1 s2.0 S0021951799925381 Main
1 s2.0 S0021951799925381 Main
1 s2.0 S0021951799925381 Main
INTRODUCTION
[2]
160
0021-9517/99 $30.00
c 1999 by Academic Press
Copyright
All rights of reproduction in any form reserved.
[1]
161
major product obtained over CeO2 alone was CO, and thus
C2 selectivity was negligibly small. It is expected that the
modification of CeO2 with other components may improve
C2 selectivity, and the preliminary study has verified this expectation (14). The present paper clarifies the effect of the
modification of CeO2 with various alkali and alkaline earth
metal oxides, in particular the synergistic effect between
CaO and CeO2 in binary catalysts of CaOCeO2. The role
of CO2 in the catalysis of C2 formation and the reaction
mechanism are also discussed on the basis of the results of
reaction kinetics and chemisorbed species.
EXPERIMENTAL
Catalyst Preparation
Modified CeO2 catalysts were prepared mainly by
impregnating powdery CeO2 (RhonePoulenc, purity
>99.5%) with aqueous solutions of alkali and alkaline earth
metal nitrates. The surface area of CeO2 measured by N2
adsorption was 7 m2 g1. The concentration of alkali or alkaline earth metal cation in the solution was 1.0 mol dm3.
The atomic ratio of M/Ce (M = alkali and alkaline earth
metal ) was 0.2, unless otherwise stated. The impregnation
was carried out at room temperature for ca. 12 h. The resultant was calcined at 850 C in an air flow (200 ml min1)
for 4 h after water was evaporated at 90 C. The calcined
catalyst was sieved to particles with 1632 mesh before use.
Among these binary catalysts, the CaOCeO2 system was
mainly used, Ca/Ce ratio usually being 0.5.
A physical mixture of CaO and CeO2 with Ca/Ce ratio of
0.2 was also used. In this case, CaO, prepared by calcining
The reaction was performed using a conventional fixedbed quartz reactor operated at atmospheric pressure. The
inner diameter of the reactor was 10 mm. For a standard reaction, 2 g of the granular catalyst with size 1632 mesh was
first loaded in the reactor and then calcined again with air
(100 ml min1) at 850 C for 1 h, followed by purge with He
(>99.9999%, 100 ml min1) for 1 h. Finally, a mixture of CH4
(>99.999%) and CO2 (>99.995%) was introduced to the
reactor. Unless otherwise described, reaction temperature
was 850 C, and partial pressures of CH4 and CO2, denoted
as P(CH4) and P(CO2) respectively, were both 30.3 kPa.
The total flow rate of the reactants diluted with He was
100 ml min1.
The effluent gas after removal of H2O was analyzed by an
on-line high-speed gas chromatograph (M200D, Microsensor Technology, Inc.). A MS-5A PLOT column was used
for the analysis of H2, CH4, and CO. CH4, CO2, C2H4, and
C2H6 were simultaneously analyzed with a PORA PLOT-Q
column. One analytical run was complete within 150 s, and
thus the sampling was repeated every 180 or 300 sec. Data
collection was automatically controlled with a computer.
The data after 2 h of reaction are described in this paper,
unless otherwise stated.
Data processing is based on the assumption that the carbon in CO2 is converted to CO and the carbon in CH4 is
converted to C2H6, C2H4, and CO. Thus, CO is produced
from both CH4 and CO2. The CO from CH4 is first calculated according to the previous method (10), in which almost all of the reactions involving CH4 and CO2 are taken
into account. Then, CH4 conversion and selectivity to C2
hydrocarbons are calculated using the following equations:
CH4 conversion =
2[C2 H6 ] + 2[C2 H4 ] + [CO from CH4 ] (mol)
[CH4 ] + 2[C2 H6 ] + 2[C2 H4 ] + [CO from CH4 ] (mol)
100 (%)
C2 selectivity =
2[C2 H6 ] + 2[C2 H4 ] (mol)
100 (%).
2[C2 H6 ] + 2[C2 H4 ] + [CO from CH4 ] (mol)
C2 yield is defined as the product of CH4 conversion and C2
selectivity.
Catalyst Characterization
Both fresh and used catalysts were characterized using
the following methods. The BET surface areas were measured by N2 adsorption at 77 K using a volumetric apparatus
162
TABLE 1
FIG. 2. Effect of the addition of alkali and alkaline earth metal oxides
to CeO2 on the reaction of CH4 and CO2. (A) CH4 conversion (h) and
C2 yield (j); (B) C2 selectivity. Reaction conditions: T = 850 C, P(CH4) =
P(CO2) = 30 kPa.
Catalysta
CH4 conv.
(%)
R(CH4)b
(mmol m2 h1)
C2H6
C2H4
C2
C2
yield
(%)
CeO2
Ca/Ce (0.1)
Ca/Ce (0.2)
Ca/Ce (0.2)c
Ca/Ce (0.5)
Ca/Ce (1.0)
CaO
12
5.1
4.9
4.0
5.0
3.4
0.3
3.5
3.6
4.0
2.3
5.2
2.0
0.12
0.2
26
31
6.1
36
28
23
0.3
20
24
4.0
26
18
13
0.5
46
55
10
62
46
36
0.1
2.3
2.7
0.4
3.2
1.6
0.1
Selectivity (%)
163
0.1
0.2
0.5
1.0
0.9
1.1
1.3
3.8
164
it is usually observed that product selectivity in partial oxidation reactions decreases with increasing partial pressure
of oxidant. For comparison, the effect of P(CO2) over a single oxide of CeO2 or CaO is also provided in Fig. 5, where
0.5 g of CeO2 is used in the former case to keep CH4 conversion at a level similar to that for the CaOCeO2 catalyst. C2
selectivity was much lower over CeO2 than over the binary
catalyst even when compared at the same level of CH4 conversion. The increase of P(CO2) did not affect C2 selectivity
over CaO and CeO2. Almost the same tendency was observed over other modified catalysts, such as MgOCeO2,
SrOCeO2, and BaOCeO2. Therefore, the considerable
increase in C2 selectivity with increasing P(CO2), observed
for the CaOCeO2 catalyst, is quite unique. These observations point out that CO2 plays crucial roles in the selective
formation of C2 hydrocarbons over this catalyst.
Kinetic Studies
Further studies were carried out to clarify the nature of
the interesting effect of P(CO2) and to elucidate the reaction mechanism over the CaOCeO2 catalyst. Figure 6
165
shows the temperature dependence of the catalytic performance at P(CO2) of 10 and 70 kPa. There was no significant effect of P(CO2) on CH4 conversion at temperatures of
800 C. However, as temperatures exceeded 800 C, CH4
conversion was higher at higher P(CO2). Such partial pressure effects became greater at higher temperatures. CH4
conversion at 900 C was 6.5 and 10.5% at 10 and 70 kPa,
respectively.
C2 selectivity at 800 C was slightly higher at 70 kPa
than at 10 kPa despite the same level of CH4 conversion.
The increase in temperature decreased C2 selectivity in both
cases, but the extent of the decline was more considerable at
low P(CO2) as the temperature was increased to >800 C.
As a result, at 900 C, C2 selectivity at 70 kPa was more
than 5 times that at 10 kPa. Although the C2H6/C2H4 ratio
in C2 hydrocarbons was not shown in Fig. 6, it decreased
with temperature, irrespective of the value of P(CO2). This
means that C2H6 is the primary product and C2H4 is formed
by secondary reactions of C2H6.
Figure 7 shows the Arrhenius plots for rates of CH4
conversion at P(CO2) of 10 and 70 kPa. A good straight
line was obtained at 70 kPa in the whole range examined
(700900 C), the apparent activation energy being calculated to be 220 kJ mol1. On the other hand, at P(CO2)
of 10 kPa, two straight lines with different slopes were required to fit the data. The activation energies calculated
were 250 kJ mol1 at 800 C and 140 kJ mol1 at 800 C.
The former one was similar to that at high P(CO2).
Figure 8 shows the effect of P(CH4) on the rate of CH4
conversion, R(CH4), at P(CO2) of 10 and 70 kPa and at
780 and 850 C. At high P(CO2), R(CH4) increased proportionally to P(CH4) irrespective of reaction temperature.
Whereas, at low P(CO2), R(CH4) at 850 C seemed to level
off with increasing P(CH4), viz., the reaction order with respect to CH4 became less than 1, although R(CH4) at 780 C
increased linearly.
The results described above show that the kinetic features
at P(CO2) of 10 kPa are different from those at P(CO2) of
70 kPa when the temperature exceeds 800 C.
Chemisorption of CO2
To examine the chemisorption of CO2 on the CaOCeO2
catalyst after reaction, TPD measurements were carried
out. Table 3 shows the TPD results both in He flow and
in CO2 flow with different P(CO2). Only one desorption
peak was observed in every case. The peak temperature was
730 C in He flow. It shifted to 810, 850, and 910 C in CO2
flow with P(CO2) of 10, 30, and 70 kPa, respectively. These
observations indicate that a pool of chemisorbed CO2 always exists on the catalyst at temperatures of 900 C under
P(CO2) of 70 kPa, whereas the pool disappears at >810 C
and >850 C under P(CO2) of 10 and 30 kPa, respectively.
TABLE 3
TPD Results for the Catalysts after Reaction of CH4
and CO2 at 850 C
CO2 desorption
Catalyst
CaOCeO2
CaOCeO2
CaOCeO2
CaOCeO2
CeO2
0
10
30
70
30
Peak temperature
( C)
Amount
(mmol)
730
810
850
910
No desorption
0.70
0.75
0.75
0.65
166
FIG. 10. Ce 3d XPS spectra for the CaOCeO2 catalyst. (a) Before
reaction. (b) and (c) After reaction at 850 C under P(CO2) of 70 and
10 kPa, respectively.
and 916.7 0.5 eV can be assigned to v, v 00, v 000, u, u00, and u000
states of Ce4+, respectively, while the peaks at 885.2 0.3
and 904.0 0.5 eV correspond to v 0 and u0 states of Ce3+.
The spectrum before reaction (curve a in Fig. 10) exhibited six peaks ascribed to Ce4+. In addition to them, two
shoulder peaks at 885.2 and 903.9 eV clearly appeared after reactions at both high and low P(CO2), which indicates
the existence of Ce3+ on the catalyst surface. Moreover, the
peaks of Ce3+ were stronger at low P(CO2), suggesting that
the concentration of Ce3+ on the surface was dependent on
P(CO2). It can thus be speculated that Ce3+ sites formed
during reaction are responsible for the activation of CO2.
DISCUSSION
FIG. 9. X-ray diffraction patterns for the CaOCeO2 catalyst. (a) Before reaction. (b) and (c) After reaction at 850 C under P(CO2) of 70 and
10 kPa, respectively.
167
FIG. 11. Proposed mechanism for selective formation of C2 hydrocarbons over CaOCeO2 catalyst.
168
REFERENCES
1. Pitchai, R., and Klier, K., Catal. Rev.Sci. Eng. 28, 13 (1986).
2. Lee, J. S., and Oyama, S. T., Catal. Rev.Sci. Eng. 30, 249 (1988).
3. Hutchings, G. J., Scurrel, M. S., and Woodhouse, J. R., Chem. Soc. Rev.
18, 251 (1989).
4. Krylov, O. V., Catal. Today 18, 209 (1993).
5. Martin, G. A., and Mirodatos, C., Fuel Process. Technol. 42, 179
(1995).
6. Lunsford, J. H., Angew. Chem. Int. Ed. Engl. 34, 970 (1995).
7. Kuo, J. W. C., Kresge, C. T., and Palermo, R. E., Catal. Today 4, 470
(1989).
8. Aika, K., and Nishiyama, T., J. Chem. Soc. Chem. Commun. 70
(1988).
9. Nishiyama, T., and Aika, K., J. Catal. 122, 346 (1990).
10. Asami, K., Fujita, T., Kusakabe, K., Nishiyama, Y., and Ohtsuka, Y.,
Appl. Catal. A: General 126, 245 (1995).
11. Asami, K., Kusakabe, K., Ashi, N., and Ohtsuka, Y., Stud. Surf. Sci.
Catal. 107, 279 (1997).
12. Asami, K., Kusakabe, K., Ashi, N., and Ohtsuka, Y., Appl. Catal. A:
General 156, 43 (1997).
13. Chen, C., Xu, Y., Li, G., and Guo, X., Catal. Lett. 42, 149 (1996).
14. Wang, Y., Takahashi, Y., and Ohtsuka, Y., Appl. Catal. A: General
172, 203 (1998).
15. Otsuka, K., Shimizu, Y., and Komatsu, T., Chem. Lett. 1835 (1987).
16. Arai, H., Kunisaki, T., Shimizu, Y., and Seiyama, T., Solid State Ionics
20, 241 (1986).
17. Zhang, Z.-L., and Baerns, M., J. Catal. 135, 317 (1992).
18. Laachir, A., Perrichon, V., Badri, A., Lamotle, J., Catherine, E.,
Lavalley, J. C., Fallah, J. E., Hilaire, L., Normand, F. le, Quem
ere,
E., Sauvion, G. N., and Touret, O., J. Chem. Soc. Faraday Trans. 87,
1601 (1991); Normand, F. le, Hilaire, L., Kili, K., Krill, G., and Maire,
G., J. Phys. Chem. 92, 2561 (1988).
19. Bradford, M. C. J., and Vannice, M. A., Catal. Rev. Sci. Eng. 41, 1 (1999).
20. Krylov, O. V., Mamedov, A. Kh., and Mirzabekova, S. R., Catal. Today
42, 211 (1998).
21. Trovarelli, A., de Leitenburg, C., and Dolcetti, G., Chemtech 27(6),
32 (1997).