High charge density metallophosphate molecular sieves

Patent metadata

Field	Value
Publication number	US-10562016-B2
Application number	US-201816101257-A
Country	US
Kind code	B2
Filing date	Aug 10, 2018
Priority date	May 25, 2016
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-17 has been synthesized. These metallophosphates are represented by the empirical formula of:

R p+ r A m + M x E y PO z

where A is an alkali metal such as potassium, R is a quaternary ammonium cation such as ethyltrimethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-17 family of molecular sieves are stabilized by combinations of alkali and organoammonium cations, enabling unique metalloalumino(gallo)phosphate compositions and exhibit the BPH topology. The PST-17 family of molecular sieves has 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 metallophosphate material having a three-dimensional framework of
[M 2+ O 4/2 ] 2− , [EO 4/2 ] − and [PO 4/2 ] +

tetrahedral units and an empirical composition in the as synthesized form and anhydrous basis expressed by an empirical formula of:
R p+ r A + m M 2+ x E y PO z

where R is at least one quaternary ammonium cation selected from the group consisting of ethyltrimethylammonium (ETMA + ), diethyldimethylammonium (DEDMA + ), hexamethonium (HM 2+ ), choline [Me 3 NCH 2 CH 2 OH] + , trimethylpropylammonium, trimethylbutylammonium, trimethylisopropylammonium, tetramethylammonium (TMA + ), 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 1.0, “p” is the weighted average valence of R and varies from 1 to 2, 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 0.1 to 1.0, M is a divalent element selected from the group of Zn, Mg, Co, Mn and mixtures thereof, “x” is the mole ratio of M to P and varies from 0.2 to about 0.9, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “y” is the mole ratio of E to P and varies from 0.1 to about 0.8 and “z” is the mole ratio of O to P and has a value determined by the equation:
z =( m+p⋅r+ 2⋅ x+ 3⋅ y+ 5)/2

and is characterized in that it has the x-ray diffraction pattern having at least the cl-spacing and intensities set forth in Table A:

TABLE A

2Θ
d(A)
I/I 0 ¾

6.90-6.64
12.80-13.31
 s-vs

7.76-7.47
11.38-11.83
m-vs

13.34-12.95
6.63-6.83
w

13.68-13.30
6.47-6.65
w-m

14.95-14.63
5.92-6.05
w

15.64-15.32
5.66-5.78
w-m

19.03-18.67
4.66-4.75
w-m

20.45-19.89
4.34-4.46
w-m

 21.5-20.98
4.13-4.23
w-m

24.03-23.58
3.70-3.77
w

24.37-23.97
3.65-3.71
w-s 

 26.75-26.386
 3.33-3.375
w-m

27.51-27.04
 3.24-3.295
w-m

27.725-27.292
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

30.012-29.505
2.975-3.025
w-m

30.38-30.06
2.94-2.97
w-m

30.92-30.38
2.89-2.94
w-m

31.59-31.03
2.83-2.88
w

33.67-33.15
2.66-2.70
w-m

34.20-33.67
2.62-2.66
w-m

35.45-34.88
2.53-2.57
w-m

36.81-36.34
2.44-2.47
w

 38.44-37.851
 2.34-2.375
w

 40.04-39.528
 2.25-2.278
w

 41.19-40.567
 2.19-2.222
w

43.849-43.167
2.063-2.094
w

49.932-49.326
1.825-1.846
w.

2. The metallophosphate material of claim 1 where A is potassium.

3. The metallophosphate material of claim 1 where E is aluminum.

4. The metallophosphate material of claim 1 where R is ethyltrimethylammonium cation, ETMA+.

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

6. The metallophosphate material of claim 1 where R is the trimethylisopropylammonium cation.

7. A crystalline modified form of the crystalline microporous metallophosphate of claim 1 , comprising a three-dimensional framework of
[M 2+ O 4/2 ] 2− , [EO 4/2 ] − and [PO 4/2 ] +

tetrahedral units and derived by modifying the crystalline microporous metallophosphate of claim 1 , the modifications comprising calcination, ammonia calcinations, ion-exchange, or the combination thereof.

Assignees

• Uop Llc

Inventors

• Lewis Gregory J
• Nicholas Christopher P
• Knight Lisa M
• Moscoso Jaime G
• Seo Seungwan
• Hong Suk Bong
• Lee Junghwan

Classifications

• C10G47/12

  Inorganic carriers · CPC title

• 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

• C10G45/60

  characterised by the catalyst used · CPC title

• C10G35/065

  containing crystalline zeolitic molecular sieves, other than aluminosilicates · CPC title

• C01B37/08

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