High charge density metallophosphate molecular sieves

Patent metadata

Field	Value
Publication number	US-2017341066-A1
Application number	US-201715588967-A
Country	US
Kind code	A1
Filing date	May 8, 2017
Priority date	May 25, 2016
Publication date	Nov 30, 2017
Grant date	—

Abstract

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-16 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 an organoammonium 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-16 family of molecular sieves are stabilized by combinations of alkali and organoammonium cations, enabling unique metalloalumino(gallo)phosphate compositions and exhibit the CGS 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

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 on an anhydrous basis expressed by an empirical formula of:
R p+r A+ m M2 +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 d-spacings and intensities set forth in Table A:

TABLE A

2Θ
d (Å)
I/I 0 %

8.28-8.06
10.67-10.96
vs

10.83-10.64
8.16-8.31
w

11.68-11.47
7.57-7.71
w-m

12.49-12.15
7.08-7.28
m-vs

13.13-12.89
6.74-6.86
w

13.36-13.11
6.62-6.75
w

16.53-16.22
5.36-5.46
m-s

16.91-16.59
5.24-5.34
w-m

17.24-16.97
5.14-5.22
w

19.28-19.03
4.60-4.66
m-vs

19.62-19.36
4.52-4.58
w-m

21.93-21.39
4.05-4.15
m

22.32-21.87
3.98-4.06
w-m

22.84-22.49
3.89-3.95
w

23.14-22.78
3.84-3.90
w-m

23.39-23.11
 3.80-3.845
w-m

23.84-23.45
3.73-3.79
w-m

24.23-23.77
3.67-3.74
m

24.92-24.61
 3.57-3.615
m-s

26.35-26.11
3.38-3.41
w-m

26.79-26.35
3.325-3.38 
w-m

27.38-26.79
3.255-3.325
m-s

29.06-28.49
3.07-3.13
m-s

29.50-28.97
3.025-3.08 
m

31.70-30.97
 2.82-2.885
w-m

32.00-31.36
2.795-2.85 
m

33.34-32.72
2.685-2.735
w-m

34.33-34.02
2.61-2.633
w-m

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 tetraethylammonium cation, TEA + .

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 including calcination, ammonia calcinations, ion-exchange, steaming, various acid extractions, ammonium hexafluorosilicate treatment, or any combination thereof.

8 . A process for preparing 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 on an 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, trimethy

Assignees

• Uop Llc

Inventors

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

Classifications

• B01J20/08

  comprising aluminium oxide or hydroxide; comprising bauxite · CPC title

• B01J29/84 Primary

  Aluminophosphates containing other elements, e.g. metals, boron · CPC title

• B01J20/28095

  Shape or type of pores, voids, channels, ducts · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title