High charge density metalloaluminophosphosilicate molecular sieves MeAPSO-83

Patent metadata

Field	Value
Publication number	US-10427144-B2
Application number	US-201816198189-A
Country	US
Kind code	B2
Filing date	Nov 21, 2018
Priority date	May 25, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

A new family of crystalline microporous metalloalumino(gallo)phosphosilicates designated MeAPSO-83 has been synthesized. These metalloalumino(gallo)phosphosilicates 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 an 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 MeAPSO-83 family of materials have the BPH topology and 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 material having a three-dimensional framework of[M 2+ O 4/2 ] 2− , [EO 4/2 ] − and [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 quaternary organoammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA + ), hexamethonium (HM 2+ ), choline [Me 3 NCH 2 CH 2 OH] + , trimethylpropylammonium, trimethylisopropylammonium, trimethylbutylammonium, tetramethylammonium (TMA + ), diethyldimethylammonium (DEDMA + ), tetraethylammonium (TEA + ), tetrapropylammonium (TPA + ) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.1 to about 1.5, “p” is the weighted average valence of R and varies from 1 to 2, A is an alkali metal such as Li + , Na + , K + , Rb + and Cs + and mixtures thereof, “m” is the mole ratio of A to P and varies from 0.1 to 1.5, 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 variesfrom 0.5 to 0.9, 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 0.8, “w”≥“x”, “y” is the mole ratio of Si to P and varies from 0.02 to about 2.5, 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

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/I 0 %

6.79-6.61
12.80-13.36
s-vs

7.63-7.47
11.40-11.82
m-vs

13.34-12.95
6.63-6.83
w-m

13.68-13.28
6.47-6.66
w-m

14.95-14.63
5.92-6.05
w-m

15.64-15.29
5.66-5.79
w-m

19.03-18.63
4.66-4.76
m

20.45-19.89
4.34-4.46
m

21.50-20.98
4.13-4.23
m

24.03-23.58
3.70-3.77
w-m

24.37-23.97
3.65-3.71
m-s

26.75-26.39
 3.33-3.375
w-m

27.51-27.04
 3.24-3.295
w-m

27.73-27.29
3.215-3.265
w-m

28.59-28.13
3.12-3.17
w-m

28.87-28.45
 3.09-3.135
w-m

30.01-29.50
2.975-3.025
m

30.38-29.96
2.94-2.98
m-s

30.92-30.38
2.89-2.94
m

31.36-30.86
 2.85-2.895
w

33.67-33.15
2.66-2.70
w-m

34.06-33.67
2.63-2.66
w-m

35.31-34.88
2.54-2.57
w-m

35.97-35.60
2.495-2.52 
w

36.73-36.27
2.445-2.475
w

38.35-37.85
2.345-2.375
w

39.95-39.49
2.255-2.28 
w

41.09-40.64
2.195-2.218
w

43.25-42.76
 2.09-2.113
w-m

43.74-43.17
2.068-2.094
w

49.84-49.27
1.828-1.848
w-m.

2. The microporous crystalline material of claim 1 where E is aluminum.

3. The microporous crystalline material of claim 1 where E is gallium.

4. The microporous crystalline material of claim 1 where R is the ethyltrimethylammonium cation, ETMA + .

5. The microporous crystalline material of claim 1 where R is the diethyldimethylammonium cation, DEDMA + .

6. A crystalline modified form of the microporous crystalline material of claim 1 , comprising a three-dimensional framework of [M 2+ O 4/2 ] 2− , [EO 4/2 ] − , [PO 4/2 ] + and SiO 4/2 tetrahedral units and derived by modifying the crystalline microporous metalloalumino(gallo)phosphosilicate of claim 1 , the modifications including ammonia calcinations, ion-exchange, or the combination thereof.

7. A process for preparing a microporous crystalline material having a three-dimensional framework of [M 2+ O 4/2 ] 2− , [EO 4/2 ] − and [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 anempirical formula of:
R p+ r A + m M 2+ w E x PSi y O z

Assignees

• Uop Llc

Inventors

• Lewis Gregory J

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

• B01J29/85 Primary

  Silicoaluminophosphates [SAPO compounds] · CPC title

• C01B37/08

  Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO} · CPC title

• C01B39/54

  Phosphates, e.g. APO or SAPO compounds · CPC title

• C10G47/20

  the catalyst containing other metals or compounds thereof · CPC title