- Lower energy consumption
Thermochemical 4 - Usually, no catalyst required
- Relatively high energy efficiency
- Zero GHG emission if coupled with
renewable energy sources, i.e. nu-
clear sources
Electrolysis 4 - Direct method provides easy access -
to H2 - High potential required for indirect
- Easy renewable energy integration
- Very little cross contamination and -
easy product separation
Biological 2 - Alternative to costly industrial
methods
- More environmentally friendly
with existing commercial H2S utilization processes such as
the Claus process [235].
Table 6 summarizes and compares some of the H2S utiliza-
tion methods described in this paper. Thermal decomposition
methods including those utilizing catalysts, despite being the
Cons Comments
- Tail gas treatment is challenging Currently, it is the most
- Highly GHG emitting mature process for H2S
- No H2 produced conversion and utilization
- Membrane requirement H2 production is possible
- Pure O2 requirement can create CO2 through partial oxidation
offset using SAC
- Low H2 yields (at least 50% less
compared to H2S decomposition
methods)
- Despite technical feasibility there is no Implementation of this
large market demand for CS2 technology would depend
- Energy intensive process (temperatures on CS2 demand to offset
above 1200 K are required) some of the costs
- High temperatures required for non- Thermal catalytic processes
catalytic routes (greater than 1200 K) are an advantageous
- Catalyst deactivation especially at high approach due to
temperatures improvement potential,
- Rich H2S streams may not be compatible economic assessment and
with membranes (less than 10 wt% H2S) technical viability
- Membrane materials may be costly and compared to other H2S
add complexity to reactor design decomposition methods
- Renewable energy is intermittent Compared to other H2S
- Lack of reliable separation processes decomposition methods,
- Catalyst deactivation, especially gas the viability of commercial
phase with high H2S concentrations application for this method
- Poor quantum efficiencies is unknown
- Yields and conversions are sensitive to Some plasma-based
systems, such as gliding arc
- Relatively complex compared to pure plasma, appear to show
thermal processes great technical viability,
improvement potential and
good energy efficiency
- Very complex chemistry, especially puri- High technical feasibility,
fication of products however complex nature
- Corrosive nature requires special may require specialized
materials reactor engineering and
- Vaporization, purification and condensa- impose unknown
tion of the solvents may impose high practicality
operating costs
Electrode passivation from sulfur Indirect electrolysis
methods, such as the FeeCl
methods (energy consumption) hybrid process, is seen a
High temperature methods facilitate promising route, with high
unwanted secondary reactions and conversation rates and low
increase corrosion voltage potentials
- May require highly pure environments, Relatively new area of
excluding other bacteria to operate research for H2S utilization,
effectively with high improvement
- Live system may require special potential
procedures
- Separation and purification may be
difficult
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 1 2 9 9 e1 3 2 7
most direct for production of H2 and S, suffer from unfavorable
thermodynamic equilibria and poor yields. Since conversion is
very low, it is beneficial to increase the reaction temperature;
however, this would impose a large capital cost. Rapidly
quenching the reaction is important to maximize H2 yields and
to avoid rapid recombination, but it would reduce the effec-
tiveness of any heat recovery equipment. Addition of mem-
branes to remove one component and influence the equilibrium
is one approach to overcoming unfavorable equilibria. However,
costs associated with retrofitting and maintaining reactors are
expected to be high. More efficient catalysts which lower oper-
ating temperatures would make this method very promising.
Significant advances have been made in the development
of photocatalysts in terms of efficiencies in operating under
visible light. It has great potential for H2 production using a
renewable energy source. For instance, liquid phase systems
using nanostructured N-doped TiO2-catalysts, have been
shown to be a promising avenue of research. However, there
has not been a reliable method to perform this reaction at
large-scale mainly due to the complexity, the lack of effective
photo reactors and separation processes. In addition, contin-
uous supply of renewable energy on a large-scale is crucial for
the implementation of this process.
Warm plasma systems may have more potential than
other thermal H2S-splitting processes because of their lower
energy consumption, and the variety of temperatures avail-
able. In particular, microwave reactors, gliding arc in tornado
and gliding arc in plasmatron, and dielectric barrier discharge
plasm, have been shown to be the most promising and effi-
cient means to produce H2 from H2S.
Thermochemical methods are among the most mature
methods discussed, often having been run at a small pilot-
scale. However, these studies reveal that the method suffers
from uncertainties such as unwanted side-reactions, corro-
sivity of the reactants under severe operating conditions, lack
of fundamental understanding of the mechanism, high
complexity of various chemical process, energy intensity and
high operation costs.
Direct electrochemical methods may not be suitable for
large-scale adoption owing to the high cost of the electricity
required, and the deterioration of metal electrodes due to
sulfur passivation can be challenging. The indirect electrolysis
process involving a FeeCl cycle, may be a promising route for
large scale implementing. Incorporation of renewable energy
may further help lower commercial costs.
Biological approaches are still emerging, and a very limited
number of studies have been performed on these methods.
Further studies are required to assess their viability as H2
producing methods.
Conclusion
Production of H2S is predicted to increase, especially from Ca-
nadian oil sands upgrading. The production of synthetic crude
oil (SCO) from bitumen is an energy-intensive process that in-
volves consumption of a large amount of H2. The current source
of H2 is mostly from natural gas steam reforming, which is also
an energy-intensive process. Because of high concentrations of
sulfur in Canadian heavy oil, hydrotreating leads to large
1321
quantities of H2S that are converted to sulfur and water by the
Claus process. If this large quantity of H2S were converted to H2,
the consumption of H2 in Alberta oil sands industry would be
reduced significantly. However, large-scale H2 production
processes from H2S decomposition have not yet been devel-
oped, due to economic or technical reasons. Therefore, H2S
utilization and more specifically H2S decomposition processes
have been a topic of increasing research interest.
Partial oxidation technologies such as the commercial
scale Claus process, are not preferred because H2S is not
usually converted to H2 despite the large capital cost for this
process. Even though the Claus process is becoming more
efficient, consuming valuable H2 to produce H2S through
hydrotreating the oil and then converting H2S to water is a
distinct drawback of this method. Another method to utilize
H2S is reformation, where methane and H2S are converted to
H2 and CS2 at high temperatures. H2S reformation suffers
catalyst deactivation because of the high temperature opera-
tion, leading to side reactions, hampering commercial
deployment. Therefore, it makes more economic sense that
H2S be decomposed to H2 instead of H2O.
A more promising outlook for H2 production are H2S
decomposition methods which have been reviewed in this
paper. Decomposition methods are broadly categorized as
thermal (catalytic/membrane-assisted), photocatalytic, non-
thermal plasma, thermochemical, electrochemical, and bio-
logical. In general, low dissociation energy of H2S provides a
foundation for developing implementable H2S decomposition
processes to produce H2 commercially. However, compared to
water-splitting, fewer fundamental studies have been per-
formed on H2S decomposition methods mainly due to the
toxicity of H2S which requires highly specialized lab equip-
ment. As well, catalyst development for H2S-splitting is more
challenging because most of the catalysts deactivate soon
after they contact sulfur species. In addition, side reactions
and lack of effective separation methods also impede process
commercialization. To tackle these technical challenges,
development of stable, low-cost catalysts with the capability
of supporting large-scale production and innovative separa-
tion methods are necessary, regardless of the decomposition
methods selected. This highlights the need for further
fundamental and applied research and development to ach-
ieve breakthrough technologies in the field.
Acknowledgments
We would like to thank Dr. Kim Kasperski for her valuable
input in reviewing this article.The authors would like to
acknowledge financial support from the Government of Can-
ada's interdepartmental Program of Research and Develop-
ment (PERD). All authors declare no competing interests.
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