GAS PHASE SYNTHESIS OF MTBE FROM METHANOL AND ISOBUTENE OVER DEALUMINATED ZEOLITES
65
by (partial) cation exchange and (as in the present study) by 18. Nikolopoulos, A. A., Kogelbauer, A., Goodwin Jr., J. G., and Marcelin,
G., Appl. Catal. 119, 69 (1994).
modifying the Si/Al ratio. Different causes have been sug-
1
2
9. Le Van Mao, R., Carli, R., Ahlafi, H., and Ragaini, V., Catal. Lett.
, 321 (1990).
gested to explain the CE (see References in (63)), the most
convincing one being the approach based on changes in the
energy levels of the transition state, proposed by Conner
6
0. Nikolopoulos, A. A., Kogelbauer, A., Goodwin Jr., J. G., and Marcelin,
G., J. Catal. 158, 76 (1996).
(
60) and modified by Patterson and Rooney (64).
21. Nikolopoulos, A.A., Kogelbauer, A., Goodwin Jr., J.G., and
Marcelin, G., Catal. Lett. 39, 173 (1996).
2
2
2
2. Rodriguez-Ramos, I., Guerrero-Ruiz, A., and Fierro, J. L. C., Prep.
Div. Petr. Chem. 36(4), 804 (1990).
3. Kogelbauer, A., Ocal, M., Nikolopoulos, A. A., Goodwin Jr., J. G., and
Marcelin, G., J. Catal. 148, 157 (1994).
4. Kogelbauer, A., Nikolopoulos, A. A., Goodwin Jr., J. G., and Marcelin,
G., J. Catal. 152, 122 (1995).
CONCLUSION
Gas phase synthesis of methyl-tertio butyl ether per-
formed over different dealuminated acid zeolites and pil-
lared clays has shown the following sequence in activity:
beta zeolite = Amb.-15 (ref.) > H-Y = Zr-PILC > omega � 25. Moreno, S., and Poncelet, G., submitted.
2
2
6. Fajula, F., Bourgeat-Lami, E., Zivkov, C., Des Couri e` res, T., and
Anglerot, D., Fr. Pat. 2,069,618 (1992).
7. Jaquinot, E., Raatz, F., Macedo, A., and Marcilly, C., in “Studies in Sur-
face Science and Catalysis,” Vol. 46, p. 118, Elsevier Sci., Amsterdem,
H-ZSM-5 > LP MOR > SP MOR > Al-PILC > SAPOs.
Dealumination has a beneficial effect on the reaction, the
highest conversions being reached for bulk Si/Al ratios be-
tween 13 and 35, according to the type of zeolite. The exter-
1989.
nal surface area appears to contribute to the reaction: beta 28. Ponthieu, E., Grange, P., Joly, J.-F., and Raatz, F., Zeolites 12, 395
(
1992).
zeolite, the most active one, also has the greater Sext value.
As discussed for the series of H-Y zeolites, extraframework
Al species (both in surface and bulk), have a detrimental
influence on the reaction.
2
3
3
3
3
9. Moreno, S., Sun Kou, R., and Poncelet, G., J. Catal. 162, 198 (1996).
0. Moreno, S., Sun Kou, R., and Poncelet, G., J. Phys. Chem., in press.
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(1988).
ACKNOWLEDGMENT
34. Barthomeuf, D., in “Studies in Surface Science and Catalysis,” Vol. 33,
F. Collignon gratefully acknowledges F.R.I.A., Belgium, for a doctoral
grant.
p. 177, Elsevier Sci., Amsterdam, 1987.
35. Ding, T. D., Sun, P. C., Jin, Q. H., Li, B. H., and Wang, J. Z., Zeolites
4, 61 (1994).
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