Crystalline metallophosphates, their method of preparation, and use

Patent metadata

Field	Value
Publication number	US-10513440-B2
Application number	US-201816036745-A
Country	US
Kind code	B2
Filing date	Jul 16, 2018
Priority date	Jul 28, 2017
Publication date	Dec 24, 2019
Grant date	Dec 24, 2019

Abstract

A new family of crystalline microporous metallophosphates designated AlPO-85 has been synthesized. These metallophosphates are represented by the empirical formula

R + r M m 2+ EP x Si y O z

where M is a framework metal alkaline earth or transition metal of valence +2, such as magnesium or zinc, R is an organoammonium cation, and E is a trivalent framework element such as aluminum or gallium. The AlPO-85 compositions are characterized by a new unique ABC-6 net structure, and have catalytic properties suitable for carrying out various hydrocarbon conversion processes, as well as characteristics suitable for adsorption applications.

First claim

The invention claimed is:

1. A microporous crystalline material having a three-dimensional framework of at least EO 4/2 − and PO 4/2 + tetrahedral units and furthermore, at least one of [M 2+ O 4/2 ] 2− and SiO 4/2 tetrahedral units and an empirical composition in the as-synthesized form and anhydrous basis expressed by an empirical formula of:
R + r M m 2+ EP x Si y O z
where M is at least one metal cation of valence +2 selected from the group consisting of Mg 2+ , Zn 2+ , Co 2+ , Mn 2+ , Fe 2+ , Ni 2+ , “m” is the mole ratio of M to E and varies from 0 to about 1.0, R is an organoammonium cation prepared from the reaction of an aqueous mixture of a cyclic secondary amine and an organic dihalide, “r” is the mole ratio of R to E and has a value of about 0.1 to about 2.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, “and “z” is the mole ratio of O to E and has a value determined by the equation:
z =(2 ·m+r+ 3+5 ·x+ 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 1:

TABLE 1

2-Theta
d (Å)
Intensity

7.93-8.14
11.14-10.85
vw-w

8.51-8.83
10.38-10.00
w

11.60-11.88
7.62-7.44
w-m

13.61-13.94
6.50-6.35
vw-w

15.75-16.02
5.62-5.53
vw-w

17.08-17.36
5.19-5.10
w

17.96-18.24
4.93-4.86
s

18.83-20.07
4.71-4.42
m-s

20.91-21.15
4.24-4.20
w-m

21.94-22.29
4.05-3.98
w

22.61-22.88
3.93-3.88
s-vs

23.32-23.65
3.81-3.76
m-s

23.71-23.95
3.75-3.71
w-m

25.72-26.01
3.46-3.42
w-m

26.93-27.34
3.31-3.26
s-vs

27.45-27.74
3.26-3.21
m-s

29.91-30.22
2.98-2.95
vw-w

30.33-30.57
2.94-2.92
w-m

32.88-33.25
2.72-2.69
m-s

33.31-33.70
2.69-2.66
m-s

34.42-34.86
2.60-2.57
w-m.

2. The microporous crystalline material of claim 1 in calcined form comprising a three-dimensional framework of at least EO 4/2 − and PO 4/2 + tetrahedral units, and furthermore, at least one of [M 2+ O 4/2 ] 2− and SiO 4/2 tetrahedral units and an empirical composition in the calcined form and anhydrous basis expressed by an empirical formula of:
H w M m 2+ EP x Si y O z
where M is at least one metal cation of valence +2 selected from the group consisting of, Mg 2+ ,Zn 2+ ,Co 2+ ,Mn 2+ ,Fe 2+ ,Ni 2+ , “m” is the mole ratio of M to E and varies from 0 to about 1.0, E is a trivalent element selected from the group consisting of aluminum, gallium, iron, boron and mixtures thereof, “x” is mole ratio of P to E and varies from 0.5 to about 2.0, “y” is the mole ratio of Si to E and varies from 0 to about 1.0, H is a proton, “w” is the mole ratio of H to E and varies from 0 to 2.5, and “z” is the mole ratio of O to E and has a value determined by the equation:
z =( w+ 2 ·m+ 3+5 ·x+ 4 ·y )/2

and characterized in that it has the x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table 2:

TABLE 2

2-Theta
d (Å)
Intensity

7.81-8.03
11.31-11.00
vw-w

11.65-11.91
7.59-7.42
s-vs

13.62-13.88
6.49-6.37
m-s

14.06-14.36
6.29-6.16
m-s

17.31-17.59
5.12-5.04
vw-w

17.97-18.22
4.93-4.86
w

19.04-19.32
4.66-4.59
m-s

20.86-21.30
4.25-4.17
vw-w

22.17-22.45
4.00-3.96
vw-w

22.66-22.94
3.92-3.87
w-m

23.62-24.03
3.76-3.70
w-m

27.37-27.62
3.25-3.23
s

Assignees

• Uop Llc

Inventors

• Yuhas Benjamin D
• Galey Melissa M
• Miller Mark A

Classifications

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• B01J20/18

  Synthetic zeolitic molecular sieves · CPC title

• C01B39/54 Primary

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

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title