Small crystal ferrierite and method of making the same
View Patent ↗There is disclosed a highly crystalline, small crystal, ferrierite zeolite prepared from a gel containing a source of silica, alumina, alkali metal and a combination of two templating agents. The resulting material includes ferrierite crystals having a particle size of about or less than about 200 nm. The desired crystal size can be achieved by using a specific composition of the gel. The purity of the material and the crystal size was determined by using X-ray powder diffraction and scanning electron microscopy. The material has excellent surface area and micropore volume as determined by nitrogen adsorption.
1. A crystalline microporous material having a ferrierite (FER) framework type, a molar ratio of greater than about 10 of a first tetravalent metal oxide to a second tetravalent or trivalent metal oxide, and a mean crystal size of about 200 nm or less,
wherein the crystalline microporous material has a surface area ranging from about 300 m 2 /g to about 450 m 2 /g and a micropore volume ranging from about 0.10 cc/g to about 0.20 cc/g.
2. The crystalline microporous material of claim 1 , wherein said material has a crystal size of about 200 nm or less in all crystal dimensions.
3. The crystalline microporous material of claim 1 , wherein said first tetravalent metal oxide comprises silica, said second tetravalent metal oxide comprises alumina, and wherein said molar silica to alumina ratio (SAR) ranges from about 10 to about 60.
4. The crystalline microporous material of claim 1 , wherein said material has a mean crystal size of about 100 nm or less in all crystal dimensions.
5. The crystalline microporous material of claim 1 , further comprising at least one hydrogenation-function metal.
6. The crystalline microporous material of claim 5 , wherein said at least one hydrogenation-function metal is chosen from Pt, Pd, Rh, Ru, Ni, Re, and mixtures thereof.
7. The crystalline microporous material of claim 1 , further comprising at least one transition metal for selective catalytic reduction of nitrogen oxides and/or catalytic decomposition of nitrous oxide.
8. The crystalline microporous material of claim 7 , wherein said at least one transition metal is chosen from Cu and Fe.
9. A method of preparing a crystalline microporous material having a ferrierite (FER) framework type, a molar silica to alumina ratio (SAR) of greater than about 10, and a mean crystal size of about 200 nm or less, said method comprising
forming a synthesis mixture comprising a silica source, an alumina source, an alkali metal source, and organic structure directing agents comprising:
a first organic structure directing agent (OSDA-1), and
a second organic structure directing agent (OSDA-2) that promotes ferrierite structure formation, wherein a molar ratio of OSDA-1 to OSDA-2 ranges from about 0.2 to about 1.0; and,
heating the synthesis mixture to a temperature ranging from about 120 to about 200° C. for a period of time sufficient to crystallize the material, to form a crystalline microporous material having a surface area ranging from about 300 m 2 /g to about 450 m 2 /g and a micropore volume ranging from about 0.10 cc/g to about 0.20 cc/g.
10. The method of claim 9 , wherein said OSDA-1 comprises a tetramethylammonium cation.
11. The method of claim 9 , wherein said OSDA-2 is chosen from pyrrolidine, ethylenediamine 1,3-diaminopropane, 1-methylpyrrolidine, piperidine, pyridine and 1,4-diaminobutane.
12. The method of claim 9 , wherein said organic structure directing agents comprise a tetramethylammonium cation and 1,3-diaminopropane.
13. The method of claim 9 , wherein said organic structure directing agents comprise a tetramethylammonium cation and pyrrolidine.
14. A catalyst comprising a crystalline microporous material having a ferrierite (FER) framework type, a molar silica to alumina ratio (SAR) of greater than about 10, a surface area ranging from about 300 m 2 /g to about 450 m 2 /g, a micropore volume ranging from about 0.10 cc/g to about 0.20 cc/g, and a mean crystal size of about 200 nm or less in all dimensions, wherein said catalyst is catalytically active for at least one process chosen from hydrocarbon conversions, selective catalytic reduction of nitrogen oxides, and catalytic decomposition of nitrous oxide.
15. The catalyst of claim 14 , further comprising at least one hydrogenation-function metal for hydrocarbon conversions.
16. The catalyst of claim 15 , wherein said at least one hydrogenation-function metal is chosen from Pt, Pd, Rh, Ru, Ni, Re, and mixtures thereof.
17. The catalyst of claim 14 , further comprising at least one transition metal for selective catalytic reduction of nitrogen oxides and/or catalytic decomposition of nitrous oxide.
18. The catalyst of claim 17 , wherein said at least one transition metal is chosen from Cu and Fe.