Zeolites using an organo-1-oxa-4-azoniumcyclohexane compound

Patent metadata

Field	Value
Publication number	US-9815706-B2
Application number	US-201414561112-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Dec 4, 2014
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

A method for synthesizing a zeolite is described. The method may include the steps of: (a) preparing an aqueous mixture comprising water, a substituted hydrocarbon, and a 1-oxa-4-azacyclohexane derivative; (b) reacting the aqueous mixture; (c) obtaining a solution comprising an organo-1-oxa-4-azoniumcyclohexane compound; (d)) forming a reaction mixture comprising reactive sources of Al, and Si, and the solution; and (e) heating the reaction mixture to form the zeolite.

First claim

What is claimed is:

1. A method for synthesizing a zeolite comprising:
(a) preparing an aqueous mixture comprising water, a substituted hydrocarbon, and a 1-oxa-4-azacyclohexane derivative wherein the substituted hydrocarbons are selected from the group consisting of halogen substituted alkanes having between 2 and 8 carbon atoms, benzyl halides, 1-halomethane naphthalene, 2-halomethane naphthalene, halo-substituted non-olefinic alkyl groups having the formula C p H 2p-1 where p is in the range from 4 to 10, α,ω-dihalogen substituted alkanes having between 3 and 6 carbon atoms, di-halogen substituted alkanes having between 3 and 8 carbon atoms, tri-halogen substituted alkanes having between 3 and 8 carbons, and combinations thereof;
(b) reacting the aqueous mixture;
(c) obtaining a solution comprising an organo-1-oxa-4-azoniumcyclohexane compound;
(d) forming a reaction mixture comprising reactive sources of Al, M, E and Si, and the solution wherein M represents at least one exchangeable cation of a metal or metals from Group 1 (IUPAC 1), Group 2 (IUPAC 2), Group 3 (IUPAC 3), or the lanthanide series of the periodic table and or zinc and E represents an element selected from the group consisting of gallium, iron, boron and combinations thereof; and
(e) heating the reaction mixture to form the zeolite.

2. The method of claim 1 , wherein the step of reacting the aqueous mixture occurs at a temperature between 20° C. and 100° C.

3. The method of claim 1 , wherein the organo-1-oxa-4-azoniumcyclohexane compound is a structure directing agent.

4. The method of claim 1 wherein the substituted hydrocarbon is a halogen substituted alkane selected from the group consisting of bromoethane, iodoethane, chloropropane, bromopropane, iodopropane, chlorobutane, 1-bromobutane, 2-bromobutane, iodobutane, 1-bromo-2-methylpropane, 2-bromo-2-methylpropane, chloropentane, bromopentane, iodopentane, 2-bromopentane, chlorohexane, bromohexane, iodohexane, benzyl halide, 1-chloro-2-phenylethane, 1-bromo-2-phenylethane, 1-iodo-2-phenylethane, 1-halomethane naphthalene, 2-halomethane naphthalene, and halo-substituted non-olefinic alkyl groups having the formula C p H 2p-1 where p is in the range from 4 to 10, and combinations thereof.

5. The method of claim 1 wherein the substituted hydrocarbon is a dihalogen substituted alkane having between 2 and 8 carbon atoms selected from the group consisting of 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,3-diiodopropane, 1,4-diiodobutane, 1,5-diiodopentane, 1,6-diiodohexane, 1,2-dibromopropane, 1,3-dibromobutane, 1,3-dibromopentane, 1,4-dibromopentane, 2,4-dibromopentane, 1,5-dibromohexane, 1,4-dibromohexane, 1,3-dibromohexane, 2,4-dibromohexane, 2,5-dibromohexane, 2,5-dibromo-3-methylhexane, 2,5-dibromo-3,3-dimethylhexane, 1,4-dibromo-2-ethylbutane, and 1,2-dibromo-2-phenylethane, and combinations thereof.

6. The method of claim 1 wherein the substituted hydrocarbon a tri-substituted alkane having from 3 to 8 carbon atoms selected from the group consisting of 1,2,3-tribromopropane, 1,2,4-tribromobutane, 1,2,3-tribromobutane, 1,3,5-tribromopentane, 1,2,4-tribromopentane, 1,2,3-tribromopentane, 1,3,6-tribromohexane, 1,2,4-tribromohexane, 1,2,5-tribromohexane, 1,2,6-tribromohexane, 1,3,4-tribromohexane, and 1,3,5-tribromohexane, and combinations thereof.

7. The method of claim 1 , wherein the substituted hydrocarbon is an α,ω-dihalogen substituted alkane.

8. The method of claim 1 , wherein the 1-oxa-4-azacyclohexane derivative has a structure of:
2-R 1 -2-R 2 -3-R 3 -3-R 4 -4-R 9 -5-R 5 -5-R 6 -6-R 7 -6-R 8 -1-oxa-4-azacyclohexane,  Formula 5:

wherein R 1 -R 9 are independently selected from H or an alkyl group having the formula C n H 2n+1 where n is in the range from 1 to 4 and the total number of C atoms in the molecule is in the range of 4 to 10.

9. The method of claim 1 , wherein the 1-oxa-4-azacyclohexane derivative is selected from 4-butylmorpholine, 4-propylmorpholine, 4-ethylmorpholine, 4-methylmorpholine, morpholine, 2-methylmorpholine, 2,4-dimethylmorpholine, 4-ethyl-2-methylmorpholine, 4-propyl-2-methylmorpholine, 3-methylmorpholine, 3,4-dimethylmorpholine, 4-ethyl-3-methylmorpholine, 4-propyl-3-methylmorpholine, 5-methylmorpholine, 2,5-dimethylmorpholine, 4-ethyl-5-methylmorpholine, 4-propyl-5-methylmorpholine, 5-ethyl-2-methylmorpholine, 6-methylmorpholine, 4,6-dimethylmorpholine, 4-ethyl-6-methylmorpholine, 4-propyl-6-methylmorpholine, 2,6-dimethylmorpholine, 2,4,6-trimethylmorpholine, 4-ethyl-2,6-dimethylmorpholine, 2,3-dimethylmorpholine, 2,3,4-tri methylmorpholine, 4-ethyl-2,3-dimethylmorpholine, 2,5-dimethylmorpholine, 2,4,5-tri methylmorpholine, 4-ethyl-2,5-dimethylmorpholine, 2,2-dimethylmorpholine, 2,2,4-trimethylmorpholine, 4-ethyl-2,2-dimethylmorpholine, 3,3-dimethylmorpholine, 3,3,4-tri methylmorpholine, 4-ethyl-3,3-dimethylmorpholine, 5,5-dimethylmorpholine, 4,5,5-tri methylmorpholine, 4-ethyl-5,5-dimethylmorpholine, 6,6-dimethylmorpholine, 4,6,6-trimethylmorpholine, 4-ethyl-6,6-dimethylmorpholine, 5-ethyl-2-methylmorpholine and combinations thereof.

10. The method of claim 1 , wherein the 1-oxa-4-azacyclohexane derivative is essentially incapable of undergoing pyramidal inversion.

11. The method of claim 1 wherein the organo-1-oxa-4-azoniumcyclohexane compound has a structure of:
2-R 1 -2-R 2 -3-R 3 -3-R 4 -4-R 9 -4-R 10 -5-R 5 -5-R 6 -6-R 7 -6-R 8 -1-oxa-4-azoniumcyclohexane + -X − ,  Formula 1:

wherein R 1 -R 8 are independently selected from H or an alkyl group having the formula C n H 2n+1 where n is in the range from 1 to 4; R 9 and R 10 form a cyclic alkyl group having the formula C m H 2m forming a heterocycle of ring size q, where m is in the range from 4 to 8, and q is in the range of 5 to m+1; X is a halide or hydroxide; and the total number of C atoms in the molecule is in a range of 8 to 17;
or
[bis-N,N′-diR 9 -(2,2′-diR 1 -2,2′-diR 2 -3,3′-diR 3 -3,3′-diR 4 -5,5′-diR 5 -5,5′-diR 8 -1,1′-oxa-4,4′-azonium cyclohexane)-R 10 ] 2+ 2X − ,  Formula 2:

wherein R 1 -R 9 are independently selected from H or an alkyl group having the formula C n H 2n+1 , where n is in the range from 1 to 4, X is halide or hydroxide, the total number of C atoms in the molecule is in the range of 11 to 24, and R 10 is an alkyl group having the formula C m H 2m , where m is in the range from 3 to 8 and is connected to the 4 and 4′ N atoms at positions x and y of the alkyl chain where x and y are independently selected from 1 to m;
or
[tris-N,N′,N″-triR 9 -(2,2′,2″-triR 1 -2,2′,2″-triR 2 -3,3′,3″-triR 3 -3,3′,3″-triR 4 -5,5′,5″-triR 5 -5,5′,5″-triR 6 -6,6′,6″-triR 7 -6,6′,6″-triR 8 -1,1′,1″-oxa-4,4′,4″-azoniumcyclohexane)-R 10 ] 3+ 3X − ,  Formula 3:

wherein R 1 -R 9 are independently selected from H or an alkyl group having the formula C n H 2n+1 , where n is in the range from 1 to 4, X is halide or hydroxide, the total number of C atoms in the molecule is the range of 15 to 36, and R 10 is an alkyl group having the formula C m H 2m-1 , where m is in the range from 3 to 8 and is connected to the 4, 4′ and 4″ N atoms at positions x, y and z of the alkyl chain where x, y and z are independently selected from 1 to m;
or
2-R 1 -2-R 2 -3-R 3 -3-R 4 -4-R 9 -4-R 10 -5-R 5 -5-R 6 -6-R 7 -6-R 8 -1-oxa-4-azoniumcyclohexane + -X − ,  Formula 4:

wherein R 1 -R 9 are independently selected from H or an alkyl group having the formula C n H 2n+1 , R 10 is selected from an alkyl group having the formula C n H 2n+1 where n is in the range from 1 to 4, benzyl, 1-methylnaphthalene, 2-methylnaphthalene and a non-olefinic alkyl group having

Assignees

• Uop Llc

Inventors

• Nicholas Christopher P
• Miller Mark A
• Galey Melissa M

Classifications

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• C01B39/04

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

• C01B39/32 Primary

  Type L · CPC title

• B01J29/60

  of the type L, as exemplified by patent document US3216789 · CPC title

• C01B39/48

  using at least one organic template directing agent · CPC title