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1. Introduction
Chemical looping has been proposed recently as an alternative
process for the combustion of carbonaceous materials, such as
coal, oil, or natural gas, providing complete CO2 capture together
with substantial reduction of thermal NOx emissions.1-4 Chemical-looping combustion (CLC) is a two-step process5 usually
carried out in two different reactors. In the first stage, called
the reduction stage, the carbonaceous material is burned using
the framework oxygen of a reducible inorganic oxide. If the
reduction reaction is fast enough and highly selective, complete
conversion of the combustible can be achieved, and consequently, the outlet gas from this reactor is exclusively composed
of CO2 and steam. These two gas components can easily be
separated by steam condensation, a crucial difference with
conventional combustion, and the pure CO2 obtained is ready
* To whom correspondence should be addressed. E-mail: jmpalacios@
icp.csic.es.
Instituto de Cata
lisis y Petroleoqumica.
Instituto de Carboqumica.
(1) Anheden, M.; Svederg, G. Exergy analysis of chemical-looping
combustion systems. Energy ConVers. Manage. 1998, 39, 1967-1980.
(2) Yu, J.; Corripio, A. B.; Harrison, D. P.; Copeland, R. J. Analysis of
the sorbent energy transfer system (SETS) for power generation and CO2
capture. AdV. EnViron. Res. 2003, 7, 335-345.
(3) Ishida, M.; Jin, H. Chemical-looping combustion power generation
plant system. U.S. Patent No. 5,447,024, 1995.
(4) Ishida, M.; Jin, H. A new advanced power-generation system using
chemical-looping combustion. Energy 1994, 19, 415-422.
(5) Lyngfelt, A.; Leckner, B.; Mattison, T. A fluidised-bed combustion
process with inherent CO2 separation; application of chemical-looping
combustion. Chem. Eng. Sci. 2001, 56, 3191-3113.
exhibited a good performance in a multicycle test in a fixedbed reactor at 900 C. Titania as support provided a high
mechanical strength to the overall carrier, additionally providing
a highly dispersed copper oxide as active phase. Consequently,
the involved reactions in both the reduction and regeneration
stages were fast, highly selective, and independent of the copper
loading in the carrier. Deposited carbon became undetected in
the reduction stage; however, copper redistribution was clearly
evidenced in the last cycles of a multicycle test. This last feature
implied that a higher number of additional pores became plugged
along the test, although it did not affect carrier performance
substantially.
In this study, a high-copper loading oxygen carrier has been
prepared by wet impregnation of a saturated aqueous solution
of copper nitrate on a highly porous silica. This support like
titania also imparts a high mechanical strength to the overall
oxygen carrier. Characterization studies of fresh, reduced, and
regenerated carriers using different techniques have allowed
identification of the chemical compounds necessary to know
the involved reactions in the reduction and regeneration stages
of a CLC of methane. To prevent copper redistribution along a
multicycle test, as observed in a prior study on titania-supported
copper carriers at 900 C,14 the operating temperature has been
lowered to 800 C. Silica, as compared with titania, presents a
different pore size distribution especially in the range of
mesopores, promoting a different dispersion of the active phase
and, presumably, higher stability of some involved oxygenated
phases in the reduction stage. By replacing titania with silica,
as a more stable support against reducing agents, we expected
that it will decrease the evolution of detrimental gas compounds,
such as CO.
2. Experimental Section
2.1. Preparation of Oxygen Carriers. Highly porous powder
silica, with a specific surface area of 380 m2/g, was added to a 10
wt % of synthetic powder graphite of particles 1-2 m in diameter
as a pore-forming additive to form a powder mixture subsequently
homogenized in a planetary ball mill. Water was added to obtain
a paste of suitable consistency to be extruded in a plastic syringe
to cylindrical extrudates 2 mm in height 2 mm in diameter,
approximately. These support extrudates were softly dried overnight
at 80 C to prevent crack formation and, then, calcined at 1100 C
for 6 h to provide thermal stability at the operating temperature of
800 C used in a multicycle test of CLC in a fixed-bed reactor and
high mechanical strength to the overall carrier. Afterward, the
support extrudates were cooled, crushed, and sieved to particles
0.2-0.4 mm to facilitate successive impregnations of the active
phase. Fresh silica-supported copper-based oxygen carriers have
been prepared by wet impregnation of these silica particles with a
saturated aqueous solution of copper nitrate as active phase
precursor. Samples with maximum copper loading were obtained
by applying successive impregnations up to saturation. After each
impregnation, the sample was calcined at 500 C simply to promote
nitrate decomposition into oxide facilitating the next impregnation.
After the last impregnation achieving maximum copper content,
to get thermal stability all samples were calcined at higher
calcination temperatures as indicated. The obtained fresh samples
were denoted, for example, as CS900, where C ) CuO, S ) silica,
and the number indicates the last calcination temperature applied
to the oxygen carrier before reactor testing.
2.2. Characterization Techniques. Since previous studies13,14
revealed that macropres play the most important role in carrier
(14) Corbella, B. M.; De Diego, L.; Garca-Labiano, F.; Adanez, J.;
Palacios, J. M. The performance in a fixed bed reactor of copper-based
oxides on titania as oxygen carriers for chemical looping combustion of
methane. Energy Fuels 2005, 19, 433-441.
Corbella et al.
G ) 72 kJ/mol
(1)
CuO
Cu2O
sample
wt %
d (nm)
wt %
d (nm)
wt %
d (nm)
SiO2
1CS500
2CS 800
3CS900
100
90
84
17
2
2
2
35
10
13
45
103
55
40
2
38
large
889
CuO + H2 f Cu + H2O
G ) -128 kJ/mol, H ) -101 kJ/mol (6)
Equation 2 is the main reaction in the reduction stage of CLC
of methane. Equation 3 is a less-favored side reaction leading
to partial oxidation of methane. Equation 4 explains that CO,
eventually produced in the bottom layers of an up-flow fixedbed reactor, is subsequently consumed by still unconverted top
layers. Consequently, CO emissions might only be expected at
the end of the reduction stage when the amount of available
oxygen in the reactor bed is already very low. Equation 5 is
the thermal decomposition of methane only plausible in the
absence of oxygenated Cu species. Equation 6 is the further
consumption of H2 by the top layers in an affixed-bed reactor.
H2 in the outlet gas of the reduction stage only may be expected
long after carrier breakthrough.
Similarly, before breakthrough, N2 from air used as feeding
gas in the regeneration stage is the only detected compound in
the outlet gas. Characterization studies of the regenerated carriers
Corbella et al.
Cu + 1/2O2 f CuO
G ) -58 kJ/mol, H ) -146 kJ/mol (7)
In this case, there are no side reactions in the regeneration stage
and the only involved reaction is fast and highly exothermic.
Consequently, carrier regeneration is usually not studied, and
the only derived effect in multicycle tests is probable accumulative thermal sintering if a good control of the operating
temperature cannot be achieved.
Profiles of the evolving gases during a thermal scan with
diluted methane are shown in Figure 5. Below 750 C, the
corresponding electrical signals detected for all gas components
are kept constant, indicating that no chemical reaction occurs
at lower temperatures. At a slightly higher temperature a
decrease of the CH4 signal together with an increase of H2O
and CO2 signals are apparent, implying that the main reaction
of CLC of methane (eq 2) takes place. No variation in the H2
signal along the thermal scan is observed, indicating there is
no thermal decomposition of methane with this type of copperbased oxygen carriers. Additionally, the O2 signal shows a peak
at 870 C, revealing that CuO apparently becomes unstable and
Vp (cm3/g)
S (m2/g)
dp (nm)
fresh
1
5
10
15
20
0.31
0.30
0.29
0.28
0.28
0.31
40
33
38
31
30
27
17
18
17
17
21
21
Cu
quartz
cycle
wt %
d (nm)
wt %
d (nm)
wt %
d (nm)
1
5
10
15
20
88
89
78
74
73
2
2
2
2
4
15
16
19
19
17
98
85
68
74
82
7
10
82
62
Corbella et al.
Acknowledgment. This research was carried out with financial
support from the European Coal and Steel Community (Project
7220-PR125) and CICYT Project CTQ2004-025565/PPQ.
EF050212N