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Sorption Enhanced Steam Reforming (SESR) A Direct Route Towards Efficient Hydrogen Production From Boimass-Derived Compounds
Sorption Enhanced Steam Reforming (SESR) A Direct Route Towards Efficient Hydrogen Production From Boimass-Derived Compounds
INTRODUCTION
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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.
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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
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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).
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Table 1.
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
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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SESR PROCESS
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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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.
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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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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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REFERENCES
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48 Martavaltzi CS, Pampaka EP, Korkakaki ES and Lemonidou AA,
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49 Peppley BA, Biomass for fuel cells: a technical and economic
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50 Abanades JC, Anthony EJ, Wang J and Oakey JE, Fluidized bed
combustion systems integrating CO2 capture with CaO. Environ
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51 Corella J, Toledo JM and Molina G, A review on dual fluidized-bed
biomass gasifiers. Ind Eng Chem Res 46:68316839 (2007).
52 Pfeifer C, Rauch R and Hofbauer H, In-bed catalytic tar reduction in
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43:16341640 (2004).
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