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Department of Physical and Inorganic Chemistry, University of Rovira I Virgili, C/ Marcel l Domingo s/n, 43007 Tarragona, Spain
Department of Inorganic Chemistry, University of Alicante, Ap. 99, E-03080 Alicante, Spain
a r t i c l e
i n f o
Article history:
Received 22 September 2012
Received in revised form 6 March 2013
Accepted 20 March 2013
Available online 24 April 2013
Keywords:
Copper catalysts
Delaminated hectorite
Diesel soot
Soot combustion mechanism
a b s t r a c t
Two microporous hectorites were prepared by conventional and microwave heating, and a delaminated
mesoporous hectorite by an ultrasound-assisted synthesis. These three hectorites were impregnated with
copper. The characterization techniques used were XRD, N2 adsorption, TEM and H2 reduction after selective
surface copper oxidation by N2O (to determine copper dispersion). The catalytic activity for soot combustion
of the copper-free and the copper-containing hectorites was tested under a gas mixture of 500 ppm NOx/5%
O2/N2 (and 5% O2/N2 in some cases), evaluating their stability through three consecutive soot combustion
experiments.
The delaminated hectorite showed the highest surface area (353 m2/g) allowing the highest dispersion of
copper. This copper-containing catalyst was the most active for soot combustion among those prepared
and tested in this study. We have also concluded that the Cu/hectorite-catalyzed soot combustion mechanism is based on the activation of the O2 molecule and not on the NO2-assisted soot combustion.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Soot particles produced by diesel engines have negative effects on
health and their emission must be controlled, being currently regulated. In order to avoid soot emissions, soot particles are collected on lters placed in the diesel exhausts, which must be periodically
regenerated by soot combustion. Diesel gas exhausts consist of a
high proportion of O2, CO2 and H2O, and in lower concentration
NOx, CO and unburned hydrocarbons. Thus, soot must be combusted
in such particular environment.
There are three oxidizing gases that can potentially react with soot
in a diesel exhaust: O2, NO and NO2. Typically, only NO and O2 are emitted by the engine, and some soot combustion catalysts (such as Pt in the
commercially available CRT system, for instance in van Setten et al.,
2001; Fino and Specchia, 2008) accelerate the oxidation of NO to NO2,
which is much more oxidizing than NO and O2.
A number of catalysts accelerate the combustion of soot, such as
noble metals (Snchez et al., 2009; Shimokawa et al., 2012), alkali metals
(Aneggi et al., 2008; Peralta et al., 2011), transition metals and metal oxides among others (Guilln-Hurtado et al., 2012; Lpez-Surez et al.,
2008, 2009; Neeft et al., 1996). Regarding these potential catalysts, copper oxide appears as an interesting solution due to its moderate activity
but low prize.
It is well known that the catalyst support (ceria, alumina, silica,
etc.) affects in some cases the activity of the main active component
of a soot combustion catalyst. However, as far as we know, the soot
combustion activity of hectorites either as catalysts or as catalytic
supports has not been reported yet.
Hectorite is a trioctahedral 2:1 clay mineral, belonging to the
+
smectites group, with idealized formula (My+nH2O)(Mg32+
yLiy )
4+
2+
+
by Li in the octaSi4 O10(OH)2,y, where some substitution of Mg
hedral (O) sheet causes the negative charge of layers. This charge is
compensated by interlayer exchangeable cations. Nanoparticles of
metals, such as Ni 0, Pd 0 or Cu 0, can be generated in the interlayer
space by ionic exchange and further reduction. Hectorites can be
used for nanocomposite preparation, in ionic adsorption and in heterogeneous catalysis among other applications (Casagrande et al.,
2005; Liu and Breen, 2005; Varma, 2002; Xue and Pinnavaia, 2008).
Smectites have been applied as catalysts, especially in acid and oxidation reactions (Casagrande et al., 2005; Varma, 2002). Additionally,
they have been widely used as supports of metal catalysts leading
to signicant results, for example, in the hydrogenation of styrene
oxide to 2-phenylethanol with hectorite and saponite-supported
nickel catalysts (Vicente et al., 2010, 2011) or in the hydrogenolysis
of glycerol to 1,2-propanediol with delaminated hectorite-supported
copper catalysts (Snchez et al., 2012).
Basal spacing
()
Hysteresis
type
Hect-Mw
Hect-Conv
Hect-Del
14.2
13.4
10.5
7.9
6.0
199
207
353
B
B
D,B
41
A delaminated hectorite, which is referred to as Hect-Del, was prepared according to the method reported by Iwasaki et al. (1998),
which was further modied by Snchez et al. (2012) using ultrasounds
for homogenization of the precursors dispersion. 8.73 g of an acidied
sodium silicate solution (SiO2 27%, d. 1.39 g/cm3, Sigma-Aldrich) was
mixed with the appropriate amounts of MgCl2 and LiF to obtain a Si:
Mg:Li molar ratio of 4:2.6:0.4. Then, a LiOH solution was added until
pH = 12. The resulting dispersion was homogenized for 15 min in an
ultrasound bath, washed and dried. Then, the solid was dispersed in
water and mixed with trimethyldodecylammonium chloride (AQ)
(98%, Sigma-Aldrich) in a molar ratio Li:AQ = 1:1. The dispersion was
submitted to a hydrothermal treatment in a conventional Teon autoclave at 180 C for 1 h. Afterwards, the precipitated sample was ltered
and calcined to 620 C for 75 min.
2.1.2. Cu/hectorite samples
Cu/hectorite samples were prepared by impregnation according to
the method described by Snchez et al. (2012). Impregnated
hectorites were prepared by mixing 1.5 g of support (Hect-Mw,
Hect-Conv or Hect-Del) with a 15 mass % copper nitrate ethanol solution under ultrasounds for 15 min, in order to obtain around 40 mass
% copper after solvent evaporation, calcination, and reduction under
pure hydrogen. Impregnated hectorites are named as Cu/Hect-Mw,
Cu/Hect-Conv and Cu/Hect-Del.
2.2. Characterization techniques
2. Experimental
2.1. Catalyst preparation
2.1.1. Hectorite samples
Two hectorites, named as Hect-Conv and Hect-Mw, were prepared
according to the procedures reported by Granquist and Pollack (1959),
and Vicente et al. (2009), respectively. In both methods, brucite sheets
were proposed to act as crystallization nuclei of hectorite. Preparation
was carried out as follows: a slurry (3 mass % solids) containing SiO2
(Aerosil 380 from Degussa), fresh brucite Mg(OH)2 (synthesized by
dropping a 10 M ammonia solution onto MgCl2(aq)), and LiF (99.9%
from Sigma-Aldrich), in a SiO2:Mg(OH)2:LiF molar ratio of 4:3:1was vigorously stirred for 1 h. Then, one of the samples was aged by microwaves
(in a Milestone Ethos Touch Control equipment) in a 85 ml Teon autoclave at 120 C for 8 h under magnetic stirring (sample Hect-Mw). Another sample was aged within a Teon autoclave by conventional
thermal heating at 120 C for 8 days (sample Hect-Conv), in order to
compare conventional aging with microwave hydrothermal treatment.
42
Cu content
(mass %)
Cu dispersion
(%)
g surface Cu/g
catalyst 102
Cu/Hect-Mw
Cu/Hect-Conv
Cu/Hect-Del
39.2
38.7
40.1
4
6
8
1.57
2.32
3.20
Dispersion%
samples were outgassed at 150 C. Specic surface areas were calculated from BET method.
Cusurface
100:
Cutotal
43
600
100
500
80
Hect-Del
No catalyst
Hect-Conv
Hect-Mw
60
400
300
40
Cu/Hect-Del
200
Cu/Hect-Mw
Cu/Hect-Conv
20
0
3600
4500
100
5400
6300
0
7200
Time (sec)
Fig. 4. Soot conversion proles corresponding to the third run performed with each hectorite sample in the 500 ppm NOx/5% O2/N2 gas ow.
1st run
2nd run
3rd run
7000
6000
5000
4000
3000
2000
1000
0
No catalyst
Hect-Del
Hect-Mw
Hect-Conv
Cu/Hect-Del
Cu/Hect-Mw
Cu/Hect-Conv
Fig. 5. Comparison of catalysts during three consecutive soot combustion runs performed in the 500 ppm NOx/5% O2/N2 gas ow.
44
100
1st run
2nd run
80
CO/COx (%)
3rd run
60
40
20
0
No catalyst
Hect-Del
Hect-Mw
Hect-Conv
Cu/Hect-Del
Cu/Hect-Mw
Cu/Hect-Conv
Fig. 6. CO selectivity in soot combustion experiments performed in the 500 ppm NOx/5% O2/N2 gas ow.
4. Conclusions
In this study, three different hectorites were prepared and impregnated with copper. The characterization and the catalytic activity for
100
600
Cu/Hect-Del
(O2/N2)
80
No catalyst
(NOx/O2/N2)
500
400
60
Cu/Hect-Del
(NOx/O2/N2)
300
40
200
20
100
0
3600
0
4500
5400
6300
7200
Time (sec)
Fig. 7. Soot combustion experiments performed with Cu/Hect-Del catalyst (fresh sample) with 5% O2/N2 and 500 ppm NOx/5% O2/N2.
45
600
50
500
NO2 formation
(soot combustion experiment)
400
300
200
NOx removal
(blank experiment)
NOx removal
(soot combustion experiment)
100
-25
0
900
1800
2700
3600
4500
5400
6300
Time (sec)
Fig. 8. NO2 formation and NOx removal in soot combustion and blank experiments performed with Cu/Hect-Del catalyst (fresh sample) with 500 ppm NOx/5% O2/N2.
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