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

Patent metadata

Field	Value
Publication number	US-9878312-B2
Application number	US-201615050839-A
Country	US
Kind code	B2
Filing date	Feb 23, 2016
Priority date	Feb 24, 2015
Publication date	Jan 30, 2018
Grant date	Jan 30, 2018

Abstract

The present disclosure is directed to producing zeolite structures with GME topologies using organic structure directing agents (OSDAs) comprising a piperidinium cation, and the compositions and structures resulting from these methods. In some embodiments, the crystalline products have a molar ratio of a molar ratio of Si:Al that is greater than 3.5.

First claim

What is claimed:

1. A process for preparing an aluminosilicate composition of CIT-9 topology, the 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):

(e) water, wherein the ratio of water to Si in the source of silicon oxide is in a range of from 11.9 to 22.1;

under conditions to crystallize a 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 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.

2. The process of claim 1 , 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.

3. The process of claim 1 , wherein the quaternary piperidinium cation of Formula (I) comprises a cis-N,N-dialkyl-3,5-lupetidinium cation:

4. The process of claim 1 , wherein the quaternary piperidinium cation of Formula (I) comprises cis-N,N-dimethyl-3,5-lupetidinium cation

and the associated anion is hydroxide.

5. The process of claim 1 , wherein the quaternary piperidinium cation has an associated fluoride or hydroxide ion.

6. The process of claim 1 , wherein:
(a) the source of aluminum oxide comprises an aluminosilicate; and
(b) the source of silicon oxide comprises an aluminosilicate, sodium silicate, or a tetra-alkyl-orthosilicate.

7. The process of claim 1 , wherein the mineralizing agent comprises an aqueous alkali metal hydroxide or alkaline earth metal hydroxide.

8. The process of claim 1 , wherein:
(a) the molar ratio of Al:Si is in a range of from 0.0067 to 0.5 (or the molar ratio of Si:Al is in a range of from 2 to 150);
(b) the molar ratio of OSDA:Si is in a range of from 0.01 to 0.75;
(c) the molar ratio of water:Si is in a range of from 11.9 to 22.1; and
(d) the molar ratio of total hydroxide:Si is in a range of 0.1 to 1.25.

9. The process of claim 1 , wherein the conditions to crystallize a crystalline microporous solid of GME topology include treatment of the hydrothermally treated composition at a temperature in a range of from 100° C. to 200° C.

10. The process of claim 1 , further comprising isolating the crystalline microporous solid of GME topology.

11. The process of claim 10 , further comprising:
(a) heating the isolated crystalline microporous solid at a temperature in a range of from 205° C. to 450° C.;
(b) contacting the isolated crystalline microporous solid with ozone or other oxidizing agent at a temperature in a range of 100° C. to 200° C.; or
(c) heating the isolated crystalline microporous solid at a temperature in a range of from 200° C. to 600° C. in the presence of an alkali, alkaline earth, transition metal, rare earth metal, ammonium or alkylammonium salt;
for a time sufficient to form a dehydrated or an OSDA-depleted product.

12. The process of claim 11 , further comprising:
(a) treating the dehydrated or OSDA-depleted project with an aqueous alkali, alkaline earth, transition metal, rare earth metal, ammonium or alkylammonium salt; or
(b) treating the dehydrated or OSDA-depleted product with at least one type of transition metal or transition metal oxide; or
(c) treating the dehydrated or OSDA-depleted product according to (a) and (b).

Assignees

• California Inst Of Techn

Inventors

• Dusselier Michiel J
• Davis Mark E

Classifications

• B01D53/8628

  Processes characterised by a specific catalyst · CPC title

• C07C29/48

  by oxidation reactions with formation of hydroxy groups · CPC title

• C07C2521/12

  Silica and alumina · CPC title

• B01D2255/20792

  Zinc · CPC title

• C07C67/37

  by reaction of ethers with carbon monoxide · CPC title