High charge density silicometallophosphate molecular sieves SAPO-79

Patent metadata

Field	Value
Publication number	US-10449527-B2
Application number	US-201715446296-A
Country	US
Kind code	B2
Filing date	Mar 1, 2017
Priority date	Mar 4, 2016
Publication date	Oct 22, 2019
Grant date	Oct 22, 2019

Abstract

A new family of high charge density crystalline microporous silicometallophosphate designated SAPO-79 has been synthesized. These silicometallophosphate are represented by the empirical formula of:

R p+ r M m + E x PSi y O z

where M is an alkali metal such as potassium, R is an organoammonium cation such as diethyldimethylammonium and E is a trivalent framework element such as aluminum or gallium. The SAPO-79 family of materials represent the first alkali-stabilized phosphate-based molecular sieves to have the ERI 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 silicometallophosphate material having a three-dimensional framework of [EO 4/2 ] − and [PO 4/2 ] + 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 p+ r M m + E x PSi y O z

where R is an organoammonium cation selected from the group consisting of diethyldimethylammonium (DEDMA + ), ethyltrimethylammonium (ETMA + ), hexamethonium (HM 2+ ), choline [Me 3 NCH 2 CH 2 OH] + , trimethylpropylammonium, tetramethylammonium (TMA + ), tetraethylammonium (TEA + ), tetrapropylammonium (TPA + ) and mixtures thereof, “r” is the mole ratio of R to P and has a value of about 0.2 to about 3.0, “p” is the weighted average valence of R and varies from 1 to 2(PRIOR ART 2), M is an alkali metal such as Li + , Na + , K + , Rb + and Cs + and mixtures thereof, “m” is the mole ratio of M to P and varies from 0.2 to 3.0, E is a trivalent element selected from the group consisting of aluminum and gallium and mixtures thereof, “x” is mole ratio of E to P and varies from 1.25 to about 4.0, “y” is the mole ratio of Si to P and varies from 0.30 to about 4.5, “y”>“x”−1, and “z” is the mole ratio of O to P and has a value determined by the equation:
z=(m+p·r+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 %

7.77-7.64
11.37-11.56
vs

9.68-9.54
9.13-9.26
w-m

11.79-11.59
7.50-7.63
w-m

13.47-13.24
6.57-6.68
m

14.11-13.91
6.27-6.36
w-m

15.53-15.32
5.70-5.78
w-m

16.62-16.37
5.33-5.41
w

17.90-17.69
4.95-5.01
w

19.54-19.28
4.54-4.60
m-vs

20.59-20.17
4.31-4.40
m-s

21.39-21.14
4.15-4.20
w-m

23.33-23.08
3.81-3.85
m-s

23.71-23.45
3.75-3.79
m-vs

24.89-24.57
3.575-3.62 
m-s

27.00-26.67
3.30-3.34
w-m

27.25-26.91
3.27-3.31
w-m

28.13-27.77
3.17-3.21
w-m

28.40-28.04
3.14-3.18
w-m

30.54-30.22
2.925-2.955
w

31.25-30.92
2.86-2.89
m-vs

31.48-31.14
2.84-2.87
m-vs

31.82-31.48
2.81-2.84
w-m

33.80-33.41
2.65-2.68
w

35.89-35.60
2.50-2.52
w-m

36.12-35.89
2.485-2.50 
w-m

40.89-40.51
2.205-2.225
w

42.72-42.30
2.115-2.135
w

43.04-42.65
 2.10-2.118
w

43.47-43.04
2.08-2.10
w

49.64-49.21
1.835-1.85 
w

51.44-51.13
1.775-1.785
w-m.

2. The silicometallophosphate material of claim 1 where M is potassium.

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

4. The silicogallophosphate material of claim 1 where E is gallium.

5. The silicometallophosphate material of claim 1 in where “y”>“x”−0.2.

6. The silicometallophosphate material of claim 1 where the silicometallophosphate material is thermally stable up to a temperature of at least 500° C.

7. The silicometallophosphate material of claim 1 where R is diethyldimethylammonium cation, DEDMA + .

8. A stable, calcined form of the crystalline microporous silicometallophosphate of claim 1 , comprising a three-dimensional framework of [EO 4/2 ] − and [PO 4/2 ] + and SiO 4/2 tetrahedral units characterized in having a x-ray diffraction pattern having at least the d-spacings and intensities set forth in Table B:

TABLE B

2Θ
d(Å)
I/I 0 %

7.81-7.67
11.31-11.52
vs

9.78-9.61
9.04-9.20
w-m

11.87-11.68
7.45-7.57
w-m

13.53-13.28
6.54-6.66
m-s

14.20-13.98
6.23-6.33
w

15.62-15.34
5.67-5.77
w

16.65-16.43
5.32-5.39
w

19.62-19.32
4.52-4.59
w-m

20.69-20.31

Assignees

• Uop Llc

Inventors

• Lewis Gregory J
• Knight Lisa

Classifications

• B01J29/85 Primary

  Silicoaluminophosphates [SAPO compounds] · 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

• C10G45/12

  containing crystalline alumino-silicates, e.g. molecular sieves · CPC title

• C10G3/49

  containing crystalline aluminosilicates, e.g. molecular sieves · CPC title

• C01P2002/74

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