Methods to produce zeolites with the gme topology and compositions derived therefrom

Patent metadata

Field	Value
Publication number	US-2021069682-A1
Application number	US-202016952486-A
Country	US
Kind code	A1
Filing date	Nov 19, 2020
Priority date	Feb 24, 2015
Publication date	Mar 11, 2021
Grant date	—

Abstract

The present disclosure is directed to microporous crystalline aluminosilicate structures with GME topologies having pores containing organic structure directing agents (OSDAs) comprising at least one piperidinium cation, the compositions useful for making these structures, and methods of using these structures. In some embodiments, the crystalline zeolite structures have a molar ratio of Si:Al that is greater than 3.5.

First claim

What is claimed:

1 . A crystalline microporous aluminosilicate composition of GME topology comprising:
(a) an oxide of silicon, and optionally an oxide of germanium; (b) an oxide of aluminum, and optionally one or more oxides of boron, gallium, hafnium, iron, tin, titanium, indium, vanadium, or zirconium, wherein the molar ratio of the metals of (a) to the metals of (b) is greater than 3.5 to about 100; and which crystalline microporous aluminosilicate composition of GME topology exhibits a powder XRD pattern having at least five peaks having 2-theta values at 7.5±0.1°, 11.6±0.1°, 14.9±0.1°, 17.9±0.2°, 19.9±0.1°, 21.75±0.15°, 28.1±0.2°, or 30.1±0.1°, wherein the crystalline microporous aluminosilicate composition has pores that contain at least one isomer of the quaternary piperidinium cation of Formula (I):

wherein
R A and R B are independently a C 1-3 alkyl, or together with the N to which they are bound form a 5 or 6 membered saturated or unsaturated ring; and
R 2 , R 3 , R 4 , R 5 , and R 6 are independently H or C 1-3 alkyl, provided at least two of R 2 , R 3 , R 4 , R 5 , and R 6 are independently C 1-3 alkyl; and
the quaternary piperidinium cation has an associated bromide, chloride, fluoride, iodide, nitrate, or hydroxide anion.

2 . The crystalline microporous aluminosilicate composition of claim 1 , having a molar ratio of Si:Al that is greater than 3.5 to about 100.

3 . The crystalline microporous aluminosilicate composition of claim 1 , that exhibits one or more of:
(a) an XRD diffraction pattern that is the same as or consistent with any one of those shown in FIG. 3 , FIG. 6 , FIG. 7 , or FIG. 13 ; (b) an 29 Si MAS spectrum having a plurality of chemical shifts of about −99.1, −104.9 and −110.5 ppm, downfield of a peak corresponding to an external standard of tetramethylsilane; (c) an 29 Si MAS spectrum that is the same as or consistent with the one shown in FIG. 13 ; (d) an 27 Al MAS NMR spectrum that is the same as or consistent with the one shown in FIG. 11 , or (e) a thermogravimetric analysis curve that is the same as or consistent with the one shown in FIG. 4 ; or (f) a 13 C CP MAS NMR spectrum that is the same as or consistent with the one shown in FIG. 5 .

4 . The crystalline microporous aluminosilicate composition of claim 1 , wherein the at least one isomer of the quaternary piperidinium cation of Formula (I) comprises at least one isomer of the quaternary piperidinium cation of Formula (IA) or (IB):

wherein R 2 R 3 , R 5 , and R 6 are independently C 1-3 alkyl.

5 . The crystalline microporous aluminosilicate composition of claim 1 , wherein the at least one isomer of the quaternary piperidinium cation of Formula (I) comprises an N,N-dialkyl-2,6-lupetidinium cation or N,N-dialkyl-3,5-lupetidinium cation:

or

6 . The crystalline microporous aluminosilicate composition of claim 1 , wherein the at least one isomer of the quaternary piperidinium cation of Formula (I) comprises cis-N,N-dimethyl-3,5-lupetidinium cation, trans-N,N-dimethyl-3,5-lupetidinium cation, cis-N,N-dimethyl-2,6-lupetidinium cation, trans-N,N-dimethyl-2,6-lupetidinium cation or a combination thereof.

7 . The crystalline microporous aluminosilicate composition of claim 1 , prepared by a process comprising hydrothermally treating an aqueous composition comprising:
(a) a source of a silicon oxide, and optionally a source of germanium oxide, or combination thereof, wherein the source of silicon oxide is an aluminosilicate, a silicate, a silica hydrogel, amorphous silica, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, a silica hydroxide, silicon alkoxide, or combination thereof; (b) a source of aluminum oxide, and optionally a source of boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, or combination or mixture thereof, wherein the source of aluminum oxide is an alkoxide, hydroxide, or oxide of aluminum, a sodium aluminate, an aluminum siloxide, an aluminosilicate, or combination thereof; (c) a mineralizing agent comprising an aqueous hydroxide; (d) an organic structure directing agent (OSDA) comprising at least one isomer of the quaternary piperidinium cation of Formula (I):

and
(e) water;
under conditions to crystallize the crystalline microporous solid of GME topology containing the at least one isomer of the quaternary piperidinium cation of Formula (I);
wherein
R A and R B are independently a C 1-3 alkyl, or together with the N to which they are bound form a 5 or 6 membered saturated or unsaturated ring; and
R 2 , R 4 , and R 6 are H and R 3 and R 5 are cis-positioned C 1-3 alkyl; wherein
the quaternary piperidinium cation has an associated bromide, chloride, fluoride, iodide, nitrate, or hydroxide anion.

8 . The crystalline microporous aluminosilicate composition of claim 7 , wherein the OSDA comprises at least one isomer of the quaternary piperidinium cation of Formula (IB):

wherein R 3 and R 5 are independently C 1-3 alkyl.

9 . The crystalline microporous aluminosilicate composition of claim 7 , wherein the quaternary piperidinium cation of Formula (I) comprises a cis-N,N-dialkyl-3,5-lupetidinium cation:

10 . The crystalline microporous aluminosilicate composition of claim 7 , wherein the quaternary piperidinium cation of Formula (I) comprises cis-N,N-dimethyl-3,5-lupetidinium cation

and the associated anion is hydroxide.

11 . An aqueous composition for preparing the crystalline microporous composition of GME topology of claim 1 , the composition comprising:
(a) a source of a silicon oxide, and optionally a source of germanium oxide; (b) a source of aluminum oxide, and optionally a source of boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, or combination or mixture thereof; (c) water; (d) a mineralizing agent comprising an aqueous hydroxide; (e) an organic structure directing agent (OSDA) comprising at least one isomer of the quaternary piperidinium cation of Formula (I):

and
(e) a compositionally consistent crystalline microporous solid of GME topology;
wherein
R A and R B are independently a C 1-3 alkyl, or together with the N to which they are bound form a 5 or 6 membered saturated or unsaturated ring; and
R 2 R 3 , R 5 , and R 6 are independently C 1-3 alkyl; and wherein

the quaternary piperidinium cation has an associated bromide, chloride, fluoride, iodide, or hydroxide anion.

12 . The aqueous composition of claim 11 , wherein the OSDA comprises
(a) at least one isomer of the quaternary piperidinium cation of Formula (IA) or (IB):

Assignees

• California Inst Of Techn

Inventors

• Dusselier Michiel J
• Davis Mark E

Classifications

• C10G49/08

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• C10G2400/22

  Higher olefins · CPC title

• C07C2521/12

  Silica and alumina · CPC title

• C01B39/48

  using at least one organic template directing agent · CPC title