Crystalline germanosilicate materials of new cit-13 topology and methods of preparing the same

Patent metadata

Field	Value
Publication number	US-2016346771-A1
Application number	US-201615169816-A
Country	US
Kind code	A1
Filing date	Jun 1, 2016
Priority date	Jun 1, 2015
Publication date	Dec 1, 2016
Grant date	—

Abstract

The present disclosure is directed to novel crystalline germanosilicate compositions and methods of producing the same. In particular, the crystalline germanosilicate compositions are extra-large-pore compositions, designated CIT-13 possessing 10- and 14-membered rings. The disclosure describes methods of preparing these compositions using substituted benzyl-imidazolium organic structure-directing agents (OSDAs). Also disclosed are methods of using these crystalline compositions.

First claim

What is claimed:

1 . A crystalline microporous germanosilicate composition comprising a three dimensional framework having pores defined by 10- and 14-membered rings.

2 . A crystalline microporous germanosilicate composition which exhibits at least one of:
(a) a powder X-ray diffraction (XRD) pattern exhibiting at least five of the characteristic peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2, 18.36±0.2, 18.63±0.2, 20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2, 26.01±0.2, and 26.68±0.2 degrees 2-θ; (b) a powder X-ray diffraction (XRD) pattern substantially the same as shown in FIG. 1(B) or FIG. 1(C) ; or (c) unit cell parameters substantially equal to the following at:

Space group
Cmmm

a (Å)
 27.4374(5)

b (Å)
 13.8000(2)

c (Å)
 10.2910(2)

V (Å 3 )
3896.6(1)

Z
  8

ρ (g/cm 3 )
  2.144(2)

λ (Å)
  0.776381(1)

3 . The crystalline microporous germanosilicate composition of claim 1 , which exhibits a powder X-ray diffraction (XRD) pattern exhibiting at least five of the characteristic peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2, 18.36±0.2, 18.63±0.2, 20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2, 26.01±0.2, and 26.68±0.2 degrees 2-θ.

4 . The crystalline microporous germanosilicate composition of claim 1 which exhibits a powder X-ray diffraction (XRD) pattern substantially the same as shown in FIG. 1(B) or 1(C) .

5 . The crystalline microporous germanosilicate composition of claim 1 which exhibits unit cell parameters substantially equal to the following:

Space group
Cmmm

a (Å)
27.4374(5)

b (Å)
13.8000(2)

c (Å)
10.2910(2)

V (Å 3 )
3896.6(1)

Z
8

ρ (g/cm 3 )
2.144(2)

λ (Å)
0.776381(1)

6 . The crystalline microporous germanosilicate composition of claim 2 , exhibiting at least two of (a), (b), or (c).

7 . The crystalline microporous germanosilicate of claim 1 , wherein the pore dimensions of the 10- and 14-membered rings are 6.2×4.5 Å and 9.1×7.2 Å, respectively.

8 . The crystalline microporous germanosilicate composition of claim 2 , comprising germanium and having a ratio of Si:Ge atoms in a range of from 2:1 to 16:1.

9 . The crystalline microporous germanosilicate of claim 2 , that is substantially free of an organic structure-directing agent (OSDA)

10 . The crystalline microporous germanosilicate composition of claim 2 , further comprising at least one substituted benzyl-imidazolium organic structure-directing agent (OSDA).

11 . The crystalline microporous germanosilicate composition of claim 10 , wherein the at least one substituted benzyl-imidazolium organic structure-directing agent has a structure:

but not

wherein m and n are independently 1, 2, or 3, and R 1 , R 2 , and R 3 are independently at each occurrence C 1-3 alkyl.

12 . The crystalline microporous germanosilicate composition of claim 11 , wherein the at least one substituted benzyl-imidazolium organic structure-directing agent has a structure:

13 . An aqueous composition comprising:
(a) a source of silicon oxide (b) a source of germanium oxide; (c) a mineralizing agent; (d) at least one substituted benzyl-imidazolium organic structure-directing agent (OSDA) having a structure:

but not

wherein m and n are independently 1, 2, or 3, and R 1 , R 2 , and R 3 are independently at each occurrence C1-3 alkyl; and
(e) a crystalline microporous germanosilicate of claim 2 .

14 . The aqueous composition of claim 13 , wherein:
(a) the source of silicon oxide comprises tetraethyl orthosilicate (TEOS); or (b) the source of germanium oxide comprises GeO 2 , or a hydrated derivative thereof; or (c) both (a) and (b).

15 . The aqueous composition of claim 13 , wherein the mineralizing agent comprises:
(a) a fluoride source comprising hydrofluoric acid, or a salt or derivative thereof; (b) an alkali metal hydroxide or alkaline earth metal hydroxide, or combination thereof.

16 . The aqueous composition of any one of claim 13 , wherein the at least one substituted benzyl-imidazolium organic structure-directing agent has a structure:

17 . The aqueous composition of any one of claim 13 , wherein the crystalline microporous germanosilicate has occluded within its pores at least one of the substituted benzyl-imidazolium organic structure-directing agents.

18 . The aqueous composition of any one of claim 13 , wherein the composition is a suspension or a gel.

19 . A method comprising hydrothermally treating an aqueous composition comprising:
(a) a source of silicon oxide (b) a source of germanium oxide; (c) a mineralizing agent; (d) at least one substituted benzyl-imidazolium organic structure-directing agent (OSDA) having a structure:

Assignees

• California Inst Of Techn

Inventors

• Schmidt Joel E
• Davis Mark E
• Boal Ben W
• Kang Jong Hun

Classifications

• C07C6/12

  of exclusively hydrocarbons containing a six-membered aromatic ring · CPC title

• C01B39/08 Primary

  the aluminium atoms being wholly replaced · CPC title

• C07C5/412

  with metal oxides or metal sulfides · CPC title

• C01B33/20 Primary

  Silicates (persilicates C01B15/14 {; containing aluminium C01B33/26}) · CPC title

• B01J29/047 Primary

  Germanosilicates; Aluminogermanosilicates (B01J29/005 takes precedence) · CPC title