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The rate and selectivity of oxidative synthesis of higher hydrocarbons from methane have been
studied as functions of the chemical composition and structural type of zeolite catalysts applied and
the nature of oxidants (02, NzO, NO, NO*, SOz). The greatest yield of higher hydrocarbons has
been received in the presence of N20. The interaction of methane with different zeolites has been
investigated by NMR and IR spectroscopy methods. Methane activation during oxidative synthesis
was shown to occur on zeolite acid sites. The mechanism of methane activation and conversion on
pentasil zeolites has been proposed. o 1989 Academic PRS, I~C.
I i
AP
.:
I
i M
! -+-+-+- Fo-.
IO 20
cont. AL203, mass."/o
FIG. 2. Plot of N20 consumption rate (W): (1) total; FIG. 4. Plot of total N20 consumption rate (W) in
(2) for the formation of HHC; and (3) for the formation reaction with methane vs. alumina content in zeolites
of carbon oxides vs alumina content in pentasils used of different structural types used as catalysts (P, pen-
as catalysts. task; M, mordenites; F, faujasites).
nated faujasites and mordenites indicate for oxidative reactions. Chemical analysis
that a decrease in A1203 content down to of zeolite catalysts applied indicated the
the value typical for pentasils does not en- iron oxides to be the most abundant admix-
hance the catalytic activity of these sam- ture and to be able to play the role of KO in
ples. the course of bifunctional oxidative synthe-
Transition metal oxides are generally sis (see scheme in Fig. 1). From the data of
considered to be the most active catalysts Table 6, it can be seen that introduction of
iron oxide into zeolite leads to insignificant
changes in catalytic activity and selectivity.
One may conclude that admixtures of iron
oxides in zeolites over the concentration
TABLE 6
The Rate and Selectivity of HHC Formation from
Methane in the Presence of NzO on Pentasils
Containing Iron Oxide
v
their catalytic activity.
J=117hz
3. NMR and IR Investigations of
Methane Adsorbed on Zeolites
IR spectra in the region of vibration fre-
quencies of zeolite OH groups are given in
Fig. 5. Methane adsorption on zeolites
leads to the decrease of the frequency of
these vibrations. Such an effect is estab-
lished at 103 K for all types of decationated
zeolites investigated and only for pentasils
dZ6hz
at room temperature. A greater shift of vi-
bration frequencies of OH groups in IR
spectra for pentasil than for faujasite after
methane adsorption at 103 K has been
found. On the basis of these observations,
j,__ -5
the interaction between methane and zeo- -10 6, PPm
lite OH groups is assumed to result in the FIG. 6. The 13CH4NMR MAS spectrum of methane
formation of the H bond, which is stronger adsorbed on the P-28 zeolite. 102methane molecules
on pentasil than on faujasite. per gram of zeolite were adsorbed.
368 SHEPELEV AND IONE
5.
I
!P
acid sites should lead to the increase of
both the first and the third steps and the
selectivity toward HHC should be low. The
increase of the methane activation rate
0. leads to the increase of the rate of the first
step only and to high selectivity of the HHC
k
Q
Loat i
-5.
A +
M
formation.
experimental
This is in compliance with our
data. So we must admit that
CH4 activation is more probable as the lim-
iting step than N20 activation. The low rate
I
-10 )
of N20 decomposition on P-28 catalyst and
w Na-P OF the NMR data presented here are additional
facts supporting this supposition.
F cont. AL203, mass.%
Decationated pentasils with high alumina
contents are much more active in the reac-
tion investigated than faujasites and mor-
FIG. 7. Plot of chemical shift in the 13CNMR spec- denites. This can be attributed to the pecu-
trum of adsorbed methane vs. alumina content. 10zo
molecules per gram of zeoiite were adsorbed. liarities of zeolite structures. One should
consider that the adsorption potential in a
narrow-pore system cn lower the activated
complex formation energy and fasten the
DISCUSSION reaction. The smaller the pore size, the
The first question arising from our obser- greater must be the adsorption potential.
vation is What kinds of catalytically active Pentasils have the narrowest pore system
sites take part in the reaction under study? among the zeolites investigated and their
The best of our catalysts was not loaded high catalytic activity can readily be ex-
with any transition metal compounds. One plained using this approach. An explana-
can presume that admixtures of said com- tion of the high catalytic activity of penta-
pounds, especially of iron oxides, form the sils in the pentane cracking reaction similar
active sites. Let us reconsider the scheme to that for faujasites and mordenites has
in Fig. 1 to answer this question. been proposed recently by Derouane and
If the catalytic activity in the first step is co-workers (13), as have pentasil advan-
related to transition metal admixtures tages in the interaction with adsorbates de-
working as KO the rate of reagent con- tectable by the NMR technique (14).
sumption must not depend on sodium or Barthomeuf (15) has also emphasized that
aluminum content in zeohte. The change in the chemical environments of zeolite acid
concentration of acid sites would affect sites should affect their acidic and catalytic
only the rate of the second step and there- properties.
fore only the process selectivity. This as- The following pictures of methane activa-
sumption contradicts our observation: the tion and transformation can be proposed
more aluminum and the less sodium zeolite for consideration (Fig. 8). Methane adsorp-
contains, the higher its catalytic activity. It tion on zeolite acid sites results in polariza-
prompts us to conclude that not only KO tion of its molecule and in increase of the
but also some sites connected with Al ions negative charge of one of the hydrogen at-
and arising upon decationation take part in oms. A high adsorption potential in narrow
the first step. Acid sites of pentasils fit these pentasil channels can support such polar-
requirements. Both reagents can be acti- ization. A partially negatively charged hy-
vated in the first step in general. However, drogen atom of a methane molecule be-
the increase of the N20 activation rate on comes accessible to attack by the N20
OXIDATIVE HYDROCARBON SYNTHESIS 369
6. Shepelev, S. S., and Ione, K. G., Appl. USSR N 13. Derouane, E. G., Andre, J.-M., and Lucas, A. A.,
1966978. J. Catal. 110,58 (1988).
7. Shepelev, S. S., and Ione, K. G., React. Kinet. 14. Derouane, E. G., and Nagy, J. B., Chem. Phys.
Catal. Lett. 23, 319 (1983). Lett. l37(4), 341 (1987).
8. Anderson, J. R., Tsai, P., Appl. Cata!. 19, 141 15. Barthomeuf, D., Mater. Chem. Phys. 17, 49
(1985). (1987).
16. Anderson, J. R., and Tsai, J. Chem. Sot. Chem.
9. Iarlagadda, P. R., Morton, L. A., Hunter, N. R.,
Commun. 19, 1435 (1987).
Gesser, H. D., Fuel. Sci. Technol. Znt. 5(2), 169
17. Hutchings, G. J., Woodhouse, J. R., and Schurrel,
(1987).
M. S., Proceedings, 9th International Congress
10. Argauer, J. R., and Landolt, G. R., U.S. Patent on Catalysis, Calgary, 1988 (M. J. Phillips and
3,702,886 (1972). M. Ternan, Eds.), Vol. 2, pp. 923-929. Chemical
11. Mishin, I. V., Klyachko, A. L., and Rubinstein, Institute of Canada, Ottawa, 1988.
A. M., Zzv. Akad. Nauk SSSR Ser. Khim. 2, 445 18. Liu, R. S., Iwamoto, M., and Lunsford, J. H., J.
(1973). Chem. Sot. Chem. Commun. 78,79 (1982).
12. Beyer, H. K., and Belenykaia, I. M., J. Chem. 19. Takahashi, N., Saito, M., Nagumo, M., and Mijin,
Sot. Faraday Trans. 1 81(11), 2885 (1985). A., Zeolites 6(6), 420 (1986).