Valderrama, Kiennemann, Goldwasser, 2008
Valderrama, Kiennemann, Goldwasser, 2008
Valderrama, Kiennemann, Goldwasser, 2008
com
Abstract
LaNi1xCoxO3 perovskite-type oxides were synthesized by the sol–gel resin method and used as catalysts precursors in the dry reforming of
methane to syngas between 600 and 800 8C at atmospheric pressure, the reaction was studied under continuous flow using an mixture of
CH4:CO2 = 1:1. The solids were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction
(TPR).
XRD analysis of the solids shows LaNiO3 and/or LaCoO3 as the main phases present on the solids depending on the degree of substitution. The
more intense peaks and cell parameters showed formation of Ni-Co solid solutions. The as-synthesized solids were reduce during catalytic tests to
form Ni0, Co0 and La2O2CO3 as the active phases which remain during the reaction and are responsible for the high activity shown by the solids
inhibiting carbon formation, with CH4 and CO2 equilibrium conversions near 100%, except for LaCoO3 that showed a poor activity.
# 2008 Elsevier B.V. All rights reserved.
Keywords: Resin method; (Ni, Co)-solid solutions; (Ni, Co)-perovskites; Dry reforming of methane; Syngas production; Catalytic activity; Carbon deposition
2. Experimental
Table 1
BET specific surface area and, XRD results of the synthesized solids at 750 8C
Precursor solid SA (m2/g) XRD initial phase XRD after redox XRD after reaction
LaNiO3 7.5 LaNiO3 Ni, La2O3 Ni, La2O2CO3
LaNi0.8Co0.2O3 6.9 LaNiO3 Ni, Co, La2O3 Ni, Co, La2O2CO3
LaNi0.7Co0.3O3 39.4 LaNiO3 Ni, Co, La2O3 Ni, Co, La2O2CO3
LaNi0.5Co0.5O3 9.5 LaNiO3, LaCoO3 Ni, Co, La2O3 Ni, Co, La2O2CO3
LaNi0.4Co0.6O3 5.6 LaCoO3 Ni, Co, La(OH)3 Ni, Co, La2O2CO3
LaNi0.2Co0.8O3 6.4 LaCoO3 Ni, Co, La2O3 Ni, Co, La2O2CO3
LaCoO3 4.2 LaCoO3 Co, La2O3 Co, La2O3
144 G. Valderrama et al. / Catalysis Today 133–135 (2008) 142–148
Table 2
Lattice parameters for hexagonal and rhombohedra symmetries
LaNi1xCoxO3 (x) Hexagonal symmetry Rhombohedra
symmetry
a (Å) b (Å) c (Å) a (Å) a
0 5.4327 5.4327 13.2210 5.4091 60.29
0.2 5.4287 5.4287 13.2218 5.4080 60.25
0.3 5.4296 5.4296 13.1608 5.3919 60.47
0.5 5.4327 5.4327 13.1304 5.3846 60.59
0.6 5.4121 5.4121 13.1468 5.3821 60.37
0.8 5.4308 5.4308 13.1178 5.3798 60.60
1.0 5.4175 5.4175 13.0927 5.3693 60.60
Fig. 3. XRD patterns of LaNi1xCoxO3 more intense peaks. Fig. 4. The rhombohedra aR cell parameters.
G. Valderrama et al. / Catalysis Today 133–135 (2008) 142–148 145
Table 3
Temperatures, reduction and coke results of the synthesized solids at 750 8C
Precursor solid 1st Peak 2nd Peak 3rd Peak Total
T (8C) Red (%) T (8C) Red (%) T (8C) Red (%) Red (%) Coke (%)
LaNiO3 360 19.1 395 12.5 540 54.3 85.9 0.7
LaNi0.8Co0.2O3 355 23.5 385 10.2 537 50.2 83.9 2.8
LaNi0.7Co0.3O3 347 20.8 385 26.9 530 38.7 86.4 0.9
LaNi0.5Co0.5O3 353 22.8 390 10.7 556 55.1 88.6 2.7
LaNi0.4Co0.6O3 348 19.8 390 13.4 562 57.3 90.5 0.1
LaNi0.2Co0.8O3 356 21.2 408 12.7 586 52.5 86.4 0.3
LaCoO3 377 25.3 420 14.6 600 57.1 97.0 0.3
146 G. Valderrama et al. / Catalysis Today 133–135 (2008) 142–148
Fig. 8. XRD patterns of peaks respect to Ni0 and Co0 phases of LaNi1xCoxO3. Fig. 10. CH4 and CO2 conversions on unreduced LaNi1xCoxO3 at 800 8C.
due to the fact that Co reduction to Co0 requires higher for high Ni (x 0.3) contents reaching a stationary state
temperatures than Ni (Table 3). of activation between 650 and 800 8C. It is evident
The observed difference in CO yield during the rise that activation of the solids occurs in situ, due to the
and decrease of temperature (Fig. 9) is known as hysteresis presence of a reducing atmosphere formed by the
phenomenon [20], which occurs due to the initial lack gases (CH4, CO, H2) in the reaction media that promotes
of activity of the solids at 650 8C, produced by the absence formation of the active species Ni0, Co0 and La2O2CO3
of Co0 active species. Such a phenomenon is not important (Table 1).
Fig. 11. Dry reforming of methane: X CH4 =X CO2 ratio. Fig. 13. XRD patterns of after-reaction LaNi1xCoxO3.
The evolution of CH4 and CO2 conversions during the dry Accordingly, the methane decomposition reaction (7)
reforming of methane at 800 8C over the solids solution increases CH4 conversion and H2 selectivity. While water
synthesized is shown in Fig. 10. It is observed that conversions gas shifts reaction (8) decreases the selectivity to CO and
of both gases are favoured on the Ni (x 0.6) rich solids, with increases H2 selectivity.
values close to the thermodynamic balance (100%) and a XRD analyses of after-reaction solids reveal the presence of
X CH4 =X CO2 ratio close to 1 (Fig. 11), suggesting that Ni favours La2O2CO3, Ni and Co phases (Fig. 13) and of very small
reaction (1). quantities of coke determined by TPR (Table 3). The high
LaCoO3 showed a poor activity (Fig. 9) due to the initial dispersion of the metallic phases, the presence of La2O2CO3
activation time needed to in situ reduce Co3+ to Co0 [21] and to that plays a very important paper in the reforming (Eq. (9)) and
the absence of La2O2CO3 phase (Table 1). However, synergetic reacts with methane and regenerate La2O3 inhibits coke
effect have also been observed in LaNi0.2Co0.8O3 with the deposits and is responsible for the high activities shown by
presence of Ni in doping quantities since presents high activity these solid solutions.
for the reaction (Fig. 9) reaching CH4 and CO2 conversions of
82 and 88%, respectively, which indicated that the presence of La2 O3 þ CO2 ! La2 O2 CO3 þ CH4 ! La2 O3 þ 2CO þ 2H2
Ni promotes Co activation and eliminates the initial induction (9)
period.
On the other hand, it is observed (Fig. 12) that the Ni It is important to point out that in spite of the severe reaction
(x 0.6) rich solids produce high selectivities toward the conditions used (Fig. 1), only small quantities of coke was
formation of syngas, with CH4 conversions slightly higher than formed (Table 3), indicating that interaction between metallic
that of CO2 and H2 selectivities slightly superior to that of CO species Ni0-Co0 cause an synergetic effect, no clearly
(Fig. 9). This indicates that the reactions (7) and (8) are understood, that play a very important role in the catalytic
occurring in a very small extension: behaviour. Therefore, we propose that doping quantities of Co,
which reduces at higher temperatures (Fig. 5), stabilize the
CH4 ¼ C þ 2H2 DH 298 ¼ 74:85 kJ=mol (7)
particles of metallic Ni inhibiting coke formation, while doping
quantities of Ni diminishes the temperature of reduction of Co
CO þ H2 O ¼ CO2 þ H2 DH 298 ¼ 41:17 kJ=mol (8)
(Fig. 5) accelerating the activation of the solid.
4. Conclusions
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