Hierarchically porous zeolites

Patent metadata

Field	Value
Publication number	US-10071914-B2
Application number	US-201414892101-A
Country	US
Kind code	B2
Filing date	Aug 6, 2014
Priority date	Sep 2, 2013
Publication date	Sep 11, 2018
Grant date	Sep 11, 2018

Abstract

The present invention concerns Y-type FAU zeolites with hierarchical porosity having an Si/Al atomic ratio strictly greater than 1.4 and less than or equal to 6, having controlled and optimised crystallinity, and having mesoporosity such that the mesoporous outer surface area is between 40 m 2 ·g −1 and 400 m 2 ·g −1 . The present invention also concerns the method for preparing said Y-type FAU zeolites with hierarchical porosity.

First claim

The invention claimed is:

1. A process for preparing a hierarchically porous zeolite having at least the following characteristics:
Si/Al atomic ratio greater than 1.4 and less than 6,
micropore volume Vμp, in cm 3 ·g −1 , which satisfies the equation Vμp=Vμp R ±15%, where Vμp R represents the micropore volume, in cm 3 ·g −1 , measured under the same conditions, for a zeolite of the same chemical nature and of the same crystalline structure, but the mesoporous outer surface area of which is less than 40 m 2 ·g −1 , and
mesoporosity such that the mesoporous outer surface area is between 40 m 2 ·g −1 and 400 m 2 ·g −1 ;
the process comprising at least the following steps:
a) preparing a growth gel for synthesizing a FAU zeolite of Y type, by mixing a source of silica with a source of alumina, at a temperature of between 0° C. and 60° C.,
b) adding to the growth gel of step a) at least one nucleating agent, at a temperature of between 0° C. and 60° C. to obtain a reaction medium,
c) adding to the reaction medium at least one structuring agent,
d) increasing the temperature to cause a crystallization reaction and obtain zeolite crystals,
e) filtering and washing the zeolite crystals obtained, and
f) drying and calcining the zeolite crystals.

2. The process according to claim 1 , wherein the nucleating agent is a nucleating gel.

3. The process according to claim 2 , wherein the amount of nucleating gel added is between 0.1% and 20%, limits inclusive, relative to the weight of the growth gel.

4. The process according to claim 1 , wherein the nucleating agent is a crystal.

5. The process according to claim 4 , wherein the amount crystal added is between 0.1% and 10% by weight relative to the total weight of growth gel.

6. The process according to claim 1 , wherein the source of silica is sodium silicate or colloidal silica and the source of alumina is alumina trihydrate.

7. The process according to claim 1 , wherein the structuring agent is an organosilane.

8. The process according to claim 1 , wherein the structuring agent is selected from the group consisting of [3-(trimethoxysilyl)propyl]octadecyldimethylammonium chloride, [3-(trimethoxysily)propyl]hexadecyldimethylammonium chloride, [3-(trimethoxysilyl)propyl]-dodecyldimethylammonium chloride, [3-(trimethoxysily)propyl]octylammonium chloride, N3-(trimethoxysilyl)propyl]aniline, 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane, N-[3-(trimethoxysilyl)propyl]-N′-(4-vinylbenzyl)ethylenediamine, triethoxy-3-(2-imidazolin-1-yl)propylsilane, 1-[3-(trimethoxysilyl)propyl]urea, N-[3-(trimethoxysilyl)propyl]-ethylenediamine, [3-(diethylamino)propyl]trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, 3-(trimethoxysilyl]propylmethacrylate, [2-(cyclohexenyl)ethyl]triethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, (3-aminopropyl)trimethoxysilane, (3-mercaptopropyl)trimethoxysilane, (3-chloropropyl)trimethoxysilane, and also mixtures of two or more thereof in all proportions.

9. The process according to claim 1 , wherein the amount of structuring agent(s) is such that the structuring agent(s)/starting/Al 2 O 3 mole ratio is between 0.005 and 0.20, limits inclusive.

10. A hierarchically porous zeolite having at least the following characteristics:
Si/Al atomic ratio greater than 1.4 and less an 6,
micropore volume Vμp, in cm 3 ·g −1 , which satisfies the equation Vμp=Vμp R ±15%, where Vμp R represents the micropore volume, in cm 3 ·g −1 , measured under the same conditions wherein the micropore volume is measured according to Dubinin and Raduskevitch by applying standard ISO 15901-3 (2007), for a zeolite of the same chemical nature and of the same crystalline structure, but the mesoporous outer surface area of which is less than 40 m 2 ·g −1 , and
mesoporosity such that the mesoporous outer surface area is between 60 m 2 ·g −1 and 150 m 2 ·g −1 .

11. A hierarchically porous zeolite having at least the following characteristics:
Si/Al atomic ratio between 1.5 and 3, limits inclusive,
micropore volume Vμp, in cm 3 ·g −1 , which satisfies the equation Vμp=Vμp R ±15%, where Vμp R represents the micropore volume, in cm 3 ·g −1 , measured under the same conditions wherein the micropore volume is measured according to Dubinin and Raduskevitch by applying standard ISO 15901-3 (2007), for a zeolite of the same chemical nature and of the same crystalline structure, but the mesoporous outer surface area of which is less than 40 m 2 ·g −1 and
mesoporosity such that the mesoporous outer surface area is between 40 and 400 m 2 ·g −1 .

12. A hierarchically porous zeolite having a leas the following characteristics:
Si/Al atomic ratio greater than 1.4 and less than 6,
a micropore volume Vμp which satisfies the equation Vμp=Vμp R ±3%, where Vμp R represents the micropore volume measured, under the same conditions, for a zeolite of the same chemical nature and of the same crystal structure wherein the micropore volume is measured according to Dubinin and Raduskevitch by applying standard ISO 15901-3(2007), which is perfectly crystalline but having a mesopore outer surface area which is less than 40 m 2 ·g −1
mesoporosity such that the mesoporous outer surface area is between 40 m 2 ·g −1 and 400 m 2 ·g −1 .

Assignees

• Arkema France

Inventors

• Nicolas Serge
• Bouvier Ludivine
• Lutz Cécile

Classifications

• C01P2006/17

  Pore diameter distribution · CPC title

• C01B39/04

  using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound · CPC title

• C01P2006/14

  Pore volume · CPC title

• C01P2002/22

  layered hydroxide-type, e.g. of the hydrotalcite-type · CPC title

• C01B39/24 Primary

  Type Y {(C01B39/205 takes precedence)} · CPC title