As-synthesized MCM-49 is a three-dimensional (3D) microporous
aluminosilicate zeolite with the MCM-22
framework topology. It is formed hydrothermally in a reaction gel
and is the first example of a zeolite with
this topology to be produced by direct synthesis, in contrast with the
conventional procedure in which a
precursor is formed first and is then calcined. When
hexamethyleneimine (HMI) is used as the directing
agent, a SiO2/Al2O3 ratio of the
framework as low as 17/1 can be achieved. X-ray powder diffraction
(XRD),
temperature programmed base desorption (TPBD) experiments, and
multinuclear NMR analyses of this zeolite
and others in this series (viz., calcined MCM-22 and its
precursor) provide new insights into the novelty of
this class of materials. TPBD and 13C NMR experiments,
for example, provide experimental evidence that
support the coexistence of different dual pore systems within both the
MCM-22 precursor and MCM-49.
The 27Al MAS NMR spectra of MCM-22 and calcined
MCM-49 exhibit three distinct Td resonances, a
feature
not previously observed for any other zeolite. And finally,
aluminum enrichment of the T1−O1−T1 bridge
in MCM-49 is postulated on the basis of the length of its unit cell
c-parameter.
It is demonstrated that zeolite β and zeolite β containing
catalysts can be dealuminated to very low acidity
levels using a novel oxalic acid treatment without reducing zeolite
integrity. The effect of the oxalic acid
treatment has been studied over a wide range of treatment conditions
for both silica-bound and unbound
zeolite β catalysts. Greater than 90% dealumination is observed
with a concomitant reduction in n-hexane-cracking activity as measured by the alpha (α) test. Removal of
framework aluminum occurs via a two-step
hydrolysis/chelation mechanism, with the oxalic acid acting both as an
acid and as a chelating agent.
Framework aluminum removal is accompanied by the formation of
internal silanol groups. Water soluble
aluminum oxalates are present in the extracted solutions. Silanol
groups are annealed with extended oxalic
acid treatment. Oxalic acid treatment results in a unique
contraction of the zeolite β lattice structure not
observed for mineral acid treated or steamed zeolite β
catalysts.
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