Journal of Cleaner Production 18 (2010) S51eS62

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Journal of Cleaner Production

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

Renewable hydrogen production: a technical evaluation based on

process simulation
Angela Miltner*, Walter Wukovits, Tobias Prll, Anton Friedl
Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9/166-2, 1060 Vienna, Austria

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 4 December 2009
Received in revised form
27 May 2010
Accepted 28 May 2010
Available online 10 June 2010

An evaluation of different hydrogen production technologies based on renewable raw materials and/or
renewable energy is presented. The evaluation comprises alkaline electrolysis, steam reforming of both
biogas and gasication gas, the coupled dark and photo fermentation as well as the coupled dark and
biogas fermentation. Each technology is investigated with different plant layouts and/or different raw
materials. All examined technologies are designed to produce hydrogen in a quality suitable for the use in
mobile fuel cells. The presented evaluation is based on the hydrogen production efciency and the
energy efciency of the processes.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Hydrogen
Biomass
Renewable energy
Process simulation

1. Introduction
The debate on global warming and the foreseeable depletion of
fossil reserves have led to worldwide initiatives for the development of renewable energy carriers. One possible future energy
carrier is hydrogen, which could be used to supply households and
industries to produce heat and electricity. But it could also be used
as the future alternative fuel for automobiles. Such a switch from
fossil energy carriers to a hydrogen based energy system will cause
changes in the energy infrastructure as well as in the technologies
used for the energy production and utilization (Knnl et al.,
2007). But the efforts of changing to a hydrogen society will be
worthwhile only if the hydrogen is produced in a sustainable way.
This means that the production has to be based on renewable raw
materials and/or renewable energies as well as on efcient
conversion technologies in the proper scale.
At present hydrogen production is mainly based on reforming of
fossil fuels (Corbo and Migliardini, 2007, 2009; Dalle Nogare et al.,
2007; de Jong et al., 2009; Kaila and Krause, 2006; Rabe et al.,
2007). The steam reforming of natural gas is the most common
state of the art technology for hydrogen production (Corbo and
Migliardini, 2009; de Jong et al., 2009). But technologies like
partial oxidation (Corbo and Migliardini, 2007; Chen et al., 2007) or
autothermal reforming (Kaila and Krause, 2006; Rabe et al., 2007;

* Corresponding author. Tel.: 43 1 58801 15923; fax: 43 1 58801 15999.

E-mail address: angela.miltner@tuwien.ac.at (A. Miltner).
0959-6526/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jclepro.2010.05.024

Hoang et al., 2006; Murata et al., 2007) of fossil fuels are also
well established technologies. Besides the reforming of fossil fuels,
there is also electrolysis of water as state of the art technology for
the production of hydrogen (Zeng and Zhang, 2010; Badwal et al.,
2006; Chafn et al., 2006; Grigoriev et al., 2006; Kreuter and
Hofmann, 1998; Marshall et al., 2007; Roy et al., 2006; de Souza
et al., 2007; Stojic et al., 2003), with alkaline electrolysis as its
most common type. Hydrogen production by electrolysis can, in
contrast to the reforming of fossil fuels, be considered as renewable
technology, if electricity from renewable resources is used for the
operation of the electrolyzer.
Biomass based hydrogen production technologies are still under
development, hence only few plant and operation data are available up to now. It is, therefore, difcult for policy makers to identify
promising technologies as well as the advantages and disadvantages of each technology. One instrument to overcome this
dilemma is the use of process simulation. This tool offers the
possibility to build up theoretical plant layouts based on real
process data that could, for instance, be taken from lab scale
experiments. The process simulation results offer the possibility to
rate different technologies and to identify hurdles and potentials.
In the present work process simulation is used to evaluate
different hydrogen production technologies. These technologies
cover the state of the art technologies steam reforming of natural gas
and alkaline water electrolysis as well as biomass based technologies. The latter comprise the reforming of biogas as well as the
reforming of biomass gasication gas, the direct production of
hydrogen from biomass by coupled dark and photo fermentation

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A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

and the coupled dark and biogas fermentation. All biomass based
technologies have been investigated with different kinds of raw
materials and/or different plant layouts. Each of the processes meets
the strict regulations for hydrogen used in mobile fuel cells,
requiring a minimum of 99.97 vol% of hydrogen (California
Department of Food and Agriculture, 2008). It is assumed that
hydrogen will only be sold in this quality at fuel stations, even if
internal hydrogen combustion engines would be able to run on
lower quality hydrogen. The size range of the biomass conversion
plants is chosen in a decentralized scale in order to offer the possibility of a sustainable hydrogen production. The steam reforming of
the produced biogas and gasication gas on the other hand is
analyzed both in a decentralized and a centralized plant size. The
process simulation results are used to evaluate all technologies
according to their hydrogen production and energy efciency.
As stated above, the present paper focuses on decentralized
hydrogen production and the application of the produced hydrogen
as mobile fuel. It is, therefore, necessary to build up overall supply
chains including the hydrogen production, the storage and transportation of the hydrogen, the fuelling stations and nally the
utilization in the hydrogen vehicles. Each of the steps within this
chain, and in particular the hydrogen storage technologies, would
be worth a detailed discussion and analysis. But this would be
beyond the scope of the present paper, hence these steps and
technologies are deliberately not considered.
2. Investigated processes and process simulation
The aim of this paper is to evaluate different processes for the
production of renewable hydrogen. However, hydrogen is not
produced in a renewable way at present but mainly by reforming of
natural gas. Hence, the steam reforming of natural gas is included in
this study as a state of the art reference technology.
Alkaline water electrolysis is another proven technology for
hydrogen production which is used in a much smaller scale
compared to natural gas steam reforming. At present electrolyzers
are typically operated with the common electricity mix that
consists mainly of non renewable electricity. However, hydrogen
can be produced in a sustainable way via electrolysis if electricity
from renewable sources is used for its operation. Within the presented analysis it is assumed that the alkaline electrolysis is operated with electricity from renewable sources. It is, therefore,
treated as a renewable hydrogen production technology.
Hydrogen can also be produced in a renewable way if biomass is
used as raw material. However, biomass based technologies are still
under development and none of the proposed technologies has been
tested in large scale yet. Among the various developed biomass
based technologies four promising technologies have been chosen
for the present analysis. These are the steam reforming of gas

produced by biogas fermentation, the steam reforming of gas

produced by biomass gasication, the direct biological production of
hydrogen via the coupled dark and photo fermentation as well as the
production of hydrogen by dark fermentation coupled with biogas
fermentation. The analysis of the biomass based technologies is
carried out for several plant layouts as shown in Fig. 1. The steam
reforming of biogas and gas from biomass gasication is either
carried out on-site, with or without prior CO2 separation, or in
a central steam reforming plant that is connected to several
decentralized gas production plants via the natural gas grid. The
technology of coupled dark and biogas fermentation is also included
with three different congurations. The biogas that is produced from
the residue of the dark fermenter is either used in a gas boiler to
produce process heat only or in a gas engine to produce both process
heat and electricity. Furthermore, the biogas can be converted to
hydrogen by on-site steam reforming of the biogas.
The evaluation of the investigated hydrogen production technologies is based on process simulation. The application of process
simulation offers the possibility to easily analyze different plant
layouts and plant sizes with various raw materials. Moreover, it can
be used to gain results for technologies that are not fully developed
yet. Within this work the process simulation is carried out with the
commercial simulation program IPSEpro. It is an equation oriented
owsheet simulation package which was originally designed to
carry out thermal power cycle calculations (Perz, 1991). The software package consists of several modules like a Model Development Kit or a Process Simulation Environment (Perz and Bergmann,
2007). The Model Development Kit (MDK) offers the possibility to
develop and implement new unit models for processes that are not
included in the standard simulation libraries. These user built unit
models contain the equations describing the behavior of the units
(e.g. mass balances of the components or energy balances) as well
as the graphical symbols of the units. The Process Simulation
Environment (PSE) on the other hand is used to build up the
owsheets of the processes graphically and to solve the process
models based on the unit model equations.
In the course of the presented work new user models have been
developed for most of the units necessary to build up the investigated hydrogen production plants. Only few of the used models
were available within the standard power plant library of the
program (Perz and Bergmann, 2003) or were taken from preceding
works (Prll et al., 2005a, 2007).
A description of all investigated hydrogen production technologies is given in the following sections.
2.1. Steam reforming of natural gas
The plant for natural gas steam reforming (see Fig. 2) contains
an adsorber (1) for the removal of hydrogen sulde and hydrogen

Fig. 1. Overview of all evaluated process chains.

A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

S53

6
2
fuel
stack
1
hydrogen
process
water
5

3
4
natural
gas
air

Fig. 2. Flowsheet of the natural gas steam reforming plant; 1: adsorber for HCl and sulfur compounds, 2: steam reformer, 3: CO shift reactor, 4: condenser, 5: PSA, 6: steam turbine.

chloride from the natural gas. This unit also includes a preceding
hydration step that converts organic sulfur compounds to hydrogen
sulde by using a small amount of the produced hydrogen for the
conversion. The cleaned natural gas enters an externally heated
catalytic steam reformer (2) that converts CH4 and steam to
hydrogen and CO at a temperature of 880  C and a pressure of
30 bar. At the same time some of the CO reacts with steam to
hydrogen and CO2 via the CO shift reaction. After a cooling step the
gas is fed into a CO shift reactor (3) where the main part of the CO is
converted to hydrogen via the CO shift reaction at 330  C to further
increase the hydrogen yield of the plant. Subsequently the gas
stream is cooled down and dried (4) and enters a pressure swing
adsorption (PSA) (5) at 40  C to purify the hydrogen to the desired
quality. The off-gas of the PSA is recycled to the steam reformer (2)
where it is mixed with additional natural gas and used as burning
fuel to supply the heat for the reforming reaction.
The steam reforming plant is equipped with a multitude of
heat exchangers for heat recovery and a steam cycle for process
steam generation. The excess process steam is used to generate
electricity in a steam turbine. The plant size is designed to produce
289 Mio. m3STP (m3 at standard temperature and pressure) of
hydrogen per year, which has been chosen according to the steam
reforming plant at the oil renery of the company OMV in
Schwechat, Austria (Pulletz and Bhme, 2003). The applied
composition of the natural gas is given in Table 1.
2.2. Alkaline water electrolysis
A typical alkaline electrolysis plant consists of several units like
water preparation, alkaline cycle and electrolyzer stack. All these
parts have been included within one unit operation model (see
Fig. 3). This model contains a detailed modeling of the alkaline

water electrolyzer itself. All other parts of the electrolysis plant are
only considered with their energy demand.
Two size ranges are analyzed for the alkaline electrolysis:
a decentralized plant with a hydrogen production capacity of
485 m3STP/h and a small plant producing only 60 m3STP/h. The latter is
supposed to be located directly at the hydrogen fuelling station
where it covers the total demand of the station. The data for the
alkaline water electrolysis plants are taken from Ivy (2004). The
decentralized plant is based on the data for the Norsk Hydro 5040
plant which is operated at 33 bar and 80  C. The small plant is based
on the Stuart IMET 1000 plant which is operated at 25 bar and
80  C. Both plants require 4.8 kWh of electricity per m3STP of
produced hydrogen.
Within the present work it is assumed that the alkaline electrolysis is operated with green electricity in order to be able to treat
this technology as renewable hydrogen production technology.
2.3. Reforming of biogas
The biogas fermentation plant is operated in continuous mode
and comprises a mashing tank (1), an anaerobic fermenter (2),
a post digestion tank (3) and a biological desulphurization reactor
(4) as shown in Fig. 4.
The mashing tank is used to mix the raw material with water in
order to get a pumpable substrate. The anaerobic fermenter is
operated at 35  C and produces roughly 80% of the total biogas. The
post digestion tank serves as storage tank for the biogas and the
fermentation residue. Moreover, up to 20% of the total produced
biogas can originate from the post digestion tank. In a typical biogas
fermentation plant, the biological desulfurization reactor is operated with air. As the nitrogen content of the air would cause severe
problems during the purication of the subsequently produced
hydrogen, it is decided to run the reactor with oxygen instead of air.

Table 1
Applied composition of natural gas.

oxygen rich gas

Volume fraction of component, %

Natural gas

CH4
C2H6
C3H8
N2
CO2
H2S

96.210
1.110
0.551
1.131
0.998
3.258  107

hydrogen rich gas

water

unused water
Fig. 3. Flowsheet of the alkaline water electrolysis.

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A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

Fig. 4. Flowsheet of the biogas fermentation plant; 1: mashing tank, 2: biogas fermenter, 3: post digestion tank, 4: biological desulfurization.

The layout and size of the plant are based on the plant in Bruck an
der Leitha, Austria. It is in a size range of about 30,000 tons of raw
material per year which corresponds to 800e900 m3STP/h of biogas,
depending on the chosen raw material. The biogas yields of the
different raw materials as well as the composition of the produced
biogas are based on experimental data (Institut fr Energetik und
Umwelt, 2006). The data used for the raw materials investigated
in the present study are given in Table 2. The bio waste represents
the separately collected biogenic residue from households in
Austria, containing mainly kitchen slops and small fractions of yard
waste.
The produced biogas is used as input in a steam reforming plant.
The connection between the biogas plant and the steam reforming
plant is examined with three different layouts. The simplest layout
utilizes the produced biogas directly in an on-site steam reforming
plant. This decentralized steam reforming plant has the same
layout as the natural gas steam reforming plant described above,
only showing a smaller size range. Beside the plant size also the
plant efciency is lower for the decentralized reforming plant
(0.723 kW H2/kW CH4 compared to 0.838 kW H2/kW CH4 for the
plant in the centralized size range, based on lower heating values).
The produced biogas is both used as a feed that is converted to
hydrogen in the reforming plant and as a combustion fuel, to
provide the necessary heat for the steam reforming reactor.
The biogas contains a huge amount of CO2 that is only dead
freight and requires additional amounts of biogas for its heating in
the steam reformer. The hydrogen yield of the combined plant can,
therefore, be increased by CO2 separation prior to the steam
reforming plant. This conguration is considered in the second
plant layout, in which the CO2 separation is realized with
membrane modules. The layout of the separation step is shown in
Fig. 5. It comprises a gas compressor (1) to provide the required

pressure difference across the membrane, a condenser (2) and the

membrane modules (3) that separate mainly CO2 from CH4 by gas
permeation. This layout is a simplied version of the process presented by Harasek et al. (2007) and Miltner et al. (2008a).
It is assumed that 4.5% of the entering CH4 are lost due to
permeation through the membrane and that 2% of the entering CO2
are not separated from the CH4 stream. Hence, the CO2-rich
permeate stream of the gas permeation plant still contains small
amounts of CH4. Due to the high global warming potential of CH4, it
is advisable to reuse this off-gas stream. In the presented layout this
stream is added to the fuel stream of the on-site steam reformer
that is already a mixture of biogas and off-gas of the pressure swing
adsorption of the steam reforming plant.
In the third plant layout the produced biogas is upgraded to
natural gas quality and supplied to the natural gas grid. The
upgraded biogas from several biogas plants is transported to
a centralized steam reforming plant via the natural gas grid. The
upgrading to natural gas quality is again done by gas permeation
similar to the process shown in Fig. 5. The plant is only extended
with a sulfur adsorption prior to the membrane modules, in order
to meet the specications of the natural gas grid. Furthermore,
a compressor is needed that feeds the gas into the gas grid at
a pressure of about 30 bar. The central steam reforming plant is
equivalent to the plant described in chapter 2.1. The advantage of
this pathway is the increased efciency of the centralized reforming plant compared to the decentralized one. One disadvantage of
the presented conguration is the fact, that the CO2-rich off-gas of
the gas permeation plant cannot be used internally. This drawback
could e.g. be eliminated, if a part of the produced biogas would be
used on-site in a gas boiler or gas engine to produce the required
process heat and electricity. In this case the off-gas could be mixed
with the biogas assuring that no CH4 would be released to the
atmosphere.

Table 2
Biogas yields and biogas composition of the investigated raw materials.

2.4. Reforming of gasication gas

Volume fraction of component, %

CH4
CO2
H2O
H2S
Biogas yield, m3STP/t raw material

Raw material
Maize silage

Potato peels

Bio waste

53.0
40.5
5.6
0.9
190.0

51.4
42.9
5.6
0.1
67.7

61.5
32.8
5.6
0.1
100.0

Among the multitude of developed biomass gasication technologies, the authors have opted for the Fast Internally Circulating
Fluidized Bed (FICFB) gasication technology. The plant layout and
size were chosen according to the plant in Gssing, Austria, which
is designed with a supplied fuel power of 8 MWth (based on lower
heating value of the fuel), as described by Prll et al. (2007). The
main parts of the gasication plant (see Fig. 6) are the FICFB gasier,

A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

S55

CO2 rich off-gas

biogas from
fermentation plant

3
CH4 rich gas to
steam reforming plant
condensate

Fig. 5. Flowsheet of the gas permeation plant for CO2 separation; 1: two stage compressor with intercooling, 2: condenser, 3: membrane modules.

which comprises a gasication chamber (1) and a combustion

chamber (2), a dust lter (3) and a tar scrubber (4).
Similar to the biogas based plants, the produced gasication gas
is converted to hydrogen in a steam reforming plant. In order to
prevent coking within the steam reformer, a second tar scrubber is
implemented additionally to the plant in Gssing, as shown in
Fig. 6. Moreover, the second tar scrubber further reduces the NH3
and H2S content of the gas, as presented by Prll et al., (2005b).
Within the present study the plant is designed to be operated with
wood chips at a fuel power of 7.8 MWth (based on lower heating
value of the fuel). The applied composition of the produced gasication gas is given in Table 3 and is based on the values given by
Prll et al. (2005b) and Rauch (2005). The net power of the
produced gasication gas is calculated with 5.6 MW (based on
lower heating value).
Similar to the biogas based technology presented in the
previous chapter, the produced gasication gas is also used as input
in a steam reforming plant. The combination of the gasication
plant and the steam reforming plant is again considered with three
different layouts. The rst layout uses the tar free gas directly as
feed and burning fuel in an on-site steam reforming plant equivalent to the one described in chapter 2.3 concerning the reforming of
biogas.

The second plant layout includes again a CO2-separation step

prior to the steam reforming plant. The gasication gas, in contrast
to biogas, has a high content of hydrogen (approx. 40 vol%, dry
base). Hence, it is not possible to use a gas permeation plant for the
separation of CO2 because this technology would also separate the
hydrogen from the methane rich stream, which would reduce the
overall hydrogen yield of the plant. Therefore, a monoethanolamine
(MEA) scrubber is used to only remove the CO2 from the gasication gas. The scrubber is operated with a MEA-water-solution with
30 mass% of MEA. It is assumed that the scrubber has a CO2removal efciency of 90% and that 3.7 MJ of steam are needed to
desorb 1 kg of CO2 in an associated desorption column. The puried
hydrogen and methane rich gas is then used as feed and burning
fuel for an on-site steam reforming plant.
In the third plant layout the gasication gas is upgraded to
natural gas quality by methanation. The upgraded gas from several
gasication plants is transported to a centralized steam reforming
plant via the natural gas grid, where it is converted to hydrogen.
The layout of the upgrading plant is shown in Fig. 7. The gasication
gas passes through an adsorber (1) to remove sulfur compounds
and HCl before it enters a methanation reactor (2) where hydrogen,
CO and CO2 are converted to methane. A subsequent membrane
separation step is used to separate the unconverted CO2 and

gasification
gas
cooling

cooling
lime
3
4

RME

olivine

raw
material

air

stack gas
ash
cooling or district heating

Fig. 6. Flowsheet of the biomass gasication plant; 1: gasication chamber, 2: combustion chamber, 3: dust lter, 4: tar scrubber.

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A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

Table 3
Composition of the main components of the raw gasication gas.
Volume fraction of dry component, %

Gasication gas

CH4
C2H4
C3H8
CO
CO2
H2
N2
H2O
NH3 (clean gas after rst tar scrubber)
H2S (clean gas after rst tar scrubber)

10.5
2
0.6
25
20.8
39.1
1.6
35.1
0.04
0.002

hydrogen content from the obtained methane rich gas, in order to

meet the gas specications of the natural gas grid. The gas
permeation plant for the CO2 separation is considered equivalent to
the one used for the CO2 removal from biogas with subsequent onsite reforming (see chapter 2.3).
The simulation of the methanation reactor was based on the
publications of Seemann et al. (2005) and Hofbauer et al. (2006).
Within the present work the efciencies of the methanation reactor
are set to 98.6% for the CO conversion and to 82.1% for the chemical
efciency (energy content of produced CH4 related to energy
content of the input stream to the methanation reactor, both based
on lower heating values). The exiting methane rich gas is assumed
to have a methane concentration of 41 vol%, a CO2 concentration of
48 vol% and a CO concentration of 0.49 vol% (all compositions on
dry basis).
2.5. Coupled dark and photo fermentation
Both dark and photo fermentation are technologies that
produce a hydrogen rich gas by biological conversion of sugars and
organic acids, respectively. The combination of both processes is
very benecial as organic acids are produced as a side product
during the dark (thermophilic) fermentation step. These acids can
be utilized as feed for the photo fermentation step whereby the
whole plant efciency is increased. Both technologies as well as
their combination are still in the laboratory phase. Hence, the plant
layout for the combined process as well as the plant size are based
on a theoretical work presented by Markowski et al. (2008).
However the layout has been adapted and simplied in some
respects as shown in Fig. 8. Experimental results for the verication
of the simulation models are taken from publications by Claassen
et al. (2000) and Claassen et al. (2005).

The rst step within the coupled dark and photo fermentation
plant is a hydrolysis step (1) that is needed to convert components
like starch into fermentable sugars. This process comprises several
steps like liquefaction and saccharication. The hydrolysis process
has been modeled simplied by considering only the overall
conversion from the raw material to the hydrolysate and the overall
energy demand, not considering in detail the individual sub-steps.
In the next step unfermentable solids are separated from the
substrate (2). The substrate is then mixed with water in order to
obtain a sugar concentration that is nontoxic for the microorganisms used in the dark fermenter. After a preheating step the
substrate is fed into the dark fermenter (3). In the dark fermenter
sugar and water are converted to gaseous H2 and CO2 as well as
liquid organic acids. 15% of the inuent sugars are utilized by the
microorganisms for their growth. The fermenter is operated at
70  C and a vacuum of 50 kPa. The vacuum is needed to evaporate
a part of the water content of the substrate in order to reduce the
partial pressure of hydrogen in the fermenter. This reduction of the
partial pressure is required since high hydrogen concentrations
cause an inhibition of the growth of the microorganisms and thus
a decrease in their hydrogen productivity (Willquist et al., 2009).
The main part of the evaporated water is condensed in a subsequent condenser (5) and fed back into the dark fermenter. After
a cooling step the liquid efuent of the dark fermenter is fed into
the photo fermenter (4) that operates at 35  C and 1 bar under
exposure to light. In the photo fermenter the organic acids, which
have been produced in the dark fermenter, and water are converted
to gaseous H2 and CO2. The gas streams from both dark and photo
fermenter are mixed and puried in a vacuum swing adsorption
(VSA) plant (6).
Within this paper the calculations for the coupled dark and
photo fermentation are carried out with either 100% conversion of
the inuent sugar within the dark fermenter (implying that no
sugar is utilized by the microorganisms for their growth) and 100%
conversion of the inuent acids within the photo fermenter or with
80% conversion in each of the fermenters. The former calculation
leads to the theoretical maximum hydrogen amount for a given
raw material, whereas the latter calculation represents a realistic
reachable production scenario. It is assumed that the liquid product
of the dark fermenter is acetic acid only. Furthermore, the
hydrogen recovery of the VSA plant has been varied between 80%
and 95% as this part of the plant shows some optimization potential. Moreover, there is a possibility to replace the VSA by
a membrane contactor with very low hydrogen loss (Modigell et al.,
2008). The composition of the utilized raw materials is given in
Table 4.

Fig. 7. Flowsheet of the methanation plant; 1: adsorber for HCl and sulfur compounds, 2: methanation reactor, 3: two stage compressor with intercooling, 4: condenser, 5:
membrane modules, 6: compressor for grid pressure level.

A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

S57

Fig. 8. Flowsheet of the coupled dark and photo fermentation plant; 1: hydrolysis, 2: solids separation, 3: dark fermenter, 4: photo fermenter, 5: condenser, 6: VSA.

2.6. Coupled dark and biogas fermentation

The utilization of the organic acid rich residue from the dark
fermenter within a photo fermenter is not the only option. It can
also be utilized in a biogas fermenter to produce a methane rich
biogas. The produced biogas can then be used in different ways,
whereof three variants are investigated within the present work.
The rst plant layout utilizes the biogas in a gas engine (7) to
produce electricity and heat that is used to heat up the substrate of
the dark fermenter (3) and the fermenter itself (see Fig. 9). The
hydrogen rich gas from the dark fermenter is puried in a vacuum
swing adsorption (VSA) plant (6) and the VSA off-gas is mixed with
the biogas from the biogas fermenter (4) and fed into the gas engine
to use the energy content of the lost hydrogen.
The biogas can also be used in a gas boiler to produce process
heat only (see Fig. 10). The process heat is again used to heat the
substrate of the dark fermenter (3) and the fermenter itself. As
before, the off-gas of the VSA (6) for the hydrogen purication is
mixed with the biogas from the biogas fermenter (4) and used as
a feed for the gas boiler (7).
The third investigated option is to separate the CO2 from the
produced biogas and to convert the obtained gas to hydrogen in an
on-site steam reforming plant. In this case a biological desulfurization reactor is needed prior to the CO2 separation to reduce the
H2S content of the biogas. The CO2 removal is implemented by a gas
permeation plant. The puried biogas is subsequently utilized as
feed and burning fuel for an on-site steam reforming plant. Both the
gas permeation and the reforming plant are implemented equivalent to the ones described in chapter 2.3. The CO2-rich permeate of
the gas permeation plant is mixed with the fuel for the steam
reformer to prevent CH4 loss to the atmosphere.
The dark fermentation step was modeled equivalent to the dark
fermenter presented in the previous chapter. The built up model for

Table 4
Composition of the utilized raw materials for the coupled dark and photo fermentation and the coupled dark and biogas fermentation.
Mass fraction of component, %

C
H
O
N
S
Water
Ash and insolubles
Starch and glucose, dry ash free component, %

Raw material
Maize corn

Potato peels

23.801
3.995
31.705
0
0
15.0
25.50
100

4.851
0.627
4.169
0.308
0.033
89.0
1.023
51.9

the biogas fermenter operated with the organic acid rich efuent of
the dark fermenter was veried with data taken from literature
(Chu et al., 2008; Kyazze et al., 2007; Zhu et al., 2008).
Due to the early stage of development of the coupled dark and
biogas fermentation it was decided, similar to the coupled dark and
photo fermentation, to base the performance calculations on
a range of conversion factors rather than on single data taken from
literature. Hence, the calculations have been carried out with 80%
conversion of the inuent sugar in the dark fermenter and 70%
conversion of the inuent acids and sugar in the biogas fermenter
as well as with 100% conversion in both fermenters (again implying
that no sugar is utilized for the growth of the microorganisms
within the dark fermenter). The lower boundaries seem to be
realistic conversion ratios and the upper limits of 100% conversion
represent the theoretical maximum. The lower conversion limit for
the dark fermenter also corresponds to the value chosen for the
coupled dark and photo fermentation. Similar to the simulation of
the dark and photo fermentation it was assumed that only acetic
acid is produced in the dark fermenter. Moreover, the hydrogen
recovery of the VSA for the purication of the hydrogen rich gas
from the dark fermenter has been varied between 80% and 95% due
to the same reasons as for the coupled dark and photo fermentation. The calculations for the coupled dark and biogas fermentation
have been carried out only with potato peels as raw material. The
investigated composition of the potato peels is equivalent to the
one used for the coupled dark and photo fermentation (see Table 4).

3. Results and discussion

3.1. Production efciency analysis
All biomass based technologies are considered in a decentralized size range that offers the possibility of sustainable supply with
the needed amounts of raw materials. The large electrolysis plant is
also investigated in a decentralized size whereas the small electrolysis plant is in a size range that can be used to produce the
hydrogen directly at a hydrogen fuelling station. The size range of
the different hydrogen production technologies is presented in
Fig. 11 showing selected raw materials and plant layouts.
The results of the specic hydrogen production for the biomass
based processes are shown in Fig. 12. It can obviously be seen that
not only the choice of the technology but also the choice of the raw
material has a strong inuence on the production performance.
A comparison between the results of the biogas fermentation
plants shows that the hydrogen yield per kg of dry raw material is
higher for maize than for potato peels and bio waste. The considerably lower yields of the plants operated with bio waste are mainly

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A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

Fig. 9. Flowsheet of the coupled dark and biogas fermentation with gas engine; 1: hydrolysis, 2: solids separation, 3: dark fermenter, 4: biogas fermenter, 5: condenser, 6: VSA, 7:
gas engine.

caused by the low biogas yield per ton of dry bio waste. Fig. 12 also
shows that the biogas fermentation plant with upgrade to natural
gas quality and a central steam reforming plant has the highest
production efciency among the biogas fermentation layouts.
Among the biomass gasication based plants the layout with gas
upgrading to natural gas quality and central steam reforming has the
lowest hydrogen yield per kg of dry raw material. The reason for this
result is that the gasication gas has a high hydrogen content of
approximately 40 vol% (dry basis). In the central steam reforming
layout this hydrogen content is converted to methane in the
methanation reactor. The methane is then converted back to
hydrogen in the central steam reforming plant with a certain
methane loss due to incomplete conversion and side reactions.
Moreover, the conversion from hydrogen to methane is incomplete
as well and some of the produced methane and almost the total
unconverted amount of hydrogen are lost in the CO2-separation step.
Beyond that, a part of the produced methane has to be used as fuel to
provide the required heat for the steam reformer. The sum of these
losses leads to a hydrogen yield that is even considerably lower than
the yield of the gasication plant with direct on-site steam reforming.
A comparison between the results of the biogas fermentation
plants and the biomass gasication plants shows that the biomass

gasication plants are leading to higher specic hydrogen yields,

except for the layout with central reforming. The gasication option
with direct on-site steam reforming even shows higher yields than
any of the biogas fermentation layouts with CO2 separation and onsite reforming. Moreover, it has a higher production efciency than
the biogas fermentation plants with central reforming operated
with potato peels and bio waste.
The theoretical yield of the coupled dark and photo fermentation of maize corn (100% conversion in each fermenter) is the
highest one of all compared plants, both for 80% and 95% hydrogen
recovery in the VSA plant. A comparison between the dark/photo
fermentation and the biogas fermentation plants operated with the
same raw material shows that the dark/photo fermentation with
80% conversion in each fermenter and 80% recovery in the VSA
leads to lower hydrogen yields than any of the biogas fermentation
plants. The result for dark/photo fermentation of maize corn with
80% conversion and 95% hydrogen recovery in the VSA is slightly
lower than that for biogas fermentation of maize silage with central
reforming but higher than the yield of any of the biogas plants
operated with potato peels. Comparing the plants operated with
potato peels, only the dark/photo fermentation with 100% conversion in the fermenters show higher yields than the biogas

Fig. 10. Flowsheet of the coupled dark and biogas fermentation with gas boiler; 1: hydrolysis, 2: solids separation, 3: dark fermenter, 4: biogas fermenter, 5: condenser, 6: VSA, 7:
gas boiler.

A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

S59

32,988

Natural gas steam reforming

Alkaline electrolysis
small

0.8238
60
0.0015
485

Alkaline electrolysis
large

0.0121

Biogas fermentation
direct on-site reforming,
maize silage

546
0.0136

Biomass gasification
direct on-site reforming,
wood chips

1,161

m/h
kg/s

0.0290

Dark-/photo fermentation
potato peels

500

Dark-/biogas fermentation
potato peels

257

0.0125

0.0064

Hydrogen production in mSTP/h or kg/s

Fig. 11. Size range of the investigated hydrogen production technologies; the volume ows are given in m3/h at standard temperature and pressure.

1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0

hydrogen recovery in the VSA plants, the yield of the dark/biogas

fermentation with on-site reforming is only slightly lower than the
corresponding yield for the dark/photo fermentation of potato
peels.
3.2. Energy efciency analysis
The energy efciencies of all examined technologies and plants
are shown in Fig. 13. The energy efciency relates the energy
content of the produced hydrogen, based on the lower heating
value, to the energy input to the process. The gure shows two
results: one result relating the hydrogen energy content to the raw

convers. 100/100%, reforming

convers. 80/70%, reforming

convers. 100/100%, boiler

convers. 80/70%, boiler

convers. 100/100%, engine

convers. 80/70%, engine

Dark/biogas ferment., potato peels

convers. 100% each fermenter

convers. 80% each fermenter

Dark/photo ferment., potato peels

convers. 100% each fermenter

convers. 80% each fermenter

Dark/photo ferment., maize corn

central reforming

on-site reforming

CO2-sep., on-site reforming

central reforming

Gasification, wood chips

on-site reforming

CO2-sep., on-site reforming

Biogas fermentation, bio waste

central reforming

CO2-sep., on-site reforming

on-site reforming

Biogas fermentation, potato peels

central reforming

CO2-sep., on-site reforming

hydrogen production, dark fermentation based

technologies: 80 % H2 recovery in VSA
hydrogen production, dark fermentation based
technologies: 95 % H2 recovery in VSA

on-site reforming

Biogas fermentation, maize silage

Hydrogen production
in mSTP/kg raw dry material

fermentation plants. This can be explained by the fact that the dark
and photo fermentation utilizes only the starch content of the
potato peels whereas the biogas fermentation is able to use a larger
part of the substrate. Hence, raw materials which offer contents
that can be converted to biogas but not to hydrogen lead to a larger
difference between the specic yields of these two technologies.
The hydrogen production yields of the coupled dark and biogas
fermentation with gas engine as well as gas boiler are, as expected,
low as only the dark fermenter produces hydrogen. But the
performance of the layout with on-site reforming is comparable to
the dark and photo fermentation of potato peels. Comparing the
realistic lower values of conversion in the fermenters and 80%

Fig. 12. Comparison of the specic hydrogen production of all biomass based technologies; the specic hydrogen production is given in m3/kg dry raw material at standard
temperature and pressure.

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A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

material energy input only (based on the lower heating value

(LHV), dry) and one result relating it to the sum of all inputted
energies (raw material, electricity and heat) minus produced
electricity.
Expectedly the energy efciency of the state of the art technology natural gas steam reforming is the highest one of all
compared technologies. Furthermore, the steam reforming plant
produces more electricity than needed for its operation. This leads
to a higher energy efciency related to the total energy input than
related to the raw material energy input only. The alkaline electrolysis has the highest energy efciency related to the total energy
input among all regenerative hydrogen production technologies.
The biogas fermentation plant with maize silage as raw material and central steam reforming plant exhibits the highest energy
efciencies among all biomass based technologies. The only
exceptions are the energy efciencies related to the raw material
input of the dark/photo fermentation plants with 100% conversion
and 95% hydrogen recovery in the VSA plant, which are only
theoretical values. In contrast to the production efciency, the
energy efciencies of the biomass gasication plants are lower
than the efciencies of the biogas fermentation plants operated
with maize silage and potato peels. This is caused by the fact, that
the lower dry heating value of the wood chips is 1.21e1.27 times
higher than the lower dry heating values of maize silage and
potato peels, respectively. On the other hand the hydrogen yield
related to the dry raw material input of the gasication plants,
disregarding the plant layout with central reforming, is only
0.97e1.25 times higher than the yield of any of the biogas
fermentation layouts operated with maize silage or potato peels.
Therefore, the energy efciencies of the gasication plants are
slightly lower than the efciencies of the named biogas fermentation plants, although the production efciencies show the
inverse characteristics. It is also remarkable that the energy efciency related to the total energy input of the gasication layout

0.9

related to raw material energy input (LHV, dry), dark

fermentation based technologies: 80 % H2 recovery in VSA
related to raw material energy input (LHV, dry), dark
fermentation based technologies: 95 % H2 recovery in VSA

0.8
0.7

related to total energy input, dark fermentation

based technologies: 80 % H2 recovery in VSA
related to total energy input, dark fermentation
based technologies: 95 % H2 recovery in VSA

0.6
0.5
0.4
0.3
0.2
0.1

Fig. 13. Comparison of the energy efciencies of all investigated technologies.

100/100% convers., reforming

80/70% convers., reforming

100/100% convers., boiler

80/70% convers., engine

100/100% convers., engine

80/70% convers., boiler

100% convers. each fermenter

Dark/biogas ferment., potato peels

80% convers. each fermenter

100% convers. each fermenter

Dark/photo ferment., potato peels

Dark/Photo ferment., maize corn

80% convers. each ferme ter

on-site reforming

CO2-sep., on-site reforming

central reforming

central reforming

Gasification, wood chips

CO2-sep., on-site reforming

on-site reforming

central reforming
Biogas fermentation, bio waste

on-site reforming

CO2-sep., on-site reforming

central reforming

Biogas fermentation, potato peels

on-site reforming
CO2-sep., on-site reforming

large
Biogas fermentation, maize silage

small

Alkaline electrolysis

0.0

Natural gas steam reforming

Energy efficiency
in MWH2/MWin

with direct on-site reforming is slightly higher than that of the

layout with preceding CO2 separation. This is caused by the high
steam energy demand of the MEA-desorption applied in the CO2separation step in the latter plant.
Comparing the reforming of biogas and the dark and photo
fermentation, only the dark/photo fermentation plants with theoretical 100% conversion in each fermenter show efciencies
comparable to the biogas fermentation plants. But it has to be
mentioned that the coupled dark and photo fermentation does not
include any use of the produced gas or residues for the self-supply
of the heat demand of the plant. The biogas reforming plants on the
other hand include the self-supply of the heat demand for both
biogas fermentation and steam reforming. The only exception is the
biogas layout with central steam reforming plant where no heat
integration is possible between the biogas and the steam reforming
plant. The use of the dark/photo fermentation residues and separated particles like lignin for process heat production could
improve the energy efciency of the dark/photo fermentation
technology. Combined with an improvement in the hydrogen
recovery of the gas upgrading system to the proposed value of 95%,
this technology could denitely be competitive to the reforming of
biogas.
The coupled dark and biogas fermentation plants with gas
engine as well as with gas boiler show again very low energy efciencies compared to the other technologies and layouts. The
energy efciency related to the total energy input of the layout with
gas engine is higher than the efciency related to the raw material
energy input, since the gas engine produces more electricity than
needed for the operation of the plant. The energy efciencies of the
layout with on-site steam reforming are comparable to those of the
dark and photo fermentation. Only the coupled dark and photo
fermentation with 100% conversion in each fermenter and 95%
hydrogen recovery in the VSA plant show considerably higher
energy efciencies.

A. Miltner et al. / Journal of Cleaner Production 18 (2010) S51eS62

4. Conclusions and outlook

The present paper evaluates different hydrogen production
pathways comprising alkaline electrolysis, reforming of biogas,
reforming of gasication gas, coupled dark and photo fermentation
as well as coupled dark and biogas fermentation. The biomass
based technologies are investigated with different plant layouts
and/or raw materials. The steam reforming of natural gas is
included as reference technology for hydrogen production.
Alkaline electrolysis shows the highest energy efciency among
the renewable technologies and it offers the advantage of independence of any biomass. This technology offers a good possibility
of sustainable hydrogen production in regions without biomass
resources or with stiff competition between the food and the
energy sector. But it has to be kept in mind that a sustainable
production of hydrogen by alkaline electrolysis can only be guaranteed if electricity from renewable sources is utilized.
The reforming of biogas obtains good results regarding both
hydrogen production and energy efciency provided that the
proper raw material is chosen. The reforming of gasication gas
shows good production efciencies but in contrast the energy
efciencies are low compared to the reforming of biogas. The
production efciency results of the coupled dark and photo
fermentation are comparable to those of the reforming of biogas
but their energy efciencies are lower. However, since this technology is in an early stage of development it still has potential for
development and might be a real alternative to reforming of biogas.
Finally, the best results for the coupled dark and biogas fermentation regarding both hydrogen production and energy efciency are
obtained for the layout with on-site steam reforming of the
produced biogas, showing efciencies comparable to the dark and
photo fermentation.
The choice of the proper technology will have to be based on the
availability of raw materials, since the kind of raw material has
a strong inuence on the performance of the technology, on the
competition between food and energy production and on the
development of raw material prices. The regional circumstances
should also be regarded. For example it would not be advisable to
build a biomass gasication plant in an agricultural region with
scarce wood resources even though the production efciency of
this technology is high. It should also be kept in mind that the
layouts with centralized steam reforming are ecologically worthwhile only if the associated hydrogen fuelling stations can be
placed in a proper range from this central plant. Hence, this
production path should only be chosen for regions with very good
infrastructure and a dense fuelling station network to avoid long
hydrogen transportation by trucks.
It would be necessary to extend the presented analysis by an
economic and ecologic analysis, e.g. a life cycle analysis, to identify
the costs and the impact on the environment of each technology
and thus evaluate the sustainability of the processes. Some
economic results based on slightly different plant layouts and an
older data base have already been presented by the authors
(Miltner et al., 2008b). However, these calculations should be
updated and extended by the coupled dark and biogas fermentation. Moreover, it would be desirable to extend the analysis to
further raw materials. Especially other refuse materials like food
production waste or sewage sludge as well as intertillage would be
advantageous preventing the competition between food and
energy production.
The analysis could also be extended with other hydrogen
production technologies. For example the presented gasication
process could be replaced by the adsorption enhanced reforming
process (Pfeifer et al., 2007) which is a gasication technology that
produces a hydrogen rich syngas.

S61

Finally, it will be necessary to determine the amount of

hydrogen that can be produced in a sustainable way within
a specic region or even worldwide. The decision whether the
future world should be based on a hydrogen society or not has to be
based on the evaluation of the general potential to produce the
needed amounts of hydrogen in an economic and sustainable way.
Acknowledgements
We gratefully acknowledge the support by Austrian Advanced
Automotive Technology, a subprogram of the Federal Ministry of
Transport, Innovation and Technology (BMVIT) in cooperation with
the Austrian Industrial Research Promotion Fund (FFG).
We also like to thank H. Hofbauer from Vienna University of
Technology and the companies Profactor and OMV for their
contribution and support.
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