THE CONVERSION OF 1-PROPANAMINE
27
and the copper metal acts as a mild dehydrogenation cata-
lyst that selectively removes the hydrogen atoms attached
to the nitrogen and adjacent carbon. The results in this pa-
per are consistent with those findings. For both the MFI
and BEA materials the amount of imine formed increases
with increasing copper loadings. Further, the maxima in the
dipropanamine partial pressure curves observed for the Cu-
MFI/VIE and Cu-BEA/VIE are consistent with the conver-
sion of dipropanamine to the imine by dehydrogenation.
7. Shyr, Y. N., and Price, G. L., Ind. Eng. Chem. Prod. Res. Des. 23, 536
1984).
(
8
9
. Corma, A., Palomeres, A., and Marques, F., J. Catal. 170, 132 (1997).
. Wichterlova, B., Dedecek, J., Sobalik, Z., Vondrova, A., and Klier, K.,
J. Catal. 169, 194 (1997).
1
1
0. Hadjiivanov, K. I., Kantcheva, M. M., and Klissurski, D. G., J. Chem.
Soc. Faraday Trans. 92, 4595 (1996).
1. Anpo, M., Matsuoka, M., Shioya, Y., Yamashita, H., Giamello, E.,
Morterra, C., Che, M., Patterson, H., Webber, S., Ouellette, S., and
Fox, M. A., J. Phys. Chem. 98, 5744 (1994).
1
2. Yamashita, H., Matsuoka, M., Tsuji, K., Shioya, Y., Anpo, M., and
Che, M., J. Phys. Chem. 100, 397 (1996).
CONCLUSIONS
13. Connerton, J., Joyner, R. W., and Padley, M. B., J. Chem. Soc. Faraday
Trans. 91, 1841 (1995).
1
1
4. Dedecek, J., and Wichterlova, B., J. Phys. Chem. 98, 572 (1994).
5. Giamello, E., Murphy, D., Magnacca, G., Morterra, C., Shioya, Y.,
Normura, T., and Anpo, M., J. Catal. 136, 510 (1992).
6. Grunert, W., Hayes, N. W., Joyner, R. W., Shpiro, E. S., Siddiqui,
M. R. H., and Baeva, G. N., J. Phys. Chem. 98, 10832 (1994).
A process has been developed for exchanging one cop-
per atom per zeolite ion-exchange site via CuCl vapor
ion-exchange followed by oxidation to convert the cop-
per to a form stable in humid air. These ions exist in
1
the form of copper hydroxyl and copper hydroxyl dimers 17. Larsen, S. C., Aylor, A., Bell, A. T., and Reimer, J. A., J. Phys. Chem.
2
+
9
8, 11533 (1994).
which are stable in air. The Cu ions can be reduced
to Cu1+ ions by either thermal treatment in an inert at-
mosphere or partial hydrogen reduction. Catalytic reac-
tions of copper zeolites with a 1-propanamine reactant
18. Jacobs, P. A., Wilde, W., Schoonheydt, R. A., Uytterhoeven, J., and
Beyer, H., J. Chem. Soc. Faraday I 72, 1221 (1976).
9. Valyon, J., and Hall, W. K., J. Catal. 143, 520 (1993).
1
2
0. Vaylon, J., and Hall, W. K., J. Phys. Chem. 97, 7054 (1993).
induces the reduction of the copper ions to dispersed cop- 21. Ward, J. W., Trans. Faraday Soc. 67, 1489 (1971).
2
2
2. Sarkany, J., and Sachtler, W. M. H., Zeolites 14, 7 (1994).
3. Texter, J., Strome, D. H., Herman, R. G., and Klier, K., J. Phys. Chem.
8
per metal and regenerates the zeolite acid sites, resulting
in a bifunctional catalyst. The zeolite acid sites selectively
dimerize 1-propanamine to dipropanamine and the dis-
persed copper metal dehydrogenates the dipropanamine to
1, 333 (1977).
4. Wichterlova, B., Dedeck, J., and Vondrova, A., J. Phys. Chem. 99, 1065
1995).
2
(
1
-propanamine, N-(1-propylidene) bythe selective removal 25. Beutel, T., Sarkany, J., Lei, G. D., Yan, J. Y., and Sachtler, W. M. H.,
J. Phys. Chem. 100, 845 (1996).
ofthe hydrogen atomsattached to the nitrogen and adjacent
carbon.
2
2
2
6. Yan, J. Y., Lei, G. D., Sachtler, W. M. H., and Kung, H. H., J. Catal.
61, 43 (1996).
7. Petunchi, J. O., Marcelin, G., and Hall, W. K., J. Phys. Chem. 96, 9967
1992).
8. Borovokov, V. Y., and Karge, H. G., J. Chem. Soc. Faraday Trans. 91,
035 (1995).
1
(
ACKNOWLEDGMENTS
2
The authors gratefully acknowledge the financial support of the Na-
tional Science Foundation Grant CTS-9634754.
2
3
9. Huang, Y., J. Catal. 30, 187 (1973).
0. Attfield, M. P., Weigel, S. J., and Cheetham, A. K., J. Catal. 170, 227
(
1997).
REFERENCES
31. Szanyi, J., and Paffett, M. T., J. Catal. 164, 232 (1996).
32. Spoto, G., Bordiga, S., Ricchiardi, G., Scarano, D., Zecchina, A., and
1
2
3
4
. Kanazirev, V. I., Price, G. L., and Dooley, K. M., J. Catal. 148, 164
1994).
. Guidry, T. F., and Price, G. L., in “CatalysisofOrganicReactions” (F. E.
Herkes, Ed.), Marcel Dekker, New York, pp. 601–606 (1998).
. Kuroda, Y., Kotani, A., Maeda, H., Moriwaki, H., Morimato, T., and
Nagao, M., J. Chem. Soc. Faraday Trans. 88, 1583 (1992).
Geobaldo, F., J. Chem. Soc. Faraday Trans. 91, 3285 (1995).
(
33. Lamberti, C., Bordiga, S., Savalggio, M., Spoto, G., Zecchina, A.,
Geobaldo, F., Vlaic, G., and Bellatreccia, M., J. Phys. Chem. B 101,
344 (1997).
34. Li, Y., and Hall, W. K., J. Catal. 129, 202 (1991).
35. Jacobs, P. A., Tielen, M., Linart, J., Uytterhoevan, J. B., and Beyer, H.,
J. Chem. Soc. Faraday I 72, 2793 (1976).
36. Blint, R. J., J. Phys. Chem. 100, 19518 (1996).
37. Trout, B. L., Chakraborty, A. K., and Bell, A. T., J. Phys. Chem. 100,
17582 (1996).
. Kuroda, Y., Kotani, A., Uemura, A., Yoshikawa, Y., and Morimato,
T., J. Chem. Soc. Chem. Commun., 1631 (1989).
5
6
. Price, G. L., and Kanazirev, V., Zeolites 18, 33 (1997).
. Kanazirev, V., Dooley, K. M., and Price, G. L., J. Catal. 146, 228 (1994).