Emerging Technologies

Received: 24 February 2012

Revised: 26 April 2012

Accepted: 27 April 2012

Published online in Wiley Online Library: 15 June 2012

(wileyonlinelibrary.com) DOI 10.1002/jctb.3857

Sorption enhanced steam reforming (SESR):

a direct route towards efficient hydrogen
production from biomass-derived compounds
Javier Fermoso, Li He and De Chen
Abstract
OVERVIEW: Efficient conversion of biomass to hydrogen is imperative in order to realize sustainable hydrogen production.
Sorption enhanced steam reforming (SESR) is an emerging technology to produce high purity hydrogen directly from biomassderived oxygenates, by integrating steam reforming, water-gas shift and CO2 separation in one-stage. Factors such as simplicity
of the hydrogen production process, flexibility in feedstock, high hydrogen yield and low cost, make the SESR process attractive
for biomass conversion to fuels.
IMPACT: Recent work has demonstrated that SESR of biomass-derived oxygenates has greater potential than conventional
steam reforming for hydrogen production. The flexibility of SESR processes resides in the diversity of feedstocks, which can be
gases (e.g. biogas, syngas from biomass gasification), liquids (e.g. bioethanol, glycerol, sugars or liquid wastes from biomass
processing) and solids (e.g. lignocellulosic biomass). SESR can be developed to realize a simple biomass conversion process but
with high energy efficiency.
APPLICATIONS: Hydrogen production by SESR of biomass-derived compounds can be integrated into existing oil refineries and
bio-refineries for hydrotreating processing, making the production of gasoline and diesel greener. Moreover, hydrogen from
SESR can be directly fed to fuel cells for power generation.
c 2012 Society of Chemical Industry

INTRODUCTION

J Chem Technol Biotechnol 2012; 87: 13671374

Figure 1 represents a simple scheme of direct pathway and

storable intermediate pathways from biomass to high purity
hydrogen through the SESR technology. Bio-syngas, bio-oils
and sugars are storable intermediates for hydrogen production,
which can be produced by three main platforms through
thermochemical conversion of biomass, namely gasification,
pyrolysis and hydrolysis.16 18 One of the notable advantages
of SESR technology over other hydrogen production technologies
is its great flexibility with respect to the feedstock in use.
This could be in gas phase (e.g. biogas from waste anaerobic
digestion and bio-syngas from biomass gasification7 ), liquid
phase (e.g. bioethanol,19,20 glycerol as by-product in the biodiesel
production,18,21 bio-oils from biomass pyrolysis22 and aqueous
solutions of sugars23 ) and solid phase (e.g. raw lignocellulosic
wastes).8,9
Here, we summarize the recent progresses in the sorption
enhanced steam reforming of biomass-derived compounds as
an emerging technology for sustainable hydrogen production.
We will address important factors for production of high purity
hydrogen by SESR of possible biomass-derived feedstocks, thermodynamic limitations, newly developed sorbents and catalysts.
We will also outline process configurations and evaluations for

Correspondence to: De Chen, Department of Chemical engineering, University

of Science and Technology, Trondheim, Norway. E-mail: chen@nt.ntnu.no
Department of Chemical engineering, University of Science and Technology,
Trondheim, Norway

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1367

A sustainable energy system is a key element in a sustainable

society where the energy supply should be secured with minimized
climate change effects. The full environmental benefit of hydrogen
application can be achieved only if hydrogen is produced from
renewable sources such as water and biomass.1,2 Recently,
sorption enhanced steam reforming (SESR) and gasification
(SESG) of biomass or biomass-derived oxygenates have gained
increasing attention in seeking new technologies for sustainable
production of hydrogen. The main principle of this technology is
the multifunctional reactor where reforming and/or gasification,
water-gas shift (WGS) and CO2 removal reactions are integrated
into one reactor over a mixture of reforming catalysts and
CO2 acceptors. The hydrogen yield and purity are expected to
be enhanced by shifting thermodynamic equilibrium towards
hydrogen through in situ CO2 removal. In fact, SESR is not the
first to combine chemical reactions and separation of products
in a single unit. The first reference to hydrogen production using
the concept of sorption enhanced reactions can be dated to
1868.3 Later, in 1933 and 1963, Williams4 and Gorin and Retallick5
issued respective patents for applications of such a concept. This
concept was not further developed due to difficulty in process
operation and low cost of available utility energy at that time.6
However, it has recently recaptured renewed interests in searching
for an efficient method of hydrogen production, particularly in the
case of biomass-based feedstocks used as hydrogen sources.7 11
In addition, new progress in development of catalysts and CO2
acceptors has made the SESR process more attractive.12 15

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J Fermoso, L He, D Chen

Figure 1. Sustainable routes for hydrogen production from lignocellulosic biomass or biomass-derived products by SESR process.

efficient hydrogen production and potential applications, depending on the end-user requirements.

THERMODYNAMIC ANALYSIS OF SESR

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The multiple reactions involved in the SESR process have been

described in a recent review by Chen and He24 using a model
biomass compound (typically, oxygenated hydrocarbons). The
merits of coupling CO2 removal with steam reforming (SR) in
a single reactor for hydrogen generation have been extensively
studied by means of thermodynamic analyses for methane.25 27
The equilibrium compositions of product gas from SESR of
more complex feedstocks have also been calculated on model
compounds such as ethanol,20 ethylene glycol,28 glycerol,18,21
dextrose,24 soluble fraction from bio-oil,10,29 sorbitol,23 glucose23
and raw biomass.30 For all of these compounds, it has been
found that the integration of in situ CO2 removal from the
gas phase during the reforming or gasification reactions will
provide a unique possibility to shift the equilibrium boundary
of the reforming and WGS reactions towards H2 production,
leading to significant enhancement in hydrogen production
and purity. Figure 2 clearly displays the enhancement effect by
comparing the product equilibrium concentrations from SR and
SESR of different-sized chemicals (C1 C6 ) as a function of reaction
temperature. SR of methane produces higher H2 concentration
than SR of oxygenates. In contrast, when a CO2 acceptor is
incorporated into the reaction system, oxygenates are able to
yield hydrogen at much higher concentrations than methane.
Hydrogen production tends to be more favored with oxygenates
with large molecular size (Fig. 2). Regardless of the feedstock
chemical identities, a suitable SESR operating temperature window
is suggested between 480 and 575 C at atmospheric pressure,
which is constrained by the equilibrium of carbonation reaction
between CaO and CO2 . However, it is rationalized that the SESR
operating window has a dependence on the CO2 acceptor applied
in SESR.

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MATERIALS
Catalysts
Figure 3 shows a scheme of reaction pathways involved in the
conversion of oxygenate (ethylene glycol as a model compound).
Selective CC cleavage pathways lead to synthesis gas formation,
while the CO bond activation leads to hydrocarbon formation.31
The formed CO is converted either to CO2 by WGS reaction or
to methane by methanation. In addition, CO bond activation
in dehydration reaction results in formation of unsaturated
intermediates on the catalyst surface, which typically have
potential for coke formation through polymerization. Therefore,
the ideal catalysts for the SESR reactions of oxygenates should
have high activity of CC and CH bond cleavage but low
activity for CO bond cleavage as well as high activity for hightemperature WGS reaction but low activity for methanation.24
In addition, the thermodynamic analysis suggests much lower
reaction temperatures of SESR (480575 C) than the conventional
SR (typically higher than 650 C) to obtain high conversions as a
benefit of the shift in equilibrium towards hydrogen production.
Accordingly, even higher activity of CC and CH bonds cleavage
is required in order to promote the low temperature SR of
oxygenates and hydrocarbons. Additionally, tar formation tends
to take place through pyrolysis of non-volatile highly oxygenated
feedstock.24 High activity of reforming catalysts is expected to
effectively convert tars to syngas and to suppress char formation.18
Single metallic catalysts hardly match all the criteria required for
the SESR catalyst and, therefore, bimetallic catalysts are preferred.
A series of NiCo catalysts derived from hydrotalcite-like material
(HT) for SESR has been developed and tested in SESR of different
biomass-derived compounds, showing promising results with
respect to H2 yield, selectivity and purity.7,9,18 20 Fig. 4 illustrates
a typical evolution profile of the product gas composition in a
dry basis during SESR of ethanol over Ni/HT catalyst.20 Hydrogen
production was enhanced with the integration of in situ CO2
removal during the pre-breakthrough period. As the acceptor
took up CO2 from the reforming reaction, the acceptor became

c 2012 Society of Chemical Industry

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Figure 2. Product equilibrium concentrations (dry basis) as a function of temperature and fuel for SR (continuous lines) and SESR with CaO as CO2 acceptor
(dashed lines). Equilibrium conditions: P = 1 atm, steam/C = 2. Colours: CH4 (black), C2 H6 O (red), C3 H8 O3 (green), C6 H14 O6 (blue) and C6 H12 O6 (grey).

J Chem Technol Biotechnol 2012; 87: 13671374

the risk of coke formation, allowing reforming reactions carried

out at relatively low steam to carbon ratios.20
It has recently been reported that almost pure hydrogen
(>99.9 vol%) with high yield (up to 90%) was produced by
sorption enhanced catalytic steam gasification of raw solid
lignocellulosic biomass (chestnut wood sawdust).9 The process
integrates pyrolysis, steam reforming, water-gas shift (WGS)
reaction and H2 separation by CO2 capture into a combined
downdraft flow fluidized bed and fixed bed reactor, where
Pd/CoNi catalyst and dolomite as CO2 acceptor were installed
together. The hydrotalcite derived Pd/CoNi catalyst has shown
a high activity in the cleavage of CC and CH bonds during the
conversion of tars and hydrocarbons resulting from fast pyrolysis
and catalytic steam gasification (CSG), as a result of which further
char formation is reduced. The catalyst, which does not require

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1369

saturated and the conventional SR reaction was considered to take

place. Table 1 summarizes the experimental results from the SESR
and SR of various biomass-derived compounds over a mixture
of NiCo/HT catalyst and calcined dolomite as CO2 acceptors.
A high purity of H2 (>99 vol%) with very low impurity of CO
(about 0.010.1 vol%) was produced from high-diversity biomassderived compounds, such as solid wood biomass,9 bio-syngas
from biomass gasification,7 sugars from hydrolysis of biomass,23
pure glycerol18 and crude glycerol from a by-product of biodiesel
production.
Compared with fossil fuels, biomass-derived oxygenates are
often characterized with a low thermal stability, having a strong
tendency to decompose under SR conditions. In addition, they
usually have a low H/C ratio, indicating a high risk of coke formation.
Coupling in situ CO2 capture to SR reaction is found to decrease

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Figure 3. Reaction pathways and selectivity challenges for production of

H2 from reactions of carbohydrates with water ( represents a surface
metal site).31

pre-reduction, has shown a good activity and stability after several

reaction-regeneration cycles.
CO2 acceptors
The selection of a proper CO2 acceptor has a great impact
on efficiency of a SESR process. There is a great amount
of published work on a diversity of CO2 acceptors, but only
few of them can be applied under severe conditions of
SESR process (high temperatures >400 C, and high steam
partial pressures). High rates of carbonation and decarbonation
reactions and good cyclic stability are characteristics of desirable
CO2 acceptors.12,14 The fuel conversion, CO2 capture, H2 yield
and purity have been reported to have a strong non-linear
dependence on both CO2 capture capacity and kinetics.13
Taking into account the above requirements for a CO2 acceptor,
Li2 ZrO3 , Na2 ZrO3 , K2 CO3 -promoted hydrotalcite and CaO-based
materials are candidates for enhancing H2 production by catalytic
reforming or gasification reactions.14 Li2 ZrO3 and Na2 ZrO3 have
shown relatively high capture capacity, good stability and low

Table 1.

J Fermoso, L He, D Chen

Figure 4. Evolution with time of the product gas composition (dry basis)
during the course of the SESR of ethanol. The experimental conditions
were temperature 550 C, atmospheric pressure, steam/ethanol = 6 and
WHSV of 0.85 gEtOH .(gcat h)1 . The catalyst bed was composed by 10 g of
calcined dolomite and 2 g of catalyst (40Ni/HT).20

regeneration temperatures. However, limited kinetic of Li2 ZrO3

at low CO2 partial pressure and stability of Na2 ZrO3 in the
presence of steam are the main obstacles for their application
in the SESR process.32,33 K2 CO3 -promoted hydrotalcite is able to
capture CO2 at a temperature of 300500 C, which has been
applied in low temperature (400 C) SESR of methane. The CO
concentration in the product gas can be lowered to ppm levels,
taking the thermodynamic benefits of sorption enhanced watergas shift (SEWGS) reaction at low temperatures.15 However, the
inadequate capture capacity (ca 0.003 g CO2 g1 acceptor) is
a barrier to the application of hydrotalcite type acceptor in
the SESR process.34 On the other hand, CaO-based materials,
which can be obtained from abundant natural resources (dolomite
and limestone), have fast kinetics and favorable thermodynamics
for removing CO2 from reforming atmosphere.26 Limestone has
greater stoichiometric capacity than dolomite (0.79 and 0.46 g CO2
g1 acceptor, respectively), and a better resistance to attrition.35
However, dolomite has shown better multi-cycle performance
than limestone.11,35 37 The multi-cycle carbonationcalcination
performance of CaO-based sorbents has been studied extensively,

Product gas composition during the SESR and SR of different biomass-derived products
Syngas7

Ethanol20

T ( C)
575
P (atm)
1
Steam/C (mol/mol)
3
Catalyst
10Ni-30Co HT
H2 yield (%)
100
Gas Composition (%vol)
H2
97.1
SESR
CH4
0.8
CO
1.4
CO2
0.7
H2 yield (%)
Gas Composition (%vol)
H2
64.3
CH4
0.9
SR
CO
12.3
CO2
22.5

575
1
3
20Ni-20Co HT
100.0

Feedstock

Glycerol18

Crude glycerol

Lignocellulosic sawdust9

575
1
3
20Ni-20Co HT
97.0

550
1
3
20Ni-20Co HT
87.6

650
1
9.4
20Ni-20Co(1Pd) HT
77.6

98.8
0.3
0.3
0.6
87.0

99.2
9.0 102
4.0 102
0.6
80.0

99.7
2.9 101
1.2 102
1.6 102
60.0

99.0
9.2 102
9.3 101
0.0
77.4

71.5
2.4
7.7
18.4

68.5
4.9
4 102
26.6

55.9
8.7
3.8
31.6

67.7
0.0
2.9
29.4

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H2 yield (% mol): [number of moles of H2 in the product gas/H2 stoich moles of biomass fuel fed] 100 H2 stoich: stoichiometrically moles of H2
per mol of biomass fuel.

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and the results revealed a significant decrease in pore volume and

surface area as the main cause of capacity degradation.11,37 40 The
presence of steam significantly enhanced the degradation of the
acceptor cyclic capacity.20,41 Therefore, it is strongly recommended
that the kinetics and stability of CO2 acceptors should be studied at
more relevant SESR conditions, namely in the presence of steam.
Nevertheless, the stability of CO2 acceptors in the presence of
steam remains a challenge.14
Recently, some efforts have been made to overcome the
loss in capacity of natural CaO-based acceptors by using
mild decarbonation conditions42 or acceptor hydration at mild
temperatures.43 On the other hand, new synthetic nanomaterials
have been developed to improve hydrothermal stability of CO2
acceptors, such as synthetic mesoporous CaO44 and CaO-based
materials doped with inert but stable oxides (e.g. CeO, ZrO2 , Al2 O3
or TiO2 ).45,46 The synthetic CaO-based acceptors with large pores,
small CaO crystals and surface dopants, such as CaOAl2 O3 and
CaOCeZrOx mixed oxides, are found to have good kinetics and
cyclic stability in ex situ CO2 capture,46,47 as well as in situ CO2
capture during SESR of methane.46,48

SESR PROCESS

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Process evaluation
The economical feasibility of a SESR process from biomass
resources relies on many factors. Hydrogen productivity and
purity are determined by many independent and dependent
variables in a SESR process. Typically, independent variables can
be reaction temperature, pressure, catalyst composition, CO2
acceptor composition, steam to carbon ratio, the mass ratio of
catalyst to CO2 acceptor, reactor configuration, residence time,
flow geometry, sweep gas in use, etc. In addition, some dependent
variables are also important in assessing and designing a SESR
process, for instance, CO concentration, fuel conversion, reactor
size, reactor weight, pressure drop, catalyst life time, catalyst
stability, CO2 acceptor life time, CO2 acceptor stability, mass and
energy integration, etc.
The economic feasibility of SESR of biomass-derived compounds
is analyzed using crude glycerol as a model feedstock. Crude glycerol is a by-product of the transesterification process for biodiesel
production, typically containing approximately 5060 wt% glycerol and 2025 wt% methanol and the rest is wastewater (a
mixture of water, leftover methyl esters, and lipids).53 Dou et al.
have reported that SESR of crude glycerol (7090 wt% glycerol)
yielded hydrogen with purity fairly close to that from highlypurified glycerol (100%).54 We have recently demonstrated that
almost pure H2 with a yield of 88% was produced by SESR of crude
glycerol, in a mixture of NiCo catalysts and calcined dolomite as
CO2 acceptor. A conceptual SESR process for hydrogen production (9500 ton year1 ) from crude glycerol was designed based
on the experimental results, containing two sequential dual fluidized reactors, Reactor-1 and -2 (Fig. 5). Each one is composed
of a reformer and a regenerator as the side body of the reactor.
Water and crude glycerol at molar ratio of 4 after pre-heating are
fed into Reactor-1. Glycerol reforming occurs at ca 580 C and
1 atm. The gas effluent from the reformer of Reactor-1 contains
dominantly H2 (86.8 vol%) and steam (12.8 vol%) as well as minor CO (0.3 vol%), CO2 (0.2 vol%) and trace of CH4 . This reactor
requires reforming catalysts having a high activity of CC bond
activation. The effluent gases are directly fed into Reactor-2 in
which hydrogen content is enriched by sorption enhanced watergas shift (SEWGS) reactions at a relatively low temperature of
400 C. The combined factors such as highly active WGS catalysts,
in-situ CO2 removal and low operating temperature lead to effluent gases containing only H2 and steam (the CH4 , CO and CO2
contents are less than 10 ppm). The very pure H2 (99.999 vol%)
is obtained by separating hydrogen and steam in a condenser.
The main advantage of the two-reactor design is that each reactor can be separately optimized to reduce the reactor size and

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The energy efficiency of the production of pure hydrogen by SESR

of methane has been analyzed, and this is similar to the SESR
processes of biomass-derived oxygenates.26 The CO2 capture
by conventional amine absorption and hydrogen separation by
pressure swing lower the energy efficiency from 86% to 71%,
resulting in an energy efficiency penalty of about 15%. The SESR of
methane using CaO-based CO2 acceptors results in a much lower
energy efficiency penalty of 4%.26 It suggests a very promising
process for H2 production with CO2 capture, which yields the
smallest energy penalty for the CO2 capture. The theoretical
maximum energy efficiency has also been analyzed in the SESR
of glycerol as a function of steam to carbon ratio, temperature
and pressure.18 The maximum energy efficiency of 8084% can
be achieved at a steam to carbon ratio of 3.
A new concept of SESR of bio-oil integrating with fuel cell for
power generation has recently been evaluated, showing a high
energy efficiency.29 The technical feasibility of biomass-fuelled
fuel cells has been proven by various systems that have already
been installed and tested.49 Different types and sizes of fuel
cells such as a 200 kW phosphoric acid fuel cell (PAFC) system
in New York, a 500 kW molten carbonate system in California
have been successfully demonstrated using biogas for hydrogen
production. These demonstration projects have overcome many
technical problems, including reforming or gasification processes
for hydrogen production and gas cleaning, and have successfully
demonstrated the technical feasibility of using fuel cells on biogas
fuels. However, the SESR of biogas can integrate conventional
steam reforming, high and low temperature water-gas shift
reaction and a burner for H2 production, which significantly
simplifies the process. More importantly, the fuel cells will
significantly benefit from the high concentration of H2 generated
by SESR, in terms of the efficiency and the size of the fuel cell
stacks. In the new conceptual process,29 bio-oil and biogas are
fed together into a reactor in which CO2 acceptor and steam
reforming catalyst are installed. The ratio of bio-oil to biogas flow
rate is adjusted to achieve autothermal reforming in which the
exothermic reaction of CO2 in biogas with CO2 acceptor generates
sufficient heat for maintaining endothermic reforming reaction
of hydrocarbons and oxygenates in bio-oil and biogas. The CO2

acceptor regeneration strategy is to couple the endothermic

decarbonation of acceptors and the exothermic oxidation of nonconverted methane and hydrogen from the fuel cell in the power
generation system. If required, additional biogas is fed to the
regenerator for supplying extra heat. About 34% heat content
(HHV) can be converted to electricity. If the additional heat
generated in the form of steam is utilized, the overall efficiency of
the power plant can be improved up to 7580%.
Most of model systems and experimental studies on SESR
are conducted with fixed-bed reactors. Fluidized-bed reactors
are usually used in processes in which catalysts need to be
continuously regenerated.50 A dual fluidized-bed reactor has been
designed particularly for a SESR system which requires two distinct
operating conditions for reforming reaction of hydrocarbons and
decarbonation of the saturated CO2 acceptor.51,52

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J Fermoso, L He, D Chen

Figure 5. Scheme of a conceptual SEHP process of glycerol.

Figure 6. Variation of hydrogen cost as a function of the final pressure in the compressor (A), being the hydrogen cost without compressing used as
reference; and the hydrogen cost as a function of glycerol price (B), being a glycerol price of 10 $/ton taken as reference.

1372

achieve high purity of hydrogen. The CO2 acceptors are circulated into the regenerator. Meanwhile, methane oxidation in the
regenerators supplies heat for the decarbonation reaction of the
acceptor. The CO2 -rich streams are released from the top of the
regenerators.
The economic study of hydrogen production using the above
process covers the capital and operating costs. The estimated cost
of hydrogen is around 34.5 $/kg, varying with many factors,
such as natural gas price (or methane price), crude glycerol price,
pressure of hydrogen after compressor, etc. The process shows a
potential to meet the DOE target of hydrogen cost (3.8 $/kg).55
The hydrogen price is sensitive to the hydrogen pressure, as
shown in Fig. 6(A). The application in transportation section such
as hydrogen filling station or transportation of liquid hydrogen,
high pressure hydrogen (about 350 atm) by an expensive 4stage compressing process is required, which results in 30%
extra cost. Normally, the hydrogen pressure from the compressor
depends on the requirements of downstream processes. Hydrogen
at low pressures can be obtained at low cost and have more
economical applications. For instance, low pressure hydrogen can
be directly consumed by fuel cells for stationary power generation
or by hydrotreating processes in refineries of petroleum oil or
bio-oil.
Crude glycerol price is an important parameter for the cost
of hydrogen production. Figure 6(B) presents the variation of
hydrogen cost as a function of the crude glycerol price by using
the above designed conceptual process. Crude glycerol price at
10 $ ton1 is taken as baseline. The hydrogen cost increases by
25% as glycerol is priced from 10 $ ton1 to 60 $ ton1 . Up to date,

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crude glycerol market price is in the range of 2546 $ ton1 , which

is much lower than refined glycerol (55 to 78 $ ton1 ).56 The results
reveal that the economical benefits of hydrogen production from
biomass by the SESR technology depend significantly on the price
of the biomass or biomass-derived compounds, as well as the
hydrogen purity and pressure.

CONCLUSIONS
The sorption enhanced steam reforming process is considered an
efficient alternative route for the production of renewable H2 from
biomass that has a strong potential for commercialization due to
the important advances in the development of new reforming
catalysts and CO2 acceptors in recent years. Diverse biomassderived compounds have been promisingly demonstrated to
produce high purity and yield of hydrogen. SESR of biomassderived compounds becomes highly attractive for the biomass
conversion to fuels due to the advantages of the simplicity of the
process, flexibility in feedstock, high hydrogen yield, purity and
energy efficiency, and low cost.

ACKNOWLEDGEMENTS
J. Fermoso acknowledges funding from Ministry of Education of
Spain, through the National Mobility Program of Human Resources
of the National Plan of I-D+i 20082011. The authors thank
A. Berss, S. Johansen, C. Lesaint and I. Nesje for their contribution
to the economical analysis of SESR of crude glycerol.

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