Uzm-45 Aluminosilicate Zeolite, Method Of Preparation And Processes Using Uzm-45

PATENT

Uzm-45 Aluminosilicate Zeolite, Method Of Preparation And Processes Using Uzm-45

United States Patent Application 20120004486

Inventors:

Lewis, Gregory J. (Santa Cruz, CA, US)

Miller, Mark A. (Niles, IL, US)

Application Number: 13/172084

Publication Date: 01/05/2012

Assignee: UOP LLC (Des Plaines, IL, US)

Abstract:

A new family of crystalline aluminosilicate zeolites has been synthesized designated UZM-45. These zeolites are represented by the empirical formula. Mmn+Rrp+Al(1-x)ExSiyOz where M is an alkali, alkaline earth, or rare earth metal such as lithium and strontium, R is an organoammonium cation such as the choline cation and E is a framework element such as gallium. These zeolites are characterized by unique x-ray diffraction patterns and compositions and have catalytic properties for carrying out various hydrocarbon conversion processes.

FIELD OF THE INVENTION

This invention relates to a new family of aluminosilicate zeolites designated UZM-45 which are represented by the empirical formula of:

Mmn+Rrp+Al1-xExSiyOz

where M is an exchangeable cation such as potassium or strontium, R is an organoammonium cation such as choline and E is a framework element such as gallium.

BACKGROUND OF THE INVENTION

Zeolites are crystalline aluminosilicate compositions which are microporous and which are formed from corner sharing AlO2 and SiO2 tetrahedra. Numerous zeolites, both naturally occurring and synthetically prepared are used in various industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis employing suitable sources of Si, Al and structure directing agents such as alkali metals, alkaline earth metals, amines, or organoammonium cations. The structure directing agents reside in the pores of the zeolite and are largely responsible for the particular structure that is ultimately formed. These species balance the framework charge associated with aluminum and can also serve as space fillers. Zeolites are characterized by having pore openings of uniform dimensions, having a significant ion exchange capacity, and being capable of reversibly desorbing an adsorbed phase which is dispersed throughout the internal voids of the crystal without significantly displacing any atoms which make up the permanent zeolite crystal structure. Zeolites can be used as catalysts for hydrocarbon conversion reactions, which can take place on outside surfaces as well as on internal surfaces within the pore.

One particular zeolite, designated UZM-22, was first disclosed by Miller in 2010, see U.S. Pat. No. 7,744,850. This patent describes the synthesis of UZM-22 from a choline structure directing agent in combination with either Li, Sr, or both cations, using the Charge Density Mismatch (CDM) approach to zeolite synthesis as described in U.S. Pat. No. 7,578,993. The UZM-22 zeolite has the MEI structure as defined by Database of Zeolite Structures, http://www.iza-structure.org/databases, which consists of 1-dimensional 12-ring pores with a 7 Å aperture, along with a perpendicular 7-ring pore system. Further work was performed with the choline structure directing agent along with various combinations of alkali and alkaline earth cations, using the CDM approach along with combinatorial high throughput synthesis methods. The screen of the choline-alkali-alkaline earth aluminosilicates yielded many known zeolite structures, including OFF, ERI, LTL, FAU, FER, LTA, CHA, BPH, MEI, and others. A new zeolite structure named UZM-45 was also generated.

Applicants have successfully prepared a new family of materials designated UZM-45. The topology of UZM-45 is unique as determined by x-ray diffraction. The materials are prepared via the use of a simple commercially available structure directing agents, such as choline hydroxide, [HO(CH2)2NMe3]+OH−, in concert with small amounts of Sr2+ and K+ together, using the CDM approach to zeolite synthesis.

SUMMARY OF THE INVENTION

As stated, the present invention relates to a new aluminosilicate zeolite designated UZM-45. Accordingly, one embodiment of the invention is a microporous crystalline zeolite having a three-dimensional framework of at least AlO2 and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:

Mmn+Rrp+Al1-xExSiyOz

where M is at least one exchangeable cation selected from the group consisting of alkali, alkaline earth, and rare earth metals, “m” is the mole ratio of M to (Al+E) and varies from 0 to about 4.0, R is an organoammonium cation selected from the group consisting of choline, ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), trimethylpropylammonium, trimethylbutylammonium, dimethyldiethanolammonium, tetraethylammonium (TEA+), tetrapropylammonium (TPA+), hexamethonium, and mixtures thereof, “r” is the mole ratio of R to (Al+E) and has a value of about 0.25 to about 4.0, “n” is the weighted average valence of M and has a value of about 1 to about 3, “p” is the weighted average valence of R and has a value of about 1 to 2, E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof, “x” is the mole fraction of E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 3 to about 20 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:

z=(m·n+r·p+3+4·y)/2

and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A

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