Method for the preparation of synthetic crystalline zeolite materials with enhanced pore volume

Patent metadata

Field	Value
Publication number	US-2018194635-A1
Application number	US-201515323112-A
Country	US
Kind code	A1
Filing date	Jul 8, 2015
Priority date	Jul 9, 2014
Publication date	Jul 12, 2018
Grant date	—

Abstract

The present invention relates to a method for the preparation of a synthetic crystalline zeolite material, to said synthetic crystalline zeolite material, and to the uses of said method and said synthetic crystalline zeolite material in various applications.

First claim

1 . A method for the preparation of a synthetic crystalline zeolite material comprising micropores and eventually mesopores, said synthetic crystalline zeolite material having a silicon to aluminum molar ratio Si/Al≥1 and, wherein said method comprises at least the following steps:
1) a step of contacting a NH 4 F solution with a dry starting crystalline zeolite material at a temperature ranging from 0° C. to 100° C., said NH 4 F solution having a NH 4 F mass concentration of at least 15 wt % and said starting crystalline zeolite material being essentially microporous and having a silicon to aluminum molar ratio Si/Al≥1;
2) a washing step;
3) a drying step at a temperature ranging from 25° C. to 120° C., for 1 h to 24 h, to recover said synthetic crystalline zeolite material.

2 . The method according to claim 1 , wherein step 1) is carried out for a time ranging from 5 to 180 minutes.

3 . The method according to claim 1 , wherein the pH of the NH 4 F solution before step 1) is 7.

4 . The method according to claim 1 , wherein the mass ratio of solid NH 4 F/starting crystalline zeolite material used in step 1) ranges from 0.5 to 25.

5 . The method according to claim 1 , wherein it further comprises a step 4) of ion exchanging.

6 . The method according to claim 1 , wherein the NH 4 F solution used in step 1) has a NH 4 F mass concentration of at least 20 wt %.

7 . The method according to claim 1 , wherein it leads to an increase of the total pore volume of at least 15%, with respect to the total pore volume of the starting crystalline zeolite material.

8 . The method according to claim 1 , wherein step 1) is carried out by contacting the starting crystalline zeolite material with the whole NH 4 F solution in only one go and/or rapidly.

9 . The method according to claim 1 , wherein step 1) is performed by:
immersing the dry starting crystalline zeolite material in the NH 4 F solution to form a heterogeneous mixture, and then by stirring said heterogeneous mixture; or pouring the NH 4 F solution on the dry starting crystalline zeolite material so as to saturate its micropore volume, and then by filtrating it so as to remove the excess of NH 4 F solution and to form an impregnated solid.

10 . The method according to claim 1 , wherein it further comprises a step 6) of functionalizing said synthetic crystalline zeolite material with at least one active compound.

11 . A synthetic crystalline zeolite material prepared according to the method as defined in claim 1 , wherein said synthetic crystalline zeolite material comprises micropores having a mean dimension of more than 1 nm, and eventually mesopores and has a silicon to aluminum molar ratio Si/Al≥1.

12 . A synthetic crystalline zeolite material according to claim 11 , wherein said synthetic crystalline zeolite material further comprises mesopores having a mean dimension of 2 to 25 nm.

13 . A synthetic crystalline zeolite material according to claim 11 , wherein said synthetic crystalline zeolite material has a mesopore volume of at least 0.05 cm 3 /g.

14 . A synthetic crystalline zeolite material according to claim 11 , wherein said synthetic crystalline zeolite material has a micropore volume of at least 0.1 cm 3 /g.

15 . The method as defined in claim 1 , wherein said method increases the total pore volume of a crystalline zeolite material which is essentially microporous.

16 . The method as defined in claim 1 , wherein said method introduces micropores having a mean dimension of more than 1 nm and/or to introduce mesopores having a mean dimension of 2 to 25 nm while maintaining or increasing the micropore volume, in a crystalline zeolite material which is essentially microporous.

17 . A synthetic crystalline zeolite material prepared according to the method as defined in claim 1 , so as to incorporate active compounds thanks to its newly created micro- and/or mesoporous network.

18 . A synthetic crystalline zeolite material prepared according to the method as defined in claim 1 , as a catalyst or adsorbent in gas-solid and liquid-solid reactions, as seed crystals for zeolite material synthesis, and for the preparation of membranes or layers.

Assignees

• Centre Nat Rech Scient

Inventors

• VALTCHEV Valentin
• Gilson Jean-Pierre
• Qin Zhengxing

Classifications

• C01B39/24

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

• B01J37/30

  Ion-exchange · CPC title

• B01J2229/38

  Base treatment · CPC title

• B01J29/18

  of the mordenite type · CPC title

• C01B39/26

  Mordenite type {(C01B39/023, C01B39/026, C01B39/06 take precedence)} · CPC title