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 biomass-
derived 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 Figure 1 represents a simple scheme of direct pathway and

A sustainable energy system is a key element in a sustainable storable intermediate pathways from biomass to high purity
society where the energy supply should be secured with minimized hydrogen through the SESR technology. Bio-syngas, bio-oils
climate change effects. The full environmental benefit of hydrogen and sugars are storable intermediates for hydrogen production,
application can be achieved only if hydrogen is produced from which can be produced by three main platforms through
renewable sources such as water and biomass.1,2 Recently, thermochemical conversion of biomass, namely gasification,
sorption enhanced steam reforming (SESR) and gasification pyrolysis and hydrolysis.16 18 One of the notable advantages
(SESG) of biomass or biomass-derived oxygenates have gained of SESR technology over other hydrogen production technologies
increasing attention in seeking new technologies for sustainable is its great flexibility with respect to the feedstock in use.
production of hydrogen. The main principle of this technology is This could be in gas phase (e.g. biogas from waste anaerobic
the multifunctional reactor where reforming and/or gasification, digestion and bio-syngas from biomass gasification7 ), liquid
water-gas shift (WGS) and CO2 removal reactions are integrated phase (e.g. bioethanol,19,20 glycerol as by-product in the biodiesel
into one reactor over a mixture of reforming catalysts and production,18,21 bio-oils from biomass pyrolysis22 and aqueous
CO2 acceptors. The hydrogen yield and purity are expected to solutions of sugars23 ) and solid phase (e.g. raw lignocellulosic
be enhanced by shifting thermodynamic equilibrium towards wastes).8,9
hydrogen through in situ CO2 removal. In fact, SESR is not the Here, we summarize the recent progresses in the sorption
first to combine chemical reactions and separation of products enhanced steam reforming of biomass-derived compounds as
in a single unit. The first reference to hydrogen production using an emerging technology for sustainable hydrogen production.
the concept of sorption enhanced reactions can be dated to We will address important factors for production of high purity
1868.3 Later, in 1933 and 1963, Williams4 and Gorin and Retallick5 hydrogen by SESR of possible biomass-derived feedstocks, ther-
issued respective patents for applications of such a concept. This modynamic limitations, newly developed sorbents and catalysts.
concept was not further developed due to difficulty in process We will also outline process configurations and evaluations for
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 Correspondence to: De Chen, Department of Chemical engineering, University
case of biomass-based feedstocks used as hydrogen sources.7 11 of Science and Technology, Trondheim, Norway. E-mail: [email protected]
In addition, new progress in development of catalysts and CO2
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Department of Chemical engineering, University of Science and Technology,

acceptors has made the SESR process more attractive.12 15 Trondheim, Norway

J Chem Technol Biotechnol 2012; 87: 13671374 www.soci.org

c 2012 Society of Chemical Industry
 www.soci.org 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, de- MATERIALS

pending on the end-user requirements. Catalysts
Figure 3 shows a scheme of reaction pathways involved in the
conversion of oxygenate (ethylene glycol as a model compound).
THERMODYNAMIC ANALYSIS OF SESR Selective CC cleavage pathways lead to synthesis gas formation,
The multiple reactions involved in the SESR process have been while the CO bond activation leads to hydrocarbon formation.31
described in a recent review by Chen and He24 using a model The formed CO is converted either to CO2 by WGS reaction or
biomass compound (typically, oxygenated hydrocarbons). The to methane by methanation. In addition, CO bond activation
merits of coupling CO2 removal with steam reforming (SR) in in dehydration reaction results in formation of unsaturated
a single reactor for hydrogen generation have been extensively intermediates on the catalyst surface, which typically have
studied by means of thermodynamic analyses for methane.25 27 potential for coke formation through polymerization. Therefore,
The equilibrium compositions of product gas from SESR of the ideal catalysts for the SESR reactions of oxygenates should
more complex feedstocks have also been calculated on model have high activity of CC and CH bond cleavage but low
compounds such as ethanol,20 ethylene glycol,28 glycerol,18,21 activity for CO bond cleavage as well as high activity for high-
dextrose,24 soluble fraction from bio-oil,10,29 sorbitol,23 glucose23 temperature WGS reaction but low activity for methanation.24
and raw biomass.30 For all of these compounds, it has been In addition, the thermodynamic analysis suggests much lower
found that the integration of in situ CO2 removal from the reaction temperatures of SESR (480575 C) than the conventional
gas phase during the reforming or gasification reactions will SR (typically higher than 650 C) to obtain high conversions as a
provide a unique possibility to shift the equilibrium boundary benefit of the shift in equilibrium towards hydrogen production.
of the reforming and WGS reactions towards H2 production, Accordingly, even higher activity of CC and CH bonds cleavage
leading to significant enhancement in hydrogen production is required in order to promote the low temperature SR of
and purity. Figure 2 clearly displays the enhancement effect by oxygenates and hydrocarbons. Additionally, tar formation tends
comparing the product equilibrium concentrations from SR and to take place through pyrolysis of non-volatile highly oxygenated
SESR of different-sized chemicals (C1 C6 ) as a function of reaction feedstock.24 High activity of reforming catalysts is expected to
temperature. SR of methane produces higher H2 concentration effectively convert tars to syngas and to suppress char formation.18
than SR of oxygenates. In contrast, when a CO2 acceptor is Single metallic catalysts hardly match all the criteria required for
incorporated into the reaction system, oxygenates are able to the SESR catalyst and, therefore, bimetallic catalysts are preferred.
yield hydrogen at much higher concentrations than methane. A series of NiCo catalysts derived from hydrotalcite-like material
Hydrogen production tends to be more favored with oxygenates (HT) for SESR has been developed and tested in SESR of different
with large molecular size (Fig. 2). Regardless of the feedstock biomass-derived compounds, showing promising results with
chemical identities, a suitable SESR operating temperature window respect to H2 yield, selectivity and purity.7,9,18 20 Fig. 4 illustrates
is suggested between 480 and 575 C at atmospheric pressure, a typical evolution profile of the product gas composition in a
which is constrained by the equilibrium of carbonation reaction dry basis during SESR of ethanol over Ni/HT catalyst.20 Hydrogen
between CaO and CO2 . However, it is rationalized that the SESR production was enhanced with the integration of in situ CO2
operating window has a dependence on the CO2 acceptor applied removal during the pre-breakthrough period. As the acceptor
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in SESR. took up CO2 from the reforming reaction, the acceptor became

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Sorption enhanced steam reforming www.soci.org

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).

saturated and the conventional SR reaction was considered to take the risk of coke formation, allowing reforming reactions carried
place. Table 1 summarizes the experimental results from the SESR out at relatively low steam to carbon ratios.20
and SR of various biomass-derived compounds over a mixture It has recently been reported that almost pure hydrogen
of NiCo/HT catalyst and calcined dolomite as CO2 acceptors. (>99.9 vol%) with high yield (up to 90%) was produced by
A high purity of H2 (>99 vol%) with very low impurity of CO sorption enhanced catalytic steam gasification of raw solid
(about 0.010.1 vol%) was produced from high-diversity biomass- lignocellulosic biomass (chestnut wood sawdust).9 The process
derived compounds, such as solid wood biomass,9 bio-syngas integrates pyrolysis, steam reforming, water-gas shift (WGS)
from biomass gasification,7 sugars from hydrolysis of biomass,23 reaction and H2 separation by CO2 capture into a combined
pure glycerol18 and crude glycerol from a by-product of biodiesel downdraft flow fluidized bed and fixed bed reactor, where
production. Pd/CoNi catalyst and dolomite as CO2 acceptor were installed
Compared with fossil fuels, biomass-derived oxygenates are together. The hydrotalcite derived Pd/CoNi catalyst has shown
often characterized with a low thermal stability, having a strong a high activity in the cleavage of CC and CH bonds during the
tendency to decompose under SR conditions. In addition, they conversion of tars and hydrocarbons resulting from fast pyrolysis
usually have a low H/C ratio, indicating a high risk of coke formation. and catalytic steam gasification (CSG), as a result of which further
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Coupling in situ CO2 capture to SR reaction is found to decrease char formation is reduced. The catalyst, which does not require

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 www.soci.org 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
Figure 3. Reaction pathways and selectivity challenges for production of calcined dolomite and 2 g of catalyst (40Ni/HT).20
H2 from reactions of carbohydrates with water ( represents a surface
metal site).31

regeneration temperatures. However, limited kinetic of Li2 ZrO3

pre-reduction, has shown a good activity and stability after several at low CO2 partial pressure and stability of Na2 ZrO3 in the
reaction-regeneration cycles. presence of steam are the main obstacles for their application
in the SESR process.32,33 K2 CO3 -promoted hydrotalcite is able to
CO2 acceptors capture CO2 at a temperature of 300500 C, which has been
The selection of a proper CO2 acceptor has a great impact applied in low temperature (400 C) SESR of methane. The CO
on efficiency of a SESR process. There is a great amount concentration in the product gas can be lowered to ppm levels,
of published work on a diversity of CO2 acceptors, but only taking the thermodynamic benefits of sorption enhanced water-
few of them can be applied under severe conditions of gas shift (SEWGS) reaction at low temperatures.15 However, the
SESR process (high temperatures >400 C, and high steam inadequate capture capacity (ca 0.003 g CO2 g1 acceptor) is
partial pressures). High rates of carbonation and decarbonation a barrier to the application of hydrotalcite type acceptor in
reactions and good cyclic stability are characteristics of desirable the SESR process.34 On the other hand, CaO-based materials,
CO2 acceptors.12,14 The fuel conversion, CO2 capture, H2 yield which can be obtained from abundant natural resources (dolomite
and purity have been reported to have a strong non-linear and limestone), have fast kinetics and favorable thermodynamics
dependence on both CO2 capture capacity and kinetics.13 for removing CO2 from reforming atmosphere.26 Limestone has
Taking into account the above requirements for a CO2 acceptor, greater stoichiometric capacity than dolomite (0.79 and 0.46 g CO2
Li2 ZrO3 , Na2 ZrO3 , K2 CO3 -promoted hydrotalcite and CaO-based g1 acceptor, respectively), and a better resistance to attrition.35
materials are candidates for enhancing H2 production by catalytic However, dolomite has shown better multi-cycle performance
reforming or gasification reactions.14 Li2 ZrO3 and Na2 ZrO3 have than limestone.11,35 37 The multi-cycle carbonationcalcination
shown relatively high capture capacity, good stability and low performance of CaO-based sorbents has been studied extensively,

Table 1. Product gas composition during the SESR and SR of different biomass-derived products

Feedstock Syngas7 Ethanol20 Glycerol18 Crude glycerol Lignocellulosic sawdust9

T ( C) 575 575 575 550 650

P (atm) 1 1 1 1 1
Steam/C (mol/mol) 3 3 3 3 9.4
Catalyst 10Ni-30Co HT 20Ni-20Co HT 20Ni-20Co HT 20Ni-20Co HT 20Ni-20Co(1Pd) HT
H2 yield (%) 100 100.0 97.0 87.6 77.6
Gas Composition (%vol)
H2 97.1 98.8 99.2 99.7 99.0
SESR CH4 0.8 0.3 9.0 102 2.9 101 9.2 102
CO 1.4 0.3 4.0 102 1.2 102 9.3 101
CO2 0.7 0.6 0.6 1.6 102 0.0
H2 yield (%) 87.0 80.0 60.0 77.4
Gas Composition (%vol)
H2 64.3 71.5 68.5 55.9 67.7
CH4 0.9 2.4 4.9 8.7 0.0
SR CO 12.3 7.7 4 102 3.8 2.9
CO2 22.5 18.4 26.6 31.6 29.4
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
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per mol of biomass fuel.

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Sorption enhanced steam reforming www.soci.org

and the results revealed a significant decrease in pore volume and acceptor regeneration strategy is to couple the endothermic
surface area as the main cause of capacity degradation.11,37 40 The decarbonation of acceptors and the exothermic oxidation of non-
presence of steam significantly enhanced the degradation of the converted methane and hydrogen from the fuel cell in the power
acceptor cyclic capacity.20,41 Therefore, it is strongly recommended generation system. If required, additional biogas is fed to the
that the kinetics and stability of CO2 acceptors should be studied at regenerator for supplying extra heat. About 34% heat content
more relevant SESR conditions, namely in the presence of steam. (HHV) can be converted to electricity. If the additional heat
Nevertheless, the stability of CO2 acceptors in the presence of generated in the form of steam is utilized, the overall efficiency of
steam remains a challenge.14 the power plant can be improved up to 7580%.
Recently, some efforts have been made to overcome the Most of model systems and experimental studies on SESR
loss in capacity of natural CaO-based acceptors by using are conducted with fixed-bed reactors. Fluidized-bed reactors
mild decarbonation conditions42 or acceptor hydration at mild are usually used in processes in which catalysts need to be
temperatures.43 On the other hand, new synthetic nanomaterials continuously regenerated.50 A dual fluidized-bed reactor has been
have been developed to improve hydrothermal stability of CO2 designed particularly for a SESR system which requires two distinct
acceptors, such as synthetic mesoporous CaO44 and CaO-based operating conditions for reforming reaction of hydrocarbons and
materials doped with inert but stable oxides (e.g. CeO, ZrO2 , Al2 O3 decarbonation of the saturated CO2 acceptor.51,52
or TiO2 ).45,46 The synthetic CaO-based acceptors with large pores,
small CaO crystals and surface dopants, such as CaOAl2 O3 and Process evaluation
CaOCeZrOx mixed oxides, are found to have good kinetics and The economical feasibility of a SESR process from biomass
cyclic stability in ex situ CO2 capture,46,47 as well as in situ CO2 resources relies on many factors. Hydrogen productivity and
capture during SESR of methane.46,48 purity are determined by many independent and dependent
variables in a SESR process. Typically, independent variables can
be reaction temperature, pressure, catalyst composition, CO2
SESR PROCESS acceptor composition, steam to carbon ratio, the mass ratio of
The energy efficiency of the production of pure hydrogen by SESR catalyst to CO2 acceptor, reactor configuration, residence time,
of methane has been analyzed, and this is similar to the SESR flow geometry, sweep gas in use, etc. In addition, some dependent
processes of biomass-derived oxygenates.26 The CO2 capture variables are also important in assessing and designing a SESR
by conventional amine absorption and hydrogen separation by process, for instance, CO concentration, fuel conversion, reactor
pressure swing lower the energy efficiency from 86% to 71%, size, reactor weight, pressure drop, catalyst life time, catalyst
resulting in an energy efficiency penalty of about 15%. The SESR of stability, CO2 acceptor life time, CO2 acceptor stability, mass and
methane using CaO-based CO2 acceptors results in a much lower energy integration, etc.
energy efficiency penalty of 4%.26 It suggests a very promising The economic feasibility of SESR of biomass-derived compounds
process for H2 production with CO2 capture, which yields the is analyzed using crude glycerol as a model feedstock. Crude glyc-
smallest energy penalty for the CO2 capture. The theoretical erol is a by-product of the transesterification process for biodiesel
maximum energy efficiency has also been analyzed in the SESR production, typically containing approximately 5060 wt% glyc-
of glycerol as a function of steam to carbon ratio, temperature erol and 2025 wt% methanol and the rest is wastewater (a
and pressure.18 The maximum energy efficiency of 8084% can mixture of water, leftover methyl esters, and lipids).53 Dou et al.
be achieved at a steam to carbon ratio of 3. have reported that SESR of crude glycerol (7090 wt% glycerol)
A new concept of SESR of bio-oil integrating with fuel cell for yielded hydrogen with purity fairly close to that from highly-
power generation has recently been evaluated, showing a high purified glycerol (100%).54 We have recently demonstrated that
energy efficiency.29 The technical feasibility of biomass-fuelled almost pure H2 with a yield of 88% was produced by SESR of crude
fuel cells has been proven by various systems that have already glycerol, in a mixture of NiCo catalysts and calcined dolomite as
been installed and tested.49 Different types and sizes of fuel CO2 acceptor. A conceptual SESR process for hydrogen produc-
cells such as a 200 kW phosphoric acid fuel cell (PAFC) system tion (9500 ton year1 ) from crude glycerol was designed based
in New York, a 500 kW molten carbonate system in California on the experimental results, containing two sequential dual flu-
have been successfully demonstrated using biogas for hydrogen idized reactors, Reactor-1 and -2 (Fig. 5). Each one is composed
production. These demonstration projects have overcome many of a reformer and a regenerator as the side body of the reactor.
technical problems, including reforming or gasification processes Water and crude glycerol at molar ratio of 4 after pre-heating are
for hydrogen production and gas cleaning, and have successfully fed into Reactor-1. Glycerol reforming occurs at ca 580 C and
demonstrated the technical feasibility of using fuel cells on biogas 1 atm. The gas effluent from the reformer of Reactor-1 contains
fuels. However, the SESR of biogas can integrate conventional dominantly H2 (86.8 vol%) and steam (12.8 vol%) as well as mi-
steam reforming, high and low temperature water-gas shift nor CO (0.3 vol%), CO2 (0.2 vol%) and trace of CH4 . This reactor
reaction and a burner for H2 production, which significantly requires reforming catalysts having a high activity of CC bond
simplifies the process. More importantly, the fuel cells will activation. The effluent gases are directly fed into Reactor-2 in
significantly benefit from the high concentration of H2 generated which hydrogen content is enriched by sorption enhanced water-
by SESR, in terms of the efficiency and the size of the fuel cell gas shift (SEWGS) reactions at a relatively low temperature of
stacks. In the new conceptual process,29 bio-oil and biogas are 400 C. The combined factors such as highly active WGS catalysts,
fed together into a reactor in which CO2 acceptor and steam in-situ CO2 removal and low operating temperature lead to efflu-
reforming catalyst are installed. The ratio of bio-oil to biogas flow ent gases containing only H2 and steam (the CH4 , CO and CO2
rate is adjusted to achieve autothermal reforming in which the contents are less than 10 ppm). The very pure H2 (99.999 vol%)
exothermic reaction of CO2 in biogas with CO2 acceptor generates is obtained by separating hydrogen and steam in a condenser.
sufficient heat for maintaining endothermic reforming reaction The main advantage of the two-reactor design is that each reac-
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of hydrocarbons and oxygenates in bio-oil and biogas. The CO2 tor can be separately optimized to reduce the reactor size and

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 www.soci.org 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.

achieve high purity of hydrogen. The CO2 acceptors are circu- crude glycerol market price is in the range of 2546 $ ton1 , which
lated into the regenerator. Meanwhile, methane oxidation in the is much lower than refined glycerol (55 to 78 $ ton1 ).56 The results
regenerators supplies heat for the decarbonation reaction of the reveal that the economical benefits of hydrogen production from
acceptor. The CO2 -rich streams are released from the top of the biomass by the SESR technology depend significantly on the price
regenerators. of the biomass or biomass-derived compounds, as well as the
The economic study of hydrogen production using the above hydrogen purity and pressure.
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, CONCLUSIONS
pressure of hydrogen after compressor, etc. The process shows a
The sorption enhanced steam reforming process is considered an
potential to meet the DOE target of hydrogen cost (3.8 $/kg).55
efficient alternative route for the production of renewable H2 from
The hydrogen price is sensitive to the hydrogen pressure, as
biomass that has a strong potential for commercialization due to
shown in Fig. 6(A). The application in transportation section such
the important advances in the development of new reforming
as hydrogen filling station or transportation of liquid hydrogen,
catalysts and CO2 acceptors in recent years. Diverse biomass-
high pressure hydrogen (about 350 atm) by an expensive 4-
derived compounds have been promisingly demonstrated to
stage compressing process is required, which results in 30%
produce high purity and yield of hydrogen. SESR of biomass-
extra cost. Normally, the hydrogen pressure from the compressor
derived compounds becomes highly attractive for the biomass
depends on the requirements of downstream processes. Hydrogen
conversion to fuels due to the advantages of the simplicity of the
at low pressures can be obtained at low cost and have more
process, flexibility in feedstock, high hydrogen yield, purity and
economical applications. For instance, low pressure hydrogen can
energy efficiency, and low cost.
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 ACKNOWLEDGEMENTS
of hydrogen production. Figure 6(B) presents the variation of J. Fermoso acknowledges funding from Ministry of Education of
hydrogen cost as a function of the crude glycerol price by using Spain, through the National Mobility Program of Human Resources
the above designed conceptual process. Crude glycerol price at of the National Plan of I-D+i 20082011. The authors thank
10 $ ton1 is taken as baseline. The hydrogen cost increases by A. Berss, S. Johansen, C. Lesaint and I. Nesje for their contribution
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25% as glycerol is priced from 10 $ ton1 to 60 $ ton1 . Up to date, to the economical analysis of SESR of crude glycerol.

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