High charge density metallophosphate molecular sieves

Patent metadata

Field	Value
Publication number	US-10159964-B2
Application number	US-201715586503-A
Country	US
Kind code	B2
Filing date	May 4, 2017
Priority date	May 25, 2016
Publication date	Dec 25, 2018
Grant date	Dec 25, 2018

Abstract

A family of highly charged crystalline microporous metallophosphate molecular sieves designated PST-19 has been synthesized. These high charge density metallophosphates are represented by the empirical formula of:

R p+ r A + m M 2+ x E y PO z

where A is an alkali metal such as potassium, R is an organoammonium cation such as tetraethylammonium, M is a divalent metal such as zinc and E is a trivalent framework element such as aluminum or gallium. The PST-19 family of materials are among the first MeAPO-type molecular sieves to be stabilized by combinations of alkali and quaternary ammonium cations, enabling unique compositions. The PST-19 family of molecular sieves has the SBS topology and 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 ] + and 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 tetraethylammonium (TEA + ), triethylpropylammonium (TEPA + ), diethylmethylpropylammonium (DEMPA + ), dimethylethylpropylammonium (DMEPA + ), dimethyldipropylammonium (DMDPA + ), methyltriethylammonium (MTEA + ), ethyltrimethylammonium (ETMA + ), diethyldimethylammonium (DEDMA + ), choline, hexamethonium (HM 2+ ), propyltrimethylammonium (PTMA + ), butyltrimethylammonium (BTMA + ), hexamethonium (HM 2+ ), tetramethylammonium (TMA + ), tetrapropylammonium (TPA + ) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.04 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 %

6.01-5.72
14.70-15.45
w-m

6.80-6.37
12.98-13.87
vs

10.22-9.94 
8.65-8.89
w

12.22-11.87
7.24-7.45
w

13.30-12.99
6.65-6.81
w

15.62-15.18
5.67-5.83
w

15.86-15.52
5.585-5.705
w

16.75-16.40
5.29-5.40
w

20.35-19.89
4.36-4.46
w-m

21.29-20.69
4.17-4.29
w

22.09-21.77
4.02-4.08
w-m

24.30-23.84
3.66-3.73
w

37.12-25.43
2.42-3.50
w-m

27.00-26.51
3.30-3.36
w-m

28.59-28.22
3.12-3.16
w-m

29.46-28.97
3.03-3.08
w-m

31.48-31.03
2.84-2.88
w-m

35.52-35.02
2.525-2.56 
w.

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

3. The metallophosphate material of claim 1 where R is tetraethylammonium cation, TEA + .

4. The metallophosphate material of claim 1 where R is the triethylpropylammonium cation, TEPA + .

5. The metallophosphate material of claim 1 where R is the diethylmethylpropylammonium cation, DEMPA + .

6. The metallophosphate material of claim 1 where R is the dimethylethylpropylammonium cation, DMEPA + .

7. The metallophosphate material of claim 1 where R is the methyltriethylammonium cation, MTEA + .

8. The metallophosphate material of claim 1 where R is the dimethyldipropylammonium cation, DMDPA + .

9. The metallophosphate material of claim 1 with crystal dimensions less than about 5 microns and preferably less than 3 microns and more preferably less than 2 microns.

10. 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 organoammonium cation selected from the group consisting of tetraethylammonium (TEA + ), triethylpropylammonium (TEPA + ), diethylmethylpropylammonium (DEMPA + ), dimethylethylpropylammonium (DMEPA + ), dimethyldipropylammonium (DMDPA + ), methyltriethylammonium (MTEA + ), ethyltrimethylammonium (ETMA + ), diethyldimethylammonium (DEDMA + ), choline, hexamethonium (HM 2+ ), propyltrimethylammonium (PTMA + ), butyltrimethylammonium (BTMA + ), hexamethonium (HM 2+ ), tetramethylammonium (TMA + ), tetrapropylammonium (TPA + ) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.04 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

Assignees

• Uop Llc

Inventors

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

Classifications

• B01J20/0292

  Phosphates of compounds other than those provided for in B01J20/048 · CPC title

• C10G11/04

  Oxides · CPC title

• C01B39/54

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

• C10G50/00

  Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation · CPC title

• B01J20/3078

  Thermal treatment, e.g. calcining or pyrolizing · CPC title