# US 10,370,257 B2 · High charge density metalloaluminophosphosilicate molecular sieves

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,370,257 B2
- Document ID: US10370257B2
- Status: Granted
- Kind: B2
- Application number: 15/593,209
- Filed: 2017-05-11
- Published: 2017-11-30
- Granted: 2019-08-06
- Earliest claimed: 2016-05-25
- Assignees: Uop LLC
- Applicants: Uop LLC
- Inventors: Gregory J. Lewis
- Web page: https://patentgrep.com/patent/US10370257B2

## CPC

- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- B01J 20/18: Synthetic zeolitic molecular sieves
- B01J 29/80: Mixtures of different zeolites
- B01J 29/84: Aluminophosphates containing other elements, e.g. metals, boron
- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01J 29/87: Gallosilicates; Aluminogallosilicates; Galloborosilicates {(B01J29/005 takes precedence)}
- B01J 37/009: {Preparation by separation, e.g. by filtration, decantation, screening}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/10: in the presence of water, e.g. steam
- B01J 20/048: {containing phosphorus, e.g. phosphates, apatites, hydroxyapatites}
- C01P 2002/70: defined by measured X-ray, neutron or electron diffraction data
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2002/78: by stacking-plane distances or stacking sequences
- Y02P 30/20: using bio-feedstock
- Y02P 30/40: Ethylene production
- 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
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A new family of crystalline microporous metalloalumino(gallo)phosphosilicate molecular sieves has been synthesized and are designated high charge density (HCD) MeAPSOs. These metalloalumino(gallo)phosphosilicate are represented by the empirical formula of: Rp+rA+mM2+wExPSiyOz where A is an alkali metal such as potassium, R is at least one quaternary ammonium cation such as ethyltrimethylammonium, M is a divalent metal such as Zn and E is a trivalent framework element such as aluminum or gallium. This family of metalloalumino(gallo)phosphosilicate materials are stabilized by combinations of alkali and quaternary ammonium cations, enabling unique, high charge density compositions. The HCD MeAPSO family of materials 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 metalloalumino(gallo)phosphosilicate material having a three-dimensional framework of [M2+ O4/2]2−, [EO4/2]−, [PO4/2]+ and SiO4/2 tetrahedral units and an empirical composition in the as synthesized form and on an anhydrous basis expressed by an empirical formula of:
Rp+rA+mM2+wExPSiyOz
where R is at least one of any quaternary ammonium cation, diquaternary ammonium cation triquaternary ammonium cation, quatroquaternary ammonium cation and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.04 to about 4.0, “p” is the weighted average valence of R and varies from 1 to 4, A is an alkali metal selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metal selected from the group consisting of Zn, Co, Mg, Mn and mixtures thereof, “w” is the mole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to 4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about 4.5, and “z” is the mole ratio of O to P and has a value determined by the equation:
z=(m+p·r+2·w+3·x+5+4·y)/2
where the T-atom compositions for M(“w”), E(“x”), Si(“y”) and P(1) are further constrained when expressed as the mole fraction composition M2+w′Alx′Siy′Pz′, where w′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) and w′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′ and z′ in a quaternary phase diagram conforms to a composition bound by the 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of the eight vertices whose coordinates are given in Table A:
TABLE A
Vertex Coordinates of MeAPSO Polyhedron
Vertex
x′ (Al)
w′ (Me2+)
z′ (P)
1
0.18499
0.00105
0.14799
2
0.42061
0.00105
0.10515
3
0.49637
0.00105
0.12409
4
0.48968
0.00105
0.39174
5
0.39841
0.09960
0.49800
6
0.47801
0.11952
0.39841
7
0.04980
0.44821
0.49801
8
0.05976
0.53785
0.39841
and defined by the plane equation/inequalities given in Table B:
TABLE B
MeAPSO Compositions - Criteria for x′, w′ and z′
Plane Vertices
Plane Equation/Inequalities
1, 2, 3, 4
w′ ≥ 0.001502
5, 6, 7, 8
x′ + w′ + z′ ≤ 0.996016
4, 5, 6
1.239 * x′ + 0.065 * w′ + 1.004 * z′ ≤ 1
1, 4, 5
x′ + 2.274 * w′ − 1.25 * z′ ≥ 0
1, 5, 7
18.471 * x′ + 18.471 * w′ − 16.463 * z′ ≥ 1
1, 7, 8
4.599 * x′ + 0.6046 * w′ + 1.004 * z′ ≥ 1
1, 2, 8
1.004 * x′ − 2.341 * w′ + 5.519 * z′ ≥ 1
2, 3, 8
x′ + 2.86 * w′ − 4.00 * z′ ≤ 0
3, 4, 6
10.009 * x′ + 0.9653 * w′ + 0.2502 * z′ ≤ 5
3, 6, 8
2.212 * x′ + 2.212 * w′ − 0.808 * z′ ≤ 1
and the crystalline microporous metalloalumino(gallo)phosphosilicate molecular sieve is characterized by a specific x-ray diffraction pattern.

### Claim 2 (depends on 1)

The metalloalumino(gallo)phosphosilicate material of claim 1 where E is aluminum.

### Claim 3 (depends on 1)

The metalloalumino(gallo)phosphosilicate material of claim 1 where E is gallium.

### Claim 4 (depends on 1)

The metalloalumino(gallo)phosphosilicate material of claim 1 where R is at least one quaternary ammonium cation selected from the group consisting of tetramethylammonium (TMA+), ethyltrimethylammonium (ETMA+), propyltrimethylammonium (PTMA+), isopropyltrimethylammonium, diethyldimethylammonium (DEDMA+), trimethylbutylammonium (TMBA+), methyltriethylammonium (MTEA+), propylethyldimethylammonium (PEDMA+), N,N-dimethylpiperidinium, N,N-dimethyl-3,5-dimethylpiperidinium, dipropyldimethylammonium (DPDMA+), diethylmethylpropylammonium, trimethylpentylammonium (TMPA+), dimethyldiisopropylammonium, tetraethylammonium (TEA+), hexyltrimethylammonium (HTMA+), methylethyldipropylammonium, triethylpropylammonium, dibutyldimethylammonium, benzyltrimethylammonium (BzTMA+), diethyldipropylammonium, octyltrimethylammonium, tetrapropylammonium (TPA+), decyltrimethylammonium, adamantyltrimethylammonium, methyltributylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, tetrabutylammonium (TBA+) and mixtures thereof.

### Claim 5 (depends on 1)

The metalloalumino(gallo)phosphosilicate material of claim 1 where R is at least one diquaternary ammonium cation selected from the group consisting of methylene-bis-(trimethylammonium), bis-1,2-(trimethylammonium)ethylene, bis-1,3(trimethylammonium)propane, bis-1,3-(trimethylammonium)-2-propanol, bis-1,4-(trimethylammonium)butane, bis-1,5-(trimethylammonium)pentane (i.e., pentamethonium), bis-1,6-(trimethylammonium)hexane (i.e., hexamethonium, HM2+), bis-1,8-(trimethylammonium)octane, bis-1,10-(trimethylammonium)decane, bis-1,5-(triethylammonium)pentane (i.e., pentaethonium), bis-1,6-(triethylammonium)hexane (i.e., hexaethonium), bis-α,α′-(dimethylethylammonium)-p-xylene, bis-α,α′-(dimethylethylammonium)-m-xylene, bis-α,α′-(dimethylethylammonium)-o-xylene, bis-1,5-(N-methylpiperidinum)pentane and bis-1,6-(N-methylpiperidinum)hexane, N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium, N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium, N,N,N′,N′-tetrmaethyl-N,N′-hexano-1,6-hexanediammonium, N,N,N′,N′-tetraethyl-N,N′-hexano-1,5-pentanediammonium, N,N,N′,N′-tetramethyl-N,N′-m-xyleno-1,6-hexanediammonium, N,N,N′,N′-tetramethyl-N,N′-o-xyleno-1,2-ethylenediammonium, N,N,N′,N′-tetramethyl-N,N′-butano-1,2-ethylenediammonium, N,N,N′,N′-tetramethyl-N,N′-hexano-1,2-ethylenediammonium and mixtures thereof.

### Claim 6 (depends on 1)

The metalloalumino(gallo)phosphosilicate material of claim 1 where R is at least one triquaternary ammonium cation selected from the group consisting of tris-1,3,5-(triethylammoniomethyl)benzene, tris-1,3,5-(trimethylammoniomethyl)benzene, tris-1,3,5-(dimethylethylammoniomethyl)benzene and mixtures thereof.

### Claim 7 (depends on 1)

The metalloalumino(gallo)phosphosilicate material of claim 1 where R is at least one quatroquaternary ammonium cation selected from the group consisting of [(C6H5CH2)(Me2)N(—CH2CH(OH)CH2N(Me2)-)3CH2C6H5]4+ (i.e., dibenzylquatroquat), tetrakis-1,2,4,5-(trimethylammoniomethyl)benzene, tetrakis-1,2,4,5-(triethylammoniomethyl)benzene, tetrakis-1,2,4,5-(dimethylethylammoniomethyl)benzene and mixtures thereof.

### Claim 8

A method for preparing a microporous crystalline metalloalumino(gallo)phosphosilicate material having a three-dimensional framework of [M2+O4/2]2−, [EO4/2]−, [PO4/2]+ and SiO4/2 tetrahedral units and an empirical composition in the as synthesized form and on an anhydrous basis expressed by an empirical formula of:
Rp+rA+mM2+wExPSiyOz
where R is at least one of any quaternary ammonium cation, diquaternary ammonium cation triquaternary ammonium cation, quatroquaternary ammonium cation and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.04 to about 4.0, “p” is the weighted average valence of R and varies from 1 to 4, A is an alkali metal selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+ and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.04 to 4.0, M is a divalent metal selected from the group Zn, Co, Mg, Mn and mixtures thereof, “w” is the mole ratio of M to P and varies from 0.00268 to 1.35, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “x” is the mole ratio of E to P and varies from 0.1 to 4.0, “y” is the mole ratio of Si to P and varies from 0.008 to about 4.5, and “z” is the mole ratio of O to P and has a value determined by the equation:
z=(m+p·r+2·w+3·x+5+4·y)/2
where the T-atom compositions for M(“w”), E(“x”), Si(“y”) and P(1) are further constrained when expressed as the mole fraction composition M2+w′Alx′Siy′Pz′, where w′=w/(w+x+y+1), x′=x/(w+x+y+1), y′=y/(w+x+y+1), z′=1/(w+x+y+1) and w′+x′+y′+z′=1, such that the plot of the allowed values of w′, x′, y′ and z′ in a quaternary phase diagram
conforms to a composition bound by the 8-vertex, 10-sided polyhedron shown in FIG. 1 consisting of the eight vertices whose coordinates are given in Table A:
TABLE A
Vertex Coordinates of MeAPSO Polyhedron
Vertex
x′ (Al)
w′ (Me2+)
z′ (P)
1
0.18499
0.00105
0.14799
2
0.42061
0.00105
0.10515
3
0.49637
0.00105
0.12409
4
0.48968
0.00105
0.39174
5
0.39841
0.09960
0.49800
6
0.47801
0.11952
0.39841
7
0.04980
0.44821
0.49801
8
0.05976
0.53785
0.39841
and defined by the plane equation/inequalities given in Table B:
TABLE B
MeAPSO Compositions - Criteria for x′, w′ and z′
Plane Vertices
Plane Equation/Inequalities
1, 2, 3, 4
w′ ≥ 0.001502
5, 6, 7, 8
x′ + w′ + z′ ≤ 0.996016
4, 5, 6
1.239 * x′ + 0.065 * w′ + 1.004 * z′ ≤ 1
1, 4, 5
x′ + 2.274 * w′ − 1.25 * z′ ≥ 0
1, 5, 7
18.471 * x′ + 18.471 * w′ − 16.463 * z′ ≥ 1
1, 7, 8
4.599 * x′ + 0.6046 * w′ + 1.004 * z′ ≥ 1
1, 2, 8
1.004 * x′ − 2.341 * w′ + 5.519 * z′ ≥ 1
2, 3, 8
x′ + 2.86 * w′ − 4.00 * z′ ≤ 0
3, 4, 6
10.009 * x′ + 0.9653 * w′ + 0.2502 * z′ ≤ 5
3, 6, 8
2.212 * x′ + 2.212 * w′ − 0.808 * z′ ≤ 1
and the crystalline microporous metalloalumino(gallo)phosphosilicate molecular sieve is characterized by a specific x-ray diffraction pattern, the process comprising forming a reaction mixture containing reactive sources of R, A, 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 metalloalumino(gallo)phosphosilicate molecular sieve, the reaction mixture having a composition expressed in terms of mole ratios of the oxides of:
aR2/pO:bM2O:cMO:E2O3:dP2O5:eSiO2:fH2O
where “a” has a value of about 2.1 to about 120, “b” has a value of about 0.1 to about 8, “c” has a value of about 0.01 to about 8, “d” has a value of about 1.69 to about 30, “e” has a value from 0.01 to about 16 and “f” has a value from 50 to about 5000.

### Claim 9 (depends on 8)

The method of claim 8 where the initial reaction mixture is a clear solution before digestion.

### Claim 10 (depends on 8)

The method of claim 8 where A is selected from the group consisting of Li+, Na+, K+, Rb+ and Cs+ and mixtures thereof and the source of A is selected from the group consisting of halide salts, nitrate salts, acetate salts, sulfate salts, hydroxide salts and mixtures thereof.

### Claim 11 (depends on 8)

The method of claim 8 where M is selected from the group consisting of Zn2+, Mn2+, Co2+ and Mg2+ and mixtures thereof and the source of M is selected from the group consisting of halide salts, nitrate salts, acetate salts, sulfate salts and mixtures thereof.

### Claim 12 (depends on 8)

The method of claim 8 where the source of E is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al(OH)3, alkali aluminate salts, aluminum metal, aluminum halide salts, aluminum sulfate salts, aluminum nitrate salts, precipitated gallium oxyhydroxide, gallium nitrate, gallium sulfate and mixtures thereof.

### Claim 13 (depends on 8)

The method of claim 8 where the silicon source is selected from the group consisting of tetraethylorthosilicate, silicon alkoxides, fumed silica, colloidal silica, alkali silicate salts, precipitated silica and mixtures thereof.

### Claim 14 (depends on 8)

The method of claim 8 where the reaction mixture is reacted at a temperature of about 95° C. to about 175° C. for a time of about 1 day to about 14 days.

### Claim 15 (depends on 8)

The method of claim 8 where R is at least one quaternary ammonium cation selected from the group of quaternary ammonium cations consisting of tetramethylammonium (TMA+), ethyltrimethylammonium (ETMA+), propyltrimethylammonium (PTMA+), isopropyltrimethylammonium, diethyldimethylammonium (DEDMA+), trimethylbutylammonium (TMBA+), methyltriethylammonium (MTEA+), propylethyldimethylammonium (PEDMA+), N,N-dimethylpiperidinium, N,N-dimethyl-3,5-dimethylpiperidinium, dipropyldimethylammonium (DPDMA+), diethylmethylpropylammonium, trimethylpentylammonium (TMPA+), dimethyldiisopropylammonium, tetraethylammonium (TEA+), hexyltrimethylammonium (HTMA+), methylethyldipropylammonium, triethylpropylammonium, dibutyldimethylammonium, benzyltrimethylammonium (BzTMA+), diethyldipropylammonium, octyltrimethylammonium, tetrapropylammonium (TPA+), decyltrimethylammonium, adamantyltrimethylammonium, methyltributylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, tetrabutylammonium (TBA+), methylene-bis-(trimethylammonium), bis-1,2-(trimethylammonium)ethylene, bis-1,3(trimethylammonium)propane, bis-1,3-(trimethylammonium)-2-propanol, bis-1,4-(trimethylammonium)butane, bis-1,5-(trimethylammonium)pentane (i.e., pentamethonium), bis-1,6-(trimethylammonium)hexane (i.e., hexamethonium, HM2+), bis-1,8-(trimethylammonium)octane, bis-1,10-(trimethylammonium)decane, bis-1,5-(triethylammonium)pentane (i.e., pentaethonium), bis-1,6-(triethylammonium)hexane (i.e., hexaethonium), bis-α,α′-(dimethylethylammonium)-p-xylene, bis-α,α′-(dimethylethylammonium)-m-xylene, bis-α,α′-(dimethylethylammonium)-o-xylene, bis-1,5-(N-methylpiperidinum)pentane and bis-1,6-(N-methylpiperidinum)hexane, N,N,N′,N′-tetramethyl-N,N′-p-xyleno-1,6-hexanediammonium, N,N,N′,N′-tetramethyl-N,N′-butano-1,6-hexanediammonium, N,N,N′,N′-tetrmaethyl-N,N′-hexano-1,6-hexanediammonium, N,N,N′,N′-tetraethyl-N,N′-hexano-1,5-pentanediammonium, N,N,N′,N′-tetramethyl-N,N′-m-xyleno-1,6-hexanediammonium, N,N,N′,N′-tetramethyl-N,N′-o-xyleno-1,2-ethylenediammonium, N,N,N′,N′-tetramethyl-N,N′-butano-1,2-ethylenediammonium, N,N,N′,N′-tetramethyl-N,N′-hexano-1,2-ethylenediammonium, tris-1,3,5-(triethylammoniomethyl)benzene, tris-1,3,5-(trimethylammoniomethyl)benzene, tris-1,3,5-(dimethylethylammoniomethyl)benzene, [(C6H5CH2)(Me2)N(—CH2CH(OH)CH2N(Me2)-)3CH2C6H5]4+ (i.e., dibenzylquatroquat), tetrakis-1,2,4,5-(trimethylammoniomethyl)benzene, tetrakis-1,2,4,5-(triethylammoniomethyl)benzene, tetrakis-1,2,4,5-(dimethylethylammoniomethyl)benzene and mixtures thereof.

### Claim 16 (depends on 8)

The method of claim 8 further comprising adding seeds of a metalloalumino(gallo)phosphosilicate material to the reaction mixture.