High meso-surface area, low Si/Al ratio pentasil zeolite

Patent metadata

Field	Value
Publication number	US-10167201-B2
Application number	US-201815996310-A
Country	US
Kind code	B2
Filing date	Jun 1, 2018
Priority date	Mar 3, 2015
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

A new family of crystalline aluminosilicate zeolites has been synthesized and designated as UZM-54. These zeolites are represented by the empirical formula:

M m n+ R 1 r1 p 1 + R 2 r2 p 2 + Al 1-x E x Si y O z

where M is an alkali, alkaline earth, or rare earth metal such as sodium or strontium, R 1 and R 2 are organoammonium cation and E is a framework element such as gallium, iron, boron, or indium. These zeolites are characterized by unique x-ray diffraction patterns, high meso-surface areas and low Si/Al 2 ratios and have catalytic properties for carrying out various hydrocarbon conversion processes.

First claim

What is claimed is:

1. A zeolite having a microporous crystalline structure comprising a framework of AlO 2 and SiO 2 tetrahedral units, and an empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
M m n+ R 1 r1 p 1 + R 2 r2 p 2 + AlSi y O z

where M is at least one exchangeable cation selected from the group consisting of alkali and alkaline earth metals, “m” is the mole ratio of M to Al and varies from about 0 to about 1, R 1 is at least one organoammonium cation selected from the group consisting of quaternary ammonium cation and diquaternary ammonium cations, “r 1 ” is the mole ratio of R 1 to Al and has a value of about 0.1 to about 3.0, R 2 is at least one organoammonium cation selected from the group consisting of protonated alkanolamines, protonated amines, protonated diamines, and quaternized alkanolammonium cations, “r 2 ” is the mole ratio of R 2 to Al and has a value of about 0 to about 3.0, “n” is the weight average valence of M and has a value of about 1 to about 2, “p 1 ” is the weighted average valence of R 1 and has a value of about 1 to about 2, “p 2 ” is the weighted average valence of R 2 and has a value of about 1 to about 2, “y” is the mole ratio of Si to Al and varies from greater than 11 to about 30 and “z” is the mole ratio of O to Al and has a value determined by the equation:
z =( m·n+r 1 ·p 1 +r 2 ·p 2 +3+4· y )/2

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

TABLE A

2Θ
d(Å)
I/Io

7.91-8.05
10.83-11.16
vs

8.84-9.01
9.80-9.99
vs

14.87-14.91
5.93-5.95
w-m

15.51-15.65
5.65-5.70
w

15.91-16.12
5.49-5.56
w

20.41-20.59
4.31-4.34
w

20.82-20.94
4.25-4.43
w

23.25-23.61
3.76-3.82
vs

23.84-23.92
3.71-3.72
m

24.35-24.75
3.59-3.65
m

26.80-26.95
3.30-3.32
w

29.33-29.46
3.02-3.04
w

30.01-30.13
2.96-2.97
w

30.32-30.32
2.94-2.94
w.

2. The zeolite of claim 1 wherein the zeolite has a mesopore surface area between 80 m 2 /g and 300 m 2 /g.

3. The zeolite of claim 1 wherein the zeolite consists of small colonies of nanocrystalline zeolite.

4. The zeolite of claim 1 wherein the zeolite has an individual crystal size from about 10-25 nm.

5. The zeolite of claim 1 further characterized by very strong peaks in the x-ray diffraction pattern at 2θ from 7.91-8.05, 8.84-9.01 and 23.25-23.61.

6. The zeolite of claim 1 wherein the zeolite is a pentasil zeolite.

7. The zeolite of claim 1 wherein the zeolite is thermally stable up to a temperature of 1000° C.

8. The zeolite of claim 1 wherein M is selected from the group consisting of lithium, sodium, potassium, cesium, strontium, calcium, barium and mixtures thereof.

9. The zeolite of claim 1 wherein M is a mixture of an alkali metal and an alkaline earth metal.

10. The zeolite of claim 1 wherein R 1 is selected from the group consisting of dimethyldipropylammonium, dimethyldipropylammonium, propyltrimethylammonium, hexamethonium, and mixtures thereof.

11. The zeolite of claim 1 wherein R 2 is selected from the group consisting of diethanolamine, N-methylethanolamine, 2-dimethylaminoethanol, N-methyldiethanolamine, 2-diethylamino ethanol, 2-isopropylamino ethanol, 2-diisopropylamino ethanol, 3-dimethylamino propanol and 2-aminopropanol and mixtures thereof.

12. The zeolite of claim 1 wherein r 2 is equal to zero.

13. The zeolite of claim 12 wherein R 1 is selected from the group consisting of dimethyldipropylamonium, dimethyldipropylammonium, propyltrimethylammonium, hexamethonium, and mixtures thereof.

14. The zeolite of claim 12 wherein R 1 is a mixture of dimethyldipropylamonium and a quaternary ammonium cation.

15. The zeolite of claim 12 wherein a silica/alumina (Si/Al 2 ) ratio is between 22 and 50.

16. The zeolite of claim 12 further characterized by a mesopore surface area greater than 80 m 2 /g.

17. The zeolite of claim 12 wherein R 1 is dimethyldipropylammonium cation, where a source of R 1 is halide or hydroxide compounds of R 1 .

18. The zeolite of claim 1 wherein a crystallite size is from 61 to about 600 Å.

19. The zeolite of claim 1 wherein a source of R 1 is dimethyldipropylammonium hydroxide.

20. The zeolite of claim 1 wherein the zeolite has a microporous crystalline structure comprising a framework of AlO 2 and SiO 2 tetrahedral units, further including the element E and having the empirical composition in the as synthesized and anhydrous basis expressed by the empirical formula of:
M m n+ R 1 r1 p 1 + R 2 r2 p 2 + Al 1-x E x Si y O z

where “m” is the mole ratio of M to (Al+E) and varies from about 0 to about 1, “r 1 ” is the mole ratio of R 1 to (Al+E) and has a value of about 0.1 to about 3.0, “r 2 ” is the mole ratio of R 2 to (Al+E) and has a value of about 0 to about 3.0, E is an element selected from the group consisting of gallium, iron, boron, indium and mixtures thereof, “x” is the mole fraction of E and has a value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) and varies from greater than 11 to about 30 and “z” is the mole ratio of O to (Al+E) and has a value determined by the equation:
z =( m·n+r 1 ·p 1 +r 2 ·p 2 +3+4· y )/2.

Assignees

• Uop Llc

Inventors

• Moscoso Jaime G
• Jan Deng-Yang

Classifications

• C01B39/36

  Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title

• B01J29/70 Primary

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• C01B39/48 Primary

  using at least one organic template directing agent · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• C01B39/40

  using at least one organic template directing agent · CPC title