Further investigations on Constraint Index testing of zeolites that contain cages

Zeolites such as SSZ-25 and SSZ-35 exhibit Constraint Indexes (CI) lower than expected. Two hypotheses for the origin of the lower CI values are that partial cages on the external surface of the zeolites significantly contribute to the overall conversions and that the large cages within the crystalline structures provide less steric hinderence at the active site than would be expected from the size of the pores. The effect of external surface activity is observed by comparing the as-synthesized materials to those passivated via dealumination with ammonium hexafluorosilicate. The external surface dealumination is verified by XPS and by the reduction in reactivity toward isopropanol dehydration observed from materials still containing their SDAs. The external surface of calcined zeolites is shown to have little influence on the CI value. Cage accessibility is investigated by comparisons of structures having larger cages to those that do not and by following the time dependent behavior of the CI values for these materials. The presence of large cages in the zeolites is shown to lower the CI values below those expected from the pore sizes, and the time dependence of the CI value can provide insight into the existence of these larger cage structures. (c) 2009 Elsevier Inc. All rights reserved.