High charge density metalloaluminophosphosilicate molecular sieves

Patent metadata

Field	Value
Publication number	US-10370257-B2
Application number	US-201715593209-A
Country	US
Kind code	B2
Filing date	May 11, 2017
Priority date	May 25, 2016
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

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:

R p+ r A + m M 2+ w E x PSi y O z

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.

First claim

The invention claimed is:

1. A microporous crystalline metalloalumino(gallo)phosphosilicate material having a three-dimensional framework of [M 2+ O 4/2 ] 2− , [EO 4/2 ] − , [PO 4/2 ] + and SiO 4/2 tetrahedral units and an empirical composition in the as synthesized form and on an anhydrous basis expressed by an empirical formula of:
R p+ r A + m M 2+ w E x PSi y O z

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 M 2+ w′ Al x′ Si y′ P z′ , 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′ (Me 2+ )
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.

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

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

4. 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.

5. 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,

Assignees

• Uop Llc

Inventors

• Lewis Gregory J

Classifications

• B01J29/87

  Gallosilicates; Aluminogallosilicates; Galloborosilicates {(B01J29/005 takes precedence)} · CPC title

• B01J20/18

  Synthetic zeolitic molecular sieves · CPC title

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title

• B01J20/048

  containing phosphorus, e.g. phosphates, apatites, hydroxyapatites · CPC title

• C01P2002/78

  by stacking-plane distances or stacking sequences · CPC title