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Sorption-Enhanced Steam Reforming of Methane in A Fluidized Bed Reactor With Dolomite As CO2CO2-Acceptor
Sorption-Enhanced Steam Reforming of Methane in A Fluidized Bed Reactor With Dolomite As CO2CO2-Acceptor
www.elsevier.com/locate/ces
Received 22 February 2005; received in revised form 15 August 2005; accepted 18 August 2005
Available online 28 September 2005
Abstract
An experimental investigation was conducted in which carbon dioxide was captured in order to shift the steam reforming equilibrium for
the production of hydrogen. An atmospheric-pressure bubbling uidized bed reactor (BFBR) of diameter 100 mm was operated cyclically
and batchwise, alternating between reforming/carbonation conditions and higher-temperature calcination conditions to regenerate the sorbent.
Equilibrium H2 -concentration of > 98% on a dry basis was reached at 600 C and 1.013 105 Pa, with dolomite as the CO2 -acceptor. The
hydrogen concentration remained at 9899 vol% (dry basis) after four reforming/calcination cycles. The total production time decreased with
an increasing number of cycles due to loss of CO2 -uptake capacity of the dolomite, but the reaction rate seemed unaffected. Variation of the
supercial gas velocity within the bubbling bed regime showed that the overall reaction rate was sufciently fast to reach equilibrium, making
bubbling bed reactors attractive for this process.
2005 Elsevier Ltd. All rights reserved.
Keywords: Hydrogen production; Sorption-enhancement; Fluidization; Catalysis; Reaction engineering; Separations
1. Introduction
Despite efforts to decrease energy consumption and greenhouse gas emissions, fossil fuels will continue to play an important role in the coming decades as developing nations increase their standard of living and major economies are slow
to adapt to change. Hydrogen is often referred to an important
potential energy carrier, but its advantages are unlikely to be
realized unless efcient means can be found to produce it with
reduced generation of CO2 .
Steam reforming of natural gas is the predominant production
route to hydrogen for large-scale industrial applications. For
methane the reactions are:
CH4 + H2 O CO + 3H2 ,
CO + H2 O CO2 + H2 ,
0
H298
= 206.2 kJ mol1 ,
(1)
0
H298
= 41.2 kJ mol1 ,
(2)
0
H298
= 165 kJ mol1 .
(3)
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membranes made of palladium or its alloys. A number of experimental and modelling studies have been carried out to prove
this concept (e.g. Adris et al., 1991, 1994; Chen et al., 2003;
Dogan et al., 2003).
Another way of shifting the equilibrium is by adding a CO2 acceptor to the reactor. Carbon dioxide is then converted to a
solid carbonate as soon as it is formed, shifting the reversible reforming and water-gas shift reactions beyond their conventional
thermodynamic limits. Regeneration of the sorbent releases relatively pure CO2 suitable for sequestration. Sorption-enhanced
steam reforming and the use of calcium based CO2 sorbents
been demonstrated in previous work (e.g. Balasubramanian et
al., 1999; Brun-Tsekhovoi et al., 1988; Han and Harrison, 1994;
Ortiz and Harrison, 2001; Silaban and Harrison, 1995; Silaban
et al., 1996). For example, Balasubramanian et al. (1999) added
a calcium-based CO2 acceptor to a commercial steam reforming catalyst producing > 95% H2 in a laboratory-scale xed
bed reactor. Han and Harrison (1994) used CaO to capture CO2 ,
overcoming the equilibrium limitation and achieving complete
CO conversion. In addition to reactions (1)(3) above, the noncatalytic highly exothermic carbonation reaction is included in
sorption-enhanced steam reforming, i.e.,
CaO(s) + CO2 (g) CaCO3 (s),
0
H298
= 178 kJ mol1 .
(4)
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catalyst and sorbent are mixed in the reformer, where sorptionenhanced steam reforming is performed. The product gas
from the reformer mainly consists of hydrogen and steam,
with minor quantities of CO, CO2 and unconverted methane.
Carbonated sorbent is transferred to the regenerator where heat
is supplied for the endothermic calcination reaction, either by
burning fuel in the regenerator or by indirect heating from an
external heat source. Heating of a dense bubbling bed could
also be accomplished by the insertion of heat transfer tubes
into the bed. Heat transfer would then occur between the uidized bed and the submerged tube surfaces. These tubes will
at the same time act as bafes reducing the gas bubble size,
enhancing interphase mass transfer. A portion of the hydrogen
produced in the reformer might be burned externally, supplying
heat to the tubes and eliminating the need for additional fossil
fuel. Indirect heating has the advantage of producing pure CO2
ready for sequestration. Direct burning of fuel inside the regenerator would be a more efcient way of supplying the heat, but
would require downstream separation of CO2 , unless hydrogen is burned with pure oxygen. To avoid separation processes
downstream, CO2 and/or H2 O can be used as the uidizing gas
in the regenerator. Calcium-based sorbents have the advantage
of being available at low cost, but cannot maintain the capture capacity upon multiple reforming/regeneration cycles. A
make-up stream of fresh sorbent must be included to maintain
capture capacity. This addition could be to the calciner, with
withdrawal in the reformer, as indicated in Fig. 2. Synthetic
sorbents, such as Li2 ZrO3 , have better multi-cycle stability,
but their cost would require them to sustain > 10, 000 cycles
to compete with natural sorbents (Abanades et al., 2004b).
Coupling of two bubbling beds would have the advantage of
low rates of attrition due to low gas and particle velocities,
and the relatively slow carbonation reaction rate will be facilitated in this ow regime. There is a lack of experimental
data on sorption-enhanced SMR in uidized beds in the open
literature.
In our work, described below, a bubbling uidized bed was
used for sequential sorption-enhanced steam reforming and regeneration of sorbent without separating the catalyst from the
1198
Table 1
Analysis of arctic dolomite SHB, data from Franzefoss AS
Species
CaO
MgO
SiO2
Al2 O3
Fe2 O3
Na2 O
TiO2
K2 O
Loss by ignition
Conc. [wt%]
32
20.3
0.7
0.1
0.1
0.003
0.005
0.004
46.3
temperatures to regenerate the dolomite. The experimental investigation can be divided into two parts: multi-cycle tests
and tests where the supercial gas velocity was varied. Fresh
dolomite and catalyst were used for the investigation of the effect of gas velocity in order to make the results for different
gas velocities comparable. The total initial bed mass was 3.1 kg
for all runs, with a catalyst-to-calcined dolomite mass ratio of
2.5. During the calcination stages of the multi-cycle tests, pure
N2 was fed to the reactor. No effort was made to separate the
catalyst from the dolomite between cycles. To ensure that the
catalyst was active, reduction of the catalyst was performed in
a H2 /N2 mixture at 650 C for 12 h prior to each reforming
period. This is equivalent to a continuous process where a portion of oxidized catalyst is returned to the reducing atmosphere
in the reformer, where it is reduced back to its active form. The
reforming reaction was always carried out at 600 C and ambient pressure. The experimental conditions for the BFBR unit
are summarized in Table 2.
3. Results and discussion
The reaction conditions corresponded to operation in the bubbling bed ow regime. With 0.9 kg calcined dolomite present,
the time required for complete carbonation of CaO in dolomite
1199
Table 2
BFBR experimental conditions
Parameters
Values
3.1
2.5
1300
0.3
150250
125300
600
0.032a , 0.064, 0.096
3
850
N2
of 170 min. After complete carbonation, the hydrogen concentration dropped to a value corresponding to equilibrium of
steam methane reforming of 73 vol% on a dry basis. At this
point, no CaO was left to react with CO2 , so that the reaction enhancement was lost. This period is often referred to as
the post-breakthrough period, and re-calcination has to be performed to reactivate the sorbent. Combining the strongly endothermic steam reforming with the exothermic carbonation
reaction makes the overall reforming reaction almost thermally
neutral. Carbonation of CaO (Eq. (4)) is a reversible reaction,
and temperature control is very important to prevent the undesired reverse calcination reaction in the reformer. Temperature
uniformity promoted by rapid mixing of the solids makes uidized beds well suited for processes where temperature uniformity is important. Two thermocouples were placed in the dense
bed zone, one (T1) just above the distributor and the other (T2)
0.19 m above. Typical temperature traces for one run are shown
in Fig. 5.
The difference in temperature between the two positions, T1
and T2, was nearly constant at 34 C during the entire course
of reaction, conrming the excellent temperature uniformity
of the bubbling uidized bed. Another feature observed from
Fig. 5 is the temperature drop after 150 min. This corresponds to the start of the breakthrough period also observed in
Fig. 4, caused by the diminishing exothermic carbonation
reaction, while the endothermic reforming reaction continues.
3.1. Multi-cycling
In order to make the process continuous, the sorbent must be
regenerated after completion of the carbonation stage. Several
previous groups (e.g. Li et al., 2005; Ortiz and Harrison, 2001;
Silaban and Harrison, 1995) have investigated the multi-cycle
performance of CaO-based sorbents. Abanades and Alvarez
(2003) included previously published multi-cycle results when
they reported an unavoidable decay in carbonation conversion
that was dependent on the number of cycles. Most of these
investigations have been carried out using thermo-gravimetric
1200
1201
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