Zeolitic adsorbents with large external surface area, process for preparing them and uses thereof

Patent metadata

Field	Value
Publication number	US-9914109-B2
Application number	US-201414917457-A
Country	US
Kind code	B2
Filing date	Sep 5, 2014
Priority date	Sep 9, 2013
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

The present invention relates to zeolitic adsorbents based on agglomerated crystals of FAU zeolite comprising barium and/or potassium, with large external surface area, combining optimum properties in terms of selectivity and mechanical strength.
These adsorbents find applications in the separation of cuts of C8-aromatic isomers and notably of xylenes, in the separation of isomers of substituted toluene such as nitrotoluene, diethyltoluene, toluenediamine, in the separation of cresols, and polyhydric alcohols, such as sugars.

First claim

The invention claimed is:

1. A zeolitic adsorbent comprising at least one FAU zeolite and comprising at least one of barium and potassium, wherein the external surface area of said zeolitic adsorbent, measured by nitrogen adsorption, is greater than 20 m 2 ·g −1 .

2. A zeolitic adsorbent according to claim 1 , having a content of barium oxide (BaO) above 10% relative to the total weight of the adsorbent, and having a barium content between 23% and 42%, inclusive, by weight relative to the total weight of the zeolitic adsorbent.

3. A zeolitic adsorbent according to claim 1 , having a content of potassium oxide K 2 O below 25% by weight relative to the total weight of the zeolitic adsorbent.

4. A zeolitic adsorbent according to claim 1 , wherein said FAU zeolite has an Si/Al atomic ratio between 1.00 and 1.50 inclusive.

5. A zeolitic adsorbent according to claim 1 , wherein no zeolitic structure other than a faujasite structure is detected by X-ray diffraction.

6. A zeolitic adsorbent according to claim 1 , wherein the fraction by weight of FAU zeolite is greater than or equal to 80% relative to the total weight of zeolitic adsorbent.

7. A zeolitic adsorbent according to claim 1 , having a loss on ignition measured at 900° C. according to standard NF EN 196-2 of less than or equal to 7.7%.

8. A zeolitic adsorbent according to claim 1 , having a total volume of macropores and mesopores, measured by mercury intrusion porosimetry, of between 0.15 cm 3 ·g −1 and 0.5 cm 3 ·g 31 1 .

9. A zeolitic adsorbent according to claim 1 , having a volume fraction of macropores of between 0.2 and 1 of the total volume of macropores and mesopores, inclusive.

10. A zeolitic adsorbent according to claim 1 , having a number-average diameter of crystalline elements of between 0.1 μm and 20 μm, inclusive.

11. A process for preparing a zeolitic adsorbent according to claim 1 , comprising at least the steps of:
a) agglomerating crystalline elements of at least one FAU type zeolite, having an external surface area greater than 40 m 2 ·g −1 , with number-average diameter between 0.1 μm and 20 μm inclusive, with a binder comprising at least 80% of clay or of a mixture of clays, optionally zeolitizable, and with up to 5% of additives as well as with an amount of water that allows forming of an agglomerated material; drying the agglomerated material at a temperature between 50° C. and 150° C. to form dried agglomerates; calcining the dried agglomerates while flushing with oxidizing and/or inert gas, optionally dry and/or decarbonated, at a temperature above 150° C. for a number of hours;
b) optionally zeolitizing some or all of the binder by bringing the agglomerated material obtained in step a) into contact with an alkaline basic solution;
c) cationic exchanging the agglomerated material from step a) and/or from step b) by bringing the agglomerated material into contact with a solution of at least one of barium ions and potassium ions;
d) optionally, cationic exchanging the agglomerated material from step c) by bringing the agglomerated material into contact with a solution of potassium ions;
e) washing and drying the agglomerated material obtained in steps c) or d), at a temperature between 50° C. and 150° C.; and
f) obtaining the zeolitic adsorbent according to claim 1 by activating the agglomerated material obtained in step e) while flushing with oxidizing and/or inert gas, optionally dry and/or decarbonated, at a temperature between 100° C. and 400° C. for a time determined as a function of the desired water content and loss on ignition of the zeolitic adsorbent.

12. A method according to claim 11 , wherein said at least one FAU type zeolite has an Si/Al atomic ratio between 1.00 and 1.50, inclusive.

13. A zeolitic adsorbent obtained by the method according to claim 11 .

14. A process for using an adsorbent, wherein the adsorbent is a zeolitic adsorbent in accordance with claim 1 and the process is selected from the group consisting of:
separating cuts of C8-aromatic isomers,
separating isomers of substituted toluenes,
separating cresols, and
separating polyhydric alcohols.

15. A process according to claim 14 , wherein the process is separating para- xylene from cuts of aromatic isomers with 8 carbon atoms.

Assignees

• Ceca Sa
• Ifp Energies Now
• Arkema France

Inventors

• Laroche Catherine
• Leflaive Philibert
• Bouvier Ludivine
• Nicolas Serge
• Lutz Cecile
• Labede Marie-Laurence

Classifications

• B01D53/08

  according to the "moving bed" method · CPC title

• C07C205/06

  having nitro groups bound to carbon atoms of six-membered aromatic rings · CPC title

• B01J20/12

  Naturally occurring clays or bleaching earth · CPC title

• C07C209/86

  Separation · CPC title

• B01J20/28061

  being in the range 100-500 m2/g · CPC title