Biomass and Bioenergy 144 (2021) 105920

Contents lists available at ScienceDirect

Biomass and Bioenergy

journal homepage: http://www.elsevier.com/locate/biombioe

Biomass-to-hydrogen: A review of main routes production, processes

evaluation and techno-economical assessment
Thibaut Lepage, Maroua Kammoun, Quentin Schmetz, Aurore Richel *
University of Liège – Gembloux Agro-Bio Tech, Biomass and Green Technologies, Passage des Déportés, 2, B-5030, Gembloux, Belgium

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

Keywords: Hydrogen is viewed as a sustainable strategic alternative to fossil fuels, especially in the field of road and air
Bioenergy transport. Currently, hydrogen production is derived from fossil fuels or is manufactured by splitting water. A
Biofuel novel option, H2-generation from lignocellulosic biomass, based on renewable resources is currently in a pilot-
Hydrogen
scale demonstration or at a commercial stage. The present study reviews the thermochemical, biological, and
Economics
Thermochemical
electrochemical approaches used for biomass-to-hydrogen. The advantages, limitations, and major improve­
Electrochemical ments of each process are presented. A techno-economic assessment is also established based on the production
Fermentation cost, technology readiness level, and industrial scalability.
Biomass The objective is to allow industrial producers to visualise the degree of technological maturity of each option,
Conversion clarify the necessary development efforts before reaching the commercial stage, determine the most relevant and
competitive routes, and assess the suitability of biomass as a feedstock for renewable hydrogen production.
In the reviewed results, the thermochemical process, particularly gasification, partial oxidation, and steam
reforming, presented the best yield for H2 production. Steam gasification is the best compromise because it is
suitable for wet and dry biomass, and it does not require an oxidising agent. As for biological conversion, dark
fermentation is more worthwhile than photo-fermentation due to its lower energy consumption. Additionally,
the electrochemical process is feasible for biomass.
The findings of this study indicate that biomass-hydrogen-based processes are promising options that
contribute to the H2 production capacity but require improvements to produce larger competitive volumes.

1. Introduction applications, mostly ammonia production (27%) and methanol

Transport (particularly road and air transport) alone is responsible
for more than 20% of anthropogenic CO2 emissions [1–3]. To address
this substantial environmental problem, the use of renewable energies,
including alternative fuels and biofuels, should reduce the overall CO2
emissions in the transport sector. Forecasts through 2050 underline the
need for all categories of renewables to account for approximately 27%
of the total transport fuel consumption [4].
Hydrogen has been closely linked to the transport and fuel sector for
many decades. Not only is this molecule involved in several operations
(hydrotreatments) in crude oil refinery but hydrogen is also exploited as
a reagent/processing agent for the production of alternative fuels (e.g,
liquefaction of micro-algae) [5–7]. Hydrogen can also be used as a
“clean” fuel as it is; its combustion generates only water vapor as a
by-product [8–10]. Besides crude-oil refining (representing more than
33% of the H2 consumption), hydrogen has been utilised in many other
manufacturing (11%) [11].
Market forecasts underline that H2 production will increase signifi­
cantly over the next few years, with a growth of 5–10% per year from 50
to 82 Mt by 2050 [12]. The industrial H2 demand is also expected to
increase, especially for ammonia and steel production, by about 2 EJ/a
for each of these activities in 2050, while the H2 demand for
hydrogen-based vehicles is estimated to reach 22 EJ/a by 2050 [12].
These forecasts also demonstrate an increased use of hydrogen in the
manufacturing of new biofuels (from algae or plant materials) that will
impact the hydrogen market and require higher production volumes in
the next few years. With a suitable policy and creation of new in­
frastructures, a hydrogen economy could emerge after 2030 [13].
Currently, more than 98% of the H2 production is ensured from fossil
resources, through either natural gas steam reforming, SMR (accounting
for 76% of the global production), or coal gasification (22%) [14]. SMR
is currently the most economical option and is responsible for

* Corresponding author.
E-mail address: a.richel@uliege.be (A. Richel).

https://doi.org/10.1016/j.biombioe.2020.105920
Received 12 March 2020; Received in revised form 24 November 2020; Accepted 3 December 2020
Available online 8 December 2020
0961-9534/© 2020 Elsevier Ltd. All rights reserved.
T. Lepage et al.
approximately 9 kg of CO2 per kg of H2 produced [14]. The alternative
to renewable feedstock instead of natural gas appears to be compulsory
to mitigate the release of greenhouse gases and would be a substantial
step toward carbon-neutral emissions [8,15,16]. However, only 2% of
the current H2 production is from renewable resources, mostly from
water electrolysis, an emerging technology, with no significant use of
vegetal/algal biomass on the industrial scale currently [11]. Water
splitting is one of the most studied processes, mostly electrolysis (TRL 9,
available at a small scale), with more innovative approaches such as
thermolysis and photolysis (TRL 1–2, under research) [17]. Considering
biomass, research has emphasised lignocellulosic matrices (e.g. wood,
forestry side-products, agricultural residues, and dedicated energy
crops) and their conversion, primarily using thermochemical (gasifica­
tion, pyrolysis) pathways [18–20]. The maturity level of these proposals
is aligned with TRL 7. Other alternatives include biological conversion
(TRL 4–5) and electrochemical conversion (TRL 2–4). The hydrogen
production costs from biomass remain quite high, ranging from 1.21 to
2.42 $/kg when choosing gasification to 1.21–2.19 $/kg for pyrolysis,
which is three times higher than that of SMR (0.75 $/kg) [21]. Even if
some scenarios involve an economic production of biomass in 2050,
biomass should be at the price of coal (ranging from to 40–100 $/MT for
coal and up to 140 $/MT for biomass) to be competitive for energy
production [22]. Currently, lignocellulosic biomass is expensive to
produce. However, forecasts indicate a decreasing price of biomass at
the expense of fossil resources that could be impacted by environmental
policies and the CO2 price [23]. Hence, an increase in the H2 costs from
coal gasification is expected from $ 1 to 2.7 $/kg in China by 2030 due to
taxation [11]. Regarding the cost of hydrogen produced from water by
electrolysis, it should decrease from $ 3 to 2.8 $/kg H2 if renewable
electricity is used and from 5.3 to 4.8 $/kg H2 using the electricity grid
by 2030. These costs would remain higher than those from the biomass
conversion forecasts [11].
This review aims to describe the different H2-production pathways
from biomass and is formatted as follows: In the second section, the two
important thermochemical and biological pathways are reviewed as
well as the description of the electrochemical conversion potential. A
comparison between the processes in terms of their performance in
hydrogen yield and their advantages and drawbacks is proposed in the
third section. Recent improvements and process optimisations are
reviewed in the fourth section, while a techno-economic assessment
based on the latest advances in the field is established in the fifth section.
An evaluation of hydrogen as a fuel is examined in the sixth section, and
key findings are highlighted in the seventh section.
2. Main production routes for H2 production from biomass
Currently, 98% of the global hydrogen used is produced from fossil
fuels, with the predominant production process as steam methane
reforming. Other options based on renewable resources are currently in
pilot-scale demonstrations or at the commercial stage, namely water
splitting and H2-generation from biomass, particularly lignocellulosic
feedstock.
Lignocellulosic biomass is derived from agri-food side products,
agricultural residues, energy crops, marine residues, and forest by-
products [24]. Dahmen et al. reported that the annual production of
lignocellulosic agricultural residue has been estimated as approximately
4.6 billion tons, of which 25% is used, and approximately 7 billion tons
are produced from grass and forest land, which is used for energy pro­
duction [25]. Biomass has attracted attention for its abundance and low
cost.
Hydrogen production from biomass allows an increase in production
quantity, contributing to the economic capacity, increasing source
flexibility, and reducing greenhouse gas emissions. Navaro et al. re­
ported that biomass can be carbon neutral due to its maintained natural
cycle. The CO2 released during the biomass-derived hydrogen process is
used during photosynthesis for plant growth (without considering the
2
Biomass and Bioenergy 144 (2021) 105920
CO2 produced from the hydrogen fossil process) [8].
Currently, several types of technology underway for the production
of H2 utilising (lignocellulosic) biomass, such as thermochemical pro­
cesses, biological conversions, and potentially electrochemically-
assisted production.
2.1. Thermochemical productions
Thermochemical conversion is the most advanced technology for
hydrogen production from biomass. The process was established based
on similar methodologies performed on biofuels, such as biomethane,
adapted from steam methane reforming (SMR) [26]. The three primary
thermochemical routes are gasification, pyrolysis, and aqueous phase
reforming [27].
Gasification is a highly endothermic process conducted in an
oxygen-deficient medium at approximately 1000 ◦ C. It consumes an
oxidising agent to produce syngas, a synthesised gas composed of
hydrogen, methane, carbon monoxide, nitrogen, and carbon dioxide.
The process differs according to the oxidising agent used and can be
designated either as air gasification, oxygen gasification, or steam
gasification [28]. In addition, minor organic and inorganic impurities
have been found in the syngas. The organic compounds include light
hydrocarbons (LHC), such as CH4, and tar (viscous liquid composed of
condensable organic compounds), and the inorganic molecules include
H2S, HCl, NH3, and alkali metals [29].
Form an operational point of view, the moist feedstock is introduced
in the gasifier to dry, releasing water (drying zone). Then, the feedstock
undergoes a pyrolysis reaction (pyrolysis zone), liberating the gaseous
compounds (CO, CO2, LHC) and tar. Reduction reactions finally occur,
and the combustion of the resulting solid from the biomass (called char)
produces hydrogen. The unconverted char is transported to the
combustor to form CO2 and provide heat for the process. The general air
gasification reaction of biomass is presented in Equation (1) [21].
Biomass + Air→N2 + CO + H2 + CO2 + CH4 + H2 O + LHC + Tar + Char
(1)
The “direct route”, based on the direct conversion of the raw
biomass, is an overall simple process suitable for a wide range of
lignocellulosic materials. However, the relatively low percentage of
hydrogen in the raw biomass (3–11 wt%), as well as the heterogeneity of
the composition, are responsible for a variable and inefficient yield of H2
and a varied quantity of impurities, such as tar and char [30]. Man­
denoğlu and co-workers revealed the difference between the hydro­
thermal catalytic gasification of lignin and cellulose, the major
components of biomass. Using K2CO3 as the catalyst at 600 ◦ C, a biomass
conversion to gaseous products of 81.2 wt% can be reached with the
cellulose, whereas only 61.4 wt% is obtained from lignin. Hydrogen
yields of 30.7 mol H2/kg are higher than those of alkali lignin (23.7 mol
H2/kg) [31]. Therefore, biomass containing a high amount of cellulose
and a low amount of lignin should favour H2 production.
In conventional gasification using a fixed-bed reactor, air (oxidising
agent) is used as a combustible for the partial burning of biomass,
resulting in a low conversion into H2 due to the high N2 and CO2 con­
tents in the gas produced. A significant challenge of air gasification is the
removal of nitrogen, a non-combustible gas that reduces the heat value
of the fuel. As an alternative, gasification can be achieved using oxygen
or steam instead of air [32]. Oxygen gasification produces a gas of
greater purity, containing a higher level of H2, no nitrogen, and less tar
and char. Wang et al. studied an oxidising agent in the gasification of
pine sawdust pellets using a pilot-scale two-stage gasifier. They
demonstrated that an increase in O2 from 20 to 100% induced an in­
crease in the H2 concentration in the gas produce from 16% to 36% [33].
However, the cost of oxygen makes the process too expensive to
implement at an industrial scale [34]. Steam gasification is used as a
compromise between air and oxygen gasification. The H2 content in the
gas is similar to that from oxygen gasification, whereas the process is
T. Lepage et al. Biomass and Bioenergy 144 (2021) 105920

cheaper. Nevertheless, tar, char, and a minor amount of N2 are present. Table 2
The general steam gasification reaction of biomass is presented in Reactions identified during steam reforming [40–42].
Equation (2). Reactions Reactants Products

Biomass + Steam→H2 + CO + CO2 + CH4 + HC + Tar Pyrolysis Biomass CO, CO2, CH4, C2H4, H2O, C,
( / ) Primary tar
+ Char ΔH O > 0 kJ mol (2) Tar cracking (pyrolysis) Primary tar CO, CO2, CH4, C2H4, H2,
Secondary tar
A comparison of the different gasification processes is summarised in Secondary CO, CO2, CH4, C2H4, H2, Tertiary
Table 1 [21,35,36]. Steam gasification appears to be the most suitable tar tar
process to produce hydrogen based on the H2 percentage in the gas Tertiary tar C, CO, H2
(40%), higher H2/CO ratio (1.6), and reduced impurities compared with Homogenous gas-gas
reactions
air gasification. Concerning the feedstock, steam gasification is feasible Combustion (oxidation) 2CH4 + O2 2CO + 2H2 (ΔH0 = − 220.0 kJ/
for wet biomass (moisture from 5 to 35 wt%), while air gasification mol)
requires a dry raw material [37]. Dry reforming CH4 + CO2 2CO + 2H2 (ΔH0 = +247.0 kJ/
Steam reforming (SR) is a concomitant purification reaction that C2H4 + 2CO2 mol)
4CO + 2H2 (ΔH0 > 0 kJ/mol)
improves the syngas composition during steam gasification by reducing
Steam reforming CH4 + H2O CO + 3H2 (ΔH0 = +206.0 kJ/mol)
the carbon-to-hydrogen mass ratio (C/H) [38]. The optimisation of C2H4 + 2CO + 4H2 (ΔH0 > 0 kJ/mol)
steam reforming has been performed to reduce the volume of light hy­ 2H2O
drocarbons and tar responsible for the corrosion and blocking of pipes Water Gas Shift CO + H2O CO2 + H2 (ΔH0 = − 40.9 kJ/mol)
due to polymerisation and condensation [39]. Different reactions occur Heterogeneous reactions
Carbon oxidation C + O2 CO2 (ΔH0 = − 393.5 kJ/mol)
during steam gasification, which are presented in Table 2 [40–42]. After Partial oxidation 2C + O2 2CO (ΔH0 = − 246.2 kJ/mol)
the drying step, the pyrolysis reaction occurs, and the biomass is con­ Boudouard reaction C + CO2 2CO (ΔH0 = +159.9 kJ/mol)
verted into a gas rich in CO, CO2, CH4, LHC (C2H4), C, and tar (primary). Water gas reaction C + H2O CO + H2 (ΔH0 = +118.5 kJ/mol)
Primary tar is a complex and condensed mixture of polycyclic aromatic
hydrocarbons and oxygenated molecules, alcohols, phenols, and furans
homogeneous reactions [46]. The char formed during the pyrolysis step
[43]. Under the temperature conditions of steam gasification
is converted into CO and CO2 primarily through slow heterogeneous
(700–1000 ◦ C), homogeneous reactions, such as cracking and steam
reactions during steam gasification, requiring the char to remain in the
reforming, occur and alter the structure of these oxygenated molecules.
reactor to maximise the conversion into gas [47]. Char can also promote
The general tar steam reforming reaction is given in Equation (3) [44].
catalytic activity by supporting the catalysts. Many parameters can be
Cx Hy Oz + (x − z)H2 O → xCO optimised to increase the H2 production yield of gasification. These
( /
+ (0.5 y + x − z)H2 (x ≥ z) ΔH O > 0 kJ mol
)
(3) parameters are highlighted in Table 3 [17,21,48].
At the end of steam gasification, the gas predominantly consists of H2
Steam gasification promotes the steam reforming reaction and in­ and CO2. Therefore, CO2-capture systems (CCS) have been integrated
creases the yield of H2 produced compared with air gasification, rather during the process to increase the concentration of H2. The separation
than promoting a combustion reaction. During the reforming reactions, must be conducted in the same reactor in which the catalysts enhance
the primary tar is cracked into secondary tar, and then into tertiary tar. the WGS reaction to promote the capture of CO2. This process is called
At extremely high temperatures (~1250 ◦ C), it is possible to eliminate sorption-enhanced hydrogen production (SEHP). H2 can be concen­
all the tar [45]. Reforming reactions take place on LHCs in the presence trated up to 99.9% using a pressure swing adsorption system (PSA). By
of H2O and CO2 to form CO and H2. During tar cracking, LHCs (CH4 and varying the pressure, the PSA allows the separation of a gas mixture
C2H4) and carbon oxides (CO and CO2) are generated together with H2. based on the different affinities for each gaseous species to be adsorbed
These compounds are stable under the operating conditions of crack­
ing/reforming. Moreover, the water gas shift (WGS) reaction converts
Table 3
CO in presence of H2O to a mixture of CO2 and H2. Steam added to the
Parameters affecting H2 yield in steam gasification [17,21,48].
gasification process enhances the reversible reaction by shifting the re­
action to H2 production. However, the WGS reaction is exothermic, and Parameters Effects

according to the Le Chatelier’s principle, an increasing temperature will Biomass type High cellulose and lignin content increase gaseous
shift the reaction to the reactants, resulting in the formation of CO and products. High cellulose content biomasses are more
easily gasified with shorter residence periods [49,50].
H2O. Finally, heterogeneous reactions, such as carbon oxidation to form
Biomass particle size Small granulometry provides a larger contact surface and
CO2 or CO, and the Boudouard reaction occur to a lesser extent than a better heat transfer during gasification, improving the
homogeneous reaction (Steam reforming, WGS).
Decreasing granulometry increases H2 yield and decreases
Table 1
tar and char content [51,52].
Comparison of the gasification processes as a function of the oxidising agent (air,
Temperature Increasing the temperature produces a higher H2 yield
oxygen, or steam) [21,35,36]. due to complete homogenous reactions [51,53].
Air gasification Oxygen Steam gasification Increasing the temperature decreases the tar content in
gasification the gas produced [45].
Steam-to-biomass Increasing S/B exhibits a higher H2 yield. Low S/B
a
Products N2, CO, H2, CO, H2, LHC (CH4, H2, CO, CO2, LHC ratio (S/B) promotes CH4 and carbon formation (reformed at higher
CO2, C2H4), CO2 (CH4, C2H4) S/B). Need to be optimised for each process [17,54].
LHC (CH4, Catalysts Increase H2 and CO production by shifting reforming
C2H4), H2O reactions and the WGS reaction [54]. Decrease tar content
Tar (g/kg) 3.7–61.9 2.2–46b 60–95 by promoting the conversion reaction (increase H2 yield).
Average H2 15% 40% 40% The most suitable catalysts for gasification reaction are
composition Ni-based catalysts, alkaline metal oxides, olivine, and
H2/CO ratio 0.75 1 1.6 dolomites [55].
Heating Value 4–7 12–28 10–18 Nickel and cerium catalysts prevent carbon deposition
(MJ/Nm3) and coking [56].
a Residence time Longer residence time increases biomass conversion to
Molecules are listed in decreasing order of presence in the gaseous product.
b gas [57].
Steam-O2 mixture.

3
T. Lepage et al.
on a liquid or solid. Calcium oxide CaO is currently the most commonly
used CO2 acceptor (forming CaCO3) and can be easily regenerated [58,
59]. The method is called “chemical looping” and releases H2 (gasifi­
cation) and CO2 (CaO regeneration) in separate reactors [28]. Scrubbing
is a separation technique used to separate the gaseous impurities, such as
H2S or water [60]. This operation occurs prior to the PSA and is an
energy-consuming separation method [61]. Steam reforming is an
interesting complementary system integrated with existing processes to
reduce the tar and char quantities, as summarised in Fig. 1.
Partial oxidation (PO) is an alternative approach to steam reforming
reactions. The reaction scheme is similar to steam reforming, except that
H2O is replaced by O2 [19]. One of the advantages is that reactions with
oxygen are exothermic, which means there is no need for either an
external energy source or the use of more-compact reactors. Different
reactions occur depending on the oxygen concentration in the reactor.
PO is widely documented for ethanol, the most described feedstock in
the literature. When hydrogen is produced with carbon monoxide as a
by-product from ethanol and low O2 quantities, the reaction is endo­
thermic (Equation (4)) and becomes exothermic when the percentage of
O2 within the reactor increases (Equation (5)). In this case, the partial
oxidation reaction is autothermal, and carbon dioxide is produced. Due
to the highly exothermic reaction, PO is carried out at lower tempera­
tures [62,63]. In the case of lower amounts of oxygen, water gas shift
(WGS) reactions could improve the H2 yield of partial oxidation with
steam (Equation (6)). This reaction is mildly exothermic, and the water
added to the system avoids deactivation of the catalysts by limiting coke
formation, as in steam reforming [64,65]. Catalysts are also necessary in
partial oxidation, as in steam reforming, except that no external heat
source is required in PO.
( / )
C2 H5 OH + 0.5 O2 →3H2 + 2CO ΔH O = + 14 kJ mol (4)
( / )
C2 H5 OH + 1.5 O2 →3H2 + 2CO2 ΔH O = − 510 kJ mol
( / )
C2 H5 OH + 0.5 O2 + 2H2 O→ 5H2 + 2CO2 ΔH O = − 68 kJ mol
Supercritical water gasification (ScWG) is an alternative thermo­
chemical route that has been developed at the laboratory scale to be
more robust for the biomass type, including wet biomass (moisture >
35%) such as wood and carbohydrates. Water requires a temperature
above 374 ◦ C and a pressure higher than 221.2 bars to become a su­
percritical fluid. Under these conditions, the dielectric constant of water
decreases as well as the quantity of hydrogen bonds. Organic com­
pounds and gases are miscible in supercritical water at high tempera­
tures, facilitating their conversion. The total reaction is endothermic and
similar to that involved in aqueous-phase reforming. Residence times
can be very low compared with other gasification processes (2–6 s), and
the reaction can be conducted at a lower temperature (600–650 ◦ C)
[66]. However, to maintain these conditions, high energy levels are
needed, increasing the costs and hindering its scalability [8]. Therefore,
no system has been developed on an industrial scale because the high
pressure required induces substantial capital and operational expendi­
tures [67]. Solving certain technical issues (waste neutralisation, reactor
design standardisation, and comprehension of chemical kinetics) are
compulsory for the development of commercial and viable ScWG sys­
tems [68]. The general biomass conversion equation for the ScWG is
Fig. 1. Schematic illustration of steam gasification of biomass combined with
stream reforming. HC refers to hydrocarbons.
Biomass and Bioenergy 144 (2021) 105920
given as Equation (7) [69].
( / )
CHx Oy + (2 − y)H2 O → CO2 + (2 − y + 0.5 x)H2 ΔH O > 0 kJ mol
(7)
(with​ x ​ = ​ element​ molar ​ ratio​ H/C ​ and​ y ​ = ​ elemental ​ molar​ ratio ​ O/C)
There are two temperature regions in ScWG systems: high temper­
ature, typically in the range 500–700 ◦ C and low temperatures of
374–500 ◦ C. At high temperatures, pyrolysis reactions take place before
gasification, splitting the feedstock without catalyst contribution.
Nevertheless, alkali catalysts can be added to increase the H2 yield by
promoting WGS reactions. At low temperatures (374–500 ◦ C), hydro­
lysed compounds are gasified and reduced by alkali-based catalysts,
transition metals, and activated carbon catalysts, which are necessary to
enable a high conversion of biomass to gas [70,71]. Moreover, a
methanation reaction occurs at low temperatures and consumes the
hydrogen produced to form CH4, requiring charcoal or another
carbon-based catalyst to solve this issue.
Pyrolysis is another tool, besides gasification, for biomass thermo­
chemical conversion. Pyrolysis is similar to gasification but can be
performed at lower temperatures and without an oxidising agent [72].
In some specific cases, a small amount of an oxidising agent can be
added to facilitate heat generation [73]. Pyrolysis typically occurs at
temperatures ranging between 400 and 800 ◦ C, under a pressure of up to
5 bar. According to the operating temperature, pyrolysis can be divided
into three classes: conventional (or slow) pyrolysis, fast pyrolysis, and
flash pyrolysis. Conventional pyrolysis is carried out at temperatures
below 450 ◦ C and results in a high charcoal content. Fast pyrolysis
produces a high bio-oil yield of up to 75 wt% at medium temperatures
(450–600 ◦ C) with a high heating rate (approximately 300 ◦ C/min) and
a short residence time [74]. Flash pyrolysis is similar to fast pyrolysis but
(5) at higher temperatures (above 600 ◦ C) and higher heating rates
(>1000 ◦ C/s), while the residence time is shorter (below 1 s), and is used
(6) to maximise the gas yield [42]. However, the fast and flash pyrolysis gas
yields are lower compared with gasification, especially because of the
lower operating temperatures [75,76]. A general pyrolysis reaction is
presented in Equation (8) [41].
Biomass + heat→H2 + CO + CO2 + CH4 + H2 O + bio − oil
( / )
+ charcoal ΔH O > 0 kJ mol (8)
Oxygenated molecules (aldehydes, ketones, alcohols, phenolic
compounds and carboxylic acids), water, and ash may be condensed
after pyrolysis to form a complex liquid fraction similar to tar called
“bio-oil”. Bio-oils can be divided into two classes: water-insoluble frac­
tion and water-soluble fraction. The insoluble fraction can be cracked
into platform molecules such as BTX or olefins and can be used in ad­
hesive applications [77]. Concerning the soluble fraction, a steam
gasification system can be added to the process to increase the H2 pro­
duction yield.
Pyrolysis–steam reforming is a two-stage thermochemical route that
has been extensively studied recently [78]. The catalysts used are the
same as for the cracking steps of gasification and are also inactivated by
carbon deposition (coke). A catalyst regeneration step enables the con­
version of coke into CO2 by combustion, unblocking the active sites [8].
Global H2 yields are similar to those for steam reforming by gasification
and range between 70% and 80% [79]. The separation of the reactors in
the pyrolysis-steam reforming process avoids reforming catalyst inhi­
bition by coke deposition [54]. The process is easy to scale up and offers
an alternative to direct gasification and bio-oil reforming [78].
Aqueous phase reforming (APR) is the third thermochemical
approach used for H2 production from biomass. APR converts mainly
oxygenated compounds into hydrogen. Feedstock molecules are dis­
solved during the aqueous phase and react with water molecules at low
temperatures (<270 ◦ C) and high pressures (up to 50 bar) [80,81]. APR
processes are suitable for biomass-derived oxygenated hydrocarbons
4
T. Lepage et al.
with a C/O ratio of 1:1 and are miscible in water, such as methanol,
ethanol, ethylene glycol, glycerol, glucose, or even polyols, such as
sorbitol [82]. The small range of effectively soluble molecules converted
in the process is the principal drawback. However, reforming pure cel­
lulose and woody biomass through APR is possible after a pre-treatment
step [27]. This involves the hydrolysis of cellulose and hemicellulose to
monomers that can be used as feedstock [83]. The reaction mechanism is
similar to steam reforming and relies on C–C bond cleavage to produce
H2. The ideal pathway for the conversion of ethylene glycol, whose
mechanism is well known, is depicted in Fig. 2. In contact with the
surface of a catalyst, the C–C bonds of ethylene glycol are cleaved to
produce carbon monoxide. The catalyst also promotes the WGS reaction,
leaving a low amount of CO remaining in the gas stream (<300 ppm).
Other reaction intermediates are possible, favouring the C–O bond
cleavage, leading to alkane (CH4, C2H6) formation and a lower H2 pro­
duction yield [84].
Choosing a metal (M)-based catalyst depends strongly on the sta­
bility of the M − C bond (enhancing the C–C cleavage pathway) and the
M − O bond (enhancing the C–O cleavage pathway). However, the price
of metal catalysts is prohibitive for large-scale development. Moreover,
the support of catalysts must be considered. Basic and neutral supports
are preferred to acidic supports because their selectivity for H2 is higher
and lower for alkanes, respectively. Indeed, alkanes are produced under
acidic conditions arising from dehydrogenation, and it is critical to opt
for a catalyst that is non-selective to alkanes while working at suitable
pH conditions [80]. Feedstock biomass and the process conditions also
influence the selectivity of APR [66,84]. The conversion of complex
oxygenated molecules, such as carbohydrates, is a challenge because
they yield lower amounts of H2 [80]. The thermal homogeneous
decomposition of carbohydrates rapidly creates large amounts of coke
responsible for catalyst deactivation and competing with the reforming
reactions.
2.2. Biological conversion
Biological conversion can be divided into three categories: biological
water gas shift reaction, dark fermentation, and photo-fermentation.
Each process depends on the nature of the enzymes used to catalyse
H2 formation [85]. Commonly, microorganisms, such as micro-algae
and cyanobacteria, produce the enzymes required to synthesise H2,
including nitrogenases and hydrogenases [86]. Nitrogenases reduce
protons (H+) from adenosine triphosphate (ATP) and electrons and
release H2, while hydrogenases reversibly catalyse the conversion of
protons to hydrogen.
In contrast to thermochemical processes, biological conversion takes
place at lower temperatures (30–60 ◦ C) and pressures (1 atm),
decreasing the energy cost. Moreover, the microorganisms used can be
easily regenerated by replication, decreasing the turnover frequency
compared with chemical catalysts easily deactivated during thermo­
chemical conversions [87]. Biological processes are particularly inter­
esting in waste management and enable the conversion of agricultural
waste, agri-food effluents, and solid residues, or municipal solid waste.
Investigations of sewage sludge have increased in the last ten years
because the nature of the material is favourable to its conversion
through different biological processes [88].
The biological water gas shift (BWGS) reaction depends on the
capacity of photoheterotrophic bacteria, using carbon monoxide as the
carbon source. These microorganisms can produce H2 (together with
Fig. 2. Mechanism for APR converting a diol component into hydrogen (and
combined with a WGS post-process).
5
Biomass and Bioenergy 144 (2021) 105920
CO2) in the dark by oxidising CO and reducing H2O through an enzy­
matic pathway, according to Equation (9) [83].
( / )
CO + H2 O⇋CO2 + H2 ΔH O < 0 kJ mol (9)
Different microorganisms can perform BWGS. Among the gram-
negative bacteria, Rhodospirillum rubrum is the most widely explored,
while Carboxydothermus hydrogenoformans is the most used gram-
positive microorganism [89,90]. An advantage compared with a ther­
mochemical WGS reaction is the lower temperatures and pressures
(30–70 ◦ C depending on the strain, atmospheric pressure). Nevertheless,
different parameters still need to be optimised. Carbon monoxide
released from the feedstock needs to be limited because it decreases
bacterial activity. In addition, microorganisms need to be improved to
increase the concentration in the bioreactor. Finally, issues concerning
the mass transfer of gas to liquid should be addressed [90].
Dark fermentation, another biological option for producing H2,
occurs when anaerobic microorganisms, such as micro-algae or specific
bacteria, are sustained in the dark at temperatures between 25 and
80 ◦ C, or even at hyperthermophilic (>80 ◦ C) temperatures, depending
on the strains. Under these conditions, the gas produced contains H2,
CO2, and small amounts of CH4, CO, and H2S, depending on the con­
verted substrate. Hydrogen is primarily produced from the anaerobic
metabolism of pyruvates generated during the catabolism of carbohy­
drates [91]. Compared with photolysis, the H2 yield in the gaseous
product is lower due to the minor gases [85]. The yield of hydrogen also
relies on the by-products of the reaction. From glucose, considered as a
model substrate, 4 mol of H2 per mol of glucose can be obtained when
acetic acid is the by-product of the reaction and 2 mol of H2 per mol of
glucose when butyric acid is obtained [92]. More hydrogen can be
produced when the reduced end-product is acetate, and that pathway
should be promoted over butyrate. However, both molecules still
contain hydrogen that could be released to increase the yield. It is
possible to direct a specific pathway for H2 production by changing the
conditions of the bioreactor [85]. Other parameters also influence H2
production, such as the pH, hydraulic retention time (HRT), and gas
partial pressure. Another advantage of dark fermentation is the possi­
bility of converting cellulosic and lignocellulosic materials, such as
wastes, to hydrogen [93,94]. This biological process has the potential to
integrate waste management into energy production. However, it still
requires the development of current technologies to be financially
competitive and have the potential for practical application and com­
mercialisation. Globally, two factors are limiting the development and
scaling of biological processes. Compared with thermochemical pro­
cesses, the H2 yield and production rate are lower (up to several months)
making biological processes less competitive, even if improvement has
been made with dark fermentation [95]. In addition, the complexity of
lignocellulosic material and agricultural waste requires the material to
be enzymatically fermentable. This additional time-consuming and
expensive process hinders the development at an industrial scale. The
variability of the feedstock notably affects the H2 yield and the economy
of the process, demonstrating that the selection of substrates is crucial.
Photo-fermentation (PF) is the latest biological process used for H2
production. PF is catalysed by nitrogenases in purple non-sulphur bac­
teria to convert organic acids or biomass into hydrogen from solar en­
ergy in a nitrogen-deficient medium. Equation (10) presents the global
reaction performed on glucose as the model substrate [96].
C6 H12 O6 + 12H2 O→ + 12H2 + 6CO2 (10)
PF can be performed either through single-step or two-stage
fermentation. The single-stage process is a low-cost approach but suf­
fers from several drawbacks, such as the high energy demand from ni­
trogenases and their low solar energy conversion. The two-stage
fermentation is a system in which dark-fermentation occurs first, and the
organic acids obtained undergo PF sequentially to produce more H2. The
disadvantages are the difficult operations to control the different
T. Lepage et al.
bacteria and the parameters between the separate stages [97,98]. Recent
studies have investigated PF as waste-prevention process to produce H2
from industrial and agricultural wastes [99,100]. However, it remains
the least financially competitive process among all the biological
methods [101].
2.3. Electrochemical conversion possibility
Electrolysis is an electrochemical process widely investigated for
hydrogen production by splitting water molecules. The mechanism oc­
curs in a fuel cell (containing a cathode and an anode) at a low tem­
perature and relies on the flow of an electric current through a
conductive electrolyte (alkali or polymer) in water. This results in the
splitting of water into O2 and H2 [102]. The conversion is fast,
straightforward, and produces pure H2 after separation. Moreover, there
are no carbon, sulphur, or nitrogen side-product compounds, saving
purification costs when compared with those of gasification processes.
The limitation of water splitting relies on thermodynamic parameters
because an electric consumption of a minimum of 45 kWh/kg H2 is
required to reach a sufficient yield of hydrogen.
Electrochemical conversion is also possible for biomass. The differ­
ence between water and biomass electrolysis lies in the reaction
occurring at the anode. The feedstock is oxidised instead of producing
gaseous oxygen from the water. Biomass electrolysis can be achieved
through two different technologies, Proton Exchange Membrane Elec­
trolysis Cell (PEMEC) and Microbial Electrolysis Cell (MEC). Both
PEMECs and MECs are commonly used for bio-based molecules such as
ethanol and glycerol. Polymeric molecules, such as cellulose or wood
sawdust, cannot be converted directly by electrolysis. These systems
require a single or two chambers containing an anode/cathode couple.
The conversion of organic matter occurs at the anode by an oxidation
reaction releasing protons (H+). A reduction reaction occurs at the
cathode, allowing the formation of H2 [103]. PEMEC systems contain a
polymeric membrane that transfers protons to obtain a high hydrogen
gaseous fraction [104]. In MEC systems, the oxidation of organic matter
to produce H+ is performed using electrochemically active microor­
ganisms as catalysts, making the process a “bio-electrochemical” system
Table 4
Comparison of the main advantages and drawbacks, and H2 yields (expressed in g/kg feedstock) of several process options.
Processes Advantages
Thermochemical processes
Biomass Existing industrial design, forest residue and industrial
Gasification waste recycling, high biomass conversion efficiency, no
expensive oxygen source required in steam gasification
Steam Existing industrial design, no expensive oxygen source
Reforming required
Partial Existing industrial design, no catalyst requirement, low
Oxidation desulfurization requirement
ScWG Suitable on biomass with high moisture content
APR Suitable for feedstock in aqueous solutions
Biomass Existing industrial design, forest residue and industrial
Pyrolysis waste recycling, versatile conversion of biomass (gas, bio-
oil, biochar), simple process
Biological processes
Dark Organic and biological waste streams recycling, conversion
fermentation of algal biomass (high growth rate), low operating
temperature and pressure, various suitable carbon sources
Photo- Organic and biological waste streams recycling, nearly
fermentation complete substrate conversion, low operating temperature
and pressure
Electrochemical processes
MEC No purification required, lower electrical consumption
(compared with water electrolysis), mild conditions
PEMEC No purification required, lower electrical consumption
(compared with water electrolysis), mild conditions
Biomass and Bioenergy 144 (2021) 105920
[105].
Classic PEMEC systems require an expensive catalyst made of noble
metals, that are extremely sensitive to CO and other impurities released
by biomass during electrolysis. Moreover, PEMECs consume a high
volume of alkaline molecules to neutralise the organic acids produced
during the electrolysis of biomass, thus making the process even more
expensive. The same findings have been reported for MEC systems
where microorganisms cannot directly use the biomass. Biomass must be
fermented and converted into organic acids or alcohols, and only those
molecules can be converted to H2 through the MEC. In addition,
although its electrical consumption is lower than that of water elec­
trolysis, the conversion rate of MEC is too slow for the process to be
competitive. These drawbacks have slowed down the development of
electrolysis systems producing H2 from biomass [106].
Even if the electrical consumption can be lowered by using bio­
ethanol instead of water (e.g. Chen et al. reduced it by 26.5 kWh/kg H2
converting ethanol using palladium nanoparticles deposited on titanium
nanotubes), the total energy balance is impacted by bioethanol pro­
duction. Indeed, this issue decreases the interest in this process because
an economically viable bioethanol is challenging to produce from
biomass, especially from lignocellulose [107]. Investigations into the
direct electrolysis of biomass should be performed in the future.
3. SWOT analysis of the main process used from biomass
Several (thermochemical, biological, and electrochemical) technol­
ogies are described below regarding their ability to produce hydrogen
from biomass. Table 4 summarises the key advantages and drawbacks of
each process.
Thermochemical conversions have the advantage of being available
at a large production scale because the technologies used are based on
current well-established methods for converting fossil fuels. Therefore,
the industrial design has already been established [116]. Despite being
carbon-neutral, thermochemical processes release CO2 and require a
combination with carbon capture systems (CCS) to achieve negative
emissions. Even if this solution is associated with an increased invest­
ment, it is the best economical solution to reach the environmental
Limitations H2 Yield (g/kg Ref.
feedstock)
CO2 emissions, tar and char formation leading to catalyst 40–190 [19,75,108,
deactivation, H2 variation due to biomass complexity and 109]
composition variations, high operating temperature, need for
catalysts regeneration, high reactor cost
CO2 emissions, high operating temperature, need for catalysts 40–130 [62,109]
regeneration
CO2 emissions, high operating temperature, high cost of 16–140 [109–111]
oxygen, adapted only for few molecules
CO2 emissions, high pressure needed, high energy consumption 20–40 [112]
CO2 emissions, adapted only for few molecules, need for pre- 1–40 [113]
treatment
CO2 emissions, tar and char formation, H2 variation due to 25–65 [114]
biomass complexity and composition variation, need for
catalysts regeneration, high reactor cost
Low H2 yield and rate production, high by-products generation, 4–44 [77,109,
need for pre-treatment 115,116]
Low H2 yield and rate production, high surface area 9–49 [77,97,109,
requirement, need to control the bacteria, high energy demand 117]
for enzymes, low energy solar conversion efficiency
Expensive catalyst, low production rate, suitable for less 15–98 [103,106,
complex molecules in solution 118]
Expensive catalyst, low production rate, suitable for less / [106]
complex molecules in solution
6
T. Lepage et al.
objectives [119]. These processes rely on essential catalysts that are
prone to deactivation. They require high temperatures compared with
biological and electrochemical routes. Overall, the best yields are ob­
tained through gasification. Gasification and pyrolysis are adapted for a
wide variety of dried feedstocks, while steam gasification and steam
reforming are the best compromise for wet complex biomass treatment.
However, the processes are more sensitive to catalyst deactivation by tar
and char formation. Partial oxidation and APR are only applicable to
simple molecules in solution, requiring an eventual pre-treatment step
that increases the cost of the processes. The ScWG system requires high
pressures, which also represents a significant cost that hinders scaling up
[120]. PO, APR, and ScWG would have less impact because their
applicability at a large scale is limited.
Biological conversion suffers from low yields and a slow conversion
rate. The production from complex biomass requires pre-treatment for
prior fermentation, hindering the processes at the pilot scale. They are
more suitable for rich liquid streams, such as molasses or food waste
[121]. Moreover, compared with APR and ScWG, the conditions of the
fermentative processes are milder, and the hydrogen yields are more
substantial due to a higher efficiency, especially in the case of dark
fermentation (80%). Even though PF has a slightly higher yield than
dark fermentation, the lower efficiency (0.1%) decreases the interest in
this technology. In addition, dark fermentation is more worthwhile
considering its higher production rate and lower energy consumption.
Therefore, dark fermentation or a combined process with PF should be
favoured.
Concerning electrochemical conversion, water electrolysis does not
directly cause carbon emissions but has a high electrical consumption
(4.5-50.6 kWh/m3 H2) [122]. Biomass electrolysis has been investigated
because lower electrical consumptions have been obtained with the
development of the MEC and PEMEC systems (0.6–1 kWh/m3 H2) [123].
This consumption is even lower than the energy required for biological
processes, while having similar conversion rates. Although MEC and
PEMEC are interesting methods for waste management, the low
hydrogen production rate is the most significant impediment to these
methods being competitive [124].
To supply the necessary amount of biomass to produce hydrogen,
two types of feedstock can be used: lignocellulosic residue and dedicated
crops. Lignocellulosic waste is available at a low cost because they are
generated at the end of the harvest season for such crops as cereal wheat
or during the transformation process. However, dedicated energy from
crops, such as sorghum, requires land use and growth time, which can be
a challenge. As mentioned by Kammoun et al. it is possible to group
biomass types according to their chemical composition (carbohydrates,
lignin, and others) to facilitate the pre-treatment required [24].
Thus, biomass represents a renewable precursor to hydrogen pro­
duction and could be comparable to water electrolysis as an alternative
to fossil feedstock for chemical production and even in the future for fuel
transportation.
4. Recent developments and perspectives for existing processes
4.1. Improvements of thermochemical approaches
Gasification is perhaps the most thoroughly studied process, and its
improvement has been abundantly described and updated. One key
element of the current research is to find suitable operating conditions
and catalysts that can effectively increase the volume of the gas pro­
duced and its quality at a low cost [125]. New efficient catalysts are
added to promote tar conversion and prevent the formation of unwanted
products. Some studies have already reviewed and compared a wide
range of available catalysts for thermochemical processes, especially
gasification [21]. Usually, these are dolomite, olivine, potassium min­
eral, and nickel-based compounds [108]. Recent results are highlighted
for these catalysts. According to Zhang et al. for a range temperature
from 450 ◦ C to 850 ◦ C, the maximum H2 yield was 204.6 mL/kg biomass
7
Biomass and Bioenergy 144 (2021) 105920
(Ficus virens leaves) using limestone/dolomite (1:1) as the catalyst
[126]. Wei et al. highlighted the variations in the H2 yield due to
biomass type and catalyst. They obtained a 10% and 15% increase in H2
concentrations in the gas produced from legume straw and sawdust
using dolomite compared with inert sand. This increase is attributed to
the catalytic steam reforming of tar. Meanwhile, varying the tempera­
ture demonstrated a significant effect on tar yield (g/Nm3) and
hydrogen yield (g/kg fuel) [127]. A significant effect on hydrogen yield
was demonstrated by Ma and co-workers in 2019 by studying dolomite
and olivine as catalysts at different temperatures. When the temperature
was increased from 700 to 900 ◦ C, the tar yield decreased from 12.5 to
7.2 g/Nm3 for dolomite and from 15.9 to 9.1 g/Nm3 for olivine. The tar
conversion led to an increased hydrogen yield from 36.2 to 46.4 g/kg
and from 32.4 to 42.3 g/kg of biomass, respectively [128]. The choice of
gasifier depends on the biomass feedstock and the conditions for H2
production. Therefore, development and optimisation steps are required
for each raw material.
Currently, the best compromise consists of gasification using steam
as an oxidising agent in terms of gas composition, impurities, and cost.
Recent developments in steam gasification have focused on decreasing
the temperature processes and the tar and char formation through
catalyst use to improve the H2 yield [42]. Moreover, steam gasification
allows more flexibility regarding the feedstock, allowing the use of wet
biomass without requiring expensive oxygen. The primary objectives are
the development of improved catalysts, especially dolomite and olivine,
to reduce the operating temperature (the total energy used), tar content,
and therefore, the cost of the process.
Linked to gasification improvement, most of the research in terms of
steam reforming (SR) is focused on new catalyst discovery, temperature
optimisation, and char and coke degradation. Guo et al. increased the
yield by using rice husk char (RHC) as a support metal catalyst, from
196.6 to 269.6 mL/g using K-RHC, 274.9 mL/g for Cu-RHC, and 342.7
mL/g for Fe-RHC. Char and char-supported catalysts promote H2, CO,
and CH4 production [129]. In addition, a high C/H ratio of biomass
induces coke formation during gasification; a carbon deposit negatively
affects the catalyst. Decreasing the C/H ratio is driven by steam
reforming, thereby reducing coke formation. In 2018, Yaghoubi et al.
studied the effect of different parameters on hydrogen production from
biomass in a dual fluidised bed gasifier. They demonstrated that H2
production could be optimised at operating temperatures between 800
and 820 ◦ C. At higher temperatures (>820 ◦ C), hydrogen production
decreases due to char combustion for energy input; thus, char is not
converted into H2. Residence time influences the specific gas formed
during gasification, which is directly linked to the steam/biomass ratio
(S/B). Typically, an S/B ratio of 1.3 allows the optimal production of H2.
Higher S/B ratios decrease the residence time and do not allow complete
gasification reactions, thereby producing less H2 and more
carbon-containing gases. Finally, decreasing the reactor diameter and
biomass particle size increases the H2 yield by gasification [130]. The
general concentration of H2 in the reported gas produced varies between
18% and 59%. This variation is due to the different catalysts used, and
studies have focused on their efficiency. Ni-based and char alkali earth
metals are the most effective and explored catalysts. For example, Liu
et al. studied catalytic tar cracking from rice hull gasification and ob­
tained a tar conversion of 94.4% with a Ni-based catalyst (Ni6/PG),
enabling a hydrogen yield of 57.7% [131]. Al-Rahbi et al. used tire
pyrolysis char as a catalyst for the gasification of wood pellets. The H2
concentration increased up to 50% and the H2 yield from 8.4 to 39.2
mmol/g biomass when the temperature was raised from 700 to 900 ◦ C
[132]. Yao et al. demonstrated that biochar is a promising catalyst and
support for biomass gasification. Biochar from CSP allows a good
interaction with the volatiles due to the alkali and alkaline earth metals
present, facilitating the conversion to H2. The addition of Ni (Ni-based
biochar) improved the production of hydrogen from 45.91 to 92.08 mg
H2/g biomass at 800 ◦ C in a two-stage fixed-bed reactor during steam
reforming [133]. Xu et al. also demonstrated the effect of alkaline earth
T. Lepage et al.
metals on gasification efficiency. Calcined calcium oxide (CaO),
comprising 5 wt% of Fe gave the highest H2 yield (26.40 mol/kg
biomass) in a fluidised bed reactor at 700 ◦ C for wood sawdust gasifi­
cation. The Fe/CaO catalyst is less efficient for gasification than some
other catalysts and for CO2 capture compared with CaO. However, Fe
impregnation prevents CaO deactivation and allows for a better tar
conversion, giving a higher H2 yield compared with CaO only (12.36
mol/kg biomass) [28]. Overall, the key perspectives in terms of R&D
reside in the discovery of cheap and bio-based catalysts that resist coke
deactivation while being easily regenerated. This could allow a better
gas quality (H2 proportion), lower tar and char content, and a process
requiring a lower amount of energy.
Regarding partial oxidation (PO), several studies have been con­
ducted to improve partial oxidation using noble metal catalysts, such as
nickel- and cerium-based catalysts; however, their cost remains a
limiting factor [61,134]. Ma and Muller investigated various catalysts
for the partial oxidation of tar from biomass gasification. They revealed
that NiO, a nickel-based catalyst, was more active in the conversion of
naphthalene, a tar model compound. A conversion yield of 95% was
obtained at 600 ◦ C in a fixed-bed reactor [135]. Using Rh as a catalyst
(0.5 wt%), Kim et al. obtained an H2 production yield of 90% at 750 ◦ C
from dimethyl ether partial oxidation in a microreactor. The study
highlights the efficiency of their developed microreactor compared with
a conventionally packed reactor [136]. Partial oxidation was also per­
formed by Zukowski and Berkowicz on methanol in a fluidised bed of a
catalyst containing iron and chromium oxides [137]. Using an equi­
molar ratio of CH3OH and N2O, a yield of 95% was achieved at 350 ◦ C.
This method occurs at a lower temperature compared with other ther­
mochemical processes. However, the reaction co-generates CO2 and N2.
Separation steps are necessary following the partial oxidation. Many
efforts have been made to develop and upgrade partial oxidation pro­
cesses at the pilot scale. Compared with steam reforming, PO has a lower
or equal efficiency in terms of H2 production depending on the substrate.
For ethanol reforming, yields are up to 50% higher for SR [138].
Moreover, PO is more adapted to the indirect route by using
derived-biomass molecules with a lower C/H ratio, such as ethanol
(having a similar C/H ratio as methane), and not on lignocellulosic
biomass feedstock. PO can be attractive in order to valorise co-products
from already settled industries, including glycerol from biodiesel pro­
duction and ethanol from breweries, producing it as a side product of
non-alcoholic beers due to an increasing market for this type of product.
For ScWG, current research is focusing on more efficient catalysts. Li
and Guo evaluated the performance of the Ni/MgAl2O4–Al2O3 catalyst
in 2018. They also studied the effects of different parameters on the
ScWG, such as the heating rate, temperature, and catalyst loading. An
increased H2 production yield was obtained when the temperature was
increased from 200 to 600 ◦ C and reached a yield of 45 mol/kg for a 5 wt
% glucose solution at 600 ◦ C and a residence time of 300 s. CO2 was the
other significant gaseous product, and a separation process after ScWG
could deliver a high-purity hydrogen gas (>80%). Temperatures above
500 ◦ C are favourable for H2 production, while CH4 is the predominant
gas produced at temperatures ranging from 400 to 500 ◦ C [139]. Nanda
et al. compared the activity of different alkali catalysts for timothy grass.
The highest hydrogen yield was 5.15 mol/kg of feedstock at 650 ◦ C for
45 min with a 1:8 biomass-to-water mass ratio. They showed that an
increase in temperature improves the WGS reaction, resulting in higher
H2 and CO2 yields. For the WGS reaction also being catalysed by alkali
catalysts, KOH produced the best results (H2 yield = 8.91 mol/kg),
followed by K2CO3, NaOH, and Na2CO3. Alkali catalysts are worth
exploring further for the production of H2-rich syngas [140].
Many developments have also been proposed for pyrolysis, in
particular aiming at elucidating the optimal process conditions. Waheed
et al. increased the temperature from 850 ◦ C to 1050 ◦ C, inducing a
hydrogen yield increase from 20.03 to 30.62 mmol/g feedstock [141].
Biomass type, particle size, heating rate, pressure, and residence time
can be adapted to maximise the production of charcoal, bio-oil, or
8
Biomass and Bioenergy 144 (2021) 105920
gaseous products. Moreover, catalysts also improve the yield of H2
production, tar decomposition, and biomass conversion. Carbonates
(Na2CO3 and CaCO3) and metal oxides (Al2O3 and Cr2O3) have been
studied and compared for different biomass species. The most effective
catalyst also depends on the biomass type selected as the feedstock
[142]. Research has also focused on the discovery of new Ni-based
catalysts and optimal operating conditions according to each type of
biomass. Akubo et al. studied the conversion of six biomass wastes (rice
husks, coconut shells, sugarcane bagasse, palm kernel shells, cotton
stalks, and wheat straw) and three biomass model components (cellu­
lose, lignin, and xylan) into hydrogen by pyrolysis-steam reforming. In a
two-stage fixed-bed reactor system, pyrolysis occurs at 550 ◦ C and steam
reforming at 750 ◦ C with a NiAl2O3 catalyst. The catalyst and steam
enable a H2 yield of 25.35 mmol/g for palm kernel shell conversion,
which represents 57.36 vol% of the gas composition. For the biomass
components, lignin exhibited the highest H2 yield (25.25 mmol/g)
compared with cellulose (19.72 mmol/g) and xylan (20.54 mmol/g).
Different mixtures of lignin/cellulose/xylan led to the conclusion that
the more the feedstock is lignified, the more hydrogen is produced,
while cellulose and hemicellulose pyrolysis release more CO and CO2
[143]. Chen et al. tested Ni/CaAlOx as catalysts on wood sawdust
through pyrolysis (T = 500 ◦ C) and steam reforming (T = 800 ◦ C). The
hydrogen yield was 15.57 mmol/g feedstock with a Ca/Al molar ratio of
1:2. Ca is a cheap alkaline metal that improves the conversion of biomass
by increasing the CO selectivity, which can be used to control the H2/CO
ratio in the syngas. With a Ca/Al ratio of 3:1, a total concentration of H2
and CO of 90 vol% was reached. However, catalyst deactivation
resulting from coke deposition is the limiting factor [144]. Nevertheless,
according to Jin et al. Ca used in the catalyst also increases hydrogen
production. Under the CaO form, CO2 is absorbed during the conversion
process. When Ca was incorporated into the Ni–Mg–Al catalyst, the
hydrogen yield increased from 10.4 to 18.2 mmol/g of wood sawdust
[145]. Dong et al. searched for a catalyst promoting hydrogen produc­
tion while minimising catalyst deactivation. The NiO–ZnO–Al2O3 cata­
lyst obtained by precipitation has been tested with different Ni contents.
The H2 yield increased from 8.2 to 20.1 mmol/g wood sawdust when the
Ni molar ratio was increased from 5 to 35%. Moreover, when the Ni
content was increased to 25 and 35%, coke deposition on the catalyst
was below 1 wt%. This study demonstrates the activity of Ni for the
conversion of biomass and its resistance to deactivation due to carbon
deposition [146].
Regarding aqueous phase reforming (APR), extensive research is
currently being conducted to improve catalyst stability and activity to
reach commercial applications and scale up. Metal catalysts (M), such as
Pt and Pd, are currently the most frequently used, as well as Ni-based
catalysts, because their activity for C–C and C–H bond cleavage is
high, leading to high H2 production. These catalysts are also necessary
for their high activity in WGS reactions. They increase the H2 yield
compared with Rh and Ru catalysts through a higher propensity for
alkane formation by promoting the C–O bond cleavage pathway. The
thermal conditions and high pressure increase the activity of the WGS
reaction and improve the conversion of oxygenates into H2. Moreover,
thermal decomposition of oxygenates is unlikely to occur, leading to less
coke deposition and catalyst deactivation. H2 can be concentrated up to
99.9% using a pressure swing adsorption system (PSA) [80]. Coke
deposition can be mitigated by converting polyols instead of carbohy­
drates. Their resistance to thermal decomposition (Maillard reaction)
due to the absence of carbonyl enables the decrease in coke deposition
and increases the reforming reactions producing H2. In addition, by
increasing the steam-to-biomass ratio, the feedstock is diluted, enabling
a yield comparable to that of polyols [84]. A solution is the reduction of
glucose to sorbitol, which has a better resistance to thermal decompo­
sition (responsible for catalyst deactivation by coke accelerated forma­
tion). Moreover, metal catalysts, such as platinum-based catalysts, have
a higher selectivity for sorbitol than sugars in H2 production because of
the reduction of their aldehyde function to alcohol [83].
T. Lepage et al.
4.2. Improvements of biological processes
When considering dark fermentation, the impact of the pre-
treatment is significant. Indeed, it improves the H2 yield by hydro­
lysing the feedstock into small-weight molecules that are easily metab­
olised by microorganisms. In 2018, Kumar et al. reviewed the hydrogen
production from various biomass types (lignocellulosic, algae, and
wastewater) by dark fermentation, while Bundhoo focused only on crop
residues [93,147]. For lignocellulosic biomass, different pre-treatments
have been tested as dilute acids. Alkali pre-treatment was carried out to
remove lignin, followed by enzymatic hydrolysis (cellulase and xyla­
nase) to obtain fermentable sugars. The combination of alkali and acid
pre-treatments has also been investigated. Among all the results, the
highest yield obtained was 176 mL H2/g cornstalk using cellulase in
lightly acidic conditions (pH 4.8, 0.2% HCl). Recent studies have
focused on hydrogen production using microalgal biomass. Lunprom
et al. produced H2 through anaerobic solid-state fermentation followed
by dark fermentation using the microalgae Chlorella sp. The H2 yield was
16.2 mL H2/g volatile solid (VS, total organic matter in the biomass)
[148]. With the help of pre-hydrolysis with simultaneous saccharifica­
tion and fermentation, Giang et al. improved the H2 yield up to 172 mL
H2/g VS and productivity (2.4 ml/g VS. h) [149]. Wang and Yin also
showed the production of hydrogen from different microalgal biomass,
and the effect of the pre-treatment increased the H2 yield by disrupting
the microalgal cells (up to 958 mL H2/g VS from Chlorella sp. with
HCl-heat pre-treatment). However, the processes are far from the in­
dustrial scale, and more studies are required to improve the profitability
of such processes [150]. More research is necessary regarding
pre-treatment to standardise the operating conditions and improve the
efficiency of the biological process. As reviewed by Zabed et al. different
types of pre-treatment exist (biological, chemical, physical, combined
treatment) [151]. Future work will focus on scaling up to generate
hydrogen in larger quantities from biomass to reach an industrial scale.
Moreover, practical and economic feasibility analyses at larger scales are
necessary to evaluate the applicability of the process [148]. Further
investigation is needed into the development and design of a
better-performing bioreactor to improve the conversion. The issue of
reducing the cost of the pre-treatment must guide researchers to affect
the cost of the process and to set up dark fermentation on a larger scale
[152]. Other research perspectives can be adopted for the identification
of new strains of more suitable bacteria or microorganisms, revealing
new opportunities [153]. Finally, at first sight, the use of biological
processes in general makes more sense to valorise effluents containing
sugars, such as molasses and vinasse, and wastewater, including sewage
sludge, that can be processed by microorganisms. Research has
increased in the last ten years because the nature of the material is
favourable to its conversion by different biological processes. The high
water content is suitable for biological conversion, but is a drawback for
major processes such as gasification.
For photo-fermentation (PF), different parameters (substrate con­
centration, C/N ratio, and phosphate concentration) were optimised by
Wang et al. to develop a single-stage process to produce hydrogen by PF
from straw biomass using Rhodobacter sphaeroides. The biomass was first
hydrolysed under acidic conditions using 5% HCl at 118 ◦ C for 30 min.
The conversion of the hydrolysate to H2 was achieved in a neutral me­
dium by two Rhodobacter sphaeroides strains: HYO1 (wild type) and
WHO4 (mutant). They obtained a higher yield (4.62 mol H2/mol
reducing sugar for the WHO4 strain) than direct sugar PF due to pH
stabilisation [154]. To improve the efficiency of PF, some researchers
have shown that combining dark fermentation with PF can improve
efficiency of the biological process. Integrated dark- and
photo-fermentation can solve the issues of the individual systems and
give higher hydrogen yields than PF under the same conditions [155].
The key perspective concerning PF consists of its combination with dark
fermentation. The dual system must be optimised to be implemented at
the pilot scale. The major improvement necessary in PF itself resides
9
Biomass and Bioenergy 144 (2021) 105920
predominantly in the development of a better-performing
photobioreactor.
4.3. Recent developments in electrochemical approaches
Current research is motivated to investigate the use of native biomass
as feedstock without the conversion into an intermediate. In 2016, Liu
et al. proposed an alternative by developing a new Chemical-Electrolysis
Conversion (CEC) using aqueous polyoxometalates (POM) as catalysts
[106]. In this case, POM is in solution and is not coated on the anode.
POM receives electrons from biomass oxidation and is enhanced by
heating or light irradiation. As POM has a low standard redox potential,
it can be easily re-oxidised, and protons are released and then reduced at
the cathode to form H2. POM acts as an electron-coupled-proton carrier.
POM has the advantage of being a low-cost self-healing catalyst (100,
000 turnovers) and is tolerant to impurities produced from the biomass.
CEC can be achieved in a PEMEC system without noble metal catalysts.
The energy consumption is extremely low (0.69 kWh/Nm3 H2)
compared with that of water electrolysis (4.13 kWh/Nm3 H2). This
process allows for the conversion of native biomass, such as wood dust,
to produce H2 at a low temperature and with low energy consumption.
Another method based on Fe3+ was developed by Yang et al., in 2017
using a similar approach to POM [156]. POM has a large molecular
weight, inducing a low rate of electrochemical conversion. In order to
improve the conversion rate, they investigated catalysts with smaller
compounds, such as Fe3+. They reported a novel method to produce H2
by electrolysis from biomass using iron ions as the catalyst in the liquid
phase. The production of hydrogen was achieved using PEMECs from
different biomasses comprising glucose, starch, and cellulose, without
any noble metals used as catalysts. During the process, Fe3+ in the so­
lution reacts with the biomass. The oxidised biomass is degraded to low
molecular weight derivatives, and Fe3+ is reduced to Fe2+. On the
cathode, Fe2+ is oxidised to Fe3+, and H+ is reduced to H2 on the anode.
The Fe ions act as an electron carrier, and their low redox potential al­
lows for low electric energy consumption. Another example of low
electric energy consumption was investigated by Hibino et al., in 2018.
They produced hydrogen by direct electrolysis of bread, sawdust, and
rice chaff at 150 ◦ C using their own anode developed with an
oxygen-functionalising carbon without any noble metals. The perfor­
mance in terms of catalytic activity was similar to that of a conventional
Pt/C anode. H3PO4, is added to the medium, hydrolysing the waste
biomass and enhancing electrolysis by increasing the solubilisation of
the compounds. The average yield was 0.25 mg H2/mg feedstock for
each biomass. In terms of perspectives, investigations should focus on
working with higher biomass quantities to scale-up the electrochemical
process [157]. Concerning the environmental impact of the process, CO2
is released during the production of hydrogen from biomass, contrary to
water electrolysis considered alone. However, the net balance for
greenhouse gas emissions is zero when considering the CO2 consump­
tion during biomass photosynthesis. In addition, a CO2 capture system,
such as CaO, can be added to improve the H2 concentrations in the
produced gas, limit emissions, and increase the total process profit­
ability [59]. Whether the process is applied to water or biomass, the CO2
released to produce the electricity used during the process must be
considered.
5. Techno-economic comparison of hydrogen producing
processes
The techno-economic assessment of an industrial hydrogen produc­
tion facility relies on two major expenses: capital investments (CAPEX)
and operational costs (OPEX). The critical issue is to reduce the CAPEX
and OPEX of the different processes while increasing the production
volume. This approach would allow the reduction of H2 production costs
from renewable resources to compete with fossil fuels. In most cases, the
CAPEX value was estimated using the software “Aspen Plus” or “Aspen
T. Lepage et al.
Hysys” in order to simulate the processes and to make economic as­
sessments [158]. Plant size and capacity have a major impact on CAPEX.
The larger the facilities, the higher the CAPEX, but leading to a decrease
in the production cost [159]. The presence of an integrated carbon
sequestration or carbon capture and storage (CCS) system also signifi­
cantly affects the total production cost, increasing the CAPEX due to the
supplementary technology used. The advancement level of the tech­
nology or technology readiness level (TRL) and the availability of
structures for the conversion processes are also critical factors to discuss
[109]. Concerning the OPEX, the price of the biomass feedstock, which
is mostly related to its availability and transport, has a significant in­
fluence on the production cost. Other parameters inherent to biomass
need to be considered, including the type of feedstock and the eventual
need for the pre-treatment step. An ideal biomass must be as cheap as
possible, resulting in a sustainable yield upon its use. In addition, the
process conditions have a significant impact on the cost of the process.
The cost includes the energy delivered to increase the temperature and
pressure, the electricity used for equipment or reactions (electrolysis),
and the type and cost of the catalyst(s). Finally, cost estimations will also
be affected by external factors, such as the fluctuation of fossil fuel
prices, the variation in the biofuel policies of a given country, and the
carbon tax related to CO2 emissions [160,161].
Table 5 presents the key TRL, CAPEX, and H2 production costs for
different technologies applied either on biomass, water, or fossil re­
sources (natural gas, coal). Thermochemical processes include tradi­
tional methods from fossil fuels. Currently, steam methane reforming
and coal gasification have the lowest H2 production cost (<1 $/kg H2),
mainly because of the large existing structures (TRL 9) and the low price
of the feedstock. However, biomass prices are expected to decrease by
2050 at the expense of fossil resources. The gasification and pyrolysis of
biomass are similar to those of technologies performed on fossil feed­
stock. They are expected to mature to reach a TRL up to 9 in the next two
decades. The critical challenges are related to the type of feedstock, cost
of the reactor, and CCS systems combined with the processes. In the case
of biomass gasification, the reactor represents up to 42.9% of the
CAPEX. In addition, Bartels et al. demonstrated that large plants with
CCS systems have higher CAPEX. For the SMR process, the integration of
CCS systems represents an increase of 25–30% for the H2 production
cost. The size of the plant will also significantly affect the H2 production
cost. For example, a small gasification plant will produce H2 for 10 $/kg
compared with a large plant, for which the cost decreases to 1.2.3.5
$/kg. OPEX accounts for 60% of the CAPEX of a gasification plant and
60% of the total production cost. Approximately 60% of the OPEX itself
is imputed to the maintenance and insurance, followed by the feedstock
price (25%) and the operational cost of the entire process (10%; energy
and electricity) [162]. The choice of a suitable catalyst will influence
Table 5
Comparison of the Technology Readiness Level (TRL), CAPEX and H2 production costs of different processes.
Process TRL Production scale
FOSSIL RESOURCES
SMR 9 Large/Available
Coal Gasification 9 Large/Available
WATER
Water Electrolysis 9 Small/Available
Vegetal/algal biomass
Gasification 7 Mid-size/Available
Steam Reforming 8 Small/Available
Pyrolysis 7 Mid-size/Available
ScWG 4 Pilot plant
APR 4–5 Pilot plant
Dark fermentation 5 Pilot plant
Photo-fermentation 4 Under research
MEC 2–4 Under research
Biomass and Bioenergy 144 (2021) 105920
both the yield and energy consumption. Regarding the oxidising agent in
gasification, steam is more beneficial than oxygen for economical
(representing a difference of 7–22 M€ for the CAPEX) and practical
reasons (WGS and CO2 removal) [163].
Among the other thermochemical processes, ScWG and APR have
been developed up to the pilot scale (TRL = 4–5). Concerning the ScWG,
the conversion of wet biomass, such as algae, sewage sludge, or organic
wastes, avoids the energy-intensive drying step. However, the key issue
is the high pressure required for the process. The resulting high energy
consumption and the specific installations increase both the OPEX and
CAPEX, making the process less competitive. Özdenkçi et al. determined
that the OPEX is an annual cost (60 M€) equivalent to the total instal­
lation cost for the ScWG of black liquor. Based on the simulation, the
current H2 production cost by SCWG is primarily affected by the OPEX
and could be decreased by developing large installations, such as for
gasification [168]. APR is performed on simple molecules, such as
ethanol. Its sustainability relies on the cost of reliably produced bio­
ethanol. Currently, alcohol production from lignocellulosic biomass is
not economically viable [170]. The future of APR is related to these
technologies.
Biological processes, widely studied at the pilot scale, have been
developed to reach the industrialisation step. The PR and dark fermen­
tation processes are two technologies of interest. Currently, fermenta­
tion processes are more adapted to a small scale. Their high H2
production costs make them less viable and competitive than thermo­
chemical conversion processes. The most significant issue is related to
the lower yield and rate of biomass conversion [171]. In addition, the
systems require expensive bioreactors and separation steps to obtain
pure H2 from gaseous products. This equipment increases the CAPEX of
the process, hindering development on an industrial scale [172]. To
improve the fermentation and enrich the hydrogen fraction,
pre-treatments can be performed on recalcitrant biomass. Physical
pre-treatments, including grinding, chipping, and milling, are the most
investigated step that are prior to biomass conversion. However, this
additional step increases the complexity of the process and can produce
inhibitors of bacterial growth, thereby impacting both the CAPEX and
the OPEX [173]. Future improvements should focus on the development
of local small-scale production plants. In addition, the optimisation of
bioreactors and development of new bacterial strains are required.
Regarding electrochemical processes, water electrolysis technologies
have a TRL as high as fossil fuel-based processes. However, industrial
production is currently performed at a smaller scale. Felgenhaur and
Hamacher compared the process efficiencies [174], and determined that
for a similar productivity (90 kg/h), the CAPEX of water electrolysis (4
M€) is lower than gasification (9.9 M€) and steam reforming (11 M€).
However, the investment cost can be substantial for large-scale
CAPEX H2 production cost ($/kg)12 Ref.
170.95–240.20 M€1 0.77 [21,80,161]
257.60 M€2 0.92–2.83 [21,80,164]
4.0 M€9 2.35–4.80 (Nuclear) [21,164,165]
8.9 M€10 5.00–10.00 (RSE13)
11 M€3 1.21–3.5 [21,61,67]
215.3 M$4
9.9 M€5 1.83–2.35 [61,166]
210–287 M$4 1.21–2.57 [21,80,167]
57.44 M€6 1.51–3.89 [168]
277.8 M$4
12.85 M$7 4.00 [169]
/ 2.57–2.80 [21]
115.6 M$8 2.83–3.89 [21,80]
2.8 M€11 1.7–4.5114 [123]
10
T. Lepage et al. Biomass and Bioenergy 144 (2021) 105920

production due to the price of an electrolyser, which can represent 60%
of the CAPEX. According to the CAPEX analysis, electrolysis is currently
more adapted to a small-scale approach (including the case of a
hydrogen refuelling station) [175]. Among all the processes listed in
Table 5, sustainable water electrolysis presents the highest costs. Elec­
trical consumption is the primary reason for the high OPEX, which in­
creases the H2 production cost, especially when renewable electricity is
used. Yao et al. showed that electrical consumption can represent up to
80% of the operational annual cost (4.8 M€/a) for alkaline electrolysis
(with a CAPEX of 4 M€) [61]. The H2 production cost is expected to
decrease in the future with the development of current technologies
from 5.0 €/kg H2 to 2.3 €/kg H2 for alkaline electrolysis [176]. This has
motivated the development of cheaper processes from renewable ma­
terials, including MEC, PEMEC, and CEC. Indeed, the current research
on MEC allows the production of hydrogen at a lower cost (1.7–4.51
$/kg) compared with water electrolysis (2.35–4.8 $/kg). With the
development of CEC technologies, which have the lowest electrical
consumption (equivalent to 16.7% of that of water electrolysis), OPEX
could be drastically reduced as well as the H2 production cost [106]. In
this case, it could also promote the installation of larger plants to
decrease the hydrogen production cost. The chemical electrolysis con­
version of biomass could provide a new method for industrial applica­
tions to overcome the high electrical consumption of water electrolysis.
CEC methods benefit from water electrolysis and are promising for areas
where biomass and waste are abundant. These two techniques comple­
ment each other based on the local abundance of biomass, water, or
green electricity production. Nevertheless, future studies are necessary
for this novel process with a low TRL to predict its impact on the future
of hydrogen. More research is required to develop biomass CEC methods
to convert more complex feedstock into hydrogen and to assess its
economic feasibility.
6. Hydrogen assessment as fuel in transportation
As a future energy, hydrogen is a potential candidate to ensure a
renewable, sustainable, and
secure fuel [177]. Compared with traditional fuels, H2 has the
characteristic of being used in both fuel cells and internal combustion
engines [5]. In fuel cells (HFC), electricity is generated through a com­
bination of hydrogen and oxygen. This electrochemical reaction is
assured by a catalyst that splits H2 into electrons and protons. The
positively charged protons cross the cathode, and the negatively charged
protons are pushed through the system to generate electricity [178]. In
internal combustion engines (HICE), hydrogen can be either sent to the
manifold as cold hydrogen or be stored in a cryogenic cylinder as liquid
hydrogen and then transformed into a cold gas though the heat
exchanger or it can be used as an alternative fuel to gasoline to form a
hydrogen-gasoline mixture, which is compressed and ignited by a
combustion spark [5].
Hydrogen-fuelled engines have several advantages in terms of min­
imum ignition energy, auto-ignition temperature, and flammability. Its
minimum ignition energy (the minimum amount of energy required to
ignite the air fuel mixture) is lower than that in gas and gasoline engines,
giving it the advantage of rapid ignition [179,180]. In addition, its
self-ignition requires a higher temperature compared with gas and
gasoline, giving it the characteristic of high compression ratios for in­
ternal combustion [180–182]. Its flammability limits in the air (the fuel
between conventional, hybrid, electric, hydrogen fuelled internal com­
bustion engines, and hydrogen fuel cells.
Hydrogen-fuelled vehicles consume roughly the same consumption
as hybrid vehicles in the case of HICE and consume more fuel than
electric vehicles, but always less than that of fossil fuel vehicles. Electric
vehicles have the lowest fuel price, followed by hydrogen-fuelled (1.69
for HICE and 1.72 for HFC) and hybrid vehicles 1.71. However, con­
ventional vehicles have the highest fuel price. The fuel dividing range
was approximately 350 km for hydrogen-fuelled vehicles, which is
almost double the distance that electric vehicles can travel. However, it
is lower than the fuel dividing range of conventional and hybrid vehi­
cles, which showed the highest dividing range [5,185–187].
Concerning the environmental impact, two major criteria are
considered: greenhouse gas (GHG) emissions, particularly CO2 gases
correlated to global warming potential, and acidification potential (AP),
essentially SO2 emissions, related to acid rains. Nanaki et al. reported
that (HICE) and (HFC) have the lowest GHG emissions (6.40 kg CO2/
100 km of vehicle travel and 7.10 kg CO2/100 km of vehicle travel,
respectively) compared with conventional, hybrid, and electric vehicles.
Regarding acidification potential, HICE and HFC also had the lowest AP
(0.02 kg SO2/100 km travel and 0.018 kg SO2/100 km travel, respec­
tively) compared with other vehicle types that oscillated between 0.04
kg SO2/100 km travel and 0.06 kg SO2/100 km travel [188].
Literature data proves that hydrogen-fuelled vehicles including in­
ternal combustion engines and fuel cells are the cleanest because they
represent the lowest CO2 and SO2 emissions. Fuel cells have the best
environmental performance and provide a sufficient dividing range.
Hydrogen fuel is promising, eco-friendly, and could be competitive with
electric vehicles, especially when the production processes are improved
in order to minimise its cost.
7. Conclusions
Among the initiatives currently taken to partially overcome global
warming, a great deal of research has been conducted on hydrogen as an
alternative energy vector. Various conversion pathways have already
been investigated to produce H2 from lignocellulosic biomass.
Thermochemical processes are the most common technologies.
Gasification is the predominant process globally and should reach the
industrial scale (TRL 9) in a few decades. Steam gasification is the best
compromise as it does not require an expensive oxidising agent (oxygen)
and is adapted to a wide variety of wet and dried feedstocks. Typically,
increasing the size of the plant will increase the CAPEX but will signif­
icantly reduce the H2 production cost. OPEX is primarily due to main­
tenance, insurance, and the feedstock price. The major drawback
remains the tar and char formation and the deactivation of the catalyst.
Current research is predominantly focused on the use of novel catalysts,
mainly Ni-based catalysts, biochar, dolomite, and olivine, to improve
the selectivity of reactions and decrease the inhibition issues. Currently,
the lowest hydrogen production cost from renewable feedstock is met
with biomass gasification.
Table 6
Comparison between Hydrogen fuelled vehicles and conventional, hybrid, and
electric vehicles [5,185–188].
Vehicles HICE HFC Hybrid Electric Conventional

volumetric concentration limits and the fuel–air mixture flammability) Fuel consumption (MJ/ 136.6 129.50 137.6 67.20 236.8
is wider than that of gas and gasoline, allowing a better fuel economy by 100 km)
Fuel price (USD/100 1.72 1.69 1.71 0.9 2.94
reducing complete combustion [183,184]. In addition, the high diffu­
km)
sivity of hydrogen allows its rapid diffusion in the air, forming a ho­ Fuel dividing range 350 355 930 160 540
mogenous mixture. When there is a leak in the system, hydrogen will be (km)
diffused in the air without harming the system or the environment [10]. GHGa emission 6.40 7.10 13.30 11.40 21.40
In order to evaluate the performance of hydrogen-based vehicles, APb 0.02 0.018 0.04 0.045 0.06

environmental efficiency and fuel assessment were chosen as the a

Kg CO2 eq. per 100 km of travel.
criteria. Table 6 presents a comparison of these selected parameters b
kg SO2 eq. per 100 km of travel.

11
T. Lepage et al.
In addition, studies have been conducted to use microorganisms that
allow the biological conversion of biomass, mostly through dark
fermentation processes. The key advantages reside under mild condi­
tions (T◦ and pressure) used. The main limitations of these processes are
the slow conversion rate and the low volumes produced, hindering the
development (TRL 5). These systems require expensive bioreactors and
separation steps to increase CAPEX. In addition, pre-treatments are
necessary for recalcitrant biomass, inducing the production of inhibitors
and negatively impacting CAPEX and OPEX. Future improvements
should be focused on the development of local small-scale production
plants as well as the development of better-performing bioreactors and
new bacterial strains. In addition, they are more suitable for liquid
streams containing sugars, such as molasses and wastewater (sewage
sludge) that can be processed by microorganisms. Interest has recently
increased concerning these feedstocks because they are easily processed
by microorganisms, while they are challenging in major processes such
as gasification.
Among the latest conversion techniques, electrochemical methods,
including biomass electrolysis, deliver promising results in terms of
yield at the laboratory scale (TRL 2–4) while consuming less electricity
than conventional water electrolysis. Notably, recently developed MEC
allows the production of hydrogen at a similar cost compared with water
electrolysis. With the development of CEC technologies, which have the
lowest electrical consumption, OPEX could be drastically reduced as
well as the H2 production cost. Combined with cheap and clean wind or
solar energy, H2 could be produced in areas producing large amounts of
biomass.
Numerous applications are currently dependent on hydrogen. The
current increasing demand is encouraging the boom of a new economy
based on hydrogen use. The conversion of biomass coupled with CSS
systems makes it possible to obtain negative CO2 emissions compared
with the reforming of fossil resources. Biomass conversion still needs
improvements and adaptations to be implemented at a larger scale,
allowing the production of larger volumes to be competitive, especially
in the biofuel sector.
Supplementary information
This paper is associated with the S1 document showing, in table
form, the H2 yields from various biomasses, estimated in g per kg of dry
biomass.
Acknowledgments
This research was supported by the European Union and the Walloon
Region with the European Funds for Regional Development 2014–2020
in the framework of the VERDIR Tropical Plant Factory program (project
BioResidu).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.biombioe.2020.105920.
References
[1] P. Capros, G. Zazias, S. Evangelopoulou, M. Kannavou, T. Fotiou, P. Siskos, A. De
Vita, K. Sakellaris, Energy-system modelling of the EU strategy towards climate-
neutrality, Energy Pol. 134 (2019) 110960, https://doi.org/10.1016/j.
enpol.2019.110960.
[2] S.E. Hosseini, M.A. Wahid, Hydrogen production from renewable and sustainable
energy resources: promising green energy carrier for clean development, Renew.
Sustain. Energy Rev. 57 (2016) 850–866, https://doi.org/10.1016/j.
rser.2015.12.112.
[3] X.-Y. Li, B.-J. Tang, Incorporating the transport sector into carbon emission
trading scheme: an overview and outlook, Nat. Hazards 88 (2017) 683–698,
https://doi.org/10.1007/s11069-017-2886-3.
12
Biomass and Bioenergy 144 (2021) 105920
[4] M. Raud, T. Kikas, O. Sippula, N.J. Shurpali, Potentials and challenges in
lignocellulosic biofuel production technology, Renew. Sustain. Energy Rev. 111
(2019) 44–56, https://doi.org/10.1016/j.rser.2019.05.020.
[5] C. Acar, I. Dincer, The potential role of hydrogen as a sustainable transportation
fuel to combat global warming, Int. J. Hydrogen Energy (in press) (n.d.). https://
doi.org/10.1016/j.ijhydene.2018.10.149.
[6] P. Crane, D.S. Scott, Efficiency and CO2 emission analysis of pathways by which
methane can provide transportation services, Int. J. Hydrogen Energy 17 (1992)
543–550, https://doi.org/10.1016/0360-3199(92)90154-O.
[7] P.E. Dodds, I. Staffell, A.D. Hawkes, F. Li, P. Grünewald, W. McDowall, P. Ekins,
Hydrogen and fuel cell technologies for heating: a review, Int. J. Hydrogen
Energy 40 (2015) 2065–2083, https://doi.org/10.1016/j.ijhydene.2014.11.059.
[8] R.M. Navarro, M.C. Sanchez-Sanchez, M.C. Alvarez-Galvan, J.L.G. Fierro, A.-
Z. Saeed, H2 production from renewables, in: Encycl. Inorg. Chem., John Wiley &
Sons Ltd., 2011, pp. 1–18, https://doi.org/10.1002/9781119951438.eibc0450.
[9] J.A. Turner, Sustainable hydrogen production, Science 305 (2004) 972–974,
https://doi.org/10.1126/science.1103197, 80.
[10] S. Sharma, S.K. Ghoshal, Hydrogen the future transportation fuel: from
production to applications, Renew. Sustain. Energy Rev. 43 (2015) 1151–1158,
https://doi.org/10.1016/j.rser.2014.11.093.
[11] International Energy Agency (IEA), The Future of Hydrogen, Japan, https://doi.
org/10.1016/S1464-2859(12)70027-5, 2019.
[12] R.C. Saxena, D. Seal, S. Kumar, H.B. Goyal, Thermo-chemical routes for hydrogen
rich gas from biomass: a review, Renew. Sustain. Energy Rev. 12 (2008)
1909–1927, https://doi.org/10.1016/j.rser.2007.03.005.
[13] E.S. Hanley, J.P. Deane, B.P.Ó. Gallachóir, The role of hydrogen in low carbon
energy futures–A review of existing perspectives, Renew. Sustain. Energy Rev. 82
(2018) 3027–3045, https://doi.org/10.1016/j.rser.2017.10.034.
[14] F. Suleman, I. Dincer, M. Agelin-Chaab, Environmental impact assessment and
comparison of some hydrogen production options, Int. J. Hydrogen Energy 40
(2015) 6976–6987, https://doi.org/10.1016/j.ijhydene.2015.03.123.
[15] Alexander E. Farrell, R.J. Plevin, B.T. Turner, A.D. Jones, M. O’Hare, D.
M. Kammen, Ethanol can contribute to energy and environmental goals, Science
80 (311) (2006) 506–509, https://doi.org/10.1126/science.1121416.
[16] G. Li, P. Cui, Y. Wang, Z. Liu, Z. Zhu, S. Yang, Life cycle energy consumption and
GHG emissions of biomass-to- hydrogen process in comparison with coal-to-
hydrogen process, Energy. (n.d.). https://doi.org/10.1016/j.energy.20
19.116588.
[17] I. Dincer, Green methods for hydrogen production, Int. J. Hydrogen Energy 37
(2012) 1954–1971, https://doi.org/10.1016/j.ijhydene.2011.03.173.
[18] Y. Kalinci, A. Hepbasli, I. Dincer, Biomass-based hydrogen production: a review
and analysis, Int. J. Hydrogen Energy 34 (2009) 8799–8817, https://doi.org/
10.1016/j.ijhydene.2009.08.078.
[19] H. Balat, E. Kirtay, Hydrogen from biomass - present scenario and future
prospects, Int. J. Hydrogen Energy 35 (2010) 7416–7426, https://doi.org/
10.1016/j.ijhydene.2010.04.137.
[20] S.E. Hosseini, M.A. Wahid, M.M. Jamil, A.A.M. Azli, M.F. Misbah, A review on
biomass-based hydrogen production for renewable energy supply, Int. J. Energy
Res. 39 (2015) 1597–1615, https://doi.org/10.1002/er.3381.
[21] P. Parthasarathy, K.S. Narayanan, Hydrogen production from steam gasification
of biomass: influence of process parameters on hydrogen yield - a review, Renew.
Energy 66 (2014) 570–579, https://doi.org/10.1016/j.renene.2013.12.025.
[22] W. Liu, J. Wang, D. Bhattacharyya, Y. Jiang, D. DeVallance, Economic and
environmental analyses of coal and biomass to liquid fuels, Energy 141 (2017)
76–86, https://doi.org/10.1016/j.energy.2017.09.047.
[23] G. Fiorese, M. Catenacci, V. Bosetti, E. Verdolini, The power of biomass: experts
disclose the potential for success of bioenergy technologies, Energy Pol. 65 (2014)
94–114, https://doi.org/10.1016/j.enpol.2013.10.015.
[24] M. Kammoun, H. Ayeb, T. Bettaieb, A. Richel, Chemical characterisation and
technical assessment of agri-food residues, marine matrices, and wild grasses in
the South Mediterranean area: a considerable inflow for biorefineries, Waste
Manag. 118 (2020) 247–257, https://doi.org/10.1016/j.wasman.2020.08.032.
[25] N. Dahmen, I. Lewandowski, S. Zibek, A. Weidtmann, Integrated lignocellulosic
value chains in a growing bioeconomy : status quo and perspectives, Bioenergy
(2019) 107–117, https://doi.org/10.1111/gcbb.12586.
[26] V. Stenberg, M. Rydén, T. Mattisson, A. Lyngfelt, Exploring novel hydrogen
production processes by integration of steam methane reforming with chemical-
looping combustion (CLC-SMR) and oxygen carrier aided combustion (OCAC-
SMR), Int. J. Greenh. Gas Control. 74 (2018) 28–39, https://doi.org/10.1016/j.
ijggc.2018.01.008.
[27] G.W. Huber, S. Iborra, A. Corma, Synthesis of transportation fuels from biomass:
chemistry, catalysts, and engineering, Chem. Rev. 106 (2006) 4044–4098,
https://doi.org/10.1021/cr068360d.
[28] C. Xu, S. Chen, A. Soomro, Z. Sun, W. Xiang, Hydrogen rich syngas production
from biomass gasification using synthesized Fe/CaO active catalysts, J. Energy
Inst. 91 (2018) 805–816, https://doi.org/10.1016/j.joei.2017.10.014.
[29] C. Srinivasakannan, N. Balasubramanian, Variations in the design of dual
fluidized bed gasifiers and the quality of syngas from biomass, Energy Sources,
Part A Recover, Util. Environ. Eff. 33 (2011) 349–359, https://doi.org/10.1080/
15567030902967835.
[30] A. Adamovics, R. Platace, I. Gulbe, S. Ivanovs, The content of carbon and
hydrogen in grass biomass and its influence on heating value, Eng. Rural Dev. 17
(2018) 1277–1281, https://doi.org/10.22616/ERDev2018.17.N014.
[31] T.G. Madenoǧlu, M. Saǧlam, M. Yüksel, L. Ballice, Hydrothermal gasification of
biomass model compounds (cellulose and lignin alkali) and model mixtures,
T. Lepage et al.
J. Supercrit. Fluids 115 (2016) 79–85, https://doi.org/10.1016/j.
supflu.2016.04.017.
[32] J. Gil, M.P. Aznar, M.A. Caballero, E. Francés, J. Corrella, Biomass gasification in
fluidized bed at pilot scale with steam-oxygen mixtures. Product distribution for
very different operating condictions, Energy Fuels 11 (1997) 1109–1118, https://
doi.org/10.1021/ef9602335.
[33] Z. Wang, T. He, J. Qin, J. Wu, J. Li, Z. Zi, G. Liu, J. Wu, L. Sun, Gasification of
biomass with oxygen-enriched air in a pilot scale two-stage gasifier, Fuel 150
(2015) 386–393, https://doi.org/10.1016/j.fuel.2015.02.056.
[34] S. Rapagná, H. Provendier, C. Petit, A. Kiennemann, P.U. Foscolo, Development of
catalysts suitable for hydrogen or syn-gas production from biomass gasification,
Biomass Bioenergy 22 (2002) 377–388, https://doi.org/10.1016/S0961-9534
(02)00011-9.
[35] P. Basu, Gasification theory and modeling of gasifiers, in: Biomass Gasif. Des.
Handb., First Edit, © 2010 Elsevier Inc., 2010, pp. 117–165, https://doi.org/
10.1016/b978-0-12-374988-8.00005-2.
[36] H. Yang, H. Chen, Biomass gasification for synthetic liquid fuel production, in:
Gasif. Synth. Fuel Prod. Fundam. Process. Appl., ©, Woodhead Publishing
Limited. All rights reserved., 2015, pp. 241–275, https://doi.org/10.1016/B978-
0-85709-802-3.00011-4, 2015.
[37] H. De Lasa, E. Salaices, J. Mazumder, R. Lucky, Catalytic steam gasification of
biomass: catalysts, thermodynamics and kinetics, Chem. Rev. 111 (2011)
5404–5433, https://doi.org/10.1021/cr200024w.
[38] Pekka Simell, E. Kurkela, P. Ståhlberg, J. Hepola, Catalytic hot gas cleaning of
gasification gas, Catal. Today 27 (1996) 55–62, https://doi.org/10.1016/S0140-
6701(97)83950-1.
[39] A. Erkiaga, G. Lopez, M. Amutio, J. Bilbao, M. Olazar, Steam gasification of
biomass in a conical spouted bed reactor with olivine and γ-alumina as primary
catalysts, Fuel Process, Technol. 116 (2013) 292–299, https://doi.org/10.1016/j.
fuproc.2013.07.008.
[40] I. Ahmed, A.K. Gupta, Evolution of syngas from cardboard gasification, Appl.
Energy 86 (2009) 1732–1740, https://doi.org/10.1016/j.apenergy.2008.11.018.
[41] H. Yang, R. Yan, H. Chen, D.H. Lee, D.T. Liang, C. Zheng, Pyrolysis of palm oil
wastes for enhanced production of hydrogen rich gases, Fuel Process. Technol. 87
(2006) 935–942, https://doi.org/10.1016/j.fuproc.2006.07.001.
[42] H.B. Goyal, D. Seal, R.C. Saxena, Bio-fuels from thermochemical conversion of
renewable resources: a review, Renew. Sustain. Energy Rev. 12 (2008) 504–517,
https://doi.org/10.1016/j.rser.2006.07.014.
[43] C. Di Blasi, Modeling chemical and physical processes of wood and biomass
pyrolysis, Prog. Energy Combust. Sci. 34 (2008) 47–90, https://doi.org/10.1016/
j.pecs.2006.12.001.
[44] L. Garcia, R. French, S. Czernik, E. Chornet, Catalytic steam reforming of bio-oils
for the production of hydrogen: effects of catalyst composition, Appl. Catal. Gen.
201 (2000) 225–239, https://doi.org/10.1016/S0926-860X(00)00440-3.
[45] C. Font Palma, Modelling of tar formation and evolution for biomass gasification:
a review, Appl. Energy 111 (2013) 129–141, https://doi.org/10.1016/j.
apenergy.2013.04.082.
[46] S. Koppatz, C. Pfeifer, H. Hofbauer, Comparison of the performance behaviour of
silica sand and olivine in a dual fluidised bed reactor system for steam gasification
of biomass at pilot plant scale, Chem. Eng. J. 175 (2011) 468–483, https://doi.
org/10.1016/j.cej.2011.09.071.
[47] A. Demirbaş, Gaseous products from biomass by pyrolysis and gasification: effects
of catalyst on hydrogen yield, Energy Convers. Manag. 43 (2002) 897–909,
https://doi.org/10.1016/S0196-8904(01)00080-2.
[48] E. Kirtay, Recent advances in production of hydrogen from biomass, Energy
Convers. Manag. 52 (2011) 1778–1789, https://doi.org/10.1016/j.
enconman.2010.11.010.
[49] M. Van de Velden, J. Baeyens, A. Brems, B. Janssens, R. Dewil, Fundamentals,
kinetics and endothermicity of the biomass pyrolysis reaction, Renew. Energy 35
(2010) 232–242, https://doi.org/10.1016/j.renene.2009.04.019.
[50] F. Safari, M. Salimi, A. Tavasoli, A. Ataei, Non-catalytic conversion of wheat
straw, walnut shell and almond shell into hydrogen rich gas in supercritical water
media, Chin. J. Chem. Eng. 24 (2016) 1097–1103, https://doi.org/10.1016/j.
cjche.2016.03.002.
[51] P.M. Lv, Z.H. Xiong, J. Chang, C.Z. Wu, Y. Chen, J.X. Zhu, An experimental study
on biomass air-steam gasification in a fluidized bed, Bioresour. Technol. 95
(2004) 95–101, https://doi.org/10.1016/j.biortech.2004.02.003.
[52] A.C.C. Chang, H.-F. Chang, F.-J. Lin, K.-H. Lin, C.-H. Chen, Biomass gasification
for hydrogen production, Int. J. Hydrogen Energy 36 (2011) 14252–14260,
https://doi.org/10.1016/j.ijhydene.2011.05.105.
[53] A. Kumar, K. Eskridge, D.D. Jones, M.A. Hanna, Steam-air fluidized bed
gasification of distillers grains: effects of steam to biomass ratio, equivalence ratio
and gasification temperature, Bioresour. Technol. 100 (2009) 2062–2068,
https://doi.org/10.1016/j.biortech.2008.10.011.
[54] A. Arregi, M. Amutio, G. Lopez, J. Bilbao, M. Olazar, Evaluation of
thermochemical routes for hydrogen production from biomass: a review, Energy
Convers. Manag. 165 (2018) 696–719, https://doi.org/10.1016/j.
enconman.2018.03.089.
[55] L. Devi, K.J. Ptasinski, F.J.J.G. Janssen, S.V.B. van Paasen, P.C.A. Bergman, J.H.
A. Kiel, Catalytic decomposition of biomass tars: use of dolomite and untreated
olivine, Renew. Energy 30 (2005) 565–587, https://doi.org/10.1016/j.
renene.2004.07.014.
[56] Y. Lu, S. Li, L. Guo, X. Zhang, Hydrogen production by biomass gasification in
supercritical water over Ni/γAl2O3 and Ni/CeO2-γAl2O3 catalysts, Int. J.
Hydrogen Energy 35 (2010) 7161–7168, https://doi.org/10.1016/j.
ijhydene.2009.12.047.
13
Biomass and Bioenergy 144 (2021) 105920
[57] A.V. Bridgwater, Renewable fuels and chemicals by thermal processing of
biomass, Chem. Eng. J. 91 (2003) 87–102, https://doi.org/10.1016/S1385-8947
(02)00142-0.
[58] L. Barelli, G. Bidini, F. Gallorini, S. Servili, Hydrogen production through
sorption-enhanced steam methane reforming and membrane technology: a
review, Energy 33 (2008) 554–570, https://doi.org/10.1016/j.
energy.2007.10.018.
[59] D.P. Harrison, Sorption-enhanced hydrogen Production : a review, Ind. Eng.
Chem. Res. 47 (2008) 6486–6501, https://doi.org/10.1021/ie800298z.
[60] S. Kurella, P.K. Bhukya, B.C. Meikap, Removal of H2S pollutant from gasifier
syngas by a multistage dual-flow sieve plate column wet scrubber, J. Environ. Sci.
Heal. Part A. 52 (2017) 515–523, https://doi.org/10.1080/
10934529.2017.1281690.
[61] J. Yao, M. Kraussler, F. Benedikt, H. Hofbauer, Techno-economic assessment of
hydrogen production based on dual fluidized bed biomass steam gasification,
biogas steam reforming, and alkaline water electrolysis processes, Energy
Convers. Manag. 145 (2017) 278–292, https://doi.org/10.1016/j.
enconman.2017.04.084.
[62] C. Pirez, W. Fang, M. Capron, S. Paul, H. Jobic, F. Dumeignil, L. Jalowiecki-
Duhamel, Steam reforming, partial oxidation and oxidative steam reforming for
hydrogen production from ethanol over cerium nickel based oxyhydride catalyst,
Appl. Catal. Gen. 518 (2016) 78–86, https://doi.org/10.1016/j.
apcata.2015.10.035.
[63] D. Rennard, R. French, S. Czernik, T. Josephson, L. Schmidt, Production of
synthesis gas by partial oxidation and steam reforming of biomass pyrolysis oils,
Int. J. Hydrogen Energy 35 (2010) 4048–4059, https://doi.org/10.1016/j.
ijhydene.2010.01.143.
[64] J.R. Salge, G.A. Deluga, L.D. Schmidt, Catalytic partial oxidation of ethanol over
noble metal catalysts, J. Catal. 235 (2005) 69–78, https://doi.org/10.1016/j.
jcat.2005.07.021.
[65] M. Tóth, E. Varga, A. Oszkó, K. Baán, J. Kiss, A. Erdohelyi, Partial oxidation of
ethanol on supported Rh catalysts: effect of the oxide support, J. Mol. Catal.
Chem. 411 (2016) 377–387, https://doi.org/10.1016/j.molcata.2015.11.010.
[66] L. He, J. Yang, D. Chen, Hydrogen from biomass: advances in thermochemical
processes, in: Renew. Hydrog. Technol. Prod., Purif., Storage, Appl. Saf., Elsevier
B.V., 2013, pp. 111–133, https://doi.org/10.1016/B978-0-444-56352-1.00006-
4.
[67] M. Kumar, A.O. Oyedun, A. Kumar, A comparative analysis of hydrogen
production from the thermochemical conversion of algal biomass, Int. J.
Hydrogen Energy 44 (2019) 10384–10397, https://doi.org/10.1016/j.
ijhydene.2019.02.220.
[68] B.R. Pinkard, D.J. Gorman, K. Tiwari, E.G. Rasmussen, J.C. Kramlich, P.
G. Reinhall, I.V. Novosselov, Supercritical water gasification: practical design
strategies and operational challenges for lab-scale, continuous flow reactors,
Heliyon 5 (2019), e01269, https://doi.org/10.1016/j.heliyon.2019.e01269.
[69] L.J. Guo, Y.J. Lu, X.M. Zhang, C.M. Ji, Y. Guan, A.X. Pei, Hydrogen production by
biomass gasification in supercritical water: a systematic experimental and
analytical study, Catal. Today 129 (2007) 275–286, https://doi.org/10.1016/j.
cattod.2007.05.027.
[70] M. Osada, T. Sato, M. Watanabe, M. Shirai, K. Arai, Catalytic gasification of wood
biomass in subcritical and supercritical water, Combust. Sci. Technol. 178 (2006)
537–552, https://doi.org/10.1080/00102200500290807.
[71] Y. Matsumura, T. Minowa, B. Potic, S.R.A. Kersten, W. Prins, W.P.M. Van Swaaij,
B. Van De Beld, D.C. Elliott, G.G. Neuenschwander, A. Kruse, M.J. Antal Jr.,
Biomass gasification in near- and super-critical water: status and prospects,
Biomass Bioenergy 29 (2005) 269–292, https://doi.org/10.1016/j.
biombioe.2005.04.006.
[72] A.B.H. Trabelsi, A. Ghrib, K. Zaafouri, A. Friaa, A. Ouerghi, S. Naoui,
H. Belayouni, Hydrogen-rich syngas production from gasification and pyrolysis of
solar dried sewage sludge: experimental and modeling investigations, BioMed
Res. Int. (2017) 1–14, https://doi.org/10.1155/2017/7831470.
[73] A.V. Bridgwater, A.J. Toft, J.G. Brammer, in: A Techno-Economic Comparison of
Power Production by Biomass Fast Pyrolysis with Gasification and Combustion,
2002, https://doi.org/10.1016/S1364-0321(01)00010-7.
[74] D. Mohan, C.U. Pittman, P.H. Steele, Pyrolysis of wood/biomass for bio-oil: a
critical review, Energy Fuels 20 (2006) 848–889, https://doi.org/10.1021/
ef0502397.
[75] A. Demirbas, Comparison of thermochemical conversion processes of biomass to
hydrogen-rich gas mixtures, Energy Sources, Part A Recover, Util. Environ. Eff. 38
(2016) 2971–2976, https://doi.org/10.1080/15567036.2015.1122686.
[76] M. Balat, Hydrogen-rich gas production from biomass via pyrolysis and
gasification processes and effects of catalyst on hydrogen yield, Energy Sources,
Part A. 30 (2008) 552–564, https://doi.org/10.1080/15567030600817191.
[77] M. Ni, D.Y.C. Leung, M.K.H. Leung, K. Sumathy, An overview of hydrogen
production from biomass, Fuel Process, Technol. 87 (2006) 461–472, https://doi.
org/10.1016/j.fuproc.2005.11.003.
[78] P. Lan, Q. Xu, M. Zhou, L. Lan, S. Zhang, Y. Yan, Catalytic steam reforming of fast
pyrolysis bio-oil in fixed bed and fluidized bed reactors, Chem. Eng. Technol. 33
(2010) 2021–2028, https://doi.org/10.1002/ceat.201000169.
[79] S. Czernik, R. Evans, R. French, Hydrogen from biomass-production by steam
reforming of biomass pyrolysis oil, Catal. Today 129 (2007) 265–268, https://doi.
org/10.1016/j.cattod.2006.08.071.
[80] V. Martinez-Merino, M.J. Gil, A. Cornejo, Biomass sources for hydrogen
production, in: Renew. Hydrog. Technol. Prod., Purif., Storage, Appl. Saf.,
Elsevier B.V., 2013, pp. 87–110, https://doi.org/10.1016/B978-0-444-56352-
1.00005-2.
T. Lepage et al.
[81] G.W. Huber, J.A. Dumesic, An overview of aqueous-phase catalytic processes for
production of hydrogen and alkanes in a biorefinery, Catal. Today 111 (2006)
119–132, https://doi.org/10.1016/j.cattod.2005.10.010.
[82] R.D. Cortright, R.R. Davda, J.A. Dumesic, Hydrogen from catalytic reforming of
biomass-derived hydrocarbons in liquid water, Nature 418 (2002) 964–967,
https://doi.org/10.1038/nature01009.
[83] A. Tanksale, J.N. Beltramini, G.M. Lu, A review of catalytic hydrogen production
processes from biomass, Renew. Sustain. Energy Rev. 14 (2010) 166–182,
https://doi.org/10.1016/j.rser.2009.08.010.
[84] R.R. Davda, J.W. Shabaker, G.W. Huber, R.D. Cortright, J.A. Dumesic, A review of
catalytic issues and process conditions for renewable hydrogen and alkanes by
aqueous-phase reforming of oxygenated hydrocarbons over supported metal
catalysts, Appl. Catal. B Environ. 56 (2005) 171–186, https://doi.org/10.1016/j.
apcatb.2004.04.027.
[85] D.B. Levin, L. Pitt, M. Love, Biohydrogen production: prospects and limitations to
practical application, Int. J. Hydrogen Energy 29 (2004) 173–185, https://doi.
org/10.1016/S0360-3199(03)00094-6.
[86] H.H. Larsen, R.K. Feidenhans’l, L. Sønderberg Petersen, Risø Energy Report 3.
Hydrogen and its Competitors, Risø National Laboratory, Roskilde, 2004.
[87] A.M. Henstra, J. Sipma, A. Rinzema, A.J. Stams, Microbiology of synthesis gas
fermentation for biofuel production, Curr. Opin. Biotechnol. 18 (2007) 200–206,
https://doi.org/10.1016/j.copbio.2007.03.008.
[88] Y. Liu, R. Lin, Y. Man, J. Ren, Recent developments of hydrogen production from
sewage sludge by biological and thermochemical process, Int. J. Hydrogen Energy
44 (2019), https://doi.org/10.1016/j.ijhydene.2019.06.044, 19676–19697.
[89] S.S. Hosseini, M. Aghbashlo, M. Tabatabaei, H. Younesi, G. Najafpour, Exergy
analysis of biohydrogen production from various carbon sources via anaerobic
photosynthetic bacteria (Rhodospirillum rubrum), Energy 93 (2015) 730–739,
https://doi.org/10.1016/j.energy.2015.09.060.
[90] M. Alfano, C. Cavazza, The biologically mediated water–gas shift reaction:
structure, function and biosynthesis of monofunctional [NiFe]-carbon monoxide
dehydrogenases, Sustain. Energy Fuels. 2 (2018) 1653–1670, https://doi.org/
10.1039/C8SE00085A.
[91] P.C. Hallenbeck, J.R. Benemann, Biological hydrogen production; fundamentals
and limiting processes, Int. J. Hydrogen Energy 27 (2002) 1185–1193, https://
doi.org/10.1016/S0360-3199(02)00131-3.
[92] F.R. Hawkes, R. Dinsdale, D.L. Hawkes, I. Hussy, Sustainable fermentative
hydrogen production: challenges for process optimisation, Int. J. Hydrogen
Energy 27 (2002) 1339–1347, https://doi.org/10.1016/S0360-3199(02)00090-
3.
[93] G. Kumar, S. Shobana, D. Nagarajan, D.-J. Lee, K.-S. Lee, C.-Y. Lin, C.-Y. Chen, J.-
S. Chang, Biomass based hydrogen production by dark fermentation — recent
trends and opportunities for greener processes, Curr. Opin. Biotechnol. 50 (2018)
136–145, https://doi.org/10.1016/j.copbio.2017.12.024.
[94] S. Eker, M. Sarp, Hydrogen gas production from waste paper by dark
fermentation: effects of initial substrate and biomass concentrations, Int. J.
Hydrogen Energy 42 (2017) 2562–2568, https://doi.org/10.1016/j.
ijhydene.2016.04.020.
[95] A. Ghimire, L. Frunzo, F. Pirozzi, E. Trably, R. Escudie, P.N.L. Lens, G. Esposito,
A review on dark fermentative biohydrogen production from organic biomass:
process parameters and use of by-products, Appl. Energy 144 (2015) 73–95,
https://doi.org/10.1016/j.apenergy.2015.01.045.
[96] P.C. Hallenbeck, Y. Liu, Recent advances in hydrogen production by
photosynthetic bacteria, Int. J. Hydrogen Energy 41 (2016) 4446–4454, https://
doi.org/10.1016/j.ijhydene.2015.11.090.
[97] E. Sagir, E. Ozgur, U. Gunduz, I. Eroglu, M. Yucel, Single-stage photofermentative
biohydrogen production from sugar beet molasses by different purple non-sulfur
bacteria, Bioproc. Biosyst. Eng. 40 (2017) 1589–1601, https://doi.org/10.1007/
s00449-017-1815-x.
[98] R. Zagrodnik, M. Laniecki, The role of pH control on biohydrogen production by
single stage hybrid dark- and photo-fermentation, Bioresour. Technol. 194 (2015)
187–195, https://doi.org/10.1016/j.biortech.2015.07.028.
[99] S. Ghosh, U.K. Dairkee, R. Chowdhury, P. Bhattacharya, Hydrogen from food
processing wastes via photofermentation using Purple Non-sulfur Bacteria (PNSB)
– a review, Energy Convers. Manag. 141 (2017) 299–314, https://doi.org/
10.1016/j.enconman.2016.09.001.
[100] H.H. Al-Mohammedawi, H. Znad, E. Eroglu, Improvement of photofermentative
biohydrogen production using pre-treated brewery wastewater with banana peels
waste, Int. J. Hydrogen Energy 44 (2019) 2560–2568, https://doi.org/10.1016/j.
ijhydene.2018.11.223.
[101] M.Y. Azwar, M.A. Hussain, A.K. Abdul-Wahab, Development of biohydrogen
production by photobiological, fermentation and electrochemical processes: a
review, Renew. Sustain. Energy Rev. 31 (2014) 158–173, https://doi.org/
10.1016/j.rser.2013.11.022.
[102] R. Kothari, D. Buddhi, R.L. Sawhney, Comparison of environmental and economic
aspects of various hydrogen production methods, Renew. Sustain. Energy Rev. 12
(2008) 553–563, https://doi.org/10.1016/j.rser.2006.07.012.
[103] A. Kadier, Y. Simayi, P. Abdeshahian, N.F. Azman, K. Chandrasekhar, M.S. Kalil,
A comprehensive review of microbial electrolysis cells (MEC) reactor designs and
configurations for sustainable hydrogen gas production, Alexandria Eng. J. 55
(2016) 427–443, https://doi.org/10.1016/j.aej.2015.10.008.
[104] R. Tunold, A.T. Marshall, E. Rasten, M. Tsypkin, L.E. Owe, S. Sunde, Materials for
electrocatalysis of oxygen evolution process in PEM water electrolysis cells, ECS
Trans 25 (2010) 103–117, https://doi.org/10.1149/1.3328515.
[105] S. Bajracharya, M. Sharma, G. Mohanakrishna, X. Dominguez Benneton, D.P.B.T.
B. Strik, P.M. Sarma, D. Pant, An overview on emerging bioelectrochemical
14
Biomass and Bioenergy 144 (2021) 105920
systems (BESs): technology for sustainable electricity, waste remediation,
resource recovery, chemical production and beyond, Renew. Energy 98 (2016)
153–170, https://doi.org/10.1016/j.renene.2016.03.002.
[106] W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, Y. Deng, High efficiency hydrogen
evolution from native biomass electrolysis, Energy Environ. Sci. 9 (2016)
467–472, https://doi.org/10.1039/C5EE03019F.
[107] Y.X. Chen, A. Lavacchi, H.A. Miller, M. Bevilacqua, J. Filippi, M. Innocenti,
A. Marchionni, W. Oberhauser, L. Wang, F. Vizza, Nanotechnology makes
biomass electrolysis more energy efficient than water electrolysis, Nat. Commun.
5 (2014) 1–6, https://doi.org/10.1038/ncomms5036.
[108] M. Shahbaz, S. Yusup, A. Inayat, D.O. Patrick, M. Ammar, The influence of
catalysts in biomass steam gasification and catalytic potential of coal bottom ash
in biomass steam gasification: a review, Renew. Sustain. Energy Rev. 73 (2017)
468–476, https://doi.org/10.1016/j.rser.2017.01.153.
[109] I. Dincer, C. Acar, Review and evaluation of hydrogen production methods for
better sustainability, Int. J. Hydrogen Energy 40 (2015) 11094–11111, https://
doi.org/10.1016/j.ijhydene.2014.12.035.
[110] Y. Wang, S. Wang, G. Zhao, Y. Guo, Y. Guo, Hydrogen production by partial
oxidation gasification of a phenol, naphthalene, and acetic acid mixture in
supercritical water, Int. J. Hydrogen Energy 41 (2016) 2238–2246, https://doi.
org/10.1016/j.ijhydene.2015.12.115.
[111] Q. Guan, C. Wei, X. Chai, P. Ning, S. Tian, J. Gu, Q. Chen, R. Miao, Energetic
analysis of gasification of biomass by partial oxidation in supercritical water,
Chin. J. Chem. Eng. 23 (2015) 205–212, https://doi.org/10.1016/j.
cjche.2014.10.001.
[112] A.M. Abdalla, S. Hossain, O.B. Nisfindy, A.T. Azad, M. Dawood, A.K. Azad,
Hydrogen production, storage, transportation and key challenges with
applications: a review, Energy Convers. Manag. 165 (2018) 602–627, https://doi.
org/10.1016/j.enconman.2018.03.088.
[113] G. Wen, Y. Xu, Z. Xu, Z. Tian, Direct conversion of cellulose into hydrogen by
aqueous-phase reforming process, Catal. Commun. 11 (2010) 522–526, https://
doi.org/10.1016/j.catcom.2009.12.008.
[114] B. Zhao, X. Zhang, L. Sun, G. Meng, L. Chen, Y. Xiaolu, Hydrogen production from
biomass combining pyrolysis and the secondary decomposition, Int. J. Hydrogen
Energy 35 (2010) 2606–2611, https://doi.org/10.1016/j.ijhydene.2009.04.011.
[115] J. Wang, Y. Yin, Fermentative hydrogen production using pretreated microalgal
biomass as feedstock, Microb. Cell Factories 17 (2018) 1–16, https://doi.org/
10.1186/s12934-018-0871-5.
[116] P. Kaparaju, M. Serrano, A.B. Thomsen, P. Kongjan, I. Angelidaki, Bioethanol,
biohydrogen and biogas production from wheat straw in a biorefinery concept,
Bioresour. Technol. 100 (2009) 2562–2568, https://doi.org/10.1016/j.
biortech.2008.11.011.
[117] A. Adessi, M. Venturi, F. Candeliere, V. Galli, L. Granchi, R. De Philippis, Bread
wastes to energy: sequential lactic and photo-fermentation for hydrogen
production, Int. J. Hydrogen Energy 43 (2018) 9569–9576, https://doi.org/
10.1016/j.ijhydene.2018.04.053.
[118] A. Kadier, M.S. Kalil, P. Abdeshahian, K. Chandrasekhar, A. Mohamed, N.
F. Azman, W. Logroño, Y. Simayi, A.A. Hamid, Recent advances and emerging
challenges in microbial electrolysis cells (MECs) for microbial production of
hydrogen and value-added chemicals, Renew. Sustain. Energy Rev. 61 (2016)
501–525, https://doi.org/10.1016/j.rser.2016.04.017.
[119] J. Sachs, S. Hidayat, S. Giarola, A. Hawkes, in: The Role of CCS and Biomass-
Based Processes in the Refinery Sector for Different Carbon Scenarios, Elsevier
Masson SAS, 2018, https://doi.org/10.1016/B978-0-444-64235-6.50239-4.
[120] V.S. Sikarwar, M. Zhao, P.S. Fennell, N. Shah, E.J. Anthony, Progress in biofuel
production from gasification, Prog. Energy Combust. Sci. 61 (2017) 189–248,
https://doi.org/10.1016/j.pecs.2017.04.001.
[121] V. Singh Yadav, R. Vinoth, D. Yadav, Bio-hydrogen production from waste
materials: a review, MATEC Web Conf 192 (2018) 1–5, https://doi.org/10.1051/
matecconf/201819202020.
[122] M.M. Rashid, M.K. Al Mesfer, H. Naseem, M. Danish, Hydrogen production by
water electrolysis: a review of alkaline water electrolysis, PEM water electrolysis
and high temperature water electrolysis, Int. J. Eng. Adv. Technol. 4 (2015)
80–93.
[123] A. Kadier, M.S. Kalil, A. Mohamed, H.A. Hasan, P. Abdeshahian, T. Fooladi, A.
A. Hamid, Microbial electrolysis cells (MECs) as innovative technology for
sustainable hydrogen production: fundamentals and perspective applications,
Hydrog. Prod. Technol. (2017) 407–457, https://doi.org/10.1002/
9781119283676.ch11.
[124] D.C. Aiken, T.P. Curtis, E.S. Heidrich, Avenues to the financial viability of
microbial electrolysis cells [MEC] for domestic wastewater treatment and
hydrogen production, Int. J. Hydrogen Energy 44 (2019) 2426–2434, https://doi.
org/10.1016/j.ijhydene.2018.12.029.
[125] M.A. Hamad, A.M. Radwan, D.A. Heggo, T. Moustafa, Hydrogen rich gas
production from catalytic gasification of biomass, Renew. Energy 85 (2016)
1290–1300, https://doi.org/10.1016/j.renene.2015.07.082.
[126] B. Zhang, L. Zhang, Z. Yang, Y. Yan, G. Pu, M. Guo, Hydrogen-rich gas production
from wet biomass steam gasification with CaO/MgO, Int. J. Hydrogen Energy 40
(2015) 8816–8823, https://doi.org/10.1016/j.ijhydene.2015.05.075.
[127] L. Wei, S. Xu, L. Zhang, C. Liu, H. Zhu, S. Liu, Steam gasification of biomass for
hydrogen-rich gas in a free-fall reactor, Int. J. Hydrogen Energy 32 (2007) 24–31,
https://doi.org/10.1016/j.ijhydene.2006.06.002.
[128] X. Ma, X. Zhao, J. Gu, J. Shi, Co-gasification of coal and biomass blends using
dolomite and olivine as catalysts, Renew. Energy 132 (2019) 509–514, https://
doi.org/10.1016/j.renene.2018.07.077.
T. Lepage et al.
[129] F. Guo, X. Li, Y. Liu, K. Peng, C. Guo, Z. Rao, Catalytic cracking of biomass
pyrolysis tar over char-supported catalysts, Energy Convers. Manag. 167 (2018)
81–90, https://doi.org/10.1016/j.enconman.2018.04.094.
[130] E. Yaghoubi, Q. Xiong, M.H. Doranehgard, M.M. Yeganeh, G. Shahriari,
M. Bidabadi, The effect of different operational parameters on hydrogen rich
syngas production from biomass gasification in a dual fluidized bed gasifier,
Chem. Eng. Process. Process Intensif. 126 (2018) 210–221, https://doi.org/
10.1016/j.cep.2018.03.005.
[131] H. Liu, T. Chen, D. Chang, D. Chen, D. Kong, X. Zou, R.L. Frost, Effect of
preparation method of palygorskite-supported Fe and Ni catalysts on catalytic
cracking of biomass tar, Chem. Eng. J. 188 (2012) 108–112, https://doi.org/
10.1016/j.cej.2012.01.109.
[132] A.S. Al-Rahbi, P.T. Williams, Hydrogen-rich syngas production and tar removal
from biomass gasification using sacrificial tyre pyrolysis char, Appl. Energy 190
(2017) 501–509, https://doi.org/10.1016/j.apenergy.2016.12.099.
[133] D. Yao, Q. Hu, D. Wang, H. Yang, C. Wu, X. Wang, H. Chen, Hydrogen production
from biomass gasification using biochar as a catalyst/support, Bioresour. Technol.
216 (2016) 159–164, https://doi.org/10.1016/j.biortech.2016.05.011.
[134] T. Miyazawa, T. Kimura, J. Nishikawa, K. Kunimori, K. Tomishige, Catalytic
properties of Rh/CeO2/SiO2 for synthesis gas production from biomass by
catalytic partial oxidation of tar, Sci. Technol. Adv. Mater. 6 (2005) 604–614,
https://doi.org/10.1016/j.stam.2005.05.019.
[135] M. Ma, M. Müller, Investigation of various catalysts for partial oxidation of tar
from biomass gasification, Appl. Catal. Gen. 493 (2015) 121–128, https://doi.
org/10.1016/j.apcata.2015.01.012.
[136] D.H. Kim, S.H. Kim, J.Y. Byun, A microreactor with metallic catalyst support for
hydrogen production by partial oxidation of dimethyl ether, Chem. Eng. J. 280
(2015) 468–474, https://doi.org/10.1016/j.cej.2015.06.038.
[137] W. Żukowski, G. Berkowicz, Hydrogen production through the partial oxidation
of methanol using N2O in a fluidised bed of an iron-chromium catalyst, Int. J.
Hydrogen Energy 42 (2017) 28247–28253, https://doi.org/10.1016/j.
ijhydene.2017.09.135.
[138] G. Rabenstein, V. Hacker, Hydrogen for fuel cells from ethanol by steam-
reforming, partial-oxidation and combined auto-thermal reforming: a
thermodynamic analysis, J. Power Sources 185 (2008) 1293–1304, https://doi.
org/10.1016/j.jpowsour.2008.08.010.
[139] S. Li, L. Guo, Stability and activity of a co-precipitated Mg promoted Ni/Al2O3
catalyst for supercritical water gasification of biomass, Int. J. Hydrogen Energy 44
(2019) 15842–15852, https://doi.org/10.1016/j.ijhydene.2018.08.205.
[140] S. Nanda, A.K. Dalai, J.A. Kozinski, Supercritical water gasification of timothy
grass as an energy crop in the presence of alkali carbonate and hydroxide
catalysts, Biomass Bioenergy 95 (2016) 378–387, https://doi.org/10.1016/j.
biombioe.2016.05.023.
[141] Q.M.K. Waheed, C. Wu, P.T. Williams, Pyrolysis/reforming of rice husks with a
Ni–dolomite catalyst: influence of process conditions on syngas and hydrogen
yield, J. Energy Inst. 89 (2016) 657–667, https://doi.org/10.1016/j.
joei.2015.05.006.
[142] G. Chen, J. Andries, H. Spliethoff, Catalytic pyrolysis of biomass for hydrogen rich
fuel gas production, Energy Convers. Manag. 44 (2003) 2289–2296, https://doi.
org/10.1016/S0196-8904(02)00254-6.
[143] K. Akubo, M.A. Nahil, P.T. Williams, Pyrolysis-catalytic steam reforming of
agricultural biomass wastes and biomass components for production of
hydrogen/syngas, J. Energy Inst. 92 (6) (2019) 1987–1996. https://doi.org/10.10
16/j.joei.2018.10.013.
[144] F. Chen, C. Wu, L. Dong, A. Vassallo, P.T. Williams, J. Huang, Characteristics and
catalytic properties of Ni/CaAlOx catalyst for hydrogen-enriched syngas
production from pyrolysis-steam reforming of biomass sawdust, Appl. Catal. B
Environ. 183 (2016) 168–175, https://doi.org/10.1016/j.apcatb.2015.10.028.
[145] F. Jin, H. Sun, C. Wu, H. Ling, Y. Jiang, P.T. Williams, J. Huang, Effect of calcium
addition on Mg-AlOx supported Ni catalysts for hydrogen production from
pyrolysis-gasification of biomass, Catal. Today 309 (2018) 2–10, https://doi.org/
10.1016/j.cattod.2018.01.004.
[146] L. Dong, C. Wu, H. Ling, J. Shi, P.T. Williams, J. Huang, Promoting hydrogen
production and minimizing catalyst deactivation from the pyrolysis-catalytic
steam reforming of biomass on nanosized NiZnAlOx catalysts, Fuel 188 (2017)
610–620, https://doi.org/10.1016/j.fuel.2016.10.072.
[147] Z.M.A. Bundhoo, Potential of bio-hydrogen production from dark fermentation of
crop residues: a review, Int. J. Hydrogen Energy 44 (2019) 17346–17362,
https://doi.org/10.1016/j.ijhydene.2018.11.098.
[148] S. Lunprom, O. Phanduang, A. Salakkam, Q. Liao, A. Reungsang, A sequential
process of anaerobic solid-state fermentation followed by dark fermentation for
bio-hydrogen production from Chlorella sp, Int. J. Hydrogen Energy 44 (2019)
3306–3316, https://doi.org/10.1016/j.ijhydene.2018.06.012.
[149] T.T. Giang, S. Lunprom, Q. Liao, A. Reungsang, A. Salakkam, Enhancing hydrogen
production from Chlorella sp. Biomass by pre-hydrolysis with simultaneous
saccharification and fermentation (PSSF), Energies 12 (2019) 1–14, https://doi.
org/10.3390/en12050908.
[150] J. Wang, Y. Yin, Fermentative hydrogen production using various biomass-based
materials as feedstock, Renew. Sustain. Energy Rev. 92 (2018) 284–306, https://
doi.org/10.1016/j.rser.2018.04.033.
[151] H.M. Zabed, S. Akter, J. Yun, G. Zhang, F.N. Awad, X. Qi, J.N. Sahu, Recent
advances in biological pretreatment of microalgae and lignocellulosic biomass for
biofuel production, Renew. Sustain. Energy Rev. 105 (2019) 105–128, https://
doi.org/10.1016/j.rser.2019.01.048.
15
Biomass and Bioenergy 144 (2021) 105920
[152] G. Yang, J. Wang, Ultrasound combined with dilute acid pretreatment of grass for
improvement of fermentative hydrogen production, Bioresour. Technol. 275
(2019) 10–18, https://doi.org/10.1016/j.biortech.2018.12.013.
[153] K.S.K. Ismail, G. Najafpour, H. Younesi, A.R. Mohamed, A.H. Kamaruddin,
Biological hydrogen production from CO: bioreactor performance, Biochem. Eng.
J. 39 (2008) 468–477, https://doi.org/10.1016/j.bej.2007.11.003.
[154] X. Wang, Y. Fang, Y. Wang, J. Hu, A. Zhang, X. Ma, H. Yang, L. Guo, Single-stage
photo-fermentative hydrogen production from hydrolyzed straw biomass using
Rhodobacter sphaeroides, Int. J. Hydrogen Energy 43 (2018) 13810–13820,
https://doi.org/10.1016/j.ijhydene.2018.01.057.
[155] J. Cai, Y. Zhao, J. Fan, F. Li, C. Feng, Y. Guan, R. Wang, N. Tang, Photosynthetic
bacteria improved hydrogen yield of combined dark- and photo-fermentation,
J. Biotechnol. 302 (2019) 18–25, https://doi.org/10.1016/j.jbiotec.2019.06.298.
[156] L. Yang, W. Liu, Z. Zhang, X. Du, J. Gong, L. Dong, Y. Deng, Hydrogen evolution
from native biomass with Fe3+/Fe2+ redox couple catalyzed electrolysis,
Electrochim. Acta 246 (2017) 1163–1173, https://doi.org/10.1016/j.
electacta.2017.06.124.
[157] T. Hibino, K. Kobayashi, M. Ito, Q. Ma, M. Nagao, M. Fukui, S. Teranishi, Efficient
hydrogen production by direct electrolysis of waste biomass at intermediate
temperatures, ACS Sustain. Chem. Eng. 6 (2018) 9360–9368, https://doi.org/
10.1021/acssuschemeng.8b01701.
[158] D. Unlu, N.D. Hilmioglu, Application of aspen plus to renewable hydrogen
production from glycerol by steam reforming, Int. J. Hydrogen Energy 45 (5)
(2020) 3509–3515. https://doi.org/10.1016/j.ijhydene.2019.02.106.
[159] Z. Liu, Economic analysis of energy production from coal/biomass upgrading;
Part 1: hydrogen production, Energy Sources, Part B Econ, Plan. Policy. 13 (2018)
132–136, https://doi.org/10.1080/15567249.2017.1410592.
[160] D. Klein-Marcuschamer, H.W. Blanch, Renewable fuels from biomass: technical
hurdles and economic assessment of biological routes, AIChE J. 61 (2015)
2689–2701, https://doi.org/10.1002/aic.14755.
[161] G. Collodi, G. Azzaro, N. Ferrari, S. Santos, Techno-economic evaluation of
deploying CCS in SMR based merchant H2 production with NG as feedstock and
fuel, Energy Procedia 114 (2017) 2690–2712, https://doi.org/10.1016/j.
egypro.2017.03.1533.
[162] A. Valente, D. Iribarren, J.L. Gálvez-Martos, J. Dufour, Robust eco-efficiency
assessment of hydrogen from biomass gasification as an alternative to
conventional hydrogen: a life-cycle study with and without external costs, Sci.
Total Environ. 650 (2019) 1465–1475, https://doi.org/10.1016/j.
scitotenv.2018.09.089.
[163] I. Hannula, Hydrogen enhancement potential of synthetic biofuels manufacture in
the European context: a techno-economic assessment, Energy 104 (2016)
199–212, https://doi.org/10.1016/j.energy.2016.03.119.
[164] C. Acar, I. Dincer, Comparative assessment of hydrogen production methods from
renewable and non-renewable sources, Int. J. Hydrogen Energy 39 (2014) 1–12,
https://doi.org/10.1016/j.ijhydene.2013.10.060.
[165] D. Graf, N. Monnerie, M. Roeb, M. Schmitz, C. Sattler, Economic comparison of
solar hydrogen generation by means of thermochemical cycles and electrolysis,
Int. J. Hydrogen Energy 33 (2008) 4511–4519, https://doi.org/10.1016/j.
ijhydene.2008.05.086.
[166] S. Zhang, Prediction of selling price of hydrogen produced from methanol steam
reforming, Energy Sources B Energy Econ. Plann. 13 (2018) 28–32, https://doi.
org/10.1080/15567249.2017.1402101.
[167] Y. Zhang, T.R. Brown, G. Hu, R.C. Brown, Techno-economic analysis of
monosaccharide production via fast pyrolysis of lignocellulose, Bioresour.
Technol. 127 (2013) 358–365, https://doi.org/10.1016/j.biortech.2012.09.070.
[168] K. Özdenkçi, C. De Blasio, G. Sarwar, K. Melin, J. Koskinen, V. Alopaeus, Techno-
economic feasibility of supercritical water gasification of black liquor, Energy 189
(2019) 116285. https://doi.org/10.1016/j.energy.2019.116284.
[169] D.A. Sladkovskiy, L.I. Godina, K.V. Semikin, E.V. Sladkovskaya, D.A. Smirnova, D.
Y. Murzin, Process design and techno-economical analysis of hydrogen
production by aqueous phase reforming of sorbitol, Chem. Eng. Res. Des. 134
(2018) 104–116, https://doi.org/10.1016/j.cherd.2018.03.041.
[170] B. Pratto, M. Suzana, A.A. Longati, R.D.S. Júnior, A. José, G. Cruz, Experimental
optimization and techno-economic analysis of bioethanol production by
simultaneous saccharification and fermentation process using sugarcane straw,
Bioresour. Technol. 297 (2020) 122494. https://doi.org/10.1016/j.biortech.201
9.122494.
[171] T. Sinigaglia, F. Lewiski, M.E. Santos Martins, J.C. Mairesse Siluk, Production,
storage, fuel stations of hydrogen and its utilization in automotive applications-a
review, Int. J. Hydrogen Energy 42 (2017) 24597–24611, https://doi.org/
10.1016/j.ijhydene.2017.08.063.
[172] K.Y. Show, Y. Yan, M. Ling, G. Ye, T. Li, D.J. Lee, Hydrogen production from algal
biomass – advances, challenges and prospects, Bioresour. Technol. 257 (2018)
290–300, https://doi.org/10.1016/j.biortech.2018.02.105.
[173] R.R. Gonzales, G. Kumar, P. Sivagurunathan, S.H. Kim, Enhancement of hydrogen
production by optimization of pH adjustment and separation conditions following
dilute acid pretreatment of lignocellulosic biomass, Int. J. Hydrogen Energy 42
(2017) 27502–27511, https://doi.org/10.1016/j.ijhydene.2017.05.021.
[174] M. Felgenhauer, T. Hamacher, State-of-the-art of commercial electrolyzers and
on-site hydrogen generation for logistic vehicles in South Carolina, Int. J.
Hydrogen Energy 40 (2015) 2084–2090, https://doi.org/10.1016/j.
ijhydene.2014.12.043.
[175] M.F. Andrea, R.H. Sara, D.Z. Luca, S.S. Giovanni, B. Enrico, Techno-economic
analysis of in-situ production by electrolysis, biomass gasification and delivery
systems for Hydrogen Refuelling Stations: rome case study, Energy Procedia 148
(2018) 82–89, https://doi.org/10.1016/j.egypro.2018.08.033.
T. Lepage et al.
[176] J. Proost, State-of-the art CAPEX data for water electrolysers, and their impact on
renewable hydrogen price settings, Int. J. Hydrogen Energy 44 (2019)
4406–4413, https://doi.org/10.1016/j.ijhydene.2018.07.164.
[177] S. Schemme, J.L. Breuer, M. Köller, M. Sven, F. Walman, R.C. Samsun, R. Peters,
D. Solten, H 2 -based synthetic fuels : a techno-economic comparison of alcohol ,
ether and hydrocarbon production, Hydrog. Ernergy. 5 (2019) 5395–5414,
https://doi.org/10.1016/j.ijhydene.2019.05.028.
[178] P. Rajangam, Hydrogen Fuel Cells as Green Energy, Hydrog. Fuel Cells as Green
Energy. Yang, P. (Eds.), Cases Green Energy Sustain. Dev. (Pp. 291-323). IGI Glob.
(n.d.) 291–293. https://doi.org/10.4018/978-1-5225-8559-6.ch011.
[179] L.M. Das, in: Hydrogen-fueled Internal Combustion Engines, Elsevier Ltd., 2016,
https://doi.org/10.1016/B978-1-78242-363-8.00007-4.
[180] M.A. Ahmed, Hydrogen fueled internal combustion Engine : a review, Int. J.
Innov. Technol. Res. 4 (2016) 3193–3198.
[181] W.W. Pulkrabek, Engineering fundamentals of the internal combustion engine,
J. Eng. Gas Turbines Power 126 (2004) 126–198.
[182] C.M. White, R.R. Steeper, A.E. Lutz, The hydrogen-fueled internal combustion
engine : a technical review, Int. J. Hydrogen Energy 31 (2006) 1292–1305,
https://doi.org/10.1016/j.ijhydene.2005.12.001.
[183] P.M. Diéguez, J.C. Urroz, S. Marcelino-Sádaba, A. Pérez-Ezcurdia, M. Benito-
Amurrio, D. Sáinz, L.M. Gandía, Experimental study of the performance and
16
Biomass and Bioenergy 144 (2021) 105920
emission characteristics of an adapted commercial four-cylinder spark ignition
engine running on hydrogen – methane mixtures, Appl. Energy 113 (2014)
1068–1076, https://doi.org/10.1016/j.apenergy.2013.08.063.
[184] M. Talibi, P. Hellier, N. Ladommatos, ScienceDirect the effect of varying EGR and
intake air boost on hydrogen-diesel co-combustion in CI engines, Int. J. Hydrogen
Energy 42 (2016) 6369–6383, https://doi.org/10.1016/j.ijhydene.2016.11.207.
[185] N. Cihat Onat, M. Kucukvar, O. Tatari, Conventional , hybrid , plug-in hybrid or
electric vehicles ? State-based comparative carbon and energy footprint analysis
in the United States, Appl. Energy 150 (2015) 36–49, https://doi.org/10.1016/j.
apenergy.2015.04.001.
[186] G. Wu, A. Inderbitzin, C. Bening, Total cost of ownership of electric vehicles
compared to conventional vehicles : a probabilistic analysis and projection across
market segments, Energy Pol. 80 (2015) 196–214, https://doi.org/10.1016/j.
enpol.2015.02.004.
[187] H.S. Das, C.W. Tan, A.H.M. Yatim, Fuel cell hybrid electric vehicles : a review on
power conditioning units and topologies, Renew. Sustain. Energy Rev. 76 (2017)
268–291, https://doi.org/10.1016/j.rser.2017.03.056.
[188] E.A. Nanaki, C.J. Koroneos, Comparative economic and environmental analysis of
conventional , hybrid and electric vehicles e the case study of Greece, J. Clean.
Prod. 53 (2013) 261–266, https://doi.org/10.1016/j.jclepro.2013.04.010.