Zeolite-based adsorbents based on LSX zeolite of controlled outer surface area, process for preparing them and uses thereof

Patent metadata

Field	Value
Publication number	US-9919289-B2
Application number	US-201515526130-A
Country	US
Kind code	B2
Filing date	Nov 13, 2015
Priority date	Nov 13, 2014
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

The present invention relates to a zeolite-based adsorbent comprising at least one zeolite of FAU structure of LSX type and comprising barium and/or potassium, in which the outer surface area of said zeolite-based adsorbent, measured by nitrogen adsorption, is between 20 m 2 ·g −1 and 100 m 2 ·g −1 , limits inclusive. The present invention also relates to the use of such a zeolite-based adsorbent as an adsorption agent, and also to the process for separating para-xylene from aromatic isomer fractions containing 8 carbon atoms.

First claim

What is claimed is:

1. A zeolite-based adsorbent comprising at least one zeolite of FAU structure of LSX type, comprising at least one of barium or potassium, the zeolite-based adsorbent having an outer surface area, wherein the outer surface area of said zeolite-based adsorbent as measured by nitrogen adsorption is between 20 m 2 ·g −1 and 100 m 2 ·g −1 , limits inclusive.

2. The zeolite-based adsorbent according to claim 1 , wherein the zeolite of FAU structure is a zeolite of FAU structure of LSX type in the form of crystals having a number-mean diameter of between 0.5 μm and 20 μm, limits inclusive.

3. The zeolite-based adsorbent according to claim 1 having a content of barium (Ba) expressed as barium oxide (BaO) of greater than 25% by weight relative to the total weight of the adsorbent.

4. The zeolite-based adsorbent according to claim 1 , having a content of potassium (K), expressed as potassium oxide (K 2 O), of less than 30% by weight relative to the total weight of the adsorbent.

5. The zeolite-based adsorbent according to claim 1 , wherein the zeolite-based adsorbent has macropores and mesopores, and wherein the total volume contained in the macropores and mesopores, measured by mercury intrusion, is between 0.15 cm 3 ·g −1 and 0.5 cm 3 ·g −1 limits inclusive.

6. The zeolite-based adsorbent according to claim 1 wherein the mass fraction of FAU zeolite in the adsorbant is greater than or equal to 85% by weight relative to the total weight of the adsorbent.

7. The zeolite-based adsorbent according to claim 1 , wherein the zeolite-based adsorbent has a macropore volume and a mesopore volume and a ratio expressed as (macropore volume)/(macropore volume+mesopore volume) ratio of between 0.2 and 1, limits inclusive.

8. A process for preparing the zeolite-based adsorbent according to claim 1 , said process comprising at least the steps of:
a) agglomerating crystals of at least one zeolite of FAU structure of LSX type, the zeolite having an outer surface area of between 20 m 2 ·g −1 and 150 m 2 ·g −1 , limits inclusive, the zeolite being in the form of crystals, wherein the number-mean diameter of the crystals is between 0.5 μm and 20 μm, limits inclusive, with a binder and also with an amount of water which allows forming of an agglomerated material, followed by drying and calcination of the agglomerated material;
b) optionally, carrying out a step involving zeolitization of all or part of the binder by placing the agglomerated material obtained in step a) in contact with an aqueous basic solution;
c) carrying out cationic exchange(s) of the agglomerated material of step b) by placing the agglomerated material in contact with a solution of at least one of barium ions or potassium ions;
d) optionally, carrying out additional cationic exchange of the agglomerated material of step c) by placing the agglomerated material in contact with a solution of potassium ions;
e) washing and drying of the agglomerates obtained in steps c) or d), at a temperature of between 50° C. and 150° C.; and
f) producing the zeolite-based adsorbent by activation of the agglomerates obtained in step e) under a stream of a gas selected from the group consisting of oxidizing gases and inert gases, wherein the gas is at a temperature of between 100° C. and 400° C.

9. A process according to claim 8 , wherein the binder is comprised of at least one clay selected from the group consisting of kaolins, kaolinites, nacrites, dickites, halloysites, attapulgites, sepiolites, montmorillonites, bentonites, illites and metakaolins, and mixtures thereof in all proportions.

10. A process, comprising using a zeolite-based adsorbent according to claim 1 as an adsorption agent in:
separating C8 aromatic isomer fractions,
separating substituted toluene isomers,
separating cresols, or
separating polyhydric alcohols.

11. A separation process for gas-phase or liquid-phase separation of xylene isomers using at least one zeolite-based adsorbent according to claim 1 .

12. The separation process according to claim 11 , wherein the process is a process for separating para-xylene from a feedstock of aromatic isomer fractions containing 8 carbon atoms.

13. The process according to claim 12 , wherein the process is performed in a simulated moving bed industrial adsorption unit, functioning in counter-current mode, under the following operating conditions:
number of beds: 4 to 24;
number of zones: at least 4 operating zones, each being located between a feed point and a withdrawal point;
temperature between 100° C. and 250° C.;
pressure between the bubble pressure of xylenes (or of toluene when toluene is chosen as desorbent) at the process temperature and 3 MPa;
ratio of the flow rates of desorbent to feedstock to be treated: 0.7 to 2.5;
recycling rate: 2 to 12, preferably 2.5 to 6;
cycle time, corresponding to the time between two injections of desorbent onto a given bed: between 4 and 25 minutes.

14. The process according to claim 13 , wherein the desorbent is toluene or para-diethylbenzene.

15. The process according to claim 13 wherein the inlet streams have a water content which is adjusted to between 20 ppm and 150 ppm.

16. The zeolite-based adsorbent comprising of claim 1 wherein the outer surface area of said zeolite-based adsorbent, as measured by nitrogen adsorption, is between 30 and 80 m 2 ·g −1 , limits inclusive.

17. The zeolite-based adsorbent according to claim 2 , wherein the zeolite of FAU structure is a zeolite of FAU structure of LSX type for which the number-mean diameter of the crystals is between 1 μm and 8 μm, limits inclusive.

18. The zeolite-based adsorbent according to claim 3 , wherein the content of barium (Ba) expressed as barium oxide (BaO) is greater than 37% by weight relative to the total weight of the adsorbent.

19. The zeolite-based adsorbent according to claim 4 , wherein the content of potassium (K), expressed as potassium oxide (K 2 O), is between 0 and 10%, limits inclusive, by weight relative to the total weight of the adsorbent.

20. The zeolite-based adsorbent according to claim 5 , wherein the total volume contained in the macropores and mesopores, measured by mercury intrusion, is between 0.20 cm 3 ·g −1 and 0.35 cm 3 ·g −1 , limits inclusive.

21. The zeolite-based adsorbent according to claim 6 , wherein the mass fraction of FAU zeolite in the adsorbent is greater than or equal to 90% by weight relative to the total weight of the adsorbent.

22. The zeolite-based adsorbent according to claim 7 , wherein the ratio expressed as (macropore volume)/(macropore volume+mesopore volume) ratio is between 0.5 and 0.9, limits inclusive.

Assignees

• Ifp Energies Now
• Arkema France

Inventors

• Bouvier Ludivine
• Lutz Cécile
• Laroche Catherine
• Grandjean Julien
• Baudot Arnaud

Classifications

• B01J20/3085

  Chemical treatments not covered by groups B01J20/3007 - B01J20/3078 · CPC title

• B01J20/183 Primary

  Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation · CPC title

• B01D2253/31

  Pore size distribution · CPC title

• B01D53/02

  by adsorption, e.g. preparative gas chromatography {(solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01)} · CPC title

• B01J20/3007

  Moulding, shaping or extruding · CPC title