RENEWABLE HYDROGEN

PRODUCTION FROM
BIOMASS
Renewable Hydrogen Production
from Biomass
Johan M Ahlström, [email protected], +46702103600

Cover Image: Scharfsinn / Shutterstock.com

Table of Contents
ABSTRACT ................................................................................................................................................ 3
ABBREVIATIONS....................................................................................................................................... 3
INTRODUCTION ....................................................................................................................................... 4
TECHNOLOGIES........................................................................................................................................ 5
Biotechnical methods .......................................................................................................................... 5
Dark fermentation ............................................................................................................................... 6
Photo fermentation ............................................................................................................................. 6
Thermochemical conversion ............................................................................................................... 7
Gasification .......................................................................................................................................... 7
DFB gasification ................................................................................................................................... 8
Entrained flow gasification ................................................................................................................ 10
Pyrolysis ............................................................................................................................................. 11
Discussion and potential improvement of thermochemical conversion .......................................... 14
Electrochemical pathway .................................................................................................................. 15
Discussion and conclusions ............................................................................................................... 16
References ......................................................................................................................................... 17
Appendix............................................................................................................................................ 23

This project has received funding from the European Union’s Horizon 2020
research and innovation programme under grant agreement No 825179.

2
ABSTRACT
Hydrogen is highlighted as a key energy carrier in a future net zero green-house gas (GHG) emission
society. It is a suitable energy carrier for many applications, e.g., heavy transportation and for industrial
use. Furthermore, combusting hydrogen or using it in a fuel cell does not cause GHG emissions at site.
This implies that, if produced without emitting GHG emissions, hydrogen can be a completely renewable
energy carrier. However, currently over 90% of the world’s hydrogen supply is produced from fossil
natural gas and coal. If hydrogen is to be used as a sustainable alternative to fossil fuels, it needs to be
produced without net emissions of GHG; one such alternative is to use forest biomass. This work
presents a literature review of technologies for hydrogen production from sustainably harvested forest
biomass. An overview of available technologies is included, but thermochemical production methods are
emphasized. Results show that biomass gasification coupled with steam methane reforming and water
gas shift reactors reaches the highest biomass to hydrogen conversion yields. Compared to other
biomass based, technological pathways, gasification and pyrolysis also have the highest technological
readiness levels. The literature review suggests hydrogen production costs from gasification or pyrolysis
reaching from 0.078 to 0.21 EUR/kWh. This compares to a production cost of 0.019 EUR/kWh for natural
gas SMR and 0.023 EUR/kWh for coal gasification and production costs of 0.045-0.12 EUR/MWh for
water electrolysis.

ABBREVIATIONS
ATR – Auto Thermal Reforming
BECCS – Bio Energy Carbon Capture and Storage
CCS – Carbon Capture and Storage
Daf – Dry, ash-free
DFB – Dual Fluidized Bed
EF – Entrained Flow
GHG – Greenhouse Gas
LCA – Life Cycle Assessment
MEC - Microbial Electrolysis Cell
NG – Natural Gas
PEM – Proton Exchange Membrane
PEMEC - Proton Exchange Membrane Electrolysis Cell
PSA – Pressure Swing Adsorption
R&D – Research and Development
SCWG – Super Critical Water Gasification
SMR – Steam Methane Reforming
TRL – Technological Readiness Level
w.b. – wet basis
WC – Wood Chips
WGS – Water Gas Shift

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INTRODUCTION
Hydrogen has a heating value (LHV, mass basis), 2.4, 2.8 and 4 times higher than that of methane,
gasoline and coal, respectively and an energy density more than 100 times higher than that of a
conventional Lithium-ion battery. Furthermore, combustion of hydrogen, or using it in fuel cells, does not
create any greenhouse gas (GHG) emissions at site. This implies that, if produced without emitting GHG
emissions, hydrogen can be an almost CO2 neutral energy carrier. Due to these desirable characteristics,
hydrogen can be applied as a renewable energy carrier and is particularly interesting for applications that
are hard to electrify, e.g., heavy transportation and for industrial applications. Owing to the fact that
hydrogen is easier to store than electricity, it is also likely to be used for electricity storage in electricity
systems reliant on intermittent electricity generation [1]. For these reasons hydrogen is viewed as a key
energy carrier in reaching the climate goals stated in the Paris Agreement and several countries have
developed hydrogen strategies as a means to reach their individual climate goals [2], [3], [4], [5]. The
current (2017) world production of hydrogen exceeds 7.7 EJ where the majority is used for ammonia
production (51%), followed by oil refining (31%) and methanol production (10%) [6]. As hydrogen is
projected to be used increasingly as a supplement to fossil energy carriers that number is expected to
increase to levels of approximately 50 EJ by 2050 [7], [8].
For hydrogen to become a sustainable alternative to fossil fuels, it is essential that it is produced using
renewable energy. Currently, around 98% of the worlds hydrogen production is based on fossil energy
sources, with the majority (76%) coming from steam methane reforming (SMR) of natural gas (NG) and
the remainder from liquid hydrocarbons and coal [9], [7]. The most discussed alternative for sustainable
hydrogen production is water electrolysis using renewable electricity [10]. Water electrolysis is a
technology with a TRL of 9 and is already responsible for around 2% of the world’s hydrogen production.
However, the technology remains relatively cost intensive and has issues competing with fossil-based
alternatives. Nonetheless, as R&D progresses and the technology is scaled up, the costs are expected to
decrease [11].
In a future where demand for electricity increases, while large branches of industry want to make use of
hydrogen (see e.g. HYBRIT [12]) and the transport sector increases its hydrogen demand, there might be
a need for alternative pathways for renewable hydrogen production. Furthermore, electrification of
society and industry will put high demands on the electricity transmission infrastructure which might
limit electricity use for hydrogen production, especially during a transition period [13]. For that purpose,
the clearest option is hydrogen production from biomass [14]. Hydrogen production from biomass might
also be beneficial in cases with specific local conditions in terms of resource availability, heat integration
opportunities and limitations in electricity transmission.
The purpose of this work is to map and briefly describe potential technologies for conversion of forest
biomass to hydrogen. The focus is on techno-economic evaluations and the work strives at mapping
biomass-to-hydrogen yield, system aspects and production costs intervals for a variety of conversion
technology options with an emphasis on thermochemical pathways. The work is not all encompassing
and should not be viewed as a complete overview of all possible biomass-to hydrogen production
technologies, rather as an overview and discussion of the promising options that are most heavily
featured in the research literature.

4
TECHNOLOGIES
The combined research literature suggests several different pathways for hydrogen production from
forest biomass. The pathways are typically categorized into biological, thermochemical and
electrochemical pathways. Figure 1 provides an overview of all the processes included in this work. For
the biological an electrochemical pathway only a brief process description and state of the art
performance is included, whereas a more in-depth description and literature review is provided for the
thermochemical pathways.

Figure 1. Technologies considered for hydrogen production from forest biomass feedstock.

All data gathered and used in the analysis is presented in tables in the appendix. A conversion factor of
0.84 EUR/$ was used for economic calculations. Biomass LHV was assumed to 18.5 MJ/kgdaf when left
unspecified in the considered studies. The LHV of hydrogen is 120 MJ/kg.

Biotechnical methods
Hydrogen can be produced from biomass by biotechnological methods by making use of the natural
capabilities of microorganisms to generate hydrogen as one of the metabolic products. For this purpose,
there are two main pathways: applying photosynthetic microorganisms, often referred to as photo
fermentation, or applying anaerobic microorganisms often referred to as dark fermentation.
Photosynthetic microorganisms use carbon dioxide and water for hydrogen gas production and
phototrophic microorganism use carbohydrates or organic acids to produce hydrogen and carbon
dioxide. The principal difference between the two pathways is the source of energy for the biomass
decomposing bacteria. In photo fermentation, the bacteria take up energy from sunlight, where as in dark
fermentation, the bacteria take up energy from the biomass itself [15].

5
Essentially both these processes build on the presence of hydrogen producing enzymes that catalyze
the chemical reaction described in equation (1) [16].
2𝐻𝐻 + + 2𝑒𝑒 − = 𝐻𝐻2 (1)

Dark fermentation
Dark fermentation is the decomposition of biomass by anaerobic bacteria that grow in the dark.
According to Łukajtis et al. [17], dark fermentation is the most promising and most well-known of all
biotechnical methods for hydrogen production from biomass. It consists of a series of complex reactions
where the main enzymes regulating the hydrogen metabolism are hydrogenases.
Dark fermentation is particularly suitable for conversion of carbohydrates, which poses certain
challenges when using lignocellulosic biomass, particularly concerning lignin, which is highly resistant to
biodegradation [17]. There are, however, several studies concerning dark fermentation for production of
hydrogen from lignocellulosic biomass, where different pretreatment methods are used to eliminate the
issues caused by the lignin part of the biomass (see e.g. [16][18][19]). Pretreatment methods can be either
biological, chemical, mechanical or a combination of two or more and include e.g. size reduction, acid
treatment and enzyme treatment [19]. Furthermore, lignocellulosic biomass feedstock needs to be
treated with hydrogeneration with water when used for hydrogen production, in order to generate enough
high-quality sugars. This can be done either in a separate step prior to the fermentation or in the same
reactor [20].
According to Lepage et al. [14], hydrogen yield for dark fermentation is in the range of 0.004-0.044 kg
H2/kg biomass, which for instance can be compared to steam gasification with a range of 0.040-0.0190
kg H2/kg biomass. Production costs are at best approximately 0.065 EUR/kWh H2 and the technology
has a TRL of around 5. These numbers are indicative, especially concerning production costs, as there
are few full plant cost estimations. Several pilot facilities are in operation, but currently no commercial
scaled plants have been constructed [21].
Although highlighted as more cost efficient than photo fermentation, dark fermentation suffers from low
energy efficiency, poor durability of catalysts and product impurities [15]. The technology is not financially
competitive and need to be further developed [22]. The need for expensive pre-treatment to make the
feedstock enzymatically fermentable adds additional complexity to the process, making it more
expensive, thus limiting its development at industrial scale [14].

Photo fermentation
Photo fermentation utilizes light energy to convert biomass into hydrogen. The process is catalyzed by
nitrogenases in purple non-sulfur bacteria [23]. This is a relatively novel process and currently the least
financially competitive, biological, method for hydrogen production [24]. Two process configurations
have been suggested for the technology, a single step and a two-step approach [25]. The single photo
fermentation reactor has a low specific investment cost, but also suffers from low efficiencies. In the
two-step approach, a dark fermentation is added before the light fermentation, where the organic acids
formed in the dark fermentation step are further degraded in the second step, thereby increasing the
overall process hydrogen yield. This process is however complex to operate. The hydrogen yields for
photo fermentation are in the same range as for dark fermentation (0.004-0.049 kg H2/kg biomass), but
the production costs are higher (approximately 0.071 EUR/kWh) [14]. As for dark fermentation, these
numbers are indicative as there are few full plant techno-economic studies published. The technology is
still under development and has an estimated TRL of 4. Although still under development, it is deemed to
be less financially competitive than dark fermentation [24].

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Thermochemical conversion
Thermochemical conversion of biomass is often categorized into pyrolysis and gasification. There are
other, more novel, technologies such as super-critical water gasification (SCWG). Here, emphasis is on
gasification and pyrolysis, SCWG is briefly described. There is also the possibility of chemical looping
gasification of biomass, where an oxygen carrier is used to separate the CO2 already in the combustion
stage [26]. This process is, however, not described further in this work.

Gasification
Gasification is the thermochemical decomposition of biomass at elevated temperatures in an
environment with limited oxygen [27]. Depending on operating conditions such as temperature, catalysts
and gasification medium, a gas consisting to varying shares of H2, CO, CO2, CH4, CxHx and tars is
produced. Gasification can in general be divided into three different categories, depending on how the
process is designed: dual fluidized bed (DFB) steam blown gasification [28], also known as indirect
gasification, direct blown, steam/oxygen or air, fluidized bed gasification [29] and entrained flow
gasification [30]. Using steam as gasification medium shifts the equilibrium to an increased share of
hydrogen in the product gas and it is therefore preferred when hydrogen is the intended end-product [31].
Prior to entering the gasification reactor, the feedstock is typically pre-treated. This often includes drying
the biomass, to achieve higher conversion efficiencies in the gasification reactor, but can also include
e.g. milling, to reach a homogeneous feedstock in terms of size [32]. A variety of product gas up-grading
and conditioning sequences can be included in the process design, depending on the considered end-
product of the gasification process. A generic flow chart of a biomass gasification process for hydrogen
production is presented in Figure 2. When producing hydrogen, the gas is often upgraded through steam-
methane reforming (SMR) (eq. 2), autothermal reforming (ATR) (eq. 3) and/or water-gas shift reaction
(WGS) (eq. 4) [33], [34].
𝐶𝐶𝐻𝐻4 + 𝐻𝐻2 𝑂𝑂 ↔ 𝐶𝐶𝐶𝐶 + 3𝐻𝐻2 (2)
2𝐶𝐶𝐻𝐻4 + 𝑂𝑂2 + 𝐶𝐶𝑂𝑂2 ↔ 3𝐻𝐻2 + 3𝐶𝐶𝐶𝐶 + 𝐻𝐻2 𝑂𝑂 (3)
𝐶𝐶𝐶𝐶 + 𝐻𝐻2 𝑂𝑂 ↔ 𝐶𝐶𝑂𝑂2 + 𝐻𝐻2 (4)
In that way CH4 and CO is utilized to increase the hydrogen yield in the product gas.
When cleaning the gas, some processes opt for a separate CO2 separation step, typically done through
amine scrubbing. This makes the final hydrogen separation sequence cheaper. In addition, it makes it
possible to store the CO2, thereby providing a potential additional revenue stream to the process, while
contributing to negative CO2 emissions. It is also possible to utilize the generated CO2 for additional fuel
production (CCU). The drawback is naturally the cost associated with separating the CO2. The hydrogen
is finally separated from other species present in the gas to a satisfactory level of pureness. This can be
done through a variety of techniques, where the far most common is pressure-swing adsorption (PSA)
[35].
There are other options to the SMR, ATR and WGS reactions coupled with CO2 separation. For instance,
chemical looping reforming is an option where the CO2 separation and ATR occurs in the same process
step [36]. Another option is to use a calcium looping reactor system where the WGS reaction and CO2
separation occurs simultaneously. In the primary reactor, the WGS-reaction is enhanced by removing
CO2 from through the carbonization reactor with CaO. In the second reactor, the CaCO3 is regenerated to
CO2 which is released and CaO that is circulated to the WGS reactor [37]. However, the number of techno-
economic studies relating these technologies to hydrogen production from forest biomass are limited.

7
Figure 2. Simplified generic flow chart of a biomass gasification process for hydrogen production

Potential benefits of thermochemically based hydrogen production from biomass, in relation to other
biomass-to-hydrogen processes and water electrolysis, includes the potential for process integration and
to have systems that have additional end-products besides hydrogen. Thermochemical process occurs
at high temperatures and typically generate large quantities of excess heat. Integrating the plant with
other industries implies that the combined heat requirements of the plant can be decreased, leading to
an overall more energy efficient process. Excess heat could also be used for heat export through district
heating or for electricity generation through steam turbines (see e.g. [38], [39]). Furthermore,
decomposing thermochemical treatment of biomass generates other products than hydrogen, e.g.
methane, biochar or off-gases, which can be exported and contribute to additional income in an
multigeneration concept (see e.g. [40]).

DFB gasification
DFB gasification builds on separating the gasification process from the combustion process required to
sustain the heat to the process. This is done with two separate reactors with a circulating bed material
stream between the two processes [28]. The benefit of this process is that it is possible to use air for
combustion of the biomass, rather than pure oxygen, which is normally the case using other technologies
if the gas is to be used for fuel synthesis. Thereby there is no need for an energy intensive air separation
unit (ASU). DFB gasification typically occurs at lower temperatures than their counter parts (700-900°C),
which results in a gas with higher concentrations of hydrocarbons, but also tars that needs to be handled
down-stream in the process [41].
There have been several studies on hydrogen production and hydrogen hybrid production systems based
on DFB gasification. Brau & Morandin [42] considered a process based on DFB gasification followed by
SMR and a 2-step sequence of water gas shift integrated with an oil refinery. The raw gas is scrubbed of
tar species using water, then the methane present in the gas is reacted to hydrogen at high temperature
(800°C) in the SMR reactor, followed by a sequence of two WGS shift reactors, first a high temperature
reactor (350°C), followed by a low temperature reactor (260°C). Hydrogen is then separated using PSA.
Part of the syngas leaving the scrubber, as well as the off gas from the PSA units are combusted to
generate the heat required by the SMR reactor. The overall hydrogen yield of the process is 0.1 kg H2/kg
biomass, which corresponds to a biomass to hydrogen efficiency of 0.67 on a HHVdaf basis. By means of
heat integrating the gasification plant with an oil refinery, while producing high pressure steam or
electricity as a by-product, the energy and exergy efficiency can be increased with 8 respectively 4

8
percentage points. Furthermore, the process contributes to lowering GHG emissions with up to 700
ktones/year if replacing H2 produced from NG in the refinery, depending on assumed marginal electricity
production technology.
Tock & Maréchal [43] considered a similar process with the addition of a torrefaction step before the
gasification reactor. The process is integrated with a CHP plant where part of the off gases from the
torrefaction step and excess heat from the process is used to generate electricity. Furthermore, parts of
the hydrogen can be combusted for additional electricity generation. Heat from the CHP plant is used to
run the SMR reactor, which means that there is no need to combust off gases. The process also differs
compared to the process described by Brau & Morandin, in the final gas cleaning step, where a CO2 amine
scrubbing step is included before the PSA unit. This means that there is a clean CO2 stream present in
the process, which potentially can be stored. Tock & Maréchal report a hydrogen yield of 0.107 kg H2/kg
biomass and a biomass to hydrogen efficiency of 0.696 on a LHVdaf basis. The process is optimized for
cost and GHG emission reduction using a multi-objective optimization approach. The resulting overall
energy efficiency for hydrogen production and electricity generation with CO2 capture was 0.6 and 0.39
respectively. This in turn corresponds to a hydrogen production cost of 0.05-0.176 EUR/kWh H2,
depending on the price of biomass feedstock.
A DFB gasification concept was also studied in a techno-economic and LCA study by Salkuyeh et al. [44].
Their process is similar to the two previously described but differs in that no SMR reactor is included.
Without the SMR reactor, there is a lower high-temperature heating demand in the process, which implies
that a smaller part of the produced gas needs to be used internally in the process for heat generation.
However, this process incorporates a tar reforming step, to increase the biomass to gas conversion,
which in turn has a heat demand that is saturated by burning product gas. The process includes an
amine-scrubbing step before the final PSA hydrogen separation, which means that a stream of pure CO2
is produced. Off gases from the PSA unit are combusted to generate electricity and supply the process
with heat. The process includes the option of liquefying the separated CO2 stream for CCS, however,
when running the liquefaction unit, additional NG needs to be co-combusted with the off gases to sustain
the process with electricity and steam. Thereby, the overall energy efficiency is decreased from 0.45 to
0.41 if operating the CO2 liquefaction step, while also making use of a fossil resource (NG) in the plant.
The hydrogen yield is 0.061 kg H2/kg biomass corresponding to an approximate efficiency of 0.4
(biomass LHVdaf assumed to be 18.5 MJ/kg). An overall hydrogen production cost of 0.061 EUR/MWh
was reported.
Hydrogen production from biomass through DFB gasification has been studied in the pilot plant in
Güssing, Austria [45]–[47]. A poly-generation concept generating hydrogen and electricity was studied in
a study from 2018 [46]. This concept builds on a three step WGS reaction sequence, followed by RME
scrubbing of tars and PSA for separating hydrogen. Here a substantial part of the hydrogen in the gas is
used for electricity and district heating generation meaning that the hydrogen yield is sacrificed for
electricity generation and a cheaper PSA unit. The overall yield is 0.03 kg H2/kg biomass which
corresponds to an approximate efficiency of 0.2 (biomass LHVdaf assumed to be 18.5 MJ/kg) while
generating 0.6 and 1.7 MW of electricity and district heating per MW of produced hydrogen. In 2017, the
same research group studied a similar process, consisting of a DFB gasifier, followed by WGS, RME
scrubbing and PSA for the sole purpose of producing hydrogen [45]. Here an overall hydrogen yield of
0.058 kg H2/kg biomass and an efficiency of 0.4 was reached. It should be mentioned that also here, a
relatively large part of the available hydrogen is recirculated from the PSA unit to be incinerated in the
combustion reactor of the gasifier. An overall production cost of 0.148 EUR/kWh hydrogen was reported.
Overall, the processes combining SMR and WGS reactors reaches the highest conversion efficiencies,
which is also theoretically supported. Turn et al. [48] experimentally studied steam gasification of
biomass for hydrogen production. They concluded that it is theoretically possible to produce up to 0.165
kg H2/kg biomass when applying WGS and SMR. In their experiments an actual maximum of 0.128 kg

9
H2/kg biomass owing to conversion losses of biomass was reached. This corresponds to an hydrogen
production rate of a factor approximately 2.1 times higher than the hydrogen available in biomass
(assuming a hydrogen content of 6% on mass basis daf) [48].
Direct blown, O2 gasification
Direct blown gasification of biomass can be performed with air as gasification medium, but as air
consists mainly of nitrogen, this creates a diluted product gas unsuitable for synthesis. Therefore, direct
blown gasification is often performed with pure oxygen and steam as gasification medium. The benefits
of this process are the simpler process design compared to the DFB gasification process and that the
gasification reactor potentially can be pressurized, which eliminates the need for compression later in
the process and potentially allows for a smaller, and thereby cheaper, gasification reactor. The draw-back
is the cost and energy penalty associated with the air-separation unit (ASU) required to sustain the
process with oxygen [42].
Brau & Morandin studied a pressurized, direct oxygen and steam blown, gasification plant in combination
with a WGS reactor for hydrogen production heat integrated with an oil refining plant [42]. The process
includes an autothermal reforming (ATR) reactor and makes use of a membrane reactor where the WGS
reaction and hydrogen separation occurs simultaneously, allowing for process intensification as
compared to the DFB process studied in the same paper (see previous sub-heading). The ATR reactor
removes the need for tar scrubbing while converting methane present in the gas to hydrogen, similarly
to SMR, with the difference that oxygen is added to the process. This process reaches an overall
hydrogen yield of 0.087 kg H2/kg biomass corresponding to an efficiency of 0.59, which implies that this
process has a lower yield than the DFB gasification concept evaluated in the same study. As in the case
of DFB gasification, the overall energy and exergy efficiency is improved through heat integration with
the oil refinery, increasing with up to 11 and 6 percentage points respectively.
Bhattacharya et al. [49] studied an oxygen blown gasification process for production of hydrogen, also
based on WGS and PSA. This process reaches a hydrogen yield of 0.102 kg H2/kg biomass meaning an
efficiency of 0.654. However, the study also highlights that the duty of the ASU will lower the overall
process energy efficiency with around 3.5 percentage points.
Economic data for direct blown biomass gasification for hydrogen production is limited. There are
however several studies for production of other types of fuels, e.g. bio methane [50]. The conclusions of
those studies differ, and it is difficult to make a clear distinction in terms of which process reaches the
lowest production costs. However, In general the economic performance of direct blown gasification is
in the same range as that of DFB gasification [51], [52].

Entrained flow gasification

Entrained flow gasification differs to the previous two gasification processes in how the gasification
reactor is designed and operated. As the name suggests, the feedstock is entrained with the gasification
medium when injected in the top of the reactor. This puts high demands on the feedstock preparation
and the feedstock needs to be grinded into a fine powder that can be sprayed into the reactor. Entrained
flow gasification occurs at high temperatures compared to the previously mentioned options (around
1300°C), which results in high conversion rates and a clean gas with low levels of hydrocarbons and tar
[53]. Hence, the process design can be simplified and thereby intensified. The drawback of this process
is the high feedstock preparation cost and, similarly to oxygen blown gasification, the costs associated
with the ASU. These facts imply that the benefits of entrained flow gasification are limited when it comes
to certain feedstocks, e.g. forest residues, where there is a high cost associated with grinding the
feedstock. On the other hand, it is suitable for feedstocks already in a fitting form, e.g. pyrolysis liquids,
black liquor (BL) and saw dust [30], [54], [55].

10
Entrained flow gasification of biomass milled to powder, for production of hydrogen was studied by
Salkuyeh et al. [44]. In this design, the gasification reactor is followed by gas cleaning sequences and
COS hydrolysis. After gas cleaning, the gas is treated in a high temperature WGS reactor, followed by a
low temperature WGS reactor. The synthesized gas is cleaned of CO2 using an amine scrubber and the
final hydrogen stream is cleaned using PSA. The hydrogen production cost was reported to be 0.085
EUR/kWh hydrogen. Like the DFB gasification process evaluated in the same study, the off gases from
the PSA unit are combusted for heat and electricity production. If the CO2 is to be liquefied, additional NG
is burned, which in this case lowers the overall energy efficiency of the process from 0.56 to 0.49. This
process has an overall yield of 0.078 kg H2/kg biomass which corresponds to a biomass to hydrogen
efficiency of 0.5 (biomass LHVdaf assumed to be 18.5 MJ/kg).
Andersson & Harvey [56] studied entrained flow black liquor (BL) gasification for hydrogen production
integrated with a generic pulp mill. The process is similar to the one studied by Salkuyeh et al. but differs
in the gas cleaning sequence as it does not include an amine scrubber, which implies that this process
does not have the possibility for CCS. The off gases from the PSA unit are instead burned for heat
generation in the biomass boiler present at the pulp mill. This process reaches a hydrogen yield of 0.055
kg H2/kg BL, which corresponds to a biomass to hydrogen efficiency of 0.54. The study assumes that all
BL available at a generic pulp mill producing 630,000 air dried tonnes (ADt) pulp/year is used for hydrogen
production and that the excess heat from the gasification process is used to generate steam used in the
pulp mill. However, steam generation is not sufficient, and the plant must import biomass. Furthermore,
when removing the recovery boiler, the electricity import of the pulp mill increases severely. Nonetheless,
if all Swedish pulp mills where to adopt this concept, it has the potential to lower national CO2 emissions
with up to 8%.,
Wang et al. [57] studied oxygen and steam blown entrained flow gasification of straw for production of
hydrogen. The process includes WGS reaction and a PSA unit to separate the hydrogen. In this process,
the off gases are combusted for heat and electricity generation. The process reaches a biomass to
hydrogen yield of 0.091 kg H2/kg biomass and a production cost of 0.03 EUR/kWh H2, while generating
0.34 MW of electricity per MW of hydrogen.
Johansson et al. [58] also studied biomass gasification for hydrogen production, integrated with an
hydroskimming refinery. In a system analysis, they compared bubbling bed O2 gasification to DFB
gasification and entrained flow gasification. The entrained flow gasification-based process is similar to
the previously described ones, with high and low temperature WGS reactors and PSA. However, in this
case, the wood product is torrefied or pyrolyzed in a pre-treatment step. The DFB process includes SMR
and two-stage WGS and the O2-gasification process includes reforming and two-step WGS reactors.
Hydrogen separation is based on PSA in both cases. In all processes, excess heat from the refinery is
utilized in the gasification processes, while off gases from the PSA step is used to replace NG for heating
in the refinery. The results show a hydrogen yield of 0.08 kg H2/kg biomass which corresponds to a
biomass to hydrogen efficiency of 0.53 for the entrained flow-based process, compared to a yield of
0.092 kg H2/kg biomass and efficiency of 0.65 for the O2 gasification case and a yield of 0.083 and
efficiency 0.6 for the DFB gasification case. The study conclude that the EF gasification process is
favorable in cases where biomass availability is unlimited, as it generates the largest quantities of excess
heat to be used in the refinery. In a scenario where biomass is limited, the O2-blown, gasification process
is favored, owing to having the highest hydrogen yield. All three considered processes lower CO2
emissions compared to NG SMR.

Pyrolysis
Pyrolysis is in many aspects similar to gasification, but it occurs at lower temperatures (400-800°C) with
the complete lack of an oxidizing agent. According to rising reaction temperature, pyrolysis is categorized

11
into three classes: slow pyrolysis, fast pyrolysis and flash pyrolysis [59]. Pyrolysis generates a gas
fraction consisting of H2, CO, CO2 and CH4, a pyrolysis liquid fraction and a charcoal fraction. The pyrolysis
liquid fraction, sometimes referred to as “bio-oil”, contains a water-soluble fraction and a non-soluble
fraction. The share of the different fractions depends on the type of pyrolysis reactor, with the highest
gas shares reached for flash pyrolysis reactors. However, the gas fraction is lower than for gasification
[14].
A generic flowchart for the production of hydrogen through biomass-based pyrolysis is presented in
Figure 3. The different fractions generated from biomass pyrolysis can be utilized in different ways when
the intended end-product is hydrogen. The most common approach is to react the water-soluble fraction
of the pyrolysis liquids in reforming reactors for hydrogen production [60]. This can be done e.g. through
catalytic steam reforming [61] or steam reforming [62]. The non-soluble fraction can potentially be
cracked into other smaller hydrocarbons, e.g. BTX, whereas the gas fraction can be separated for
hydrogen production or used for heat recovery. Nonetheless, fast-pyrolysis typically yields a small gas
fraction and it might not be economically feasible to separate out hydrogen from the gas fraction [63].
The charcoal fraction is typically used to provide the process with heat, although it is possible to use it
for other applications as well.

Figure 3. Generic flowchart for hydrogen production from biomass-based pyrolysis.

The research literature on techno-economic assessments of biomass pyrolysis for hydrogen production
is scarcer compared to gasification and there are few results for biomass-to-hydrogen yields and
production costs. Czernik et al. [64] studied a pyrolysis process generating ”bio-oil” which subsequently
is reacted with catalytic steam reforming to generate hydrogen. A bio-oil to hydrogen yield of 0.12 kg of
hydrogen per kg of bio oil was reached (biomass-to-bio-oil yield was left unspecified in the study).
However, this study was solely experimental and did not include a full process design for hydrogen
separation and energy recovery.
Zhao et al. [65] evaluated a hydrogen production process based on pyrolysis of rice husk followed by
catalytic steam reforming of the gas and liquid fractions. This process generates a gas with hydrogen
molar concentrations over 60%, with an overall yield of 0.065 kg H2/kg biomass. However, also this study
was experimental, with external heating and the gas mixture was not separated. No economic data was
published.

12
Arregi et al. [66] studied pyrolysis of pine sawdust and HDPE (plastic) for production of biomass. The
experimental process includes a fluidized bed, Ni catalyzed, steam reforming reactor. The results show
a hydrogen yield of 0.1 kg H2/kg biomass & HDPE which corresponds to an approximate biomass to
hydrogen efficiency of 0.65, when using only biomass as feedstock. If the same process is operated with
100% HDPE, the hydrogen yield can be increased to 0.373 kg H2/kg HDPE. This study was also solely
experimental and only focused on the pyrolysis reactor and following reforming reactor.
Czernik & French [67] studied a process using an autothermal reforming reactor to produce hydrogen
from pyrolysis liquids. This process reaches a pyrolysis liquid to hydrogen yield of 0.11 H2/kg pyrolysis
liquid (full biomass to hydrogen yield was not specified in the study). According to the economic
estimates this would correspond to a hydrogen production cost of 0.11 EUR/kg for a plant producing
1,500 kg H2 a day, of which 53% are related to the feedstock cost.
In a recent literature review of hydrogen production pathways from biomass performed by Lepage et al.
[14], the production cost for hydrogen from pyrolysis was estimated to be in the range of 0.031-0.064
EUR/kWh hydrogen which is in the same range as what they estimate for gasification (0.031-0.088
EUR/kWh). These results where contradicted by Balat [68] who concluded that gasification of biomass
followed by reforming results in higher hydrogen yields than fast pyrolysis followed by reforming of the
soluble fraction of the bio oil, thereby implying lower production costs. In the same study, the TRL of
different biomass-to-hydrogen processes where estimated. Both gasification and pyrolysis where
estimated to be at a TRL of 7, the highest of any, non-commercial, technologies considered.
Super critical water gasification
SCWG of biomass is the decomposing of biomass using water in a super critical condition (373.9°C,
22.06 kPa) [69]. An ideal reaction for complete conversion of biomass to hydrogen is displayed in
equation (5), with glucose as a generic representative for biomass.
𝐶𝐶6 𝐻𝐻12 𝑂𝑂6 + 6𝐻𝐻2 𝑂𝑂 → 6𝐶𝐶𝑂𝑂2 + 12𝐻𝐻2 (5)
However, in the reaction carbon monoxide is also formed, which reacts with water to form carbon dioxide
and hydrogen according to equation (6).
𝐶𝐶𝐶𝐶 + 𝐻𝐻2 𝑂𝑂 ↔ 𝐶𝐶𝑂𝑂2 + 𝐻𝐻2 (6)
A clear benefit of SCWG is that water is a reactant. This means that using wet biomass does not
contribute to lower efficiencies, which is the case in gasification and pyrolysis processes.
SCWG yields a clean product gas, mainly consisting of hydrogen and carbon dioxide. Dos Santos et al.
showed how, given a specific scenario, concentrations of H2 at around 68, 67 and 66 % can be reached
with a feedstock consisting of guaiacol, phenol and glucose, respectively [70]. This process yields a clean
gas consisting of H2, CO2 and small amounts of CH4 and other hydrocarbons. However, SCWG is sensitive
to type of biomass, catalysts and operating conditions. For these reasons it is often considered
expensive.
SCWG has been successfully demonstrated in the VERENA plant at Karlruhe Institute of Technology [71],
where a gas mixture of hydrogen, CO2 and methane was produced from biomass feedstock. After CO2
separation the gas reached H2 concentration of up to 77% for operating temperatures of 540-600°C.
Fiori et al. [72] constructed a process flowsheet model in Aspen plus for a SCWG plant for production of
hydrogen to a fuel cell. A biomass/water mixture is pre-heated in two steps before the gasification
reactor, where the first heat exchanger is heated with the gas/water mixture leaving the reactor. The
generated gas mix is cooled in two steps. Water is separated out and reused in the process. The syngas
is then sent to a hydrogen separation step based on the HYSEP technology, where a palladium filter is
used at elevated temperature and pressure (300°C, 60 bar). Hydrogen is then pure enough to be used in
fuel cells (or exported), and the remaining gas, consisting mainly of CH4, CO and CO2, is combusted to

13
produce heat to the gasification reactor. Their results indicate that, using glycerol feedstock with a
concentration of 25%w.b., it is possible to reach a hydrogen yield of 0.085 kg H2/kg biomass.
Gutiérrez Ortiz et al. [73] also studied SCWG of glycerol for production of hydrogen using process
modeling in software Aspen plus. Glycerol and water are mixed and heated before the reactor and the
product stream is cooled, similarly to the process design by Fiori et al. [72]. However, in this process, a
water-gas-shift reactor is included to further increase the hydrogen share of the syngas. A flash-reactor
is used to separate the liquid phase from the gas, but a H2 separation sequence is not included in their
model, which would be required to get a pure stream of H2. The report shows a final syngas stream with
a mole fraction of maximally around 70% H2, around 28% CO2 and traces of CO and no remaining CH4.
Their results also show how the molar fraction of hydrogen in the syngas decreases with an increase of
biomass concentration in the feed. This highlights potential issues with scaling up the process; large
reactors and high water-consumption are required for an efficient generation of H2.
There are few technoeconomic assessments of SCWG for hydrogen production. However, Özdenkçi et
al. [74] performed a techno economic assessment of SCWG of black liquor for hydrogen production. The
process uses PSA to separate out hydrogen from the product gas exiting the SCWG reactor. A production
cost between 0.03-0.1 EUR/kWh H2 was reported.
According to Correa et al. [69], SCWG is still facing issues related to production costs and lack of
knowledge of operation with different biomass feedstocks. Most new experiments are conducted using
glucose as feedstock. The technology has only been investigated at experimental scale and although
there have been promising results, the TRL is at 4, which is low, especially in comparison to more
developed technologies such as gasification [14].

Discussion and potential improvement of thermochemical

conversion
The yields for biomass-based hydrogen production through thermochemical pathways reaches from
0.057-0.107 kg H2/kg biomass feedstock depending on process design and eventual by-products. This
corresponds to a production cost of 0.078 to 0.21 EUR/kWh H2. Lepage et al. [14] claim production cost
for both pyrolysis and gasification reaching down to 0.03 kg/kWh H2. However, the specific technology
used was left unspecified and the author has not been able to verify the numbers. It should be highlighted
that the presented cost estimations are indicative. The different studies assume different time horizons,
are performed at different years, some assume nth plant construction costs (meaning that several similar
plants have been constructed before, which contributes to lower investment costs), whereas others
estimate cost for a new plant. Furthermore, feedstock cost, electricity price and other costs vary between
the studies, as do assumptions for interest rate and economic lifetime. Thereby these numbers should
be compared with caution.
There are two clear technical pathways to improve the performance of thermochemical methods for
hydrogen production: CCS or using electricity to increase the carbon efficiency of the process. In all
thermochemical processes for hydrogen production, there is CO2 present in the gas, which needs to be
separated out to reach a clean enough product [75]. Storing CO2 emissions from processes utilizing
biomass contributes to lowering the GHG concentration in the atmosphere; the emissions are negative.
This concept is often referred to as bioenergy carbon capture and storage (BECCS). Negative emissions
of GHG might be required to reach stringent climate targets and for that purpose BECCS is highlighted
as a key technology [76]. Thus, in a future with high charges on GHG emissions, separating out and
storing the CO2 can provide additional income to a biofuel plant while increasing the climate benefit.
There have been several studies of BECCS in relation to thermochemical biofuel production (see e.g. [77],
[78], [79]), however there are currently no studies relating BECCS to hydrogen production from biomass
gasification. Such a process would need to include a separate CO2 separation sequence, through e.g.

14
amine scrubbing, as is done in some of publications included in this review (e.g. [43]). Nonetheless, in
hydrogen production from biomass, or production other biofuels via thermochemically based processes,
there is a need to remove CO2 to produce a pure product stream. Thereby the additional cost of CCS is
smaller in comparison to e.g. applying the concept to a flue gas stream or using direct air capture of CO2.
Nonetheless, there are additional costs associated with compressing or liquefying, transporting and
storing CO2.
The option of making use of electricity in the hydrogen plant intends to increase the biomass to hydrogen
yield. All thermochemical processes are endothermic, which means that they need to be supplied with
heat. Furthermore, both SMR and ATR reactors are endothermic, which increases the heat needs of the
process. These heat needs are generally sustained by combusting part of the feedstock and/or the
product gas. By instead using electricity for heating, it is possible to increase the share of biomass that
ends up in the product stream. There are two clear options to achieve this in a thermochemical-based
hydrogen production process. The first option is to use electricity for direct heating in the gasification or
pyrolysis reactor. The effects of electric heating in a DFB gasification process was studied by Alamia et
al. [80]. Their results show that by adding electricity to the reactor, corresponding to 3%LHV,daf of the energy
in the feedstock, it is possible to reach a higher char gasification rate and increase the cold gas efficiency
of the plant. Another option is to use electricity to heat the SMR reactor. The concept of electricity SMR
(eSMR) was studied by Wismann et al [81]. Their result show that it is possible to use electricity instead
of combustion to heat SMR reactors, and by doing so, it might be possible to decrease the reactor size
with up to a factor of 100. Naturally, for these concepts to be interesting from a sustainability perspective,
the electricity used in the process should be renewable.
Besides utilizing technical innovations such as eSMR and BECCS, there are also clear cost and efficiency
benefits to be made from process integration and multi product systems, as highlighted through this
work. Generating steam from high temperature excess heat from the gasification for direct use in other
processes or electricity production contributes to increased energy and exergy efficiency. Process
integration is essential in creating overall efficient value chains for thermochemical bio fuel processes
[82]. As shown by e.g. Tock et al. and by Brau & Morandin, proper process integration with a host industry
or power plant, can contribute to increased energy efficiency, also in the case of hydrogen production
from biomass gasification [42], [43].

Electrochemical pathway
Biological electrolysis is similar to electrolysis of water with the difference being that the reaction occurs
at the anode rather than the cathode and the fact that biomass is the main feedstock. There are currently
two different technologies for this purpose: Proton Exchange Membrane Electrolysis Cell (PEMEC) and
Microbial Electrolysis Cell (MEC) [24]. The benefit of biological electrolysis is that it is more energy
efficient than water electrolysis. The main drawback is naturally that the feedstock comes at a severely
higher cost (water/biomass). Furthermore, it is not possible to use the technology on cellulosic biomass
without pre-treatment. The feedstock needs to be fermented and converted into organic acids or alcohols
before it can be treated. Thereby the capital cost and complexity of the process is increased, which makes
commercialization of the technology more difficult [83]. An alternative pre-treatment is to first produce
bioethanol from biomass and use it as feedstock for biological electrolysis. Chen et al. [84] showed how
electricity consumption can be decreased with up to 26.5 kWh/kg H2 compared to an PEM electrolyzer.
However, the efficiency loss from the methanol process is too high to make the process economically
viable. The biological electrolysis process is also penalized by low production rates. Kadier et al. [85]
reports hydrogen production costs from biological electrolysis of biomass reaching from 0.11-0.42
EUR/kWh H2.

15
Out of all the technologies considered in this work, biological electrolysis has the lowest TRL at 3 [14].
Therefore, although interesting, more development is required before biological electrolysis for hydrogen
production can be comparable to thermochemical options for hydrogen production.

Discussion and conclusions

This work gives an overall presentation of potential technologies for hydrogen production from biomass.
The collected literature suggests multiple pathways, including biological, thermochemical and
electrochemical conversion technologies. Overall, the pyrolysis and gasification pathways have the
highest technology readiness levels and among the highest production yields and lowest production
costs. Furthermore, thermochemical processes for production of hydrogen are suitable for process
integration and has the possibility to be part of multi-product system. This study has shown that by
efficient process integration and by considering by-products such as HP-steam and/or electricity, the
overall process energy efficiency is increased. This conclusion is also supported by previous studies on
production of other types of biofuels via thermochemically based processes. Ultimately, this implies that
if implemented carefully, thermochemical processes for hydrogen production contributes to more
efficient use of biomass.
There are several technologies such as SCWG and biological electrolysis, which theoretically also can
reach low production costs. However, the literature is scarce on these technologies and most studies are
only experimental; there are few technoeconomic assessments. A lot of the data that can be found is
also based on other types of biomass, e.g. sugar beets, and those processes are likely less suitable for
conversion of forest biomass. This makes it hard to estimate realistic yields and production costs.
Furthermore, these technologies have low TRL and a lot of R&D remains before they can be considered
interesting from a commercial perspective.
Between the different gasification pathways and pyrolysis, it is hard to differentiate as there is more
techno-economic data published on different gasification processes compared to pyrolysis-based
production. Some studies suggest that the production costs are equal for pyrolysis and gasification (see
e.g. [14]), however, the literature included in this work suggests slightly higher hydrogen yields and lower
production costs for gasification-based production. Of the three considered gasification processes, the
results are relatively difficult to compare as they are sensitive to assumptions on e.g. by-products and
raw materials. However, the overall interpretation is that DFB gasification of biomass in combination with
SMR and WGS general reaches the highest biomass-to-hydrogen conversion efficiencies, although
entrained flow gasification also has a high potential, especially as reported in some studies. Concerning
economic performance, the research literature is even scarcer. However, DFB gasification seems to
reach the lowest production costs although it should be highlighted that the differences are small.
This literature review shows how it is possible to produce hydrogen from biomass using gasification or
pyrolysis to a cost from 0.078 to 0.21 EUR/kWh. This compares to a production cost of 0.019 EUR/kWh
for natural gas SMR and 0.023 EUR/kWh for coal gasification, meaning that hydrogen production from
biomass cannot compete with fossil hydrogen production without economic policy support. However,
water electrolysis reaches production costs of 0.045-0.12 EUR/MWh, highly dependent on the electricity
price [3][14]. Thereby, hydrogen production from biomass can potentially be competitive with water
electrolysis, depending on development of capital costs as both technology types matures and
depending on electricity price development in relation to the development of biomass prices.
This literature review also shows how it might be possible to make gasification-based hydrogen
production more economically attractive by combining BECCS with the plant. Another potential option is
to increasingly electrify the plant, this could e.g. be achieved through direct economic heating in the
biomass conversion reactor, or by means eSMR.

16
References
[1] V. Walter, “THESIS FOR THE DEGREE OF LICENTIATE OF ENGINEERING Variation management
for cost-efficient integration of variable renewable electricity,” 2020. Accessed: Apr. 01, 2021.
[Online]. Available: https://research.chalmers.se/publication/519486/file/519486_Fulltext.pdf.
[2] C. F. Schleussner et al., “Science and policy characteristics of the Paris Agreement temperature
goal,” Nature Climate Change, vol. 6, no. 9. Nature Publishing Group, pp. 827–835, Aug. 25, 2016,
doi: 10.1038/nclimate3096.
[3] T. Leperecq, “Hydrogen is the New Oil - How 7 energy battles are giving birth to a carbon free
world.” https://inis.iaea.org/search/search.aspx?orig_q=RN:50058793 (accessed Feb. 26, 2021).
[4] I. Staffell et al., “The role of hydrogen and fuel cells in the global energy system,” Energy and
Environmental Science, vol. 12, no. 2. Royal Society of Chemistry, pp. 463–491, Feb. 01, 2019, doi:
10.1039/c8ee01157e.
[5] J. Laurikko et al., “National Hydrogen Roadmap for Finland,” Nov. 2020, Accessed: Apr. 01, 2021.
[Online]. Available: https://www.h2knowledgecentre.com/content/government621.
[6] H. Council, “Hydrogen Scaling Up: A sustainable pathway for the global energy transition,” Nov.
2017, Accessed: Apr. 01, 2021. [Online]. Available:
https://www.h2knowledgecentre.com/content/policypaper1201.
[7] M. Shahabuddin, B. B. Krishna, T. Bhaskar, and G. Perkins, “Advances in the thermo-chemical
production of hydrogen from biomass and residual wastes: Summary of recent techno-economic
analyses,” Bioresource Technology, vol. 299. Elsevier Ltd, p. 122557, Mar. 01, 2020, doi:
10.1016/j.biortech.2019.122557.
[8] “• Hydrogen demand worldwide 2015-2050 | Statista.”
https://www.statista.com/statistics/435467/hydrogen-demand-worldwide/ (accessed Apr. 01,
2021).
[9] F. Suleman, I. Dincer, and M. Agelin-Chaab, “Environmental impact assessment and comparison
of some hydrogen production options,” Int. J. Hydrogen Energy, vol. 40, no. 21, pp. 6976–6987, Jun.
2015, doi: 10.1016/j.ijhydene.2015.03.123.
[10] S. Bourne, “The future of fuel: The future of hydrogen,” Fuel Cells Bull., vol. 2012, no. 1, pp. 12–15,
Jan. 2012, doi: 10.1016/S1464-2859(12)70027-5.
[11] O. Schmidt, A. Gambhir, I. Staffell, A. Hawkes, J. Nelson, and S. Few, “Future cost and performance
of water electrolysis: An expert elicitation study,” Int. J. Hydrogen Energy, vol. 42, no. 52, pp. 30470–
30492, Dec. 2017, doi: 10.1016/j.ijhydene.2017.10.045.
[12] “Hydrogen steelmaking for a low-carbon economy : A joint LU-SEI working paper for the HYBRIT
project.” https://lup.lub.lu.se/search/publication/e8289959-1fa9-48e0-87d6-e3f79cb93aac
(accessed Feb. 26, 2021).
[13] A. Guminski, F. Böing, A. Murmann, and S. von Roon, “System effects of high demand-side
electrification rates: A scenario analysis for Germany in 2030,” Wiley Interdiscip. Rev. Energy
Environ., vol. 8, no. 2, p. e327, Mar. 2019, doi: 10.1002/wene.327.
[14] T. Lepage, M. Kammoun, Q. Schmetz, and A. Richel, “Biomass-to-hydrogen: A review of main
routes production, processes evaluation and techno-economical assessment,” Biomass and
Bioenergy, vol. 144. Elsevier Ltd, p. 105920, Jan. 01, 2021, doi: 10.1016/j.biombioe.2020.105920.
[15] M. Wang, G. Wang, Z. Sun, Y. Zhang, and D. Xu, “Review of renewable energy-based hydrogen
production processes for sustainable energy innovation,” Glob. Energy Interconnect., vol. 2, no. 5,

17
 pp. 436–443, Oct. 2019, doi: 10.1016/j.gloei.2019.11.019.
[16] S. Manish and R. Banerjee, “Comparison of biohydrogen production processes,” Int. J. Hydrogen
Energy, vol. 33, no. 1, pp. 279–286, Jan. 2008, doi: 10.1016/j.ijhydene.2007.07.026.
[17] R. Łukajtis et al., “Hydrogen production from biomass using dark fermentation,” Renewable and
Sustainable Energy Reviews, vol. 91. Elsevier Ltd, pp. 665–694, Aug. 01, 2018, doi:
10.1016/j.rser.2018.04.043.
[18] N. Q. Ren, L. Zhao, C. Chen, W. Q. Guo, and G. L. Cao, “A review on bioconversion of lignocellulosic
biomass to H2: Key challenges and new insights,” Bioresource Technology, vol. 215. Elsevier Ltd,
pp. 92–99, Sep. 01, 2016, doi: 10.1016/j.biortech.2016.03.124.
[19] M. L. Chong, V. Sabaratnam, Y. Shirai, and M. A. Hassan, “Biohydrogen production from biomass
and industrial wastes by dark fermentation,” International Journal of Hydrogen Energy, vol. 34, no.
8. Pergamon, pp. 3277–3287, May 01, 2009, doi: 10.1016/j.ijhydene.2009.02.010.
[20] N. Q. Ren, L. Zhao, C. Chen, W. Q. Guo, and G. L. Cao, “A review on bioconversion of lignocellulosic
biomass to H2: Key challenges and new insights,” Bioresource Technology, vol. 215. Elsevier Ltd,
pp. 92–99, Sep. 01, 2016, doi: 10.1016/j.biortech.2016.03.124.
[21] M. A. Salam, K. Ahmed, N. Akter, T. Hossain, and B. Abdullah, “A review of hydrogen production
via biomass gasification and its prospect in Bangladesh,” International Journal of Hydrogen Energy,
vol. 43, no. 32. Elsevier Ltd, pp. 14944–14973, Aug. 09, 2018, doi: 10.1016/j.ijhydene.2018.06.043.
[22] A. Ghimire et al., “A review on dark fermentative biohydrogen production from organic biomass:
Process parameters and use of by-products,” Applied Energy, vol. 144. Elsevier Ltd, pp. 73–95, Apr.
05, 2015, doi: 10.1016/j.apenergy.2015.01.045.
[23] P. C. Hallenbeck and Y. Liu, “Recent advances in hydrogen production by photosynthetic bacteria,”
Int. J. Hydrogen Energy, vol. 41, no. 7, pp. 4446–4454, Feb. 2016, doi:
10.1016/j.ijhydene.2015.11.090.
[24] M. Y. Azwar, M. A. Hussain, and A. K. Abdul-Wahab, “Development of biohydrogen production by
photobiological, fermentation and electrochemical processes: A review,” Renewable and
Sustainable Energy Reviews, vol. 31. Pergamon, pp. 158–173, Mar. 01, 2014, doi:
10.1016/j.rser.2013.11.022.
[25] R. Zagrodnik and M. Laniecki, “The role of pH control on biohydrogen production by single stage
hybrid dark- and photo-fermentation,” Bioresour. Technol., vol. 194, pp. 187–195, Oct. 2015, doi:
10.1016/j.biortech.2015.07.028.
[26] J. Udomsirichakorn and P. A. Salam, “Review of hydrogen-enriched gas production from steam
gasification of biomass: The prospect of CaO-based chemical looping gasification,” Renew.
Sustain. Energy Rev., vol. 30, pp. 565–579, Feb. 2014, doi: 10.1016/J.RSER.2013.10.013.
[27] A. Molino, S. Chianese, and D. Musmarra, “Biomass gasification technology: The state of the art
overview,” J. Energy Chem., vol. 25, no. 1, pp. 10–25, Jan. 2016, doi:
10.1016/j.jechem.2015.11.005.
[28] H. Thunman et al., “Advanced biofuel production via gasification - lessons learned from 200 man-
years of research activity with Chalmers’ research gasifier and the GoBiGas demonstration plant,”
Energy Sci. Eng., vol. 6, no. 1, pp. 6–34, Feb. 2018, doi: 10.1002/ese3.188.
[29] I. Hannula and E. Kurkela, “A semi-empirical model for pressurised air-blown fluidised-bed
gasification of biomass,” Bioresour. Technol., vol. 101, no. 12, pp. 4608–4615, Jun. 2010, doi:
10.1016/j.biortech.2010.01.072.

18
[30] F. Weiland, H. Hedman, M. Marklund, H. Wiinikka, O. Öhrman, and R. Gebart, “Pressurized oxygen
blown entrained-flow gasification of wood powder,” Energy and Fuels, vol. 27, no. 2, pp. 932–941,
Feb. 2013, doi: 10.1021/ef301803s.
[31] N. Nipattummakul, I. I. Ahmed, S. Kerdsuwan, and A. K. Gupta, “Hydrogen and syngas production
from sewage sludge via steam gasification,” Int. J. Hydrogen Energy, vol. 35, no. 21, pp. 11738–
11745, Nov. 2010, doi: 10.1016/j.ijhydene.2010.08.032.
[32] J. M. Ahlström, A. Alamia, A. Larsson, C. Breitholtz, S. Harvey, and H. Thunman, “Bark as feedstock
for dual fluidized bed gasifiers—Operability, efficiency, and economics,” Int. J. Energy Res., vol. 43,
no. 3, pp. 1171–1190, Mar. 2019, doi: 10.1002/er.4349.
[33] L. Barelli, G. Bidini, F. Gallorini, and S. Servili, “Hydrogen production through sorption-enhanced
steam methane reforming and membrane technology: A review,” Energy, vol. 33, no. 4. Elsevier
Ltd, pp. 554–570, Apr. 01, 2008, doi: 10.1016/j.energy.2007.10.018.
[34] D. S. Newsome, “The Water-Gas Shift Reaction,” Catal. Rev., vol. 21, no. 2, pp. 275–318, Jan. 1980,
doi: 10.1080/03602458008067535.
[35] S. Sircar, “Pressure swing adsorption,” Industrial and Engineering Chemistry Research, vol. 41, no. 6.
American Chemical Society, pp. 1389–1392, Mar. 20, 2002, doi: 10.1021/ie0109758.
[36] M. Anwar, S. Lou, L. Chen, H. Li, and Z. Hu, “Recent advancement and strategy on bio-hydrogen
production from photosynthetic microalgae,” Bioresource Technology, vol. 292. Elsevier Ltd, p.
121972, Nov. 01, 2019, doi: 10.1016/j.biortech.2019.121972.
[37] N. Armbrust, G. D. (Varela), H. Dieter, and G. Scheffknecht, “Calcium Looping Cycle for Hydrogen
Production from Biomass Gasification Syngas: Experimental Investigation at a 20 kWth Dual
Fluidized-Bed Facility,” Ind. Eng. Chem. Res., vol. 54, no. 21, pp. 5624–5634, Jun. 2015, doi:
10.1021/ACS.IECR.5B00070.
[38] M. J. Rahimi, B. Ghorbani, M. Amidpour, and M. H. Hamedi, “Configuration Optimization of a Multi-
generation Plant Based on Biomass Gasification,” Energy, p. 120457, Mar. 2021, doi:
10.1016/j.energy.2021.120457.
[39] M. Pavlas, P. Stehlík, J. Oral, J. Klemeš, J. K. Kim, and B. Firth, “Heat integrated heat pumping for
biomass gasification processing,” Appl. Therm. Eng., vol. 30, no. 1, pp. 30–35, Jan. 2010, doi:
10.1016/j.applthermaleng.2009.03.013.
[40] F. Yilmaz, M. Ozturk, and R. Selbas, “Development and techno-economic assessment of a new
biomass-assisted integrated plant for multigeneration,” Energy Convers. Manag., vol. 202, p.
112154, Dec. 2019, doi: 10.1016/j.enconman.2019.112154.
[41] A. Larsson, M. Kuba, T. Berdugo Vilches, M. Seemann, H. Hofbauer, and H. Thunman, “Steam
gasification of biomass – Typical gas quality and operational strategies derived from industrial-
scale plants,” Fuel Process. Technol., vol. 212, p. 106609, Feb. 2021, doi:
10.1016/j.fuproc.2020.106609.
[42] J. F. Brau and M. Morandin, “Biomass-based hydrogen for oil refining: Integration and
performances of two gasification concepts,” Int. J. Hydrogen Energy, vol. 39, no. 6, pp. 2531–2542,
Feb. 2014, doi: 10.1016/j.ijhydene.2013.10.157.
[43] L. Tock and F. Maréchal, “Co-production of hydrogen and electricity from lignocellulosic biomass:
Process design and thermo-economic optimization,” Energy, vol. 45, no. 1, pp. 339–349, Sep. 2012,
doi: 10.1016/j.energy.2012.01.056.
[44] Y. K. Salkuyeh, B. A. Saville, and H. L. MacLean, “Techno-economic analysis and life cycle
assessment of hydrogen production from different biomass gasification processes,” Int. J.

19
 Hydrogen Energy, vol. 43, no. 20, pp. 9514–9528, May 2018, doi: 10.1016/j.ijhydene.2018.04.024.
[45] J. Yao, M. Kraussler, F. Benedikt, and 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., vol. 145, pp. 278–292, 2017, doi:
10.1016/j.enconman.2017.04.084.
[46] M. Kraussler, M. Binder, P. Schindler, and H. Hofbauer, “Hydrogen production within a
polygeneration concept based on dual fluidized bed biomass steam gasification,” Biomass and
Bioenergy, vol. 111, pp. 320–329, Apr. 2018, doi: 10.1016/j.biombioe.2016.12.008.
[47] S. Fail et al., “Wood gas processing to generate pure hydrogen suitable for PEM fuel cells,” ACS
Sustain. Chem. Eng., vol. 2, no. 12, pp. 2690–2698, Dec. 2014, doi: 10.1021/sc500436m.
[48] S. Turn, C. Kinoshita, Z. Zhang, D. Ishimura, and J. Zhou, “An experimental investigation of
hydrogen production from biomass gasification,” Int. J. Hydrogen Energy, vol. 23, no. 8, pp. 641–
648, Aug. 1998, doi: 10.1016/s0360-3199(97)00118-3.
[49] A. Bhattacharya, A. Bhattacharya, and A. Datta, “Modeling of hydrogen production process from
biomass using oxygen blown gasification,” Int. J. Hydrogen Energy, vol. 37, no. 24, pp. 18782–
18790, Dec. 2012, doi: 10.1016/j.ijhydene.2012.09.131.
[50] M. Gassner and F. Maréchal, “Thermo-economic process model for thermochemical production
of Synthetic Natural Gas (SNG) from lignocellulosic biomass,” Biomass and Bioenergy, vol. 33, no.
11, pp. 1587–1604, Nov. 2009, doi: 10.1016/j.biombioe.2009.08.004.
[51] D. Brown, M. Gassner, T. Fuchino, and F. Maréchal, “Thermo-economic analysis for the optimal
conceptual design of biomass gasification energy conversion systems,” Appl. Therm. Eng., vol. 29,
no. 11–12, pp. 2137–2152, Aug. 2009, doi: 10.1016/j.applthermaleng.2007.06.021.
[52] S. Heyne, H. Thunman, and S. Harvey, “Exergy-based comparison of indirect and direct biomass
gasification technologies within the framework of bio-SNG production,” Biomass Convers.
Biorefinery, vol. 3, no. 4, pp. 337–352, Jun. 2013, doi: 10.1007/s13399-013-0079-1.
[53] K. Qin, W. Lin, P. A. Jensen, and A. D. Jensen, “High-temperature entrained flow gasification of
biomass,” Fuel, vol. 93, pp. 589–600, Mar. 2012, doi: 10.1016/j.fuel.2011.10.063.
[54] J. Zetterholm, K. Pettersson, S. Leduc, S. Mesfun, J. Lundgren, and E. Wetterlund, “Resource
efficiency or economy of scale: Biorefinery supply chain configurations for co-gasification of black
liquor and pyrolysis liquids,” Appl. Energy, vol. 230, pp. 912–924, Nov. 2018, doi:
10.1016/j.apenergy.2018.09.018.
[55] M. Naqvi, J. Yan, and E. Dahlquist, “Black liquor gasification integrated in pulp and paper mills: A
critical review,” Bioresource Technology, vol. 101, no. 21. Elsevier, pp. 8001–8015, Nov. 01, 2010,
doi: 10.1016/j.biortech.2010.05.013.
[56] E. Andersson and S. Harvey, “System analysis of hydrogen production from gasified black liquor,”
Energy, vol. 31, no. 15, pp. 3426–3434, Dec. 2006, doi: 10.1016/j.energy.2006.03.015.
[57] Y. Wang, G. Li, Z. Liu, P. Cui, Z. Zhu, and S. Yang, “Techno-economic analysis of biomass-to-
hydrogen process in comparison with coal-to-hydrogen process,” Energy, vol. 185, pp. 1063–1075,
Oct. 2019, doi: 10.1016/j.energy.2019.07.119.
[58] D. Johansson, P. åke Franck, and T. Berntsson, “Hydrogen production from biomass gasification
in the oil refining industry - A system analysis,” Energy, vol. 38, no. 1, pp. 212–227, Feb. 2012, doi:
10.1016/j.energy.2011.12.011.
[59] D. Mohan, C. U. Pittman, and P. H. Steele, “Pyrolysis of wood/biomass for bio-oil: A critical review,”

20
 Energy and Fuels, vol. 20, no. 3. American Chemical Society , pp. 848–889, May 2006, doi:
10.1021/ef0502397.
[60] P. Lan, Q. Xu, M. Zhou, L. Lan, S. Zhang, and Y. Yan, “Catalytic Steam Reforming of Fast Pyrolysis
Bio-Oil in Fixed Bed and Fluidized Bed Reactors,” Chem. Eng. Technol., vol. 33, no. 12, pp. 2021–
2028, Dec. 2010, doi: 10.1002/ceat.201000169.
[61] P. Lan, Q. Xu, M. Zhou, L. Lan, S. Zhang, and Y. Yan, “Catalytic Steam Reforming of Fast Pyrolysis
Bio-Oil in Fixed Bed and Fluidized Bed Reactors,” Chem. Eng. Technol., vol. 33, no. 12, pp. 2021–
2028, Dec. 2010, doi: 10.1002/CEAT.201000169.
[62] George W. Huber, and Sara Iborra, and A. Corma*, “Synthesis of Transportation Fuels from
Biomass:  Chemistry, Catalysts, and Engineering,” Chem. Rev., vol. 106, no. 9, pp. 4044–4098, Sep.
2006, doi: 10.1021/CR068360D.
[63] P. Parthasarathy and K. S. Narayanan, “Hydrogen production from steam gasification of biomass:
Influence of process parameters on hydrogen yield - A review,” Renewable Energy, vol. 66. Elsevier
Ltd, pp. 570–579, Jul. 01, 2014, doi: 10.1016/j.renene.2013.12.025.
[64] S. Czernik, R. Evans, and R. French, “Hydrogen from biomass-production by steam reforming of
biomass pyrolysis oil,” Catal. Today, vol. 129, no. 3–4, pp. 265–268, Dec. 2007, doi:
10.1016/j.cattod.2006.08.071.
[65] B. Zhao, X. Zhang, L. Sun, G. Meng, L. Chen, and Y. Xiaolu, “Hydrogen production from biomass
combining pyrolysis and the secondary decomposition,” Int. J. Hydrogen Energy, vol. 35, no. 7, pp.
2606–2611, Apr. 2010, doi: 10.1016/j.ijhydene.2009.04.011.
[66] A. Arregi et al., “Hydrogen-rich gas production by continuous pyrolysis and in-line catalytic
reforming of pine wood waste and HDPE mixtures,” Energy Convers. Manag., vol. 136, pp. 192–201,
Mar. 2017, doi: 10.1016/j.enconman.2017.01.008.
[67] S. Czernik and R. French, “Distributed production of hydrogen by auto-thermal reforming of fast
pyrolysis bio-oil,” Int. J. Hydrogen Energy, vol. 39, no. 2, pp. 744–750, Jan. 2014, doi:
10.1016/j.ijhydene.2013.10.134.
[68] M. Balat, “Hydrogen-rich gas production from biomass via pyrolysis and gasification processes
and effects of catalyst on hydrogen yield,” Energy Sources, Part A Recover. Util. Environ. Eff., vol. 30,
no. 6, pp. 552–564, Jan. 2008, doi: 10.1080/15567030600817191.
[69] C. Rodriguez Correa and A. Kruse, “Supercritical water gasification of biomass for hydrogen
production – Review,” Journal of Supercritical Fluids, vol. 133. Elsevier B.V., pp. 573–590, Mar. 01,
2018, doi: 10.1016/j.supflu.2017.09.019.
[70] P. F. dos Santos and C. G. Pereira, “Study of the gasification process of liquid biomasses in
supercritical water using a thermodynamic mathematical model,” J. Supercrit. Fluids, vol. 168, Feb.
2021, doi: 10.1016/j.supflu.2020.105049.
[71] O. Yakaboylu, J. Harinck, K. Smit, and W. de Jong, “Supercritical Water Gasification of Biomass: A
Literature and Technology Overview,” Energies, vol. 8, no. 2, pp. 859–894, Jan. 2015, doi:
10.3390/en8020859.
[72] L. Fiori, M. Valbusa, and D. Castello, “Supercritical water gasification of biomass for H2 production:
Process design,” Bioresour. Technol., vol. 121, pp. 139–147, Oct. 2012, doi:
10.1016/j.biortech.2012.06.116.
[73] F. J. Gutiérrez Ortiz, P. Ollero, A. Serrera, and A. Sanz, “Thermodynamic study of the supercritical
water reforming of glycerol,” Int. J. Hydrogen Energy, vol. 36, no. 15, pp. 8994–9013, Jul. 2011, doi:
10.1016/j.ijhydene.2011.04.095.

21
[74] K. Özdenkçi, C. De Blasio, G. Sarwar, K. Melin, J. Koskinen, and V. Alopaeus, “Techno-economic
feasibility of supercritical water gasification of black liquor,” Energy, vol. 189, p. 116284, Dec. 2019,
doi: 10.1016/j.energy.2019.116284.
[75] M. Fridahl and M. Lehtveer, “Bioenergy with carbon capture and storage (BECCS): Global potential,
investment preferences, and deployment barriers,” Energy Res. Soc. Sci., vol. 42, pp. 155–165, Aug.
2018, doi: 10.1016/j.erss.2018.03.019.
[76] C. Azar, D. J. A. Johansson, and N. Mattsson, “Meeting global temperature targets - The role of
bioenergy with carbon capture and storage,” Environ. Res. Lett., vol. 8, no. 3, p. 34004, Jul. 2013,
doi: 10.1088/1748-9326/8/3/034004.
[77] T. Detchusananard, S. Sharma, F. Maréchal, and A. Arpornwichanop, “Generation and selection of
Pareto-optimal solution for the sorption enhanced steam biomass gasification system with solid
oxide fuel cell,” Energy Convers. Manag., vol. 196, pp. 1420–1432, Sep. 2019, doi:
10.1016/j.enconman.2019.06.033.
[78] B. Erlach, B. Harder, and G. Tsatsaronis, “Combined hydrothermal carbonization and gasification
of biomass with carbon capture,” Energy, vol. 45, no. 1, pp. 329–338, Sep. 2012, doi:
10.1016/j.energy.2012.01.057.
[79] G. D. Oreggioni, S. Brandani, M. Luberti, Y. Baykan, D. Friedrich, and H. Ahn, “CO2 capture from
syngas by an adsorption process at a biomass gasification CHP plant: Its comparison with amine-
based CO2 capture,” Int. J. Greenh. Gas Control, vol. 35, pp. 71–81, Apr. 2015, doi:
10.1016/j.ijggc.2015.01.008.
[80] A. Alamia, A. Larsson, C. Breitholtz, and H. Thunman, “Performance of large-scale biomass
gasifiers in a biorefinery, a state-of-the-art reference,” Int. J. Energy Res., vol. 41, no. 14, pp. 2001–
2019, Nov. 2017, doi: 10.1002/er.3758.
[81] S. T. Wismann et al., “Electrified methane reforming: A compact approach to greener industrial
hydrogen production,” Science, vol. 364, no. 6442, pp. 756–759, May 2019, doi:
10.1126/science.aaw8775.
[82] J. M. Ahlström, K. Pettersson, E. Wetterlund, and S. Harvey, “Value chains for integrated
production of liquefied bio-SNG at sawmill sites – Techno-economic and carbon footprint
evaluation,” Appl. Energy, vol. 206, pp. 1590–1608, Nov. 2017, doi:
10.1016/j.apenergy.2017.09.104.
[83] W. Liu, Y. Cui, X. Du, Z. Zhang, Z. Chao, and Y. Deng, “High efficiency hydrogen evolution from
native biomass electrolysis,” Energy Environ. Sci., vol. 9, no. 2, pp. 467–472, Feb. 2016, doi:
10.1039/c5ee03019f.
[84] Y. X. Chen et al., “Nanotechnology makes biomass electrolysis more energy efficient than water
electrolysis,” Nat. Commun., vol. 5, no. 1, pp. 1–6, Jun. 2014, doi: 10.1038/ncomms5036.
[85] A. Kadier et al., “Microbial Electrolysis Cells (MECs) as Innovative Technology for Sustainable
Hydrogen Production: Fundamentals and Perspective Applications,” in Hydrogen Production
Technologies, Hoboken, NJ, USA: John Wiley & Sons, Inc., 2017, pp. 407–457.

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Appendix

Table 1. Conceptual and techno-economic studies on biomass gasification-based hydrogen production.

Biomass-to-
H2 Yield [kg
Efficiency H2/kg of dry Cost
Reference Technology Feedstock [LHV] biomass] [EUR/kWh]
DFB+WGS+
PSA (tar
[45] removed) WC 40 0.058 0.148
Anaerobic
digestion +
Steam maize
[45] reforming sillage 47 0 0.152
[45] Electrolysis water 66.4 0 0.191
[44] DFB pine wood 0.38 0.061 0.078
[44] EF+WGS pine wood 0.50 0.078 0.086
pine
[42] DFB +SMR (nordic) 67% HHV 0.1 N.a.
O2
gasification
with WGS pine
[42] and PSA (nordic) 59% HHV 0.087 N.a.
Torrefaction
+DFB+SMR+
WGS (2-
[43] step) pine 69.6 0.107 0.05-0.176
DFB+WGS
(3-
step)+PSA
(tar
[46] removed) pine 0.19 0.03 0.21
O2+SMR+W
[48] GS wood fuel 0.82 0.126 N.a.
O2+WGS+P
[49] SA wood 0.65 0.102 N.a.
[56] EF +WGS wood fuel 0.54 0.055 N.a.
[58] EF +WGS wood fuel 0.53 0.081 N.a.
[58] O2 +WGS wood fuel 0.6 0.085 N.a.

23
Table 2. Conceptual and techno-economic studies on pyrolysis-based hydrogen production.

Efficiency Yield [kgH2/kg Cost

Reference Technology Feedstock [LHV] of dry biomas] [EUR/kWh]
Fast
Pyrolysis +
steam
[64] reforming hard wood n.a 0.12 n.a
Fast
pyrolysis +
unknown
high
temperature
[65] upgrading rice husk n.a 0.065 n.a
Continious
pyrolysis biomass
[66] +reforming (pine) 0.65 0.10 n.a
Pyrolysis oil
and auto
thermal pyrolysis
[67] reforming oil n.a 0.11 0.11
Pyrolysis oil
and auto
thermal
[14] reforming wood n.a 0.03 n.a
Pyrolysis oil
and auto
thermal
[14] reforming wood n.a 0.065 n.a

24
Table 3. Indicative biomass to hydrogen efficiency and yield for all considered processes.

Technology
Yield [kgH2/kg Readiness
Fossil Reference Efficiency [LHV] feedstock] Level (TRL)
SMR (NG) [14] N.a 0.019 9
Coal gasification [14] N.a 0.023 9
Biological pathways
Dark fermentation [63] 0.044 0.066 5
Photo fermentation [63] 0.049 0.071 4
Electrochemical pathways
Bio electrolysis [85] 0.015-0.1 0.059 3
Water Electrolysis 9
(nuclear) [14] N.a 0.059
Thermochemical pathways
DFB gasification [44] 0,061 0.078 7
O2 gasification [49] 0.065 0.1 7
Entrained flow 7
gasification [44] 0.078 0.086
Pyrolysis [67] n.a 0,12 7
SCWG [74] 0.02 0.043 4

25