Fuel 244 (2019) 184–195

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Full Length Article

Hydrogen production through steam reforming of bio-oils derived from T

biomass pyrolysis: Thermodynamic analysis including in situ CO2 and/or H2
separation
M.A. Soria , Diogo Barros, L.M. Madeira
⁎

LEPABE, Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias s/n, 4200-465 Porto, Portugal

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: A thermodynamic analysis based on the minimization of the Gibbs free energy method was performed in order to study the
Bio-oil steam reforming of real bio-oils (obtained from biomass fast pyrolysis) from different sources. For comparison purposes,
Steam reforming four types of reactors were used, namely: traditional reactor (TR), membrane reactor (MR) with H2 separation, sorption-
Hydrogen enhanced reactor (SER) with CO2 sorption, and sorption-enhanced membrane reactor (SEMR) with both H2 and CO2
Sorption-enhanced reactor
separation. The CO2 capture was studied varying the sorbent (CaO) to feed molar ratio (SFR) while the effect of the H2
Membrane reactor
Sorption-enhanced membrane reactor
removal was assessed with the use of a removal fraction (fH2) of 0 to 0.8 (typical recoveries for an H2-selective membrane).
The simulated results obtained for the TR showed a good agreement with those reported in literature ex-
perimental works at similar operation conditions. The optimum conditions for the production of hydrogen were
obtained in the SEMR in which it was possible to obtain 99% of the maximum theoretical yield for spruce bio-oil
and 97% of the maximum yield for wheat bio-oil. Furthermore, this reactor configuration minimizes CH4, H2,
CO, CO2 and coke yields. In addition, the effect of pressure in a range of 1 to 10 bar was also assessed for the
reactor configurations with H2 removal. It was shown that the increase of pressure decreases H2 yield; never-
theless, this can be offset by moderately increasing the WFR.

1. Introduction threats created by their exploitation, such use is a growing concern for
the society. This has led to an increasing demand for clean and re-
Fossil fuels are the main energy sources at present, but considering newable energy sources. Biomass is seen as an attractive primary en-
their non-sustainable consumption coupled with the environmental ergy source (renewable resource) if managed in a sustainable way.

⁎
Corresponding author.
E-mail address: masoria@fe.up.pt (M.A. Soria).

https://doi.org/10.1016/j.fuel.2019.01.156
Received 5 November 2018; Received in revised form 19 December 2018; Accepted 27 January 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
M.A. Soria et al. Fuel 244 (2019) 184–195

Nomenclature T Temperature, [K]

V Volume, [m3]
List of variables Yieldi Yield of the species i, dimensionless
Hr298K Standard enthalpy of reaction, [kJ/mol]
Symbol Definition, Unit µi Chemical potential of species i, [kJ/mol]
fH2 H2 separation factor, dimensionless
G Gibbs free energy, [kJ] List of acronyms
k Represents each sub-separator (from 1 to N), dimension-
less Acronym Definition
mbio oil (feed) Molar flow rate of bio-oil in the feed of the R1 Gibbs MR Membrane Reactor
reactor, [mol/h] RWGS Reverse Water-Gas Shift
mi ,k Outlet molar flow of species i in the sub-separator k, [mol/ SEMR Sorption-Enhanced Membrane Reactor
h] SER Sorption-Enhanced Reactor
miout
,N +1 Molar flow rate of species i in the outlet stream of the SFR Sorbent to Feed Molar Ratio
(RN + 1) Gibbs Reactor, [mol/h] SR Steam Reforming
ni Number of moles of each component in the system, [mol] TR Traditional Reactor
P Pressure, [kPa] WFR Water to Feed Ratio
S Entropy, [kJ/K] WGS Water-Gas Shift

Furthermore, it can be converted in a large array of biofuels through
several processes, whose combustion has low (or overall null) carbon
emissions [1]. Biomass conversion into different kinds of fuels can be
done through thermal, biological or mechanical processes [2–5].
Among the thermal processes, combustion is used in the production of
heat that can be used to generate electrical energy (e.g. via a steam
turbine). Gasification is mainly used to produce syngas that may have
different downstream applications [6]. Pyrolysis is the thermal de-
composition of the biomass in the absence of oxygen, yielding charcoal,
fuel-gas and bio-oil, also called pyrolysis oil; the quantity in which
these products are formed as well as their content on oxygenated
compounds depends on the residence time, heating rate and tempera-
ture of the process and on the composition of the biomass source. There
are different modes of pyrolysis: fast, intermediate and slow [5,7,8].
The fast pyrolysis (which occurs at high heating rates, 450–600 °C and
less than 2 s of residence time) provides a higher yield in bio-oil, while
the other sub-products (charcoal and fuel-gas) can be used to generate
heat for the pyrolysis process itself [5]. The big advantage of producing
these bio-oils is that they have a volumetric energy density up to ten
times higher than that of biomass; consequently, they are much more
suited (more cost-efficient) for transportation [9,10]. These oils can be
used directly as combustion fuels, but their poor volatility and high
viscosity and coking result in problems for the combustion equipment.
They can also be used to extract some chemicals like acetic acid or
methanol, but these compounds can usually be obtained at a lower cost
from other feedstock. Finally, they can be converted into transport fuels
like bio-diesel or hydrogen; even though there are still some challenges,
this is an attractive application for bio-oils [11]. Hydrogen is a great
energy solution as it has a high calorific power and also acts as an
excellent energy vector. Nowadays, 95% of the world’s production of
hydrogen uses fossil fuels as raw material [12], mainly through me-
thane steam reforming. However, the use of this technology for the
reforming of pyrolysis oils is particularly interesting because not only it
is an environmentally friendly alternative, but also, it is an application
that can turn a product that is otherwise viewed as waste (biomass) into
a useful fuel. Experimental studies performed in traditional reactors
(TRs) with both raw bio-oil and bio-oil model compounds like acetic
acid, acetone and phenol showed that catalytic bio-oil steam reforming
is a viable technology [13–18].
The possible reactions involved in bio-oil steam reforming process
are presented in Table 1; these reactions were considered based on
previous studies carried out for steam reforming of oxygenated com-
pounds [13,15,19–21]. The bio-oil derived from biomass fast pyrolysis
and steam are converted into synthesis gas (mixture of carbon

Table 1
Reactions considered for the reforming process simulations.
Reaction Hr298K (kJ mol−1) No.

Steam Reforming
>0 (1)
Cn Hm Ok + (n k ) H2 O (
nCO + n +
m
2 )
k H2
Water-gas shift
CO + H2 O CO2 + H2 −41 (2)
Overall steam reforming equation
>0 (3)
Cn Hm Ok + (2n k ) H2 O (
nCO2 + 2n +
m
2 )
k H2
Thermal decomposition of oxygenated compounds
Cn Hm Ok H2, CO, smaller oxygenated compounds hydrocarbons, coke >0 (4)
Methanation
CO + 3H2 CH4 + H2 O −206 (5)
Methane steam reforming
CH4 + H2 O 3H2 + CO a 206 (6)
Methane dry reforming
CH4 + CO2 2CO + 2H2 b 247 (7)
Carbon Formation
2CO CO2 + C −172 (8)
CH4 2H2 + C 75 (9)
CO + H2 H2 O + C −131 (10)
CO2 + 2H2 2H2 O + C c −90 (11)

a b c
Reverse of Eq. (5); Sum of reverse of Eq. (2) and Eq. (6); Sum of Eq.(10) and reverse of Eq.(2).

185
M.A. Soria et al.
Fig. 1. Scheme of the sorption-enhanced membrane reactor for bio-oil steam
reforming.
monoxide and hydrogen) – Eq. (1). Following this step, carbon mon-
oxide is converted into hydrogen and carbon dioxide through the water-
gas shift (WGS) reaction – Eq. (2). There are also secondary reactions
associated with this process that form several by-products (see Table 1).
To minimize the formation of coke, CO and CH4 and thus enhance the
H2 yield, different types of multifunctional reactors can be used, which
allow to shift the equilibrium of the reactions involved by selectively
removing the reaction products (CO2 and/or H2). Such multifunctional
reactors can be for instance a membrane reactor (MR), a sorption-en-
hanced reactor (SER) or a sorption-enhanced membrane reactor (SEMR;
Fig. 1) [22,23]. The MR allows the H2 produced to be selectively re-
moved from the reaction zone as a permeate stream. Palladium-based
membranes have been largely studied and applied in hydrogen se-
paration/production processes, since they are very selective towards H2
[24–26]. In the case of the SER, the CO2 capture can be achieved by
filling the reactor with a mixture of steam reforming catalyst and CO2
sorbent. One of the most used CO2 sorbents is calcium oxide (CaO),
which has been previously used in theoretical glycerol reforming stu-
dies and in experimental acetic acid reforming, employed as a bio-oil
model compound [21,27]. To further shift the steam reforming reaction
to the reaction products, the in-situ separation of both CO2 and H2 (that
are involved in most of the equilibrium-limited reactions reported in
Table 1) was carried out. The simultaneous removal of CO2 and H2 from
the reaction zone provides a hybrid new reactor concept (SEMR) that
can originate a substantial improvement in the hydrogen yield and
minimize the undesired by-products formation [23].
Although there are some thermodynamic studies of bio-oil steam
reforming, these were carried out considering only model compounds
[20,28,29]. The purpose of this work is to further explore biomass
valorisation through the steam reforming of pyrolysis oils, analysing the
process attainable efficiency, i.e. on the thermodynamic equilibrium.
For comparison reasons, several real fractions of bio-oil derived from
biomass fast pyrolysis, whose composition depends on the sources (e.g.
wood, sugar, palm oil, etc.), are considered. Moreover, the performance
of different types of reactors, such as TR, MR, SER and SEMR, will be
compared with the aim of identifying the optimal operating conditions
for high-purity hydrogen production.
In this work, and as far as we know, a thermodynamic study assessing
bio-oil steam reforming with several real bio-oil mixtures and comparing
different multifunctional hybrid reactors is performed for the first time.
Although the optimal operating conditions correspond to the equilibrium,
they provide valuable information for operation under real conditions since
they indicate the limits that can be reached and the variables that can be
modified in order to optimize the hydrogen yield and avoid (or minimize)
the coke formation, which is responsible for catalyst deactivation.
2. Methodology
To determine the equilibrium composition of the chemical species in
the system, a non-stoichiometric approach was employed. This
186
Fuel 244 (2019) 184–195
approach involves the minimization of the Gibbs free energy and allows
for an easy achievement of convergence in computation without the
need to select the chemical reaction(s) occurring and an accurate esti-
mation of the initial equilibrium composition, only needing to define
the chemical species involved according to the possible reaction(s)
[30].
The Gibbs free energy (G) depends on the temperature (T), pressure
(P) and molar quantities of the N components present in the system. Its
differential form can be written as follows:
N
dG = SdT + VdP + i=i
µi dni (12)
where S stands for the entropy, V is the volume, ni the number of moles
of each component in the system and µi is the respective chemical po-
tential. When the system operates in isothermal and isobaric conditions,
the differential equation becomes:
dG =
N
µi dni
i=i (13)
The used approach implies that equation (12) is equal to zero since
at the equilibrium the system has the minimum Gibbs free energy. A
more detailed description of the methodology is available elsewhere
[31,32].
With the aim of studying the influence of T, P and feed composition
on the hydrogen yield, the thermodynamic analysis of the different bio-
oils in the steam reforming process was performed using Aspen Plus®
V8.8 software. To calculate the equilibrium composition of the system
at certain T, P and feed composition, the Gibbs reactor (RGIBBS) block,
which is a reactor model based on the minimization of the Gibbs free
energy method, was utilized. As mentioned, the method herein applied
does not require reaction stoichiometry input but it is only necessary to
provide information about the chemical compounds present in the
system (reagents and products), which were defined according to the
reactions present in Table 1. The compounds common to all the simu-
lations are H2, CO, CO2, H2O, CH4 and carbon, as well as smaller hy-
drocarbons (C2H6 to C4H10) and oxygenated compounds (CH4O to
C4H10O) that can be formed due to reaction (4); however, these small
hydrocarbons and oxygenated compounds were not found in all the
simulations presented herein.
In the cases where the type of reactor involves a hydrogen perme-
able membrane such as MR and SEMR, the use of only one RGIBBS
block is not enough to perform the simulation. Therefore, to simulate
the in-situ H2 removal a sequential modular approach is employed
(Fig. 2). The MR (or SEMR) is divided into several (N + 1) sub-re-
formers (represented as R in Fig. 2) and (N) membrane sub-separators
(represented as SEP). The latter is a block that allows to separate che-
mical compounds which number (N) depends on the defined split
fraction or flow (herein called hydrogen removal or recovery fraction).
This split fraction is in practice related to membrane factors like its
selectivity, permeability, thickness, area and process conditions (e.g.
temperature, sweep-gas flow or pressure across the membrane). This
methodology has been also implemented in previous studies
[21,31,33].
In order to assess the performance reached, for a given set of con-
ditions employed in the simulations, the yield of the species at equili-
brium was calculated according to the equation bellow:
N
miout
, N +1 + k = 1 mi,k
Yieldi = mbio oil (feed ) (14)
where mbio oil (feed) stands for the molar flow rate of bio-oil in the feed of
the R1 unit, miout
, N + 1 is the molar flow rate of species i in the outlet stream
N
of the (RN + 1) RGIBBS unit and k = 1 mi ,k is the sum of the outlet
molar flow of each chemical species i in the N sub-separators (please
refer to Fig. 2). This last sum will always be equal to zero, except for
hydrogen in the MR and in the SEMR since the N sub-separators act as
H2 perm-selective membranes (with infinite selectivity towards H2).
The separation factor (fH2) is defined as shown in Eq. (15):
M.A. Soria et al.
Fig. 2. Diagram of modular approach used for simulation of bio-oil stem reforming in the different reactor configurations.
Table 2
Reactions involved in the carbon dioxide capture with calcium oxide.
Reaction Hr298K (kJ mol−1)
CaO + H2 O Ca (OH ) 2 −65
Ca (OH )2 + CO2 CaCO3 + H2 O −113
N
k=1
m H2, k
fH2 = N
m H2, k + m Hout
k=1 2, N + 1
where k represents each sub-separator, m H2, k represents the sum of
N
k=1
the hydrogen molar flow rate in the permeate stream of each sup-se-
parator and m Hout
2, N + 1
the outlet hydrogen molar flow rate in the last sub-
reformer. The number of sub-separators needed in the simulation de-
pends on the separation factor set. The higher the separation factor
(fH2), the more sub-separators will need to operate. To simulate the
variations of temperature, water to feed molar ratio and sorbent to feed
molar ratio, the Sensitivity Analysis Tool from Aspen was employed,
where the analysed variable and its range of variation is introduced.
To simulate the sorption-enhanced reactor for CO2 capture, three
more components need to be defined, namely the sorbent (CaO), and
the products resulting from the reactions: calcium hydroxide (Ca(OH)2)
and calcium carbonate (CaCO3) – cf. Table 2). Calcium oxide is there-
fore added as an inlet stream to the RGIBBS unit (represented as R1 in
Fig. 2). The CaO-to-feed molar ratio (SFR) can be varied in order to find
the optimal value in terms of hydrogen yield and total CO2 capture.
3. Results and discussion
3.1. Comparison of different bio-oils in a conventional steam reforming
reactor
As it was previously stated, bio-oil is originated from the pyrolysis of
biomass, which can come from a large diversity of sources. Thus, de-
pending on the biomass origin, the bio-oil will have different oxygenated
compounds in its composition (see Supporting information; Tables SI.1 to
SI.11). In this section, several bio-oils were used as feedstock, for the
steam reforming process, in order to compare the yield of the products,
varying either the water to feed molar ratio (WFR) or the temperature.
Considering only the overall steam reforming equation (3) and the ele-
mental composition (C, H and O) of each bio-oil, it is possible to estimate
the stoichiometric WFR required and the maximum H2 yield that is
possible to be produced (assuming that no parallel reactions occur) for
each bio-oil considered (see values in Table 3).
Fuel 244 (2019) 184–195
Whatever the original biomass, the presence of hydrocarbons and oxy-
genated compounds were not observed, meaning that there is total con-
version in all the simulations carried out, even bellow the stoichiometric
No. WFR, not only because of the steam reforming process itself, but also due to
the thermal degradation of the chemical compounds present in the feed – cf.
(16) Eq. 4. Such equations are thus indicated as being irreversible in Table 1.
(17)
3.1.1. Effect of water to feed molar ratio
The variation of the products yield as a function of the WFR for
(15) different bio-oils are represented in Fig. 3. In order to compare the
results obtained for a conventional reactor with those obtained for a
membrane reactor and a sorption-enhanced (membrane) reactor (in the
next sections), a temperature of 400 °C was chosen; such temperature is
suitable to operate with both Pd-Ag membrane and CaO sorbent.
As shown in Fig. 3, all the bio-oils exhibit a similar trend. As it can
be seen, below the stoichiometric WFR there is coke formation, which
probably occurs from Eqs. 8, 9 and 10. As the WFR increases, coke
production is inhibited, meaning that the reverse of Eq. 10 is promoted;
simultaneously, Eqs. 8 and 9 are inhibited (so CH4 and CO yields in-
crease) because the WGS reaction is favoured (producing CO2 and H2)
with the increases of WFR. As a consequence, there is more CO and H2
and, for not excessive WFR, the methanation reaction (reverse of me-
thane steam reforming) is favoured, showing an increase of CH4 yield.
The H2 yield increases with the WFR as it shifts the equilibrium of
both WGS and methane steam reforming reaction towards the right side
(Eqs. 2 and 6, respectively, in Table 1). Accordingly, the excess of
water, beyond the stoichiometric value, also causes a slight decrease in
methane production since the methanation reaction (Eq. 5) is inhibited.
Carbon monoxide yield has a similar behaviour to that of CH4 since it
decreases slightly when reaching the WFR stoichiometric value, al-
though only very few CO is formed when compared to the other pro-
ducts, very probably due to the fact that it is consumed by the WGS.
Regarding coke production, it is inhibited with excess water as can be
elucidated by the carbon formation reactions where water is present
(Eq. 10); thus, there is no coke above the WFR stoichiometric value,
which varies from one bio-oil to another (see also Table 3).
Fig. 3 also shows that hydrogen yields are still far from the theo-
retical (maximum) yields predicted, as reported in Table 3. In order to
better compare the performance of the different bio-oils, the variation
of the relative yield (i.e., H2 yield/maximum H2 yield) with the nor-
malized WFR (related to the stoichiometric WFR) was plotted in Fig. 4.
It is possible to observe that the higher the WFR/WFRsq ratio, the higher
the relative hydrogen yield difference between the different bio-oils
used. Bio-oil obtained from rice produces the highest relative hydrogen
yield while oak (and maple) or eucalyptus the lowest ones, depending
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M.A. Soria et al. Fuel 244 (2019) 184–195

Table 3 Table 3). All the bio-oils exhibit a similar behaviour in terms of H2, CO,
Stoichiometric water to feed molar ratio (WFR) and maximum H2 yield for the CO2, CH4 and coke yield with the rise of the temperature (Fig. 5).
different bio-oils. Obtained hydrogen yields for each bio-oil are in line with the sequence
Original Biomass Stoichiometric Maximum H2 Yield for the maximum expected yields reported in Table 3. As stated above,
WFR* and whatever the original biomass, total conversion was reached in all
the simulations, meaning that steam reforming of the bio-oils is com-
Spruce wood 3 4.75
plete. So, the effect of temperature is related with other reactions. In-
Sugar Bagasse 3 4.66
Rice husk 7 8.36 creasing temperature promotes the formation of more hydrogen mainly
Maize stalk 7 9.53 due to the progressive inhibition of the methanation reaction (3 mol of
Pine sawdust 6 8.73 H2 for each mole of CH4), which is highly exothermic (Eq. (5) – reverse
Mesquite sawdust 7 9.92
of methane steam reforming, Eq. 6); this happens until a maximum
Wheat shell 9 11.94
Oil palm shells 8 10.35
around 700 °C and then the hydrogen yield decreases. This maximum
Oak 2 3.71 occurs because the WGS is slightly exothermic and for temperatures
Maple 2 3.76 above 700 °C, reverse water-gas shift (RWGS) is more favoured. Carbon
Eucalyptus wood 5 7.94 dioxide, which is also involved in RWGS and coke formation (Eq. 8; for
T less than 550 °C), has a similar behaviour to hydrogen but its max-
* Rounded up values.
imum happens at lower temperatures (close to 550 °C). This difference
of maximum temperatures happens because while H2 is being con-
on the amount of steam fed. While for low values of the WFR/WFRsq
sumed through RWGS and saved through the inhibition of methanation
ratio all bio-oils exhibit a very similar behaviour, it is possible to ob-
(the maximum yield of H2 matches with the almost complete inhibition
serve that even when the WFR is twice the WFRsq, H2 yield is still far
of methane formation), CO2 is no longer produced from Eq. 8 at high
from the maximum yield possible. This means that there is a possibility
temperatures and is only being consumed through RWGS. Concerning
for improvement, either changing the reaction conditions or the reactor
carbon monoxide, until 500 °C its yield is very close to zero because it is
type, as proposed in the following sections.
consumed by WGS, methanation and coke formation (Eqs. 8 and 10) –
all exothermic reactions. However, it increases from around 500 °C,
since higher temperatures favour either the RWGS reactions or the in-
3.1.2. Effect of temperature
The temperature effect on the products yield was studied for the hibition of methanation and coke formation. As it was already stated,
for high temperatures the methanation reaction is inhibited, so CH4 is
different bio-oils at the stoichiometric WFR of each of them (reported in

Fig. 3. Effect of water to feed molar ratio (WFR) on the yield of the products for several bio-oils in a conventional steam reforming reactor at 400 °C and 1 bar.

188
M.A. Soria et al. Fuel 244 (2019) 184–195

Fig. 4. Normalized H2 yield as a function of the normalized water to feed molar ratio for several bio-oils in a conventional reactor at 400 °C and 1 bar.

Fig. 5. Effect of temperature on the yield of the products for several bio-oils in a conventional steam reforming reactor at stoichiometric WFR conditions and 1 bar.

no longer produced for temperatures above 700 °C. Besides that, for
high temperatures coke formation also does not occur as most carbon
formation reactions are exothermic.
In the discussions above (and below), the species yields are ex-
plained considering mostly methanation and WGS (or RWGS) reactions;
actually, the reader should consider that methane steam reforming is
the reverse of methanation and methane dry reforming is a linear
combination of the methanation and RWGS as indicated in the foot-
notes “a” and “b” in Table 1, respectively.
The ratio between the H2 yield and the maximum theoretical yield
as a function of the temperature is represented in Fig. 6. It can be seen
that the different bio-oils behave in a similar way, being the highest

189
M.A. Soria et al.
relative H2 yield of about 0.7 reached at 700 °C. This means that the H2
yield can be further improved, namely using other types of reactors,
which are able to shift the equilibrium of the involved reactions, such as
a membrane reactor, a sorption-enhanced reactor or a sorption-en-
hanced membrane reactor. Since the bio-oils have similar behaviours,
the thermodynamic analysis for these multifunctional reactors was
performed only for two of them. The bio-oils chosen were the one from
wheat shell, as it has the highest H2 production potential (see Table 3),
and the one from spruce wood, as it is one with the lowest H2 pro-
duction potential and is an abundant natural resource in Portugal. The
other bio-oils seem to have a performance in between these two ex-
tremes.
The results obtained herein by simulation were compared with ex-
perimental results from the literature [16,17]. Experiments of steam
reforming of raw bio-oil, whose composition is very similar to that used
in this work for pine sawdust, were performed in a conventional reactor
with Ni-based catalysts at atmospheric pressure, temperatures between
550 and 750 °C, and different WFRs. Simulated results performed at
stoichiometric WFR and similar P and T show full conversion and
normalized H2 yield between 0.6 and 0.75, which are very close to the
experimental values (∼0.6 for 600 °C and ∼0.75 for 750 °C) obtained
in a thermodynamic regime i.e., for high values of space-time. It was
also observed that the increase in both temperature and WFR lead to an
attenuation of coke deposition. Therefore, the predictions obtained at
similar conditions in a TR show a very good consistency regarding the
experimental observations.
3.2. Sorption-enhanced reactor (SER)
The objective of the SER is to remove CO2 from the reaction zone
using CaO as a CO2 sorbent (Eqs. (16) and (17)), which allows to shift
the equilibrium of the steam reforming reaction, enhancing the pro-
duction of H2. For this type of reactor, a parametric analysis varying the
temperature, the water-to-feed molar ratio (WFR) and the sorbent-to-
feed molar ratio (SFR) was addressed.
The effect of the temperature and SFR on the H2 yield for bio-oil
derived from the pyrolysis of spruce and wheat is shown in Fig. 7a and
b, respectively. For a given temperature (in the range of 450 °C to
700 °C), the H2 yield rises with SFR until reaching a maximum and then
remains nearly constant; this happens from SFR = 2 for spruce and
from SFR = 5 for wheat (see the projections in the bottom plane of
Fig. 7). The fact that the maximum H2 yield is reached between 450 and
700 °C shows that this is the range of temperature where the sorption
reactions are more favoured (when coupled with the steam reforming
process) as the sorption reactions are exothermic. However, in such
Fig. 6. Normalized H2 yield as a function of temperature for several bio-oils in a conventional reactor at stoichiometric WFR and 1 bar.
190
Fuel 244 (2019) 184–195
range of temperature the H2 yield remained constant, in spite of the SFR
increases, because the sorption process needs H2O to occur (Eq. (16))
and for the stoichiometric WFR of bio-oil steam reforming (which are
the conditions employed in Fig. 7) there is not enough water to make
the sorption reaction fully happen, leaving unreacted CaO in the reac-
tion zone.
As reported in the Supporting Information section (Figures SI.1 and
SI.2), with the increase of the SFR the CO2 yield decreases, in the
temperature range in which the sorption reaction operates
(450–700 °C), reaching zero at SFR = 2 for spruce and SFR = 5 for
wheat (i.e. complete CO2 sorption). The removal of CO2 promotes the
WGS (Eq. 2) consuming CO and, consequently, in the range above
mentioned, the CH4 yield is much lower than that obtained in the
conventional reactor as methanation (reverse of methane steam re-
forming) is inhibited.
The optimum values of hydrogen yield obtained varying the tem-
peratures for SFR = 2 were 3.87 mol H2/mol of bio-oil (81% of the
theoretical maximum – Table 3) in the case of spruce, and for SFR = 5
the maximum yield was 10.17 mol H2/mol of bio-oil (85% of the
maximum theoretical) in the case of wheat, both at 450 °C. Analysing
the whole range of temperatures, it is worth mentioning that the re-
moval of CO2 shifts the WGS to produce more H2, thus consuming CO;
therefore, between 450 and 600 °C (where carbon monoxide was pre-
sent in the TR), this product is nearly inexistent in the SER, as can be
seen in Figures SI.1 and SI.2. With the temperature increase, CO2
sorption is inhibited because the sorption reaction is exothermic and
RWGS becomes more favoured, so CO formation increases. Carbon di-
oxide yield increases with the increase of temperature until it reaches a
maximum, then decreases due to the inhibition of the sorption reaction
and the promotion of RWGS; when there is no CaO (conventional re-
actor – SFR = 0) this maximum is reached at a lower temperature since
only RWGS happens and not the sorption reactions. Due to the reduc-
tion of CO and the removal of CO2, coke formation in the SER only
occurs at very low temperatures with low SFR, as its formation depends
on these two compounds (Eqs. 8–11).
As in the conventional reformer, for the sorption-enhanced reactor
the H2 yield increases with the WFR (Fig. 8a and b) as it favours WGS
and also the sorption reaction(s), while inhibiting the methanation (see
reactions in Tables 1 and 2). Consequently, it allows a higher CO2 re-
moval, so that for high SFR values CO2 is nearly inexistent (see Figures
SI.3 and SI.4 in the Supporting Information). Moreover, for high SFRs
there is no carbon monoxide because the CO2 removal by the use of the
sorbent promotes the WGS reaction to completion. As stated above, the
increase in the water to feed molar ratio also promotes the WGS
(consuming CO), therefore, this indirectly contributes to the inhibition
M.A. Soria et al.
Fig. 7. Hydrogen yield as a function of temperature and sorbent-to-feed ratio for a) spruce bio-oil and b) wheat bio-oil in the sorption-enhanced reactor at stoi-
chiometric water-to-feed ratio and 1 bar.
of methanation (reverse of methane steam reforming). Thus, for high
values of SFR and WFR methane is not present (Figures SI.3 and SI.4).
In addition, both the increase of SFR and WFR inhibit the formation of
coke, which is only present for low values of both variables. The hy-
drogen yield will keep increasing with the increase of WFR until it al-
most reaches the theoretical maximum. The best H2 yield values ob-
tained were 4.71 mol H2/mol of bio-oil for spruce at SFR = 3 and
WFR = 15 and 11.32 mol H2/mol of bio-oil for wheat at SFR = 5 and
WFR = 20. Although these values correspond to 99% (for spruce) and
95% (for wheat) of the theoretical maxima reported in Table 3, WFR
values well above the stoichiometric are required, implying high op-
erating costs that can be reduced with other reactor configurations.
3.3. Membrane reactor (MR)
The employment of a hydrogen permselective membrane in the
multifunctional reactor is expected to improve the hydrogen yield. The
study of the MR was made analysing the behaviour of the bio-oils while
varying the temperature (Fig. 9a and b) and water-to-feed ratio
(Fig. 10a and b) for different hydrogen removal fractions ( fH2 ). A re-
moval fraction superior to 0.8 was not simulated since it is not expected
to be experimentally feasible; moreover, the temperature range used
was between 300 °C and 500 °C due to the commonly reported metallic
(e.g. Pd-based) membrane limitations.
With the increase of the hydrogen removal fraction, for a given
temperature, the hydrogen yield increases because it inhibits the me-
thanation (reverse of methane steam reforming), which consumes
Fig. 8. Hydrogen yield as a function of water-to-feed ratio and sorbent-to-feed ratio for a) spruce bio-oil and b) wheat bio-oil in the sorption-enhanced reactor at
400 °C and 1 bar.
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Fuel 244 (2019) 184–195
hydrogen (Eq. 5), and it shifts the WGS reaction to the hydrogen pro-
duction side – Eq. 2 (see Fig. 9a and b, and specifically the projections
in the bottom plane). This increase also happens with the increase of
temperature (from 300 to 500 °C), mostly due to the progressive in-
hibition of the exothermic methanation reaction, (Eq. (5)). It is note-
worthy that it is possible to obtain a high hydrogen yield when using
the MR compared to a conventional reactor. Actually, the maximum
value occurred for fH2 = 0.8 at 500 °C and stoichiometric WFR and was
3.44 mol of H2/mol of bio-oil for spruce and 9.31 mol of H2/mol of bio-
oil for wheat; in the same conditions, yields in the conventional re-
former were 1.52 and 3.70, respectively.
As stated above, with the removal of hydrogen the methanation
reaction is inhibited. Thus, the yield of CO should increase when fH2
increases, however, it remains nearly constant because CO is consumed
mainly by WGS (Figures SI.5 and SI.6). With the increase of tempera-
ture CO formation increases due to the RWGS and inhibition of coke
(reverse of Eqs. (2) and (8), both being endothermic). Likewise, because
of the inhibition of methanation, for high removal fractions of H2 the
CH4 yield decreases (particularly at higher temperatures). CO2 shows
the same behaviour of hydrogen because of the WGS reaction, although
H2 yield increases in a higher degree due to the methanation inhibition.
Inherently, the increase of the yield of CO2 and CO for higher H2 re-
moval fractions implies a higher coke yield (although its value is very
low), since they are involved in the coke formation reactions (Eqs. 8, 10
and 11). Because prevailing coke formation reactions are exothermic,
its formation is reduced for high temperatures.
The increase of both the H2 removal fraction and water-to-feed
M.A. Soria et al. Fuel 244 (2019) 184–195

Fig. 9. Hydrogen yield as a function of temperature and hydrogen removal fraction for a) spruce bio-oil and b) wheat bio-oil at stoichiometric WFR and 1 bar in the
membrane reactor.

Fig. 10. Hydrogen yield as a function of the water-to-feed molar ration and hydrogen removal fraction for a) spruce bio-oil and b) wheat bio-oil at 400 °C and 1 bar in
the membrane reactor.

molar ratio promote the improvement of the hydrogen yield for both
bio-oils considered (Fig. 10a and b). It is worth noting that when WFR
increases beyond the stoichiometric value (3 for spruce and 9 for
wheat), the coke formation is completely avoided (Figures SI.7 and
SI.8). Therefore, increased WFR promotes the WGS (increasing H2 and
CO2 yield) and inhibits the methanation reaction, particularly at high
fH2 (Fig. 10a and b). The increase of both WFR and fH2 inhibits me-
thanation; so, CH4 yield decreases with the increase of these variables.
In this reactor configuration, for the temperatures and WFR ranges
tested, the best values obtained for H2 yield were 4.66 mol H2/mol of
bio-oil for spruce (98% of the theoretical maximum – Table 3) at
WFR = 15 and 8.83 mol H2/mol of bio-oil for wheat (74% of the the-
oretical maximum) at WFR = 20, all with a removal fraction of 0.8.
Once again, very high values of WFR are required meaning high op-
erating costs that can be reduced with other reactor configurations, as
detailed bellow.
3.4. Sorption-enhanced membrane reactor (SEMR)
This hybrid multifunctional reactor configuration combines both in-
situ carbon dioxide and hydrogen removal, which could further im-
prove the hydrogen yield. In order to compare the SEMR with other

Fig. 11. Comparison of hydrogen yield as a function of temperature for a) spruce bio-oil in TR, SER (SFR = 2), MR (fH2 = 0.8) and SEMR (SFR = 2, fH2 = 0.8) and b)
for wheat bio-oil in TR, SER (SFR = 5), MR (fH2 = 0.8) and SEMR (SFR = 5, fH2 = 0.8) both at stoichiometric WFR and 1 bar.

192
M.A. Soria et al.
reactor types, a combination of the optimal conditions (that provided
the highest H2 yield) of each reactor previously studied was selected,
which were as follows: for the SER, a SFR of 2 and 5 for bio-oil derived
from spruce and wheat respectively; for the MR, a hydrogen removal
fraction of 0.8. This comparison was addressed at different tempera-
tures and water to feed molar ratios.
Regarding the effect of temperature, the simulations were run for
the respective stoichiometric WFR of each stream. It is observed from
Fig. 11 that for the SEMR it is possible to achieve the highest hydrogen
yield (although below the theoretical maximum) at 360 °C for spruce
and at 420 °C for wheat, while for the other type of reactors the max-
imum H2 yield (always below that for the SEMR) is achieved at higher
temperatures. It is also noteworthy that whatever the temperature, the
removal of CO2 (given by the used SFR) has a more significant effect on
the hydrogen yield improvement than the removal of H2 (fH2 = 0.8).
Also, when capture of carbon dioxide occurs, there is a very significant
reduction of the other by-products like CO, CO2 and coke. Methanation
is also almost fully inhibited in the SEMR (Figures SI.9 and SI.10).
To further compare the different type of reactors studied and to
demonstrate how the performance is improved with the use of the
hybrid reactors, the hydrogen yield was plotted at SEMR optimal
temperature conditions (Fig. 12a and b). It is observed that all the
hybrid reactors improve the performance as compared to the conven-
tional reactor and the best configuration is clearly the SEMR. As com-
pared to the TR, impressive improvements of over 1000% and 330%
can be reached for spruce and wheat bio-oil, respectively.
Concerning the variation of water to feed molar ratio (Fig. 13), the
study was carried out at 400 °C. The increase of the WFR increases the
hydrogen yield in all reactor configurations; the maximum yield was
achieved at a WFR higher than 6 for spruce bio-oil (stoichiometric
WFR = 3) and 10 for wheat bio-oil (stoichiometric WFR = 9) for the
SEMR, which is the only reactor able to achieve the maximum (theo-
retical) H2 yield possible for spruce bio-oil (Fig. 13a), although this is
not verified for wheat bio-oil (Fig. 13b) as methanation is still occur-
ring. The increase of steam promotes the WGS, whereas methanation is
inhibited, and so the only by-product whose formation increases is
carbon dioxide, which will be removed in the reactor configurations
with CO2 sorption, while carbon monoxide, methane and coke are re-
duced (Figures SI.11 and SI.12).
Fig. 14a and b represent the comparison between the different types
of reactor at optimum WFR for the SEMR. In that figures are also de-
noted the improvement percentage of the SEMR regarding to the other
types of reactor. It is again observed the same performance trends than
those of the comparison at optimal temperature conditions, namely:
SEMR > SER > MR > TR.
The total pressure favours the CO2 sorption capacity of the sorbent
and the driving force for H2 permeation through a H2 perm-selective
membrane [34]. Therefore, when working with membranes it is not
realistic to expect to achieve hydrogen removal fractions as high as 0.8
at 1 bar; otherwise, a huge membrane area would be required (with the
Fig. 12. Comparison of hydrogen yield as a function of the reactor type for a) spruce bio-oil in TR, SER (SFR = 2), MR (fH2 = 0.8) and SEMR (SFR = 2, fH2 = 0.8) at
360 °C and b) for wheat bio-oil in TR, SER (SFR = 5), MR (fH2 = 0.8) and SEMR (SFR = 5, fH2 = 0.8) at 420 °C, in both cases at stoichiometric WFR and 1 bar.
193
Fuel 244 (2019) 184–195
inherent grow of cost). For this reason, for the SEMR the effect of the
pressure was assessed for the conditions in which these reactors showed
the highest hydrogen yields. The results obtained are presented in
Fig. 15a and b for bio-oil derived from pyrolysis of spruce and wheat,
respectively. Since the bio-oil conversion is complete and there is no
coke present, the variation of the yields of the products with the total
pressure is only ascribed to the methanation (the WGS reaction is not
affected by pressure changes). At low WFR, whatever the bio-oil used,
the pressure meaningfully affects the H2 yield. Nevertheless, the ne-
gative effect of pressure can be offset by the increase of WFR as it in-
hibits methanation, which leads to a more stable H2 yield as a function
of pressure. Therefore, at WFR of 6 for spruce and 10 for wheat, the H2
yield decreases 12% and 26% respectively when the total pressure is
increased from 1 bar to 8 bar. However, such decreases is only of 4%
and 6% at WFR of 8 and 14 for spruce and wheat, respectively.
4. Conclusions
An equilibrium thermodynamic analysis of the steam reforming
process was carried out for several pyrolysis bio-oils in order to access
the effects of different important operating parameters on the hydrogen
(and by-products) yield. This analysis was performed in different re-
actor types and the effect of the main operating conditions was assessed
as well.
In the case of the traditional reformer, temperature and water to
feed ratio (WFR) showed a positive effect on the production of hy-
drogen. However, the H2 yields observed by such traditional reactor
(TR) are still far from the maximum theoretical yields as considerable
by-products are formed. Compared to the TR, the in-situ CO2 removal
using calcium oxide as sorbent in a sorption-enhanced reactor (SER)
and the in-situ removal of H2 through a selective permeable membrane
(membrane reactor - MR) allowed to increase the hydrogen production
while also inhibiting the formation of carbon monoxide, methane and
coke. Both the MR and the SER allow to reach high hydrogen yields at
lower temperatures than those employed in the conventional steam
reforming reactor.
On the other hand, the sorption-enhanced membrane reactor
(SEMR) allows to attain the highest hydrogen yield, namely: 4.72 for
spruce (at 400° C, WFR = 6, SFR = 2, fH2 = 0.8 and 1 bar) and 11.62
for wheat (at 400° C, WFR = 10, SFR = 5, fH2 = 0.8 and 1 bar) derived
bio-oils. Therefore, this multifunctional reactor is the one that provides
the best hydrogen yield (even reaching, in certain cases, the maximum
theoretical value at not very severe operating conditions), from a
thermodynamic standpoint. Since pressures higher than atmospheric
are needed to obtain high hydrogen removal fractions in a membrane
reactor, and increase the CO2 breakthrough time in a SER, the effect of
pressure on the H2 yield was addressed for the SEMR. Results showed
that hydrogen yield decreased with pressure, however, this can be
offset by increasing the WFR.
M.A. Soria et al. Fuel 244 (2019) 184–195

Fig. 13. Comparison of hydrogen yield as a function of the water to feed molar ratio for a) spruce bio-oil in TR, SER (SFR = 2), MR(fH2 = 0.8) and SEMR (SFR = 2,
fH2 = 0.8) and b) for wheat bio-oil in TR, SER (SFR = 5), MR(fH2 = 0.8) and SEMR (SFR = 5, fH2 = 0.8) both at 400 °C and 1 bar.

Fig. 14. Comparison of hydrogen yield as a function of the reactor type for a) spruce bio-oil in TR, SER (SFR = 2), MR (fH2 = 0.8) and SEMR (SFR = 2, fH2 = 0.8) at
WFR = 6 and b) for wheat bio-oil in TR, SER (SFR = 5), MR (fH2 = 0.8) and SEMR (SFR = 5, fH2 = 0.8) at WFR = 10, in both cases at 400 °C, and 1 bar.

Fig. 15. Hydrogen yield as a function of pressure and water-to-feed ratio (WFR) in the SEMR for a) spruce bio-oil at 400 °C, fH2 = 0.8 and SFR = 2 and b) for wheat
bio-oil at 400 °C, fH2 = 0.8 and SFR = 5.

Acknowledgments Appendix A. Supplementary data

The authors are grateful to LEPABE – Laboratory for Process
Engineering, Environment, Biotechnology and Energy, and the project
NORTE‐01‐0145‐FEDER‐000005 – LEPABE-2-ECO-INNOVATION, sup-
ported by North Portugal Regional Operational Programme (NORTE
2020), under the Portugal 2020 Partnership Agreement, through the
European Regional Development Fund (ERDF), for his research grant.
M.A. Soria is grateful to the FCT for the postdoctoral grant (SFRH/BPD/
88444/2012), with financing from the European Social Fund (ESF) and
the Human Potential Operational Programme (POPH).
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2019.01.156.
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