# US 2014/0154176 A1 · Silicometallophosphate molecular sieves, method of preparation and use

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- Number: US 2014/0154176 A1
- Document ID: US20140154176A1
- Status: Published application
- Kind: A1
- Application number: 13/689,887
- Filed: 2012-11-30
- Published: 2014-06-05
- Earliest claimed: 2012-11-30
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Gregory J. Lewis; Lisa M. Knight; Paulina Jakubczak; Justin E. Stanczyk
- Web page: https://patentgrep.com/patent/US20140154176A1

## CPC

- C07F 19/00: Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
- C01B 37/002: {Metallophosphates not containing aluminium, e.g. gallophosphates or silicogallophosphates}
- C01B 37/08: Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO}
- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

A new family of crystalline microporous metallophosphates designated MAPSO-64 has been synthesized. These metallophosphates are represented by the empirical formula RrMmn+EPxSiyOz where R is an organoammonium cation such as ETMA+ or DEDMA−, M is a divalent metal such as an alkaline earth or transition metal, and E is a framework element such as aluminum or gallium. The microporous MAPSO-64 compositions BPH topology and have catalytic properties for carrying out various hydrocarbon conversion processes and separation properties for separating at least one component.

## Claims

### Claim 1

A microporous crystalline silicometallophosphate material having a three-dimensional framework of EO2−, PO2+, [M2+O2]2− and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
RrM2+mEPxSiyOz
where M is at least one divalent cation selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0.01 to about 1.5, R is an organoammonium cation selected from the group of choline, tetrametylammonium (TMA+), ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), methyltriethylammonium (MTEA+), propyltrimethylammonium (PTMA+), dimethyldiethanolammonium, tetraethylammonium (TEA+), dipropyldimethylammonium (DPDMA+), tetrapropylammonium (TPA+) and mixtures thereof, “r” is the mole ratio of R to E and has a value of about 0.1 to about 2, E is an trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is the mole ratio of P to E and has a value of 0.5 to about 2.5, “y” is the mole ratio of Si to E and varies from 0.01 to about 1.0 and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(2·m+r+3+5·x+4·y)/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2Θ
d(Å)
I/I0
6.81-6.61
12.98-13.34
m-vs
7.75-7.55
11.40-11.70
m-vs
13.36-13.14
6.62-6.73
w-m
13.51-13.32
6.55-6.64
w-m
14.98-14.68
5.91-6.03
w
15.51-15.34
5.71-5.77
w-m
18.99-18.79
4.67-4.72
w-m
20.26-20.07
4.38-4.42
w-m
21.50-21.24
4.13-4.18
w-s
24.10-23.84
3.69-3.73
w-m
24.30-24.03
3.66-3.70
w-m
24.57-24.23
3.62-3.67
w-m
26.83-26.51
3.32-3.36
w-m
27.59-27.42
3.23-3.25
w-m
27.86-27.59
3.20-3.23
w
28.68-28.49
3.11-3.13
w
28.87-28.59
3.09-3.12
w
30.06-29.76
2.97-3.00
w-m
30.27-29.96
2.95-2.98
w-m
31.03-30.70
2.88-2.91
w-m
33.80-33.54
2.65-2.67
w-m
34.06-33.80
2.63-2.65
w
35.60-35.31
2.52-2.54
w-m
36.65-36.34
2.45-2.47
w
38.44-38.10
2.34-2.36
w

### Claim 2 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 in which E is aluminum.

### Claim 3 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where M is selected from the group consisting of magnesium, zinc, cobalt, manganese, and mixtures thereof.

### Claim 4 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where the silicometallophosphate material is thermally stable up to a temperature of at least 400° C.

### Claim 5 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where the silicometallophosphate material is thermally stable up to a temperature of at least 500° C.

### Claim 6 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where R is DEDMA+.

### Claim 7 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where R is ETMA+.

### Claim 8 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where R is DEDMA+ and one of TMA+, ETMA+, TEA+, TPA+, DPDMA+, choline, or PTMA+ cations.

### Claim 9 (depends on 1)

The microporous crystalline silicometallophosphate material of claim 1 where R is ETMA+ and one of TMA+, DEDMA+, TEA+, TPA+, DPDMA+, choline, or PTMA+ cations.

### Claim 10

A process for preparing a microporous crystalline silicometallophosphate material having a three-dimensional framework of at least EO2−, PO2+, [M2+O2]2− and SiO2 tetrahedral units and an empirical composition in the as synthesized and anhydrous basis expressed by an empirical formula of:
RrMm2+EPxSiyOz
where M is at least one divalent cation selected from the group consisting of alkaline earth and transition metals, “m” is the mole ratio of M to E and varies from 0.01 to about 1.5, R is an organoammonium cation selected from the group consisting of choline, tetramethylammonium (TMA+), ethyltrimethylammonium (ETMA+), diethyldimethylammonium (DEDMA+), methyltriethylammonium (MTEA+), propyltrimethylammonium (PTMA+), dimethyldiethanolammonium, tetraethylammonium (TEA+), dipropyldimethylammoniun (DPDMA+), tetrapropylammonium (TPA+) cations and mixtures thereof, “r” is the mole ratio of R to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is the mole ratio of P to E and varies from 0.5 to about 2.5, “y” is the mole ratio of Si to E and varies from 0.01 to about 1.0 and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(2·m+r+3+5·x+4·y)/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2Θ
d(Å)
I/I0
6.81-6.61
12.98-13.34
m-vs
7.75-7.55
11.40-11.70
m-vs
13.36-13.14
6.62-6.73
w-m
13.51-13.32
6.55-6.64
w-m
14.98-14.68
5.91-6.03
w
15.51-15.34
5.71-5.77
w-m
18.99-18.79
4.67-4.72
w-m
20.26-20.07
4.38-4.42
w-m
21.50-21.24
4.13-4.18
w-s
24.10-23.84
3.69-3.73
w-m
24.30-24.03
3.66-3.70
w-m
24.57-24.23
3.62-3.67
w-m
26.83-26.51
3.32-3.36
w-m
27.59-27.42
3.23-3.25
w-m
27.86-27.59
3.20-3.23
w
28.68-28.49
3.11-3.13
w
28.87-28.59
3.09-3.12
w
30.06-29.76
2.97-3.00
w-m
30.27-29.96
2.95-2.98
w-m
31.03-30.70
2.88-2.91
w-m
33.80-33.54
2.65-2.67
w-m
34.06-33.80
2.63-2.65
w
35.60-35.31
2.52-2.54
w-m
36.65-36.34
2.45-2.47
w
38.44-38.10
2.34-2.36
w
the process comprising forming a reaction mixture containing reactive sources of R, E, P, M and Si and heating the reaction mixture at a temperature of about 60° C. to about 200° C., for a time sufficient to form the silicometallophosphate material, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
aR2O:bMO:E2O3:cP2O5:dSiO2:eH2O
where “a” has a value of about 0.75 to about 16, “b” has a value of about 0.01 to about 3.0, “c” has a value of about 0.8 to about 8, “d” has a value of about 0.01 to about 4, and “e” has a value of about 20 to 800.

### Claim 11 (depends on 10)

The process of claim 10 where M is selected from the group consisting of magnesium, zinc, cobalt, manganese, nickel, iron (II) and mixtures thereof.

### Claim 12 (depends on 10)

The process of claim 10 where the source of M is selected from the group consisting of halide salts, nitrate salts, acetate salts, sulfate salts and mixtures thereof.

### Claim 13 (depends on 10)

The process of claim 10 where the source of E is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH)3, aluminum metal, aluminum salts, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride and mixtures thereof.

### Claim 14 (depends on 10)

The process of claim 10 where the silicon source is selected from the group consisting of tetraethylorthosilicate, fumed silica, colloidal silica and precipitated silica.

### Claim 15 (depends on 10)

The process of claim 10 where the reaction mixture is reacted at a temperature of about 125° C. to about 175° C. for a time of about 1 day to about 7 days.

### Claim 16 (depends on 10)

The process of claim 10 where R is DEDMA+.

### Claim 17 (depends on 10)

The process of claim 10 where R is ETMA+.

### Claim 18 (depends on 10)

The process of claim 10 where R is a combination of DEDMA+ and at least one organoammonium cation selected from the group consisting of choline, TMA+, ETMA+, MTEA+, PTMA+, dimethyldiethanolammonium, TEA+, DPDMA+ and TPA+.

### Claim 19 (depends on 10)

The process of claim 10 where R is a combination of ETMA+ and at least one organoammonium cation selected from the group consisting of choline, TMA+, MTEA+, DEDMA+, PTMA+, dimethyldiethanolammonium, TEA+, and TPA+.

### Claim 20 (depends on 10)

The process of claim 10 further comprising adding MAPSO-64 seeds to the reaction mixture.

### Claim 21 (depends on 1)

A modified form of the silicometallophosphate of claim 1, said modification comprising ammonia calcination under ammonia calcination conditions, and optionally an additional ion-exchange to form a modified microporous silicometallophosphate, MAPSO-64M, having a three-dimensional framework of EO2−, PO2+, [M2+O2]2− and SiO2 tetrahedral units the composition given on an anhydrous basis by the empirical formula:
M′np+Mm2+EPxSiyOz
where M is at least one divalent metal cation selected from the group consisting of Be2+, Mg2−, Zn2+, Co2+, Mn2+, Fe2+, Ni2−, and mixtures thereof, “m” is the mole ratio of M to E and varies from 0.01 to about 1.5, M′ is NH4−, H+, alkali metals, alkaline earth metals, and rare earth metals and mixtures thereof, “n” is the mole ratio of M′ to E and has a value of about 0.03 to about 2.0, “p” is the weighted average valence of M′, E is an trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.5, “y” is the mole ratio of Si to E and varies from 0.01 to about 1.0 and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(p·n+2·m+3+5·x+4·y)/2
and is characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table A:
TABLE A
2Θ
d(Å)
I/I0
6.81-6.61
12.98-13.34
m-vs
7.75-7.55
11.40-11.70
m-vs
13.36-13.14
6.62-6.73
w-m
13.51-13.32
6.55-6.64
w-m
14.98-14.68
5.91-6.03
w
15.51-15.34
5.71-5.77
w-m
18.99-18.79
4.67-4.72
w-m
20.26-20.07
4.38-4.42
w-m
21.50-21.24
4.13-4.18
w-s
24.10-23.84
3.69-3.73
w-m
24.30-24.03
3.66-3.70
w-m
24.57-24.23
3.62-3.67
w-m
26.83-26.51
3.32-3.36
w-m
27.59-27.42
3.23-3.25
w-m
27.86-27.59
3.20-3.23
w
28.68-28.49
3.11-3.13
w
28.87-28.59
3.09-3.12
w
30.06-29.76
2.97-3.00
w-m
30.27-29.96
2.95-2.98
w-m
31.03-30.70
2.88-2.91
w-m
33.80-33.54
2.65-2.67
w-m
34.06-33.80
2.63-2.65
w
35.60-35.31
2.52-2.54
w-m
36.65-36.34
2.45-2.47
w
38.44-38.10
2.34-2.36
w

### Claim 22 (depends on 1)

A stable, calcined form of the crystalline microporous silicometallophosphate of claim 1, MAPSO-64C, consisting of heating the silicometallophosphate of claim 1 under calcination conditions to remove the organic cations in the presence of air and ambient water vapor, said MAPSO-64 having a three-dimensional framework of EO2−, PO2−, SiO2 and [M2+O2]2− tetrahedral units characterized by the empirical formula:
HaMm2+EPxSiyOz
where M is at least one divalent metal cation selected from the group consisting of Be2+, Mg2+, Zn2+, Co2+, Mn2+, Fe2+, Ni2+, and mixtures thereof, “m” is the mole ratio of M to E and varies from 0.01 to about 1.0, H is a proton, “a” is the mole ratio of H to E and has a value of about 0.1 to about 2.0, E is an trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.5, “y” is the mole ratio of Si to E and varies from 0.01 to about 1.0 and “z” is the mole ratio of O to E and has a value determined by the equation:
z=(a+2·m+3+5·x+4·y)/2.