Processes for preparing zincoaluminosilicates with aei, cha, and gme topologies and compositions derived therefrom

Patent metadata

Field	Value
Publication number	US-2016243531-A1
Application number	US-201615050885-A
Country	US
Kind code	A1
Filing date	Feb 23, 2016
Priority date	Feb 24, 2015
Publication date	Aug 25, 2016
Grant date	—

Abstract

The present disclosure is directed to methods of producing zincoaluminosilicate structures with AEI, CHA, and GME topologies using organic structure directing agents (OSDAs), and the compositions and structures resulting from these methods.

First claim

What is claimed:

1 . A process for preparing a zincoaluminosilicate composition, 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; (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; and (c) a source of a zinc oxide; (d) a mineralizing agent; and (e) an organic structure directing agent (OSDA) comprising at least one isomer of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline microporous zincoaluminosilicate solid of AEI or 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 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; 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 (IA) or (TB):

wherein R 2 R 3 , R 5 , and R 6 are independently C 1-3 alkyl. In other Aspects of this Embodiment, the quaternary piperidinium cation has an associated bromide, chloride, fluoride, iodide, nitrate, or hydroxide anion.

3 . The process of claim 1 , wherein the quaternary piperidinium cation of Formula (I) comprises an N,N-dialkyl-2,6-lupetidinium cation or an 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, 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:

and the associated anion is hydroxide.

5 . A process for preparing a zincoaluminosilicate composition of CHA 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; (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; and (c) a source of a zinc oxide; (d) a mineralizing agent; and (e) an organic structure directing agent (OSDA) comprising a trialkyladamantylammonium cation of Formula (II) or an optionally substituted trialkylbenzylammonium cation of Formula (III):

under conditions effective to crystallize a crystalline microporous zincoaluminosilicate solid of CHA topology;
wherein:
R 7 , R 8 , and R 9 are independently C 1-6 alkyl or C 1-3 alkyl; and wherein the quaternary trialkyladamantyl- or trialkylbenzyl-ammonium cation has an associated bromide, chloride, fluoride, iodide, nitrate, or hydroxide anion, and wherein
the phenyl group of the trialkylbenzylammonium cation is optionally substituted with one to three fluoro or optionally fluorinated or perfluorinated C 1-3 alkyl groups.

6 . The process of claim 5 , wherein R 7 , R 8 , and R 9 are each methyl.

7 . The process of claim 1 , wherein the composition being hydrothermally treated comprises a source of silicon oxide, a source of aluminum oxide, and a source of zinc oxide.

8 . The process of claim 1 , wherein:
(a) the source of silicon oxide is or comprises an aluminosilicate, a zincoaluminosilicate, zincosilicate a silicate, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, a silica hydroxide or combination thereof; (b) the source of aluminum oxide is or comprises an alkoxide, hydroxide, or oxide of aluminum, a sodium aluminate, an aluminum siloxide, an aluminosilicate, a zincoaluminosilicate, zincoaluminate or combination thereof; (c) the source of zinc oxide is or comprises a zinc(II) dicarboxylate, zinc(II) halide, zinc(II) hydroxide, zinc(II)oxide, zinc(II)nitrate, zincosilicate, zincoaluminate or zincoaluminosilicate.

9 . The process of claim 1 , wherein the source of silicon oxide comprises sodium silicate, the source of Al comprises a FAU-zeolite, and the source of zinc oxide comprises zinc acetate.

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

11 . The process of claim 1 , wherein:
(a) the molar ratio of Al:Si is in a range of 0.005 to 0.2. (b) the molar ratio of OSDA:Si is in a range of 0.1 to 0.75; (c) the molar ratio of water:Si is in a range of 5 to 50. (d) the molar ratio of total hydroxide:Si is in a range of 0.1 to 1.25; and (e) the molar ratio of Zn:Si is in a range of 0.01 to 0.2.

12 . The process of claim 1 , wherein the conditions effective to crystallize a crystalline microporous zincoaluminosilicate solid of AEI, CHA, or GME topology include treatment of the hydrothermally treated composition at a temperature in a range of from 100° C. to 200° C. for a time effective for crystallizing the crystalline microporous zincoaluminosilicate solid.

13 . The process of claim 1 , further comprising isolating the crystalline microporous zincoaluminosilicate solid.

14 . The process of claim 13 , further comprising the steps of:
(a) heating the isolated crystalline microporous zincoaluminosilicate solid at a temperature in a range of from about 250° C. to about 600° C.; or (b) contacting the isolated crystalline microporous zincoaluminosilicate 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 zincoaluminosilicate solid at a temperature in a range of from about 200° C. to about 600° C. in the presence of an alkali, alkaline earth, transition metal, rare earth metal, ammonium or alkylammonium salt; for a time sufficicient to form a dehydrated or an OSDA-depleted product.

15 . The process of claim 14 , further comprising treating the dehydrated or OSDA-depleted product with an aqueous ammonium or metal cation salt.

16 . The process of claim 14 , further comprising treating at least some pores of the calcined crystalline microporous zincoaluminosilicate solid with at least one type of transition metal or transition metal oxide.

17 . A composition comprising:
(a) a source of a silicon oxide, and optionally a source of germanium oxide, 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; and (c) a source zinc oxide; (d) a mineralizing agent; (e)

Assignees

• California Inst Of Techn

Inventors

• Dusselier Michiel J
• Davis Mark E

Classifications

• C07C2523/06

  of zinc, cadmium or mercury · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• C07C209/14

  by substitution of hydroxy groups or of etherified or esterified hydroxy groups · CPC title

• C07C1/22

  by reduction · CPC title

• C07C4/06

  Catalytic processes {(C07C4/025 takes precedence)} · CPC title