Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – And additional al or si containing component
Reexamination Certificate
1998-07-31
2001-12-18
Griffin, Steven P. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
And additional al or si containing component
C502S060000, C502S062000, C502S064000, C502S071000, C502S077000, C502S079000, C502S085000, C423S701000, C423S705000, C423S708000, C423SDIG002, C423SDIG002, C423SDIG002
Reexamination Certificate
active
06331500
ABSTRACT:
BACKGROUND
There has been an enormous interest in recent years in exploiting the uniformly sized ar shaped channels and cavities of zeolites and related crystalline molecuar sieves for shape-selective adsorbents and catalysts. Unfortunately, the range of potential substrates and/or reactions are limited by the types of active site functionalities that may be currently engineered into these systems.
Most of the difficulty appears to be related to the small size of the micropores. While playing an essential role in the shape selectively of zeolites and relate molecular sieves, the size restriction also limits the ability to modify the micropores using post-synthetic procedures. For example, in a typical scheme, the free silanol groups dispersed throughout the structure are targeted for further functionalization. However, because exterior surface silanols are much more accessible than those in the interior, most of the functionalization occurs at these exterior sites where shape selectivity is generally not possible.
In another context, organic structure-directing agents (“SDAs”) that contain silicon alkoxides that are covalently attached have been prepared. These organosilanes are used to direct the formation of molecular sieves. In this case, the organic component completely fills the void space. Removal of the organic is the only way to create void spaces in these materials and this yields only an inorganic solid. Hence, using organosilanes as structure-directing agents is not a viable vehicle for functionalization since the SDAs' removal would also eliminate the intended functionality.
As a result, new strategies are required for incorporating functional groups into zeolites and related molecular sieves to fully exploit their potential as shape-selective adsorbents and catalysts.
SUMMARY OF THE INVENTION
The present invention generally relates to molecular sieves which have a crystalline framework and include micropores of substantially uniform size and shape formed therein. These micropores contain one or more accessible organic moieties that are linked to the crystalline framework by a carbon-silicon bond. Shape selectivity of the inventive molecular sieves may be modulated by varying the size and shape of the micropores (which is a function of the particular molecular sieve being synthesized) and the organic moiety incorporated therein.
In general, the inventive methods involve crystallizing a mixture which includes a source of silica and at least one organosilane of the formula
to form a crystalline product, wherein:
n is an integer from 1 to 5;
X is a substituted or unsubstituted moiety and
R
a
i
, R
b
i
, R
c
i
are a set of R
a
, R
b
, and R
c
, s for i=1 to i=n (i.e., R
a
1
, R
b
1
, R
c
1
. . . R
a
n−1
, R
b
n−1
, R
c
n−1
, R
a
n
, R
b
n
, and R
c
n
) wherein each R is independently either any hydrolyzable group, or a substituted or unsubstituted moiety, wherein the moiety is selected from the group consisting of C
1
-C
20
alkyl, C
2
-C
10
alkenyl, C
2
-C
20
alkynyl, cycloalkyl, cycloalkenyl, aryl, and heteroaryl, each optionally substituted with one or more substituents selected from the group consisting of C
1
-C
5
alkyl, C
2
-C
5
alkenyl, C
2
-C
5
alkynyl, cycloalkyl, cycloalkenyl, aryl, and heteroaryl, and a functional group, provided that at least one R in the organosilane compound is a hydrolyzable group. In preferred embodiments, at least one R in a set of R
a
, R
b
, and R
c
is a hydrolyzable group.
The present invention may be practiced both in the presence or absence of a structure directing agent. In preferred embodiments, the inventive methods result in molecular sieves that include crosslinked monomers of the formula
wherein n, X, R
a
i
, and R
b
i
are as previously described. Optionally, the organic moieties incorporated into the micropores may be further modified post-synthetically to include additional organic groups or to form a coordination complex with a metal or metal-containing ion.
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Davis Mark E.
Jones Christopher W.
Tsuji Katsuyuki
Bengtsson W. Patrick
California Institute of Technology
Garde Tanuja V.
Griffin Steven P.
Ildebrando Christina
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