Producing zeolite ssz-39 using isomeric mixtures of organic structure directing agents

Patent metadata

Field	Value
Publication number	US-2016122192-A1
Application number	US-201514929571-A
Country	US
Kind code	A1
Filing date	Nov 2, 2015
Priority date	Nov 3, 2014
Publication date	May 5, 2016
Grant date	—

Abstract

The present disclosure is directed to producing zeolite structures, especially Zeolite SSZ-39, using organic structure directing agents (OSDAs). In particular, the OSDAs comprise isomeric mixtures of N,N-dialkyl piperidinium cations.

First claim

What is claimed:

1 . A process comprising hydrothermally treating a composition comprising:
(a) at least one source of silicon oxide, germanium oxide, or a combination thereof; (b) water; and (c) an organic structure directing agent mixture comprising at least two isomers of the quaternary piperidinium cation of Formula (I):

under conditions effective to crystallize a crystalline composition having an AEI framework 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 a C 1-3 alkyl, provided at least one of R 2 , R 3 , R 4 , R 5 , and R 6 is independently C 1-3 alkyl.

2 . The process of claim 1 , wherein the composition further comprises at least one source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, or a combination thereof.

3 . The process of claim 1 or 2 , wherein R 2 =R 4 =R 6 =H and R 3 =R 5 =methyl.

4 . The process of claim 1 or 2 , wherein R 3 =R 4 =R 5 =H and R 2 =R 6 =methyl.

5 . The process of claim 1 or 2 , wherein R A and R B are independently a C 1-3 alkyl.

6 . The process of claim 1 or 2 , wherein both R A and R B , together with the N to which they are bound, form a spiro-pyrrolidinium or spiro-piperidinium moiety:

or wherein both R A and R B , together with the N to which they are bound, form a spiro-2,5-dihydro-1H-pyrrolium moiety:

7 . The process of claim 1 or 2 , wherein at least two isomers of the quaternary piperidinium cation of Formula (I) are structural isomers of one another.

8 . The process of claim 1 or 2 , wherein at least two isomers of the quaternary piperidinium cation of Formula (I) are stereo-isomers of one another.

9 . The process of claim 1 or 2 , wherein the quaternary piperidinium cation of Formula (I) is an N,N-dialkyl-3,5-lupetidinium cation, N,N-dialkyl-2,6-lupetidinium cation, or a combination thereof.

10 . The process of claim 9 , wherein the quaternary piperidinium cation of Formula (I) is an N,N-dimethyl-3,5-lupetidinium cation, N,N-dimethyl-2,6-lupetidinium cation, N,N-diethyl-3,5-lupetidinium cation, N,N-diethyl-2,6-lupetidinium cation, a 6,10-dimethyl-5-azonia-spiro[4.5]decane, a 1,5-dimethyl-6-azonia-spiro[5.5]undecane, a 7,9-dimethyl-5-azonia-spiro[4.5]decane, a 2,4-dimethyl-6-azonia-spiro[5.5]undecane, or a combination thereof:

11 . The process of claim 1 or 2 , wherein the at least two isomers of the quaternary piperidinium cation of Formula (I) comprise cis-N,N-dialkyl-3,5-lupetidinium cation, trans-N,N-dialkyl-3,5-lupetidinium cation, cis-N,N-dialkyl-2,6-lupetidinium cation, trans-N,N-dialkyl-3,5-lupetidinium cation, or a combination thereof.

12 . The process of claim 11 , wherein the at least two isomers of the quaternary piperidinium cation of Formula (I) comprise 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-3,5-lupetidinium cation, or a combination thereof.

13 . The process of claim 1 or 2 , wherein the at least two isomers of the quaternary piperidinium cation of Formula (I) comprise a mixture of cis-N,N-dimethyl-3,5-lupetidinium cation and trans-N,N-dimethyl-3,5-lupetidinium cation in a ratio of about 95% cis/10% trans to about 10% cis/95% trans.

14 . The process of claim 1 or 2 , wherein the organic structure directing agent mixture comprises a bromide, chloride, fluoride, iodide, or hydroxide salt.

15 . The process of any one of claim 1 or 2 , wherein the source of silicon oxide comprises a silicate, silica hydrogel, silicic acid, fumed silica, colloidal silica, tetra-alkyl orthosilicate, a silica hydroxide or combination thereof.

16 . The process of claim 2 , wherein the source of aluminum oxide comprises an alkoxide, hydroxide, or oxide of aluminum, a sodium aluminate, an aluminum siloxide, an aluminosilicate, or combination thereof.

17 . The process of claim 2 , wherein the source of boron oxide, gallium oxide, germanium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, zirconium oxide, or combination or mixture thereof comprises an alkoxide, hydroxide, oxide, or combination thereof of the corresponding metal.

18 . The process of claim 2 , wherein the mole ratio of Si:Al in the composition is in a range of from about 5:1 to about 250:1.

19 . The process of claim 1 or 2 , wherein the mole ratio of water to Si is in a range of from about 2:1 to about 50:1.

20 . The process of claim 1 or 2 , wherein the mole ratio of piperidinium cation to Si is in a range of from about 0.01:1 to about 1:1.

21 . The process of claim 1 or 2 , wherein the composition to be hydrotreated further comprises aqueous hydroxide.

22 . The process of Embodiment 21, wherein the mole ratio of hydroxide to Si in the composition is in a range of from about 0.5:1 to about 1:1.

23 . The process of claim 1 or 2 , wherein the hydrothermal treating is done at a temperature in a range of from about 100° C. to about 200° C. for a time effective for crystallizing the crystalline microporous solid.

24 . The process of claim 1 or 2 , further comprising isolating the crystalline microporous solid.

25 . The process of claim 1 or 2 , further comprising calcining the crystalline microporous solid at a temperature in a range of from about 350° C. to about 850° C.

26 . The process of claim 25 , further comprising treating the calcined material with an aqueous ammonium salt.

27 . The process of claim 25 , further comprising treating at least some pores of the calcined crystalline microporous solid with at least one type of alkaline earth metal or alkaline earth metal oxide, transition metal or transition metal oxide.

28 . A composition comprising:
(a) at least one source of silicon oxide, germanium oxide, or a combination thereof; (b) water; (c) an organic structure directing agent mixture comprising at least two isomers of the quaternary piperidinium cation of Formula (I):

and
(d) a compositionally consistent crystalline microporous solid of an AEI framework;
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 a C 1-3 alkyl, provided at least one, preferably two of R 2 , R 3 , R

Assignees

• California Inst Of Techn

Inventors

• Dusselier Michiel J
• Davis Mark E
• Schmidt Joel E

Classifications

• C01B39/04 Primary

  using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title

• B01D2255/9205

  Porosity · CPC title

• B01D2255/20715

  Zirconium · CPC title

• B01D2255/20707

  Titanium · CPC title