# US 9,751,772 B2 · Aluminophosphate molecular sieves using an organo-1-oxa-4-azoniumcyclohexane compound

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- Number: US 9,751,772 B2
- Document ID: US9751772B2
- Status: Granted
- Kind: B2
- Application number: 14/561,121
- Filed: 2014-12-04
- Published: 2016-06-09
- Granted: 2017-09-05
- Earliest claimed: 2014-12-04
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Benjamin D. Yuhas; Christopher P. Nicholas; Mark A. Miller; Melissa M. Galey
- Web page: https://patentgrep.com/patent/US9751772B2

## CPC

- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- B01J 29/83: Aluminophosphates [APO compounds]
- B01J 29/84: Aluminophosphates containing other elements, e.g. metals, boron
- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01J 37/0018: {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)}
- B01J 37/10: in the presence of water, e.g. steam
- C01B 37/08: Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO}
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A method for synthesizing an aluminophosphate based molecular sieve 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 P, and the solution; and (e) heating the reaction mixture to form the molecular sieve.

## Claims

### Claim 1

A method for synthesizing an aluminophosphate based molecular sieve comprising:
(a) preparing an aqueous mixture comprising water, a substituted hydrocarbon, and a 1-oxa-4-azacyclohexane derivative wherein said 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 CpH2p−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, Me, and P, and the solution wherein Me represents an element sleeted from the group consist of Mg, Zn, Be, Ga or an element from the first, second or third transition series of elements; and
(e) heating the reaction mixture to form the molecular sieve.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 1)

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 CpH2p-1 where p is in the range from 4 to 10, and combinations thereof.

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 1)

The method of claim 1, wherein the substituted hydrocarbon is a tri-halogen 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.

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 1)

The method of claim 1, wherein the 1-oxa-4-azacyclohexane derivative has a structure of:
2-R1-2-R2-3-R3-3-R4-4-R9-5-R5-5-R6-6-R7-6-R8-1-oxa-4-azacyclohexane, Formula 5:
wherein R1-R9 are independently selected from H or an alkyl group having the formula CnH2n+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.

### Claim 9 (depends on 1)

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-trimethylmorpholine, 4-ethyl-2,3-dimethylmorpholine, 2,5-dimethylmorpholine, 2,4,5-trimethylmorpholine, 4-ethyl-2,5-dimethylmorpholine, 2,2-dimethylmorpholine, 2,2,4-trimethylmorpholine, 4-ethyl-2,2-dimethylmorpholine, 3,3-dimethylmorpholine, 3,3,4-trimethylmorpholine, 4-ethyl-3,3-dimethylmorpholine, 5,5-dimethylmorpholine, 4,5,5-trimethylmorpholine, 4-ethyl-5,5-dimethylmorpholine, 6,6-dimethylmorpholine, 4,6,6-trimethylmorpholine, 4-ethyl-6,6-dimethylmorpholine, 5-ethyl-2-methylmorpholine and combinations thereof.

### Claim 10 (depends on 1)

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

### Claim 11 (depends on 1)

The method of claim 1 wherein the organo-1-oxa-4-azoniumcyclohexane compound has a structure of:
2-R1-2-R2-3-R3-3-R4-4-R9-4-R10-5-R5-5-R6-6-R7-6-R8-1-oxa-4-azoniumcyclohexane+-X−, Formula 1:
wherein R1-R8 are independently selected from H or an alkyl group having the formula CnH2n+1 where n is in the range from 1 to 4; R9 and R10 form a cyclic alkyl group having the formula CmH2m 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′-diR9-(2,2′-diR1-2,2′-diR2-3,3′-diR3-3,3′-diR4-5,5′-diR5-5,5′-diR6-6,6′-diR7-6,6′-diR8-1,1′-oxa-4,4′-azonium cyclohexane)-R10]2+2X−, Formula 2:
wherein R1-R9 are independently selected from H or an alkyl group having the formula CnH2n+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 R10 is an alkyl group having the formula CmH2m, 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″-triR9-(2,2′,2″-triR1-2,2′,2″-triR2-3,3′,3″-triR3-3,3′,3″-triR4-5,5′,5″-triR5-5,5′,5″-triR6-6,6′,6″-triR7-6,6′,6″-triR8-1,1′,1″-oxa-4,4′,4″-azoniumcyclohexane)-R10]3+3X−, Formula 3:
wherein R1-R9 are independently selected from H or an alkyl group having the formula CnH2n+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 R10 is an alkyl group having the formula CmH2m−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-R1-2-R2-3-R3-3-R4-4-R9-4-R10-5-R5-5-R6-6-R7-6-R8-1-oxa-4-azoniumcyclohexane+-X−, Formula 4:
wherein R1-R9 are independently selected from H or an alkyl group having the formula CnH2n+1, R10 is selected from an alkyl group having the formula CnH2n+1 where n is in the range from 1 to 4, benzyl, 1-methylnaphthalene, 2-methylnaphthalene and a non-olefinic alkyl group having the formula CpH2p−1 where p is in the range from 4 to 10, X is halide or hydroxide, and the total number of C atoms in the molecule is in the range of 4 to 16;
or combinations thereof.

### Claim 12 (depends on 1)

The method of claim 1 wherein step (d) comprises forming a first mixture of the reactive sources of Al, Si, P and the optional seeds of a crystalline molecular sieve, and adding the solution to the first mixture without cooling the first mixture.

### Claim 13 (depends on 1)

The method of claim 1 wherein step (d) comprises forming a reaction mixture of a composition expressed in terms of mole ratios of the oxides of:
rR:Al2O3:eMeOj/2:pP2O5:sSiO2:gH2O
where, “r” has a value from about 0.01 to about 10, “e” has a value of 0 to about 1.0, “j” has a value from 2 to 4, “p” has a value of about 0.5 to about 8.0, “s” has a value of 0 to about 1.0, and “g” has a value of about 5 to about 4000.

### Claim 14 (depends on 1)

The method of claim 1 wherein the reaction mixture comprises from about 1 to about 10 wt.-% of seed aluminophosphate based on the total mass of oxides in the reaction mixture.

### Claim 15

An aluminophosphate based molecular sieve prepared by a process comprising:
(a) preparing an aqueous mixture comprising water, a substituted hydrocarbon, and a 1-oxa-4-azacyclohexane derivative wherein said 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 CpH2p−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, Me, and P, and the solution wherein Me represents an element selected from the group consistent of Mg, Zn, Be, Ga or an element from the first, second or third transition series of elements; and
(e) heating the reaction mixture to form the molecular sieve.

### Claim 16 (depends on 15)

The molecular sieve of claim 15 wherein the organo-1-oxa-4-azoniumcyclohexane compound is a structure directing agent and an organic solvent is not used in obtaining the structure directing agent.

### Claim 17 (depends on 15)

The molecular sieve of claim 15 wherein the 1-oxa-4-azacyclohexane derivative is essentially incapable of undergoing pyramidal inversion.

### Claim 18 (depends on 15)

The molecular sieve of claim 15 wherein step (d) comprises forming a first mixture of the reactive sources of Al, Si, P and the optional seeds of a crystalline molecular sieve, and adding the solution to the first mixture without cooling the first mixture.

### Claim 19 (depends on 15)

The molecular sieve of claim 15 wherein step (d) comprises forming a reaction mixture of a composition expressed in terms of mole ratios of the oxides of:
rR:Al2O3:eMeOj/2:pP2O5:sSiO2:gH2O
where “r” has a value from about 0.01 to about 10, “e” has a value of 0 to about 1.0, “j” has a value from 2 to 4, “p” has a value of about 0.5 to about 8.0, “s” has a value of 0 to about 1.0, and “g” has a value of about 5 to about 4000.

### Claim 20 (depends on 15)

The molecular sieve of claim 15 wherein the reaction mixture comprises from about 1 to about 10 wt.-% of seed aluminophosphate based on the total mass of oxides in the reaction mixture.