H

Hydrogen Production Through Pyrolysis of Methane: A Suitable Alternative

Pyrolysis Pyrolysis of Hydrogen Sulfide: Energy Delivery
and Decontamination
Ali Bakhtyari, Mohammad Amin Makarem and Conclusion, Further Studies, and Outlook
Mohammad Reza Rahimpour Bibliography
Department of Chemical Engineering, Shiraz
University, Shiraz, Iran
Introduction

Article Outline Growing worldwide consumption of energy dur-

ing the last decades is an outcome of growing
Introduction world’s population and also the strong depen-
Hydrogen: A Clean and Sustainable Energy dence of human’s lifestyle to energy carriers. As
Carrier an example, 20% of global energy consumption
Hydrogen Market: A Criterion for Decision belongs to the transportation section. Although
Hydrogen Applications: Wide Usefulness fossil hydrocarbon-based energy carriers opened
Hydrogen Production: Wide Spread of Routes new vistas within the procedures of energy pro-
Pyrolysis: An Efficient Route duction, decreasing sources of natural gas and
Hydrogen from Biomass Feedstock: crude oil is making the governments and indus-
A Renewable and Sustainable Route tries explore alternatives and even invent novel
Biomass: Cheap and Abundant Feedstock methods for manufacturing fuels. In addition to
Bio-oil the depletion of fossil hydrocarbon sources,
Pyrolysis of Biomass increasing emission of greenhouse gases (GHG),
Liquefaction of Biomass as well as NOx and SOx, is a real challenge of
Pyrolysis vs. Liquefaction consuming fossil fuels. Global warming, change
Pyrolysis Specifications in climate patterns, and defects in biodiversity are
The Kinetics of Gas Generation Reactions in the the potential drawbacks of such emissions
Pyrolysis of Biomass [1–6]. Besides, necessities of primary separation

# Springer Science+Business Media LLC 2018

R.A. Meyers (ed.), Encyclopedia of Sustainability Science and Technology,
https://doi.org/10.1007/978-1-4939-2493-6_956-1
2 Hydrogen Production Through Pyrolysis

of impurities such as nitrogen, carbon dioxide, • High ignition temperature

hydrogen sulfide, mercaptans, and salt from
hydrocarbon sources make their processing
tough and costly [7–10]. As a whole, introducing
new routes for manufacturing energy carriers and
downstream products that are more environmen-
tally friendly than the current status is state of the
art.
• Fast flame speed
• High diffusivity
Furthermore, the variety of production
methods is another advantage of hydrogen. In a
general point of view, hydrogen is produced from
the following sources [11]:

Hydrogen: A Clean and Sustainable • Fossil fuels such as natural gas, crude oil, and
Energy Carrier coal
• Unprocessed hydrocarbons such as shale oil
Due to the aforementioned problems of fossil and oil from tar sands
fuels, there is an urgent need to develop new • Fusion nuclear reactions
routes and technologies for renewable and sus- • Water hydrolysis reaction
tainable energy manufacturing. Such routes and • Bio-based sources such as biomass
technologies must be able to meet the current and
planned global energy demand. From a practical In the following sections, more details of these
point of view, the alternative energy sources, its methods with the focus on the pyrolysis are
production, and application must be feasible, eco- presented.
nomically competitive, environmentally friendly,
and easily accessible [11, 12].
Hydrogen, which is the lightest element in the
periodic table, is so available in large quantities
Hydrogen Market: A Criterion for
that it is the most abundant one in the universe. Decision
Hydrogen is colorless, odorless, tasteless, and
Currently, the worldwide market for hydrogen is
nontoxic. In a wide range of pressure and temper-
estimated to be greater than 40 billion dollars per
ature, hydrogen exists in the gaseous state. Hydro-
year. As reported by Balat [12], an almost 6% per
gen is present in small quantities in the air (i.e.,
year increase in the sales of hydrogen was
100 ppm) [13]. The properties of hydrogen are
reported during 2003–2008. Such an increase is
tabulated in Table 1. Accordingly, due to high
due to developed hydrogen applications in the
energy density and abundance, hydrogen can be
refinery industry with the aim of high-quality
considered as the most promising candidate for
fuel processing. An increasing trend was also
energy delivery. In fact, hydrogen has the highest
observed during the last years [19, 20]. However,
energy density compared with the conventional
hydrogen supply and demand in the future
fuels and is the most available element. The
strongly depend on the following factors [12]:
energy yield of hydrogen is about 120 kJ/g. This
quantity is more than two times greater than that
• Progress trend of the technologies producing/
of hydrocarbon fossil fuels [12, 16]. Table 2 sum-
consuming hydrogen
marizes the energy contents of various substances.
• Expense of hydrogen in the future
The followings are unique characteristics of
• Potential long-term regulations on the emis-
hydrogen introducing it as an alternative energy
sions of GHG
carrier [12]:
• Expense of rival energy carriers
• Very low ignition energy (i.e., 20 kJ)
• Broad range of flammability Up to 2008, a hydrogen production capacity of
• Broad range of detonation if confined 500 billion cubic meters per year was
Hydrogen Production Through Pyrolysis 3

Hydrogen Production Through Pyrolysis, Table 1 Properties of hydrogen (Adopted from [12, 14, 15])
Property Quantity Unit
Critical point
Critical temperature 33.24 K
Critical pressure 1.297 Mpa
Critical density 30.77 Kg.m
3
Compressibility factor 0.304 –
Gaseous
Density 1.33 Kg.m
3
Compressibility factor 0.906 –
Enthalpy 1447.4 J.mol
1
Entropy 78.94 J.mol
1.K
1
Constant pressure heat capacity 24.6 J.mol
1.K
1
Constant volume heat capacity 13.2 J.mol
1.K
1
Viscosity 1.11  10
3 mPa.s
Thermal conductivity 16.5  10
3 W.m
1.K
1
Liquid
Normal boiling point 20 K
Heat of vaporization 891.2 J.mol
1
Density 70.96 Kg.m
3
Compressibility factor 0.017 –
Enthalpy 548.3 J.mol
1
Entropy 34.92 J.mol
1.K
1
Constant pressure heat capacity 19.7 J.mol
1.K
1
Constant volume heat capacity 11.6 J.mol
1.K
1
Viscosity 13.3  10
3 mPa.s
Thermal conductivity 100  10
3 W.m
1.K
1
Combustion
Autoignition temperature 858 K
Low heating value 119.9 kJ.g
1
High heating value 141.8 kJ.g
1
Diffusion coefficient in air at STP 0.61 cm2.s
1
Detonability limits in air 18.3–59 Volume %
Limiting oxygen index 5 Volume %
Flammability limits in air 4–75 Volume %
Minimum energy of ignition in air 20 kJ
Flame temperature in air 2318 K

approximated. Such a quantity was equal to 2% of
global energy demand [21]. By 2040, it is pre-
dicted that hydrogen consumption, as an energy
carrier in the vehicles, could save about 18.3
million barrels of petroleum per day, which is
equal to approximately 150 million tons of hydro-
gen. Furthermore, if petroleum reforming was
applied to produce such quantity of hydrogen,
11 million barrels per day would be saved [22].
The long-term hydrogen economy requires to
deal with the challenges of hydrogen production
routes, feedstocks, facilities of storage and han-
dling, and developments in all the sections of the
energy economy [23]. More discussions with an
economic point of view could be found
elsewhere [12].
4 Hydrogen Production Through Pyrolysis

Hydrogen Production Through Pyrolysis, • Rapid burning speed

Table 2 Energy contents of various substances • High effective octane number
(Adopted from [16–18])
• No toxicity
Substance Energy contenta • Wide limits of flammability in air
Coke 27.0 • Wide gas range in cold weather
Methane 55.5 • Clean combustion product
Bagasse 9.6
• Small quantities of nitrogen oxides
Propane 49.6
Ethanol 29.6
Methanol 19.7 In addition to its potential in energy delivery,
Hydrogen 120.0 hydrogen is largely consumed in different aspects
Dry wood 16.2 of refining, petrochemical, and chemical indus-
Aviation gasoline 46.8 tries such as the following [21, 22, 30, 31]:
Automotive diesel 45.6
Automotive gasoline 46.4 • Refining and hydro-threating
Liquefied natural gas (LNG) 54.4 • Fischer–Tropsch synthesis to manufacture
a
MJ.kg‑1 alternative fuels
• Gas-to-liquid (GTL) technology to manufac-
ture liquid fuels
Hydrogen Applications: Wide Usefulness • Ammonia, methanol, ethanol, and dimethyl
ether manufacturing
The utilization of hydrogen as a combustible fuel • Nitrogenized fertilizers manufacturing
in the stationary and transportation sections such • Hydrogenation of acetylene to ethane and
as rockets, internal combustion engines, fuel cell ethylene
electric vehicles, and high-temperature industrial • Bio-oil upgrading by hydrodeoxygenation
furnaces is currently receiving more attentions • Hydrogenation of dangerous residues, e.g.,
[24, 25]. In a commercial point of view on the dioxins and polychlorinated biphenyls
transportation section, the development of fuel
cell electric vehicles is more practical due to Ammonia manufacturing with about 50% con-
higher efficiency. In the case of reusing the tribution in the global hydrogen consumption is
waste heat, energy efficiency of fuel cell electric the leading process in industrial hydrogen con-
vehicles is enhanced up to 90% [12, 24, 26]. The sumption [12, 30].
most important advantage of hydrogen, as a fuel,
is its carbon neutral ignition. In fact, in the hydro-
gen ignition, carbon oxides are not generated, and Hydrogen Production: Wide Spread of
water vapor is the only produced oxidized com- Routes
pound. Besides, for the direct ignition of hydro-
gen in the internal combustion engines, such as A summary of possible routes for hydrogen pro-
gasoline-ignited engines, no further changes in the duction is presented in Fig. 1. Accordingly, fossil
structure is required [27]. Blends of hydrogen fuels and renewable sources are two major feed-
with alcohols could produce potential non- stocks for hydrogen production. Based on the
petroleum fuels in the internal combustion review of Kothari et al. [11], up to 2008, 96% of
engines. Accordingly, Al Baghdadi [28, 29] produced hydrogen was obtained directly from
investigated the performance and pollutant emis- fossil-fuel sources. In fact, almost all the primary
sion of ignition engines working with blends of sources of energy could be utilized for hydrogen
hydrogen and ethanol as fuel. Other advantages of production. Currently, the major part of hydrogen
hydrogen as a direct transportation fuel are as is produced by serving light hydrocarbons such as
follows [12, 28, 29]: natural gas. However, coal and petroleum coke
Hydrogen Production Through Pyrolysis
Hydrogen Production Through Pyrolysis, Fig. 1 Hydrogen production routes
could be practically utilized for hydrogen genera-
tion [32]. Accordingly, it was reported that up
until the present, methane (i.e., natural gas),
heavier hydrocarbons such as naphtha, and solids
such as coal had, respectively, 48%, 30%, and
18% shares in the production of hydrogen [11,
33–35].
There is a wide variety of methods to convert
the available sources to hydrogen. Thermochem-
ical method [36, 37], electrochemical method
[38], photochemical method [38, 39], photo-
catalytic method [40], and photo-electrochemical
method [41, 42] are well-known among which
thermochemical method is currently the most
common one. In this method, hydrogen is pro-
duced through thermally enhanced chemical reac-
tions, e.g., steam reforming and partial oxidation.
In this method, both catalytic and non-catalytic
routes are possible, and hydrocarbons and water
are the reactants of hydrogen releasing chemical
reactions. The main advantages of thermochemi-
cal method for hydrogen production are consider-
ably high overall efficiency and low production
cost [12].
5
In the current status, various pioneer thermo-
chemical methods for large-scale hydrogen pro-
duction from different fossil-fuel sources are
conventional steam reforming [43–54], partial
oxidation (PO) [55–59], autothermal reforming
(ATR) [60–62], dry reforming [63, 64], and pyrol-
ysis of methane [65, 66] and hydrogen sulfide
[67]. However, some new technologies such as
chemical looping combustion [46, 68–70], chem-
ical looping reforming [71–75], and onboard
dehydrogenation [76–80] have been developed
recently. Onboard hydrogen production as a valu-
able by-product of dehydrogenation reactions is
currently the state of art. This approach has further
benefits such as negligible emissions of carbon
oxides and elimination of storage and transporta-
tion facilities [31, 81]. Among the
abovementioned processes, catalytic steam meth-
ane (or natural gas) reforming (SMR) is a widely
used route for hydrogen production with 80–85%
contribution in the world’s total hydrogen produc-
tion capacity [43–46, 82]. This is due to abun-
dance of natural gas (i.e., methane) sources [83].
6 Hydrogen Production Through Pyrolysis
Although it is prevalent and energy efficient,
SMR needs high-temperature condition, and the
most common strategy for providing such condi-
tion is burning natural gas. SMR is applied to
produce hydrogen in three steps. Methane
(or natural gas) is primarily reformed with steam
at high temperature and pressure condition to
obtain a mixture of hydrogen, carbon monoxide,
carbon dioxide, and water. A catalytic water gas
shift (WGS) reaction is then carried out to convert
carbon monoxide and water to carbon dioxide and
hydrogen. The gaseous hydrogen-rich mixture is
then purified by a variety of purification processes
such as pressure swing adsorption (PSA) [84] or
membranes [85, 86]. More details of SMR method
could be found elsewhere [82, 83].
PO is an exothermic reaction of hydrocarbons
(e.g., natural gas) in the presence of oxygen. An
alternative to both SMR and PO is autothermal
reforming (ATR), in which SMR and PO reactions
are carried out simultaneously in a single reactor.
Accordingly, natural gas, steam, and air are
injected into the reactor, and internal combustion
of the natural gas (i.e., PO reaction) that is an
exothermic reaction drives the endothermic reac-
tions (i.e., SMR reactions). As a consequence of
authothermality inside the reactor, a stand-alone
system for hydrogen production from natural is
managed [25, 86–88]. In addition to this, high
system efficiency, high hydrogen-to-carbon ratio,
and relatively low cost are advantages of ATR
method [25, 89, 90].
Pyrolysis: An Efficient Route
The main focus of the present contribution is on
the production of hydrogen by pyrolysis of vari-
ous feedstocks. Accordingly, more details of the
processes employing pyrolysis for hydrogen pro-
duction are provided in this section. Pyrolysis is a
well-known route for hydrogen production, in
which hydrogen-containing compounds such as
hydrocarbons are the only reactants. In fact,
these compounds are decomposed by heating in
the absence of oxygen. In this regard, pyrolysis of
biomass as a renewable source and pyrolysis of
methane and hydrogen sulfide as the feedstocks
obtained from fossil fuels are investigated with
details.
Hydrogen from Biomass Feedstock:
A Renewable and Sustainable Route
Although the abovementioned processes have
their merits, in almost all the cases, hydrogen
production leads to the generation of side products
such as carbon dioxide. Hence, due to the pres-
ence of compounds magnifying the GHG effect,
they are considered as non-sustainable routes with
non-renewable energy sources [12, 33,
91]. Recently, Nikolaidis and Poullikkas [66]
have presented a detailed discussion on the
methods applied to produce hydrogen from
fossil-fuel sources. Owing to declining fossil
fuels and increasing attention to GHG effects,
the contribution of renewable routes is expected
to increase in the near future. Furthermore, it is
predicted to become the dominant route in the
long term [66, 92–95].
As presented in Fig. 1, there are renewable
sources for the hydrogen production. In fact, the
aforementioned drawbacks prove the necessity of
exploring new sources and developing new routes
for hydrogen production. Accordingly, hydrogen
production from water sources by means of vari-
ous natural intermediates such as solar energy [96,
97], hydropower energy [98], geothermal energy
[99], wind energy [96], and nuclear energy [100]
has been extensively studied by different
researchers. As shown in Fig. 1, water splitting
by means of photolysis, thermolysis, or electroly-
sis is a candidate for renewable and sustainable
hydrogen production.
Although, in the current status, it is not a com-
mon route, hydrogen can be obtained from bio-
based procedures. Unlimited quantities of hydro-
gen are anticipated to be produced from biomass
sources in the near future [12, 33, 91]. In this
regard, the following are different routes for
biohydrogen production:
• Solid biomass such as crops and waste bio-
mass to hydrogen
• Fermentation of liquid manure to hydrogen
Hydrogen Production Through Pyrolysis
• Biological hydrogen production
In a general point of view, methods of
biohydrogen production from biomass are split
into two categories of thermochemical and bio-
logical methods. The category of thermochemical
routes is made of the following processes:
• Pyrolysis
• Gasification
• Combustion
• Liquefaction
while the major biological routes are as
follows:
• Direct bio-photolysis
• Indirect bio-photolysis
• Dark fermentation
• Photo-fermentation
• Sequential dark/photo-fermentation
Based on the economic evaluation of Padró
and Putsche [101], hydrogen production from
pyrolysis of biomass is a cost-effective route com-
paring the one from wind electrolysis and photo-
voltaic electrolysis systems. In fact, the costs of
the process are considerably lower in the case of
pyrolysis of biomass. More details on the process
capability and economic aspects of biological
routes and water splitting for renewable hydrogen
production are well presented in the recent studies
of Nikolaidis and Poullikkas [66] and Shah [102].
Among the bio-based procedures, conversion
of solid biomass seems to be more practical than
other two routes (i.e., fermentation and biological
routes). However, fermentative biohydrogen pro-
duction from sweet sorghum biomass was
declared to be an economic route [103]. Based
on the work of Encinar et al. [104], woody bio-
mass and agricultural residues could be econom-
ically converted to hydrogen by pyrolysis or
gasification in the presence of carbon dioxide.
As reported by Ni et al. [17], conversion of bio-
mass obtained from organic wastes is a potential
route for economic and environmentally friendly
hydrogen production. As an instance, the
7
accessible energy by biohydrogen production is
predicted to be as much as 40% of total energy
consumed in the transportation section [12, 33,
91].
As mentioned previously, thermochemical and
biological routes are the two common ones for
conversion of biomass to hydrogen. Thermo-
chemical routes are faster than biological ones,
and also they provide higher stoichiometric
hydrogen yield with applying gasification
method. On the other hand, thermochemical
routes, in terms of economic and environmental
rules, are introduced as promising candidates for
hydrogen production from biomass feedstocks
[105, 106]. Biological routes are more environ-
mentally friendly and less energy intensive since
they are accomplished under mild conditions.
However, they offer lower rates and hydrogen
yields (i.e., mol produced hydrogen/mol con-
sumed biomass) depending on the biomass feed-
stock type [33, 103, 107]. Hence, the knowledge
of biomass types and proper selection is of a great
importance. Accordingly, in the following sec-
tion, a short introduction of biomass and the prod-
ucts derived from biomass is presented. In fact,
the knowledge of biomass and the properties of its
derivatives could help to proceed with the opti-
mum route for biohydrogen production.
Biomass: Cheap and Abundant
Feedstock
The first step in the biohydrogen production is
providing cheap and abundant biomass feedstock.
Biomass, which is a renewable energy carrier, is
obtained from a vast variety of materials such as
plants, animal residues, and urban wastes
[108]. With this regard, the following are consid-
ered as the primary sources of biomass feedstocks
[109]:
• Waste substances, e.g., urban residues, crop
residues, agricultural residues, and wood
• Products of forests, e.g., trees, shrubs, wood,
and residues of logging
8 Hydrogen Production Through Pyrolysis
• Energy and starch crops, e.g., corn, wheat,
barley, sugar crops, grasses, and vegetable
oils
• Water-based substances or creatures such as
water weed, water hyacinth, and algae
Based on the sources, biomass feedstocks are
classified into three main categories as the follow-
ing [109]:
• Cellulosic biomass
• Starch/sugar biomass
• Triglyceride biomass
Although cellulosic biomass is the cheapest
and the most abundant type, its conversion to
other products is constrained. This is because of
its solid state and low energy density. Hence,
available technologies for conversion of cellulosic
biomass feedstocks impose extra charges [6,
109]. Considering the influence of biomass type
on the composition of the gaseous product and the
yield of biohydrogen, properties of different bio-
mass types are of great significance. Cellulosic
biomass consists of cellulose, hemicellulose, and
lignin, in which cellulose and hemicellulose are
the most abundant ones. On the other hand, cellu-
lose and hemicellulose are constituents of approx-
imately 90% of terrestrial biomass (i.e., the
biomass generated from earth). More details of
their chemical structures are available in the liter-
ature [109–111]. The major difficulty in the cellu-
losic biomass processing is providing efficient
technologies to convert the solid-state biomass to
a proper fluid. The following are the available
technologies to transform the solid cellulosic bio-
mass to fluid [6, 109, 111–115]:
• Hydrolysis to generate aqueous sugar
solutions
• Pyrolysis and liquefaction to generate bio-oils
and syngas
• Gasification to generate syngas
Edible biomass or starch/sugar biomass is
almost gained from vegetables. This type of bio-
mass is potentially transformed into fuels in
simpler procedures [6]. Triglyceride biomass (i.e.,
fats) is gained from vegetable oils, animal fats, and
even water-based substances or creatures such as
algae. This type of biomass is transformed into
glycerol and fatty acids which could be then prac-
tically converted to hydrogen by steam reforming,
to olefins by catalytic upgrading, and to biodiesel
by transesterification [6, 116–118]. However, the
major difficulty with the triglyceride biomass is
their high processing cost in comparison with cel-
lulosic biomass [6, 116]. More details on the bio-
mass feedstocks and physical and chemical
properties are available in a recent contribution
by Stedile et al. [119]. A practical route to produce
biohydrogen is bio-oil transformation. On the
other hand, conversion of cellulosic biomass into
bio-oil followed by a second process such as pyrol-
ysis, reforming, and gasification is an indirect route
to produce hydrogen from biomass feedstock [6,
120]. In fact, solid biomass is converted into a fluid
that is more practical to be processed, and then the
fluid is transformed to valuable products such as
hydrogen. However, a portion of hydrogen is pro-
duced through the process of biomass pyrolysis
into bio-oil. Hence, identification of bio-oil char-
acteristics is of a great interest.
Bio-oil
Bio-oil is mostly derived from cellulosic biomass
feedstock such as wood, agricultural residues, and
forest wastes by either pyrolysis [6, 109,
121–125] or liquefaction [126–128]. However,
algae transformation into bio-oil is currently the
state of art [129, 130]. Bio-oil composition
strongly depends on biomass type, the method of
biomass conversion to bio-oil, and operating con-
ditions. Accordingly, more than 400 compounds,
including aromatics, phenols, aldehydes, alco-
hols, esters, ketones, and acids could, exist in the
bio-oil [6, 128].
Pyrolysis of Biomass
In the pyrolysis method, biomass feedstock is
instantaneously heated in the absence of oxygen
Hydrogen Production Through Pyrolysis
and water to reach a high temperature (i.e.,
375–525  C) in a short time. As a result of thermal
decomposition, a liquid mixture is generated
inside a gaseous mixture, which then liquefies
[6, 109, 121–125]. The rate of heating, residence
time, and temperature range are the effective fac-
tors in the generation of solid, liquid, and gas
product during pyrolysis. As stated by Klass
[131] and Huber et al. [6, 120], at very high
heating rates, temperature ranges of
1000–3000  C, and residence times less than 1 s,
the gaseous product is obtained by flash pyrolysis.
However, at a lower temperature range (i.e.,
400–900  C), the generation of liquid product is
certain. Furthermore, higher residence times lead
to the formation of solid product (i.e., charcoal).
Although solid product could be useful in further
processes such as metallurgy and chemical indus-
tries, its formation during pyrolysis decreases the
yields of gaseous product and bio-oil. Therefore,
fast or flash pyrolysis (i.e., pyrolysis with short
residence time and high heating rate) is more
desirable. An advantage of biomass pyrolysis is
low-pressure operation (i.e., 0.1–0.5 MPa)
[108]. Up to 80% yield was reported in the previ-
ous studies of fast pyrolysis [122,
132]. Bridgwater [121] summarized the character-
istics of conventional reactor configurations for
fast pyrolysis of biomass feedstock. In this regard,
the performances of fixed beds, bubbling fluid
beds, circulating fluid beds, transported beds,
and rotating cone reactors were evaluated based
on their production rate, heating rate, solid pro-
duction rate, and separation mechanism. More
details on the commercial processes of biomass
pyrolysis to bio-oil could be found elsewhere
[121, 122, 128, 132, 133].
Liquefaction of Biomass
In liquefaction method, which is a high-pressure
and low-temperature (i.e., up to 20 MPa and
250–325  C) process, reaction rates and mecha-
nisms are controlled to derive liquid bio-oil [6,
126–128]. Thus, a bio-oil type, which is insoluble
in water, is generated. Although bio-oil produc-
tion by pyrolysis method is less expensive, the one
9
obtained by liquefaction method contains less
oxygenated compounds. It means that applying
liquefaction method leads to bio-oil with higher
quality [6]. Catalyst type, pressure range, and
reducing gases are the effective means for con-
trolling the rates and mechanisms of desired reac-
tions for high-quality bio-oil. Slurry feed stream
made of catalyst particles, biomass, liquid solvent,
and reducing gas is injected into the reactor. Dif-
ferent types of liquefaction such as hydrothermal,
solvolysis, and hydropyrolysis are well intro-
duced in the literature [126–128, 134, 135]. Dif-
ferences in their solvents and pressure conditions
of these processes make them distinct. Goudriaan
et al. [136] developed a commercial liquefaction
process for bio-oil production.
Pyrolysis vs. Liquefaction
Typical properties of bio-oils generated by fast
pyrolysis and liquefaction reveal that the one pro-
duced by fast pyrolysis contains higher moisture
and oxygen contents and lower carbon and hydro-
gen contents [6, 133, 137–140]. Such characteris-
tics lead to lower heating specifications, lower
viscosity, and the pH in the range of acids.
Although higher carbon and lower oxygen con-
tents of liquefaction bio-oils lead to higher heating
value, its viscosity makes further processes such
as ignition in engine fuels and reforming difficult
and less efficient. As a whole, the chemical com-
position of bio-oil has significant effects on the
homogeneity, polarity, heating specifications, vis-
cosity, blending, and acidity. Properties of some
bio-oil samples are summarized by Gollakota
et al. [141]. Liquefaction bio-oils have character-
istics more similar to conventional petroleum oil.
Thus, it seems to be more beneficial in long term.
However, in terms of process economy, the
required capital cost for high-pressure equipment
in the liquefaction process makes it less attractive
for the industries and persuades them to develop
fast pyrolysis for bio-oil production [6, 128, 136,
137, 142, 143]. It is worth mentioning that the bio-
oil per se is a low value energy carrier. Hence,
conversion of bio-oil into value-added energy car-
riers such as hydrogen is currently the state of art.
10 Hydrogen Production Through Pyrolysis

As mentioned previously, thermochemical Although these routes are considered as distinct

routes, in which biomass feedstock is transformed ones, the associated reactions might occur simul-
into hydrogen or even hydrogen-rich gaseous taneously in each case. The following are the
streams, are the most practical ones [144]. In major gaseous products obtained from biomass
fact, hydrogen production from biomass or the in each route [12]:
derived syngas from biomass could be an effec-
tive step in a climate with zero GHG emission, Pyrolysis : Biomass
which is vital in the development of sustainable ! H2 þ CO þ CO2
and renewable energy systems [145]. Although þ Gaseous hydrocarbons (1)
combustion and liquefaction are proposed, ther-
mochemical routes mainly include pyrolysis and Gasification : Biomass
gasification. The main reasons of preferring pyrol- ! H2 þ CO þ CO2 þ N2 (2)
ysis and gasification over the first two are the
emission of pollutants in the combustion and Steam reforming : Biomass
necessity of high-pressure facilities in the lique- ! H2 þ CO þ CO2 (3)
faction. However, both pyrolysis and gasification
produce methane and carbon monoxide in addi- In addition to differences in the hydrogen
tion to hydrogen, which could be subsequently yield, the side products are different through var-
converted into hydrogen through steam reforming ious biomass treatments.
and WGS reactions [146]. Although pyrolysis of Generally, the following are the chemical reac-
biomass was introduced as an option for bio-oil tions of each step in a biomass pyrolysis process
production, it could be singly applied to produce followed by further complementary steam
hydrogen. On the other hand, pyrolysis is a ther- reforming and WGS reactors:
mochemical route of producing bio-oil (liquid oil)
and charcoal (solid) inside a gaseous stream by Pyrolysis Biomass þ Q
heating the biomass in the total absence of oxy- ! H2 þ CO þ CO2 þ CH4
gen. In addition to hydrogen, considerable quan- þ Hydrocarbons þ tar þ char (4)
tities of methane and light hydrocarbons exist in
the gaseous stream, which could be then steam Steam reforming Cn Hm þ nH2 O
reformed to produce more hydrogen. Besides,

presented carbon monoxide in the gaseous steam 1
! nCO þ n þ m H2 (5)
could be converted into hydrogen and carbon 2
dioxide by further WGS reaction [106, 108,
147]. Afterward, the desired purity of hydrogen WGS CO þ H2 O ! CO2 þ H2 (6)
is obtained by proper separation units such as
pressure swing adsorption (PSA) [84] and mem- In this route, the yield of hydrogen production
branes [148–150]. The process is well presented strongly depends on the type of biomass feed-
in Fig. 2. stock, characteristics of catalyst, temperature
As a whole, pyrolysis, gasification, and steam range, and residence time (or heating rate)
gasification are the most effective routes to pro- [105]. The syngas obtained from gasification is
duce hydrogen from biomass [106, 108, treated in the same way as the gaseous product
151–153]. As an instance, Demirbas and Caglar obtained from pyrolysis of biomass. In steam gas-
[154] conducted an experimental study on the ification of biomass, the yield of hydrogen pro-
hydrogen production by steam reforming of duction is higher than that of fast pyrolysis. With
pyroligneous oils obtained from the pyrolysis of the overall efficiency (i.e., thermal to hydrogen
lignocellulosic biomass. As declared, this route ratio) which could be managed up to 52%, steam
could be potentially a cost-effective rival for con- gasification is considered as an efficient and
ventional routes of hydrogen production. renewable hydrogen production alternative.
Hydrogen Production Through Pyrolysis
Hydrogen Production Through Pyrolysis, Fig. 2 Schematic diagram of biomass feedstock pyrolysis (Adopted from
[66])
A steam gasification unit with subsequent steam
reforming and PSA units is estimated to require
about 2.4 TJ of input primary energy per TJ of
produced hydrogen [155]. Besides, in a plant with
hydrogen production capacity of 139.7 metric
tons per day, with the price of biomass feedstock
in the range of 46–80 dollar per tons (dry basis),
the hydrogen production cost is estimated to be
1.77–2.05 dollar per kg hydrogen
[156]. Depending on the equipment size and bio-
mass feedstock type, the cost of hydrogen produc-
tion by pyrolysis is estimated to be in the range of
8.86–15.52 dollar per GJ energy (i.e., 1.25–2.20
dollar per kg hydrogen) [146].
In a comprehensive study by Hossain et al.
[16], the prospect of hydrogen production from
oil palm biomass was investigated. In this regard,
a cost analysis of different hydrogen production
routes was carried out. A portion of results is
adopted and summarized in Table 3. Clearly,
11
routes that are using biomass have the least feed-
stock cost. Although process employing natural
gas has similar selling price, its process of con-
version (i.e., SMR) has higher capital and feed-
stock costs comparing the process employing
biomass. Besides, natural gas sources are not per-
manently available like biomass. As clear, pyrol-
ysis of biomass with very low feedstock and
capital costs as well as the reasonable retail selling
price of hydrogen is a promising route. In a recent
study, Nikolaidis and Poullikkas [66] compared
different routes of hydrogen production, i.e., con-
ventional and new renewable ones, comprehen-
sively and presented relating data for the
assessment of technical and economic aspects.
Although some advantages are proposed for con-
ventional routes such as SMR, PO, and ATR,
pyrolysis of hydrocarbons offers the possibility
of reduced step and even emission-free procedure.
Furthermore, carbon is the only side product
12
Hydrogen Production Through Pyrolysis, Table 3 Cost analysis of different hydrogen production routes (Adopted
from [16])
Route Feedstock
Pyrolysis (high estimate) Biomass
Pyrolysis (low estimate) Biomass
Gasification (low estimate) Biomass
Gasification (high estimate) Biomass
Gasification Biomass
Steam methane reforming Methane
Gasification with sequestration Coal
a
$/GJ
b
M$
c
$/kg
requiring treatment. It was previously mentioned
that the produced carbon could be utilized in other
processes. Considering the advantages of utilizing
biomass such as renewability, low price, and
abundance, the pyrolysis process provides an
effective route of hydrogen production with the
efficiencies in the range of 35–50%. A major
drawback of applying biomass pyrolysis is vary-
ing hydrogen content as a result of seasonal avail-
ability and impurities existing in the biomass
feedstock. The major advantages and disadvan-
tages of other possible routes are collected in the
review of Nikolaidis and Poullikkas [66]. It could
be concluded that large-scale hydrogen produc-
tion from biomass feedstock is only feasible by
means of thermochemical pathways such as
pyrolysis and gasification, while biological bio-
mass treatments offer small-scale facilities for
hydrogen production. Pyrolysis of woody bio-
mass with a 3.1–53.4 M$ capital cost for a
2.7–72.9 tons per day hydrogen production capac-
ity and 1.25–2.20 dollars per kg hydrogen cost
proposes a cost-effective route [66].
Pyrolysis Specifications
As mentioned previously, pyrolysis of biomass is
of the promising candidates for large-scale hydro-
gen production. Hence, investigating the effect of
operating parameters on the performance of this
process is currently of a great interest.
Hydrogen Production Through Pyrolysis
Hydrogen retail
Feedstock costa Capital costb selling pricec
0.92 4.20 2.57
2.57 73.70 1.47
2.57 241.40 1.44
0.92 8.80 2.83
2.81 167.50 1.99
10.55 254.10 2.55
562.5 1.24 1.25
Temperature, residence time, type of catalyst,
and type of biomass feedstock are the most deter-
mining factors which control the yield of hydro-
gen production in the pyrolysis of biomass. In a
general point of view, higher temperature, longer
residence time, and selective catalysts are crucial
[157]. However, there are some evidences in the
literature proving the negative effect of long res-
idence time on the yield of hydrogen [158].
In order to adjust the determining factors pre-
cisely, selection of feedstock source and appropri-
ate reactor type and heat transfer pattern is
essential. Accordingly, investigation of different
biomass feedstocks is available in the literature.
Besides, solid–solid conductive and gas–solid
convective patterns are the available heat transfer
strategies [159]. Bridgwater et al. [159] summa-
rized the characteristics of various reactors that are
operational in the pyrolysis process, i.e., ablative,
fluidized bed, circulating fluidized bed, and
entrained flow. The fluidized-bed reactor was
introduced as the most suitable one for hydrogen
production due to higher heating rate, which is
essential in the fast pyrolysis of biomass. In addi-
tion to this, in order to eliminate the deposition of
coke and char on the surface of catalyst particles
and then to enhance the operability of biomass
pyrolysis toward hydrogen production, fluidiza-
tion is applied [160].
Demirbaş and his colleague [157, 161] inves-
tigated the effect of temperature on the perfor-
mance of pyrolysis process. In this regard, Fig. 3
Hydrogen Production Through Pyrolysis 13

a 55
Yield of Gas
b 50
Yield of Gas
50 Yield of Char Yield of Char
Yield of Liquid 45 Yield of Liquid
45
Yield of Product (wt.%)

Yield of Product (wt.%)

40
40

35 35

30
30
25
25
20

15 20
475 500 525 550 575 600 625 650 675 700 725 750 775 475 500 525 550 575 600 625 650 675 700 725 750 775
Temperature [∞C] Temperature [∞C]

c 50
Yield of Gas
d 50
Olive Husk
Yield of Char Tea Factory Waste
45
Yield of Liquid 45 Cotton Concoon Shell
Yield of Product (wt.%)

Yield of Product (wt.%)

40
40

35
35
30

30
25

25
20

15 20
475 500 525 550 575 600 625 650 675 700 725 750 775 475 500 525 550 575 600 625 650 675 700 725 750 775
Temperature [∞C] Temperature [∞C]

Hydrogen Production Through Pyrolysis, Fig. 3 The effect of temperature on the yields of (a) cotton cocoon shell,
(b) tea factory waste, and (c) olive husk biomass and (d) the gaseous product in pyrolysis process

shows the effect of temperature on the yields of
gaseous, liquid, and solid (char) products of three
biomass samples processed in fast pyrolysis. It is
obvious that the yields of gaseous products are
increased by increasing temperature. The yields of
liquid and char products show decrease in the
studied temperature range. However, the trends
are not strictly descending. Besides, the effect of
temperature on the yield of hydrogen production
in the pyrolysis of various biomass feedstocks is
presented in Fig. 4. As shown, increasing temper-
ature in the range of 377–752  C leads to consid-
erable enhancement in the yields of hydrogen.
The trends vary by changing the feedstock.
Yang et al. [158] carried out an experimental
study on the hydrogen production by pyrolysis of
palm oil wastes in a fixed-bed reactor flowing
countercurrently. In this regard, the effects of
various parameters such as temperature, residence
time, and catalyst characteristics on the yield of
hydrogen production were investigated.
Figure 5 is to show the effect of temperature on
the yield of gaseous product and hydrogen in the
pyrolysis of palm oil wastes in two cases, i.e.,
without catalyst and with 5 wt % catalyst
(Ni) [158]. Increasing the yield of gaseous product
and hydrogen with increasing temperature in two
cases and enhancing yields by adding the catalyst
are evident. The interesting feature is the similar
trend of the yield of hydrogen production with
temperature in two cases. However, the yields of
gaseous product are different in two cases. The
thermal cracking of heavier hydrocarbons such as
tar and shift reactions at the higher temperatures
could be the reason of such observations [158,
14 Hydrogen Production Through Pyrolysis

Hydrogen Production
Through Pyrolysis,
Fig. 4 The effect of
temperature on the yield of
hydrogen production in the
pyrolysis of various
biomass feedstocks

Hydrogen Production
Through Pyrolysis,
Fig. 5 The effect of
temperature on the yield of
gaseous product and
hydrogen by pyrolysis of
palm oil wastes

162]. Accordingly, the following reaction net- H2 O þ CH4 ! CO þ 3H2 (9)

work was presented by Yang et al. [158]:
C þ H2 O ! CO þ H2 (10)
Biomass ! GasðH2 , CO, CO2 , Cm Hn Þ
þ H2 O þ Tar þ Char (7) CO þ H2 O ! CO2 þ H2 (11)

Tar þ Q ! H2 O þ Cm Hn þ CH4 þ H2 (8) C þ CO2 ! 2CO (12)

C þ 2H2 ! CH4 (13)

Hydrogen Production Through Pyrolysis
Hydrogen Production
Through Pyrolysis,
Fig. 6 The effect of
residence time on the yield
of gaseous product and
hydrogen by pyrolysis of
palm oil wastes
CH4 þ CO2 ! 2CO þ 2H 2 (14)
Cm Hn þ 2nH2 O ! nCO2
h mi
þ 2n þ H 2 (15)
2
h mi
Cm Hn þ nH2 O ! nCO þ n þ H 2 (16)
2 other gaseous components such as carbon oxides
Reactions (7), (8), (9), (10), (11), (14), (15),
and (16) are responsible for hydrogen production.
Steam reforming of methane (i.e., reaction (9))
cannot proceed at higher temperatures. However,
in the presence of an active catalyst, this reaction
could proceed even at higher temperatures. As a
result, the higher yield of hydrogen production in
the presence of the catalyst is justified.
Another determining factor in the pyrolysis of
biomass is residence time. Figure 6 shows the
effect of residence time on the yield of gaseous
product and hydrogen by pyrolysis of palm oil
wastes in the absence of catalyst [158]. The total
gas product volume increases first with increasing
residence time and reaches the maximum value at
about 14 s. Then, it starts to decrease slightly with
further increase in the residence time. In a differ-
ent manner, lengthening the residence time leads
to early sudden decrease in the yield of hydrogen,
while further increase of the residence time results
15
in higher hydrogen production. However, exces-
sive increase in residence time leads to the reduc-
tion of hydrogen production. Although
lengthening residence time makes the system pro-
ceed toward thermal cracking of heavier hydro-
carbons (i.e., reaction (8)) and thus higher gas
production rate, it leads to the production of
and methane.
Utilizing catalysts in the pyrolysis of biomass
may lead to production of various components.
This is due to the surface characteristics of catalyst
and their effects on the product selectivity. In this
regard, Yang et al. [158] investigated the effect of
adding various catalysts in the pyrolysis of palm
oil wastes. The results are presented in Fig. 7.
Obviously, the presence of a catalyst, regardless
of type, leads to higher yields of gaseous product.
Besides, Ni catalyst provides stronger catalytic
effect than the other ones. In fact, pyrolysis of
palm oil wastes in the presence of Ni catalyst is
carried out with almost 160% increase in the total
yield of gaseous product, whereas the presence of
CaMg(CO3)2 (i.e., dolomite) shows a less cata-
lytic effect on the total yield of gaseous product.
The presence of catalyst, in almost all the cases,
improves the yield of hydrogen production. How-
ever, sodium carbonate (i.e., Na2CO3) and potas-
sium carbonate (i.e., K2CO3) show less selectivity
toward hydrogen. The highest hydrogen content
16
Hydrogen Production Through Pyrolysis, Fig. 7 The effect of adding various catalysts in the pyrolysis of palm oil
wastes
(i.e., 38.45 vol. %) was obtained by utilizing
La/Al2O3 catalyst. By considering both the yield
of gas and hydrogen selectivity, Ni catalyst pro-
vides higher hydrogen production rate. The effect
of temperature on the yield of gaseous product and
hydrogen content in the presence of Ni catalyst
was previously shown in Fig. 5.
Garcia et al. [163] investigated the effect of
catalyst (Ni/Al) pretreatment on the pyrolysis of
sawdust biomass at the temperature range of
650–700  C. They found that the temperature of
catalyst calcination has a significant effect on the
reaction performance. By calcination of the cata-
lyst at 850  C, the highest yield of hydrogen was
obtained. Inside the catalytic effect, the load of the
catalyst has a further effect on the yield of hydro-
gen production. In this regard, Chen et al. [164]
found that oxide of chromium (Cr2O3) is the most
effective catalyst for the pyrolysis of rice straw
and sawdust biomass feedstocks. In addition, they
stated that at least 30 wt. % of catalyst load is
recommended for practical pyrolysis process in
the further studies.
Hydrogen Production Through Pyrolysis
Other researchers have studied the potential of
catalyst type in the pyrolysis of biomass toward
hydrogen production. In this regard, gasification of
tar and dissociation of heavier hydrocarbons by
utilizing various catalysts such as CaMg(CO3)2
and CaO [165]; zeolite Y [166]; Ni-based catalysts
[167]; carbonates such K2CO3, Na2CO3, and
CaCO3 [164]; and different metal oxides such as
Cr2O3 [164], Al2O3, SiO2, ZrO2, and TiO2 [168]
were evaluated. Generally, utilizing Ni-based cat-
alyst significantly improves the hydrogen produc-
tion rate. Positive effects of utilizing Ni catalyst on
the hydrogen production from pyrolysis of palm
oil wastes were previously shown in Fig. 5. It is
worth mentioning that further hydrogen produc-
tion could be managed by applying subsequent
steam reforming or WGS reactions [168, 169].
In an earlier study, Zanzi et al. [170] conducted
an experimental study on the fast pyrolysis of
agricultural wastes in the range of 800–1000  C.
The obtained results in terms of gas yield
(weight %) and hydrogen content (volume %) are
presented in Fig. 8. As prefigure, biomass feed-
stock type strongly affects the pyrolysis process,
Hydrogen Production Through Pyrolysis
Hydrogen Production Through Pyrolysis, Fig. 8 The effect of biomass feedstocks in the pyrolysis process
the yield of gaseous product, and the hydrogen
content. Besides, increasing temperature from
800  C to 1000  C results in higher yield of gas-
eous product and hydrogen content in all the cases.
The biomass feedstock prepared from birchwood
provides a higher yield of gaseous product,
whereas the biomass feedstock of straw offers a
higher hydrogen content. Besides, Fig. 4 shows the
differences between capabilities of various bio-
mass feedstocks in hydrogen production by pyrol-
ysis. As stated by Zabaniotou et al. [171], biomass
feedstocks containing higher cellulose and hemi-
cellulose lead to gaseous products with higher
hydrogen contents. The results of Demirbaş and
his colleagues [157, 161] presented in Fig. 4 con-
firm such a statement. The structural analysis of
biomass feedstocks presented in Fig. 4 is presented
in the study of Demirbaş and Arin [161]. Up to the
present, pyrolysis of a vast variety of biomass
feedstocks with the aim of hydrogen production
was the object of researchers. In this regard, the
potentials of peanut shell [172, 173], plastics, trap
grease, synthetic polymers, mixed biomass [169],
rapeseed [174], and agricultural wastes [175] were
evaluated by different researchers.
17
The Kinetics of Gas Generation Reactions
in the Pyrolysis of Biomass
Because of the complexity of biomass composi-
tion, it is difficult to determine the involved reac-
tions in the biomass processing routes completely.
Therefore, some simplified reactions are consid-
ered either in series or parallel [176]. As an
instance, Shafizadeh [177] considered a set of
parallel reactions for the decomposition of cellu-
losic biomasses feedstocks (e.g., woody biomass).
These reactions were applied to describe the rates
of tar, char, and gaseous products. Afterwars, tar
decomposing can also lead to char and gaseous
products by further reactions. Balci et al. [178]
developed a more complex reaction pathway
based on the nature of pyrolysis.
In a general point of view, different kinetic
models of pyrolysis reactions could be catego-
rized in the following classes [179]:
• Single-step global reaction models
• Multiple-step models
• Semi-global models
18
Although single-step models are in reasonable
agreement with the experimental data, they assume
that the mass ratios of products (i.e., volatiles and
chars) are constant. Such an assumption prevents
the accurate prediction of the yields of products at
different process conditions [180]. In the semi-
global models, it is assumed that pyrolysis prod-
ucts are categorized into chars, tars, and volatiles.
Such an approach is beneficial in evaluating and
correlating the kinetic data from various biomass
feedstocks under similar reaction conditions.
However, it is not suitable for comprising
thermal decomposition data gained from the dis-
similar reaction conditions [181]. Accordingly,
researchers have put effort to develop more com-
plex models (i.e., multiple-step models). Such
models utilize three [182], seven [183], ten [184],
or even twelve [185] consecutive pyrolytic reac-
tions to evaluate the process. More details of the
pyrolytic reactions are well provided in the review
of White et al. [179]. In this regard, a comprehen-
sive study was conducted to review the established
kinetic models and mathematical approximations
applicable in the analysis of solid-state reactions.
Pyrolysis of Methane: A Suitable
Alternative
As mentioned previously, in the pyrolysis,
hydrogen-containing compounds such as hydro-
carbons are decomposed by heating in the absence
of oxygen. Accordingly, their thermal decompo-
sition through the following general reaction leads
to hydrogen release [65]:
1 from the manufacturing cycle [65, 66, 186–188].
Cn Hm ! nC þ mH2 (17)
2
Catalytic thermal decomposition of light hydro-
carbons (with the boiling point range of 50–200  C)
leads to the generation of elemental carbon inside
hydrogen, while in the case of utilizing heavier
hydrocarbons (with the boiling point range higher
than 350  C), a two-step procedure consisted of
hydrogasification, and methane cracking is applied
to produce hydrogen. In the hydrogasification step,
the reaction of hydrocarbons with hydrogen leads to
Hydrogen Production Through Pyrolysis
the generation of intermediate methane, followed by
methane decomposition to elemental carbon and
hydrogen. In this regard, the following reactions
are carried out [65, 66]:
Hydrogasification : CH1:6 þ 1:2 H2
! CH4 (18)
Methane cracking : CH4 ! C þ 2 H2 (19)
Overall : CH1:6 ! C þ 0:8 H2 (20)
In a different manner, hydrogen could be pro-
duced by atmospheric direct decarbonization of
methane at temperature up to 980  C. The whole
process, which is schematically shown in Fig. 9, is
carried out in the absence of oxygen and water.
Lower energy consumption (i.e., 37.6 kJ per
moles of hydrogen) of pyrolysis comparing con-
ventional steam methane reforming (i.e., 63.3 kJ
per moles of hydrogen) is the major primacy of
this process. Furthermore, the omission of WGS
steps and subsequent carbon dioxide removal and
storage sections are other significant advantages.
Besides, by carbon management, which is useful
in the metallurgy and downstream chemical
industries, extra benefits are managed. As a result,
large-scale developments of this process could
lead to 25–30% lower cost of hydrogen produc-
tion. Moreover, a suitable market for the carbon
byproduct leads to the reduction of production
cost. Considering environmental aspects,
converting natural gas (i.e., methane) into hydro-
gen by catalytic decomposition would be more
beneficial than the conventional SMR. Such supe-
riority is due to the elimination of carbon dioxide
A possible strategy to increase the conversion
of methane in the pyrolysis process is in situ
hydrogen separation by utilizing perm-selective
membranes. Metallic membranes such as multi-
layered vanadium and palladium are the promis-
ing candidates for in situ hydrogen removal from
reaction side due to their suitable hydrogen per-
meability. However, the latter suffers from low
mechanical strength, while the former provides
appropriate mechanical properties inside suitable
hydrogen diffusivity [148, 149]. Palladium-silver
Hydrogen Production Through Pyrolysis
Hydrogen Production Through Pyrolysis, Fig. 9 Schematic diagram of methane pyrolysis process (Adopted from
[66])
(Pd/Ag) membranes are typical candidates for this
purpose [150]. Besides, such a strategy makes it
possible to accomplish the process at lower tem-
peratures as well as to reduce the coke formation.
However, low-pressure condition in this process
could lead to weak hydrogen separation. Prob-
lems arising from limited membrane durability
and further clean up are other drawbacks of this
strategy [76–79, 189].
Pyrolysis of Hydrogen Sulfide: Energy
Delivery and Decontamination
Although there exist conventional routes for the
elimination of hydrogen sulfide (H2S) and then
sulfur recovery (e.g., the well-known Claus pro-
cess [190]), the elemental hydrogen is consumed
and converted into other compounds in these
routes. Owing to the aforementioned interest for
hydrogen production, simultaneous hydrogen sul-
fide removal, sulfur recovery, and hydrogen pro-
duction is currently state of the art. In fact,
hydrogen production from the hazardous com-
pound is a multipurpose process as a combination
of a decontamination strategy with the
manufacturing of valuable chemicals and a new
energy source is managed [191]. Hence, due to
several favorable environmental impacts, it is
19
currently of a great interest. Accordingly, thermo-
lysis (i.e., thermal pyrolysis), photocatalysis, cat-
alytic methods, and multi-step non-catalytic
dissociation method are the possible routes for
this purpose [192]. Pyrolysis of hydrogen sulfide,
which is one of the pioneer techniques, is accom-
plished according to the following reaction [192]:
 kJ
H2 S ! H2 0:5S2 DH ¼ 20:4 (21)
mol
Based on the investigation of Kaloidas and
Papayannakos [193], lower pressures and higher
temperatures are suitable for hydrogen production
through pyrolysis of hydrogen sulfide. However,
theoretical and experimental investigations reveal
that this process suffers from low conversion
problem due to the combined effects of undesir-
able thermodynamic and kinetic constraints
concerning the reversibility of Eq. (21). In fact,
at ordinary pressures, the conversion is less than
10% [192]. In situ removal of the products by
utilizing selective membranes, condensation of
sulfur, or even thermal diffusion is wisely pro-
posed to thermodynamically shift the reaction
toward higher hydrogen sulfide conversion
[148]. As mentioned previously, palladium-silver
membranes are the suitable options [148–150].
Pyrolysis of hydrogen sulfide is generally
accomplished in plug flow reactors with different
20
Hydrogen Production Through Pyrolysis, Fig. 10 Schematic diagram of hydrogen sulfide pyrolysis process
(Adopted from [192])
heat sources. In small-scale hydrogen production,
i.e., pilot plants or laboratory scales, the reaction
side is heated by utilizing furnaces or thermoelec-
tric modules [192, 194]. Cox et al. [195] carried
out a feasibility study on the economics of indus-
trial applications of hydrogen sulfide pyrolysis
and then compared the feasible process schemes.
As a general procedure, two different configura-
tions are proposed for pyrolysis of hydrogen sul-
fide, first of which is a set of parallel plug flow
reactors with external burners. The burners are
supplied by natural gas. In the second one, in
order to recover the generated heat of an
in-operation Claus process and then to enhance
the thermal efficiency of the unit, the assembly of
plug flow reactors is installed in the burner of the
Claus plant. The simplified pyrolysis plug flow
reactor is schematically presented in Fig. 10.
Although the first configuration is definitely
more cost-effective than the second one, none of
them could be, in terms of hydrogen price, the
rival of the conventional SMR process
[195]. Adewale et al. [196] studied hydrogen pro-
duction from the thermal decomposition of hydro-
gen sulfide in a commercial sulfur recovery unit
and then analyzed the economic benefits
obtaining by retrofitting a Claus burner for this
purpose. Although an early reduction in the sulfur
recovery of the unit was observed, economic ana-
lyses showed that the return of capital investment
is feasible within less than four years.
Hydrogen Production Through Pyrolysis
Pyrolysis of hydrogen sulfide is possible even
in catalytic mode. However, at the temperature
ranges higher than 800  C, the kinetics of reac-
tions allows to achieve chemical equilibria in a
short time. Hence, application of catalyst does not
make sense in such conditions [197]. Neverthe-
less, application of catalyst might be beneficial if
the options concerning material resistance and
shorter residence times are considered. In this
regard, Zaman and Chakma [148] provided a
comprehensive review on the literature of cata-
lytic decomposition of hydrogen sulfide. Transi-
tion metal sulfides, e.g., sulfides of iron, cobalt,
nickel, copper, molybdenum, tungsten, vanadium,
and zinc were investigated in the literature. More
details on the catalytic hydrogen sulfide decom-
position could be found in their contribution
[148]. More recently, a portion of researches has
been devoted to the evaluation of non-
conventional catalysts with super performance.
The work of Ozaki et al. [198] is a case in point
in which they compared the performance of an
activated carbon catalyst composed of 3% ferro-
cene with an as-produced carbon catalyst sample
synthesized without added ferrocene. As reported,
the ferrocene-containing sample in a fixed-bed
reactor offers lower temperature range (i.e.,
300–400  C) for hydrogen sulfide dissociation to
hydrogen with reasonable conversion. More
recently, Guldal et al. [199] developed a new
class of catalysts composed of rare-earth metals
and transition-element cations for hydrogen
Hydrogen Production Through Pyrolysis
production via pyrolysis of hydrogen sulfide. The
samples containing molybdenum were more
active in the temperature range less than 850  C
with considerably higher conversion compared
with the non-catalytic case.
Developing fluidized-bed catalytic reactors
could lead to some merits in the pyrolysis of
hydrogen sulfide. Elimination of mass transfer
limitations and minimizing catalyst deactivation
are of these kinds. In this regard, Cao and Adesina
[200] evaluated the transition bimetallic sulfide
catalysts in a fluidized-bed reactor for hydrogen
production by decomposition of hydrogen sulfide.
Accordingly, the combination of ruthenium
(Ru) and molybdenum (Mo) provided the best
catalysis characteristics for hydrogen production.
The obtained results of their study prove the supe-
riority of fluidized-bed over the fixed-bed reactor
in the same operating condition. On the other
hand, conversion of hydrogen sulfide in the
fluidized-bed reactor loaded with Ru/Mo catalyst
particles is higher than the case in the fixed-bed
one. Besides, fluidization close to the minimum
bubbling point could lead to conversions higher
than the equilibrium values. This observation
could be possibly due to the membranous effect
occurring in the fluidized beds, which would be
favorable in shifting the reactions toward higher
hydrogen production rate. However, by increas-
ing the flow beyond this condition, a considerable
conversion drop was observed owing to the onset
of slugging [200].
Conclusion, Further Studies, and
Outlook
Owing to the undeniable necessity of exploring
new routes for sustainable energy generation, pro-
duction of hydrogen by applying pyrolysis pro-
cess from different sources was investigated in the
present contribution. Production of hydrogen by
pyrolysis of biomass, natural gas, and hydrogen
sulfide feedstocks was introduced as an efficient
route. The impacts of various variables such as
temperature, residence time, feedstock type, and
catalyst characteristics on the production of
21
hydrogen by pyrolysis of biomass feedstocks
were investigated.
In spite of the mentioned defects in the devel-
oped commercial plants for hydrogen production
from fossil hydrocarbon sources and even grow-
ing theoretical and experimental studies over pro-
duction of hydrogen from bio-based sources, lack
of codified regulations for large-scale production
from such sources is still felt. However, there are
currently some examples of efforts that developed
the theoretical achievements into the practical
ones, as mentioned in the literature [121]. In
spite of this, investigation and application of
new efficient technologies for the production of
biohydrogen is still a vast and novel field of
research and study. New recuperative configura-
tions such as membrane reactors, energy-efficient
thermally coupled reactors, the configurations
combining these two concepts and the chemical
looping concept are the examples of such technol-
ogies [74, 77–79, 201–204].
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