Modified zeolite catalyst compositions and methods of use
A modified zeolite catalyst composition is disclosed formed from a zeolite, alumina binder, and matrix. The modified zeolite catalyst composition may contain fluorine. Also disclosed, are methods for the preparation of pyridine and/or its alkylpyridine derivatives in high yield utilizing the modified zeolite catalyst composition.
1 . A method for the preparation of pyridine and/or its alkylpyridine derivatives in high yield the method comprising:
reacting a C2 to Cs aldehyde, a C3 to Cs ketone or a mixture thereof, with ammonia and, optionally formaldehyde, and in the presence of an effective amount of a modified zeolite catalyst composition comprising a zeolite, an alumina binder, and matrix,
wherein at least one of the zeolite, alumina binder, or matrix has been treated with one or more ions of or compounds containing fluorine, wherein the one or more compounds containing fluorine comprise a fluorosilicate.
2 . The method of claim 1 , wherein the zeolite has a constraint index of about 1 to 12.
3 . The method of claim 2 , wherein the zeolite comprises ZSM-5.
4 . The method of claim 1 , wherein the zeolite comprises a modified zeolite that has been modified by treatment with one or more metal ions or compounds of tungsten, zinc, or tin.
5 . The method of claim 1 , wherein the matrix comprises kaolin.
6 . The method of claim 1 , wherein the alumina binder has been treated with one or more compounds containing fluorine prior to being combined with the zeolite and matrix.
7 . The method of claim 1 , wherein the zeolite has been treated with one or more compounds containing fluorine prior to being combined with the alumina binder and matrix.
8 . The method of claim 1 , wherein the matrix has been treated with one or more compounds containing fluorine prior to being combined with the zeolite and alumina binder.
9 . The method of claim 1 , wherein the modified zeolite catalyst comprises from about 30% to about 40% by weight of zeolite, from about 7% to about 12% by weight of alumina binder, and from about 35% to about 48% by weight of matrix.
10 . The method of claim 1 , wherein the fluorosilicate comprises ammonium fluorosilicate, zinc hexafluorosilicate, or combinations thereof.
11 . The method of claim 1 , comprising loading the modified zeolite catalyst composition into a fluid bed reactor and exposing the C2 to C5 aldehyde, the C3 to C5 ketone or a mixture thereof, ammonia and, optionally, formaldehyde to the modified zeolite catalyst composition in the fluid bed reactor.
12 . The method of claim 11 , wherein the C2 to C5 aldehyde, a C3 to C5 ketone or a mixture thereof, ammonia and, optionally, formaldehyde are exposed to the modified zeolite catalyst in the fluid bed reactor for reaction time of at least 4 hours.
13 . The method of claim 1 , where the zeolite comprises a silica to alumina ratio of from about 20:1 to about 60:1.
14 . The method of claim 1 , wherein the modified zeolite catalyst composition comprises one or more particles, wherein the one or more particles have an average particle size of from about 20 μm to about 100 μm.